芳香偶氮类锌酞菁的合成与性能-有机化学专业论文.docxVIP

中北大学学位论文 中北大学学位论文 万方数据 万方数据 收特征。通过热重分析了目标化合物的热稳定性，四个芳基偶氮锌酞菁在 200 oC 以上全 部表现出良好的热稳定性。 通过循环伏安法计算了四种芳基偶氮锌酞菁的 LUMO 和 HOMO 能级以及电化学带 隙，四个光敏染料的 LUMO 能级光电子有效注入 TiO2 导带，HOMO 能级都能很好的保 证氧化态染料的还原。电化学带隙与由紫外-可见吸收光谱计算的光学带隙值吻合较好。 构建了有机染料敏化太阳能电池(DSSC)，研究了四种芳香偶氮类锌酞菁光敏染料的 光伏性能，其中 α-萘酚通过氮氮双键(N=N)与酞菁母核连结的锌酞菁的光电转化效率最 高。 芳基偶氮锌酞菁类光敏染料光吸收范围宽，基本表现出了全光谱吸收，但是光电转 化效率不理想，主要和光敏染料分子在纳米 TiO2 表面的积聚，以及对称的分子结构导 致的光电子流动方向性差有关。 关键词：芳香偶氮苯，酞菁，吸收光谱，电化学，染料敏化太阳能电池 Aromatic azo-coupled zinc phthalocyanines: Synthesis and properties Abstract Phthalocyanines (Pcs) and their metal complexes are typical NIR dyes. Pcs have strong absorptions on two distinct edges of visible region, namely, the Q-band at around 680 nm and the Soret-band at around 350 nm. The facile modification chromophore skeleton of phthalocyanines provides potential for molecular design. Up to now, various chromophores have been introduced into the phthalocyanine core to tune the absorptions. However, almost all the chromophores were introduced through oxygen bridge, thioetherbondor C?C bond and the characteristic absorptions of these chromophores were overlapped with the Soret-band of phthalocyanines as well. Moreover, the absorption bands of these phthalocyanines red shifted slightly. In the paper, azo dyes were chosen as chromophores and were connected onto the Pc ring through N=N double bond. Pcs and azo dyes show great attractiveness due to their broad availability and perfectly complementary absorption regions. The synthesis and properties of the azo-coupled Pcs were researched. The absorptions in the spectral window between 400 and 600 nm of four azo-coupled phthalocyanines were remarkable. The coupling reactions between arenediazonium ion and phenol derivatives was used to prepare the azo-coupled phthalonitriles: 4-(4-hydroxyphenylazo)phthalonitrile (2), 4-(4 -hydroxy-naphthalen-1-ylazo)phthalonitrile (3), 4-(2-hydroxyl-5-ethyl-oxycarbonyl-phenyla- zo)phthalonitrile (4) and 4-[2-hydroxyl-3-methoxyl-4-(4-carboxyl-benzylidene