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

利用二聚体的桥接配体制备了具有分子内相互作用的双核配合物聚合物。对所制备的聚合物进行了导电和磁性研究。所得结果可分为以下两组：1。采用一种双核配合物[Ru_2^<II，II>(O_2CMe)_4]与吡嗪（pyz）、4,4′-联吡啶（4,4′-bpy）和1,4-重氮杂环[2.2.2]辛烷进行了反应。得到的聚合物配合物[Ru_2^<II，II>(O_2CCMe)_4(L)]_n （L=pyz, 4,4′-bpy和dabco）通过桥接配体没有明显的磁相互作用。在L=pyz和4,4'-bpy的情况下，Ru_2^<II，II> -> Ru_2^<II，III>在聚合物中的部分氧化导致电导率从σ<10^<-10> S cm^<-1> σ=10^<-6> ~ 10^<-7>的增加。制备了其他类型的聚合物配合物[Ru_2^<II，III>(O_2CR)_4(X)]_n (X=OCN^-，SCN^-和SeCN^-)，并对其磁性能进行了研究，结果表明在Ru_2^<II，III>双核单元之间存在J= ~ 10 cm^<-1>。此外，还制备了具有长烷基链的聚合物配合物（R=CH_3(CH2)_<m->,m=5 ~ 8），可产生液晶性质，但熔点随m值的增加而增加，目前尚未观察到。双核铜（II）酞菁（pc）配合物，其中两个pc由一个共同的苯环或席夫碱连接。在双核配合物中没有观察到任何重要的磁相互作用。然而，从光谱上发现的相互作用表明，双核配合物的桥接聚合物在磁性和导电性方面具有有趣的性质。

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.