Syntheses and Magnetic and Conductive Properties of New Low-Dimensional Complexes

众所周知，酞菁（Pcs）在其部分氧化时表现出显著的电导率增加，这是由于酞菁环基于增强的π-π相互作用而不断堆叠。然而，当温度降低时，电导率突然下降，这可以用佩尔斯转变来解释。本研究新制备了一种双核酞菁铜（CuPc(t-Bu)_3） _2，用于研究双核酞菁配合物在层叠结构中产生π-π以外的相互作用来消除佩尔斯问题的能力。观察到的分子内Pc-Pc相互作用表明，双核pc有望以这种方式开发低维材料。然而，没有观察到金属离子之间的分子内磁相互作用，尽管这种相互作用被认为对低维化合物的性质起着重要作用。对其他具有二核酞菁碱配体的顺磁性金属离子进行了研究。用双核金属配合物M_2(O_2CR)_4 (M = Ru(II，III), Rh（II), Mo(II)）和各种桥接配体制备了聚合物配合物。钌（II，III）二聚体有三个未成对电子。与氮氧自由基反应得到钌（II，III）二聚体的聚合物，由自由基轴向连接。磁性数据表明二聚体与自由基之间存在很强的相互作用，但没有观察到基于交替S=3/2 （Ru_2）和S=1/2（氮氧化物）排列的预期的铁磁性。铑（II）二聚体与吡嗪、4,4′-联吡啶和1,4 -重氮双环[2.2.2]辛烷相连。通过x射线晶体分析证实了该聚合物的结构。还制备了含对醌（9,10 -蒽醌、1,4 -萘醌和2,6 -二甲基- 1,4 -苯醌）的钼（II）聚合物。对其x射线结构的详细分析表明二聚体与对醌之间存在相互作用。上述结果表明，具有金属-金属键的二聚体配合物是与链接配体结合的金属组装配合物的有用构建块。少

Phthalocyanines (Pcs) are well known to show remarkable increase in electrical conductivity on their partial oxidation, being originated from continuously stacking of the phthalocyanine rings based on the enhanced π-π interaction. However, the conductivity abruptly decreases when the temperature is lowered, which is explained in terms of Peierls-transition. In this research, a dinuclear copper (II) phthalocyanine ([CuPc(t-Bu)_3]_2) was newly prepared for investigation on ability of the dinuclear phthalocyanine complexes to get rid of the Peierls problem by giving rise to interaction other than the π-π one in the stacked structure. The observed intramolecular Pc-Pc interaction indicated that the dinuclear Pcs would be promising for developing low-dimensional materials in this way. However, no significant intramolecular magnetic interaction between the metal ions was observed although the interaction is considered to play an important role for the properties of the low-dimensional compou … More nds. The investigation on the other paramagnetic metal ions with dinucleating phthalocynine ligands will be performed.Polymer complexes have been prepared using dinuclear metal complexes M_2(O_2CR)_4 (M = Ru(II,III), Rh(II), Mo(II)) and various bridging ligands. The ruthenium (II,III) dimers have three unpaired electrons. Reactions with nitroxide radicals gave polymers of ruthenium (II,III) dimers axially linked by the radicals. The magnetic data showed strong interactions between the dimers and radicals, though an expected ferrimagentic property based on the alternated S=3/2 (for Ru_2) and S=1/2 (for nitroxide) arrangement was not observed. The rhodium (II) dimers were linked with pyrazine, 4, 4'-bipyridine, and 1, 4-diazabicyclo [2.2.2] octane. The polymer structure was confirmed by X-ray crystal analysis for the bipyridine complex. The molybdenum (II) polymers with p-quinones (9, 10-anthraquinone, 1, 4-naphthquionone, and 2, 6-dimethyl-1, 4-benzoquinone) were also prepared. The detailed analyses based on their X-ray structures indicated existence of interactions between the dimers and p-quinones. The above obtained results implies that the dimer complexes having metal-metal bonds are useful building blocks for metal-assembled complexes in combination with linkage ligands. Less