山田 道夫 （ヤマダ ミチオ）
| 自然科学系 基礎自然科学講座 分子化学分野 | 准教授 |
研究者情報 （担当授業科目については、ページ一番下の「授業ガイド（シラバス検索）」をご利用ください。）
基本情報
経歴
- 日本学術振興会
2007年04月01日 - 2008年03月31日, 特別研究員（DC2） - 日本学術振興会
2008年04月01日 - 2009年03月31日, 特別研究員（PD） - スイス連邦工科大学チューリッヒ校
2008年04月01日 - 2009年03月31日, 有機化学研究所, 客員研究員 - スイス連邦工科大学チューリッヒ校
2009年04月01日 - 2010年03月31日, 有機化学研究所, 博士研究員 - 東京学芸大学
2010年04月01日 - 2015年03月31日, 教育学部, 助教 - 筑波大学
2010年10月 - 2013年03月, 生命領域学際研究センター, 客員研究員 - 東京学芸大学
2015年04月 - 現在, 教育学部, 准教授
所属学協会
共同研究・競争的資金等の研究課題
- 徳山科学技術振興財団研究助成, 光電変換材料を指向した剛直なフラーレン誘導体の創製と配列制御, 徳山科学技術振興財団研究助成, 2022年04月 - 2023年03月, 競争的資金
- 松籟科学技術振興財団研究助成, 空間を介したフラーレンπ電子共役系の拡張と制御に関する研究, 松籟科学技術振興財団研究助成, 2022年03月 - 2024年03月, 競争的資金
- 公益財団法人国際科学振興財団
金属内包フラーレンの分子変換法の創出と機能開拓, 基盤研究(C), 2020年04月01日 - 2023年03月01日, 競争的資金 - 東京学芸大学
フラーレンの多重開口反応による湾曲ナノカーボン分子のトップダウン合成, 基盤研究(C), 2020年04月01日 - 2023年03月01日, 競争的資金 - 旭硝子財団研究助成, フラーレンを基盤とする阻害剤開発のための分子間相互作用の計測と評価, 旭硝子財団研究助成, 2019年04月01日 - 2021年03月31日, 競争的資金
- 野口研究所野口遵研究助成金, 鉄原子内包フラーレン合成への挑戦, 野口研究所野口遵研究助成金, 2019年04月01日 - 2020年03月31日, 競争的資金
- 公益財団法人国際科学振興財団
金属内包フラーレンの化学修飾による機能開拓, 基盤研究(C), 2017年04月01日 - 2020年03月01日, 競争的資金 - 東京学芸大学
動的共有結合を介したポルフィリンの組織化に基づくナノカーボンの分子認識, 若手研究(B), 2016年04月01日 - 2019年03月01日, 競争的資金 - 戸部真紀財団研究助成, 遷移金属触媒を用いたカスケード反応によるフラーレンのワンポット分子変換法の開発, 戸部真紀財団研究助成, 2016年04月01日 - 2017年03月31日, 競争的資金
- 国際科学技術財団研究助成, 遷移金属カルベン錯体を用いたフラーレンの分子変換による革新的な光電変換材料の開発, 国際科学技術財団研究助成, 2015年04月01日 - 2016年03月31日, 競争的資金
- 東京学芸大学
ナノカーボンの分子変換による革新的近赤外発光プローブの創製, 基盤研究(B), 2014年04月01日 - 2017年03月01日, 競争的資金 - 東京学芸大学
捩じれたπ電子系分子ピンセットを用いたカーボンナノチューブの光学分割, 若手研究(B), 2012年04月01日 - 2015年03月01日, 競争的資金 - 倉田記念日立科学技術財団倉田奨励金, カーボンナノチューブのキラリティを認識するπ電子系分子ピンセットの開発, 倉田記念日立科学技術財団倉田奨励金, 2011年04月01日 - 2012年03月31日, 競争的資金
- 筑波大学
π空間に閉じ込められた物質系の創製と機能, 新学術領域研究(研究領域提案型), 2008年04月01日 - 2013年03月31日, 競争的資金 - 筑波大学
組織化常磁性フラーレンの創製と機能, 基盤研究(A), 2008年04月01日 - 2012年03月31日, 競争的資金
研究活動情報
書籍等出版物
- Handbook of Fullerene Science and Technology
2022年09月25日, Functionalization of Fullerenes: Addition Reaction, Springer, 978-981-16-8993-2 - 導電性材料の設計, 導電性制御および最新応用展開
2021年12月, (2) SWNTsの界面活性剤を用いた分散液の調製と分散処理が及ぼす発光特性への影響, 技術情報協会 - カーボンナノチューブの表面処理・分散技術と複合化事例
2019年12月27日, 前田優, 山田道夫, 紺野優以, 鈴木光明, 第2章第2節 有機溶媒系におけるカーボンナノチューブの分離精製, 技術情報協会, 978-4-86104-772-5 - フラーレンの化学
2016年11月, 共立出版（東京）, 9784320044227 - Chemical Science of pi-Electron Systems
2015年11月, Endohedral Metallofullerenes: From Chemical Reactivity to Material Performance, Springer (Tokyo), 9784431553564 - 導電性フィラー，導電助剤の分散性向上，評価，応用
2015年06月, (4) 単層カーボンナノチューブとアミンの相互作用, 技術情報協会 - Endohedral Metallofullerenes: Basics and Applications
2014年12月, NMR Spectroscopic and X-Ray Crystallographic Characterization of Endohedral Metallofullerenes, Boca Raton, 9781466593947 - Organic Nanomaterials
2013年11月, Fundamental and Applied Aspects of Endohedral Metallofullerenes as Promising Carbon Nanomaterials, John Wiley & Sons - ぬれ性，溶解性，分散性，含浸性，接着性向上などを目的とした工業用炭素材料，ナノカーボン材料の表面処理—ノウハウ—
2011年12月, カーボンナノチューブへのカルボキシル基導入とその官能基変換, 技術情報協会 - ぬれ性，溶解性，分散性，含浸性，接着性向上などを目的とした工業用炭素材料，ナノカーボン材料の表面処理—ノウハウ—
2011年12月, 前田優, 赤阪健, 山田道夫, 長谷川正, アミンによる炭層カーボンナノチューブの分散と分離, 技術情報協会 - Handbook of Carbon Nano Materials
2011年11月, 145-184, World Scientific Publishing Co. (Singapore) - Handbook of Fullerene Science and Technology
2022年09月, Functionalization of Fullerenes: Addition Reactions, Springer (Singapore), 9789811689932 - カーボンナノチューブの表面処理・分散技術と複合化事例
2019年12月, 有機溶媒系におけるカーボンナノチューブの分離精製, 技術情報協会 - Handbook of Carbon Nano Materials
2011年11月, New Vistas in Endohedral Metallofullerenes, World Scientific Publishing Co. (Singapore), 9789814327817
論文
- Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes
2024年01月, Michio Yamada, 単著, Beilstein Journal of Organic Chemistry, Beilstein Institut, 20, 研究論文（学術雑誌） - Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity
2023年12月, Yutaka Maeda, Saeka Akita, Mitsuaki Suzuki, Michio Yamada, Takeshi Akasaka, Kaoru Kobayashi, Shigeru Nagase, 共著, Beilstein Journal of Organic Chemistry, Beilstein Institut, 19, 研究論文（学術雑誌） - Control of functionalized single-walled carbon nanotube photoluminescence via competition between thermal rearrangement and elimination
2023年09月, Yutaka Maeda, Rina Morooka, Pei Zhao, Michio Yamada, Masahiro Ehara, 共著, Chemical Communications, Royal Society of Chemistry, 59, 研究論文（学術雑誌） - One-Step Synthesis of Cyclobutene-Annulated Fullerenes through a Cascade Reaction
2023年09月, Michio Yamada, Yuta Uokawa, Shino Sasaki, Naohiro Iha, Yoshihisa Hashimoto, Yuya Nagasaki, Yutaka Maeda, Mitsuaki Suzuki, 共著, European Journal of Organic Chemistry, European Chemical Societies Publishing, 26, 35, 研究論文（学術雑誌） - Stepwise Functionalization of Single-Walled Carbon Nanotubes with Subsequent Molecular Conversion to Control Photoluminescence Properties
2023年09月, Yui Konno, Michio Yamada, Mitsuaki Suzuki, Yutaka Maeda, 共著, Chemistry A European Journal, European Chemical Societies Publishing, 29, 51, 研究論文（学術雑誌） - Selective emergence of photoluminescence at telecommunication wavelengths from cyclic perfluoroalkylated carbon nanotubes
2023年07月, Yutaka Maeda, Yasuhiro Suzuki, Yui Konno, Pei Zhao, Nobuhiro Kikuchi, Michio Yamada, Masaya Mitsuishi, Anh T. H. Dao, Hitoshi Kasai, Masahiro Ehara, 共著, Communications Chemistry, Springer Nature, 6, 研究論文（学術雑誌） - Synthesis and Conformational Analysis of Fullerene Torsion Balances for Assessing the Contribution of Dispersion and Anionic Character in Non-covalent Arene–Fullerene Interactions
2023年08月, Michio Yamada, Koki Sahara, Masaaki Koizumi, Yutaka Maeda, Mitsuaki Suzuki, 共著, Chemistry A European Journal, European Chemical Societies Publishing, 29, 44, 研究論文（学術雑誌）, 10.1002/chem.202300877 - Photoluminescence Properties of Single-Walled Carbon Nanotubes Influenced by the Tether Length of Reagents with Two Reactive Sites
2023年06月, Yui Konno, Rina Morooka, Tatsunari Morishita, Pei Zhao, Naoto Miyasaka, Kazuki Ono, Akira Noda, Daiki Uchida, Ren Iwasaki, Michio Yamada, Masahiro Ehara, Yutaka Maeda, 共著, Chemistry A European Journal, European Chemical Societies Publishing, 29, 36, 研究論文（学術雑誌）, 10.1002/chem.202300766 - Unraveling the Nature and Strength of Non-covalent Interactions on the Surface of Fullerenes
2023年03月, Michio Yamada, 単著, ChemPlusChem, Wiley, 研究論文（学術雑誌）, 10.1002/cplu.202300062 - Transition-metal-catalyzed synthesis of organophosphate-appended cyclobutanofullerenes from C60 and secondary propargylic phosphates
2023年01月31日, Michio Yamada, Yui Ueno, Yuta Uokawa, Yutaka Maeda, 共著, Tetrahedron Lett., Elsevier, 115, 研究論文（学術雑誌）, 10.1016/j.tetlet.2022.154299 - Controlling Near-Infrared Photoluminescence Properties of Single-Walled Carbon Nanotubes by Substituent Effect in Stepwise Chemical Functionalization
2023年01月24日, Yutaka Maeda, Rina Morooka, Pei Zhao, Daiki Uchida, Yui Konno, Michio Yamada, Masahiro Ehara, 共著, J. Phys. Chem. C, American Chemical Society, 127, 研究論文（学術雑誌）, 10.1021/acs.jpcc.2c06153 - Understanding the Nature and Strength of Noncovalent Face-to-Face Arene–Fullerene Interactions
2022年09月06日, Michio Yamada, Yukiyo Kurihara, Masaaki Koizumi, Kasumi Tsuji, Yutaka Maeda, Mitsuaki Suzuki, 共著, Angew. Chem. Int. Ed., Wiley, 61, 研究論文（学術雑誌）, 10.1002/anie.202212279 - 核磁気共鳴分光法と質量分析法の基礎：有機化合物の構造をどのように調べるか？
2022年04月20日, 山田道夫, 単著, 化学と教育, 日本化学会, 70, （MISC）総説・解説（その他） - Photoreactions of Sc3N@C80 with Disilirane, Silirane, and Digermirane: A Photochemical Method to Separate Ih and D5h Isomers
2022年02月07日, M. Kako, K. Miyabe, S. Fukazawa, S. Kanazawa, M. Yasui, M. Yamada, Y. Maeda, Z. Slanina, F. Uhlik, L. Adamowicz, I, Papadopoulos, D. M. Guldi, M. Furukawa, S. Nagase, T. Akasaka, 共著, Photochem, MDPI, 2, 1, 研究論文（学術雑誌） - Li@C60 thin films: characterization and nonlinear optical properties
2021年12月21日, M. Wolf, S. Toyouchi, P. Walke, K. Umemoto, A. Masuhara, H. Fukumura, Y. Takano, M. Yamada, Hirai, E. Fron, H. Uji-i, 共著, RSC Adv., ROYAL SOCIETY OF CHEMISTRY, 12, 研究論文（学術雑誌） - Copper-Mediated Cascade Synthesis of Open-Cage Fullerenes
2020年04月, M. Yamada, A. Ishitsuka, Y. Maeda, M. Suzuki, H. Sato, 共著, Organic Letters, American Chemical Society, 22, 9, 研究論文（学術雑誌）, 1523-7060, An open-cage fullerene bearing an eight-membered ring orifice has been synthesized in one pot by the reaction of C60 with propargylic phosphate in the presence of CuCl. The reaction cascade involves the transformation of the phosphate to the 1,3-dienyl phosphate, which enables the reaction with C60 by [4 + 2] cycloaddition to form the cyclohexene-annulated intermediate, and subsequent intramolecular syn-elimination of the phosphodiester affords the cyclohexadiene-annulated fullerene derivative as the precursor for the open-cage fullerene.Published: April 21, 2020 - Thermodynamic control of quantum defects on single-walled carbon nanotubes
2019年11月25日, Y. Maeda, H. Murakoshi, H. Tambo, P. Zhao, K. Kuroda, M. Yamada, X. Zhao, S. Nagase, M. Ehara, 共著, Chem. Commun., 55, 研究論文（学術雑誌）, 10.1039/C9CC05623H - Influence of local strain caused by cycloaddition on the band gap control of functionalized single-walled carbon nanotubes
2019年05月08日, Y. Maeda, K. Kuroda, H. Tambo, H. Murakoshi, Y. Konno, M. Yamada, P. Zhao, X. Zhao, S. Nagase, M. Ehara, 共著, RSC Adv., 9, 研究論文（学術雑誌）, 10.1039/C9RA02183C - Reaction of C60 radical anion with alkyl halide
2019年03月26日, Y. Maeda, M. Sanno, T. Morishita, K. Sakamoto, E. Sugiyama, S. Akita, M. Yamada, M. Suzuki, 共著, New J. Chem., The Royal Society of Chemistry, 43, 17, 研究論文（学術雑誌）, 10.1039/C9NJ01043B, 1144-0546 - Effective derivatization and extraction of insoluble missing lanthanum metallofullerenes La@C2n (n = 36–38) with iodobenzene
2015年11月, Yutaka Maeda
Takayoshi Tsuchiya
Takashi Tsuchiya
Hidefumi Nikawa
Tao Yang
Xiang Zhao
Zdenek Slanina
Mitsuaki Suzuki
Michio Yamada
Yongfu Lian
Shigeru Nagase
Xing Lu
Takeshi Akasaka, 共著, Carbon, 98, 研究論文（学術雑誌）, 10.1016/j.carbon.2015.10.088. - Isolation and characterization of [5,6]-pyrrolidino-Sc3N@I-h-C-80 diastereomers
2014年08月05日, Maeda Y
Kimura M
Ueda C
Yamada M
Kikuchi T
Suzuki M
Wang WW
Mizorogi N
Karousis N
Tagmatarchis N
Hasegawa T
Olmstead MM
Balch AL
Nagase S
Akasaka T, 共著, Chemical communications (Cambridge, England), ROYAL SOC CHEMISTRY, 50, 83, 研究論文（学術雑誌）, 10.1039/c4cc04946b, 1359-7345, Reactions of Sc3N@I-h-C-80 with aziridine derivatives were conducted to afford the corresponding mono-adducts. A pair of diastereomers of the mono-adduct [5,6]-pyrrolidino-Sc3N@I-h-C-80 was isolated and characterized by means of mass spectrometry, vis-NIR absorption spectroscopy, and electrochemical measurements. Structural analysis of the mono-adducts was conducted by NMR and single-crystal X-ray structure determinations. - Application of MCD spectroscopy and TD-DFT to endohedral metallofullerenes for characterization of their electronic transitions
2013年03月14日, Michio Yamada
Zdenek Slanina
Naomi Mizorogi
Atsuya Muranaka
Yutaka Maeda
Shigeru Nagase
Takeshi Akasaka
Nagao Kobayashi, 共著, Physical Chemistry Chemical Physics, 15, 10, 研究論文（学術雑誌）, 10.1039/c3cp44096f, 1463-9076, We describe, for the first time, the application of magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations using B3LYP and M06-2X functionals to characterize the electronic transitions of endohedral metallofullerenes (EMFs). Results revealed that the electronic transitions of La@C2v-C82, La 2@Ih-C80, and Sc3N@I h-C80 can be assigned using these techniques. Particularly, a difference in the electronic transitions between La 2@Ih-C80 and Sc3N@I h-C80, which is invisible in absorption spectra, was observed clearly in MCD spectra. The observed MCD bands agree well with the oscillator strengths calculated using the B3LYP functional. In addition, the MCD bands of La2@Ih-C80 were altered upon [5,6]-addition, demonstrating that the MCD spectroscopy is sensitive to chemical functionalization of EMFs, and that it is therefore powerful to distinguish [5,6]-adducts from pristine La2@Ih-C80, although no marked difference exists in their absorption spectra. © 2013 the Owner Societies. - Regioselective Exohedral Functionalization of La@C-82 and its 1,2,3,4,5-Pentamethylcyclopentadiene and Adamantylidene Adducts
2010年02月08日, Yutaka Maeda
Satoru Sato
Koji Inada
Hidefumi Nikawa
Michio Yamada
Naomi Mizorogi
Tadashi Hasegawa
Takahiro Tsuchiya
Takeshi Akasaka
Tatsuhisa Kato
Zdenek Slanina
Shigeru Nagase, 共著, Chem. Eur. J., Wiley, 16, 7, 研究論文（学術雑誌）, 10.1002/chem.200902512, 0947-6539, The first regioselective functionalization of La@C-82 by two different groups has been performed. Bis-adducts of La@C-82 With Cp* and adamantylidene were synthesized by using two different routes and characterized, Spectroscopic analysis and theoretical calculations reveal that the addition position is controlled by the charge density and p-orbital axis vector value of the fullerene cage. - Helicity Sorting and Optical Resolution of Functionalized Single-Walled Carbon Nanotubes and Their Optical Properties
2020年09月21日, Maeda, Y., Konno, Y., Yamada, M., 共著, J. Phys. Chem. C, American Chemical Society, 124, 研究論文（学術雑誌）, 10.1021/acs.jpcc0c07963 - New Horizons in Chemical Functionalization of Endohedral Metallofullerenes
2020年08月10日, Yamada, M., Liu, M. T. H., Nagase, S., Akasaka, T., 共著, Molecules, MDPI, 25, 研究論文（学術雑誌）, 10.3390/molecules25163626 - A Fullerene-Based Molecular Torsion Balance for Investigating Noncovalent Interactions at the C60 Surface
2020年06月29日, Yamada, M., Narita, H., Maeda, Y., 共著, Angew. Chem. Int. Ed., Wiley VCH, 59, 研究論文（学術雑誌）, 10.1002/anie.202005888 - Salvaging Reactive Fullerenes from Soot by Exohedral Derivatization
2018年10月, M. Yamada, T. Akasaka, S. Nagase, 共著, Angew. Chem. Int. Ed., Wiley, 57, 41, 研究論文（学術雑誌）, 10.1002/anie.201713145, 1433-7851 - リサーチ・ナビ 文部科学省科学研究費補助金 新学術領域研究(研究領域提案型) 高次π空間の創発と機能開発
2012年09月, 山田 道夫, 安蘇 芳雄, 磯部 寛之, 共著, 未来材料, エヌ・ティー・エス, 12, 9, 1346-0986 - 高大連携による国際バカロレアディプロマプログラム（IBDP）化学の実践と検証
2020年07月, 鮫島 朋美, 前田 優, 山田 道夫, 内田 大貴, 吉原 伸敏, 共著, 東京学芸大学附属学校研究紀要, 東京学芸大学附属学校研究会, 47, 研究論文（大学，研究機関紀要）, 0285-4309 - Sonochemical reaction to control the near-infrared photoluminescence properties of single-walled carbon nanotubes
2020年02月03日, Y. Maeda, Y. Konno, A. Nishino, M. Yamada, S. Okudaira, Y. Miyauchi, K. Matsuda, J. Matsui, M. Mitsuichi, M. Suzuki, 共著, Nanoscale, ROYAL SOCIETY OF CHEMISTRY, 12, 研究論文（学術雑誌）, 10.1039/D0NR00271B - Synthesis of Fullerene-Fluorene Dyads through the Platinum-Catalyzed Reactions of [60]Fullerene with 9-Ethynyl-9H-fluoren-9-yl Carboxylates
2019年07月, M. Yamada, M. Takizawa, Y. Nukatani, M. Suzuki, Y. Maeda, 共著, J. Org. Chem., 84, 14, 研究論文（学術雑誌）, 10.1021/acs.joc.9b00932, 0022-3263 - Addition of S-Heterocyclic Carbenes to Fullerenes: Formation and Characterization of Dithiomethano-Bridged Derivatives
2019年04月, M. Kako, Y. Arikawa, S. Kanzawa, M. Yamada, Y. Maeda, M. Furukawa, T. Akasaka, 共著, Helv. Chim. Acta, Wiley, 102, 研究論文（学術雑誌）, 10.1002/hlca.201900064 - Mechanistic Study of the Diels-Alder Reaction of Paramagnetic Endohedral Metallofullerene: Reaction of La@C-82 with 1,2,3,4,5-Pentamethylcyclopentadiene
2013年04月, Satoru Sato
Yutaka Maeda
Jing-Dong Guo
Michio Yamada
Naomi Mizorogi
Shigeru Nagase
Takeshi Akasaka, 共著, J. Am. Chem. Soc., American Chemical Society, 135, 15, 研究論文（学術雑誌）, 10.1021/ja309763f, 0002-7863, The reaction mechanism of the Diels-Alder reaction of paramagnetic endohedral metallofullerene, La@C-82, and 1,2,3,4,5-pentamethylcyclopentadiene was studied theoretically and experimentally. Theoretical calculations revealed that this reaction proceeds via a concerted mechanism that includes formation of a stable intermediate. The activation energy of a retro-Diels-Alder reaction was also studied experimentally, which is in good agreement with theoretical results. - Helicity-Selective Photoreaction of Single-walled Carbon Nanotubes with Organosulfur Compounds in the Presence of Oxygen
2013年04月24日, Yutaka Maeda
Junki Higo
Yuri Amagai
Jun Matsui
Kei Ohkubo
Yusuke Yoshigoe
Masahiro Hashimoto
Kazuhiro Eguchi
Michio Yamada
Tadashi Hasegawa
Yoshinori Sato
Jing Zhou
Jing Lu
Tokuji Miyashita
Shunichi Fukuzumi
Tatsuya Murakami
Kazuyuki Tohji
Shigeru Nagase
Takeshi Akasaka, 共著, Journal of the American Chemical Society, 135, 16, 研究論文（学術雑誌）, 10.1021/ja402199n, 0002-7863,1520-5126, This report describes a helicity-selective photoreaction of single-walled carbon nanotubes (SWNTs) with disulfide in the presence of oxygen. The SWNTs were characterized using absorption, photoluminescence (PL), Raman, and X-ray photoelectron spectroscopy, scanning electron microscopy, and current-voltage (I-V) measurements. Results showed remarkable helicity-selective (metallic SWNTs/semiconducting SWNTs and diameter) functionalization of SWNTs. The reaction rate decreases in the order of metallic SWNTs >
semiconducting SWNTs and small-diameter SWNTs >
large-diameter SWNTs. Control experiments conducted under various experimental conditions and ESR and femtosecond laser flash photolysis measurements revealed that the helicity-selective reaction proceeds via a photoinduced electron transfer reaction. The PL and I-V measurements showed that the photoreaction is effective not only to control SWNT conductivity but also for the band gap modulation of semiconducting SWNTs. © 2013 American Chemical Society. - 初等中等教育と大学教育の化学教育の現場における実践の報告 スモールスケール実験 : フラーレンC₆₀の分離と化学反応
2019年09月20日, 前田 優, 山田 道夫, 共著, 化学と教育, 日本化学会, 67, 9, 研究論文（大学，研究機関紀要）, 0386-2151 - 化学修飾によるカーボンナノチューブの機能化と評価
2019年04月, 前田 優, 山田 道夫, 江原 正博, 共著, 炭素, 炭素材料学会, 2019, 290, （MISC）総説・解説（その他）, 0371-5345,After their discovery carbon nanotubes (CNTs) have attracted significant interest due to their outstanding mechanical properties and intrinsic optical and electronic properties. The chemical functionalization of CNTs has been investigated to reveal their chemical reactivity, to increase dispersibility, to add functionalities, etc. This review focuses on the structures and reactivities of single-walled carbon nanotubes (SWCNTs) and the methods of evaluating functionalized SWCNTs. A recent topic, the formation of SWCNTs quantum defects is described, focusing on our results.
- Effect of substituents and initial degree of functionalization of alkylated single-walled carbon nanotubes on their thermal stability and photoluminescence properties
2017年02月03日, Y. Maeda, T. Yuya, D. Jing-Shuang, M. Suzuki, M. Yamada, S. Nagase, 共著, Chem. Eur. J., Wiley, 23, 8, 研究論文（学術雑誌）, 0947-6539, Alkylated single-walled carbon nanotubes (SWNTs) have been thermally treated to determine the influence of substituents and the degree of functionalization on their thermal stability and photoluminescence (PL) properties. Alkylated SWNTs were prepared by treating SWNTs with sodium naphthalenide and alkyl bromide. The defunctionalization of the alkylated SWNTs was monitored by absorption and Raman spectra. Selective recovery of the characteristic absorption and radial breathing mode peaks was observed during the thermal treatment, which indicates that the thermal stability of the alkylated SWNTs decreases with increases in SWNT diameter and degree of functionalization. n-Butylated and phenethylated SWNTs showed higher thermal stability than sec-butylated and benzylated SWNTs for a similar degree of functionalization, respectively. The diameter selectivity and effect of substituents on the thermal elimination reaction were confirmed by density functional theory. In addition, it was shown that the initial degree of functionalization of the alkylated SWNTs, with the alkyl group and degree of functionalization being kept constant after thermal treatment, strongly affects their PL properties; Stokes shift, and PL peak intensity. - アンケート調査に基づく小学校教員の理科の観察,実験に対する「教えにくい」学習項目とその理由の経年変化
2016年09月, 吉原 伸敏, 前田 優, 山田 道夫, 原田 和雄, 松川 正樹, 共著, 東京学芸大学紀要. 自然科学系, 東京学芸大学学術情報委員会, 68, 研究論文（大学，研究機関紀要）, 1880-4330 - 金属内包フラーレンの構造決定
2016年04月, 鈴木 光明, 山田 道夫, 前田 優, 永瀬 茂, 赤阪 健, 共著, 日本結晶学会誌, 日本結晶学会, 58, 2, 研究論文（研究会，シンポジウム資料等）, 0369-4585, For the structure determination of endohedral metallofullerenes (EMFs), X-ray crystallographic study is very powerful because it provides detailed information of the positions of encapsulated species as well as the cage structures. We have reported a number of X-ray crystal structures of EMFs and their derivatives, which are in good agreement with those suggested by theoretical calculations as well as NMR analyses. Herein we show the importance of interplay between experiments and theoretical calculations for the structure determination of EMFs by taking up La@C82, Gd@C82, and Sc2@C66 as the representative examples. - 新結晶・新物質 不飽和直線状トリキナン構造をもつ金属内包フラーレンSc₂@C₆₆
2015年04月, 山田 道夫, 赤阪 健, 永瀬 茂, 共著, 固体物理, アグネ技術センター, 50, 4, （MISC）総説・解説（商業誌）, 0454-4544 - Control of near infrared photoluminescence properties of single-walled carbon nanotubes by functionalization with dendrons
2018年12月, Y. Maeda, Y. Konno, M. Yamada, P. Zhao, X. Zhao, M. Ehara, S. Nagase, 共著, Nanoscale, 10, 48, 研究論文（学術雑誌）, 10.1039/c8nr07983h, 2040-3364 - Photoreactions of Sc3N@Ih-C80 and Lu3N@Ih-C80 with disilirane: Isolation and characterization of labile 1,2-adducts
2018年12月18日, M. Kako, F. Ozeki, S. Kanzawa, S. Fukazawa, K. Sato, M. Yamada, Y. Maeda, M. Furukawa, T. Akasaka, 共著, Heteroatom Chem., Wiley, 10, 研究論文（学術雑誌）, 10.1002/hc.21477 - Enhancing Solution-Phase Supramolecular Interactions between Monomeric Porphyrins and [60]Fullerene by Simple Chemical Modification
2017年11月29日, M. Yamada, G. Murakami, S. Kobayashi, Y. Maeda, 共著, Tetrahedron Lett., Elsevier, 58, 10.1016/j.tetlet.2017.10.037 - 科学的思考力と問題解決力を高めるための中等教育教員養成（理科）の有機化学実験の授業改善
2017年09月29日, 前田優, 山田道夫, 共著, 東京学芸大学紀要, 東京学芸大学, 69, 研究論文（大学，研究機関紀要） - Transition-metal-catalyzed divergent functionalization of [60]fullerene with propargylic esters
2017年09月15日, M. Yamada, R. Ochi, Y. Yamamoto, S. Okada, Y. Maeda, 共著, Org. Biomol. Chem., ROYAL SOCIETY OF CHEMISTRY, 15, 研究論文（学術雑誌）, 10.1039/c7ob02168b - Temperature Dependence of Anisotropic Transient Conductivity of a La@C-2v-C-82(Ad) Crystal
2017年07月, M. Yamada, S. Sato, W. Choi, S. Seki, T. Abe, M. Suzuki, Y. Maeda, S. Nagase, T. Akasaka, 単著, Chem. Lett., CHEMICAL SOC JAPAN, 46, 7, 研究論文（学術雑誌）, 10.1246/cl.170279, 0366-7022, The temperature dependence of the anisotropic transient conductivity of a La@C-2v-C-82(Ad) crystal was investigated using flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements. Results showed that the transient conductivity along the c-axis of the single-crystal increased as the temperature decreased, proving that electron transport can be described by the electronic band-conduction model instead of the electron-hopping model. - Synthesis and Photo-Induced Electron Transfer Reactions in a La2@Ih-C80-Phenoxazine Conjugate
2017年07月, T. Akasaka, A. Nakata, M. Rudolf, W.-W. Wang, M. Yamada, M. Suzuki, Y. Maeda, R. Aoyama, T. Tsuchiya, S. Nagase, D. M. Guldi, 共著, ChemPlusChem, Wiley, 82, 研究論文（学術雑誌）, 10.1002/cplu.201600391 - Preparation, Structural Determination, and Characterization of Electronic Properties of [5,6]- and [6,6]-Carbosilylated Sc3 N@Ih -C80.
2017年06月, Kako M
Sugiura T
Miyabe K
Yasui M
Yamada M
Maeda Y
Guo JD
Nagase S
Akasaka T, 共著, Chem. Asian J., 12, 12, 10.1002/asia.201700506, 1861-4728 - Fullerene C70 as a Nanoflask that Reveals the Chemical Reactivity of Atomic Nitrogen
2017年06月, Yuta Morinaka
Rui Zhang
Satoru Sato
Hidefumi Nikawa
Tatsuhisa Kato
Ko Furukawa
Michio Yamada
Yutaka Maeda
Michihisa Murata
Atsushi Wakamiya
Shigeru Nagase
Takeshi Akasaka
Yasujiro Murata, 共著, Angew. Chem. Int. Ed., Wiley, 56, 23, 研究論文（学術雑誌）, 10.1002/anie.201701158, 1433-7851, To investigate the intrinsic reactivity of atomic nitrogen, which had previously been accomplished only by examining its decay in the gas phase using special equipment, a nitrogen atom was inserted into a series of molecule-encapsulating C-60 and C-70 fullerenes. Among the studied endofullerenes, H-2@C-70 was able to encapsulate an additional nitrogen atom within the fullerene cage under radiofrequency plasma conditions. The product was analyzed by ESR spectroscopy and mass spectrometry in solution, which revealed that the nitrogen atom with a quartet ground state does not react but weakly interact with the H-2 molecule, thus demonstrating the utility of such fullerenes as "nanoflasks". - Photoreactions of Endohedral Metallofullerene with Siliranes: Electronic Properties of Carbosilylated Lu3N@I-h-C-80
2017年05月, Masahiro Kako
Kazuya Minami
Taiki Kuroiwa
Shinpei Fukazawa
Yuki Arikawa
Michio Yamada
Yutaka Maeda
Qiao-Zhi Li
Shigeru Nagase
Takeshi Akasaka, 共著, Molecules, MDPI, 22, 5, 研究論文（学術雑誌）, 10.3390/molecules22050850, 1420-3049, Photochemical carbosilylation of Lu3N@I-h-C-80 was performed using siliranes (silacyclopropanes) to afford the corresponding [5,6]- and [6,6]-adducts. Electrochemical studies indicated that the redox potentials of the carbosilylated derivatives were shifted cathodically in comparison with those of the [5,6]-pyrrolidino adducts. The electronic effect of the silirane addends on Lu3N@I-h-C-80 was verified on the basis of density functional theory calculations. - Adamantylidene Addition to M3N@I-h-C-80 (M=Sc, Lu) and Sc3N@D-5h-C-80: Synthesis and Crystallographic Characterization of the [5,6]-Open and [6,6]-Open Adducts
2017年05月, Michio Yamada
Tsuneyuki Abe
Chiharu Saito
Toshiki Yamazaki
Satoru Sato
Naomi Mizorogi
Zdenek Slanina
Filip Uhlik
Mitsuaki Suzuki
Yutaka Maeda
Yongfu Lian
Xing Lu
Marilyn M. Olmstead
Alan L. Balch
Shigeru Nagase
Takeshi Akasaka, 共著, Chem. Eur. J., Wiley, 23, 27, 研究論文（学術雑誌）, 10.1002/chem.201700049, 0947-6539, Additions of adamantylidene (Ad) to M3N@I-h-C-80 (M=Sc, Lu) and Sc3N@D-5h-C-80 have been accomplished by photochemical reactions with 2-adamantyl-2,3-[3H]-diazirine (1). In M3N@I-h-C-80, the addition led to rupture of the [6,6]- or [5,6]-bonds of the I-h-C-80 cage, forming the [6,6]-open fulleroid as the major isomer and the [5,6]-open fulleroid as the minor isomer. In Sc3N@D-5h-C-80, the addition also proceeded regioselectively to yield three major isomeric Ad mono-adducts, despite the fact that there are nine types of C-C bonds in the D-5h-C-80 cage. The molecular structures of the seven Ad mono-adducts, including the positions of the encaged trimetallic nitride clusters, have been unambiguously determined through single-crystal XRD analyses. Furthermore, results have shown that stepwise addition of Ad to Lu3N@I-h-C-80 affords several Ad bis-adducts, two of which have been isolated and characterized. The X-ray structure of one bis-adduct clearly revealed that the second Ad addition took place at a [6,6]-bond close to an endohedral metal atom. Theoretical calculations have also been performed to rationalize the regioselectivity. - D-2d(23)-C-84 versus Sc2C2@D-2d(23)-C-84: Impact of Endohedral Sc2C2 Doping on Chemical Reactivity in the Photolysis of Diazirine
2016年12月, Michio Yamada
Yukiko Tanabe
Jing-Shuang Dang
Satoru Sato
Naomi Mizorogi
Makoto Hachiya
Mitsuaki Suzuki
Tsuneyuki Abe
Hiroki Kurihara
Yutaka Maeda
Xiang Zhao
Yongfu Lian
Shigeru Nagase
Takeshi Akasaka, 共著, J. Am. Chem. Soc., American Chemical Society, 138, 50, 研究論文（学術雑誌）, 10.1021/jacs.6b10751, 0002-7863, We compared the chemical reactivity of D-2d(23)-C-84 and that of Sc2C2@D-2d(23)-C-84, both having the same carbon cage geometry, in the photolysis of 2-adamantane-2,3'-[3H]-diazirine, to clarify metal-atom doping effects on the chemical reactivity of the carbon cage. Experimental and computational studies have revealed that the chemical reactivity of the D-2d(23)-C-84 carbon cage is altered drastically by endohedral Sc2C2 doping. The reaction of empty D-2d(23)-C-84 with the diazirine under photoirradiation yields two adamantylidene (Ad) adducts. NMR. spectroscopic studies revealed that the major Ad monoadduct (C-84(Ad)-A) has a fulleroid structure and that the minor Ad monoadduct (C-84(Ad)-B) has a methanofullerene structure. The latter was also characterized using X-ray crystallography. C-84(Ad)-A is stable under photoirradiation, but it interconverted to C-84(Ad)-B by heating at 80 degrees C. In contrast, the reaction of endohedral Sc2C2@D-2d(23)-C-84 with diazirine under photoirradiation affords four (Sc2C2@C-84(Ad)-A, Sc2C2@C-84(Ad)-B, Sc2C2@C-84(Ad)-C, and Sc2C2@C-84(Ad)-D). The structure Sc2C2@C-84(Ad)-C was characterized using X-ray crystallography. Thermal interconversion of Sc2C2@C-84(Ad)-A and Sc2C2@C-84(Ad)-B to Sc2C2@C-84(Ad)-C was also observed. The reaction mechanisms of the Ad addition and thermal interconversion were elucidated from theoretical calculations. Calculation results suggest that C-84(Ad)-B and Sc2C2@C-84(Ad)-C are thermodynamically favorable products. Their different chemical reactivities derive from Sc2C2 doping, which raises the HOMO and LUMO levels of the D-2d(23)-C-84 carbon cage. - The Unanticipated Dimerization of Ce@C-2v(9)-C-82 upon Co-crystallization with Ni(octaethylporphyrin) and Comparison with Monomeric M@C-2v(9)-C-82 (M = La, Sc, and Y)
2016年12月, Mitsuaki Suzuki
Michio Yamada
Yutaka Maeda
Satoru Sato
Yuta Takano
Filip Uhlik
Zdenek Slanina
Yongfu Lian
Xing Lu
Shigeru Nagase
Marilyn M. Olmstead
Alan L. Balch
Takeshi Akasaka, 共著, Chem. Eur. J., Wiley, 22, 50, 研究論文（学術雑誌）, 10.1002/chem.201602595, 0947-6539, We report that Ce@C-2v(9)-C-82 forms a centrosymmetric dimer when co-crystallized with Ni(OEP) (OEP = octaethylporphyrin dianion). The crystal structure of {Ce@C-2v(9)-C-82}(2)center dot 2[Ni(OEP)]center dot 4C(6)H(6) shows that a new C-C bond with a bond length of 1.605(5) angstrom connects the two cages. The high spin density of the singly occupied molecular orbital (SOMO) on the cage and the pyramidalization of the cage are factors that favor dimerization. In contrast, the treatment of Ni(OEP) with M@C-2v(9)-C-82 (M = La, Sc, and Y) results in crystallization of monomeric endohedral fullerenes. A systematic comparison of the X-ray structures of M@C-2v(9)-C-82 (M = Sc, Y, La, Ce, Gd, Yb, and Sm) reveals that the major metal site in each case is located at an off-center position adjacent to a hexagonal ring along the C-2 axis of the C-2v(9)-C-82 cage. DFT calculations at the M06-2X level revealed that the positions of the metal centers in these metallofullerenes M@C-2v(9)-C-82 (M = Sc, Y, and Ce), as determined by single-crystal X-ray structure studies, correspond to an energy minimum for each compound. - Thermal Stability of Oxidized Single-Walled Carbon Nanotubes: Competitive Elimination and Decomposition Reaction Depending on the Degree of Functionalization
2016年10月, Yutaka Maeda
Erika Sone
Akane Nishino
Yuri Amagai
Wei-Wei Wang
Michio Yamada
Mitsuaki Suzuki
Jun Matsui
Masaya Mitsuishi
Toshiya Okazaki
Shigeru Nagase, 共著, Chem. Eur. J., Wiley, 22, 43, 研究論文（学術雑誌）, 10.1002/chem.201602944, 0947-6539, The thermal stability of oxidized single-walled carbon nanotubes ( SWNTs) with various degrees of oxidation was investigated. The oxidized SWNTs exhibited lower absorption and radial breathing mode ( RBM) peaks and a higher intensity ratio of the D band to the G band ( D/G) in their absorption and Raman spectra than those of the pristine SWNTs. After the thermal treatment, the D/G ratio of the oxidized SWNTs almost recovered its original intensity, regardless of the degree of oxidation. The absorption, photoluminescence ( PL), and RBM peaks could not recover their original intensities when the oxidation degree was high. The results indicate that the elimination and decomposition reactions proceeded competitively depending on the degree of oxidation. In addition, a new PL peak was observed in the near-infrared region, and the PL peak intensity increased with the subsequent thermal treatment. The theoretical calculations provided an insight into the possible pathways for the decomposition of oxidized SWNTs, showing that the O-2 elimination and CO/CO2 evolution proceed competitively during thermal treatment. - Tuning of photoluminescence and up-conversion photoluminescence properties of single-walled carbon nanotubes by chemical functionalization
2016年08月, Y. Maeda, S. Minami, Y. Takehana, J.-S. Dang, S. Aota, K. Matsuda, Y. Miyauchi, M. Yamada, M. Suzuki, R.-S. Zhao, X. Zhao, S. Nagase, 共著, Nanoscale, ROYAL SOCIETY OF CHEMISTRY, 8, 研究論文（学術雑誌）, 10.1039/C6NR04214G - Preparation, Structural Determination, and Characterization of Electronic Properties of Bis-silylated and Bis-germylated Lu3N@I-h-C-80
2015年11月, Masahiro Kako
Kyosuke Miyabe
Kumiko Sato
Mitsuaki Suzuki
Naomi Mizorogi
Wei-Wei Wang
Michio Yamada
Yutaka Maeda
Marilyn M. Olmstead
Alan L. Balch
Shigeru Nagase
Takeshi Akasaka, 共著, Chem. Eur. J., Wiley, 21, 46, 研究論文（学術雑誌）, 10.1002/chem.201502511, 0947-6539, Bis-silylated and bis-germylated derivatives of Lu3N@I-h-C-80 (3, 4, 5) were successfully synthesized by the photochemical addition of disiliranes 1a, 1b or digermirane 2, and fully characterized by spectroscopic, electrochemical, and theoretical studies. Interestingly, digermirane 2 reacts more efficiently than disiliranes 1a and 1b because of its good electron-donor properties and lower steric hindrance around the GeGe bond. The 1,4-adduct structures of 3, 4, 5 were unequivocally established by single-crystal X-ray crystallographic analyses. The electrochemical and theoretical studies reveal that the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the 1,4-adducts are remarkably smaller than those of Lu3N@I-h-C-80, because the electron-donating groups effectively raise the HOMO levels. It is also observed that germyl groups are slightly more electron-donating than the silyl groups on the basis of the redox properties and the HOMO-LUMO energies of 4 and 5. Bis-silylation and bis-germylation are effective and versatile methods for tuning the electronic characteristics of endohedral metallofullerenes. - Control of the photoluminescence properties of single-walled carbon nanotubes by alkylation and subsequent thermal treatment
2015年07月16日, Yutaka Maeda
Yuya Takehana
Michio Yamada
Mitsuaki Suzuki
Tatsuya Murakami, 共著, Chem. Commun., ROYAL SOCIETY OF CHEMISTRY, 51, 70, 研究論文（学術雑誌）, 10.1039/c5cc04020e, 1359-7345, Dibutylated single-walled carbon nanotubes (Bu-SWNTs-Bu) with varying degrees of functionalization were prepared by two-step reductive alkylation and subsequent thermal treatment. A new photoluminescence peak at around 1240 nm was observed and increased drastically after the thermal treatment. The results indicate that thermally treated Bu-SWNTs-Bu are promising NIR photoluminescent materials. - Regioselective Cage Opening of La-2@D-2(10611)-C-72 with 5,6-Diphenyl-3-(2-pyridyl)-1,2,4-triazine
2015年02月, Michio Yamada
Yasuhiro Muto
Hiroki Kurihara
Zdenek Slanina
Mitsuaki Suzuki
Yutaka Maeda
Yves Rubin
Marilyn M. Olmstead
Alan L. Balch
Shigeru Nagase
Xing Lu
Takeshi Akasaka, 共著, Angew. Chem. Int. Ed., Wiley, 54, 7, 研究論文（学術雑誌）, 10.1002/anie.201410012, 1433-7851, The thermal reaction of the endohedral metallofullerene La-2@D-2(10611)-C-72, which contains two pentalene units at opposite ends of the cage, with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine proceeded selectively to afford only two bisfulleroid isomers. The molecular structure of one isomer was determined using single-crystal X-ray crystallography. The results suggest that the [4+2] cycloaddition was initiated in a highly regioselective manner at the C-C bond connecting two pentagon rings of C-72. Subsequent intramolecular electrocyclization followed by cycloreversion resulted in the formation of an open-cage derivative having three seven-membered ring orifices on the cage and a significantly elongated cage geometry. The reduction potentials of the open-cage derivatives were similar to those of La-2@D-2-C-72 whereas the oxidation potentials were shifted more negative than those of La-2@D2C72. These results point out that further oxidation could occur easily in the derivatives. - Hiding and Recovering Electrons in a Dimetallic Endohedral Fullerene: Air-Stable Products from Radical Additions
2015年01月, Michio Yamada
Hiroki Kurihara
Mitsuaki Suzuki
Masayoshi Saito
Zdenek Slanina
Filip Uhlik
Toshihiro Aizawa
Tatsuhisa Kato
Marilyn M. Olmstead
Alan L. Balch
Yutaka Maeda
Shigeru Nagase
Xing Lu
Takeshi Akasaka, 共著, J. Am. Chem. Soc., American Chemical Society, 137, 1, 研究論文（学術雑誌）, 10.1021/ja509956y, 0002-7863, Fullerenyl radicals can be generated by addition of a free radical to a fullerene surface, by nucleophilic addition followed by one-electron oxidation, or by thermal dissociation of singly bonded fullerene dimers. However, fullerenyl radicals are usually very reactive and generally cannot be isolated. On the contrary, we have found that the reactions of the dimetallic endofullerenes, La-2@I-h-C-80 and La-2@D-5h-C-80, with 3-chloro-5,6-diphenyltriazine resulted in mono-addition of the triazinyl radical to the fullerene cages to yield isolable fullerenyl radicals. The unusual stability of these fullerenyl radicals arises from the confinement of the unpaired electron to an internal, metalmetal bonding orbital. Accordingly, the fullerene cage protects the radical center from other reactive species. Furthermore, we demonstrate that the fullerenyl radical adduct of La-2@I-h-C-80 reacts with toluene to afford additional benzylation. Interestingly, the benzylated derivative is diamagnetic in solution, while it forms a paramagnetic dimer when crystallized. - Emergence of Highly Elaborated pi-Space and Extending Its Functionality Based on Nanocarbons: New Vistas in the Fullerene World
2014年12月, M. Yamada, T. Akasaka, 共著, Bull. Chem. Soc. Jpn., The Chemical Society of Japan, 87, 研究論文（学術雑誌） - 新しいフラーレン構造の発見−実験と理論のインタープレイ
2014年11月, 山田道夫、赤阪健、永瀬茂, 共著, 化学, 化学同人, 69 - Sc2@C66 revisited: An endohedral fullerene with scandium ions nestled within two unsaturated linear triquinanes
2014年05月28日, Michio Yamada
Hiroki Kurihara
Mitsuaki Suzuki
Jing Dong Guo
Markus Waelchli
Marilyn M. Olmstead
Alan L. Balch
Shigeru Nagase
Yutaka Maeda
Tadashi Hasegawa
Xing Lu
Takeshi Akasaka, 共著, Journal of the American Chemical Society, American Chemical Society, 136, 21, 研究論文（学術雑誌）, 10.1021/ja5035649, The geometries of fullerenes are governed by the isolated pentagon rule (IPR), which states that stable fullerenes have each of their 12 pentagons surrounded by five hexagons. At the dawn of fullerene science, it was widely believed that the IPR would also be applicable for endohedral fullerenes. In 2000, that idea was altered by the discovery of the first non-IPR fullerenes, Sc2@C66 and Sc3N@C68. The structural data for Sc2@C66 were interpreted to indicate the presence of a pair of doubly fused pentagons. However, that structure has remained a long-standing mystery, since it is thermodynamically unfavorable. Here, we demonstrate definitively that Sc2@C66 does not have the structure that was long believed to be but a brand new type. 2D NMR spectroscopic and single-crystal X-ray analyses disclose that Sc 2@C66 has a C2v(4059)-C66 cage containing two sets of unsaturated linear triquinanes (ULTs), in which three pentagons abut one another and two scandium ions are located within the folds of each of the ULT units. © 2014 American Chemical Society. - Photochemical Behavior of Single-Walled Carbon Nanotubes in the Presence of Propylamine
2014年04月, Y. Maeda, Y. Hasuike, K. Ohkubo, A. Tashiro, S. Kaneko, M. Kikuta, M. Yamada, T. Hasegawa, T. Akasaka, J. Zhou, J. Lu, S. Nagase, S. Fukuzumi, 共著, ChemPhysChem, WILEY-VCH, 15 - Computations on metallofullerenes derivatized during extraction: La@C80-C6H3Cl2 and La@C82-C6H3Cl2
2014年01月, Z. Slanina, F. Uhlik, S.-L. Lee, L. Adamowicz, H. Kurihara, H. Nikawa, X. Lu, M. Yamada, S. Nagase, T. Akasaka, 共著, Fullerenes, Nanotubes, Carbon Nanostruct., Taylor and Francis, 22, 1-3 - Thermal reactions of C60 with siliranes: Carbosilylation and silylene addition of fullerenes
2014年01月, M. Kako, R. Iida, Y. Maeda, M. Yamada, T. Hasegawa, 共著, Fullerenes, Nanotubes, Carbon Nanostruct., Taylor and Francis, 22 - Ground and Excited State Electronic Interactions in Push–Pull-Chromophore–[60]Fullerene Conjugates
2014年01月, M. Yamada, F. Tancini, M. Sekita, D. M. Guldi, C. Boudon, J.-P. Gisselbrecht, M. N. Alberti, W. B. Schweizer, F. Diederich, 共著, Fullerenes, Nanotubes, Carbon Nanostruct., Taylor and Francis, 22 - Intermolecular Interaction of [60]Fullerene with Troger's Base Analogues
2014年01月, M. Yamada, K. Tokutomi, A. Takehara, Y. Sakai, Y. Maeda, T. Hasegawa, 共著, Fullerenes, Nanotubes, Carbon Nanostruct., Taylor and Francis, 22 - La2@Cs(17490)-C76: A New Non-IPR Dimetallic Metallofullerene Featuring Unexpectedly Weak Metal-Pentalene Interactions
2013年11月, M. Suzuki, N. Mizorogi, T. Yang, F. Uhlik, Z. Slanina, X. Zhao, M. Yamada, Y. Maeda, T. Hasegawa, S. Nagase, X. Lu, T. Akasaka, 共著, Chem. -Eur. J, WILEY-VCH, 19 - A versatile approach to functionalisation of [60]fullerene using 3-trifluoromethyl-3-phenyldiazirine derivatives as photolabelling reagents
2013年08月, Michio Yamada, Kenji Harada, Yutaka Maeda, Tadashi Hasegawa, 共著, New Journal of Chemistry, ROYAL SOCIETY OF CHEMISTRY, 37 - Carbene Additions to Fullerenes
2013年07月, Michio Yamada, Takeshi Akasaka, Shigeru Nagase, 共著, Chemical Reviews, American Chemical Society, 113 - Mapping the metal positions inside spherical C80 cages: Crystallographic and theoretical studies of Ce2@D5h-C80 and Ce2@Ih-C80
2013年01月, L. Feng, M. Suzuki, N. Mizorogi, L. Xing, M. Yamada, T. Akasaka, S. Nagase, 共著, Chem. Eur. J., WILEY-VCH, 19 - Analysis of Functionalization Degree of Single-Walled Carbon Nanotubes Having Various Substituents
2012年10月, Y. Maeda, K. Saito, N. Akamatsu, Y. Chiba, S. Ohno, Y. Okui, M. Yamada, T. Hasegawa, M. Kako, T. Akasaka, 共著, J. Am. Chem. Soc., American Chemical Society, 134 - Electron transport through single endohedral Ce@C82 metallofullerenes
2012年09月, S. Kaneko, L. Wang, G. Luo, S. Nagase, S. Sato, M. Yamada, Z. Slanina, T. Akasaka, M. Kiguchi, 共著, Physical Review B, American Physical Society, 86 - Interaction of Single-walled carbon Nanotubes with amine
2012年02月, Y. Maeda, M. Yamada, T. Hasegawa, T. Akasaka, J. Lu, S. Nagase, 共著, NANO, World Scientific, 7 - Oxygen atom transfer from peroxide intermediates to fullerenes
2011年12月, Y. Maeda, Y. Niino, T. Kondo, M. Yamada, T. Hasegawa, T. Akasaka, 共著, Chem. Lett., The Chemical Society of Japan, 40, 12 - Synthesis of endohedral metallofullerene glycoconjugates by carbene addition
2011年11月, M. Yamada, C. I. Someya, T. Nakahodo, Y. Maeda, T. Tsuchiya, T. Akasaka, 共著, Molecules, MDPI, 16 - 金属内包フラーレン−その構造と電子的特性を制御する
2011年10月, 山田道夫・佐藤悟・赤阪健・永瀬茂, 共著, 化学, 化学同人, 66, 10 - Preparation and characterization of transparent and conductive thin films of single-walled carbon nanotubes
2011年03月, Y. Maeda, K. Komoriya, K. Sode, J. Higo, T. Nakamura, M. Yamada, T. Hasegawa, T. Akasaka, T. Saito, J. Lu, S. Nagase, 共著, Nanoscale, ROYAL SOCIETY OF CHEMISTRY, 3, 10.1039/C0NR00940G - Regioselective Cycloaddition of La-2@/(h)-C-80 with Tetracyanoethylene Oxide: Formation of an Endohedral Dimetallofullerene Adduct Featuring Enhanced Electron-Accepting Character
2011年03月, Michio Yamada
Mari Minowa
Satoru Sato
Zdenek Slanina
Takahiro Tsuchiya
Yutaka Maeda
Shigeru Nagase
Takeshi Akasaka, 共著, Journal of the American Chemical Society, AMER CHEMICAL SOC, 133, 11, 研究論文（学術雑誌）, 10.1021/ja2000243, 0002-7863, We describe the regioselective cycloaddition of La-2@I-h-C-80 with tetracyanoethylene oxide (TCNEO), which enabled the formation of the corresponding adduct having a tetracyanotetrahydrofuran moiety. X-ray crystallographic analysis revealed that the cycloaddition took place as a [5,6] addition. Along with dynamic swing motion of the metal atoms, the results of this electrochemical study demonstrate that TCNEO addition enhanced the electron-accepting character of La-2@I-h-C-80 and that the first reduction potential of the adduct reached -0.21 V versus the ferrocene/ferrocenium couple, which is the lowest value reported for endohedral metallofullerenes and their derivatives to date. - Thermal Carbosilylation of Endohedral Dimetallofullerene La2@Ih-C80 with Silirane
2010年11月, M. Yamada, M. Minowa, S. Sato, M. Kako, Z. Slanina, N. Mizorogi, T. Tsuchiya, Y. Maeda, S. Nagase, T. Akasaka, 共著, J. Am. Chem. Soc., ACS, 132 - Separation of metallic single-walled carbon nanotubes using various amines
2010年11月, Y. Maeda, K. Komoriya, K. Sode, M. Kanda, M. Yamada, T. Hasegawa, T. Akasaka, J. Lu, S. Nagase, 共著, Phys. Status Solidi B, WILEY-VCH, 247, 11-12 - Unprecedented Thermal Rearrangement of Push-Pull-Chromophore-[60]Fullerene Conjugates: Formation of Chiral 1,2,9,12-Tetrakis-Adducts
2010年06月, M. Yamada, W. B. Schweizer, F. Shoenebeck, F. Diederich, 共著, Chem. Commun., RSC, 46 - A Molecular Ce2@Ih-C80 Switch–Unprecedented Oxidative Pathway in Photoinduced Charge Transfer Reactivity
2010年06月, D, M. Guldi, L. Feng, S. G. Radhakrishnan, H. Nikawa, M. Yamada, N. Mizorogi, T. Tsuchiya, T. Akasaka, S. Nagase, M. A. Herranz, N. Martin, 共著, J. Am. Chem. Soc., ACS, 132 - Optical Stability of Axially Chiral Push-Pull-Substituted Buta-1,3-dienes: Effect of a Single Methyl Group on the C60 Surface
2010年04月, M. Yamada, P. Rivera-Fuentes, W. B. Schweizer, F. Diederich, 共著, Angew. Chem. Int. Ed., WILEY-VCH, 49 - In-Depth Understanding of π-Electron Systems: New Vistas in Fullerene Endohedrals
2010年02月, M. Yamada, T. Tsuchiya, T. Akasaka, S. Nagase, 共著, Pure Appl. Chem., IUPAC, 82, 研究論文（学術雑誌） - Endohedral Metal Atoms in Pristine and Functionalized Fullerene Cages
2010年01月, M. Yamada, T. Akasaka, S. Nagase, 共著, Acc. Chem. Res., ACS, 43 - Two Regioisomers of Endohedral Pyrrolidinodimetallofullerenes M2@Ih-C80(CH2)2NTrt (M = La, Ce; Trt = trityl): Control of Metal Atom Positions by Addition Positions
2009年09月, M. Yamada, M. Okamura, S. Sato, C. I. Someya, N. Mizorogi, T. Tsuchiya, T. Akasaka, T. Kato, S. Nagase, 共著, Chem. –Eur. J., WILEY-VCH, 15 - Anisotropic magnetic behavior of anionic Ce@C82 carbene adducts
2009年06月, Y. Takano, M. Aoyagi, M. Yamada, H. Nikawa, Z. Slanina, N. Mizorogi, M. O. Ishitsuka, T. Tsuchiya, Y. Maeda, T. Akasaka, T. Kato, S. Nagase, 共著, J. Am. Chem. Soc., ACS, 131 - Synthesis and Characterization of the D5h Isomer of the Endohedral Dimetallofullerene Ce2@C80: Two-Dimensional Circulation of Encapsulated Metal Atoms Inside a Fullerene Cage
2009年04月, M. Yamada, N. Mizorogi, T. Tsuchiya, T. Akasaka, S. Nagase, 共著, Chem. –Eur. J., WILEY-VCH, 15 - Radical Coupling Reaction of Paramagnetic Endohedral Metallofullerene La@C82
2008年11月, Y. Takano, A. Yomogida, H. Nikawa, M. Yamada, T. Wakahara, T. Tsuchiya, M. O. Ishitsuka, Y. Maeda, T. Akasaka, T. Kato, Z. Slanina, N. Mizorogi, S. Nagase, 共著, J. Am. Chem. Soc., ACS, 130 - Spectroscopic and theoretical study of endohedral dimetallofullerene having a non-IPR fullerene cage: Ce2@C72
2008年07月, M. Yamada, T. Wakahara, T. Tsuchiya, Y. Maeda, T. Akasaka, N. Mizorogi, S. Nagase, 共著, J. Phys. Chem. A, ACS, 112 - Location of the Metal Atoms in Ce2@C78 and Its Bis-Silylated Derivative
2008年02月, M. Yamada, T. Wakahara, T. Tsuchiya, Y. Maeda, M. Kako, T. Akasaka, K. Yoza, E. Horn, N. Mizorogi, S. Nagase, 共著, Chem. Commun., RSC - Metal Atoms Collinear with the Spiro Carbon of 6,6-Open Adducts, M2@C80(Ad) (M = La and Ce, Ad = Adamantylidene)
2008年01月, M. Yamada, C. Someya, T. Wakahara, T. Tsuchiya, Y. Maeda, T. Akasaka, K. Yoza, E. Horn, M. T. H. Liu, N. Mizorogi, S. Nagase, 共著, J. Am. Chem. Soc., ACS, 130 - Photo-Labeling of C60 with 3-Trifluoromethyl-3-phenyldiazirine
2007年07月, S. Sato, M. Yamada, T. Wakahara, T. Tsuchiya, M. O. Ishitsuka, T. Akasaka, M. T. H. Liu, 共著, Tetrahedron Lett., Elsevier, 48 - Two-dimensional Hopping Motion of Encapsulated La Atoms in Silylated La2@C80
2007年04月, T. Wakahara, M. Yamada, S. Takahashi, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, M. Kako, K. Yoza, E. Horn, N. Mizorogi, S. Nagase, 共著, Chem. Commun., RSC - Analysis of Lanthanide-Induced NMR Shifts of the Ce@C82 Anion
2006年01月, M. Yamada, T. Wakahara, Y. Lian, T. Tsuchiya, T. Akasaka, M. Waelchli, N. Mizorogi, S. Nagase, K. M. Kadish, 共著, J. Am. Chem. Soc., ACS, 128 - Synthesis and Structural Characterization of Endohedral Pyrrolidinodimetallofullerene: La2@C80(CH2)2NTrt
2006年01月, M. Yamada, T. Wakahara, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, K. Yoza, E. Horn, N. Mizorogi, S. Nagase, 共著, J. Am. Chem. Soc., ACS, 128 - Positional Control of Encapsulated Atoms Inside a Fullerene Cage by Exohedral Addition
2005年10月, M. Yamada, T. Nakahodo, T. Wakahara, T. Tsuchiya, Y. Maeda, T. Akasaka, M. Kako, K. Yoza, E. Horn, N. Mizorogi, K. Kobayashi, S. Nagase, 共著, J. Am. Chem. Soc., ACS, 127, 研究論文（学術雑誌） - Synthesis and Characterization of Exohedrally Silylated M@C82 (M = Y and La)
2005年03月, M. Yamada, L. Feng, T. Wakahara, T. Tsuchiya, Y. Maeda, Y. Lian, M. Kako, T. Akasaka, T. Kato, K. Kobayashi, S. Nagase, 共著, J. Phys. Chem. B, ACS, 109, 研究論文（学術雑誌） - Characterization of Ce@C82 and Its Anion
2004年03月, T. Wakahara, J.-i. Kobayashi, M. Yamada, Y. Maeda, T. Tsuchiya, M. Okamura, T. Akasaka, M. Waelchli, K. Kobayashi, S. Nagase, T. Kato, M. Kako, K. Yamamoto. K. M. Kadish, 共著, J. Am. Chem. Soc., ACS, 126, 研究論文（学術雑誌） - Two-fold addition reaction of silylene to C60: structural and electronic properties of a bis-adduct
2024年05月22日, Masahiro Kako; Masato Kai; Masanori Yasui; Michio Yamada; Yutaka Maeda; Takeshi Akasaka, Beilstein Journal of Organic Chemistry, Beilstein Institut, 20, 研究論文（学術雑誌）, 10.3762/bjoc.20.100, The addition reaction of C60 with silylene 1, a silicon analog of carbene, yielded the corresponding bis-adduct 3. The structure of 3 was determined by single-crystal X-ray structure analysis, representing the first example of a crystal structure of a silirane (silacyclopropane) derivative of fullerenes. Electrochemical measurements confirmed that the redox potentials of 3 are shifted cathodically compared to those of the parent mono-adduct 2. Density functional theory (DFT) calculations provided the basis for the electronic properties of compound 3. - Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity
2023年12月11日, Yutaka Maeda; Saeka Akita; Mitsuaki Suzuki; Michio Yamada; Takeshi Akasaka; Kaoru Kobayashi; Shigeru Nagase, Beilstein Journal of Organic Chemistry, Beilstein Institut, 19, 研究論文（学術雑誌）, 10.3762/bjoc.19.138, Endohedral metallofullerenes have excellent redox properties, which can be used to vary their reactivity to certain classes of molecules, such as alkyl halides. In this study, the thermal reaction of the La@C2v-C82 anion with benzyl bromide derivatives 1 at 110 °C afforded single-bonded adducts 2–5 with high regioselectivity. The products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and visible–near infrared spectroscopy. The reaction of La@C2v-C82 with alkyl halides using the same conditions showed no consumption of La@C2v-C82, indicating that the reactivity of La@C2v-C82 toward alkyl halides was effectively increased by one-electron reduction. Single-crystal X-ray diffraction analysis of the single-bonded adduct 3a revealed the addition site of the p-methoxybenzyl group on La@C2v-C82. Theoretical calculations indicated that the addition site carbons in neutral La@C2v-C82 have high spin density, whereas those in the La@C2v-C82 anion do not have high charge densities. Thus, the reaction is believed to occur via electron transfer, followed by the radical coupling of La@C2v-C82 and benzyl radicals, rather than by bimolecular nucleophilic substitution reaction of La@C2v-C82 anion with 1. - One‐Step Synthesis of Cyclobutene‐Annulated Fullerenes through a Cascade Reaction
2023年08月24日, Michio Yamada; Yuta Uokawa; Shino Sasaki; Naohiro Iha; Yoshihisa Hashimoto; Yuya Nagasaki; Yutaka Maeda; Mitsuaki Suzuki, European Journal of Organic Chemistry, Wiley, 26, 35, 研究論文（学術雑誌）, 10.1002/ejoc.202300633, 1434-193X, Abstract
The physicochemical properties of fullerene‐based materials typically vary depending on the type and mode of addition of functional groups; therefore, developing fullerene derivatives with novel structures is imperative for further progress in materials science. In this study, we develop an efficient one‐step strategy for synthesizing cyclobutene‐annulated fullerene derivatives (cyclobutenofullerenes) and characterize their electronic properties. Despite the steric strain, cyclobutenofullerenes can be easily prepared via a one‐step reaction of C60 with a secondary propargylic phosphate. Structural analysis of the reaction intermediates suggests that the cascade reaction proceeds through a formal [2+2] cycloaddition of C60 with an allene, caused by the 1,3‐migration of the propargylic phosphate, followed by an additional 1,3‐migration and the subsequent 1,2‐elimination of the phosphodiester moiety. - Stepwise Functionalization of Single‐Walled Carbon Nanotubes with Subsequent Molecular Conversion to Control Photoluminescence Properties
2023年08月04日, Yui Konno; Michio Yamada; Mitsuaki Suzuki; Yutaka Maeda, Chemistry – A European Journal, Wiley, 29, 51, 研究論文（学術雑誌）, 10.1002/chem.202301707, 0947-6539, Abstract
Functionalization of single‐walled carbon nanotubes (SWCNTs) has attracted interest because it alters the near‐infrared (NIR) photoluminescence (PL) wavelength and emission efficiency. These modifications depend on the binding configuration and degree of functionalization. Excessive functionalization reduces the emission efficiency as the integrity of the conjugated π system decreases; thus, controlling the degree of functionalization is essential. Because the binding configurations and degree of functionalization are affected by the reagent structure, a stepwise approach combining SWCNTs functionalization and subsequent reactions to introduce functional groups into the addenda could effectively control their PL properties and functionalities. We studied this approach by implementing the reductive alkylation of SWCNTs by using bromoalkanes with t‐butyl carbamate (Boc)‐protected amino groups and subsequent deprotection and amidation reactions. The reaction products were analyzed based on absorption, PL, and Raman spectroscopy and the Kaiser test. Depending on the structure of the reagent, deprotection and amidation reactions competed with the elimination reaction of addenda, altering the PL properties of the SWCNTs. Furthermore, the elimination reaction was inhibited in the adducts functionalized using dibromoalkane with Boc‐protected amino groups, demonstrating that the use of appropriate reagents enables the molecular conversion of the functional groups of SWCNT adducts without affecting their PL properties. - Selective emergence of photoluminescence at telecommunication wavelengths from cyclic perfluoroalkylated carbon nanotubes
2023年07月31日, Yutaka Maeda; Yasuhiro Suzuki; Yui Konno; Pei Zhao; Nobuhiro Kikuchi; Michio Yamada; Masaya Mitsuishi; Anh T. N. Dao; Hitoshi Kasai; Masahiro Ehara, Communications Chemistry, Springer Science and Business Media LLC, 6, 1, 研究論文（学術雑誌）, 10.1038/s42004-023-00950-1, Abstract
Chemical functionalisation of semiconducting single-walled carbon nanotubes (SWNTs) can tune their local band gaps to induce near-infrared (NIR) photoluminescence (PL). However, tuning the PL to telecommunication wavelengths (>1300 nm) remains challenging. The selective emergence of NIR PL at the longest emission wavelength of 1320 nm was successfully achieved in (6,5) SWNTs via cyclic perfluoroalkylation. Chiral separation of the functionalised SWNTs showed that this functionalisation was also effective in SWNTs with five different chiral angles. The local band gap modulation mechanism was also studied using density functional theory calculations, which suggested the effects of the addenda and addition positions on the emergence of the longest-wavelength PL. These findings increase our understanding of the functionalised SWNT structure and methods for controlling the local band gap, which will contribute to the development and application of NIR light-emitting materials with widely extended emission and excitation wavelengths. - Synthesis and Conformational Analysis of Fullerene Torsion Balances for Assessing the Contribution of Dispersion and Anionic Character in Non‐Covalent Arene–Fullerene Interactions
2023年06月16日, Michio Yamada; Koki Sahara; Masaaki Koizumi; Yutaka Maeda; Mitsuaki Suzuki, Chemistry – A European Journal, Wiley, 29, 44, 研究論文（学術雑誌）, 10.1002/chem.202300877, 0947-6539, Abstract
We employ a molecular torsion balance displaying bifurcated conformational isomerism to quantitatively evaluate the non‐covalent interactions between the fullerene surface and substituted arene moieties containing elements with high atomic numbers, as well as the thermodynamic processes involved in the folding equilibrium using nuclear magnetic resonance spectroscopy. The interaction between fullerene and haloaryl groups was stronger in cases where the introduced halogen had a higher atomic number, indicating that dispersion forces play a significant role in the interaction between fullerenes and 4‐haloaryl groups. The dispersion term also significantly contributed to the interaction between fullerene and the 4‐mercaptophenyl group. Moreover, the addition of an appropriate base to the 4‐mercaptophenyl‐appended torsion balance formed the corresponding thiophenolate anion, resulting in a large negative change in the folding free energy in CDCl3. Detailed analysis suggested that the observed attractive anionic arene–fullerene interactions predominantly originated from solvation effects. - Photoluminescence Properties of Single‐Walled Carbon Nanotubes Influenced by the Tether Length of Reagents with Two Reactive Sites
2023年05月05日, Yui Konno; Rina Morooka; Tatsunari Morishita; Pei Zhao; Naoto Miyasaka; Kazuki Ono; Akira Noda; Daiki Uchida; Ren Iwasaki; Michio Yamada; Masahiro Ehara; Yutaka Maeda, Chemistry – A European Journal, Wiley, 29, 36, 研究論文（学術雑誌）, 10.1002/chem.202300766, 0947-6539 - Transition-metal-catalyzed synthesis of organophosphate-appended cyclobutanofullerenes from C60 and secondary propargylic phosphates
2023年01月, Michio Yamada; Yui Ueno; Yuta Uokawa; Yutaka Maeda, Tetrahedron Letters, Elsevier BV, 115, 31, 研究論文（学術雑誌）, 10.1016/j.tetlet.2022.154299, 0040-4039 - Control of functionalized single-walled carbon nanotube photoluminescence via competition between thermal rearrangement and elimination
2023年, Yutaka Maeda; Rina Morooka; Pei Zhao; Michio Yamada; Masahiro Ehara, Chemical Communications, Royal Society of Chemistry (RSC), 59, 78, 研究論文（学術雑誌）, 10.1039/d3cc02965d, 1359-7345, We conducted the chiral separation of functionalized single-walled carbon nanotubes (SWNTs) with dibromopropane derivatives. - Photoreactions of Sc3N@C80 with Disilirane, Silirane, and Digermirane: A Photochemical Method to Separate Ih and D5h Isomers
2022年02月, Masahiro Kako; Kyosuke Miyabe; Shinpei Fukazawa; Shinji Kanzawa; Masanori Yasui; Michio Yamada; Yutaka Maeda; Zdeněk Slanina; Filip Uhlík; Ludwik Adamowicz; Ilias Papadopoulos; Dirk M. Guldi; Makoto Furukawa; Shigeru Nagase; Takeshi Akasaka, Photochem, 2, 1, 研究論文（学術雑誌）, 10.3390/photochem2010010 - Functionalization of Fullerenes: Addition Reactions
2022年01月01日, Michio Yamada; Shigeru Nagase; Takeshi Akasaka, Handbook of Fullerene Science and Technology, 学位論文（修士）, 10.1007/978-981-16-8994-9_33, This chapter begins with the nucleophilic reactions of fullerenes, in which Grignard reagents, alkyllithium, and other carbon nucleophiles, as well as silicon and phosphorous nucleophiles, have been employed for the synthesis of a variety of fullerene adducts. In some cases, multiple adducts have been synthesized regioselectively. The second part deals with electrophilic reactions, although reported examples of these reactions are still limited. The third part is devoted to addition-elimination reactions, which have been recognized as one of the most powerful methodologies to construct methanofullerenes. Other types of cycloadducts can also be obtained by modifying the substrates. Carbenes and silylenes are also reactive toward fullerenes; this reactivity is described in the fourth part. A variety of 1, 3-dipolar cycloadditions, including the well-known Prato reactions, are summarized in the fifth part. The sixth part deals with nitrene additions, as these are relevant to 1, 3-dipolar cycloadditions. The seventh part is devoted to phosphine-mediated reactions. Notably, azafulleroids and azamethanofullerenes have also been prepared via 1, 3-dipolar cycloadditions followed by N2 extrusion. Several examples of [2 + 2] cycloadditions are described in the eighth part. Finally, a variety of Diels-Alder reactions are summarized in the final part. Noteworthily, some Diels-Alder cycloadducts obtained from the reactions of fullerenes with nitrogen-containing aromatic compounds provide useful precursors for the preparation of open-cage fullerenes and endohedral fullerenes. In addition, the reversibility of the Diels-Alder reaction of C60 with 9, 10-dimethylanthracene has been applied to achieve the regioselective synthesis of hexaadducts. - Li@C60 thin films: characterization and nonlinear optical properties
2022年, Mathias Wolf; Shuichi Toyouchi; Peter Walke; Kazuki Umemoto; Akito Masuhara; Hiroshi Fukumura; Yuta Takano; Michio Yamada; Kenji Hirai; Eduard Fron; Hiroshi Uji-i, RSC Advances, Royal Society of Chemistry (RSC), 12, 1, 研究論文（学術雑誌）, 10.1039/d1ra08051b, A facile way is shown to obtain thin films of Li@C60 as well as their characterization and nonlinear optical properties. Our results suggest Li@C60 to be a suitable candidate for high-harmonic generation. - Copper-Mediated Cascade Synthesis of Open-Cage Fullerenes
2020年04月21日, Michio Yamada; Asumi Ishitsuka; Yutaka Maeda; Mitsuaki Suzuki; Hiroyasu Sato, Organic Letters, 22, 9, 研究論文（学術雑誌）, 10.1021/acs.orglett.0c01119, 1523-7060 - A Fullerene-Based Molecular Torsion Balance for Investigating Noncovalent Interactions at the C60 Surface
2020年, Michio Yamada; Haruna Narita; Yutaka Maeda, Angewandte Chemie - International Edition, 59, 37, 研究論文（学術雑誌）, 10.1002/anie.202005888 - Helicity Sorting and Optical Resolution of Functionalized Single-Walled Carbon Nanotubes and Their Optical Properties
2020年, Yutaka Maeda; Yui Konno; Michio Yamada, The Journal of Physical Chemistry C, 124, 39, 研究論文（学術雑誌）, 10.1021/acs.jpcc.0c07963 - Sonochemical reaction to control the near-infrared photoluminescence properties of single-walled carbon nanotubes
2020年, Yutaka Maeda; Yui Konno; Akane Nishino; Michio Yamada; Saki Okudaira; Yuhei Miyauchi; Kazunari Matsuda; Jun Matsui; Masaya Mitsuishi; Mitsuaki Suzuki, Nanoscale, Royal Society of Chemistry (RSC), 12, 11, 研究論文（学術雑誌）, 10.1039/d0nr00271b, 2040-3364,A simple one-step operation to control the PL properties of SWNTs by ultrasonic irradiation was developed with an appropriate surfactant under the optimized conditions of the irradiation time, SWNT concentration, and reaction atmosphere.
- Synthesis of Fullerene-Fluorene Dyads through the Platinum-Catalyzed Reactions of [60]Fullerene with 9-Ethynyl-9 H-fluoren-9-yl Carboxylates
2019年07月, Michio Yamada; Mayu Takizawa; Yoko Nukatani; Mitsuaki Suzuki; Yutaka Maeda, The Journal of Organic Chemistry, 84, 14, 研究論文（学術雑誌）, 10.1021/acs.joc.9b00932, 0022-3263 - Reaction of the C60 radical anion with alkyl halides
2019年03月26日, Yutaka Maeda; Makoto Sanno; Tatsunari Morishita; Kodai Sakamoto; Eiichiro Sugiyama; Saeka Akita; Michio Yamada; Mitsuaki Suzuki, New Journal of Chemistry, The Royal Society of Chemistry, 43, 17, 研究論文（学術雑誌）, 10.1039/c9nj01043b, 1144-0546 - Addition of S-Heterocyclic Carbenes to Fullerenes: Formation and Characterization of Dithiomethano-Bridged Derivatives
2019年, Masahiro Kako; Yuki Arikawa; Shinji Kanzawa; Michio Yamada; Yutaka Maeda; Makoto Furukawa; Takeshi Akasaka, Helvetica Chimica Acta, 102, 5, 研究論文（学術雑誌）, 10.1002/hlca.201900064 - Photoreactions of Sc3N@Ih-C80 and Lu3N@Ih-C80 with disilirane: Isolation and characterization of labile 1,2-adducts
2018年, Masahiro Kako; Fumiaki Ozeki; Shinji Kanzawa; Shinpei Fukazawa; Kumiko Sato; Michio Yamada; Yutaka Maeda; Makoto Furukawa; Takeshi Akasaka, Heteroatom Chemistry, 29, 5-6, 研究論文（学術雑誌）, 10.1002/hc.21477 - Enhancing solution-phase supramolecular interactions between monomeric porphyrins and [60]fullerene by simple chemical modification
2017年11月, Michio Yamada; Gota Murakami; Shuhei Kobayashi; Yutaka Maeda, Tetrahedron Letters, PERGAMON-ELSEVIER SCIENCE LTD, 58, 48, 研究論文（学術雑誌）, 10.1016/j.tetlet.2017.10.037, 0040-4039, The supramolecular interactions of N-methylporphyrin and iridium porphyrin with C-60 in toluene solution were investigated using NMR spectroscopy and absorption spectroscopy. Our results demonstrate that both the N-methylation and iridium metalation of porphyrin are effective means to enhance the binding affinity to C-60, resulting in 1:1 complexation for N-methylporphyrin/C-60 and 2:1 complexation for iridium porphyrin/C-60. (C) 2017 Elsevier Ltd. All rights reserved. - Transition-metal-catalyzed divergent functionalization of [60] fullerene with propargylic esters
2017年10月, Michio Yamada; Rika Ochi; Yuhei Yamamoto; Sae Okada; Yutaka Maeda, Organic & Biomolecular Chemistry, ROYAL SOC CHEMISTRY, 15, 40, 研究論文（学術雑誌）, 10.1039/c7ob02168brsc.li/obc, 1477-0520, We have demonstrated that transition-metal-catalyzed divergent reactions between [60] fullerene (C-60) and propargylic esters allow easy access to formal [2 + 2] and [4 + 2] cycloadducts in reasonable yields, and that the production ratios depend on the metal catalyst used. The molecular structures of the cycloadducts were characterized by means of spectroscopic analyses and theoretical calculations. A plausible reaction mechanism is proposed that shows that two competing routes are likely to be involved after the initial transition-metal-activated cyclization of the carbonyl group and the CC triple bond in the 6-endo-dig mode. Further rearrangement into allenol esters followed by formal [2 + 2] cycloaddition with C60 gives the [2 + 2] cycloadducts, whereas rearrangement into 1,3-dienyl esters followed by [4 + 2] cycloaddition with C60 gives the [4 + 2] cycloadducts. - Synthesis and Photoinduced Electron-Transfer Reactions in a La2@Ih-C80-Phenoxazine Conjugate
2017年07月, Takeshi Akasaka; Akira Nakata; Marc Rudolf; Wei-Wei Wang; Michio Yamada; Mitsuaki Suzuki; Yutaka Maeda; Ryo Aoyama; Takahiro Tsuchiya; Shigeru Nagase; Dirk M. Guldi, ChemPlusChem, WILEY-V C H VERLAG GMBH, 82, 7, 研究論文（学術雑誌）, 10.1002/cplu.201600391, 2192-6506, A newly designed electron donor-acceptor conjugate consisting of an endohedral dimetallofullerene (La-2@I-h-C-80) and phenoxazine (POZ) was successfully synthesized under Prato conditions. Our results document that the 1,3-dipolar cycloaddition took place across the [5,6] junction to afford exclusively the corresponding [5,6] cycloadduct. The structure of the conjugate was characterized by means of NMR spectroscopy, absorption spectroscopy, and electrochemical studies. Computational calculations suggest that the electron density of the highest occupied molecular orbital (HOMO) is distributed on the POZ moiety, whereas that of the lowest unoccupied molecular orbital (LUMO) is located at the endohedral La atoms, leading to efficient separation of the HOMO and LUMO in the conjugate. Time-resolved absorption spectroscopic investigations and spectroelectrochemical measurements corroborate the formation of the energetically low-lying (La-2@I-h-C-80)C@ (POZ) C+ radical-ion-pair state by means of ultrafast throughspace electron transfer. - Temperature Dependence of Anisotropic Transient Conductivity of a La@C2v-C82(Ad) Crystal
2017年07月, Michio Yamada; Satoru Sato; Wookjin Choi; Shu Seki; Tsuneyuki Abe; Mitsuaki Suzuki; Yutaka Maeda; Shigeru Nagase; Takeshi Akasaka, Chemistry Letters, CHEMICAL SOC JAPAN, 46, 7, 研究論文（学術雑誌）, 10.1246/cl.170279, 0366-7022, The temperature dependence of the anisotropic transient conductivity of a La@C-2v-C-82(Ad) crystal was investigated using flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements. Results showed that the transient conductivity along the c-axis of the single-crystal increased as the temperature decreased, proving that electron transport can be described by the electronic band-conduction model instead of the electron-hopping model. - Preparation, Structural Determination, and Characterization of Electronic Properties of [5,6]- and [6,6]-Carbosilylated Sc3N@Ih-C80
2017年06月, Masahiro Kako; Takeshi Sugiura; Kyosuke Miyabe; Masanori Yasui; Michio Yamada; Yutaka Maeda; Jing-Dong Guo; Shigeru Nagase; Takeshi Akasaka, Chemistry – An Asian Journal, WILEY-V C H VERLAG GMBH, 12, 12, 研究論文（学術雑誌）, 10.1002/asia.201700506, 1861-4728, Photochemical carbosilylation of Sc3N@I-h-C-80 with silirane 1 afforded two corresponding [5,6]-adducts, 2 and 3, and a [6,6]-adduct, 4. The structural and electronic properties of these products were characterized by means of spectroscopic, electrochemical, and theoretical methods. The structure of 2 was disclosed by means of single-crystal X-ray crystallographic analysis. Thermal isomerization of 3 to 2 was observed, whereas that of 2 to 3 proceeded less efficiently at 100 degrees C. Upon heating under the same conditions, adduct 4 underwent facile decomposition to afford Sc3N@I-h-C-80, or isomerized into small amounts of 2 and 3. The relative stabilities of 2, 3, and 4 were rationalized through the results of theoretical calculations. In contrast, adducts 2, 3, and 4 were stable under the photolytic conditions employed for carbosilylation. The photochemical functionalization of Sc3N@I-h-C-80 represents a convenient synthetic method to obtain thermally labile fullerene-based products. - Adamantylidene Addition to M3N@Ih-C80 (M=Sc, Lu) and Sc3N@D5h-C80: Synthesis and Crystallographic Characterization of the [5,6]-Open and [6,6]-Open Adducts
2017年05月, Michio Yamada; Tsuneyuki Abe; Chiharu Saito; Toshiki Yamazaki; Satoru Sato; Naomi Mizorogi; Zdenek Slanina; Filip Uhlik; Mitsuaki Suzuki; Yutaka Maeda; Yongfu Lian; Xing Lu; Marilyn M. Olmstead; Alan L. Balch; Shigeru Nagase; Takeshi Akasaka, Chemistry – A European Journal, WILEY-V C H VERLAG GMBH, 23, 27, 研究論文（学術雑誌）, 10.1002/chem.201700049, 0947-6539, Additions of adamantylidene (Ad) to M3N@I-h-C-80 (M=Sc, Lu) and Sc3N@D-5h-C-80 have been accomplished by photochemical reactions with 2-adamantyl-2,3-[3H]-diazirine (1). In M3N@I-h-C-80, the addition led to rupture of the [6,6]- or [5,6]-bonds of the I-h-C-80 cage, forming the [6,6]-open fulleroid as the major isomer and the [5,6]-open fulleroid as the minor isomer. In Sc3N@D-5h-C-80, the addition also proceeded regioselectively to yield three major isomeric Ad mono-adducts, despite the fact that there are nine types of C-C bonds in the D-5h-C-80 cage. The molecular structures of the seven Ad mono-adducts, including the positions of the encaged trimetallic nitride clusters, have been unambiguously determined through single-crystal XRD analyses. Furthermore, results have shown that stepwise addition of Ad to Lu3N@I-h-C-80 affords several Ad bis-adducts, two of which have been isolated and characterized. The X-ray structure of one bis-adduct clearly revealed that the second Ad addition took place at a [6,6]-bond close to an endohedral metal atom. Theoretical calculations have also been performed to rationalize the regioselectivity. - Photoreactions of Endohedral Metallofullerene with Siliranes: Electronic Properties of Carbosilylated Lu₃N@Ih-C80
2017年05月, Masahiro Kako; Kazuya Minami; Taiki Kuroiwa; Shinpei Fukazawa; Yuki Arikawa; Michio Yamada; Yutaka Maeda; Qiao-Zhi Li; Shigeru Nagase; Takeshi Akasaka, Molecules, MDPI AG, 22, 5, 研究論文（学術雑誌）, 10.3390/molecules22050850, 1420-3049, Photochemical carbosilylation of Lu3N@I-h-C-80 was performed using siliranes (silacyclopropanes) to afford the corresponding [5,6]- and [6,6]-adducts. Electrochemical studies indicated that the redox potentials of the carbosilylated derivatives were shifted cathodically in comparison with those of the [5,6]-pyrrolidino adducts. The electronic effect of the silirane addends on Lu3N@I-h-C-80 was verified on the basis of density functional theory calculations. - Effect of Substituents and Initial Degree of Functionalization of Alkylated Single-Walled Carbon Nanotubes on Their Thermal Stability and Photoluminescence Properties
2017年02月, Yutaka Maeda; Yuya Takehana; Jing-Shuang Dang; Mitsuaki Suzuki; Michio Yamada; Shigeru Nagase, Chemistry – A European Journal, WILEY-V C H VERLAG GMBH, 23, 8, 研究論文（学術雑誌）, 10.1002/chem.201604282, 0947-6539, Alkylated single-walled carbon nanotubes (SWNTs) have been thermally treated to determine the influence of substituents and the degree of functionalization on their thermal stability and photoluminescence (PL) properties. Alkylated SWNTs were prepared by treating SWNTs with sodium naphthalenide and alkyl bromide. The defunctionalization of the alkylated SWNTs was monitored by absorption and Raman spectra. Selective recovery of the characteristic absorption and radial breathing mode peaks was observed during the thermal treatment, which indicates that the thermal stability of the alkylated SWNTs decreases with increases in SWNT diameter and degree of functionalization. n-Butylated and phenethylated SWNTs showed higher thermal stability than sec-butylated and benzylated SWNTs for a similar degree of functionalization, respectively. The diameter selectivity and effect of substituents on the thermal elimination reaction were confirmed by density functional theory. In addition, it was shown that the initial degree of functionalization of the alkylated SWNTs, with the alkyl group and degree of functionalization being kept constant after thermal treatment, strongly affects their PL properties; Stokes shift, and PL peak intensity. - The Unanticipated Dimerization of Ce@C2v(9)-C82 upon Co-crystallization with Ni(octaethylporphyrin) and Comparison with Monomeric M@C2v(9)-C82 (M = La, Sc, and Y)
2016年12月, Mitsuaki Suzuki; Michio Yamada; Yutaka Maeda; Satoru Sato; Yuta Takano; Filip Uhlik; Zdenek Slanina; Yongfu Lian; Xing Lu; Shigeru Nagase; Marilyn M. Olmstead; Alan L. Balch; Takeshi Akasaka, Chemistry – A European Journal, WILEY-V C H VERLAG GMBH, 22, 50, 研究論文（学術雑誌）, 10.1002/chem.201602595, 0947-6539, We report that Ce@C-2v(9)-C-82 forms a centrosymmetric dimer when co-crystallized with Ni(OEP) (OEP = octaethylporphyrin dianion). The crystal structure of {Ce@C-2v(9)-C-82}(2)center dot 2[Ni(OEP)]center dot 4C(6)H(6) shows that a new C-C bond with a bond length of 1.605(5) angstrom connects the two cages. The high spin density of the singly occupied molecular orbital (SOMO) on the cage and the pyramidalization of the cage are factors that favor dimerization. In contrast, the treatment of Ni(OEP) with M@C-2v(9)-C-82 (M = La, Sc, and Y) results in crystallization of monomeric endohedral fullerenes. A systematic comparison of the X-ray structures of M@C-2v(9)-C-82 (M = Sc, Y, La, Ce, Gd, Yb, and Sm) reveals that the major metal site in each case is located at an off-center position adjacent to a hexagonal ring along the C-2 axis of the C-2v(9)-C-82 cage. DFT calculations at the M06-2X level revealed that the positions of the metal centers in these metallofullerenes M@C-2v(9)-C-82 (M = Sc, Y, and Ce), as determined by single-crystal X-ray structure studies, correspond to an energy minimum for each compound. - D2d(23)-C84 versus Sc2C2@D2d(23)-C84: Impact of Endohedral Sc2C2 Doping on Chemical Reactivity in the Photolysis of Diazirine
2016年12月, Michio Yamada; Yukiko Tanabe; Jing-Shuang Dang; Satoru Sato; Naomi Mizorogi; Makoto Hachiya; Mitsuaki Suzuki; Tsuneyuki Abe; Hiroki Kurihara; Yutaka Maeda; Xiang Zhao; Yongfu Lian; Shigeru Nagase; Takeshi Akasaka, Journal of the American Chemical Society, AMER CHEMICAL SOC, 138, 50, 研究論文（学術雑誌）, 10.1021/jacs.6b10751, 0002-7863, We compared the chemical reactivity of D-2d(23)-C-84 and that of Sc2C2@D-2d(23)-C-84, both having the same carbon cage geometry, in the photolysis of 2-adamantane-2,3'-[3H]-diazirine, to clarify metal-atom doping effects on the chemical reactivity of the carbon cage. Experimental and computational studies have revealed that the chemical reactivity of the D-2d(23)-C-84 carbon cage is altered drastically by endohedral Sc2C2 doping. The reaction of empty D-2d(23)-C-84 with the diazirine under photoirradiation yields two adamantylidene (Ad) adducts. NMR. spectroscopic studies revealed that the major Ad monoadduct (C-84(Ad)-A) has a fulleroid structure and that the minor Ad monoadduct (C-84(Ad)-B) has a methanofullerene structure. The latter was also characterized using X-ray crystallography. C-84(Ad)-A is stable under photoirradiation, but it interconverted to C-84(Ad)-B by heating at 80 degrees C. In contrast, the reaction of endohedral Sc2C2@D-2d(23)-C-84 with diazirine under photoirradiation affords four (Sc2C2@C-84(Ad)-A, Sc2C2@C-84(Ad)-B, Sc2C2@C-84(Ad)-C, and Sc2C2@C-84(Ad)-D). The structure Sc2C2@C-84(Ad)-C was characterized using X-ray crystallography. Thermal interconversion of Sc2C2@C-84(Ad)-A and Sc2C2@C-84(Ad)-B to Sc2C2@C-84(Ad)-C was also observed. The reaction mechanisms of the Ad addition and thermal interconversion were elucidated from theoretical calculations. Calculation results suggest that C-84(Ad)-B and Sc2C2@C-84(Ad)-C are thermodynamically favorable products. Their different chemical reactivities derive from Sc2C2 doping, which raises the HOMO and LUMO levels of the D-2d(23)-C-84 carbon cage. - Tuning of the photoluminescence and upconversion photoluminescence properties of single-walled carbon nanotubes by chemical functionalization
2016年, Yutaka Maeda; Shun Minami; Yuya Takehana; Jing-Shuang Dang; Shun Aota; Kazunari Matsuda; Yuhei Miyauchi; Michio Yamada; Mitsuaki Suzuki; Rui-Sheng Zhao; Xiang Zhao; Shigeru Nagase, Nanoscale, ROYAL SOC CHEMISTRY, 8, 38, 研究論文（学術雑誌）, 10.1039/c6nr04214g, 2040-3364, Single-walled carbon nanotubes (SWNTs) were subjected to alkylation using alkyl bromide and alkyl dibromide, and the photoluminescence (PL) properties of the resulting alkylated SWNTs were characterized. Two new PL peaks were observed along with the intrinsic PL peak at 976 nm when alkyl bromide was used (SWNT-Bu: similar to 1095 and 1230 nm, SWNT-Bn: 1104 and 1197 nm). In contrast, the use of a, a'-dibromo-o-xylene as an alkyl dibromide primarily resulted in only one new PL peak, which was observed at 1231 nm. The results revealed that the Stokes shift of the new peaks was strongly influenced by the addition patterns of the substituents. In addition, the time-resolved PL decay profiles of the alkylated SWNTs revealed that the PL peaks possessing a larger Stokes shift had longer exciton lifetimes. The up-conversion PL (UCPL) intensity of the alkylated SWNTs at excitation wavelengths of 1100 and 1250 nm was estimated to be similar to 2.38 and similar to 2.35 times higher than that of the as-dispersed SWNTs, respectively. - Effective derivatization and extraction of insoluble missing lanthanum metallofullerenes La@C2n (n = 36-38) with iodobenzene
2016年, Yutaka Maeda; Takahiro Tsuchiya; Takashi Kikuchi; Hidefumi Nikawa; Tao Yang; Xiang Zhao; Zdenek Slanina; Mitsuaki Suzuki; Michio Yamada; Yongfu Lian; Shigeru Nagase; Xing Lu; Takeshi Akasaka, Carbon, 98, 研究論文（学術雑誌）, 10.1016/j.carbon.2015.10.088 - Preparation, Structural Determination, and Characterization of Electronic Properties of Bis-silylated and Bis-germylated Lu3N@Ih-C80
2015年11月, Masahiro Kako; Kyosuke Miyabe; Kumiko Sato; Mitsuaki Suzuki; Naomi Mizorogi; Wei-Wei Wang; Michio Yamada; Yutaka Maeda; Marilyn M. Olmstead; Alan L. Balch; Shigeru Nagase; Takeshi Akasaka, Chemistry – A European Journal, WILEY-V C H VERLAG GMBH, 21, 46, 研究論文（学術雑誌）, 10.1002/chem.201502511, 0947-6539, Bis-silylated and bis-germylated derivatives of Lu3N@I-h-C-80 (3, 4, 5) were successfully synthesized by the photochemical addition of disiliranes 1a, 1b or digermirane 2, and fully characterized by spectroscopic, electrochemical, and theoretical studies. Interestingly, digermirane 2 reacts more efficiently than disiliranes 1a and 1b because of its good electron-donor properties and lower steric hindrance around the GeGe bond. The 1,4-adduct structures of 3, 4, 5 were unequivocally established by single-crystal X-ray crystallographic analyses. The electrochemical and theoretical studies reveal that the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the 1,4-adducts are remarkably smaller than those of Lu3N@I-h-C-80, because the electron-donating groups effectively raise the HOMO levels. It is also observed that germyl groups are slightly more electron-donating than the silyl groups on the basis of the redox properties and the HOMO-LUMO energies of 4 and 5. Bis-silylation and bis-germylation are effective and versatile methods for tuning the electronic characteristics of endohedral metallofullerenes. - Preparation, Structural Determination, and Characterization of Electronic Properties of Bis-Silylated and Bis-Germylated Lu3 N@Ih -C80.
2015年11月, Kako M; Miyabe K; Sato K; Suzuki M; Mizorogi N; Wang WW; Yamada M; Maeda Y; Olmstead MM; Balch AL; Nagase S; Akasaka T, Chemistry (Weinheim an der Bergstrasse, Germany), 21, 46, 10.1002/chem.201503579, 0947-6539 - Regioselective Cage Opening of La2@D2(10611)-C72 with 5,6-Diphenyl-3-(2-pyridyl)-1,2,4-triazine
2015年02月, Michio Yamada; Yasuhiro Muto; Hiroki Kurihara; Zdenek Slanina; Mitsuaki Suzuki; Yutaka Maeda; Yves Rubin; Marilyn M. Olmstead; Alan L. Balch; Shigeru Nagase; Xing Lu; Takeshi Akasaka, Angewandte Chemie International Edition, WILEY-V C H VERLAG GMBH, 54, 7, 研究論文（学術雑誌）, 10.1002/anie.201410012, 1433-7851, The thermal reaction of the endohedral metallofullerene La-2@D-2(10611)-C-72, which contains two pentalene units at opposite ends of the cage, with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine proceeded selectively to afford only two bisfulleroid isomers. The molecular structure of one isomer was determined using single-crystal X-ray crystallography. The results suggest that the [4+2] cycloaddition was initiated in a highly regioselective manner at the C-C bond connecting two pentagon rings of C-72. Subsequent intramolecular electrocyclization followed by cycloreversion resulted in the formation of an open-cage derivative having three seven-membered ring orifices on the cage and a significantly elongated cage geometry. The reduction potentials of the open-cage derivatives were similar to those of La-2@D-2-C-72 whereas the oxidation potentials were shifted more negative than those of La-2@D2C72. These results point out that further oxidation could occur easily in the derivatives. - Control of the photoluminescence properties of single-walled carbon nanotubes by alkylation and subsequent thermal treatment
2015年, Yutaka Maeda; Yuya Takehana; Michio Yamada; Mitsuaki Suzuki; Tatsuya Murakami, Chemical Communications, ROYAL SOC CHEMISTRY, 51, 70, 研究論文（学術雑誌）, 10.1039/c5cc04020e, 1359-7345, Dibutylated single-walled carbon nanotubes (Bu-SWNTs-Bu) with varying degrees of functionalization were prepared by two-step reductive alkylation and subsequent thermal treatment. A new photoluminescence peak at around 1240 nm was observed and increased drastically after the thermal treatment. The results indicate that thermally treated Bu-SWNTs-Bu are promising NIR photoluminescent materials. - Photochemical Behavior of Single-Walled Carbon Nanotubes in the Presence of Propylamine
2014年06月, Yutaka Maeda; Yuhei Hasuike; Kei Ohkubo; Atsushi Tashiro; Shinya Kaneko; Masayuki Kikuta; Michio Yamada; Tadashi Hasegawa; Takeshi Akasaka; Jing Zhou; Jing Lu; Shigeru Nagase; Shunichi Fukuzumi, ChemPhysChem, WILEY-V C H VERLAG GMBH, 15, 9, 研究論文（学術雑誌）, 10.1002/cphc.201301045, 1439-4235, This report describes the photochemical behavior of single-walled carbon nanotubes (SWNTs) in the presence of propylamine. The SWNTs are characterized by absorption and Raman spectroscopy. The spectral changes due to photoirradiation indicate that reactions occur predominantly with the metallic SWNTs and small-diameter SWNTs. The detection of amine radicalcation species by ESR spectroscopy reveals photoinduced electron transfer from the amine to the excited SWNTs. After exposure of the photoirradiated SWNTs to air, the characteristic spectra were recovered, except for that of the small-diameter SWNTs. The results suggest that, after photoreduction of the SWNTs, subsequent selective sidewall functionalization of the small-diameter SWNTs occurs. - Isolation and characterization of [5,6]-pyrrolidino-Sc3N@Ih-C80 diastereomers
2014年, Yutaka Maeda; Masato Kimura; Chihiro Ueda; Michio Yamada; Toru Kikuchi; Mitsuaki Suzuki; Wei-Wei Wang; Naomi Mizorogi; Nikolaos Karousis; Nikos Tagmatarchis; Tadashi Hasegawa; Marilyn M. Olmstead; Alan L. Balch; Shigeru Nagase; Takeshi Akasaka, Chemical Communications, ROYAL SOC CHEMISTRY, 50, 83, 研究論文（学術雑誌）, 10.1039/c4cc04946b, 1359-7345, Reactions of Sc3N@I-h-C-80 with aziridine derivatives were conducted to afford the corresponding mono-adducts. A pair of diastereomers of the mono-adduct [5,6]-pyrrolidino-Sc3N@I-h-C-80 was isolated and characterized by means of mass spectrometry, vis-NIR absorption spectroscopy, and electrochemical measurements. Structural analysis of the mono-adducts was conducted by NMR and single-crystal X-ray structure determinations. - Ground and excited state electronic interactions in push-pull-chromophore- [60]fullerene conjugates
2014年, Michio Yamada; Francesca Tancini; Michael Sekita; Dirk M. Guldi; Corinne Boudon; Jean-Paul Gisselbrech; Mariza N. Alberti; W. Bernd Schweizer; Francois Diederich, Fullerenes, Nanotubes and Carbon Nanostructures, 22, 1-3, 研究論文（学術雑誌）, 10.1080/1536383X.2013.794342 - Thermal Reactions of C60 with Siliranes: Carbosilylation and Silylene Addition of Fullerenes
2014年01月, Masahiro Kako; Ryosuke Iida; Yutaka Maeda; Michio Yamada; Tadashi Hasegawa, Fullerenes, Nanotubes and Carbon Nanostructures, TAYLOR & FRANCIS INC, 22, 1-3, 研究論文（学術雑誌）, 10.1080/1536383X.2013.798722, 1536-383X, Thermal reactions of C-60 with siliranes (1a, b) afforded carbosilylated C-60 derivatives. When a bicyclic fused silirane (1c) was employed instead of 1a and 1b, a silylene adduct and its hydrolyzed compound were obtained through thermal extrusion of silylenes from 1c. These products were determined to be 1,2-adducts at 6,6-junctions of C-60 by MS, UV, and NMR analyses. These results provide a complementary method to the photochemical addition of reactive silicon compounds, which have been long employed for silylation of C-60. Electrochemical analyses revealed the redox properties of the silylated products, indicating the perturbation caused by silyl groups introduced on the C-60 cage. Theoretical calculations were also conducted for understanding of the electronic property of the silylated product. - Computations on Metallofullerenes Derivatized during Extraction: La@C80-C6H3Cl2 and La@C82-C6H3Cl2
2014年01月, Zdenek Slanina; Filip Uhlik; Shyi-Long Lee; Ludwik Adamowicz; Hiroki Kurihara; Hidefumi Nikawa; Xing Lu; Michio Yamada; Shigeru Nagase; Takeshi Akasaka, Fullerenes, Nanotubes and Carbon Nanostructures, TAYLOR & FRANCIS INC, 22, 1-3, 研究論文（学術雑誌）, 10.1080/1536383X.2013.798724, 1536-383X, Recently, an extraction of la metallofullerenes from soot using 1,2,4-trichlorobenzene has been reported for La@C-80 and La@C-82. In both cases, the cages were derivatized by the solvent (forming La@C-80-C6H3Cl2 and La@C-82-C6H3Cl2) and the following X-ray analysis disclosed rather unexpected cages: C-80(C-2v;3) and C-82(C-3v;7). In order to explain the challenging observations, a two-step computational treatment is presented. The first step deals with the high-temperature gas-phase formation of the underivatized endohedrals while the second step models the reaction with the solvent. The Gibbs free energies were evaluated for representative temperatures and the computational scheme was able to confirm high relative populations for the observed derivatized cages. - La2@Cs(17490)-C76: A New Non-IPR Dimetallic Metallofullerene Featuring Unexpectedly Weak Metal-Pentalene Interactions
2013年12月, Mitsuaki Suzuki; Naomi Mizorogi; Tao Yang; Filip Uhlik; Zdenek Slanina; Xiang Zhao; Michio Yamada; Yutaka Maeda; Tadashi Hasegawa; Shigeru Nagase; Xing Lu; Takeshi Akasaka, Chemistry – A European Journal, WILEY-V C H VERLAG GMBH, 19, 50, 研究論文（学術雑誌）, 10.1002/chem.201302821, 0947-6539, Although all the pure-carbon fullerene isomers above C-60 reported to date comply with the isolated pentagon rule (IPR), non-IPR structures, which are expected to have different properties from those of IPR species, are obtainable either by exohedral modification or by endohedral atom doping. This report describes the isolation and characterization of a new endohedral metallofullerene (EMF), La-2@C-76, which has a non-IPR fullerene cage. The X-ray crystallographic result for the La-2@C-76/[Ni-II(OEP)] (OEP=octaethylporphyrin) cocrystal unambiguously elucidated the C-s(17490)-C-76 cage structure, which contains two adjacent pentagon pairs. Surprisingly, multiple metal sites were distinguished from the X-ray data, which implies dynamic behavior for the two La3+ cations inside the cage. This dynamic behavior was also corroborated by variable-temperature (LaNMR)-La-139 spectroscopy. This phenomenon conflicts with the widely accepted idea that the metal cations in non-IPR EMFs invariably coordinate strongly with the negatively charged fused-pentagon carbons, thereby providing new insights into modern coordination chemistry. Furthermore, our electrochemical and computational studies reveal that La-2@C-s(17490)-C-76 has a larger HOMO-LUMO gap than other dilanthanum-EMFs with IPR cage structures, such as La-2@D-3h(5)-C-78 and La-2@I-h(7)-C-80, which implies that IPR is no longer a strict rule for EMFs. - Helicity-selective photoreaction of single-walled carbon nanotubes with organosulfur compounds in the presence of oxygen
2013年04月24日, Yutaka Maeda; Junki Higo; Yuri Amagai; Jun Matsui; Kei Ohkubo; Yusuke Yoshigoe; Masahiro Hashimoto; Kazuhiro Eguchi; Michio Yamada; Tadashi Hasegawa; Yoshinori Sato; Jing Zhou; Jing Lu; Tokuji Miyashita; Shunichi Fukuzumi; Tatsuya Murakami; Kazuyuki Tohji; Shigeru Nagase; Takeshi Akasaka, Journal of the American Chemical Society, 135, 16, 研究論文（学術雑誌）, 10.1021/ja402199n, 0002-7863, This report describes a helicity-selective photoreaction of single-walled carbon nanotubes (SWNTs) with disulfide in the presence of oxygen. The SWNTs were characterized using absorption, photoluminescence (PL), Raman, and X-ray photoelectron spectroscopy, scanning electron microscopy, and current-voltage (I-V) measurements. Results showed remarkable helicity-selective (metallic SWNTs/semiconducting SWNTs and diameter) functionalization of SWNTs. The reaction rate decreases in the order of metallic SWNTs >
semiconducting SWNTs and small-diameter SWNTs >
large-diameter SWNTs. Control experiments conducted under various experimental conditions and ESR and femtosecond laser flash photolysis measurements revealed that the helicity-selective reaction proceeds via a photoinduced electron transfer reaction. The PL and I-V measurements showed that the photoreaction is effective not only to control SWNT conductivity but also for the band gap modulation of semiconducting SWNTs. © 2013 American Chemical Society. - Mapping the Metal Positions inside Spherical C80 Cages: Crystallographic and Theoretical Studies of Ce2@D5h-C80 and Ce2@Ih-C80
2013年01月, Lai Feng; Mitsuaki Suzuki; Naomi Mizorogi; Xing Lu; Michio Yamada; Takeshi Akasaka; Shigeru Nagase, Chemistry – A European Journal, WILEY-V C H VERLAG GMBH, 19, 3, 研究論文（学術雑誌）, 10.1002/chem.201202341, 0947-6539, The dynamic positions of the dimetallic cluster inside the mid-sized spherical cages of C80C82 have been seldom studied, despite the high abundance of M2@C2n (2n=80, 82) species among various endohedral metallofullerenes. Herein, using crystallographic methods, we first unambiguously map the metal positions for both Ce2@D5h-C80 and Ce2@Ih-C80, showing how the symmetry or geometrical change in cage structure can influence the motional behavior of the cluster. Inside the D5h cage, the primary cerium sites have been identified along a cage belt of the contiguous hexagons, which suggests the significant influence of such a cage motif on endohedral cluster motion. Further analysis revealed a distorted D5h cage owing to the punch-out effect of cerium atoms. The consequence is the presence of two localized electrostatic potential minima inside the cage of (D5h-C80)6-, thus reflecting the primary ionic ceriumcage interaction. In contrast, a different motional behavior of Ce2 cluster was observed inside the Ih cage. With the major cerium sites, the molecule of Ce2@Ih-C80 presented an approximate D2h configuration. With the combined theoretical study, we propose that the additional unidentified influence of NiII(OEP) (OEP=octaethylporphyrin) might be also relevant for the location of cerium sites inside the Ih cage. - A versatile approach to functionalisation of [60]fullerene using 3-trifluoromethyl-3-phenyldiazirine derivatives as photolabelling reagents
2013年, Michio Yamada; Kenji Harada; Yutaka Maeda; Tadashi Hasegawa, New Journal of Chemistry, ROYAL SOC CHEMISTRY, 37, 11, 研究論文（学術雑誌）, 10.1039/c3nj00796k, 1144-0546, The photolysis of para-substituted 3-trifluoromethyl-3-phenyldiazirine derivatives in the presence of [60]fullerene (C-60) allowed easy access to the functionalised methanofullerenes 2b-2d in reasonable yields. The reaction is believed to take place via the addition of the carbene intermediate to a [6,6] double bond of C-60. Succinimidyl-appended methanofullerene 2b serves as an active site for the attachment of other molecules via amidation. In fact, not only 2c-2d but also biotin-appended methanofullerene 2e were successfully synthesised by the amidation of 2b with the corresponding amines under mild conditions. The electrochemical properties of 2b-2d were characterised using cyclic voltammetry and differential pulse voltammetry. In addition, standard HABA assays in DMSO revealed the binding ability of the biotin moiety in 2e to avidin. - Electron transport through single endohedral Ce@C82 metallofullerenes
2012年10月, Satoshi Kaneko; Lu Wang; Guangfu Luo; Jing Lu; Shigeru Nagase; Satoru Sato; Michio Yamada; Zdenek Slanina; Takeshi Akasaka; Manabu Kiguchi, Physical Review B, AMER PHYSICAL SOC, 86, 15, 研究論文（学術雑誌）, 10.1103/PhysRevB.86.155406, 1098-0121, The electron transport through a single endohedral Ce@C-82 metallofullerene bridging between metal electrodes was investigated with experimental (break junction) as well as theoretical (density functional theory coupled with the nonequilibrium Green's function formalism) techniques. The single Ce@C-82 molecule junction showing a high and fixed conductance value was fabricated by direct binding of the metallofullerene to Ag electrodes. The junction had a conductance of 0.28(+/- 0.05)G(0) (G(0) = 2e(2)/h), which was much larger than that of single molecule junctions having anchoring groups (<0.01G(0)), but only half that of the single C-60 molecule junction of 0.5G(0). The unexpected reduced conductance of the single Ce@C-82 molecule junction compared with that of the single C-60 molecule junction was supported by the ab initio quantum transport calculations and was explained in terms of the localization of electrons in the C-82 cage. In the case of the Au electrodes, the single Ce@C-82 molecule junction was not formed by the break junction technique because the Ce@C-82 molecule could not be trapped in the large Au nanogap, which was formed just after breaking the Au contacts. - Oxygen Atom Transfer from Peroxide Intermediates to Fullerenes
2011年12月05日, Yutaka Maeda; Yasuyuki Niino; Takuya Kondo; Michio Yamada; Tadashi Hasegawa; Takeshi Akasaka, Chemistry Letters, Oxford University Press (OUP), 40, 12, 研究論文（学術雑誌）, 10.1246/cl.2011.1431, 0366-7022, Abstract
Photoreaction of C60 and C70 with adamantylideneadamantane or sulfide under oxygen flow gives fullerene epoxide together with adamantylideneadamantane epoxide or sulfoxide via peroxide intermediates. - Synthesis of Endohedral Metallofullerene Glycoconjugates by Carbene Addition
2011年11月, Michio Yamada; Chika I. Someya; Tsukasa Nakahodo; Yutaka Maeda; Takahiro Tsuchiya; Takeshi Akasaka, Molecules, MDPI AG, 16, 11, 研究論文（学術雑誌）, 10.3390/molecules16119495, 1420-3049, Endohedral metallofullerene glycoconjugates were synthesized under mild conditions by carbene addition using appropriate glycosylidene-derived diazirine with La(2)@I(h)-C(80). NMR spectroscopic studies revealed that the glycoconjugate consists of two diastereomers of [6,6]-open mono-adducts. The electronic properties were characterized using Vis/NIR absorption spectroscopy and electrochemical measurements. This study demonstrates that glycosylidene carbene is useful to incorporate carbohydrate moieties onto endohedral metallofullerene surfaces. - Regioselective Cycloaddition of La2@Ih-C80 with Tetracyanoethylene Oxide: Formation of an Endohedral Dimetallofullerene Adduct Featuring Enhanced Electron-Accepting Character
2011年03月, Michio Yamada; Mari Minowa; Satoru Sato; Zdenek Slanina; Takahiro Tsuchiya; Yutaka Maeda; Shigeru Nagase; Takeshi Akasaka, Journal of the American Chemical Society, AMER CHEMICAL SOC, 133, 11, 研究論文（学術雑誌）, 10.1021/ja2000243, 0002-7863, We describe the regioselective cycloaddition of La-2@I-h-C-80 with tetracyanoethylene oxide (TCNEO), which enabled the formation of the corresponding adduct having a tetracyanotetrahydrofuran moiety. X-ray crystallographic analysis revealed that the cycloaddition took place as a [5,6] addition. Along with dynamic swing motion of the metal atoms, the results of this electrochemical study demonstrate that TCNEO addition enhanced the electron-accepting character of La-2@I-h-C-80 and that the first reduction potential of the adduct reached -0.21 V versus the ferrocene/ferrocenium couple, which is the lowest value reported for endohedral metallofullerenes and their derivatives to date. - Preparation and characterization of transparent and conductive thin films of single-walled carbon nanotubes
2011年, Yutaka Maeda; Kazuki Komoriya; Katsuya Sode; Junki Higo; Takayuki Nakamura; Michio Yamada; Tadashi Hasegawa; Takeshi Akasaka; Takeshi Saito; Jing Lu; Shigeru Nagase, Nanoscale, ROYAL SOC CHEMISTRY, 3, 4, 研究論文（学術雑誌）, 10.1039/c0nr00940g, 2040-3364, Single-walled carbon nanotubes (SWNTs), synthesized using the arc-discharge method and the direct-injection-pyrolytic synthesis (DIPS) method, were dispersed in a tetrahydrofuran solution containing propylamine and used to prepare transparent and conductive thin films on PET films using an airbrush technique. The SWNTs were analyzed using vis-near infrared absorption spectroscopy, Raman spectroscopy, scanning electron microscopy, and atomic force microscopy. The surface resistivity of the SWNT films on the substrates was measured using a four-point probe conductivity measurement. The results revealed that the purity, length, and proportion of the metallic SWNTs are important factors in decreasing the sheet resistance. - 異なる2つの置換基を有する金属内包フラーレンの位置選択的合成
2011年, 佐藤 悟; 前田 優; 稲田 浩二; 二川 秀史; 山田 道夫; 溝呂木 直美; 長谷川 正; 土屋 敬広; 赤阪 健; 加藤 立久; Zdenek Slanina; 永瀬 茂, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 2010, 10.11494/kisoyuki.2010.0.a25.0, 我々は金属内包フラーレンLa@C82とペンタメチルシクロペンタジエン(Cp*)との反応を行い、付加反応が可逆的かつ位置特異的に進行することを明らかにし、さらに単結晶X線結晶構造解析により誘導体の構造解析に成功した。また、La@C82Cp*に求電子試薬であるアダマンチリデンカルベン(Ad:)を、La@C82AdにCp*を付加させることで、異なる置換基を有する金属内包フラーレン誘導体の位置選択的合成を行なった。 - 化学修飾によるLa2@C80の電子アクセプター性制御
2011年, 山田 道夫; 美野輪 まり; 佐藤 悟; 溝呂木 直美; スラニナ ズデネク; 前田 優; 加固 昌寛; 永瀬 茂; 赤阪 健, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 2011, 10.11494/kisoyuki.2011.0.79.0, フラーレンは優れた電子アクセプターとして知られており、様々な応用が提案されている。本研究では化学修飾を施すことによって、金属内包フラーレンLa2@C80の電子アクセプター性を制御できることを明らかにした。 - 金属内包フラーレンCe2@ D5h-C80の分子構造
2011年, 馮 莱; 鈴木 光明; 溝呂木 直美; 蘆 興; 山田 道夫; 土屋 敬広; 赤阪 健; 永瀬 茂, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 2011, 10.11494/kisoyuki.2011.0.365.0, 金属内包フラーレンCe2@ D5h-C80の分子構造 - Thermal Carbosilylation of Endohedral Dimetallofullerene La2@Ih-C80 with Silirane
2010年12月, Michio Yamada; Mari Minowa; Satoru Sato; Masahiro Kako; Zdenek Slanina; Naomi Mizorogi; Takahiro Tsuchiya; Yutaka Maeda; Shigeru Nagase; Takeshi Akasaka, Journal of the American Chemical Society, AMER CHEMICAL SOC, 132, 50, 研究論文（学術雑誌）, 10.1021/ja108671b, 0002-7863, Thermal carbosilylation of endohedral dimetallofullerene La-2@I-h-C-80 with silirane (silacyclopropane) is reported herein for the first time. Two diastereomers of the carbosilylated La-2@I-h-C-80 have been isolated and characterized. The fascinating molecular structure of one diastereomer of the carbosilylated derivatives has been determined unambiguously using X-ray crystallographic analysis. Detailed characteristics of the molecular structures including their metal atom movements have also been revealed using NMR spectroscopic studies and computational calculations. Results revealed that two La atoms move dynamically inside the carbon sphere. Furthermore, electrochemical study has demonstrated that carbosilylation is effective to fine-tune the La-2@I-h-C-80 electronic properties. - Separation of metallic single-walled carbon nanotubes using various amines
2010年12月, Yutaka Maeda; Kazuki Komoriya; Katsuya Sode; Makoto Kanda; Michio Yamada; Tadashi Hasegawa; Takeshi Akasaka; Jing Lu; Shigeru Nagase, Physica Status Solidi B -Basic Solid State Physics, WILEY-V C H VERLAG GMBH, 247, 11-12, 研究論文（学術雑誌）, 10.1002/pssb.201000205, 0370-1972, Separation of metallic single-walled carbon nanotubes (m-SWNTs) using various amines in different concentrations was investigated. The SWNTs dispersions were characterized with Vis-NIR and Raman spectrometers. The proportion of m-SWNTs toward semiconducting SWNTs increased with an increase of concentration of amines. SWNTs thin films were prepared from the SWNTs dispersion. The sheet resistance of SWNTs films decreased with an increase of proportion of m-SWNTs. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim - A Molecular Ce2@Ih-C80 Switch-Unprecedented Oxidative Pathway in Photoinduced Charge Transfer Reactivity
2010年07月, Dirk M. Guldi; Lai Feng; Shankara Gayathri Radhakrishnan; Hidefumi Nikawa; Michio Yamada; Naomi Mizorogi; Takahiro Tsuchiya; Takeshi Akasaka; Shigeru Nagase; M. Angeles Herranz; Nazario Martin, Journal of the American Chemical Society, AMER CHEMICAL SOC, 132, 26, 研究論文（学術雑誌）, 10.1021/ja101856j, 0002-7863, We report for the first time the versatile Ce-2@I-h-C-80 building block toward synthesizing a novel electron donor-acceptor conjugate, Ce-2@I-h-C-80-ZnP (1) A systematic investigation of the charge transfer chemistry documents a reductive charge transfer (i e, formation of (Ce-2@I-h-C-80)(center dot-)-(ZnP)(center dot+)) in nonpolar media (i e, toluene/THF), while an oxidative charge transfer (i.e., formation of (Ce-2@I-h-C-80)(center dot+)(ZnP)(center dot-)) dominates in polar media (i.e, benzonitnle/DMF). Reduction of the [Ce-2](6+) cluster, which is highly localized and collinearly arranged with respect to the quaternary bridge carbon, is sufficiently exothermic in all solvents. Notably weak is the electronic coupling between the [Ce-2](6+) cluster and the electron-donating ZnP The oxidation of C-80(6-) and the simultaneous reduction of ZnP, on the other hand, necessitate solvent stabilization In such a case, the strongly exothermic (Ce-2@I-h-C-80)(center dot-)(ZnP)(center dot 4) radical ion pair state formation is compensated within the framework of a nonadiabatic charge transfer by a C-80(6-)/ZnP electronic matrix element, as the sum of good overlap and short distance, that exceeds that for [Ce-2](6+)/ZnP. - Regioselective Exohedral Functionalization of La@C82 and its 1,2,3,4,5-Pentamethylcyclopentadiene and Adamantylidene Adducts
2010年, Yutaka Maeda; Satoru Sato; Koji Inada; Hidefumi Nikawa; Michio Yamada; Naomi Mizorogi; Tadashi Hasegawa; Takahiro Tsuchiya; Takeshi Akasaka; Tatsuhisa Kato; Zdenek Slanina; Shigeru Nagase, Chemistry – A European Journal, WILEY-BLACKWELL, 16, 7, 研究論文（学術雑誌）, 10.1002/chem.200902512, 0947-6539, The first regioselective functionalization of La@C-82 by two different groups has been performed. Bis-adducts of La@C-82 With Cp* and adamantylidene were synthesized by using two different routes and characterized, Spectroscopic analysis and theoretical calculations reveal that the addition position is controlled by the charge density and p-orbital axis vector value of the fullerene cage. - Optical Stability of Axially Chiral Push-Pull-Substituted Buta-1,3-dienes: Effect of a Single Methyl Group on the C60 Surface
2010年, Michio Yamada; Pablo Rivera-Fuentes; W. Bernd Schweizer; Francois Diederich, Angewandte Chemie International Edition, WILEY-BLACKWELL, 49, 20, 研究論文（学術雑誌）, 10.1002/anie.200906853, 1433-7851 - Unprecedented thermal rearrangement of push-pull-chromophore-[60]fullerene conjugates: formation of chiral 1,2,9,12-tetrakis-adducts
2010年, Michio Yamada; W. Bernd Schweizer; Franziska Schoenebeck; Francois Diederich, Chemical Communications, ROYAL SOC CHEMISTRY, 46, 29, 研究論文（学術雑誌）, 10.1039/c0cc00881h, 1359-7345, Push-pull-chromophore-[60]fullerene conjugates featuring N,N-dimethylanilino-substituted 1,1,4,4-buta-1,3-dienes directly attached to the carbon sphere are transformed into chiral 1,2,9,12-tetrakis-adducts by a novel thermal rearrangement pathway. - Anisotropic Magnetic Behavior of Anionic Ce@C82 Carbene Adducts
2009年07月, Yuta Takano; Motoki Aoyagi; Michio Yamada; Hidefumi Nikawa; Zdenek Slanina; Naomi Mizorogi; Midori O. Ishitsuka; Takahiro Tsuchiya; Yutaka Maeda; Takeshi Akasaka; Tatsuhisa Kato; Shigeru Nagase, Journal of the American Chemical Society, AMER CHEMICAL SOC, 131, 26, 研究論文（学術雑誌）, 10.1021/ja902106a, 0002-7863, Derivatives of Ce@C-82(C-2v) have been synthesized and fully characterized, and their anisotropic magnetism has been observed as paramagnetic shifts in NMR measurements. Carbene addition by photochemical reaction afforded two isomers of Ce@C-82(C-2v)Ad (Ad = adamantylidene), 2a and 2b, demonstrating high regioselectivity. The two isomers were characterized using MALDI-TOF mass spectrometry, vis-NIR absorption spectroscopy, H-1 and C-13 NMR spectroscopy, and electrochemistry. The structure of the minor isomer (2b) was elucidated by single-crystal X-ray structural analysis. C-13 and H-1 NMR measurements revealed the characteristic anisotropic interaction between the f electron on the Ce atom and nuclear spins of the carbon atoms of the cage and the protons of the Ad group, respectively. - Synthesis and Characterization of the D5h Isomer of the Endohedral Dimetallofullerene Ce2@C80: Two-Dimensional Circulation of Encapsulated Metal Atoms Inside a Fullerene Cage
2009年, Michio Yamada; Naomi Mizorogi; Takahiro Tsuchiya; Takeshi Akasaka; Shigeru Nagase, Chemistry – A European Journal, WILEY-BLACKWELL, 15, 37, 研究論文（学術雑誌）, 10.1002/chem.200900713, 0947-6539, Herein we show the synthesis and characterization of the second known Ce-2@C-80 isomer. A C-13 NMR spectroscopic study revealed that the structure of the second isomer has D-5h, symmetry. Paramagnetic NMR spectral analysis and theoretical calculation display that the encapsulated Cc atoms circulate two-dimensionally along a band of ten contiguous hexagons inside a D-5h-C-80 cage, which is in sharp contrast to the three-dimensional circulation of two Ce atoms in an I-h-C-80 cage. The electronic properties were revealed by means of electrochemical measurements. The D-5h isomer of Ce-2@C-80 has a much smaller HOMOLUMO gap than cluster fullerenes (M3N@C-80, M=Sc, Tm, and Lu) with the same D-5h-C-80 cages. The chemical reactivity was investigated by using disilirane as a chemical probe. The high thermal reactivity toward 1,1,2,2-tetramesityl-1,2-disilirane is consistent with the trends of the redox potentials and the lower LUMO level of the D-5h isomer of Ce-2@C-80 compared with that of C-60. - Two Regioisomers of Endohedral Pyrrolidinodimetallofullerenes M2@Ih-C80(CH2)(2)NTrt (M = La, Ce; Trt = trityl): Control of Metal Atom Positions by Addition Positions
2009年, Michio Yamada; Mayuko Okamura; Satoru Sato; Chika I. Someya; Naomi Mizorogi; Takahiro Tsuchiya; Takeshi Akasaka; Tatsuhisa Kato; Shigeru Nagase, Chemistry – A European Journal, WILEY-V C H VERLAG GMBH, 15, 40, 研究論文（学術雑誌）, 10.1002/chem.200900993, 0947-6539, The two regioisomers of endohedral pyrrolidinodimetallofullerenes M-2@I-h-C-80(CH2)(2)NTrt (M = La, Cc; Trt=trityl) were synthesized, isolated, and characterized. X-ray crystallographic analyses of [6,6]-La-2@I-h-C-80-(CH2)(2)NTrt and. [6,6]-Ce-2@I-h-C-80-(CH2)(2)NTrt revealed that the encapsulated metal atoms are located at the slantwise positions on the mirror plane that parallels the pyrrolidine ring. Paramagnetic NMR analyses of [6,6]- and [5,6]-Ce-2@Ih-C-80(CH2)(2)NTrt were also carried out to clarify the metal positions. As for the [6,6]-adduct, the metal positions obtained by paramagnetic NMR analysis agree well with the Xray structure. In contrast, paramagnetic NMR analysis of the [5,6]-adduct showed that the two Cc atoms are collinear with the pyrrolidine ring. We also compared the observed para magnetic effects of the pyrrolidinodimetallofullerenes with those of other cerium-encapsulating fullerene derivation tives such as bis-silylated Ce-2@I-h,-C-80 and a carbene adduct of Ce-2@I-h-Cs-80 We found that the metal positions can be explained by the electrostatic potential maps of the corresponding [6,6]and [5,6]-adducts of [Ih-C-80(CH2)(2)NTrt](6-). These findings clearly show that metal positions inside fullerene cages can be controlled by means of the addition positions of the addends. In addition, the radical anions of the pyriolidinodinietallofullerenes were prepared by bulk controlled-potential electrolysis and characterized by X-band EPR spectral study. - Ce@C82カルベン付加体アニオンの合成と磁気異方性観測
2009年, 高野 勇太; 青柳 元喜; 山田 道夫; 二川 秀史; SLANINA Zdenek; 溝呂木 直美; 生沼 みどり; 土屋 敬広; 前田 優; 赤阪 健; 加藤 立久; 永瀬 茂, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 2009, 10.11494/kisoyuki.2009.0.46.0, 今回我々は、カルベン付加によるCe@C82の誘導体化を行い、2種類の一付加体(2a, 2b)を高収率・高選択的に得た。吸収スペクトルをはじめとする各種スペクトル測定により構造解析を行った。バルク電解による電気化学的な一電子還元を各々の付加体に対して行い、得られたアニオン体の各種温度における1H及び13C NMR測定から、付加体のf電子に由来する磁気異方的な挙動の観測に成功した。 - 異なる置換基による金属内包フラーレン誘導体の位置選択的化学修飾
2009年, 佐藤 悟; 前田 優; 稲田 浩二; 二川 秀史; 山田 道夫; 溝呂木 直美; 長谷川 正; 土屋 敬広; 赤阪 健; 加藤 立久; Zdenek Slanina; 永瀬 茂, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 2009, 10.11494/kisoyuki.2009.0.153.0, 私たちは金属内包フラーレンLa@C82とペンタメチルシクロペンタジエン(Cp*)との反応を検討し、付加反応が可逆的かつ位置特異的に進行することを明らかにし、単結晶X線構造解析により付加体の構造解析に成功した。
さらにLa@C82Cp*に対しアダマンチル基(Ad)を、また、La@C82Adに対しCp*を反応させ、これら異なる二つのルートから高選択的に二付加体が得られることを見出したので報告する。 - Radical Coupling Reaction of Paramagnetic Endohedral Metallofullerene La@C82
2008年12月, Yuta Takano; Akinori Yomogida; Hidefumi Nikawa; Michio Yamada; Takatsugu Wakahara; Takahiro Tsuchiya; Midori O. Ishitsuka; Yutaka Maeda; Takeshi Akasaka; Tatsuhisa Kato; Zdenek Slanina; Naomi Mizorogi; Shigeru Nagase, Journal of the American Chemical Society, AMER CHEMICAL SOC, 130, 48, 研究論文（学術雑誌）, 10.1021/ja802748q, 0002-7863, The thermal reaction of La@C-82(C-82) with 3-triphenylmethyl-5-oxazolidinone (1) in toluene affords benzyl monoadducts La@C-82(C-2v)(CH2C6H5) (2a-2d). The same monoadducts are also obtained by the photoirradiation of La@C-82(C-2v) in toluene without the existence of 1. These reactions are applicable to paramagnetic metallofullerenes, such as La@C-82(C-s) and Ce@C-82(C-2v). The photoirradiation of La@C-82(C-2v) in 1,2-dichlorobenzene in the presence of alpha,alpha,2,4-tetrachlorotoluene also affords the monoadducts La@C-82(C-2v)(CHClC6H3Cl2) (3a-3d). The monoadducts are fully characterized by spectroscopic analyses. Single-crystal X-ray structure analysis for 3d reveals the unique structure. Theoretical calculations show that the cage carbons having high,spin densities are selectively attacked by radical species to form the monoadducts linked by a carbon-carbon single bond. The thermal reaction of La@C-82(C-2v) with 1 in benzene affords metallofulleropyrrolidine La@C-82(C-2v)(C2H4NCPh3) (5), unlike the reaction in toluene. - Spectroscopic and theoretical study of endohedral dimetallofullerene having a Non-IPR fullerene cage: Ce2@C72
2008年08月, Michio Yamada; Takatsugu Wakahara; Takahiro Tsuchiya; Yutaka Maeda; Takeshi Akasaka; Naomi Mizorogi; Shigeru Nagase, The Journal of Physical Chemistry A, AMER CHEMICAL SOC, 112, 33, 研究論文（学術雑誌）, 10.1021/jp804260d, 1089-5639, The endohedral dimetalloftillerene having a non-IPR fullerene cage, Ce-2@C-72, is spectroscopically and theoretically characterized. The C-13 NMR measurements display large temperature-dependent signals caused by paramagnetic shifts, indicating that the Ce atoms are located near the two fused pentagons in the C-72 cage. Theoretical. calculations are performed to clarify the metal position, which are in good agreement with the result obtained by the paramagnetic C-13 NMR analysis. Electrochemical measurements reveal that Ce-2@C-72 has particularly lower oxidation and higher reduction potentials than other endohedral dimetallofullerenes. - Metal atoms collinear with the spiro carbon of 6,6-open adducts, M2@C80(Ad) (M = La and Ce, Ad = adamantylidene)
2008年01月, Michio Yamada; Chika Someya; Takatsugu Wakahara; Takahiro Tsuchiya; Yutaka Maeda; Takeshi Akasaka; Kenji Yoza; Ernst Horn; Michael T. H. Liu; Naomi Mizorogi; Shigeru Nagase, Journal of the American Chemical Society, AMER CHEMICAL SOC, 130, 4, 研究論文（学術雑誌）, 10.1021/ja073924w, 0002-7863, The photochemical reaction Of M-2@C-80 (M=La and Ce) with 2-adamantane-2,3'-[3H]-diazirine (1) affords the corresponding adducts by carbene addition. The adducts were characterized by spectroscopic and single-crystal X-ray structure analyses. Crystallographic data for the adduct La-2@C-80(Ad) (2, Ad = adamantylidene) reveal that the two La atoms are collinear with the Spiro carbon of the 6,6-open adduct. It is noteworthy that the La-La distance is highly elongated by the addition of carbene. Paramagnetic C-13 NMR spectral analysis of the adduct Ce-2@C-80(Ad) (3) indicates that the two Ce atoms are also collinear with the Spiro carbon at room temperature in solution. The unique metal positions were confirmed by density functional calculations. - Location of the metal atoms in Ce2@C78 and its bis-silylated derivative
2008年, Michio Yamada; Takatsugu Wakahara; Takahiro Tsuchiya; Yutaka Maeda; Masahiro Kako; Takeshi Akasaka; Kenji Yoza; Ernst Horn; Naomi Mizorogi; Shigeru Nagase, Chemical Communications, ROYAL SOC CHEMISTRY, 5, 研究論文（学術雑誌）, 10.1039/b712568b, 1359-7345, Endohedral metallofullerenes have received extensive attention for their fascinating structures, properties and chemical reactivities.(1) Especially, considerable interest is now directed toward the dimetallofullerenes such as La-2@C-80(2) and Ce-2@C-80(3) because of the three-dimensional random motion of the two metal atoms inside the fullerene cage. However, the dynamic behavior of the metal atoms in other dimetallofullerenes has not been clarified. Recently we reported the first isolation, C-13 NMR characterization, and theoretical studies of a new dimetallo-fullerene, La-2@C-78.(4) The C-13 NMR study showed that La-2@C-78 has a D-3h-C-78 cage, because five lines with full intensity and three lines with half intensity were observed. Although there are two D-3h IPR cage isomers for C-78,5 further structural determination of La-2@C-78 was not achieved experimentally. Herein we report the synthesis and characterization of Ce-2@C-78 and its bis-silylated derivative. The location of the metal atoms in Ce-2@C-78 and the bis-silylated derivative has been investigated by means of spectroscopic and single-crystal X-ray structural analyses.
Ce-2@C-78 was synthesized and isolated for the first time using a recently developed method.(6) The purity of the isolated Ce-2@C-78 is > 99.9%, as confirmed by mass spectroscopic and HPLC analyses. The visible-NIR spectrum of Ce-2@C-78 shows characteristic absorptions at 644, 553, and 526 nm, which resembles that of La-2@C-78. The colors of Ce-2@C-78 in solution and in the solid state are dark blue and black, respectively. The C-13 NMR spectrum of Ce-2@C-78 at 298 K shows a total of distinct eight lines derived from the C-78 cage; five lines (full intensity) at 104.9, 141.8, 152.4, 155.8, and 156.3 ppm and three lines (half intensity) at 131.6, 150.3, and 162.0 ppm. This C-13 NMR pattern is unambiguously attributed to the fact that the carbon cage of Ce-2@C-78 has D-3h symmetry(5). - 金属内包フラーレンLa@C82の可逆反応
2008年, 佐藤 悟; 前田 優; 稲田 浩司; 山田 道夫; 土屋 敬広; 石塚 みどり; 長谷川 正; 赤阪 健; 加藤 立久; 溝呂木 直美; Zdenek Slanina; 永瀬 茂, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 2008, 10.11494/kisoyuki.2008.0.142.0, フラーレンの可逆付加反応はフラーレンの分離法や位置選択的多段階付加反応を制御し得るテンプレートとして有用である。すでに私達は金属内包フラーレンLa@C82とシクロペンタジエンとの反応を検討し、付加反応が高選択的に進行することを報告している。また逆反応が速やかに進行することを見出した。本研究では反応機構の解明と付加体の安定性の向上を目的として、1,2,3,4,5-ペンタメチルシクロペンタジエンとの反応を検討した。付加体の構造を単結晶X線構造解析により明らかにし、化学反応性および位置選択性を理論計算に基づいて明らかにしたので合わせて報告する。 - Photo-labeling of C60 with 3-trifluoromethyl-3-phenyldiazirine
2007年09月, Satoru Sato; Michio Yamada; Takatsugu Wakahara; Takahiro Tsuchiya; Midori O. Ishitsuka; Takeshi Akasaka; Michael T. H. Liu, Tetrahedron Letters, PERGAMON-ELSEVIER SCIENCE LTD, 48, 36, 研究論文（学術雑誌）, 10.1016/j.tetlet.2007.07.027, 0040-4039, The photochemical reaction of C-60 With 3-trifluoromethyl-3-phenyldiazirine affords a photo-labeled C-60 derivative. The derivative was characterized by mass, UV-vis absorption, NMR spectroscopy, and X-ray crystallographic analysis. The redox potentials of this derivative were also investigated by means of CV and DPV. This photo-labeling method to the fullerene surface is expected to be effective for constructing various kinds of bio-functionalized fullerenes. (c) 2007 Elsevier Ltd. All rights reserved. - Two-dimensional hopping motion of encapsulated La atoms in silylated La2@C80
2007年, Takatsugu Wakahara; Michio Yamada; Satomi Takahashi; Tsukasa Nakahodo; Takahiro Tsuchiya; Yutaka Maeda; Takeshi Akasaka; Masahiro Kako; Kenji Yoza; Ernst Horn; Naomi Mizorogi; Shigeru Nagase, Chemical Communications, ROYAL SOC CHEMISTRY, 26, 研究論文（学術雑誌）, 10.1039/b703473c, 1359-7345, The La-139 NMR study of the exohedrally functionalized derivatives of La-2@C-80 metallofullerene, La-2@C-80(Ar2Si)(2)CH2 (3a: Ar = Mes, Mes = mesityl, 3b: Ar = Dep, Dep = 2,6-diethylphenyl), reveal that the two La atoms hop between two sites along the equator of the C-80 cage. - La@C82とシクロペンタジエン誘導体の可逆付加反応
2007年, 佐藤 悟; 前田 優; 稲田 浩司; 長谷川 正; 山田 道夫; 土屋 敬広; 赤阪 健; 加藤 立久; 溝呂木 直美; 永瀬 茂, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 57, 10.11494/kisoyuki.57.0.43.0, Diels-Alder反応を用いたフラーレンの可逆付加反応は、フラーレンの分離法や位置選択的な多段階付加反応を制御しえるテンプレートとして利用されている大変興味深い反応系である。すでに我々は、金属内包フラーレンLa@C82・シクロペンタジエン誘導体の合成を行い、付加反応に高い位置選択性があることを見出した。さらに、誘導体の反応速度について明らかにした。しかしこの付加反応は逆反応が非常に早く進行してしまう。
そこで、反応機構の検証および付加体の安定性を向上させる目的でペンタメチルシクロペンタジエンを用いて反応を行なった。各種測定結果により付加反応の選択性と付加体の安定性について検討を行なったのでこれらを報告する。 - 化学修飾によるフラーレンケージに内包された金属原子の配向制御
2007年, 山田 道夫; 染谷 知香; 若原 孝次; 土屋 敬広; 赤阪 健; 前田 優; 与座 健治; 溝呂木 直美; 永瀬 茂, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 37, 10.11494/kisoyuki.37.0.67.0, C80ケージに金属原子を二個内包した金属内包フラーレンM2@C80は、Ih対称という非常に高い対称を有しており、C60よりも小さいHOMO-LUMOギャップを有することなどから注目を集めている。特に、NMR解析などにより金属原子がフラーレンの内部空間で三次元のランダムな回転運動を有していることが明らかになっており、内包金属原子の動的挙動に興味が持たれている。本研究ではM2@C80に種々の化学修飾を施すことにより、外界から隔絶された金属原子の配向を水平方向、斜め方向、垂直方向へと自在に制御することに成功した。 - Analysis of lanthanide-induced NMR shifts of the Ce@C82 anion
2006年02月, Michio Yamada; Takatsugu Wakahara; Yongfu Lian; Takahiro Tsuchiya; Takeshi Akasaka; Markus Waelchli; Naomi Mizorogi; Shigeru Nagase; Karl M. Kadish, Journal of the American Chemical Society, AMER CHEMICAL SOC, 128, 5, 研究論文（学術雑誌）, 10.1021/ja055882m, 0002-7863 - Synthesis and structural characterization of endohedral pyrrolidinodimetallofullerene: La2@C80(CH2)(2)NTrt
2006年02月, Michio Yamada; Takatsugu Wakahara; Tsukasa Nakahodo; Takahiro Tsuchiya; Yutaka Maeda; Takeshi Akasaka; Kenji Yoza; Ernst Horn; Naomi Mizorogi; Shigeru Nagase, Journal of the American Chemical Society, AMER CHEMICAL SOC, 128, 5, 研究論文（学術雑誌）, 10.1021/ja056560l, 0002-7863 - フラーレンケージに内包された金属原子の動的挙動制御
2006年, 山田 道夫; 若原 孝次; 仲程 司; 土屋 敬広; 赤阪 健; 前田 優; 与座 健治; 溝呂木 直美; 永瀬 茂, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 18, 10.11494/kisoyuki.18.0.191.0, フラーレンケージの内部空間に金属原子を内包した金属内包フラーレンは、金属原子が外部環境から孤立して存在しているため非常に興味深い化学種である。中でも金属原子を二個内包した金属内包フラーレンM2@C80は、内包原子がケージ内部の中空空間で三次元の自由回転をしており, その動的挙動に興味が持たれている。
本研究ではM2@C80（M = La and Ce）に対し含ケイ素三員環化合物であるジシリランを用いたケイ素化反応およびアゾメチンイリドを用いた1,3-双極子環化付加反応を行ない、付加体を合成した。NMRスペクトル解析および単結晶X線構造解析により、ジシリラン付加体では内包原子が二次元的回転に変化するのに対し、1,3-双極子環化付加体では一箇所に局在化することを見出した。 - Positional control of encapsulated atoms inside a fullerene cage by exohedral addition
2005年10月, Michio Yamada; Tsukasa Nakahodo; Takatsugu Wakahara; Takahiro Tsuchiya; Yutaka Maeda; Takeshi Akasaka; Masahiro Kako; Kenji Yoza; Ernst Horn; Naomi Mizorogi; Kaoru Kobayashi; Shigeru Nagase, Journal of the American Chemical Society, AMER CHEMICAL SOC, 127, 42, 研究論文（学術雑誌）, 10.1021/ja054346r, 0002-7863 - Synthesis and characterization of exohedrally silylated M@C82 (M = Y and La)
2005年04月, Michio Yamada; Lai Feng; Takatsugu Wakahara; Takahiro Tsuchiya; Yutaka Maeda; Yongfu Lian; Masahiro Kako; Takeshi Akasaka; Tatsuhisa Kato; Kaoru Kobayashi; Shigeru Nagase, The Journal of Physical Chemistry B, AMER CHEMICAL SOC, 109, 13, 研究論文（学術雑誌）, 10.1021/jp050657b, 1520-6106, The silylation of endohedral mono-metallofullerenes (Y@C-82 and La@C-82) and isolation of the corresponding adducts by HPLC separation have been accomplished. The redox properties of the silylated mono-metallofullerene were first clarified by CV and DPV measurements, indicating that the bis-silylated mono-metallofullerenes have lower oxidation and higher reduction potentials than the parent mono-metallofullerenes. These results reveal that bis-silylation is very effective for producing the electronegatively mono-metallofullerene derivatives as well as empty fullerenes. - 金属内包フラーレンM2@C80の化学修飾
2005年, 山田 道夫; 若原 孝次; 仲程 司; 土屋 敬広; 赤阪 健; 前田 優; Markus Waelchli; 与座 健治; Ernst Horn; 溝呂木 直美; 小林 郁; 永瀬 茂, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 55, 10.11494/kisoyuki.55.0.56.0, 金属内包フラーレンM2@C80（M = 内包された金属原子）は, 内包原子がフラーレンの内部空間で三次元の自由回転をしており, その動的挙動に興味が持たれている. この動的挙動はケージ内部の静電ポテンシャル分布から説明でき, 化学修飾を施し静電ポテンシャル分布を制御することによって内包原子の動的挙動を制御できると期待できる. 本研究ではM2@C80に対しジシリランを用いたケイ素化反応, アゾメチンイリドを用いた1,3-双極子環化付加反応を行ない, ジシリラン付加体では内包金属原子が二次元的回転に変化するのに対し, 1,3-双極子環化付加体では一箇所に局在化することを見出した. - 金属内包フラーレンの化学修飾
2004年, 若原 孝次; 前田 優; 土屋 敬広; 生沼 みどり; 赤阪 健; 小林 郁; 永瀬 茂; 加藤 立久; Horn Ernst; 与座 健治; Waelchli Markus; 山田 道夫, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 基礎有機化学会（基礎有機化学連合討論会）, 17, 10.11494/kisoyuki.17.0.57.0, 金属内包フラーレンの化学反応による誘導体の合成に成功した。誘導体の構造は各種NMRあるいはESRの測定及び、最終的にはX-線結晶構造解析により決定した。誘導体の電気的特性についても併せて報告する。 - Characterization of Ce@C82 and Its Anion
2004年, Takatsugu Wakahara; Jun-ichi Kobayashi; Michio Yamada; Yutaka Maeda; Takahiro Tsuchiya; Mutsuo Okamura; Takeshi Akasaka; Markus Waelchli; Kaoru Kobayashi; Shigeru Nagase; Tatsuhisa Kato; Masahiro Kako; Kazunori Yamamoto; Karl M. Kadish, Journal of the American Chemical Society, 126, 15, 研究論文（学術雑誌）, 10.1021/ja039865d, 1520-5126
講演・口頭発表等
- ねじり天秤分子モデルを用いた芳香環–フラーレン相互作用の定量評価
2024年03月21日, 日本化学会第104春季年会, 口頭発表（一般） - プロパルギルリン酸エステルを用いたフラーレンの分子変換
2023年12月09日, 第50回有機典型元素化学討論会, 口頭発表（一般） - カスケード反応によるシクロブテノフラーレンの一段階合成
2023年09月12日, 第33回基礎有機化学討論会, ポスター発表 - ブチル化単層カーボンナノチューブ付加体の化学修飾率と発光特性に及ぼすフッ素原子置換数の効果
2024年03月21日, 第104春季年会, 口頭発表（一般） - ペルフルオロアルキル化反応によるカーボンナノチューブの光通信領域における近赤外発光の制御
2023年09月14日, 第33回基礎有機化学討論会, 口頭発表（一般） - Relationship of Binding Configurations to Photoluminescence Properties of Functionalized Single-Walled Carbon Nanotubes
2023年09月04日, 第65回フラーレン・ナノチューブ・グラフェン総合シンポジウム - Effect of the tether length of reagents with two reactive sites on the band gap of single-walled carbon nanotubes
2023年03月23日, 日本化学会第103春季年会, 口頭発表（一般） - 近赤外発光の測定と付加基の定量によるデンドロン修飾カーボンナノチューブの付加様式の考察
2022年09月21日, 第32回基礎有機化学討論会, ポスター発表 - アレン-フラーレン間に働くFace-to-Face型非共有結合性相互作用の評価
2022年09月20日, 第32回基礎有機化学討論会, ポスター発表 - Control of the photoluminescence properties of single-walled carbon nanotubes by chemical functioalization and quantification of their terminal amino groups
2022年09月01日, 第63回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - Synthesis and Characterization of Cyclobutenofullerenes
2022年09月01日, 第63回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - デンドロンを用いた単層カーボンナノチューブの化学修飾による近赤外発光制御とその末端官能基の変換
2022年03月25日, 日本化学会第102春季年会, 口頭発表（一般） - 化学修飾による単層カーボンナノチューブの近赤外発光特性の制御と導入した官能基の変換
2021年09月21日, 第31回基礎有機化学討論会 - Thermodynamic control of quantum defects on functionalized single-walled carbon nanotubes
2021年06月08日, NT21: International Conference on the Science and Application of Nanotubes and Low-Dimensional Materials, ポスター発表 - Sonochemical reaction to control the near-infrared photoluminescence properties of single-walled carbon nanotubes
2021年06月08日, NT21: International Conference on the Science and Application of Nanotubes and Low-Dimensional Materials, ポスター発表 - C60表面に働く非共有結合性相互作用の定量的な評価
2021年03月22日, 日本化学会第101春季年会, 口頭発表（一般） - Photoreaction of C70 with disilirane: Electronic properties of silylated adducts
2021年03月02日, 第60回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - Chirality and helicity sorting of functionalized single-walled carbon nanotube
2021年03月01日, 第60回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - 超音波照射による簡便で効果的な単層カーボンナノチューブの発光特性制御
2020年09月16日, 第59回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - ジブロモアルカンを用いた単層カーボンナノチューブの発光特性の制御：反応基質の鎖長の影響
2020年03月24日, 日本化学会第100春季年会, 口頭発表（一般） - Control of the photoluminescence property of single-walled carbon nanotubes by chemical functionalization and its subsequent transformation of functional groups
2020年03月23日, 日本化学会第100春季年会, 口頭発表（一般） - Measurement of Fullerene–Arene Interactions Using Molecuar Torsion Balances
2020年03月22日, 日本化学会第100春季年会, ポスター発表 - 超音波照射による簡便で効果的な単層カーボンナノチューブの発光特性制御
2020年03月16日, 第58回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - Reactions of S-Heterocyclic Carbenes with Fullerenes: Preparation and Characterization of Dithiomethano-derivatives
2020年03月15日, 第58回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - CuCl-Mediated Reaction of C60 with Propargylic Phosphate
2020年03月15日, 第58回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - 修飾SWNTs量子ドットの設計とバンドギャップ制御
2019年09月05日, 第57回フラーレン・ナノチューブ・グラフェン総合シンポジウム, 口頭発表（一般） - Co-crystal of La@Cs(6)-C82 with Ni(OEP)
2019年07月23日, The 18th International Symposium on Novel Aromatic Compounds (ISNA-18), ポスター発表 - Selectivity in Emergence of Red-shifted Photoluminescence of Single-Walled Carbon Nanotubes by Functionalization using Bulky Reagents
2019年07月23日, The 18th International Symposium on Novel Aromatic Compounds (ISNA-18), ポスター発表 - Fullerene-Based Molecular Torsion Balance for Investigating Noncovalent Interactions on the C60 Surface
2019年07月22日, The 18th International Symposium on Novel Aromatic Compounds (ISNA-18), ポスター発表 - Platinum-catalyzed reaction of [60]fullerene with 9-ethynyl-9H-fluoren-9-yl carboxylates
2019年03月, 第56回フラーレン・ナノチューブ・グラフェン総合シンポジウム - Photoreactions of Sc3N@Ih-C80 and Lu3N@Ih-C80 with Disilirane: Characterization of Labile 1,2-Adducts
2019年03月, 第56回フラーレン・ナノチューブ・グラフェン総合シンポジウム - Synthesis and characterization of fullerene-based molecular torsion balance for investigating noncovalent fullerene-arene interaction
2019年03月, 第56回フラーレン・ナノチューブ・グラフェン総合シンポジウム - Control of near infrared photoluminescence properties of single walled carbon nanotubes by functionalization with dendrons
2019年03月, 日本化学会第99春季年会 - Functionalization of fullerene C60 via one electron reduction
2019年03月, 日本化学会第99春季年会 - デンドロンによる単層カーボンナノチューブの化学修飾：修飾率と近赤外発光特性の制御
2018年09月, 第55回フラーレン・ナノチューブ・グラフェン総合シンポジウム - La@Cs(6)-C82とNi(OEP)の共結晶化
2018年09月, 第29回基礎有機化学討論会, ポスター発表 - C60還元体を用いたメタノフラーレン合成
2018年09月, 第29回基礎有機化学討論会, ポスター発表 - Divergent reactivity of C60 with propargylic esters in the presence of transition metal catalyst
2018年03月, 口頭発表（一般） - Temperature dependence of anisotropic transient conductivity of a La@C2v-C82(Ad) crystal
2018年03月, 第54回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - Photoreaction of Sc3N@Ih-C80 with Disilirane: Formation and Isomerization of 1,2-, 1,3-, and 1,4-Adducts
2018年03月, 第54回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - Chemical functionalization of single-walled carbon nanotubes to control their PL properties for bioimaging application
2018年03月, 日本化学会第98春季年会, ポスター発表 - ジスルフィドによって光酸化した単層カーボンナノチューブの発光特性と熱処理
2017年12月, 第44回有機典型元素化学討論会, 口頭発表（一般） - 特異な金属内包フラーレン及びその誘導体の電子状態
2017年11月, 第56回電子スピンサイエンス学会年会, 口頭発表（招待・特別） - Effect of Initial Degree of Functionalization of Alkylated Single-Walled Carbon Nanotubes on Their Thermal Stability and Photoluminescence Properties
2017年09月, 第53回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - Unveiling the Unique Chemical Reactivity of Endohedral Metallofullerenes
2017年06月, 2nd International Symposium on NanoCarbons -- Fullerenes, Endofullerenes, Carbon Nanotubes, Graphenes and Carbon Nanostructures, 口頭発表（招待・特別） - フェナントレンが縮環したインダセンとその類縁体の合成と物性
2017年03月, 日本化学会第97春季年会, 口頭発表（一般） - Competitive elimination and decomposition reaction of oxidized single-walled carbon nanotubes depending on the degree of functionalization
2017年02月, 第52回フラーレン・ナノチューブ・グラフェン総合シンポジウム, 口頭発表（一般） - Photochemical Addition of Silicones to Sc3N@Ih-C80: Interconversion of the [6,6]-and [5,6]-Adducts
2017年02月, 第52回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - Control of photoluminescence properties of single-walled carbon nanotubes
2016年09月, 第51回フラーレン・ナノチューブ・グラフェン総合シンポジウム, 口頭発表（一般） - フェナントレンが縮環したインダセン誘導体とそのラジカルカチオンの合成と物性
2016年09月, 第27回基礎有機化学討論会, ポスター発表 - Substituent effects on defunctionalization of alkylated single-walled carbon nanotubes
2016年02月, 第50回フラーレン•ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - Preparation, Structural Determination, and Characterization of Electronic Properties of Carbosilylated Sc3N@Ih-C80
2016年02月, 第50回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - ケイ素およびゲルマニウム化合物を用いた金属内包フラーレン誘導体の合成
2015年10月, 第5回CSJ化学フェスタ, ポスター発表 - The Structure of Endohedral Metallofullerene Sc2@C66 Having Two Unsaturated Linear Triquinane Units
2015年03月, 日本化学会第95春季年会, 口頭発表（一般） - 光酸化した単層カーボンナノチューブの評価
2015年03月, 日本化学会第95春季年会, ポスター発表 - フラーレン還元体とベンジルブロミド誘導体の反応
2015年03月, 日本化学会第95春季年会, ポスター発表 - Hiding and Recovering Electrons in a Dimetallic Endohedral Fullerene: Air-Stable Products from Radical Additions
2015年03月, 日本化学会第95春季年会, 口頭発表（一般） - [5,6]-pyrrolidino-Sc3N@Ih-C80ジアステレオマーの単離とキャラクタリゼイション
2015年02月, the 48th Fullerenes-Nanotubes-Graphene General Symposium, ポスター発表 - Unsaturated linear triquinane: A new motif in fullerene cage geometry
2014年10月, International Symposium on the Synthesis and Application of Curved Organic pi-Molecules and Materials, ポスター発表 - Sc2@C66 Revisited: An Endohedral Fullerene with Scandium Ions Nestled within Two Unsaturated Linear Triquinanes
2014年09月, the 47th Fullerenes-Nanotubes-Graphene General Symposium, 口頭発表（一般） - 常磁性内包フラーレンSc3C2@C80とベンジルブロミドの付加反応とその誘導体の構造解析
2014年09月, 第25回基礎有機化学討論会, 口頭発表（一般） - C602–とベンジルブロミド誘導体の反応
2014年09月, 第25回基礎有機化学討論会, ポスター発表 - 有機硫黄化合物を用いた単層カーボンナノチューブの酸化反応
2014年03月, 第94春季年会, ポスター発表 - Thermal Bis-silylation, Carbosilylation, and Bis-germylation of Fullerenes
2014年03月, 第46回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - プロピルアミン存在下におけるSWNTsの光化学的挙動
2014年03月, 第46回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - Excited State Electronic Interactions in Push-Pull Chromophore-[60]Fullerene Conjugates
2014年03月, 第46回フラーレン・ナノチューブ・グラフェン総合シンポジウム, ポスター発表 - Excited State Electronic Interactions in Push–Pull-Chromophore–[60]Fullerene Conjugates
2013年12月, 第7回有機π電子系シンポジウム, ポスター発表 - M@C2v(9)-C82の内包金属イオンとフラーレンケージの関係
2013年09月, 第24回基礎有機化学討論会, 口頭発表（一般） - Reaction of Trimetallic Nitride Template-endohedral Metallofullerene (TNT-EMFs) with Aziridine
2013年03月, The 44th Fullerenes-Nanotubes-Graphene General Symposium, ポスター発表 - Thermal Reactions of C60 with Siliranes: Formation of Carbosilylated Fullerenes
2013年03月, The 44th Fullerenes-Nanotubes-Graphene General Symposium, ポスター発表 - 3-トリフルオロメチル-3-フェニルジアジリン誘導体を用いたフラーレンC60の機能化
2013年03月, 第93春季年会, 口頭発表（一般） - 異なる置換基を有する単層カーボンナノチューブの化学修飾率の評価
2013年03月, 第93春季年会, 口頭発表（一般） - カーボンナノチューブの脱酸素反応における選択性
2013年03月, 第93春季年会, ポスター発表 - 活性酸化種を用いたフラーレンの酸化反応
2012年12月, 第39回有機典型元素討論会, 口頭発表（一般） - 3-トリフルオロ-3-フェニルジアジリン誘導体を用いたフラーレンC60の機能化
2012年09月, 第23回基礎有機化学討論会, 口頭発表（一般） - Application of MCD Spectroscopy and TD-DFT to Endohedral Metallofullerenes. New Insights into Characterization of Their Electron Transitions
2012年09月, The 43rd Fullerenes-Nanotubes-Graphene General Symposium Abstracts, その他 - The 3rd Tsukuba International Mini-symposium on Hybridization between Main Group Element Chemistry and p-electron Chemistry - ICHAC-10 Pre-symposium in Tsukuba
2012年07月, The 2nd symposium on "Carbon Nanoforms", ポスター発表 - Rational design of twisted bis-porphyrin tweezer for noncovalent interaction of single-walled carbon nanotubes
2012年05月, The 3rd Tsukuba International Mini-symposium on Hybridization between Main Group Element Chemistry and p-electron Chemistry - ICHAC-10 Pre-symposium in Tsukuba, 口頭発表（招待・特別） - 1-ベンゾイルアセチルピペラジン誘導体と関連化合物の光反応
2012年03月, 第92春季年会, 口頭発表（一般） - ベンゾイルアセトアミド誘導体の光環化における水素移動の選択性に及ぼす置換基効果
2012年03月, 第92春季年会, 口頭発表（一般） - Reactions of C60 with disilirane and silirane in the presence of transition metal complexes
2012年03月, The 42nd Fullerenes-Nanotubes-Graphene General Symposium, ポスター発表 - 金属内包フラーレンとアジリジンの反応
2011年12月, 第38回有機典型元素化学討論会, ポスター発表 - Endohedral metallofullerenes: new building blocks for photoactive donor-acceptor system
2011年12月, 1st International Symposium on Creation of Functional Materials, ポスター発表 - Synthesis and photophysical properties of metallofullerene-zinc porphyrin dyads: impact of endohedral clusters
2011年11月, 3rd International Symposium on Emergence of Highly Elaborated pi-Space and Its Function, その他 - 金属内包フラーレンCe2@ D5h-C80の分子構造
2011年09月, 第22回基礎有機化学討論会, ポスター発表, 金属内包フラーレンCe2@ D5h-C80の分子構造 - Molecular structure of endohedral metallofullerene Ce2@D5h-C80
2011年09月, 第22回基礎有機化学討論会, ポスター発表 - 遷移金属錯体を用いた環状ケイ素化合物とC60との反応
2011年09月, 第22回基礎有機化学討論会, その他 - カーボンナノチューブのハロゲン化アルキルによる還元的化学修飾
2011年09月, 第22回基礎有機化学討論会, ポスター発表 - 化学修飾によるLa2@C80の電子アクセプター性制御
2011年09月, 第22回基礎有機化学討論会, 口頭発表（一般） - フラーレン表面に見られる軸不斉発現
2011年09月, 第一回フラーレン•ナノチューブ・グラフェン若手研究会, 口頭発表（招待・特別） - Electronic Tuning of La2@C80 by Chemical Modification
2011年08月, 43rd IUPAC World Chemistry Congress, その他 - Electronic Modulation of Endohedral Metallofullerenes by Chemical Functionalization
2011年07月, 14th International Symposium on Novel Aromatic Compounds, 口頭発表（一般） - Tuning of electronic properties of endohedral dimetallofullerene La2@C80 by exohedral chemical functionalization
2011年06月, The first symposium on "Carbon Nanoforms", 口頭発表（一般） - カーボンナノチューブのハロゲン化アルキルによる還元的化学修飾
2011年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 単層カーボンナノチューブの化学修飾は、分散性の制御や機能化の観点から大変注目されている。今回、SWNTs還元体とアルキル化SWNTs還元体を調製し、これらと種々のハロゲン化アルキルとの反応を試みた。得られたアルキル化SWNTsの化学修飾率を吸収スペクトル、ラマンスペクトル、熱重量分析により評価したところ、ハロゲン化アルキルの置換基効果によって、化学修飾率が制御できることが明らかとなった。 - 遷移金属錯体を用いた環状ケイ素化合物とC60との反応
2011年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, シリル化フラーレンは、これまでジシリランやシリレンを用いた光反応により得られてきた。我々のグループでは、新たに遷移金属錯体を用いた付加反応を検討した。パラジウムやニッケル錯体を触媒として、C60とジシリランやオキサジシリランの熱反応において、1:1付加体が生成することがわかった。さらにシラシクロプロパンを用いた付加反応についても報告する予定である。 - 化学修飾によるLa2@C80の電子アクセプター性制御
2011年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, フラーレンは優れた電子アクセプターとして知られており、様々な応用が提案されている。本研究では化学修飾を施すことによって、金属内包フラーレンLa2@C80の電子アクセプター性を制御できることを明らかにした。 - Push-Pull型クロモフォア－[60]フラーレン連結系の新規な熱転位反応: キラルな1,2,9,12-テトラキス付加体の形成
2011年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 発表者はこれまで、電子ドナー性置換基と電子アクセプター性置換基から成るクロモフォアがフラーレンに直接結合した、Push-Pull型クロモフォアー[60]フラーレン連結系の構築に成功している。今回、このクロモフォアーフラーレン連結系が熱的に特異な転位反応を起こし、キラルな1,2,9,12-テトラキス付加体へと変換することを見出したので報告する。 - 異なる2つの置換基を有する金属内包フラーレンの位置選択的合成
2011年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 我々は金属内包フラーレンLa@C82とペンタメチルシクロペンタジエン(Cp*)との反応を行い、付加反応が可逆的かつ位置特異的に進行することを明らかにし、さらに単結晶X線結晶構造解析により誘導体の構造解析に成功した。また、La@C82Cp*に求電子試薬であるアダマンチリデンカルベン(Ad:)を、La@C82AdにCp*を付加させることで、異なる置換基を有する金属内包フラーレン誘導体の位置選択的合成を行なった。 - Thermal Carbosilylation of Dimetallofullerene La2@Ih-C80
2010年12月, The International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2010), ポスター発表 - Axially Chiral Push-Pull-Substituted Buta-1,3-dienes Enforced by a Single Methyl Group on the [60]Fullerene Surface
2010年01月, International Conference on Molecular Electronics, ポスター発表 - Electronic Modulation of Fullerenes through Conjugation to Push-Pull Chromophores
2009年07月, 13th International Symposium on Novel Aromatic Compounds (ISNA-13), ポスター発表 - Electronic Modulation of Fullerenes through Conjugation to Push-Pull Chromophores
2009年06月, SwissNano2009, ポスター発表 - Ce@C82カルベン付加体アニオンの合成と磁気異方性観測
2009年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 今回我々は、カルベン付加によるCe@C82の誘導体化を行い、2種類の一付加体(2a, 2b)を高収率・高選択的に得た。吸収スペクトルをはじめとする各種スペクトル測定により構造解析を行った。バルク電解による電気化学的な一電子還元を各々の付加体に対して行い、得られたアニオン体の各種温度における1H及び13C NMR測定から、付加体のf電子に由来する磁気異方的な挙動の観測に成功した。 - Positional Control of Encapsulated Atoms Inside a Fullerene Cage by Exohedral Chemical Functionalization
2008年05月, 213th ECS meeting, 口頭発表（一般） - 金属内包フラーレンLa@C82の可逆反応
2008年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, フラーレンの可逆付加反応はフラーレンの分離法や位置選択的多段階付加反応を制御し得るテンプレートとして有用である。すでに私達は金属内包フラーレンLa@C82とシクロペンタジエンとの反応を検討し、付加反応が高選択的に進行することを報告している。また逆反応が速やかに進行することを見出した。本研究では反応機構の解明と付加体の安定性の向上を目的として、1,2,3,4,5-ペンタメチルシクロペンタジエンとの反応を検討した。付加体の構造を単結晶X線構造解析により明らかにし、化学反応性および位置選択性を理論計算に基づいて明らかにしたので合わせて報告する。 - 化学修飾によるフラーレンケージに内包された金属原子の配向制御
2007年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, C80ケージに金属原子を二個内包した金属内包フラーレンM2@C80は、Ih対称という非常に高い対称を有しており、C60よりも小さいHOMO-LUMOギャップを有することなどから注目を集めている。特に、NMR解析などにより金属原子がフラーレンの内部空間で三次元のランダムな回転運動を有していることが明らかになっており、内包金属原子の動的挙動に興味が持たれている。本研究ではM2@C80に種々の化学修飾を施すことにより、外界から隔絶された金属原子の配向を水平方向、斜め方向、垂直方向へと自在に制御することに成功した。 - La@C82とシクロペンタジエン誘導体の可逆付加反応
2007年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, Diels-Alder反応を用いたフラーレンの可逆付加反応は、フラーレンの分離法や位置選択的な多段階付加反応を制御しえるテンプレートとして利用されている大変興味深い反応系である。すでに我々は、金属内包フラーレンLa@C82・シクロペンタジエン誘導体の合成を行い、付加反応に高い位置選択性があることを見出した。さらに、誘導体の反応速度について明らかにした。しかしこの付加反応は逆反応が非常に早く進行してしまう。そこで、反応機構の検証および付加体の安定性を向上させる目的でペンタメチルシクロペンタジエンを用いて反応を行なった。各種測定結果により付加反応の選択性と付加体の安定性について検討を行なったのでこれらを報告する。 - フラーレンケージに内包された金属原子の動的挙動制御
2006年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, フラーレンケージの内部空間に金属原子を内包した金属内包フラーレンは、金属原子が外部環境から孤立して存在しているため非常に興味深い化学種である。中でも金属原子を二個内包した金属内包フラーレンM2@C80は、内包原子がケージ内部の中空空間で三次元の自由回転をしており, その動的挙動に興味が持たれている。 本研究ではM2@C80（M = La and Ce）に対し含ケイ素三員環化合物であるジシリランを用いたケイ素化反応およびアゾメチンイリドを用いた1,3-双極子環化付加反応を行ない、付加体を合成した。NMRスペクトル解析および単結晶X線構造解析により、ジシリラン付加体では内包原子が二次元的回転に変化するのに対し、1,3-双極子環化付加体では一箇所に局在化することを見出した。 - Silylation of endohedral Dimetallofullerenes
2005年12月, International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2005), 口頭発表（一般） - 金属内包フラーレンM2@C80の化学修飾
2005年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 金属内包フラーレンM2@C80（M = 内包された金属原子）は, 内包原子がフラーレンの内部空間で三次元の自由回転をしており, その動的挙動に興味が持たれている. この動的挙動はケージ内部の静電ポテンシャル分布から説明でき, 化学修飾を施し静電ポテンシャル分布を制御することによって内包原子の動的挙動を制御できると期待できる. 本研究ではM2@C80に対しジシリランを用いたケイ素化反応, アゾメチンイリドを用いた1,3-双極子環化付加反応を行ない, ジシリラン付加体では内包金属原子が二次元的回転に変化するのに対し, 1,3-双極子環化付加体では一箇所に局在化することを見出した. - Chemical Functionalization of Dimetallofullerenes
2004年10月, 206th ECS Meeting (2004 Joint International Meeting), ポスター発表 - 金属内包フラーレンの化学修飾
2004年, 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）, 金属内包フラーレンの化学反応による誘導体の合成に成功した。誘導体の構造は各種NMRあるいはESRの測定及び、最終的にはX-線結晶構造解析により決定した。誘導体の電気的特性についても併せて報告する。
外部資金の獲得
- フラーレンへの位置選択的二重開口反応を駆使する筒状ナノカーボン分子の創製
科学研究費補助金, 代表者, 代表者 - 光電変換材料を指向した剛直なフラーレン誘導体の創製と配列制御
その他外部資金, 代表者, 代表者 - 空間を介したフラーレンπ電子共役系の拡張と制御に関する研究
その他外部資金, 代表者, 代表者 - 金属内包フラーレンの分子変換法の創出と機能開拓
科学研究費補助金, 分担者, 分担者 - フラーレンの多重開口反応による湾曲ナノカーボン分子のトップダウン合成
科学研究費補助金, 代表者, 代表者 - フラーレンを基盤とする阻害剤開発のための分子間相互作用の計測と評価
その他外部資金, 代表者, 代表者 - 鉄原子内包フラーレン合成への挑戦
その他外部資金, 代表者, 代表者 - 金属内包フラーレンの化学修飾による機能開拓
科学研究費補助金, 分担者, 分担者 - 動的共有結合を介したポルフィリンの組織化に基づくナノカーボンの分子認識
科学研究費補助金, 代表者, 代表者 - 遷移金属触媒を用いたカスケード反応によるフラーレンのワンポット分子変換法の開発
その他外部資金, 代表者, 代表者 - 遷移金属カルベン錯体を用いたフラーレンの分子変換による革新的な光電変換材料の開発
その他外部資金, 代表者, 代表者 - 捩じれたπ電子系分子ピンセットを用いたカーボンナノチューブの光学分割
科学研究費補助金, 代表者, 代表者 - カーボンナノチューブのキラリティを認識するπ電子系分子ピンセットの開発
その他外部資金, 代表者, 代表者 - π空間に閉じ込められた物質系の創製と機能
科学研究費補助金, 分担者, 分担者
