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

导电性多孔配位聚合物是一种有趣的材料，因为它的导电性会随着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在混合氧化态中存在氧化还原位点。我们采用桨轮式配合物作为氧化还原活性位点。它的中性和单离子配合物与碘化钠反应得到混合氧化态的金刚石网络材料，是一个σ = 3.8 × 10^<-4> S cm^<-1>的半导体，Arrhenius活化能为160 meV。该配合物及相关配合物的电子谱表明，电导率可以用一个很小的极化子机制来很好地模拟，转移相互作用很小（β = 33 meV）。当压力增加到2gpa时，电导率单调增加到常压下的3倍，没有任何相变迹象。在电流半导体脱水后，电导率下降了几个数量级。脱水后的半导体吸附了一些小分子，如CO_2、C_2H_2、CH_3OH和CH_3CN。当脱水半导体吸附CH_3OH或CH_3CN时，其电导率提高。目前络合物的几何结构不是很强，无法对其电导率对吸附物的依赖性进行详细的研究。我们还合成了一系列卤化物桥接的terakis(acetamidato) di钌链配合物。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