α和β-四(4-甲氧基苯氧基)酞菁锌的合成、表征和电化学性质

Studies on Electrochemical Properties of α-and β-Tetrakis(4-methoxyphenoxy)phthalocyaninatozinc

以3-硝基邻苯二腈和4-硝基邻苯二腈为原料经过两步反应合成了α和β-四甲氧基苯氧基酞菁锌,通过IR光谱、UV-Vis光谱、MS谱、1H NMR谱和元素分析表征了其结构,其结果与标题化合物的结构一致.这两种酞菁在有机溶剂中有良好的溶解性.通过循环伏安法研究其能带结构和电化学过程,结果表明,甲氧基苯氧基在α-位时(与苯氧基在β-位时相比)酞菁单体的HOMO能级升高,LUMO能级降低,带隙变窄,有利于酞菁分子的电子传输.它们在二氯甲烷中的电化学过程都是单电子准可逆过程,而且氧化还原过程均发生在酞菁环上.最后提出了两种酞菁的电化学反应机理.

With 3-nitrobenzene-1,2-dicarbonitrile and 4-nitrobenzene-1,2-dicarbonitrile as raw materials,α-and β-tetrakismethoxyphenoxy phthalocyaninatozinc were synthesized via two-step reaction.The structure of two compounds were characterized by IR,UV-Vis,MS,1H NMR spectra and elemental analysis,and the results are consistent with the structures of title compounds.Two phthalocyanine compounds have good solubility in organic solvents.The energy band structures and electrochemical processes were studied by cy-clic voltammetry.The results indicated the phthalocyanine monomer has higher HOMO energy levels,lower LUMO energy levels and more narrow band gap when the methoxyphenoxy lies on α-site than on β-site,which are favorable for the electron transfer of phthalocyanine molecules.The results showed that the elec-trochemical processes of two compounds were all quasi-reversible single-electron processes in dichloro-methane,and the oxidation-reduction reactions occurred in phthalocyanine ring.Finally,the electrochemical reaction mechanism of two phthalocyanine compounds were put forward.