具有不同芳氧基取代酞菁钯聚集行为研究

Study on Aggregation Behavior of Tetraphenoxyphthalocyaninatopallidium with Dif ferent Phenoxy-substituents

为了研究具有不同芳氧基取代酞菁的聚集行为 ,合成了 5种酞菁如 1,8,15,2 2 四 (2 ,4 二氯芳氧基 )酞菁钯 (Pc1) ;1,8,15,2 2 四芳氧基酞菁钯 (Pc2 ) ;1,8,15,2 2 四 (2 ,4 二特丁基芳氧基 )酞菁钯 (Pc3 ) ;1,8,15,2 2 四 (2 ,5 二特丁基芳氧基 )酞菁钯 (Pc4)和 1,8,15,2 2 四 (2 ,6 二溴 4 甲基芳氧基 )酞菁钯 (Pc5) .酞菁的聚集行为由芳氧基的性质不同决定 .在四氢呋喃(THF)溶液中浓度在 10 - 6 ～ 10 - 5 mol·dm- 3 范围内 ,计算得到 5种酞菁的聚集常数分别为 1.61× 10 - 5 mol- 1·dm3,3 .87×10 - 5 mol- 1·dm3,2 .60× 10 - 5 mol- 1·dm3 ,1.2 1× 10 - 5 mol- 1·dm3 ,2 .57× 10 - 5 mol- 1·dm3.除了Pc1外 ,其余酞菁的单体和二聚体吸收行为类似 .在薄膜状态下 ,不同取代基对酞菁的吸收性质影响较大 .成膜后 5种酞菁的吸收光谱都发生了改变 ,其中Pc1的吸收形状改变最大 。

In order to study the aggregation behavior of phthalocyanines with different phenoxy-substituents, five tetraphenoxyphthalocyaninatopallidium with different phenoxy substituents ( e. g. 2, 4-dichlorophenoxy, Pc1; phenoxy, Pc2; 2, 4-dibutylphenoxy, Pc3; 2, 5-dibutylphenoxy, Pc4; 2, 6-dibromo-4-methylphenoxy, Pc5) were synthesized. The aggregation degree is dependent on the properties of the phenoxy-substituents. The dimerization constants of Pc1 similar to 5 in THF with concentration of 10(-6) similar to 10(-5) mol (.) L-1 were obtained by calculation, giving 1.61 x 10(5) mol(-1.)dm(3), 3.87 x 10(5) mol(-1.)dm(3), 2.60 x 10(5) mol(-1.)dm(3), 1.21 x 10(5) mol(-1.)dm(3) and 2.57 x 10(5) mol(-1.)dm(3), respectively. There are similar absorption spectra of the monomer and the corresponding dimmer for all the compounds except Pc1. The effect of substituents on the absorption spectra of the thin solid film is diversity with respect to the different substituents. By comparing the absorption spectra in the solution with those in the solid film, large differences can be observed in which spectrum shape is mostly changed for Pc1 and lambda(max) was mostly shifted for Pc5.