Construction of Nano Strucutures Based on Metal Cluster Complexes and Their Chemistry

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Main results are classified into three groups.A.Oligomers of triruthenium cluster [Ru_3(O)(CH_3COO)_6L_3]^<n+>.We found the existence of"Charge Transfer Isomer"in the asymmetric mixrd valence state of the pyrazine bridged cluster dimer, and studied their dynamic behavior in intramolecular elecron transfer by means of IR spectro-electrochemical method. The fact that"charge transfer isomers"exist in a single oxidation statte of mixed valence state is extremely rare. Rate constants of intramolecular electron transfer within each isomer, which results in the interconversion of the charge transfer isomer, were on the IR time scale. These results have been published in Angew.Chem.Int., 43, 1376-1381 (2004).We prepared linear oligomers of the cluster, pyrazine bridged trimer and tetramer. These oligomers were designed specifically to show multiple one electron reversible redox waves in their cyclic voltammograms. The trimer and tetramer showed, respecively, 11-step/12-electron and 14-step/15= … More electron reversible redox waves. These results have been published in Bull.Chem.Soc.Jpn.,78,591-598(2005).B.Use of Pt(II)to metal dative bond,Previously we had reported that carbon donor ligands exerted strong ligand field for platinum(II) ion, and that such platinum(II)complexes often form strong platinum to metal dative bonds. Using this idea, we prepared many of nano-sized cluster complexes with the platinum to metal dative bond. Typical examples are a tetranuclear platinum-rhodium-rhodium-platinum cluster complex and a one dimensional linear complex in which silver(I) and platinum(II) are alternately arranged. Manuscript of this study for publication is in preparation.C.Use of metal cluster forming ligand.We found in this study that p-tert-butyl-thiacalix[6]arene and p-tert-butyl-sulfonylcalix[4]arene act as cluster forming ligand. p-tert-butyl-sulfonylcalix[4]arene reacted with an excess of copper acetate to give a nano-sized decacopper cluster complex. And we found that a ferromagnetic interzcton operated in this cluster. This has been published in J.Am.Chem.Soc.,124,11274(2002). p-Tert-butyl-sulfonylcalix[4]arene reacted with lanthanoide ions to afford nano-sized compound with wheel like structure which sonsists of eight lanthanoide ions and four callixarene ligands. This study has been published in Angew.Chem.Int.,43,1382-1385(2004). Less