作者:Shoko Kume、Hiroshi Nishihara
DOI:10.1039/c0dt01084g
日期:——
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.
我们构建了一系列含有不对称的4,6取代的2-吡啶基配位单元的铜配合物,这些配合物通过吡啶环的旋转形成两种配位异构体。我们在吡啶的4位引入了红氧还原活性铁氟酚基团作为这些配合物中的旋转单元。旋转异构体的稳定性和动态性可以通过调节转子结构来实现,以适应配合物内空间的大铁氟酚基团。在这些化合物中,一个含有铁氟酚烯取代基的配合物表现出铜与铁氟酚基团之间的同步分子内电子转移与旋转运动。也就是说,铁氟酚单元的氧化态依赖于其在循环轨迹中的位置。