Sensitized and Self‐Sensitized Photocatalytic Carbon Dioxide Reduction Under Visible Light with Ruthenium Catalysts Shows Enhancements with More Conjugated Pincer Ligands
Sensitized and Self‐Sensitized Photocatalytic Carbon Dioxide Reduction Under Visible Light with Ruthenium Catalysts Shows Enhancements with More Conjugated Pincer Ligands
复制标题
钌催化剂在可见光下的敏化和自敏化光催化二氧化碳还原显示出更多共轭钳配体的增强
DOI：
10.1002/ejic.202101016
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发表时间：
2022
影响因子：
2.3
通讯作者：
Papish, Elizabeth T.
中科院分区：
文献类型：
--
作者：
Das, Sanjit;Nugegoda, Dinesh;Yao, Wenzhi;Qu, Fengrui;Figgins, Matthew T.;Lamb, Robert W.;Webster, Charles Edwin;Delcamp, Jared H.;Papish, Elizabeth T.
本文介绍了一种合成[(CNC)RuII(NN)L]n+型配合物的新方法，其中CNC是由两个（benz）咪唑衍生的NHC环和一个吡啶环组成的三齿钳形结构，NN是双齿芳香二亚胺配体，L=溴或乙腈，n=1或2。根据这种新方法，合成了一系列六种新的配合物，并通过光谱、分析、晶体学和计算方法对其进行了表征。用循环伏安法研究了它们在n2和co2两种气氛下的电化学性质。使用这些配合物在存在（敏化）和不存在（自敏化）外部光敏剂的情况下将co2光催化还原为CO。本研究评估了不同的CNC、NN和L配体在敏化和自敏化光催化中的作用。与含有咪唑衍生CNC钳的催化剂相比，含有苯并咪唑衍生CNC钳的催化剂在敏化和自敏化光催化方面都表现出更好的活性。此外，自敏光催化需要一个二亚胺配体来还原co2，其中催化剂2acn2是该系列中最活跃的催化剂，TON=85， TOF=22 h - 1，带有一个供电子的4,4 ' -二甲基- 2,2 ' -联吡啶（dmb）配体和一个苯并咪唑衍生的CNC钳。
A new method to synthesize complexes of the type [(CNC)RuII(NN)L]n+has been introduced, where CNC is a tridentate pincer composed of two (benz)imidazole derived NHC rings and a pyridyl ring, NN is a bidentate aromatic diimine ligand, L=bromide or acetonitrile, and n=1 or 2. Following this new method a series of six new complexes has been synthesized and characterized by spectroscopic, analytic, crystallographic, and computational methods. Their electrochemical properties have been studiedviacyclic voltammetry under both N2and CO2atmospheres. Photocatalytic reduction of CO2to CO was performed using these complexes both in the presence (sensitized) and absence (self‐sensitized) of an external photosensitizer. This study evaluates the effect of different CNC, NN, and L ligands in sensitized and self‐sensitized photocatalysis. Catalysts bearing the benzimidazole derived CNC pincer show much better activity for both sensitized and self‐sensitized photocatalysis as compared to catalysts bearing the imidazole derived CNC pincer. Furthermore, self‐sensitized photocatalysis requires a diimine ligand for CO2reduction with catalyst2ACNbeing the most active catalyst in this series with TON=85 and TOF=22 h−1with an electron donating 4,4′‐dimethyl‐2,2′‐bipyridyl (dmb) ligand and a benzimidazole derived CNC pincer.