School of Chemical Sciences, SRC in Solar Energy Conversion, Dublin City University, Dublin 9, Ireland.
Phys Chem Chem Phys. 2014 Mar 21;16(11):5229-36. doi: 10.1039/c3cp55347g.
Two BODIPY-cobaloxime complexes; [{Co(dmgH)2Cl}{3-[bis-(4-ethyl-3,5-dimethyl-1H-pyrrol-2-yl)-methyl]-pyridine-borondiflouride}] (1a) and [{Co(dmgH)2Cl}{4-[bis-(4-ethyl-3,5-dimethyl-1H-pyrrol-2-yl)-methyl]-pyridine-borondiflouride}] (2a) (BODIPY = boron dipyrromethene), (dmgH = dimethylglyoxime) have been synthesised and studied as model catalytic systems for the generation of hydrogen gas in aqueous media. Under photochemical conditions, neither complex catalysed the reduction of water to hydrogen. However, both complexes showed considerable activity under electrochemical conditions. Turn-over-numbers for hydrogen production of 1.65 × 10(4) and 1.08 × 10(4) were obtained for 1a and 2a respectively following potentiostatic electrolysis at -1.2 V vs. Ag/AgCl after 1 hour. Quantum chemical calculations were performed to provide an explanation for the lack of photochemical activity.
两个 BODIPY-钴配合物; [{Co(dmgH)2Cl}{3-[双-(4-乙基-3,5-二甲基-1H-吡咯-2-基)-甲基]-吡啶-硼二氟化物}] (1a) 和 [{Co(dmgH)2Cl}{4-[双-(4-乙基-3,5-二甲基-1H-吡咯-2-基)-甲基]-吡啶-硼二氟化物}] (2a) (BODIPY = 硼二吡咯甲川), (dmgH = 二甲基乙二肟) 已被合成并作为模型催化体系研究用于在水介质中产生氢气。在光化学条件下，没有一种配合物能催化水还原为氢气。然而，在电化学条件下，这两种配合物都表现出相当大的活性。在 -1.2 V 相对于 Ag/AgCl 的电位下进行 1 小时的恒电位电解后，分别获得了 1a 和 2a 的产氢周转数为 1.65×10(4)和 1.08×10(4)。进行了量子化学计算，以解释缺乏光化学活性的原因。
