鎖と環の遷移金属クラスターを用いた単電子機能を目指した超分子組織体の創製

• Project Area: Coordination Programming - Science of Molecular Superstructures for Chemical Devices
• Project/Area Number: 24108727
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Nara Women's University
• Principal Investigator: 棚瀬 知明 奈良女子大学, 自然科学系, 教授 (50207156)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥8,710,000 (Direct Cost: ¥6,700,000、Indirect Cost: ¥2,010,000); Fiscal Year 2013: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2012: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
• Keywords: 遷移金属 / 量子細線 / 合成化学 / 多座ホスフィン / 超分子化学 / 少数電子素子 / 金属クラスター / 機能性分子 / 配位プログラム

Research Abstract

（1）鎖状遷移金属クラスターの合成とそれらを量子ドットとした超分子構造の構築：これまでに合成したPt6, Pt4Pd2, Pd8等の直鎖状低原子価遷移金属クラスターを量子ドットと考え，その両末端にトンネル障壁となりうる末端配位子や有機連結基の導入により1次元単分子素子の開発を行った。これら分子モジュールの合成と機能解析，さらに，それらを連結した超分子構造体の構築を分子化学的ボトムアップ手法により試み，特に，直鎖状Pd八核クラスターの構造と電子状態，吸収スペクトルの温度変化等に関し詳細な分析を行い分子軌道に基づく理解に至った。このような知見を基に，金属鎖に沿ったチャンネルを経由する量子伝導素子としての可能性を調べる目的で，基底状態及び遷移状態の密度汎関数法による分子軌道計算とそれらにもとづく量子伝導シミュレーションを班員間の共同研究として行った。さらに，Pd8核錯体の溶存状態の温度変化に関する測定から，高温ではPd8核鎖かPd4核フラグメントに解離するが室温では自己集合的に整列しPd8核鎖を再生することを明らかにし，さらに低温ではPd16核，Pd24核種が微量ではあるが生成することを見出した。また，Pd8核錯体の酸化還元挙動についても研究を行い，水素発生に関する電気化学触媒となり得ることを見出した。（2）環状遷移金属クラスターの合成とそれらを用いた機能素子の開発：Au4M2Cu2 (M = Au, Ag, Cu)環状金属クラスターや強発光性Au4核錯体に関する成果をまとめ論文発表した。Cu(I)を用いたクラスター合成に関しては，四座配位子dpmppmを用いた新奇なCu2, Cu4, Cu6, Cu9, Cu16ヒドリドクラスターに関する研究を進め，特に，Cu2核ヒドリド錯体が温和な条件で二酸化炭素と反応しギ酸錯体を生成することを新たに見出した。

Current Status of Research Progress

Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Strongly Luminous Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands, meso- or rac-Bis[(diphenylphosphinomethyl)phenylphosphino]methane (2014)
  • Author(s): T. Tanase, R. Otaki, T. Nishida, H. Takenaka, Y. Takemura, B. Kure, T. Nakajima, Y. Kitagawa, T. Tsubomura
  • Journal Title: Chem. Euro. J. Volume: 20 Issue: 6 Pages: 1577-1596
  • DOI: 10.1002/chem.201303729
  • Peer Reviewed
• [Journal Article] Electron-Deficient Pt2M2Pt2 Hexanuclear Metal Strings (M = Pt, Pd) Supported by Triphosphine Ligands (2014)
  • Author(s): E. Goto, R. A. Begum, C. Ueno, A. Hosokawa, C. Yamamoto, K. Nakamae, B. Kure, T. Nakajima, T. Kajiwara, and T. Tanase
  • Journal Title: Organometallics Volume: ３３ Issue: 8 Pages: 1893-1904
  • DOI: 10.1021/om401211d
  • Peer Reviewed
• [Journal Article] One-dimensional Anisotropic Metal Organic Module Containing a Pt6 Chain Terminated with Redox Active Ferrocenyl Units (2014)
  • Author(s): T. Tanase, C. Yamamoto, B. Kure, and T. Nakajima
  • Journal Title: Chem. Lett. Volume: ４３ Issue: 6 Pages: 913-915
  • DOI: 10.1246/cl.140161
  • NAID: 130004868205
  • Peer Reviewed
• [Journal Article] Reversible Dioxygen Binding on Asymmetric Dinuclear Rhodium Centres (2013)
  • Author(s): T. Nakajima, M. Sakamoto, S. Kurai, B. Kure, and T. Tanase
  • Journal Title: Chem. Commun. Volume: ４９ Issue: 46 Pages: 5250-5252
  • DOI: 10.1039/c3cc41815d
  • Peer Reviewed
• [Journal Article] Flexible, linear, tetranuclear palladium complexes supported by tetrapho sphine ligands with electron-withdrawing groups (2013)
  • Author(s): 棚瀬知明, 中前佳那子
  • Journal Title: Dalton Trans Volume: VOL.42 Issue: 45 Pages: 15941-15952
  • DOI: 10.1039/c3dt51433a
  • Peer Reviewed
• [Journal Article] Configurational Isomerization of Dinuclear Iridium and Rhodium Complexes with a Series of NPPN Ligands, 2-PyCH2(Ph)P(CH2)nP(Ph)CH2-2-Py (Py = pyridyl, n = 2-4) (2013)
  • Author(s): T. Nakajima, Y. Fukushima, M. Tsuji, N. Hamada, B. Kure, and T. Tanase
  • Journal Title: Organometallics Volume: ３２ Issue: 24 Pages: 7470-7477
  • DOI: 10.1021/om400965j
  • Peer Reviewed
• [Journal Article] Systematic Conversion of Single Walled Carbon Nanotubes into n-type Thermoelectric Materials by Molecular Dopants (2013)
  • Author(s): Y. Nonoguchi, K. Ohashi, R. Kanazawa, K. Ashiba, K. Hata, T. Nakagawa, C. Adachi, T. Tanase, and T. Kawai
  • Journal Title: Scientific Reports (Nature Publishing) Volume: 3:3344 Issue: 1 Pages: 1-7
  • DOI: 10.1038/srep03344
  • Peer Reviewed
• [Journal Article] Synthesis and structure of a dinuclear NiIIIrIII hydride complex supported by a N3S2 bridging ligand: Comparison of property and reactivity of dinuclear NiII(m-H)MIII units (M = Rh, Ir) in aqueous media (2013)
  • Author(s): B. Kure, T. Nakajima, and T. Tanase
  • Journal Title: J. Organomet. Chem. Volume: 733 Pages: 28-35
  • DOI: 10.1016/j.jorganchem.2013.03.005
  • Peer Reviewed
• [Journal Article] Wheel-Shaped Icosanuclear Homo- and Heterometallic Complexes of NiII, CoII, and CuII Ions Supported by Unsymmetrical Aminoalcohol Ligands (2012)
  • Author(s): Masahiro Mikuriya, Takayuki Nakajima
  • Journal Title: Inorg. Chem. Volume: 51 Issue: 22 Pages: 12503-12510
  • DOI: 10.1021/ic3019106
  • Peer Reviewed
• [Journal Article] Hydride-Bridged Pt2M2Pt2 Hexanuclear Metal Strings (M = Pt, Pd) Derived from Reductive Coupling of Pt2M Building Blocks Supported by Triphosphine Ligands (2012)
  • Author(s): E. Goto, R. A. Begum, A. Hosokawa, C. Yamamoto, B. Kure, T. Nakajima, and T. Tanase
  • Journal Title: Organometallics Volume: 31 Issue: 24 Pages: 8482-8497
  • DOI: 10.1021/om300680p
  • Peer Reviewed
• [Journal Article] Hydride-bridged NiRh Complexes with Tunable N3S2 Dithiolato Ligands and Their Utilization as Catalysts for Hydrogenation of Aldehydes and CO2 in Aqueous Media (2012)
  • Author(s): B. Kure, A. Taniguchi, T. Nakajima, and T. Tanase
  • Journal Title: Organometallics Volume: 31 Issue: 13 Pages: 4791-4800
  • DOI: 10.1021/om300350u
  • Peer Reviewed
• [Journal Article] Cyclic Trinuclear Rh_2M Complexes(M=Rh, Pt, Pd, Ni) Supported by meso-1, 3-Bis-{(diphenylphosphinomethyl) phenylphosphino} pr opane (2012)
  • Author(s): T. Nakajima, S. Kurai, S. Noda, M. Zouda, B. Kure, and T. Tanase
  • Journal Title: Organometallics Volume: (in press) Issue: 11 Pages: 4283-4294
  • DOI: 10.1021/om300278k
  • Peer Reviewed
• [Journal Article] Structural, Photo physical, and Mesomorphic Properties of Luminescent Platinum(II)-salen Schiff Base Complexes (2012)
  • Author(s): Y. Abe, Y. Takagi, M. Nakamura, T. Takeuchi, T. Tanase, M. Yokokawa, H. Mukai, T. Megumi, A. Hachisuga, and K. Ohta
  • Journal Title: Inorg. Chim. Acta Volume: (in press) Pages: 254-260
  • DOI: 10.1016/j.ica.2012.02.041
  • Peer Reviewed
• [Journal Article] Heterotrinuclear Complexes with Pd, Rh, and Ir Ions Assembled by Conformational Switch of a Tetraphosphine Ligand around Pd Center (2012)
  • Author(s): A. Yoshii, H. Takenaka, H. Nagata, S. Noda, K. Nakamae, B. Kure, T. Nakajima, and T. Tanase
  • Journal Title: Organometallics Volume: 31 Issue: 1 Pages: 133-143
  • DOI: 10.1021/om2006744
  • Peer Reviewed
• [Presentation] Self-Alignment of Low-Valent Extended Metal Atom Chains (2014)
  • Author(s): Tomoaki Tanase
  • Organizer: International Symposium on Coordination Programming 2014
  • Place of Presentation: Tokyo (Japan)
  • Invited
• [Presentation] Low-Valent Extended Metal Atom Chains Supported by Polyphosphines (2014)
  • Author(s): Tomoaki Tanase
  • Organizer: The 41st International Conference on Coordination Chemistry (ICCC41)
  • Place of Presentation: Singapore
  • Invited
• [Presentation] Low-Valent Extended Metal Atom Chains (2013)
  • Author(s): Tomoaki Tanase
  • Organizer: The 1st Japan-Taiwan-Singapore Joint Symposium on Coordination Chemistry
  • Place of Presentation: Osaka (Japan)
  • Invited
• [Presentation] Low-Valent Extended Metal Atom Chains (2013)
  • Author(s): Tomoaki Tanase
  • Organizer: The 2nd Japan-France Coordination Chemistry Symposium
  • Place of Presentation: Nara (Japan)
  • Invited
• [Presentation] Low-Valent Extended Metal Atom Chains (2013)
  • Author(s): Tomoaki Tanase
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2013
  • Place of Presentation: Beijing (China)
  • Invited
• [Presentation] Low-Valent Extended Metal Atom Chains (invited lecture) (2012)
  • Author(s): T. Tanase
  • Organizer: Japanese-German Symposium on Coordination Programming 2012
  • Place of Presentation: Munster (Germany)
  • Year and Date: 2012-10-25
  • Invited
• [Book] ハウスクロフト 無機化学 （下） (2012)
  • Author(s): 巽，西原，穐田，酒井監訳，棚瀬（28章分担翻訳）
  • Total Pages: 541
  • Publisher: 東京化学同人
• [Remarks] Tanase Group Home Page
  • URL: http://www.chem.nara-wu.ac.jp/~tanase/TanaseGroup/
• [Remarks] Tanase Group Home Page
  • URL: http://www.chem.nara-wu.ac.jp/~tanase/TanaseGroup/