Lang Philipp, Habermehl Johannes, Troyanov Sergey I, Rau Sven, Schwalbe Matthias
Institute of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
Department of Inorganic Chemistry I, University of Ulm, Albert-Einstein-Allee 11, 89077, Ulm, Germany.
Chemistry. 2018 Mar 2;24(13):3225-3233. doi: 10.1002/chem.201704999. Epub 2018 Feb 5.
A series of heterodinuclear complexes, M-1-PtX with M=H , Zn, Cu or Co, X=Cl or I, has been synthesized, and first results on their photocatalytic activity in visible light driven proton reduction are presented. The compounds are based on a phenanthroline extended meso-tetramesityl-porphyrin bridging ligand (H -1) incorporating different metal centers in the porphyrin moiety, which functions as a photosensitizer unit. The well-known catalytically active PtX fragment resides in the phenanthroline coordination pocket. The synthesis was optimized, compounds were fully characterized and a solid-state structure could be obtained for selected complexes. Photocatalytic studies in acetonitrile/water mixtures using triethylamine as sacrificial electron donor showed that the activity of the complexes depends strongly on the metal center in the porphyrin moiety as well as the halogen ions bound at the platinum(II) center.
已合成了一系列异双核配合物M-1-PtX，其中M = H、Zn、Cu或Co，X = Cl或I，并首次展示了它们在可见光驱动质子还原中的光催化活性。这些化合物基于一种菲咯啉扩展的中位四(对甲苯基)卟啉桥连配体（H -1），该配体在卟啉部分引入了不同的金属中心，其作为光敏剂单元发挥作用。著名的具有催化活性的PtX片段位于菲咯啉配位口袋中。优化了合成方法，对化合物进行了全面表征，并获得了所选配合物的固态结构。使用三乙胺作为牺牲电子供体在乙腈/水混合物中进行的光催化研究表明，配合物的活性强烈依赖于卟啉部分的金属中心以及铂(II)中心上结合的卤素离子。
