Various photofunctional metal complexes with functional groups, i.e. bromo and vinyl groups, were integrated into hetero-multinuclear complexesusing the Mizoroki–Heck reaction. The obtained trinuclear complexes absorb a wide range of visible light and have a long excited state lifetime and the photocatalytic ability to obtain CO2 reduction.
Synthesis of Os(<scp>ii</scp>)–Re(<scp>i</scp>)–Ru(<scp>ii</scp>) hetero-trinuclear complexes and their photophysical properties and photocatalytic abilities
作者:Yasuomi Yamazaki、Osamu Ishitani
DOI:10.1039/c7sc04162d
日期:——
Photofunctional trinuclearcomplexes containing three different central metals, i.e. Os(II), Re(I) and Ru(II), were synthesised for the first time using stepwise Mizoroki–Heck reactions. The vinylene groups in the bridging ligands of the Os(II)–Re(I)–Ru(II) trinuclearcomplexes were selectively reduced by photochemical hydrogenation in moderate yield, affording novel supramolecular photocatalysts which
首次使用逐步 Mizoroki-Heck 反应合成了包含三种不同中心金属即Os( II )、Re( I ) 和 Ru( II ) 的光功能三核配合物。Os( II )-Re( I )-Ru( II )三核配合物的桥配体中的亚乙烯基通过光化学加氢以中等收率选择性还原,提供了一种新型超分子光催化剂,可吸收高达730 nm 并诱导 CO 2具有高选择性和耐久性的还原性。CO形成的周转数超过4300。还报道了这些新的三核配合物的光物理性质,特别是它们的分子内激发-能量转移现象的详细信息。
Photochemical Hydrogenation of π-Conjugated Bridging Ligands in Photofunctional Multinuclear Complexes
Vinylene or ethynylene linkers in the bridgingligands of photofunctional multinuclear complexes synthesized by various coupling reactions, such as the Mizoroki–Heck reaction, olefin metathesis, and Sonogashira coupling, were successfully converted to their corresponding saturated carbon chains using photochemical hydrogenation, which proceeded in an MeCN–pyridine–CF3COOH (3:1:0.1 v/v/v) mixed solution
通过各种偶合反应(如Mizoroki-Heck反应,烯烃复分解和Sonogashira偶合)合成的光官能多核配合物的桥联配体中的乙烯基或乙炔基连接体已通过光化学加氢成功转化为相应的饱和碳链,并在的MeCN-吡啶-CF 3 COOH(3:1:0.1 v / v / v)的混合的含起始金属配合物和1,3-二甲基-2-苯基-2,3-二氢-1-溶液ħ -苯并[ d ]咪唑(BIH)作为可见光照射下的牺牲电子供体,产率很高。Ru 2 -Re三核络合物中连接基的加氢提高了CO 2还原的光催化能力。