Two polypyridine complexes containingμ‐OH,μ‐O2dicobalt(III)cores,[(TPA)CoIII(μ‐OH)(μ‐O2)CoIII(TPA)](ClO4)3and[(BPMEN)CoIII(μ‐OH)(μ‐O2)CoIII(BPMEN)](ClO4)3(TPA=tris(2‐pyridylmethyl)amine,BPMEN=N,N′‐dimet...Two polypyridine complexes containingμ‐OH,μ‐O2dicobalt(III)cores,[(TPA)CoIII(μ‐OH)(μ‐O2)CoIII(TPA)](ClO4)3and[(BPMEN)CoIII(μ‐OH)(μ‐O2)CoIII(BPMEN)](ClO4)3(TPA=tris(2‐pyridylmethyl)amine,BPMEN=N,N′‐dimethyl‐N,N′‐bis(pyridin‐2‐ylmethyl)ethane‐1,2‐diamine),have previously been reported as inactive in the light‐driven water oxidation reaction(ACS Catal.,2016,6,5062?5068).Herein,another dicobalt(III)compound,μ‐OH,μ‐O2‐[{(enN4)2Co2}](ClO4)3(enN4=1,6‐bis(2‐pyridyl‐2,5‐diazaocta‐2,6‐diene),with a similar core structure was synthesized,characterized,and applied to the light‐driven water oxidation reaction.Collective experiments showed that the complex itself was also inactive in the light‐driven water oxidation,and that the activity observed originated from Co(II)impurities.This research establishes that complexes possessing aμ‐OH,μ‐O2dicobalt(III)core structure are not appropriate choices for true molecular catalysts ofwater oxidation.展开更多
基金financially supported by the National Natural Science Foundation of China (21173105, 21773096)Fundamental Research Funds for the Central Universities (lzujbky-2016-k08)+1 种基金Open fund by Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (KHK1701)the Natural Science Foundation of Gansu (17JR5RA186)~~
文摘Two polypyridine complexes containingμ‐OH,μ‐O2dicobalt(III)cores,[(TPA)CoIII(μ‐OH)(μ‐O2)CoIII(TPA)](ClO4)3and[(BPMEN)CoIII(μ‐OH)(μ‐O2)CoIII(BPMEN)](ClO4)3(TPA=tris(2‐pyridylmethyl)amine,BPMEN=N,N′‐dimethyl‐N,N′‐bis(pyridin‐2‐ylmethyl)ethane‐1,2‐diamine),have previously been reported as inactive in the light‐driven water oxidation reaction(ACS Catal.,2016,6,5062?5068).Herein,another dicobalt(III)compound,μ‐OH,μ‐O2‐[{(enN4)2Co2}](ClO4)3(enN4=1,6‐bis(2‐pyridyl‐2,5‐diazaocta‐2,6‐diene),with a similar core structure was synthesized,characterized,and applied to the light‐driven water oxidation reaction.Collective experiments showed that the complex itself was also inactive in the light‐driven water oxidation,and that the activity observed originated from Co(II)impurities.This research establishes that complexes possessing aμ‐OH,μ‐O2dicobalt(III)core structure are not appropriate choices for true molecular catalysts ofwater oxidation.
