2005 Fiscal Year Final Research Report Summary
Structures and properties of weakly associated polyoxometalate-transition metal complexes
| Project/Area Number |
15550047
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
OZEKI Tomoji Tokyo Institute of Technology, Graduate School of Science and Engineering, Associate Professor, 大学院・理工学研究科, 助教授 (60214136)
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| Project Period (FY) |
2003 – 2005
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| Keywords | polyoxometalates / transition metal ions / x-ray diffraction / crystal structure / synchrotron radiation / non-linear optical properties / protonation |
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| Research Abstract |
This research project aims at synthesizing complexes of polyoxometalates with transition metal ions, analyzing their crystal structures, and then examining the physicochemical properties that are specific to their structures. First, the magnetic properties of [Cu_2(OH)_2(OH_2)_6][Cu_2(OH_2)_8][V_<10>O_<28>]-4(CH_3)_2CO, which was first synthesized and characterized by the investigator, were investigated. The compound has two pairs of Cu^<2+> cations on the two sides of the [V_<10>O_<28>]^<6-> core, which are separated by 2.89 Å and 3.37 Å, respectively. The unpaired electrons of these pairs were not coupled and each Cu^<2+> atom works as an independent spin center. Second, double salts of [V_<10>O_<28>]^<6-> with Cu^<2+> and NH_4^+, K^+ or Rb^+ were synthesized and their crystal structures were determined. In these crystals, a water molecule coordinating to the cation supports a hydrogen atom on the [V_<10>O_<28>]^<6-> core via hydrogen bond and stabilizes a monoprotonated species, [HV
… More
_<10>_O<28>]^<5->. In these crystals, the precise location of the protons on the monoprotonated decavanadate anion was first determined unambiguously. Also, the structure determination of [SiW_<11>O_<39>]^<8-> crystallized with Na^+ and guanidinium cations revealed that the compound exhibits a novel screw structure of [SiW_<11>O_<39>]^<8-> linked by Na^+ cation, although transition metals were not incorporated into the compound. Its structure indicated a possibility that it would show non-linear optical properties and thus pulsed laser light with the wavelength of 800 nm was irradiated, resulting in the observation of second harmonic generation. In parallel with these studies, the investigator has installed and upgraded diffractometers at two synchrotron facilities : SPring-8 and Photon Factory of High Energy Accelerator Research Organization. These efforts have profited the precise structure analyses of abovementioned NLO active silicotungstate crystals as well as the structural elucidation of the molecular growth and intermolecular condensation of mixed valence molybdenum giant clusters with nanometer sized ring shape. Less
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Research Products
(45 results)
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[Journal Article] The effect of carbon chain length of the diphosphine ligand on the aurophilic interaction. Synthesis and X-ray structural study for a series of Au(I) compounds with Ph_2P-R-PPh_2 and S-(CH_2)_n-py ligands2005
Author(s)
S.Onaka, M.Yaguchi, R.Yamauchi, T.Ozeki, M.Ito, T.Sunahara, Y.Sugiura, M.Shiotsuka, K.Nunokawa, M.Horibe, K.Okazaki, A.Iida, H.Chiba, K.Inoue, H.Imai, K.Sako
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Journal Title
J. Organomet. Chem. 690
Pages: 57-68
Description
「研究成果報告書概要(和文)」より
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[Journal Article] Exploration on Au(S-4-py)PR_3 complexes as a viable building block for constructing hetero-nuclear supramolecules : synthesis and X-ray study on M(acac')_2[Au(S-4-py)PR_3]_2(ClO_4)_x (M = Cr, Cu; acac' = acetylacetonate, hexafluoro-acetylacetonate; x = 0 or 1)2005
Author(s)
K.Nunokawa, S.Onaka, Y.Mizuno, K.Okazaki, T.Sunahara, M.Ito, M.Yaguchi, H.Imai, K.Inoue, T.Ozeki, H.Chiba, T.Yosida
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Journal Title
J. Organomet. Chem. 690
Pages: 48-56
Description
「研究成果報告書概要(和文)」より
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[Journal Article] A New 19-Metal-Atom Cluster [(Me_2PhP)_<10>Au_<12>Ag_7(NO_3)_9] with a Nearly Staggered-Staggered M_5 Ring Configuration2005
Author(s)
K.Nunokawa, M.Ito, T.Sunahara, S.Onaka, T.Ozeki, H.Chiba, Y.Funahashi, H.Masuda, T.Yonezawa, H.Nishihara, M.Nakamoto, M.Yamamoto
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Journal Title
Dalton Trans.
Pages: 2726-2730
Description
「研究成果報告書概要(和文)」より
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[Journal Article] Exploration on Au(S-4-py)PR_3 complexes as a viable building block for constructing hetero-nuclear supramolecules : synthesis and X-ray study on M(acac')_2[Au(S-4-py)PR_3]_2(ClO_4)_x(M=Cr, Cu ; acac'=acetylacetonate, hexafluoro-acetylacetonate ; x=0 or 1)2005
Author(s)
K.Nunokawa, S.Onaka, Y.Mizuno, K.Okazaki, T.Sunahara, M.Ito, M.Yaguchi, H.Imai, K.Inoue, T.Ozeki, H.Chiba, T.Yosida
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Journal Title
J.Organomet.Chem. 690
Pages: 48-56
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] The effect of carbon chain length of the diphosphine ligand on the aurophilic interaction.Synthesis and X-ray structural study for a series of Au(I) compounds with Ph_2P-R-Ph_2 and S-(CH_2)_n-py ligands2005
Author(s)
S.Onaka, M.Yaguchi, R.Yamauchi, T.Ozeki, M.Ito, T.Sunahara, Y.Sugiura, M.Shiotsuka, K.Nunokawa, M.Horibe, K.Okazaki, A.Iida, H.Chiba, K.Inoue, H.Imai, K.Sako
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Journal Title
J.Organomet.Chem. 690
Pages: 57-68
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] A New 19-Metal-Atom Cluster [(Me_2PhP)_<10>Au_<12>Ag_7(NO_3)_9] with a Nearly Staggered-Staggered M_5 Ring Configuration2005
Author(s)
K.Nunokawa, M.Ito, T.Sunahara, S.Onaka, t.Ozeki, H.Chiba, Y.Funahashi, H.Masuda, T.Yonezawa, H.Nishihara, M.Nakamoto, M.Yamamoto
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Journal Title
Dalton Trans.
Pages: 2726-2730
Description
「研究成果報告書概要(欧文)」より
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