A photo- and electrochemical investigation of BODIPY-cobaloxime complexes for hydrogen production, coupled with quantum chemical calculations

作者：Manton Jennifer C; Long Conor; Vos Johannes G; Pryce Mary T^*

来源：Physical Chemistry Chemical Physics, 2014, 16(11): 5229-5236.

DOI：10.1039/c3cp55347g

Two BODIPY-cobaloxime complexes; [{Co(dmgH)(2)Cl}{3-[bis-(4-ethyl-3,5-dimethyl-1H-pyrrol-2-yl)-methyl]-pyridine- borondiflouride}] (1a) and [{Co(dmgH)(2)Cl}{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 x 10(4) and 1.08 x 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.

• 出版日期2014