Chemical stability and characterization of rhodium-diisocyanide coordination polymers.
Chemical stability and characterization of rhodium-diisocyanide coordination polymers.
复制标题
铑-二异氰化物配位聚合物的化学稳定性和表征。
DOI：
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发表时间：
2007
影响因子：
3.3
通讯作者：
R. Tannenbaum
中科院分区：
文献类型：
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作者：
C. Carson;R. Gerhardt;R. Tannenbaum
聚[Rh（1，4-phenylene diisocyanide）+4/2（Cl）-]具有二维模板结构，其中Rh原子在x-y平面上通过共轭的1，4-phenylene diisocyanide（pdi）配体键合，在z方向上通过重叠的dz轨道键合。z方向上的导电性更高的金属键在电导率中产生各向异性。poly-[Rh（pdi）+4/2（Cl）-]的各向异性和独特的几何结构使其成为研究金属-异氰化物分子线系统中电性能和化学稳定性之间关系的有用测试床。估计聚-[Rh（pdi）+4/2（Cl）-]的本体粉末具有3.4 × 10（-11）S × cm（-1）的室温本体电导率、0.9 eV的电激活能和7.5的介电常数。本文用交流阻抗谱和X射线粉末衍射研究了聚[Rh（pdi）+4/2（Cl）-]粉末的金属-金属键合对导电性的影响。热重分析和X射线光电子能谱被用来证明在聚合物的空气敏感性和阐明的氧化降解的机制。
Poly-[Rh(1,4-phenylene diisocyanide)+4/2(Cl)-] has a two-dimensional template structure, where Rh atoms are bonded by the -conjugated 1,4-phenylene diisocyanide (pdi) ligands in the x-y plane and through overlapping dz orbitals in the z direction. The more conductive metallic bonds in the z direction create anisotropy in the electrical conductivity. The anisotropy and unique geometry of poly-[Rh(pdi)+4/2(Cl)-] make it a useful test bed for examining the relationship between electrical properties and chemical stability in metal-isocyanide molecular wire systems. The bulk powder of poly-[Rh(pdi)+4/2(Cl)-] is estimated to have a room-temperature bulk conductivity of 3.4 x 10(-11) S x cm(-1), an electrical activation energy of 0.9 eV, and a dielectric constant of 7.5. In this paper, impedance spectroscopy and X-ray powder diffraction were used to show the dependence of the electrical conductivity on the metal-metal bonding of pressed bulk powders of poly-[Rh(pdi)+4/2(Cl)-]. Thermo-gravimetric analysis and X-ray photoelectron spectroscopy were used to demonstrate air sensitivity in the polymer and elucidate the mechanism of oxidative degradation.