四-[邻(叔丁氧羰甘氨酸)氨基苯基]卟啉锌配合物的合成、表征及其对咪唑类配体的分子识别  

Synthesis, Characterization and Molecular Recognition of meso Tetrakis( o BocGlyamidophenyl)porphyrinatozinc

作　　者：王传忠[1] 朱志昂[1] 阮文娟[1] 李瑛[1] 严诗楷[1] 陈荣悌[1] 

机构地区：[1]南开大学化学系,天津300071

出　　处：《高等学校化学学报》1999年第10期1509-1514,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金;元素有机化学国家重点实验室开放基金;南京大学配位化学国家重点实验室资助课题

摘　　要：合成并表征了四－［邻（叔丁氧羰甘氨酸）氨基苯基］卟啉Ｈ２Ｔ（ｏ－ＢｏｃＧｌｙ）ＡＰＰ（１）及其锌（Ⅱ）配合物ＺｎＴ（ｏ－ＢｏｃＧｌｙ）ＡＰＰ（２）． 用紫外－可见光谱滴定法测定了配合物２ 与６ 种咪唑类配体轴向配位反应的平衡常数， 研究了它作为主体分子对咪唑类小分子的识别． 研究结果表明， 各配体的缔合常数按Ｋ（Ｉｍ ）＞ Ｋ（２－ＣＨ３Ｉｍ ）＞ Ｋ（ＥＭＩｍ ）＞ Ｋ（Ｎ－ＣＨ３Ｉｍ ）＞ Ｋ（２－ＨＯＣＨ２Ｉｍ ）＞ Ｋ（ＧＭＺ）的顺序依次减小． 计算了卟啉的侧链取代基Ｒ与咪唑取代基Ｒ′的排斥作用能． 测定了轴向配位反应的ΔｒＧ○—ｍ ， ΔｒＨ○—ｍ 及ΔｒＳ○—ｍ ， 发现该反应是放热、熵减小的过程， 该反应体系中存在焓熵补偿关系． 实验发现， Ｒ是影响配合物２meso\% Tetrakis( o BocGlyamido)porphyrin\[H 2T( o BocGly)APP),1\] and its zinc complex [ZnT( o BocGly)APP, 2] were synthesized and characterized. By means of spectrophotometer technique, the equilibrium constants of the axial coordination reaction were measured between complex 2 and a series of imidazoles, molecular recognition of imidazoles by the receptor porphyrin 2 was studied. The results show that the equilibrium constants decrease in the orders of K (Im)> K (2 CH 3Im)> K (EMIm)> K (2 HOCH 2Im) and K (Im)>\{ K ( N CH 3Im)\}> K (GMZ), suggesting that the steric effect was the key factor, the data of steric effect were calculated, the thermodynamic parameters Δ r G ○? ? m , Δ r H ○? ? m and Δ r S ○? ? m were investigated by van′t Hoff′s equation, the phenomenon of enthalpy entropy compensation was the observed in the coordination process.

关 键 词：卟啉锌 咪唑类配体 分子识别 锌卟啉 识别 

分 类 号：O627.23[理学—有机化学] O626.23[理学—化学]