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Noble and transition metal aromatic frameworks: Synthesis, properties, and stability.

机译：贵金属和过渡金属芳香族骨架：合成，性质和稳定性。

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In the first section, the electrical conductivity of rhodium phenylene-diisocyanide polymer is reported to be 3.4 x 10-11 S·cm-1. However, the conductivity also exhibits an inverse exponential decay in air with tau = 8 days. This change is attributed to the oxidation of the isocyanide functional group to an isocyanate, leading to a degradation in the long-range metal-metal bonding, the dominant conductivity mechanism. Using a more stable carboxylate ligand, the Cu terephthalate (TPA) system is studied and compared against the Mg, Co, Ni, and Zn terephthalates. A synthesis in N,N-dimethylformamide (DMF) is developed and large quantities of the Cu(TPA)·DMF can be synthesized in air. The crystal structure of the Cu(TPA)·DMF is shown to be in the C 2/m spacegroup. Upon desolvation, the Cu(TPA) is shown to have a large surface area of 625 m2g-1. The magnetic susceptibility of the Cu(TPA) indicates anti-ferromagnetic coupling between adjacent Cu centers in the same dimer. The thermal stability of the Zn, Ni, Co, and Mg terephthalates is shown to increase with decreasing symmetric carboxylate stretch in the IR. The magnetic susceptibilities of the Co and Ni terephthalates have paramagnetic behavior, with a Weiss temperature of theta = -12.9 K and theta = 8.8 for Co(TPA)·DMF and Ni(TPA)·DMF respectively. A heterometallic Zn-Cu terephthalate is synthesized with Cu concentrations ranging from 0 to 100%. Upon the addition of Cu, Zn-rich frameworks increase in surface area, change in thermal stability, and increase solvent retention from 16% to 25%. Zn is shown to couple with Cu in the same dimer at a high rate, changing the behavior of the dimer from anti-ferromagnetic to paramagnetic. The Weiss temperature suggests weak ferromagnetic interaction.
机译：在第一部分中，铑亚苯基二异氰酸酯聚合物的电导率据报道为3.4 x 10-11 S·cm-1。但是，电导率在tau = 8天时在空气中也表现出反指数衰减。该变化归因于异氰酸酯官能团被氧化为异氰酸酯，导致长程金属-金属键的降解，这是主要的导电机理。使用更稳定的羧酸盐配体，对苯二甲酸铜（TPA）系统进行了研究，并与对苯二甲酸Mg，Co，Ni和Zn进行了比较。已开发出在N，N-二甲基甲酰胺（DMF）中的合成方法，并且可以在空气中合成大量的Cu（TPA）·DMF。 Cu（TPA）·DMF的晶体结构显示为C 2 / m空间群。脱溶剂后，显示出Cu（TPA）具有625 m2g-1的大表面积。 Cu（TPA）的磁化率表明同一二聚体中相邻Cu中心之间的反铁磁耦合。红外图中显示，对苯二甲酸锌，镍，钴和镁的热稳定性随对称羧酸盐拉伸量的减少而增加。钴和对苯二甲酸镍的磁化率具有顺磁性，Co（TPA）·DMF和Ni（TPA）·DMF的Weiss温度分别为theta = -12.9 K和theta = 8.8。合成的杂金属Zn-Cu对苯二甲酸酯的Cu浓度范围为0至100％。加入铜后，富锌骨架的表面积增加，热稳定性发生变化，溶剂保留率从16％增加到25％。 Zn在同一二聚体中与Cu的耦合速率很高，从而将二聚体的行为从反铁磁性变为顺磁性。魏斯温度表明铁磁相互作用弱。

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