苯基席夫碱取代锌酞菁的合成与性能研究

Synthesis and Properties studies of Benzylidene Schiff Base Substituted Zinc Phthalocyanine

摘要:

以AlCl3/Et3N为催化剂，4-氨基邻苯二甲腈、4-甲基苯甲醛和4-甲氧基苯甲醛为主要原料，制得两种苯基席夫碱取代邻苯二甲腈，经四聚反应生成2(3), 9(10), 16(17), 23(24)-四-(4-甲基-苯亚胺基)锌酞菁(SPc)和2(3), 9(10), 16(17), 23(24)-四-(4-甲氧基-苯亚胺基)锌酞菁(SOPc)。利用IR、1HNMR、13CNMR和元素分析对其结构进行了表征，并通过UV-Vis光谱、循环伏安法检测其性能。结果表明：SPc和SOPc的Q带相比于无取代酞菁分别红移了35 nm和43 nm，在450~600 nm范围内具有较弱吸收。SPc 和SOPc在0.002~0.010 mmol/L DMF溶液中，主要以单体形式存在，无聚集。用循环伏安法研究合成酞菁的氧化还原性质，结果表明：SPc和SOPc的ELUMO值分别为-3.24 eV、 -3.29eV，EHOMO值分别为-4.88eV、-4.71eV，且SPc和SOPc的能级结构与纳米TiO2的导带能级结构相匹配。

Abstract:

Two kinds of benzylidene schiff base substituted phthalonitriles were prepared by 4-aminophthalonitrile, 4-methylbenzaldehyde and 4-methoxybenzaldehyde, using AlCl3/Et3N as catalyst. 2(3), 9(10), 16(17), 23(24)-tetra-[(4-methylbenzylidene)amino]zinc phthalocyanine(SPc) and 2(3), 9(10), 16(17), 23(24)-tetra-[(4-methoxylbenzylidene)amino]zinc phthalocyanine(SOPc) were synthesised on the basis of cyclotetramerization of benzylidene schiff base substituted phthalonitrile. The target compounds were fully characterized by Fourier Transform infrared spectroscopy, elemental analyses, 1HNMR, 13CNMR, UV–Vis spectroscopy and cyclic voltammetry. Compared with the unsubstituted zinc phthalocyanine the Q band of SPc and SOPc had red-shifted about 35 nm and 43 nm, had a weak absorption within the range between 450 nm and 600 nm. And the target compounds existed in a form of monomer in DMF solution at the range of 0.002~0.010 mmol/L mol/L. The redox behavior was studied by cyclic voltammetry, the SPc and SOPc had been found to have a low LUMO (-3.24 eV, -3.29eV) and a deep HOMO (-4.88 eV, -4.71 eV) energy level. The results indicated that the LUMO and HOMO energy level of target compounds matched with the energy level of nano-TiO2.