Pfeffer M G, Zedler L, Kupfer S, Paul M, Schwalbe M, Peuntinger K, Guldi D M, Guthmuller J, Popp J, Gräfe S, Dietzek B, Rau S
University of Ulm, Institute of Inorganic Chemistry Materials and Catalysis, Albert-Einstein-Allee 11, 89081 Ulm, Germany.
Dalton Trans. 2014 Aug 14;43(30):11676-86. doi: 10.1039/c4dt01034e. Epub 2014 Jun 20.
The synthesis and characterisation of an asymmetric potential bridging ligand bmptpphz (bmptpphz = 2,17-bis(4-methoxyphenyl)tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j] phenazine) is presented. This ligand contains a 1,10-phenanthroline (phen) and a 2,9-disubstituted phen sphere and possesses a strong absorbance in the visible. Facile coordination of the phen sphere to a Ru(tbbpy)2 core leads to Ru(bmptpphz) ((tbbpy)2Ru(bmptpphz)2; tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). UV-vis, emission, resonance Raman and theoretical investigations show that this complex possesses all properties associated with a Ru(tpphz) ((tbbpy)2Ru(tpphz)2; tpphz = tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j] phenazine) moiety and that the ligand based absorbances in the vis-part also populate an MLCT like state. The coordination of a Pd-core in the new 2,9-disubstituted phen sphere is possible, leading to a cyclometallation. The tridentate complexation leads to changes in the UV-vis and emission behaviour. Furthermore, the stability of the Pd-coordination is significantly enhanced if compared to the unsubstituted Ru(tpphz). Ru(bmptpphz)PdCl proved to be an active photocatalyst for H2 evolution, albeit with lower activity than the mother compound Ru(tpphz)PdCl2.
本文介绍了一种不对称电位桥连配体bmptpphz（bmptpphz = 2,17-双（4-甲氧基苯基）四吡啶并[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]菲嗪）的合成与表征。该配体包含一个1,10-菲咯啉（phen）和一个2,9-二取代的菲咯啉球，在可见光区具有较强的吸收。菲咯啉球与Ru(tbbpy)2核的简便配位导致形成Ru(bmptpphz)（(tbbpy)2Ru(bmptpphz)2；tbbpy = 4,4'-二叔丁基-2,2'-联吡啶）。紫外可见光谱、发射光谱、共振拉曼光谱和理论研究表明，该配合物具有与Ru(tpphz)（(tbbpy)2Ru(tpphz)2；tpphz = 四吡啶并[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]菲嗪）部分相关的所有性质，并且配体在可见光部分的吸收也填充了类似MLCT的状态。在新的2,9-二取代菲咯啉球中配位一个Pd核是可能的，导致环金属化。三齿配位导致紫外可见光谱和发射行为发生变化。此外，与未取代的Ru(tpphz)相比，Pd配位的稳定性显著增强。Ru(bmptpphz)PdCl被证明是一种用于析氢的活性光催化剂，尽管其活性低于母体化合物Ru(tpphz)PdCl2。
