| Project/Area Number |
18550058
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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 | Kobe University |
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Principal Investigator |
SETSUNE Jun-ichro Kobe University, Graduate Schcol of Science, Department of Chemsilay, Professor (10117997)
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| Co-Investigator(Kenkyū-buntansha) |
LINTULUTOT Juha Mikael Kobe University, Graduate Scheel of Science, and Technology, Department of Chemsitry, Assistant Professor (20379481)
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| Project Period (FY) |
2006 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥3,950,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2007: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2006: ¥2,000,000 (Direct Cost: ¥2,000,000)
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| Keywords | porphyrinoids / octaphyrin / rhodium / palladium / pyrrole / bipyrrole / multinuclear complexes |
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| Research Abstract |
Novel multinuclear complexes of porphyrinoids are of interest because their dipyrrylmethene components can serve as monoanionic bidentate ligation to various metal. Two new dipyrrole building blacks for the porphyrinoids have been developed in this study. α-Free bipynoles having various aromatic spacers between the pyrroles were synthesized via Suzuki-coupling reactions of α-borylpyrrole with aryl dihalides. bis(azafulvene)s having various substituents were prepared via dehydration reaction from the dipyrrole dicarbinols. These new building blocks served as donors and acceptors in the macrocyclization reactions to give good yields of porphyrinoids having various aromatic spacers such as 1,4-phenylene, 1,3-phenylene, 2,5-thienylene, and 2,6-pyridylene groups. Dinurlear Rh complexes of tetraphyrins with two 1,3-phenylene spacers and the corresponding RhPd heterodinuclear complexes, the trinalear Rh complex of hexaphyrin with three 2,5-thienylene spacers, and the tetranudear Rh complex of octaphyrin with four 2,5-thienylene spacers were synthesized and their structures were determined by X-ray crystallography. Metallation of the porphyrinoids reduces flexibility of the macroring skeleton and thus the spatial arrangement of metal atoms tends to be fixed. This leads to new multi metallo sites for binding substrates and their transformations. A bowl shaped trinulear Rh complexes and a saddle shaped tetranuclear Rh complexes are of great interest as host molecules for molecular recognition. In fact, chloroform molecules were incorporated into the cavity of the tetranudear complexes in the crystal structure. The carbonyl ligands on Rh and the π-allyl ligand on Pd in the heterodinuelear RhPd complexes are considered to be very cloes. Novel cage compounds having three dipynylpyridine chains have been created in this study and their interesting binding ability was proven
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