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

用二聚体的双齿桥联配体合成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学研究。得到的结果分为两类：1.分子中含有金属-金属的双核配合物[Ru_2^&lt；II，II&gt；(O_2CMe)_4]用于与吡嗪(PYZ)、4，4‘-联吡啶(4，4’-bpy)和1，4-二氮杂双环[2.2.2]辛烷的反应。得到的聚合物配合物[Ru_2^&lt；II，II&gt；(O_2CCMe)_4(L)]_n(L=PYZ，4，4‘-bpy和dabco)通过桥联配体没有表现出明显的磁相互作用。在L=PYZ和4，4‘-BPY的情况下，聚合物中Ru_2^&lt；II，II&gt；-&gt；Ru_2^&lt；-6&gt；~10^&lt；-7&gt；σ=σ&lt；10^&lt；-10&gt；-1&gt；-1&gt；我们还合成了另一类聚合物配合物[Ru_2^&lt；II，III&gt；(O_2CR)_4(X)]_n(X=OCN^-，SCN^-和SECN^-)，并研究了它们的磁性。此外，我们还合成了具有长烷基链的聚合物络合物(R=CH3(CH2)_&lt；m-&gt；，m=5~8)，虽然它们的熔点随着m值的增加而升高，但在现阶段还没有观察到的液晶性质。2.双核铜(II)酞菁(PC)络合物，其中两个PC通过共同的苯环或Schiff碱连接。没有观察到双核配合物的任何重要的磁相互作用。然而，光谱上发现的相互作用表明，双核配合物的桥联聚合物可以在磁性和导电性能方面提供有趣的性质。

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.