Luminescence Control of Transition Metal Complexes Based on Zero-magnetic-field Splitting

• Project/Area Number: 25620035
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Inorganic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: KITAMURA Noboru 北海道大学, 理学(系)研究科(研究院), 教授 (50134838)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2014: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2013: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: ゼロ磁場分裂 / 励起三重項状態 / 金属6核クラスター / 発光収率・寿命 / ゼロ磁場 / 金属６核クラスター / トリアリールホウ素ルテニウム（ＩＩ）錯体 / 発光制御

Outline of Final Research Achievements

Temperature dependences of the emission spectra and lifetimes of a series of octahedral hexanuclear molybdenum clusters were studied and the zero-magnetic-field splitting (zfs) parameters of the clusters in the excited triplet state were evaluated. It was found that the clusters having larger zfs energies in the excited triplet states showed more intense and longer emission. The photophysical properties of a series of hexanuclear molybdenum complexes having terminal carboxylate ligands were also investigated and it was demonstrated that the photophysical properties of the clusters could be controlled by the acidity of the terminal carboxylate ligands. The present study demonstrataed that the luminescence properties of transition metal complexes could be controlled by the zfs energies in the excited triplet states.

Research Products

• [Journal Article] Dual Emissions from Ruthenium(II) Complexes Having 4-Arylethynyl-1,10- phenanthroline at Low Temperature (2015)
  • Author(s): E. Sakuda, C. Matsumoto, Y. Ando, A. Ito, K. Mochida, A. Nakagawa, N. Kitamura
  • Journal Title: Inorganic Chemistry Volume: 54 Issue: 7 Pages: 3245-3252
  • DOI: 10.1021/ic502843x
  • Peer Reviewed
• [Journal Article] Synthetic Control of Spectroscopic and Photophysical Properties of Triarylborane Derivatives Having Peripheral Electron-Donating Groups (2014)
  • Author(s): Akitaka Ito, Kazuyoshi Kawanishi, Eri Sakuda and Noboru Kitamura
  • Journal Title: Chem.-Eur. J. Volume: 20 Issue: 14 Pages: 3940-3953
  • DOI: 10.1002/chem.201304207
  • Peer Reviewed / Open Access
• [Journal Article] A Highly Emissive Inorganic Hexamolybdenum Cluster Complex as a Handy Precursor for the Preparation of New Luminescent Materials (2014)
  • Author(s): O. A. Efremova, M. A. Shestopalov, N. A. Chirtsova, A. I. Smolentsev, Y. V. Mironov, N. Kitamura, K. A. Brylev, A. J. Sutherland
  • Journal Title: Dalton Transaction Volume: 43 Issue: 16 Pages: 6021-6025
  • DOI: 10.1039/c3dt53126k
  • Peer Reviewed
• [Journal Article] The First Water-Soluble Hexarhenium Cluster Complexes with a Hetrocyclic Ligand Environment:Synthesis, Luminescence, and Biological Properties (2014)
  • Author(s): M. A. Shestopalov, K. E. Zubareva, O. P. Khirpko, A. O. Soloviera, N. V. Kurtieva, Y. V. Mironov, N. Kitamura, V. E. Fedorov, K. A. Brylev
  • Journal Title: Inorganic Chemistry Volume: 53 Pages: 9006-9013
  • Peer Reviewed
• [Journal Article] Photoinduced Electron Transfer Reactions of Hexarhenium(III) Cluster: Oxidative Quenching of [Re6S8Cl6]4- Emission by Electron Acceptors (2014)
  • Author(s): N. Kitamura, N. Kobayashi, S. Ishizaka, T. Yoshimura, H.-B. Kim, Y. Sasaki
  • Journal Title: Journal of Cluster Science Volume: 26 Issue: 1 Pages: 211-221
  • DOI: 10.1007/s10876-014-0729-x
  • NAID: 120005593443
  • Peer Reviewed / Open Access
• [Journal Article] Controlled Synthesis and Luminescence Properties of trans-[Re6S8(CN)4(OH)2-n(H2O)n]n-4 Octahedral Rhenium(III) Clusters (n = 0, 1, or 2). (2014)
  • Author(s): A. Y. Ledneva, K. A. Brylev, A. I. Smolentsev, Y. V. Mironov, Y. Molard, S. Cordier, N. Kitamura, and N. G. Naumov
  • Journal Title: Polyhedron Volume: 67 Pages: 351-359
  • DOI: 10.1016/j.poly.2013.09.015
  • Peer Reviewed
• [Journal Article] Synthesis and Crystal Structure of Azide K4[Re6Se8(N3)6]4H2O: Luminescence, Redox, and DFT Investigations of the [Re6Se8(N3)6]4- Cluster Unit (2013)
  • Author(s): A. Gandubert, K. A. Brylev, T. T. Nguyen, N. G. Naumov, N. Kitamura, Y. Molard, R. Gautier, and N. G. Naumov
  • Journal Title: Zeitshrift fur Anorganische und Allgemeine Chemie Volume: 639 Issue: 10 Pages: 1756-1762
  • DOI: 10.1002/zaac.201300151
  • Peer Reviewed
• [Journal Article] Dithiolene Dimetalic Molybdenum(V) Complexes Displaying Intraligand Charge Transfer (ILCT) Emission. (2013)
  • Author(s): D. Recatala, A. L. Gushchin, R. Llusar, F. Galindo, K. A. Brylev, M. R. Ryzhikov, and N. Kitamura
  • Journal Title: Dalton Transaction Volume: 42 Issue: 36 Pages: 12947-12955
  • DOI: 10.1039/c3dt51102b
  • Peer Reviewed
• [Journal Article] Akynyl Complexes of High-Valence Clusters. Synthesis and Luminescence Properties of [Mo6I8(C=CC(O)OMe)6]2- - The First Homoleptic Organometallic Complex in the Family of Octahedral {M6X8} Clusters (2013)
  • Author(s): M. N. Sokolov, M. A. Miklailov, K. A. Brylev, A. V. Virovets, C. Vicent, N. G. Kompankov, N. Kitamura, and V. P. Fedin
  • Journal Title: Inorganic Chemistry Volume: 52 Issue: 21 Pages: 12477-12481
  • DOI: 10.1021/ic401377g
  • Peer Reviewed
• [Presentation] Spectroscopic and Photophysical Properties of Novel Tricarbonyl Rhenium(I) Complexes with Two Arylborane Charge Transfer Units (2014)
  • Author(s): Y. Knag, A. Ito, E. Sakuda, N. Kitamra
  • Organizer: 2014 International Conference on Artificial Photosynthesis
  • Place of Presentation: 淡路夢舞台国際会議場（淡路市）
  • Year and Date: 2014-11-24 – 2014-11-28
• [Presentation] Photophysical Properties of Ruthenium(II) Complexes Having Arylborane-Appended Ligands (2014)
  • Author(s): N. Kitamura
  • Organizer: 8th Asian Photochemistry Conference
  • Place of Presentation: Lavav Ghandi Conference Center (Trivandaram, India)
  • Year and Date: 2014-11-10 – 2014-11-13
  • Invited
• [Presentation] 強発光性Mo(II)六核クラスターの光化学物性 (2014)
  • Author(s): 赤木壮一郎、作田絵里、伊藤亮孝、喜多村昇
  • Organizer: 第64回錯体化学討論会
  • Place of Presentation: 中央大学（東京都）
  • Year and Date: 2014-09-18 – 2014-09-20
• [Presentation] Excited Triplet States of Octahedral Hexanuclear Metal Cluster Complexes (2014)
  • Author(s): N. Kitamura
  • Organizer: IVth International Workshop on Transition Metal Cluster Complexes
  • Place of Presentation: Nikolaev Institite of Inorganic Chemistry (Novosibirsk, Russia)
  • Year and Date: 2014-09-08 – 2014-09-11
  • Invited
• [Presentation] (n-Bu4N)2[Mo6X8(C3F7COO)6](X = I, Br, Cl)の励起三重項状態 (2014)
  • Author(s): 赤木壮一郎、作田絵里、伊藤亮孝、喜多村昇
  • Organizer: 第26回配位化合物の光化学討論会
  • Place of Presentation: 首都大学東京（八王子市）
  • Year and Date: 2014-08-06 – 2014-08-08
• [Presentation] アリールホウ素置換基を有するRu(II)錯体を用いたCO2光還元反応の検討 (2014)
  • Author(s): 石崎七海、田中麻衣、作田絵里、喜多村昇
  • Organizer: 北海道支部2014年冬季研究発表会
  • Place of Presentation: 北海道大学（札幌市）
• [Presentation] 正八面体型金属６核クラスターの励起三重項状態 (2014)
  • Author(s): 赤木圭一、作田絵里、喜多村昇
  • Organizer: 北海道支部2014年冬季研究発表会
  • Place of Presentation: 北海道大学（札幌市）
• [Presentation] アリールホウ素置換基を有するRu(II)ポリピリジル錯体発光の還元的消光 (2014)
  • Author(s): 吉松泉、作田絵里、喜多村昇
  • Organizer: 北海道支部2014年冬季研究発表会
  • Place of Presentation: 北海道大学（札幌市）
• [Presentation] アリールホウ素置換基を導入したルテニウム(II)ポリピリジン錯体の光化学物性に対する配位子構造の効果 (2013)
  • Author(s): 中川淳史、作田絵里、伊藤亮孝、喜多村昇
  • Organizer: 2014年光化学討論会
  • Place of Presentation: 愛媛大学（松山市）
• [Presentation] ジメシチルボリル基とジメチルアミノ基を有する新規ルテニウム(II)ポリピリジン錯体の光化学物性に対する配位子構造の効果 (2013)
  • Author(s): 中川淳史、作田絵里、伊藤亮孝、喜多村昇
  • Organizer: 錯体化学会第６３討論会
  • Place of Presentation: 琉球大学（那覇市）
• [Book] 光の事典 (2014)
  • Author(s): 喜多村曻（分担執筆） 光化学の事典編集委員会（伊藤紳三郎他1９４名）
  • Publisher: 朝倉書店