Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan.
Dalton Trans. 2011 Mar 14;40(10):2299-305. doi: 10.1039/c0dt01084g. Epub 2011 Jan 6.
We have constructed a series of copper complexes with asymmetric 4,6-substituted 2-pyrimidyl coordination units, which form two coordination isomers via rotation of the pyrimidine ring. Redox-active ferrocenyl moieties were introduced at the 4-positions of the pyrimidine as rotating units in these complexes. The stability and dynamics of the rotative interconversion could be tuned using the structure of the rotor to accommodate a large ferrocene unit within the inner space of the complex. Among these compounds, a complex with a ferrocenylvinyl substituent showed synchronized intramolecular electron transfer between the copper and the ferrocenyl moiety with rotational motion. That is, the oxidation state of the ferrocenyl unit depended on its position within a cyclic trajectory.
我们构建了一系列带有不对称 4,6-取代 2-嘧啶配位单元的铜配合物，这些配合物通过嘧啶环的旋转形成两种配位异构体。氧化还原活性二茂铁部分作为旋转单元被引入到嘧啶的 4-位。通过转子的结构可以调节旋转互变异构的稳定性和动力学，以适应大的二茂铁单元在配合物内部空间中的存在。在这些化合物中，具有二茂铁乙烯基取代基的配合物表现出铜和二茂铁部分之间的同步分子内电子转移以及旋转运动。也就是说，二茂铁单元的氧化态取决于其在循环轨迹中的位置。
