Syntheses of asymmetrically fused polyoxometalate-silver ethynide composite clusters and their luminescence properties

• Project/Area Number: 26620042
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Inorganic chemistry
• Research Institution: Nihon University
• Principal Investigator: OZEKI Tomoji 日本大学, 文理学部, 教授 (60214136)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2014: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
• Keywords: 複合クラスター / ポリオキソメタレート

Outline of Final Research Achievements

We have successfully synthesized novel composite clusters by directly fusing polyoxometalates and silver ethynide clusters. Our design strategy is to use polyoxometalates with asymmetric surface charge distribution so that the silver ethynide moieties will attach to more negatively charged moiety of the precursor polyoxometalates. Single crystal X-ray diffraction experiments of the resultant samples revealed that the silver atoms selectively attach to the electron-rich part of the polyoxometalate, as designed. Solution studies using multi-nuclear and multi-dimensional nuclear magnetic resonances and sedimentation velocity analysis using an analytical ultracentrifuge demonstrated the structural integrity of the composite clusters. The composite clusters also exhibited photoluminescent properties.

Research Products

• [Journal Article] Reaction of the Hydrogen-bonded Hexamolybdoplatinate Tetramer [H23(PtMo6O24)4]9- with Methanol: Formation of the Methylated Hydrogen-bonded Hexamolybdoplatinate Trimer [(H4Me2PtMo6O24)(H3Me3PtMo6O24)2]6- (2016)
  • Author(s): J. Imai, T. Ozeki, A. Yagasaki
  • Journal Title: Chemistry Letters Volume: 45 Issue: 1 Pages: 19-20
  • DOI: 10.1246/cl.150897
  • NAID: 130005118777
  • Peer Reviewed
• [Journal Article] Control over the preference for binding sites of polyoxometalates to silver ethynide clusters by surface charge modification (2015)
  • Author(s): S. Tamari, K. Ono, M. Hashimoto, T. Ozeki
  • Journal Title: Dalton Transactions Volume: 44 Issue: 44 Pages: 19056-19058
  • DOI: 10.1039/c5dt02972d
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Asymmetrically Fused Polyoxometalate–Silver Alkynide Composite Cluster (2015)
  • Author(s): M. Kurasawa, F. Arisaka, T. Ozeki
  • Journal Title: Inorganic Chemistry Volume: 54 Issue: 4 Pages: 1650-1654
  • DOI: 10.1021/ic502644v
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, structure and valence-trapping vs. detrapping for new trinuclear iron pentafluoro benzoate complexes: possible recognition of organic molecules by 57Fe Mössbauer spectroscopy (2014)
  • Author(s): S. Onaka, Y. Sakai, T. Ozeki, T. Nakamoto, Y. Kobayashi, M. Takahashi, R. Ogiso, T. Takayama, M. Shiotsuka
  • Journal Title: Dalton Transactions Volume: 43 Issue: 18 Pages: 1477-9226
  • DOI: 10.1039/c3dt53623h
  • Peer Reviewed
• [Journal Article] Formation of a Kagome Lattice with Huge Channels by Very Large Spherical Anions (2014)
  • Author(s): M. Saito, T. Ozeki
  • Journal Title: Photon Factory Activity Report 2012 Part A, Highlights and Facility Report Volume: 2012 Pages: 36-37
  • Peer Reviewed
• [Journal Article] Synthesis and Structural Characterization of Isomers of Ru-Substituted Keggin-Type Germanotungstate with dmso Ligand (2014)
  • Author(s): N. Shimizu, T. Ozeki, H. Shikama, T. Sano, M. Sadakane
  • Journal Title: Journal of Cluster Science Volume: 25 Issue: 3 Pages: 755-770
  • DOI: 10.1007/s10876-013-0641-9
  • Peer Reviewed
• [Journal Article] ポリオキソメタレートイオンの対称性と結晶構造 (2014)
  • Author(s): 尾関智二
  • Journal Title: 触媒 Volume: 56 Pages: 330-335
  • Peer Reviewed
• [Presentation] 小角散乱を用いたポリオキソメタレートの溶液内会合状態の研究 (2016)
  • Author(s): 尾関智二
  • Organizer: PF研究会「徹底討論！小角散乱の魅力～基礎・応用・産業利用」
  • Place of Presentation: 高エネルギー加速器研究機構物質構造化学研究所、茨城県つくば市
  • Year and Date: 2016-03-30
• [Presentation] The stability difference of MO42- (M = Mo, W) encapsulating silver(I) ethynide clusters (2016)
  • Author(s): K. Ohashi, T. Kojima, M. Sadakane, M. Hashimoto, T. Ozeki
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学京田辺キャンパス、京都府京田辺市
  • Year and Date: 2016-03-24
• [Presentation] Designer polyoxometalate - silver alkynide chimera cluster (2015)
  • Author(s): T. Ozeki, M. Kurasawa, F. Arisaka
  • Organizer: The International Chemical Congress of Pacific Basin Societies 2015 (Pacifichem 2015)
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] MO42- (M = Mo, W) encapsulating silver(I) ethynide clusters formed by template exchange reactions abstracting MO42- groups from the Keggin-type polyoxometalates (2015)
  • Author(s): K. Ohashi, T. Kojima, M. Sadakane, M. Hashimoto, T. Ozeki
  • Organizer: The International Chemical Congress of Pacific Basin Societies 2015 (Pacifichem 2015)
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Hydrogen-bonded trimer of methylated molybdoplatinate (2015)
  • Author(s): J. Imai, T. Ozeki, A. Yagasaki
  • Organizer: The International Chemical Congress of Pacific Basin Societies 2015 (Pacifichem 2015)
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2015-12-15
  • Int'l Joint Research / Invited
• [Presentation] Template effects on the formation and stabilities of silver tetracosa clusters (2015)
  • Author(s): K. Ohashi, T. Kojima, M. Sadakane, M. Hashimoto, T. Ozeki
  • Organizer: 錯体化学会 第65回討論会
  • Place of Presentation: 奈良女子大学、奈良県奈良市
  • Year and Date: 2015-09-21
• [Remarks] 日本大学文理学部化学科尾関研究室
  • URL: http://ozekilab.jimdo.com/