质子化和脱质子化对酞菁光谱的影响(英文)  

Effects of Protonation and Deprotonation on Phthalocyanine's Spectra

作　　者：刘剑波[1] 赵瑜[1] 赵福群[1] 张复实[1] 唐应武[1] 宋心琦[1] 周福添[2] 

机构地区：[1]清华大学化学系,北京100084 [2]香港理工大学应用生物及化学科技学系

出　　处：《物理化学学报》1996年第3期202-207,共6页Acta Physico-Chimica Sinica

摘　　要：系统地研究了四异丙氧基酞菁的质子化和脱质子化对吸收和发射光谱的影响．研究表明，三氟乙酸可对酞菁分子连续质子化，分别生成[H2Pc(OiPr)4·H+]+和[H2Pc(OiPr)4·2H+]2+而硫酸可使酞菁形成[H2Pc(OiPr)4·4H+]4+此外，NaOH／EtOH可使酞菁分子脱质子化生成[Pc(OiPr)4]2-，反应一步完成，表明分子中的两个吡咯-NH-同步酸解，质子化可使吸收光谱的Q带和荧光发射峰显著红移，证明酞菁激发态的碱性强于基态．对这些实验现象，利用四轨道电子跃迁模型作了合理的解释．The absorption and edrission properties of H2Pc(OiPr)4 were studiedas a function of protonation and deprotonation. Stepwise protonation using TFAyielded [H2Pc(OiPr)4·H+]+ and [H2Pc(OiPr)4·2H+]2+. [H2Pc(OiPr)4·4H+]4+ can beformed in concentrated sulfuric acid. Additionally, the NaOH/EtOH can deprotonateH2Pc(OiPr)4 to [Pc(OiPr)4]2-, the acid-dissociation of the two pyrrolic -NH occurredsynchronous. Manifest bathochromic shifts of the Q band absorption for each boundproton indicated the basicity of phthalocyanine in the excited state is stronger thanthat in the ground state. In order to explain the experimental phenomena, the effectsof protonation and deprotonation on MOs were proposed.

关 键 词：酞菁 质子化 脱质子化 吸收光谱 

分 类 号：O626.13[理学—有机化学] O657.3[理学—化学]