富勒烯吡咯金属配合物的合成、表征及光电性能

Synthesis,Characterization and Photovoltaic Property of Pyrrolidine Ring-fused Metallo-fullerenes

采用肌氨酸甲酯(CH_3NHCH_2COOMe)与C_(60)光化学反应制得富勒烯吡咯衍生物(C_(60)Pyr),产率为67％(基于已反应的C_(60)),并以其为配体,在N_2气气氛下利用配体取代法合成了富勒烯吡咯金属配合物(PyrC_(60))-Pd(dppe),产率为51％(基于C_(60)吡咯衍生物)。采用元素分析、质谱、紫外-可见吸收光谱、红外光谱、X射线光电子能谱和核磁共振(^(31)P NMR)等测试技术对中间物及产物进行了表征,同时在光电化学电池中于GaAs电极上测量了化合物(PyrC_(60))-Pd(dppe)的光伏效应(PVE),研究了介质电对、配合物薄膜厚度对光电性能的影响。研究结果表明,(PyrC_(60))-Pd(dppe)/GaAs电极的值比单纯的GaAs电极的ΔV和ΔI相应值大得多,这种化合物具有优良的光电性能。尤其在O_2/H_2O介质电对中,光生电压值最大可达230 mV,光生电流最大可达8．7μA。镀层厚度在0．5～1μm时,光伏效应值较大。

Pyrrolidine ring-fused fullerene derivative （C60Pyr） was prepared by photolysis via the reaction of C60 with CH3NHCH2COOMe in 67% yield（ based on consumed C60）. The product （PyrCro） -Pd（dppe） was obtained by the method of ligand substitution via the reaction of C60Pyr with Pd（dppe） 2 in nitrogen atmosphere at room temperature in 51% yield（ relative to C60Pyr）. The products were characterized by means of elemental analysis, IR, UV-Vis, X-ray photoelectron spectroscopy and ^31P NMR. The photovoltaic effect（PVE） of the compound on GaAs electrode in electrochemical photovohaic cell were measured. Influences of various redox couples and the thickness of the complex film were observed. The results show that the values of ΔV and ΔI for （PyrC60）-Pd（dppe）-GaAs electrode are much greater than those for pure GaAs electrode. So that the photoelectric properities for the compound are excellent, especially in the O2/H2O redox couple, the greatest value of photovohaic potential was 230 mV, and the greatest value of photovohaic current was 8.7 μA. The results showed that （ PyrC60 ） -Pd（ dppe）/GaAs electrode at 0. 5 - 1 μm for thinckness of （ PyrC60 ） -Pd （ dppe ） film was the best.