席夫碱锌酞菁的合成及其性能研究

Synthesis of Schiff base zinc phthalocyanines and to study the properties

摘要:

以4-硝基邻苯二甲腈为主要原料，合成两种席夫碱锌酞菁：2(3),9(10),16(17),23(24)-四(4-苯亚胺苯氧基)锌酞菁(C84H52N12O4Zn)(APc)和2(3)-[(2-甲基-8-羟基喹啉基]-9(10),16(17),23(24)-三(4-苯亚胺苯氧基)锌酞菁(C81H50N12O4Zn)(BPc)。通过核磁、红外、紫外、元素分析等手段对其结构进行表征。结果表明：浓度在1.499×10-5～2.407×10-5 mol/L时，APc有J聚集存在，而BPc在所测浓度范围内不发生聚集；APc和BPc的Q带的最大吸收峰分别在672nm和676nm，与无取代的酞菁锌669nm相比，明显红移。采用循环伏安法对其电化学性质和能级结构进行研究，这两种锌酞菁的LUMO(－5.411 eV，－5.384 eV)和HOMO(－4.214 eV，－4.210 eV)与纳米TiO2 导带能级匹配。

Abstract:

2(3),9(10),16(17),23(24)-tri-(4-phenylimine phenoxy) phthalocyanine zinc(Ⅱ) (C84H52N12O4Zn)(APc) and 2(3)-(2-methyl-8-quinolinoxy)-9(10),16(17),23(24)-tetra- (4-phenylimine phenoxy phthalocyanine zinc(Ⅱ) (C81H50N12O4Zn) (BPc) were synthesized from 4-hydroxybenzaldehyde and characterized by UV-Vis, IR, 1H NMR spectra and elemental analysis. The aggregative behavior was studied in DMF by UV-Vis. The results show that BPc is not aggregative in DMF. However, APc is aggregative in DMF at the concentration of 1.499×10-5 mol/L～2.407×10-5 mol/L. The Q-band maximum absorption peaks of APc and BPc at 672nm and 676nm, compared with the unsubstituted zinc phthalocyanine(669nm) have red shift obviously. The electrochemical properties and energy band structure are studied by cyclic voltammetry. They have low LUMO (－5.411 eV，－5.384 eV) and a deep HOMO (－4.214 eV，－4.210 eV) energy level. It is indicated that APc and BPc matches with the energy level of the nanocrystalline of TiO2.