期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 25, 期 17, 页码 4509-4519出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201806347
关键词
CO2 reduction; electron transfer; photocatalysis; porphyrins; rhenium
资金
- German Science Foundation (DFG) [SCHW 1454/3-2]
- Australian Research Council [ARC-DP160100870/DP170101895]
- excellence cluster Unifying Concepts in Catalysis (DFG) [EXC 314]
The hetero-Pacman architecture places two different metal coordination sites in close proximity, which can support efficient energy and/or electron transfer and allow for cooperative activation of small molecules. Here, the synthesis of dyads consisting of a porphyrin unit as photosensitizer and a rhenium unit as catalytically active site, which are held together by the rigid xanthene backbone, is presented. Mononuclear [(NN)Re(CO)(3)(Cl)] complexes for CO2 reduction in which NN represents a bidentate diimine ligand (e.g., bipyridine or phenanthroline) lack light absorption in the visible region, resulting in poor photocatalysis upon illumination with visible light. To improve their visible-light absorption, we have focused on the incorporation of a strongly absorbing free base or zinc porphyrin unit. Resulting photocatalytic experiments showed a strong dependence of the catalytic performance on both the type of photosensitizer and the excitation wavelengths. Most notably, the intramolecular hetero-Pacman system containing a zinc porphyrin unit showed much better catalytic activity in the visible region (excitation wavelengths >450 nm) than the free base porphyrin version or the corresponding mononuclear rhenium compound or an intermolecular system comprised of a 1:1 mixture of the mononuclear analogues.
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