Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, PR China.
Chem Asian J. 2010 Aug 2;5(8):1796-803. doi: 10.1002/asia.201000087.
To mimic [FeFe] hydrogenases (H(2)ases) in nature, molecular photocatalysts 1 a, 1 b, and 1 c anchoring rhenium(I) complex S to one of the iron cores of [FeFe]-H(2)ases model complex C, have been constructed for H(2) generation by visible light in homogeneous solution. The time-dependence of H(2) evolution and a spectroscopic study demonstrate that the orientation of S and the specific bridge in 1 a, 1 b, and 1 c are important both for the electron-transfer step from the excited S* to the catalytic C, and the formation of unprecedented long-lived charge separation for 1 a (780 micros), 1 b, and 1 c (>2 ms) in [FeFe]-H(2)ases mimics. The fast forward electron-transfer step from the excited S* to the catalytic C but the slow back electron-transfer step of the charge-recombination in the designed photocatalysts 1 a, 1 b, and 1 c are reminiscent of the behavior of [FeFe]-H(2)ases in nature.
为了模拟自然界中的[FeFe]氢化酶（H（2）ases），将钌（I）配合物 S 锚定到[FeFe]-H（2）ases 模型配合物 C 的一个铁核上的分子光催化剂 1a、1b 和 1c 已被构建用于在均相溶液中通过可见光产生 H（2）。H（2）演化的时间依赖性和光谱研究表明，S 的取向和 1a、1b 和 1c 中特定桥的方向对于从激发态 S到催化 C 的电子转移步骤以及前所未有的长寿命电荷分离的形成都很重要在 [FeFe]-H（2）ases 模拟物中，1a（780 微秒）、1b 和 1c（>2 ms）。从激发态 S到催化 C 的快速正向电子转移步骤，但在设计的光催化剂 1a、1b 和 1c 中电荷复合的缓慢反向电子转移步骤，类似于自然界中[FeFe]-H（2）ases 的行为。
