Syntheses and properties of new conducting ligand-bridged polymers made up by using dinuclear complexes with an intramolecular interaction and bridging ligands

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Polymers of dinuclear complexes with an intramolecular interactions have been prepared using didentate bridging ligands for the dimers. Conductive and magnetic studies have been performed for the prepared polymers. The obtained results are classified into following two groups.1.A dinuclear complex [Ru_2^<II,II>(O_2CMe)_4], which has a metal-metal within the molecule, was employed for reactions with pyrazine(pyz), 4,4'-bipyridine(4,4'-bpy), and 1,4-diazabicyclo[2.2.2]octane. The obtained polymer complexes [Ru_2^<II,II>(O_2CCMe)_4(L)]_n (L=pyz, 4,4'-bpy, and dabco) showed no significant magnetic interactions through the bridging ligands. Partial oxidations of Ru_2^<II,II> -> Ru_2^<II,III> in the polymers gave rise to the increase in conductivity (σ=10^<-6>〜10^<-7> from σ<10^<-10> S cm^<-1>) in the case of L=pyz and 4,4'-bpy. The other type of polymer complexes [Ru_2^<II,III>(O_2CR)_4(X)]_n (X=OCN^-,SCN^-, and SeCN^-) have been also prepared and investigated on their magnetic properties, showing the existence of J=〜10 cm^<-1> between the Ru_2^<II,III> dinuclear units. Furthermore, the polymer complexes with long alkyl chains (R=CH_3(CH2)_<m->,m=5〜8) have been prepared to produce the liquid-crystalline properties, which have not observed at the present stage although their melting points increased in accordance with the increase in the m value.2.Dinuclear copper(II) pthalocyanine(pc) complexes, in which two pcs are connected by a common benzene ring or Schiff-base. Any important magnetic interactions were not observed for the dinuclear complexes. However, the interactions found spectroscopically imply that the bridged polymers of the binuclear complexes could give interesting properties in magnetic and conductive properties.