Andrade Gabriel A, Pistner Allen J, Yap Glenn P A, Lutterman Daniel A, Rosenthal Joel
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE, 19716.
ACS Catal. 2013 Aug 2;3(8):1685-1692. doi: 10.1021/cs400332y.
Harnessing of solar energy to drive the reduction of carbon dioxide to fuels requires the development of efficient catalysts that absorb sunlight. In this work, we detail the synthesis, electrochemistry and photophysical properties of a set of homologous -Re(CO) complexes containing either an ancillary phenyl () or BODIPY () substituent. These studies demonstrate that both the electronic properties of the rhenium center and BODIPY chromophore are maintained for these complexes. Photolysis studies demonstrate that both assemblies and are competent catalysts for the photochemical reduction of CO to CO in DMF using triethanolamine (TEOA) as a sacrificial reductant. Both compounds and display TOFs for photocatalytic CO production upon irradiation with light (λ ≥ 400 nm) of ~5 hr with TON values of approximately 20. Although structural and photophysical measurements demonstrate that electronic coupling between the BODIPY and -Re(CO) units is limited for complex , this work clearly shows that the photoactive BODIPY moiety is tolerated during catalysis and does not interfere with the observed photochemistry. When taken together, these results provide a clear roadmap for the development of advanced rhenium bipyridine complexes bearing ancillary BODIPY groups for the efficient photocatalytic reduction of CO using visible light.
利用太阳能驱动二氧化碳还原为燃料需要开发能吸收太阳光的高效催化剂。在这项工作中，我们详细阐述了一组含有辅助苯基（）或BODIPY（）取代基的同系 -Re(CO) 配合物的合成、电化学和光物理性质。这些研究表明，对于这些配合物，铼中心和BODIPY发色团的电子性质均得以保持。光解研究表明，组件 和 都是在N,N-二甲基甲酰胺（DMF）中使用三乙醇胺（TEOA）作为牺牲还原剂将CO光化学还原为CO的有效催化剂。化合物 和 在波长（λ≥400 nm）的光照下进行约5小时的光催化CO生成反应时均显示出催化转化频率（TOF），总转化数（TON）值约为20。尽管结构和光物理测量表明，对于配合物 ，BODIPY和 -Re(CO) 单元之间的电子耦合有限，但这项工作清楚地表明，光活性BODIPY部分在催化过程中是可耐受的，并且不会干扰所观察到的光化学过程。综合来看，这些结果为开发带有辅助BODIPY基团的先进铼联吡啶配合物以利用可见光高效光催化还原CO提供了清晰的路线图。
