硫代多联吡啶铂(Ⅱ)配合物的合成、性质及在光催化制氢中的应用

合成了2个新配体4-(4-硫代乙酸)甲苯基-6-苯基-2,2'-联吡啶HC^N^N(PhCH₂SCOCH₃)(L3)和6-(4-硫代乙酸)甲苯基-2,2'-联吡啶 HC^N^N (CH₂SCOCH₃)(L5)及其发光的铂(Ⅱ)配合物ClPtC^N^N(PhCH₂SCOCH₃)(C3)和ClPtC^N^N(CH₂SCOCH₃)(C5). 通过¹H NMR谱和质谱对它们的结构进行了表征, 采用X射线单晶衍射分析确定了C3的晶体结构. 利用紫外-可见吸收光谱、 发射光谱及激发态寿命测定研究了它们的光物理性质和电化学性质, 以及配合物作为光敏剂在光催化制氢中的应用. 通过系列配合物产氢效率的比较, 揭示了它们的产氢效率和激发态寿命的关系.

Syntheses,Properties and Photocatalytic Hydrogen Evolution Efficiency of Cyclometalated Pt(Ⅱ) Complexes Bearing S-methylphenyl Group†

Two new ligands 4-(p-thioacetic-S-methylphenyl)-6-phenyl-2,2'-bipyridineHC^N^NPh·(CH₂SCOCH₃), L3] and 6-(p-thioacetic-S-methylphenyl)-2,2'-bipyridine HC^N^N(CH₂SCOCH₃), L5] as well as their platinum(Ⅱ) complexes ClPtC^N^N(PhCH₂SCOCH₃)(C3) and ClPtC^N^N·(CH₂SCOCH₃)(C5) were synthesized and characterized by ¹H nuclear magnetic resonance(¹H NMR), electrospray ionization mass spectra(ESI-MS) and X-ray diffraction(XRD) analysis. Photophysical and electrochemical properties of the complexes were studied based on the UV-Vis absorption and emission spectra, excited-state lifetime measurements. It was found that photogenerated hydrogen efficiencies of ClPtC^N^N(CH₃)(PhCH₃)](C1), ClPtC^N^N(PhCH₃)](C2), C3, ClPtC^N^N(CH₃)](C4) and C5 are in accordance with their emission lifetimes, and are arranged in the order C4>C1>C5>C2>C3.