Preparation and Properties of Network Complexes with Meta-Metal Bond Redox Sites in Mixed Oxidation State

导电多孔配位聚合物是一种很有意义的材料，因为它的导电性会随吸附物分子的变化而变化。这是分子识别的电转换。导电材料的一个重要关键是存在混合氧化态的氧化还原位点。我们采用了桨轮式铑配合物作为氧化还原活性中心。它的中性和单阳离子配合物与碘化钠反应，得到混合氧化态的类金刚石网络材料，它是一种半导体，σ = 3.8 × 10^<-4>S cm^<-1>，Arrhenius活化能为160 meV。电子光谱的这一点和相关的配合物表明，电导是很好地模拟了一个小极化子机制与一个相当小的转移相互作用（β = 33 meV）。当压力增加到2 GPa时，电导率单调增加到比在大气压下观察到的值大三倍，而没有任何相变的迹象。在当前半导体脱水后，电导率降低了几个数量级。脱水后的半导体能吸附CO_2、C_2H_2、CH_3OH和CH_3CN等小分子。脱水后的半导体吸附CH_3OH或CH_3CN后，电导率增加。目前配合物的几何结构不是很强，执行详细的研究其电导率的吸附质依赖性。我们还合成了一系列卤素桥联的四（乙酰胺基）双钌链状配合物。这些配合物的特点是零场分裂常数大，相邻二钌位之间的交换作用小

Conductive porous coordination polymer is an interesting material because its conductivity may shift depending on adsorbate molecules. This is an electrical transformation of molecular recognition. An important key for conductive material is presence of redox sites in mixed oxidation state. We adopted a paddlewheel type dirhodium complex as the redox active site. Its neutral and monocationic complexes are reacted with sodium iodide to give a diamondoid network material in a mixed oxidation state and it was a semiconductor with σ = 3.8 x 10^<-4> S cm^<-1> and Arrhenius activation energy of 160 meV. Electronic spectra of this and related complexes suggested that the conductance is well modeled by a small polaron mechanism with a quite small transfer interaction (β = 33 meV). When pressure increases to 2 GPa, the conductivity increased monotonically to a three times larger value than observed at the atmospheric pressure without any indication of phase-transition. Upon dehydration of the current semiconductor, the conductivity decreased orders of magnitudes. The dehydrated semiconductor adsorbs some small molecules such as CO_2, C_2H_2, CH_3OH, and CH_3CN. When the dehydrated semiconductor adsorbed CH_3OH or CH_3CN, its conductivity increased. The geometrical structure of the current complex is not very strong to execute detailed study on the adsorbate dependence of its conductivity. We also synthesized a series halide-bridged terakis(acetamidato)diruthenium chain complexes. Characteristics of these complexes are large zero-field splitting constant and small exchange interactions between neighboring diruthenium sites