四-β-(氨甲基)酞菁锌盐酸盐的合成及光物理光化学性质研究  

Synthesis,Photophysical and Photochemical Properties of β-Tetrakis(aminomethyl) phthalocyaninato Zinc(Ⅱ) Hydrochloride

作　　者：许秀枝[1] 王艰[1] 李柱来[1] 严文锦[1] 蚩会丽[1] 陈文斌[1] 卓世昌[1] 陈耐生[2] 

机构地区：[1]福建医科大学药学院,福州350004 [2]福州大学功能材料研究所,福州350002

出　　处：《无机化学学报》2011年第5期877-885,共9页Chinese Journal of Inorganic Chemistry

基　　金：福建省青年人才创新基金(No.2007F3038);福建医科大学青年骨干教师基金(2009-2011)资助项目

摘　　要：四-β-(邻苯二甲酰亚胺甲基)酞菁锌(ZnPcP4)与85%水合肼反应得到四-β-(氨甲基)酞菁锌(ZnPcN4,分子式C36H28N12Zn),其盐酸盐为ZnPcN4.HCl。测试合成得到的标题化合物紫外-可见电子吸收光谱,荧光光谱和单线态氧生成速率。标题化合物在水中聚集,在90%1,2-丙二醇/水中主要以单体形式存在。目标酞菁锌配合物在90%DMF/水的中性溶液存在聚集体,在弱酸性条件下,随酸度增大,675 nm处Q带单体吸收峰升高,在DMF/water(10%,V/V)/HCl(1.2 mmol·L-1)溶液中10-5 mol·L-1的酞菁配合物基本上没有聚集;在强酸性条件下,随酸度增大,675 nm处Q带单体吸收峰下降的同时,在713 nm处酞菁单质子化吸收峰强度有所增加。ZnPcN4.HCl在DMF体系中聚集,荧光量子产率和单线态氧量子产率变小,但其在DMF/water(10%,V/V)/HCl(1.2mmol·L-1)体系中主要以单体形式存在,荧光量子产率为0.19,单线态氧量子产率0.58,光敏活性与标准无取代酞菁锌相近。β-Tetrakis（aminomethyl）phthalocyaninato zinc（Ⅱ）（ZnPcN4） was synthesized from the reaction of β-tetrakis（phthalimidomethyl）phthalocyaninato zinc（Ⅱ）（ZnPcP4） with 85% NH2NH2·H2O and the hydrochloride of ZnPcN4（ZnPcN4·HCl） was obtained.UV-Visible electronic absorption spectra,fluorescence spectra and singlet oxygen quantum yield of ZnPcN4·HCl were determined.ZnPcN4·HCl was found to be aggregated in aqueous media but was partially or fully disaggregated on addition of DMF or ROH to the water solution.In the DMF/water（10%,V/V）/HCl media,as the concentration of HCl increased,the absorbance intensity of monomer increased gradually in the weak acid solution.It is no aggregation in DMF/water（10%,V/V）/HCl（1.2 mmol·L-1） media in the concentration of 10-5 mol·L-1.However,in the strong acid solution,as the concentration of HCl increased,the absorbance intensity of monomer decreased gradually,meanwhile the absorbance intensity of monoprotonation peak at 713 nm increased to a small extent.The maximum absorbance and emission wavelength of ZnPcN4·HCl is 675 nm and 681 nm in DMF/water（10%,V/V）/HCl（1.2 mmol·L-1） media,respectively.ZnPcN4·HCl was found to be aggregated in DMF,so its fluorescence quantum yield and singlet oxygen quantum yield were small.A value of 0.19 was calculated for the fluorescence quantum yield of this photosensitizer in DMF/water（10%,V/V）/HCl（1.2 mmol·L-1）.The photodynamic activity of ZnPcN4·HCl was evaluated using 9,10-dimethylanthracene（DMA）.The singlet oxygen quantum yield was 0.58 close to ZnPc with a promising anti-tumor photosensitizer for the further research.

关 键 词：酞菁锌 聚集 单线态氧 质子化 

分 类 号：O614.24[理学—无机化学] O627.23[理学—化学]