多联吡啶Pt(Ⅱ)、Pd(Ⅱ)配合物的合成及制氢研究

Synthesis and photocatalytic H_2 of novel platinum(Ⅱ) and palladium(Ⅱ) polypyridine complexes

把电子受体苄基紫精引入到多联吡啶中,设计合成了新型三齿多吡啶配体[HC∧N∧N(PhMV2+Ph)],并以其合成了新配合物[C1Pt{C∧N∧N(PhMV2+Ph)}](ClO4)、[C1Pd{C∧N∧N(PhMV2+Ph}](PF6)2。用核磁共振氢谱表征了配体和配合物的结构,证实所得合成产物与设计结构一致;利用UV研究了配体及配合物的光谱性质,两种配合物在可见光区有MLCT吸收;采用三组分的"S-R/D/C"体系,对配合物[C1Pt{C∧N∧N(PhMV2+Ph)}](ClO4)2的光解水制氢行为进行了初步研究,并与[ClPt{C^N^N(PhMV2+)}](PF6)2及没有实现敏化剂与电子中继体MV2+直接连接的四组分体系ClPt[C∧N∧N(PhCH3)]做了对比。结果表明对于光敏剂与电子受体共价连接的Pt(Ⅱ)多吡啶类配合物,制氢效果并没有提高。

The novel ligand, [ C∧N∧N（PhMV2＋ Ph） ], has been designed and synthesized, combining the electron acceptor benzyl viologen group with polypyridine,which then was used to synthesize[ C1Pt{ C∧N∧N（PhMV2＋Ph） J ] （C104）2 and[ C1Pd{C∧N∧N（PhMV2＋Ph/ ] （PF6）2. The ligand and the complexes had been characterized by ^1H NMR, confirming that their structure was consistent with the design. The spectral properties of the ligand and the complexes were investigated using UV. The complexes had MLCT absorption in the visible spectral region. Photoeatalytic water splitting by visible light of[ C1Pt{C∧N∧N（PhMV2＋Ph） } ] （ ClO4） 2 was studied by the＂ S-R/D/C＂ systems, comparing with [ C1Pt { C ^ N ^ N （ PhMV2＋ ） } ] （ PF6 ） 2, and C1Pt [ C ^ N ^ N （PhCH3 ） ] ,which was a four-part system not linking photosensitizer and MV2＋. It showed that the effect for hydrogen generation of polypyridyl Pt（ II）complexes about photosensitizer and electron aeeeptor covalently linked had not been improved.