Basic information

Other affiliation

• Tokyo Gakugei University, Science, Associate Professor
• Tokyo Gakugei University, Natural Sciences DivisionFundamental Natural Sciences 分子化学分野, Associate Professor

Research History

• JSPS
  01 Apr. 2007 - 31 Mar. 2008, 特別研究員（DC2）
• JSPS
  01 Apr. 2008 - 31 Mar. 2009, 特別研究員（PD）
• ETH Zurich
  01 Apr. 2008 - 31 Mar. 2009, Laboratory of Organic Chemistry, Visiting Postdoctoral Fellow
• ETH Zurich
  01 Apr. 2009 - 31 Mar. 2010, Laboratory of Organic Chemistry, Postdoctoral fellow
• Tokyo Gakugei University
  01 Apr. 2010 - 31 Mar. 2015, Faculty of Education, assistant professor
• University of Tsukuba
  Oct. 2010 - Mar. 2013, Life Science Center of Tsukuba Advanced Research Alliance (TARA), 客員研究員
• Tokyo Gakugei University
  Apr. 2015 - Present, Faculty of Education, 准教授

Education

• University of Tsukuba
  Mar. 2003, 第一学群, 自然学類
• University of Tsukuba
  Mar. 2008, 数理物質科学研究科, 化学専攻, doctor course, completed

Degree

• Doctor of Philosophy in Science

Professional Memberships

• 日本理科教育学会
  Apr. 2021
• 有機合成化学協会
  Apr. 2019
• 基礎有機化学会
  Sep. 2010
• American Chemical Society
  Oct. 2009
• フラーレン・ナノチューブ･グラフェン学会
  Jan. 2004
• 日本化学会
  Dec. 2003

Licenses and Qualifications

• 危険物取扱者（甲種）
  Dec. 2013

Research Areas

• Structural organic chemistry and physical organic chemistry

Research Interests

• Fullerene
• カーボンナノチューブ
• π電子系
• Physical Organic Chemistry

Research Projects

• 池谷科学技術振興財団単年度研究助成, 平面ヘテロ接合での配列制御に適したフラーレン系n型半導体材料の開発, Apr. 2024 - Mar. 2025
• 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, 基盤研究(C), Apr. 2023 - Mar. 2026, Competitive research funding
• 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, Apr. 2022 - Mar. 2023, Competitive research funding
• 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, Mar. 2022 - Mar. 2024, Competitive research funding
• Creation of Molecular Functionalization of Endohedral Metallofullerene and Its Function, Grant-in-Aid for Scientific Research (C), 01 Apr. 2020 - 01 Mar. 2023, Competitive research funding
• 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, Grant-in-Aid for Scientific Research (C), 01 Apr. 2020 - 01 Mar. 2023, Competitive research funding
• 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, 01 Apr. 2019 - 31 Mar. 2021, Competitive research funding
• 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, 01 Apr. 2019 - 31 Mar. 2020, Competitive research funding
• Creation of functionalized endohedral metallofullerenes and its function, Grant-in-Aid for Scientific Research (C), 01 Apr. 2017 - 01 Mar. 2020, Competitive research funding
• Molecular recognition of nanocarbons based on assembling porphyrins through dynamic covalent bonds, Grant-in-Aid for Young Scientists (B), 01 Apr. 2016 - 01 Mar. 2019, Competitive research funding
• 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, 01 Apr. 2016 - 31 Mar. 2017, Competitive research funding
• 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, 01 Apr. 2015 - 31 Mar. 2016, Competitive research funding
• Creation of innovative near-infrared photoluminescence probe based on nanocarbons by chemical functionalization, Grant-in-Aid for Scientific Research (B), 01 Apr. 2014 - 01 Mar. 2017, Competitive research funding
• Twisted pi-electronic molecular tweezers for chiral resolution of carbon nanotubes, Grant-in-Aid for Young Scientists (B), 01 Apr. 2012 - 01 Mar. 2015, Competitive research funding
• 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, 01 Apr. 2011 - 31 Mar. 2012, Competitive research funding
• Construction and properties of molecular systems inside the π-space, Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area), 01 Apr. 2008 - 31 Mar. 2013, Competitive research funding
• Construction and properties of aggregated paramagnetic fullerenes, Grant-in-Aid for Scientific Research (A), 01 Apr. 2008 - 31 Mar. 2012, Competitive research funding

Books and Other Publications

• Handbook of Fullerene Science and Technology
  25 Sep. 2022, 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
  Dec. 2021, (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
  27 Dec. 2019, 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
  Nov. 2016, 共立出版（東京）, 9784320044227
• Chemical Science of pi-Electron Systems
  Nov. 2015, 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
  Jun. 2015, (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
  Dec. 2014, NMR Spectroscopic and X-Ray Crystallographic Characterization of Endohedral Metallofullerenes, Boca Raton, 9781466593947
• Organic Nanomaterials
  Nov. 2013, 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—
  Dec. 2011, 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—
  Dec. 2011, 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
  Nov. 2011, 145-184, World Scientific Publishing Co. (Singapore)
• 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
  Dec. 2019, 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
  Nov. 2011, New Vistas in Endohedral Metallofullerenes, World Scientific Publishing Co. (Singapore), 9789814327817

Papers

• Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes
  22 Jan. 2024, Michio Yamada, only, Beilstein Journal of Organic Chemistry, Beilstein Institut, 20, Research paper (scientific journal), 10.3762/bjoc.20.13
• Controlling the reactivity of La@C82 by reduction: reaction of the La@C82 anion with alkyl halide with high regioselectivity
  Dec. 2023, Yutaka Maeda; Saeka Akita; Mitsuaki Suzuki; Michio Yamada; Takeshi Akasaka; Kaoru Kobayashi; Shigeru Nagase, joint, Beilstein Journal of Organic Chemistry, Beilstein Institut, 19, Research paper (scientific journal)
• One-Step Synthesis of Cyclobutene-Annulated Fullerenes through a Cascade Reaction
  03 Aug. 2023, Michio Yamada, Yuta Uokawa, Shino Sasaki, Naohiro Iha, Yoshihisa Hashimoto, Yuya Nagasaki, Yutaka Maeda, Mitsuaki Suzuki, joint, European Journal of Organic Chemistry, European Chemical Societies Publishing, 26, 35, Research paper (scientific journal)
• Stepwise Functionalization of Single-Walled Carbon Nanotubes with Subsequent Molecular Conversion to Control Photoluminescence Properties
  17 Jul. 2023, Yui Konno; Michio Yamada; Mitsuaki Suzuki; Yutaka Maeda, joint, Chemistry – A European Journal, European Chemical Societies Publishing, 29, 51, Research paper (scientific journal)
• Selective emergence of photoluminescence at telecommunication wavelengths from cyclic perfluoroalkylated carbon nanotubes
  31 Jul. 2023, Yutaka Maeda; Yasuhiro Suzuki; Yui Konno; Pei Zhao; Nobuhiro Kikuchi; Michio Yamada; Masaya Mitsuishi; Anh T. H. Dao; Hitoshi Kasai; Masahiro Ehara, joint, Communications Chemistry, Springer Nature, 6, Research paper (scientific journal)
• Unraveling the Nature and Strength of Non-covalent Interactions on the Surface of Fullerenes
  Mar. 2023, Michio Yamada, only, ChemPlusChem, Wiley, 88, 3, Research paper (scientific journal), 10.1002/cplu.202300062
• Controlling Near-Infrared Photoluminescence Properties of Single-Walled Carbon Nanotubes by Substituent Effect in Stepwise Chemical Functionalization
  24 Jan. 2023, Yutaka Maeda, Rina Morooka, Pei Zhao, Daiki Uchida, Yui Konno, Michio Yamada, Masahiro Ehara, joint, The Journal of Physical Chemistry C, American Chemical Society, 127, Research paper (scientific journal), 10.1021/acs.jpcc.2c06153
• Understanding the Nature and Strength of Noncovalent Face-to-Face Arene–Fullerene Interactions
  06 Sep. 2022, Michio Yamada; Yukiyo Kurihara; Masaaki Koizumi; Kasumi Tsuji; Yutaka Maeda; Mitsuaki Suzuki, joint, Angewandte Chemie - International Edition, Wiley, 61, Research paper (scientific journal), 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？
  20 Apr. 2022, 山田道夫, only, 化学と教育, 日本化学会, 70, (MISC) Introduction and explanation (others)
• Thermodynamic control of quantum defects on single-walled carbon nanotubes
  25 Nov. 2019, Y. Maeda; H. Murakoshi; H. Tambo; P. Zhao; K. Kuroda; M. Yamada; X. Zhao; S. Nagase; M. Ehara, joint, Chemical Communications, Royal Society of Chemistry (RSC), 55, Research paper (scientific journal), 10.1039/C9CC05623H
• Influence of local strain caused by cycloaddition on the band gap control of functionalized single-walled carbon nanotubes
  08 May 2019, Y. Maeda; K. Kuroda; H. Tambo; H. Murakoshi; Y. Konno; M. Yamada; P. Zhao; X. Zhao; S. Nagase; M. Ehara, joint, RSC Advances, Royal Society of Chemistry (RSC), 9, Research paper (scientific journal), 10.1039/C9RA02183C
• Application of MCD spectroscopy and TD-DFT to endohedral metallofullerenes for characterization of their electronic transitions
  14 Mar. 2013, Michio Yamada; Zdenek Slanina; Naomi Mizorogi; Atsuya Muranaka; Yutaka Maeda; Shigeru Nagase; Takeshi Akasaka; Nagao Kobayashi, joint, Physical Chemistry Chemical Physics, Royal Society of Chemistry (RSC), 15, 10, Research paper (scientific journal), 10.1039/c3cp44096f, 1463-9076
• New Horizons in Chemical Functionalization of Endohedral Metallofullerenes
  10 Aug. 2020, Michio Yamada; Michael M. T. H. Liu; Shigeru Nagase; Takeshi Akasaka, joint, Molecules, MDPI, 25, Research paper (scientific journal), 10.3390/molecules25163626
• Salvaging Reactive Fullerenes from Soot by Exohedral Derivatization
  Oct. 2018, M. Yamada; T. Akasaka; S. Nagase, joint, Angewandte Chemie - International Edition, Wiley, 57, 41, Research paper (scientific journal), 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
  Sep. 2012, 山田 道夫, 安蘇 芳雄, 磯部 寛之, joint, 未来材料, エヌ・ティー・エス, 12, 9, 1346-0986

  URL1(公開)
• 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
  Jul. 2020, 鮫島 朋美, 前田 優, 山田 道夫, 内田 大貴, 吉原 伸敏, joint, 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, Research paper (bulletin of university, research institution), 0285-4309

  URL1(公開)
• Mechanistic Study of the Diels-Alder Reaction of Paramagnetic Endohedral Metallofullerene: Reaction of La@C-82 with 1,2,3,4,5-Pentamethylcyclopentadiene
  Apr. 2013, Satoru Sato; Yutaka Maeda; Jing-Dong Guo; Michio Yamada; Naomi Mizorogi; Shigeru Nagase; Takeshi Akasaka, joint, Journal of the American Chemical Society, American Chemical Society (ACS), 135, 15, Research paper (scientific journal), 10.1021/ja309763f, 0002-7863
• 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
  20 Sep. 2019, 前田 優, 山田 道夫, joint, Chemistry & Education, 日本化学会, 67, 9, Research paper (bulletin of university, research institution), 0386-2151

  URL1(公開)
• 化学修飾によるカーボンナノチューブの機能化と評価
  Apr. 2019, 前田 優, 山田 道夫, 江原 正博, joint, 炭素, 炭素材料学会, 2019, 290, (MISC) Introduction and explanation (others), 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.

  URL1(公開)
• 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
  Sep. 2016, 吉原 伸敏, 前田 優, 山田 道夫, 原田 和雄, 松川 正樹, joint, 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, Research paper (bulletin of university, research institution), 1880-4330

  URL1(公開)
• 金属内包フラーレンの構造決定
  Apr. 2016, 鈴木 光明, 山田 道夫, 前田 優, 永瀬 茂, 赤阪 健, joint, 日本結晶学会誌, 日本結晶学会, 58, 2, Research paper (research society, symposium materials, etc.), 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.

  URL1(公開)
• 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
  Apr. 2015, 山田 道夫, 赤阪 健, 永瀬 茂, joint, 固体物理, アグネ技術センター, 50, 4, (MISC) Introduction and explanation (commerce magazine), 0454-4544

  URL1(公開)
• Control of near infrared photoluminescence properties of single-walled carbon nanotubes by functionalization with dendrons
  Dec. 2018, Y. Maeda; Y. Konno; M. Yamada; P. Zhao; X. Zhao; M. Ehara; S. Nagase, joint, Nanoscale, Royal Society of Chemistry (RSC), 10, 48, Research paper (scientific journal), 10.1039/c8nr07983h, 2040-3364
• 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
  29 Sep. 2017, 前田優, 山田道夫, joint, 東京学芸大学紀要, 東京学芸大学, 69, Research paper (bulletin of university, research institution)
• Temperature Dependence of Anisotropic Transient Conductivity of a La@C-2v-C-82(Ad) Crystal
  Jul. 2017, M. Yamada; S. Sato; W. Choi; S. Seki; T. Abe; M. Suzuki; Y. Maeda; S. Nagase; T. Akasaka, only, Chemistry Letters, The Chemical Society of Japan (CSJ), 46, 7, Research paper (scientific journal), 10.1246/cl.170279, 0366-7022

  URL1(公開)
• Fullerene C70 as a Nanoflask that Reveals the Chemical Reactivity of Atomic Nitrogen
  Jun. 2017, 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, joint, Angewandte Chemie - International Edition, Wiley, 56, 23, Research paper (scientific journal), 10.1002/anie.201701158, 1433-7851
• Thermal Stability of Oxidized Single-Walled Carbon Nanotubes: Competitive Elimination and Decomposition Reaction Depending on the Degree of Functionalization
  Oct. 2016, Yutaka Maeda; Erika Sone; Akane Nishino; Yuri Amagai; Wei-Wei Wang; Michio Yamada; Mitsuaki Suzuki; Jun Matsui; Masaya Mitsuishi; Toshiya Okazaki; Shigeru Nagase, joint, Chemistry – An European Journal, Wiley, 22, 43, Research paper (scientific journal), 10.1002/chem.201602944, 0947-6539
• Hiding and Recovering Electrons in a Dimetallic Endohedral Fullerene: Air-Stable Products from Radical Additions
  Jan. 2015, 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, joint, Journal of the American Chemical Society, American Chemical Society, 137, 1, Research paper (scientific journal), 10.1021/ja509956y, 0002-7863
• Emergence of Highly Elaborated pi-Space and Extending Its Functionality Based on Nanocarbons: New Vistas in the Fullerene World
  Dec. 2014, Michio Yamada; Takeshi Akasaka, joint, Bulletin of the Chemical Society of Japan, The Chemical Society of Japan (CSJ), 87, Research paper (scientific journal)
• 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
  Nov. 2014, 山田道夫、赤阪健、永瀬茂, joint, 化学, 化学同人, 69
• Sc2@C66 revisited: An endohedral fullerene with scandium ions nestled within two unsaturated linear triquinanes
  28 May 2014, 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, joint, Journal of the American Chemical Society, American Chemical Society (ACS), 136, 21, Research paper (scientific journal), 10.1021/ja5035649
• Thermal reactions of C60 with siliranes: Carbosilylation and silylene addition of fullerenes
  Jan. 2014, M. Kako; R. Iida; Y. Maeda; M. Yamada; T. Hasegawa, joint, Fullerenes, Nanotubes, and Carbon Nanostructures, Taylor and Francis, 22, Research paper (scientific journal)
• Intermolecular Interaction of [60]Fullerene with Troger's Base Analogues
  Jan. 2014, Michio Yamada; Konomi Tokutomi; Ayaka Takehara; Yusuke Sakai; Yutaka Maeda; Tadashi Hasegawa, joint, Fullerenes, Nanotubes, and Carbon Nanostructures, Taylor and Francis, 22, Research paper (scientific journal)
• Carbene Additions to Fullerenes
  Jul. 2013, Michio Yamada; Takeshi Akasaka; Shigeru Nagase, joint, Chemical Reviews, American Chemical Society (ACS), 113, Research paper (scientific journal)
• Analysis of Functionalization Degree of Single-Walled Carbon Nanotubes Having Various Substituents
  Oct. 2012, Y. Maeda; K. Saito; N. Akamatsu; Y. Chiba; S. Ohno; Y. Okui; M. Yamada; T. Hasegawa; M. Kako; T. Akasaka, joint, Journal of the American Chemical Society, American Chemical Society (ACS), 134
• Interaction of Single-walled carbon Nanotubes with amine
  Feb. 2012, Y. Maeda; M. Yamada; T. Hasegawa; T. Akasaka; J. Lu; S. Nagase, joint, NANO, World Scientific, 7, Research paper (scientific journal)
• Synthesis of endohedral metallofullerene glycoconjugates by carbene addition
  Nov. 2011, Michio Yamada; Chika I. Someya; Tsukasa Nakahodo; Yutaka Maeda; Takahiro Tsuchiya; Takeshi Akasaka, joint, Molecules, MDPI, 16, Research paper (scientific journal)
• 金属内包フラーレン−その構造と電子的特性を制御する
  Oct. 2011, 山田道夫・佐藤悟・赤阪健・永瀬茂, joint, 化学, 化学同人, 66, 10
• In-Depth Understanding of π-Electron Systems: New Vistas in Fullerene Endohedrals
  Feb. 2010, Michio Yamada; Takahiro Tsuchiya; Takeshi Akasaka; Shigeru Nagase, joint, Pure and Applied Chemistry, International Union of Pure and Applied Chemistry (IUPAC), 82, Research paper (scientific journal)
• Endohedral Metal Atoms in Pristine and Functionalized Fullerene Cages
  Jan. 2010, Michio Yamada; Takeshi Akasaka; Shigeru Nagase, joint, Accounts of Chemical Research, American Chemical Society (ACS), 43, Research paper (scientific journal)
• Two-fold addition reaction of silylene to C₆₀: structural and electronic properties of a bis-adduct
  22 May 2024, Masahiro Kako; Masato Kai; Masanori Yasui; Michio Yamada; Yutaka Maeda; Takeshi Akasaka, joint, Beilstein Journal of Organic Chemistry, Beilstein Institut, 20, Research paper (scientific journal), 10.3762/bjoc.20.100
• Synthesis and Conformational Analysis of Fullerene Torsion Balances for Assessing the Contribution of Dispersion and Anionic Character in Non‐Covalent Arene–Fullerene Interactions
  16 Jun. 2023, Michio Yamada; Koki Sahara; Masaaki Koizumi; Yutaka Maeda; Mitsuaki Suzuki, joint, Chemistry – A European Journal, Wiley, 29, 44, Research paper (scientific journal), 10.1002/chem.202300877, 0947-6539
• Photoluminescence Properties of Single‐Walled Carbon Nanotubes Influenced by the Tether Length of Reagents with Two Reactive Sites
  05 May 2023, Yui Konno; Rina Morooka; Tatsunari Morishita; Pei Zhao; Naoto Miyasaka; Kazuki Ono; Akira Noda; Daiki Uchida; Ren Iwasaki; Michio Yamada; Masahiro Ehara; Yutaka Maeda, joint, Chemistry – A European Journal, Wiley, 29, 36, Research paper (scientific journal), 10.1002/chem.202300766, 0947-6539
• Transition-metal-catalyzed synthesis of organophosphate-appended cyclobutanofullerenes from C60 and secondary propargylic phosphates
  Jan. 2023, Michio Yamada; Yui Ueno; Yuta Uokawa; Yutaka Maeda, joint, Tetrahedron Letters, Elsevier BV, 115, 31, Research paper (scientific journal), 10.1016/j.tetlet.2022.154299, 0040-4039
• Control of functionalized single-walled carbon nanotube photoluminescence via competition between thermal rearrangement and elimination
  01 Sep. 2023, Yutaka Maeda; Rina Morooka; Pei Zhao; Michio Yamada; Masahiro Ehara, joint, Chemical Communications, Royal Society of Chemistry (RSC), 59, 78, Research paper (scientific journal), 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
  Feb. 2022, 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, Research paper (scientific journal), 10.3390/photochem2010010
• Li@C60 thin films: characterization and nonlinear optical properties
  2022, 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, Research paper (scientific journal), 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
  21 Apr. 2020, Michio Yamada; Asumi Ishitsuka; Yutaka Maeda; Mitsuaki Suzuki; Hiroyasu Sato, Organic Letters, 22, 9, Research paper (scientific journal), 10.1021/acs.orglett.0c01119, 1523-7060
• A Fullerene-Based Molecular Torsion Balance for Investigating Noncovalent Interactions at the C60 Surface
  26 May 2020, Michio Yamada; Haruna Narita; Yutaka Maeda, joint, Angewandte Chemie - International Edition, Wiley, 59, 37, Research paper (scientific journal), 10.1002/anie.202005888
• Helicity Sorting and Optical Resolution of Functionalized Single-Walled Carbon Nanotubes and Their Optical Properties
  2020, Yutaka Maeda; Yui Konno; Michio Yamada, The Journal of Physical Chemistry C, 124, 39, Research paper (scientific journal), 10.1021/acs.jpcc.0c07963
• Sonochemical reaction to control the near-infrared photoluminescence properties of single-walled carbon nanotubes
  2020, 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, Research paper (scientific journal), 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
  Jul. 2019, Michio Yamada; Mayu Takizawa; Yoko Nukatani; Mitsuaki Suzuki; Yutaka Maeda, joint, The Journal of Organic Chemistry, American Chemical Society, 84, 14, Research paper (scientific journal), 10.1021/acs.joc.9b00932, 0022-3263
• Reaction of the C60 radical anion with alkyl halides
  26 Mar. 2019, 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, Research paper (scientific journal), 10.1039/c9nj01043b, 1144-0546
• Addition of S-Heterocyclic Carbenes to Fullerenes: Formation and Characterization of Dithiomethano-Bridged Derivatives
  2019, Masahiro Kako; Yuki Arikawa; Shinji Kanzawa; Michio Yamada; Yutaka Maeda; Makoto Furukawa; Takeshi Akasaka, Helvetica Chimica Acta, 102, 5, Research paper (scientific journal), 10.1002/hlca.201900064
• Photoreactions of Sc3N@Ih-C80 and Lu3N@Ih-C80 with disilirane: Isolation and characterization of labile 1,2-adducts
  2018, Masahiro Kako; Fumiaki Ozeki; Shinji Kanzawa; Shinpei Fukazawa; Kumiko Sato; Michio Yamada; Yutaka Maeda; Makoto Furukawa; Takeshi Akasaka, Heteroatom Chemistry, 29, 5-6, Research paper (scientific journal), 10.1002/hc.21477
• Enhancing solution-phase supramolecular interactions between monomeric porphyrins and [60]fullerene by simple chemical modification
  Nov. 2017, Michio Yamada; Gota Murakami; Shuhei Kobayashi; Yutaka Maeda, Tetrahedron Letters, PERGAMON-ELSEVIER SCIENCE LTD, 58, 48, Research paper (scientific journal), 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
  Oct. 2017, Michio Yamada; Rika Ochi; Yuhei Yamamoto; Sae Okada; Yutaka Maeda, Organic & Biomolecular Chemistry, ROYAL SOC CHEMISTRY, 15, 40, Research paper (scientific journal), 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
  Jul. 2017, 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, Research paper (scientific journal), 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
  Jul. 2017, 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, Research paper (scientific journal), 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
  Jun. 2017, 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, Research paper (scientific journal), 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
  May 2017, 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, Research paper (scientific journal), 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
  May 2017, 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, Research paper (scientific journal), 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
  Feb. 2017, 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, Research paper (scientific journal), 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)
  Dec. 2016, 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, Research paper (scientific journal), 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
  Dec. 2016, 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, joint, Journal of the American Chemical Society, American Chemical Society (ACS), 138, 50, Research paper (scientific journal), 10.1021/jacs.6b10751, 0002-7863
• Tuning of the photoluminescence and upconversion photoluminescence properties of single-walled carbon nanotubes by chemical functionalization
  2016, 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, Research paper (scientific journal), 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, 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, Research paper (scientific journal), 10.1016/j.carbon.2015.10.088
• Preparation, Structural Determination, and Characterization of Electronic Properties of Bis-silylated and Bis-germylated Lu3N@Ih-C80
  Nov. 2015, 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, Research paper (scientific journal), 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.
• Regioselective Cage Opening of La2@D2(10611)-C72 with 5,6-Diphenyl-3-(2-pyridyl)-1,2,4-triazine
  Feb. 2015, 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, Research paper (scientific journal), 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, Yutaka Maeda; Yuya Takehana; Michio Yamada; Mitsuaki Suzuki; Tatsuya Murakami, Chemical Communications, ROYAL SOC CHEMISTRY, 51, 70, Research paper (scientific journal), 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
  Jun. 2014, 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, Research paper (scientific journal), 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, 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, Research paper (scientific journal), 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, 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, Research paper (scientific journal), 10.1080/1536383X.2013.794342
• Thermal Reactions of C60 with Siliranes: Carbosilylation and Silylene Addition of Fullerenes
  Jan. 2014, Masahiro Kako; Ryosuke Iida; Yutaka Maeda; Michio Yamada; Tadashi Hasegawa, Fullerenes, Nanotubes and Carbon Nanostructures, TAYLOR & FRANCIS INC, 22, 1-3, Research paper (scientific journal), 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
  Jan. 2014, 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, Research paper (scientific journal), 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
  Dec. 2013, 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, Research paper (scientific journal), 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
  24 Apr. 2013, 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, Research paper (scientific journal), 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
  Jan. 2013, 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, Research paper (scientific journal), 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
  29 Aug. 2013, Michio Yamada; Kenji Harada; Yutaka Maeda; Tadashi Hasegawa, joint, New Journal of Chemistry, Royal Society of Chemistry, 37, 11, Research paper (scientific journal), 10.1039/c3nj00796k, 1144-0546
• Electron transport through single endohedral Ce@C82 metallofullerenes
  Oct. 2012, 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, Research paper (scientific journal), 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
  05 Dec. 2011, Yutaka Maeda; Yasuyuki Niino; Takuya Kondo; Michio Yamada; Tadashi Hasegawa; Takeshi Akasaka, Chemistry Letters, Oxford University Press (OUP), 40, 12, Research paper (scientific journal), 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
  Nov. 2011, Michio Yamada; Chika I. Someya; Tsukasa Nakahodo; Yutaka Maeda; Takahiro Tsuchiya; Takeshi Akasaka, Molecules, MDPI AG, 16, 11, Research paper (scientific journal), 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
  Mar. 2011, 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, Research paper (scientific journal), 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, 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, Research paper (scientific journal), 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.
• Thermal Carbosilylation of Endohedral Dimetallofullerene La2@Ih-C80 with Silirane
  Dec. 2010, 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, Research paper (scientific journal), 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
  Dec. 2010, 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, Research paper (scientific journal), 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
  Jul. 2010, 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, joint, Journal of the American Chemical Society, American Chemical Society, 132, 26, Research paper (scientific journal), 10.1021/ja101856j, 0002-7863
• Regioselective Exohedral Functionalization of La@C82 and its 1,2,3,4,5-Pentamethylcyclopentadiene and Adamantylidene Adducts
  2010, 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, Research paper (scientific journal), 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, Michio Yamada; Pablo Rivera-Fuentes; W. Bernd Schweizer; Francois Diederich, Angewandte Chemie International Edition, WILEY-BLACKWELL, 49, 20, Research paper (scientific journal), 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, Michio Yamada; W. Bernd Schweizer; Franziska Schoenebeck; Francois Diederich, Chemical Communications, ROYAL SOC CHEMISTRY, 46, 29, Research paper (scientific journal), 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
  Jul. 2009, 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, Research paper (scientific journal), 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, Michio Yamada; Naomi Mizorogi; Takahiro Tsuchiya; Takeshi Akasaka; Shigeru Nagase, Chemistry – A European Journal, WILEY-BLACKWELL, 15, 37, Research paper (scientific journal), 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, 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, Research paper (scientific journal), 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.
• Radical Coupling Reaction of Paramagnetic Endohedral Metallofullerene La@C82
  Dec. 2008, 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, Research paper (scientific journal), 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
  Aug. 2008, 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, Research paper (scientific journal), 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)
  Jan. 2008, 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, Research paper (scientific journal), 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, 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, Research paper (scientific journal), 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).
• Photo-labeling of C60 with 3-trifluoromethyl-3-phenyldiazirine
  Sep. 2007, Satoru Sato; Michio Yamada; Takatsugu Wakahara; Takahiro Tsuchiya; Midori O. Ishitsuka; Takeshi Akasaka; Michael T. H. Liu, joint, Tetrahedron Letters, PERGAMON-ELSEVIER SCIENCE LTD, 48, 36, Research paper (scientific journal), 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, Takatsugu Wakahara; Michio Yamada; Satomi Takahashi; Tsukasa Nakahodo; Takahiro Tsuchiya; Yutaka Maeda; Takeshi Akasaka; Masahiro Kako; Kenji Yoza; Ernst Horn; Naomi Mizorogi; Shigeru Nagase, joint, Chemical Communications, Royal Society of Chemistry (RSC), 26, Research paper (scientific journal), 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.
• Analysis of lanthanide-induced NMR shifts of the Ce@C82 anion
  Feb. 2006, 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, Research paper (scientific journal), 10.1021/ja055882m, 0002-7863
• Synthesis and structural characterization of endohedral pyrrolidinodimetallofullerene: La2@C80(CH2)(2)NTrt
  Feb. 2006, Michio Yamada; Takatsugu Wakahara; Tsukasa Nakahodo; Takahiro Tsuchiya; Yutaka Maeda; Takeshi Akasaka; Kenji Yoza; Ernst Horn; Naomi Mizorogi; Shigeru Nagase, joint, Journal of the American Chemical Society, American Chemical Society (ACS), 128, 5, Research paper (scientific journal), 10.1021/ja056560l, 0002-7863
• Positional control of encapsulated atoms inside a fullerene cage by exohedral addition
  Oct. 2005, 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, Research paper (scientific journal), 10.1021/ja054346r, 0002-7863
• Synthesis and characterization of exohedrally silylated M@C82 (M = Y and La)
  Apr. 2005, Michio Yamada; Lai Feng; Takatsugu Wakahara; Takahiro Tsuchiya; Yutaka Maeda; Yongfu Lian; Masahiro Kako; Takeshi Akasaka; Tatsuhisa Kato; Kaoru Kobayashi; Shigeru Nagase, joint, The Journal of Physical Chemistry B, American Chemical Society (ACS), 109, 13, Research paper (scientific journal), 10.1021/jp050657b, 1520-6106
• Characterization of Ce@C82 and Its Anion
  25 Mar. 2004, 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, joint, Journal of the American Chemical Society, American Chemical Society (ACS), 126, 15, Research paper (scientific journal), 10.1021/ja039865d, 1520-5126
• Switching Photoluminescence Wavelength of Arylated Single‐walled Carbon Nanotubes by Utilizing Steric Hindrance in Reductive Arylation
  20 Jan. 2025, Yutaka Maeda; Yui Iguchi; Pei Zhao; Atsushi Suwa; Yasunari Taki; Kentaro Kawada; Michio Yamada; Masahiro Ehara; Masahiro Kako, joint, Chemistry – A European Journal, Wiley, 31, 13, Research paper (scientific journal), 10.1002/chem.202404529, 0947-6539, (6,5)‐enriched single‐walled carbon nanotubes (SWCNTs) were reductively arylated using sodium naphthalenide and monosubstituted and disubstituted iodobenzene derivatives to control their photoluminescence (PL) properties. In the reactions with substituted iodobenzenes, the degree of functionalization was influenced by the substituents on the aryl groups depending on their position, which allowed us to realize control of the PL intensity. The substituents at the 2‐position and methyl groups at the 3,5‐positions of the phenyl group respectively increased the E11** PL and E11* PL selectivity at ~1230 and ~1100 nm. Methyl groups at the 2,6‐positions emerged two new E11** PL peaks. These PL characteristics were prominently observed in the (6,4) SWCNT adducts, which were separated by gel chromatography. Theoretical calculations of model compounds showed that the effect of the substituent at the 2‐position on the relative stability of the isomers with different binding configurations was greater for the diarylated SWCNTs than for the hydroarylated SWCNTs. Experimental and theoretical calculation results revealed that the choice of substituents on the benzene ring was effectively used to modulate the PL wavelength, and these substituents had a considerable effect on the favorable binding configuration of the SWCNT adduct and relative stability and PL wavelength of the conformational isomers.

  URL1(公開)
• Synthesis, Characterization, and Thin‐Film Properties of Post‐Functionalized N,N‐Dimethylanilinoethynyl‐Substituted Cyclobutenofullerenes
  29 Nov. 2024, Michio Yamada; Haruki Sakuma; Waner He; Hiromichi Araki; Yutaka Maeda; Mitsuaki Suzuki; Tsuyoshi Michinobu, joint, Chemistry – An Asian Journal, Wiley, 20, 3, Research paper (scientific journal), 10.1002/asia.202401111, 1861-4728, A π‐extended cyclobutenofullerene containing an N,N‐dimethylanilinoethynyl group was synthesized via a one‐pot cascade reaction of C₆₀ with the corresponding propargylic phosphate. The cyclobutenofullerene was further modified using either one‐pot or sequential post‐functionalization methods, yielding derivatives containing altered addend structures. During one‐pot post‐functionalization, hydration reaction of the alkyne moiety continued after the formation of cyclobutenofullerenes. The sequential post‐functionalization approach involved introducing the tetracyanobutadiene structure through formal [2+2] cycloaddition and a subsequent retroelectrocyclization reaction with tetracyanoethylene. The electronic and optical properties of the derivatives in solution, as well as their field‐effect transistor behavior in thin films, were thoroughly assessed to elucidate the optoelectronic differences arising from various addend structures. The properties of the three characteristic cyclobutenofullerene derivatives in the solution and thin films significantly varied depending on the addends. Among the three derivatives studied, only cyclobutenofullerene, featuring a folded structure induced by the hydration of the alkyne moiety, exhibited n‐type semiconductor behavior in the thin films. The findings of this study present a novel methodology for synthesizing and functionalizing fullerene derivatives, together with a conceptual framework for tailoring molecular properties.

  URL1(公開)

Presentations

• カーボンナノチューブの環化付加反応と熱転位による近赤外発光特性の制御
  Sep. 2024, 第34回基礎有機化学討論会, Poster presentation
• プロパルギル炭酸エステルを用いたフラーレン開口反応
  13 Sep. 2024, 第34回基礎有機化学討論会, Oral presentation(general)
• Quantification of Noncovalent Arene–Fullerene Interactions Using a Molecular Torsion Balance
  21 Mar. 2024, 日本化学会第104春季年会, Oral presentation(general)
• 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
  09 Dec. 2023, 第50回有機典型元素化学討論会, Oral presentation(general)
• 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
  12 Sep. 2023, 第33回基礎有機化学討論会, Poster presentation
• 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
  21 Mar. 2024, 第104春季年会, Oral presentation(general)
• 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
  14 Sep. 2023, 第33回基礎有機化学討論会, Oral presentation(general)
• Relationship of Binding Configurations to Photoluminescence Properties of Functionalized Single-Walled Carbon Nanotubes
  04 Sep. 2023, 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
  23 Mar. 2023, The 103rd CSJ Annual Meeting, Oral presentation(general)
• 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
  21 Sep. 2022, 第32回基礎有機化学討論会, Poster presentation
• 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
  20 Sep. 2022, 第32回基礎有機化学討論会, Poster presentation
• Control of the photoluminescence properties of single-walled carbon nanotubes by chemical functioalization and quantification of their terminal amino groups
  01 Sep. 2022, The 63rd Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• Synthesis and Characterization of Cyclobutenofullerenes
  01 Sep. 2022, The 63rd Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• 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
  25 Mar. 2022, 日本化学会第102春季年会, Oral presentation(general)
• 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
  21 Sep. 2021, 第31回基礎有機化学討論会
• Thermodynamic control of quantum defects on functionalized single-walled carbon nanotubes
  08 Jun. 2021, NT21: International Conference on the Science and Application of Nanotubes and Low-Dimensional Materials, Poster presentation
• Sonochemical reaction to control the near-infrared photoluminescence properties of single-walled carbon nanotubes
  08 Jun. 2021, NT21: International Conference on the Science and Application of Nanotubes and Low-Dimensional Materials, Poster presentation
• Quantitative evaluation of non covalent interactions at the C60 surface
  22 Mar. 2021, The 101st CSJ Annual Meeting, Oral presentation(general)
• Photoreaction of C70 with disilirane: Electronic properties of silylated adducts
  02 Mar. 2021, The 60th Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• Chirality and helicity sorting of functionalized single-walled carbon nanotube
  01 Mar. 2021, The 60th Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• Simple and Effective Method to Control Photoluminescence Properties of Single-walled Carbon Nanotubes by Ultrasonic Irradiation
  16 Sep. 2020, The 59th Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• Control of the photoluminescence properties of single-walled carbon nanotubes by chemical functionalizaition using dibromoalkanes：Influence of alkyl chain lengths of dibromoalkanes
  24 Mar. 2020, The 100th CSJ Annual Meeting, Oral presentation(general)
• Control of the photoluminescence property of single-walled carbon nanotubes by chemical functionalization and its subsequent transformation of functional groups
  23 Mar. 2020, The 100th CSJ Annual Meeting, Oral presentation(general)
• Measurement of Fullerene–Arene Interactions Using Molecuar Torsion Balances
  22 Mar. 2020, The 100th CSJ Annual Meeting, Poster presentation
• Simple and Effective Method to Control Photoluminescence Properties 76 of Single-walled Carbon Nanotubes by Ultrasonic Irradiation
  16 Mar. 2020, The 58th Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• Reactions of S-Heterocyclic Carbenes with Fullerenes: Preparation and Characterization of Dithiomethano-derivatives
  15 Mar. 2020, The 58th Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• CuCl-Mediated Reaction of C60 with Propargylic Phosphate
  15 Mar. 2020, The 58th Fulerenes-Nanotubes-Graphene General Symposium, Poster presentation
• Design and control of band gap of functionalized single-walled carbon nanotube quantum dots
  05 Sep. 2019, The 57th Fullerenes-Nanotubes-Graphene General Symposium, Oral presentation(general)
• Co-crystal of La@Cs(6)-C82 with Ni(OEP)
  23 Jul. 2019, The 18th International Symposium on Novel Aromatic Compounds (ISNA-18), Poster presentation
• Selectivity in Emergence of Red-shifted Photoluminescence of Single-Walled Carbon Nanotubes by Functionalization using Bulky Reagents
  23 Jul. 2019, The 18th International Symposium on Novel Aromatic Compounds (ISNA-18), Poster presentation
• Fullerene-Based Molecular Torsion Balance for Investigating Noncovalent Interactions on the C60 Surface
  22 Jul. 2019, The 18th International Symposium on Novel Aromatic Compounds (ISNA-18), Poster presentation
• Platinum-catalyzed reaction of [60]fullerene with 9-ethynyl-9H-fluoren-9-yl carboxylates
  Mar. 2019, 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
  Mar. 2019, 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
  Mar. 2019, 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
  Mar. 2019, 日本化学会第99春季年会
• Functionalization of fullerene C60 via one electron reduction
  Mar. 2019, 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
  Sep. 2018, 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
• Cocrystallization of La@Cs(6)-C82 with Ni(OEP)
  Sep. 2018, 第29回基礎有機化学討論会, Poster presentation
• Synthesis of methanofullerenes from C60 radical anion
  Sep. 2018, 第29回基礎有機化学討論会, Poster presentation
• Divergent reactivity of C60 with propargylic esters in the presence of transition metal catalyst
  Mar. 2018, Oral presentation(general)
• Temperature dependence of anisotropic transient conductivity of a La@C2v-C82(Ad) crystal
  Mar. 2018, 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, Poster presentation
• Photoreaction of Sc3N@Ih-C80 with Disilirane: Formation and Isomerization of 1,2-, 1,3-, and 1,4-Adducts
  Mar. 2018, 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, Poster presentation
• Chemical functionalization of single-walled carbon nanotubes to control their PL properties for bioimaging application
  Mar. 2018, 日本化学会第98春季年会, Poster presentation
• 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
  Dec. 2017, 第44回有機典型元素化学討論会, Oral presentation(general)
• 特異な金属内包フラーレン及びその誘導体の電子状態
  Nov. 2017, 第56回電子スピンサイエンス学会年会, Oral presentation(invited, special)
• Effect of Initial Degree of Functionalization of Alkylated Single-Walled Carbon Nanotubes on Their Thermal Stability and Photoluminescence Properties
  Sep. 2017, 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, Poster presentation
• Unveiling the Unique Chemical Reactivity of Endohedral Metallofullerenes
  Jun. 2017, 2nd International Symposium on NanoCarbons -- Fullerenes, Endofullerenes, Carbon Nanotubes, Graphenes and Carbon Nanostructures, Oral presentation(invited, special)
• 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
  Mar. 2017, 日本化学会第97春季年会, Oral presentation(general)
• Competitive elimination and decomposition reaction of oxidized single-walled carbon nanotubes depending on the degree of functionalization
  Feb. 2017, 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, Oral presentation(general)
• Photochemical Addition of Silicones to Sc3N@Ih-C80: Interconversion of the [6,6]-and [5,6]-Adducts
  Feb. 2017, 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, Poster presentation
• Control of photoluminescence properties of single-walled carbon nanotubes
  Sep. 2016, 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, Oral presentation(general)
• 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
  Sep. 2016, 第27回基礎有機化学討論会, Poster presentation
• Substituent effects on defunctionalization of alkylated single-walled carbon nanotubes
  Feb. 2016, 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, Poster presentation
• Preparation, Structural Determination, and Characterization of Electronic Properties of Carbosilylated Sc3N@Ih-C80
  Feb. 2016, 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, Poster presentation
• 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
  Oct. 2015, 第5回CSJ化学フェスタ, Poster presentation
• The Structure of Endohedral Metallofullerene Sc2@C66 Having Two Unsaturated Linear Triquinane Units
  Mar. 2015, 日本化学会第95春季年会, Oral presentation(general)
• 光酸化した単層カーボンナノチューブの評価
  Mar. 2015, 日本化学会第95春季年会, Poster presentation
• フラーレン還元体とベンジルブロミド誘導体の反応
  Mar. 2015, 日本化学会第95春季年会, Poster presentation
• Hiding and Recovering Electrons in a Dimetallic Endohedral Fullerene: Air-Stable Products from Radical Additions
  Mar. 2015, 日本化学会第95春季年会, Oral presentation(general)
• Isolation and characterization of [5,6]-pyrrolidino-Sc3N@Ih-C80 diastereomers
  Feb. 2015, the 48th Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• Unsaturated linear triquinane: A new motif in fullerene cage geometry
  Oct. 2014, International Symposium on the Synthesis and Application of Curved Organic pi-Molecules and Materials, Poster presentation
• Sc2@C66 Revisited: An Endohedral Fullerene with Scandium Ions Nestled within Two Unsaturated Linear Triquinanes
  Sep. 2014, the 47th Fullerenes-Nanotubes-Graphene General Symposium, Oral presentation(general)
• 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
  Sep. 2014, 第25回基礎有機化学討論会, Oral presentation(general)
• C602–とベンジルブロミド誘導体の反応
  Sep. 2014, 第25回基礎有機化学討論会, Poster presentation
• 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
  Mar. 2014, 第94春季年会, Poster presentation
• Thermal Bis-silylation, Carbosilylation, and Bis-germylation of Fullerenes
  Mar. 2014, 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, Poster presentation
• プロピルアミン存在下におけるSWNTsの光化学的挙動
  Mar. 2014, 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, Poster presentation
• Excited State Electronic Interactions in Push-Pull Chromophore-[60]Fullerene Conjugates
  Mar. 2014, 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, Poster presentation
• Excited State Electronic Interactions in Push–Pull-Chromophore–[60]Fullerene Conjugates
  Dec. 2013, 第7回有機π電子系シンポジウム, Poster presentation
• M@C2v(9)-C82の内包金属イオンとフラーレンケージの関係
  Sep. 2013, 第24回基礎有機化学討論会, Oral presentation(general)
• Reaction of Trimetallic Nitride Template-endohedral Metallofullerene (TNT-EMFs) with Aziridine
  Mar. 2013, The 44th Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• Thermal Reactions of C60 with Siliranes: Formation of Carbosilylated Fullerenes
  Mar. 2013, The 44th Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• 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
  Mar. 2013, 第93春季年会, Oral presentation(general)
• 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
  Mar. 2013, 第93春季年会, Oral presentation(general)
• カーボンナノチューブの脱酸素反応における選択性
  Mar. 2013, 第93春季年会, Poster presentation
• 活性酸化種を用いたフラーレンの酸化反応
  Dec. 2012, 第39回有機典型元素討論会, Oral presentation(general)
• 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
  Sep. 2012, 第23回基礎有機化学討論会, Oral presentation(general)
• Application of MCD Spectroscopy and TD-DFT to Endohedral Metallofullerenes. New Insights into Characterization of Their Electron Transitions
  Sep. 2012, The 43rd Fullerenes-Nanotubes-Graphene General Symposium Abstracts, Other
• The 3rd Tsukuba International Mini-symposium on Hybridization between Main Group Element Chemistry and p-electron Chemistry - ICHAC-10 Pre-symposium in Tsukuba
  Jul. 2012, The 2nd symposium on "Carbon Nanoforms", Poster presentation
• Rational design of twisted bis-porphyrin tweezer for noncovalent interaction of single-walled carbon nanotubes
  May 2012, The 3rd Tsukuba International Mini-symposium on Hybridization between Main Group Element Chemistry and p-electron Chemistry - ICHAC-10 Pre-symposium in Tsukuba, Oral presentation(invited, special)
• 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
  Mar. 2012, 第92春季年会, Oral presentation(general)
• 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
  Mar. 2012, 第92春季年会, Oral presentation(general)
• Reactions of C60 with disilirane and silirane in the presence of transition metal complexes
  Mar. 2012, The 42nd Fullerenes-Nanotubes-Graphene General Symposium, Poster presentation
• 金属内包フラーレンとアジリジンの反応
  Dec. 2011, 第38回有機典型元素化学討論会, Poster presentation
• Endohedral metallofullerenes: new building blocks for photoactive donor-acceptor system
  Dec. 2011, 1st International Symposium on Creation of Functional Materials, Poster presentation
• Synthesis and photophysical properties of metallofullerene-zinc porphyrin dyads: impact of endohedral clusters
  Nov. 2011, 3rd International Symposium on Emergence of Highly Elaborated pi-Space and Its Function, Other
• Molecular structure of endohedral metallofullerene Ce2@D5h-C80
  Sep. 2011, 第22回基礎有機化学討論会, Poster presentation, 金属内包フラーレンCe2@ D5h-C80の分子構造

  URL1(公開)
• Molecular structure of endohedral metallofullerene Ce2@D5h-C80
  Sep. 2011, 第22回基礎有機化学討論会, Poster presentation
• 遷移金属錯体を用いた環状ケイ素化合物とC60との反応
  Sep. 2011, 第22回基礎有機化学討論会, Other
• 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
  Sep. 2011, 第22回基礎有機化学討論会, Poster presentation
• Tuning of Electron-Accepting Properties of La2@C80 by Chemical Modification
  Sep. 2011, 第22回基礎有機化学討論会, Oral presentation(general)
• フラーレン表面に見られる軸不斉発現
  Sep. 2011, 第一回フラーレン•ナノチューブ・グラフェン若手研究会, Oral presentation(invited, special)
• Electronic Tuning of La2@C80 by Chemical Modification
  Aug. 2011, 43rd IUPAC World Chemistry Congress, Other
• Electronic Modulation of Endohedral Metallofullerenes by Chemical Functionalization
  Jul. 2011, 14th International Symposium on Novel Aromatic Compounds, Oral presentation(general)
• Tuning of electronic properties of endohedral dimetallofullerene La2@C80 by exohedral chemical functionalization
  Jun. 2011, The first symposium on "Carbon Nanoforms", Oral presentation(general)
• 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, 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。

  URL1(公開)
• 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, 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。

  URL1(公開)
• 化学修飾によるLa₂@C₈₀の電子アクセプター性制御
  2011, 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。

  URL1(公開)
• 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, 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。

  URL1(公開)
• 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, 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。

  URL1(公開)
• Thermal Carbosilylation of Dimetallofullerene La2@Ih-C80
  Dec. 2010, The International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2010), Poster presentation
• Axially Chiral Push-Pull-Substituted Buta-1,3-dienes Enforced by a Single Methyl Group on the [60]Fullerene Surface
  Jan. 2010, International Conference on Molecular Electronics, Poster presentation
• Electronic Modulation of Fullerenes through Conjugation to Push-Pull Chromophores
  Jul. 2009, 13th International Symposium on Novel Aromatic Compounds (ISNA-13), Poster presentation
• Electronic Modulation of Fullerenes through Conjugation to Push-Pull Chromophores
  Jun. 2009, SwissNano2009, Poster presentation
• 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, 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。

  URL1(公開)
• Positional Control of Encapsulated Atoms Inside a Fullerene Cage by Exohedral Chemical Functionalization
  May 2008, 213th ECS meeting, Oral presentation(general)
• 金属内包フラーレンLa@C₈₂の可逆反応
  2008, 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。

  URL1(公開)
• 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, 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、I_h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。

  URL1(公開)
• La@C₈₂とシクロペンタジエン誘導体の可逆付加反応
  2007, 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。

  URL1(公開)
• 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, 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。

  URL1(公開)
• Silylation of endohedral Dimetallofullerenes
  Dec. 2005, International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2005), Oral presentation(general)
• 金属内包フラーレンM2@C80の化学修飾
  2005, 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.

  URL1(公開)
• Chemical Functionalization of Dimetallofullerenes
  Oct. 2004, 206th ECS Meeting (2004 Joint International Meeting), Poster presentation
• 金属内包フラーレンの化学修飾
  2004, 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。

  URL1(公開)

Acquisition of external funds

• 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
  Grants-in-Aid for Scientific Research, Representative, Representative
• 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
  Other external funds, Representative, Representative
• 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
  Other external funds, Representative, Representative
• 金属内包フラーレンの分子変換法の創出と機能開拓
  Grants-in-Aid for Scientific Research, Allotter, Allotter
• 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
  Grants-in-Aid for Scientific Research, Representative, Representative
• 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
  Other external funds, Representative, Representative
• 鉄原子内包フラーレン合成への挑戦
  Other external funds, Representative, Representative
• 金属内包フラーレンの化学修飾による機能開拓
  Grants-in-Aid for Scientific Research, Allotter, Allotter
• 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
  Grants-in-Aid for Scientific Research, Representative, Representative
• 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
  Other external funds, Representative, Representative
• 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
  Other external funds, Representative, Representative
• 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
  Grants-in-Aid for Scientific Research, Representative, Representative
• 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
  Other external funds, Representative, Representative
• π空間に閉じ込められた物質系の創製と機能
  Grants-in-Aid for Scientific Research, Allotter, Allotter

Awards

• 2015 PCCP Prize for Outstanding Achievement of Young Scientists in Physical Chemistry and Chemical Physics
  Mar. 2015
• 第4回大澤賞
  Mar. 2008
• 学長表彰
  Mar. 2008
• 第4回研究科長賞
  Mar. 2008