Photochemical CO2 Reduction Catalyzed by Phenanthroline Extended Tetramesityl Porphyrin Complexes Linked with a Rhenium(I) Tricarbonyl Unit.
Photochemical CO2 Reduction Catalyzed by Phenanthroline Extended Tetramesityl Porphyrin Complexes Linked with a Rhenium(I) Tricarbonyl Unit.
复制标题
DOI：
10.1021/acs.inorgchem.5b01717
复制
发表时间：
2015-10
影响因子：
4.6
通讯作者：
Corinna Matlachowski;B. Braun;S. Tschierlei;M. Schwalbe
中科院分区：
文献类型：
--
作者：
Corinna Matlachowski;B. Braun;S. Tschierlei;M. Schwalbe
以邻菲罗啉（phen）扩展四烷基卟啉配体（H2-1）为基础，制备了一系列杂双核配合物（M-1-Re）。该配体的苯基部分选择性地配位一个Re(I)三羰基氯单元，而卟啉部分的金属则是多种多样的：即使用Cu， Pd, Zn， Co或Fe。这些双核配合物用标准分析方法完全表征。此外，还获得了Cu-1-Re·5.5（C7H8）·0.5（C6H6）的晶体结构，并进行了延长时间分辨发射寿命的测量。此外，还研究了它们催化CO2光化学还原为CO的能力。以三乙胺（TEA）为牺牲电子供体，在二甲基甲酰胺（DMF）中进行了光驱动CO2还原实验。测定了CO的t（周转数），发现其惊人的催化活性明显不依赖于卟啉金属的氧化还原活性。我们最近已经证明母体M-1化合物是活性光催化剂，但催化活性取决于卟啉金属的氧化还原活性。在本研究报道的新的杂核配合物M-1-Re中，催化活性中心似乎是Re(I)部分，而不是卟啉。令人惊讶的是，Zn-1-Re被证明是该系列中活性最高的化合物，在使用>375 nm截止滤光片照射24小时后，TONCO为13，而在此条件下，所有其他化合物的活性都最低。
A series of heterodinuclear complexes (M-1-Re) based on a phenanthroline (phen) extended tetramesityl porphyrin ligand (H2-1) has been prepared. The phen moiety of this ligand selectively coordinates a Re(I) tricarbonyl chloride unit, whereas the metal in the porphyrin moiety has been varied: namely, Cu, Pd, Zn, Co, or Fe was used. These dinuclear complexes were fully characterized by standard analytical methods. Additionally, a crystal structure of Cu-1-Re·5.5(C7H8)·0.5(C6H6) could be obtained, and extended time-resolved emission lifetime measurements were conducted. Furthermore, their ability to catalyze the photochemical reduction of CO2 to CO was investigated. Light-driven CO2 reduction experiments were performed in dimethylformamide (DMF) using triethylamine (TEA) as the sacrificial electron donor. The TONs (turnover numbers) of CO were determined and revealed a surprising catalytic activity that is obviously independent from the redox activity of the porphyrin metal. We have recently shown that the parent M-1 compounds are active photocatalysts, but the catalytic activity was dependent on the redox activity of the porphyrin metal. In the case of the new heterodinuclear complexes M-1-Re reported in this study, the catalytic active center seems to be the Re(I) moiety and not the porphyrin. Surprisingly, Zn-1-Re proved to be the most active compound in this series showing a TONCO of 13 after 24 h of illumination using a >375 nm cutoff filter while all other compounds showed minimal activity under this condition.