| Budget Amount *help |
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 2006: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2005: ¥1,100,000 (Direct Cost: ¥1,100,000)
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| Research Abstract |
Main results are four following studies.
A. linear oligomers of redox active trirthenium cluster [Ru_3(O)(CH_3COO)_6L_3]^<n+>.
We published redox properties of linear oligomers of triruthenium cluster in a technical book of the redox chemistry area, "Redox Systems Under Nano-Space Control" (Springer, 2006). The compounds reported in this book were designed specifically to show multistep-one electron reversible redox waves in their cyclic voltammograms.
B. Mixed valence isomers.
We prepared two asymmetric mixed valence clusters, dimmers of trirthenium cluster [Ru_3(O)(CH_3COO)_6L_3]^<nn+>, bridged by 2-methyl-pyrazine. The dynamic behavior of these compounds concerning intramolecular elecron transfer has been studied by means of IR spectro- electrochemistry. The results show that "mixed-valence isomers" exist in a single oxidation statte of each mixed valent compound, and that rate constants of intramolecular electron transfer within each isomer, which results in the interconversion of the
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charge transfer isomer, were on the IR time scale (J. Am. Chem. Soc., 127, 2382-2383 (2005)).
C Ferromagnetic coupling promoted by k^3N : k^2N bridging system.
Syntheses, structures and magnetic properties of four novel trinuclear complexes of the same motif [M{Cu(pz_2bg)_2}M]^<4+> (M = Cu^<II>, Ni^<II>, Co^<II>, Mn^<II>), which include the complex ligand [Cu(pz_2bg)_2], are reported (pz_2bg-= di(pyrazolecarbimido)aminate; bis-pyrazolyl derivative of biguanidate). The ferromagnetic interaction operated in all the compounds was ascribed to the strict orthogonality of magnetic dσ orbitals, which are controlled by the k^3N : k^2N bridging geometry of pz_2bg-ligands (Inorg. Chem., 46, 6460-6466 (2006)).
D. Tetranuclear cluster complexes supported by a cluster forming ligand, p-tert-butylsulfonylcalix[4]arene.
Three square-planar tetranuclear clusters [M_4(L)(AcO) _4 (μ_4-OH)] (M=Mn^<II>, Co^<II>, and Ni^<II>) were synthesized using tetra-anionic p- tert-butylsulfonylcalix[4]arene (L^<4->)as a cluster forming ligand. Their structures and properties are reported along with syntheses. Less
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