新型双膦酸酯杯[4]吡咯过渡受体离子对识别的理论计算  

Theoretical calculation of the ion-pair recognition for new Calix[4]pyrrole bis-phosphonate transition receptor

作　　者：张东升[1] 钱彭华 刘晶静[3] 王腾[2] 申和跃 孔亚婷[2] 贾琳琳[2] 张瑞[2] 陈红余[2] 王玉民[2] 孙宏伟[4] 

机构地区：[1]泰山医学院放射学院,山东泰安271016 [2]泰山医学院化工学院,山东泰安271016 [3]泰山学院化学与化工学院,山东泰安271021 [4]南开大学化学学院,天津300071

出　　处：《计算机与应用化学》2015年第12期1523-1529,共7页Computers and Applied Chemistry

基　　金：山东省自然科学基金(ZR2013BL014;ZR2013BQ022);山东省优秀中青年科学家科研奖励基金(BS2013YY061);国家自然科学基金子课题(31370575-1);泰山医学院高层次课题培育计划(2012GCC07);泰山学院引进人才科研启动基金(Y-01-2014013)资助项目

摘　　要：含有2个膦酸酯基团的芳环扩展的新型杯[4]吡咯系列化合物可以作为客体烷基铵/鏻氯盐的离子对受体。使用量子力学计算和新的非共价弱相互作用分析方法研究了过渡受体io的离子对识别行为。计算的离子对结合能表明,io与四级鏻氯盐和一级铵氯盐的优势结合模式分别为分离式和接触式,阳离子-π和氢键分别在其中起主导作用。结合前面的计算结果,发现三种受体对于这2种氯盐的结合能力顺序与实验结果完全一致,io在其中显示出明显的过渡性质。对几何构型、弱相互作用和基于自然键轨道的电荷转移进行了分析,阐释了io具有过渡性质的原因。本项工作进一步揭示了新型双膦酸酯杯[4]吡咯受体离子对识别机制,为设计基于杯[4]吡咯的离子对受体提供了理论基础。A new family of aryl-extended calix[4]pyrroles with two phoshonate groups can act as ion-pair receptors for guest alkylammonium/phosphonium chloride salts. The ion-pair binding behavior of transition receptor io was investigated using quantum mechanics calculations and new nonconvalent weak interaction analysis method. The binding energy suggests that separated and contact arrangements are the favorable binding modes for io when binding quaternary phosphonium chloride salt and primary ammonium chloride salt respectively, and the cation–π and hydrogen bonding interactions play a critical role in corresponding recognition respectively. Combined with previous study, the order of binding affinity for the three receptors towards the two guests is in agreement with the experimental results, and receptor io shows obvious transitional characteristic. The geometry, the nonconvalent weak interactions, and the charge transfer based on natural bond orbital have been analyzed in detail to unravel the reason why receptor io has transitional characteristic. This work further unveils the mechanism of ion-pair recognition by new calix[4]pyrrole bis-phosphonate receptors, while opening exciting perspectives for the design of novel calix[4]pyrrole-based ion-pair receptors.

关 键 词：杯吡咯 量子力学 非共价弱相互作用 离子对 分子识别 

分 类 号：O641[理学—物理化学]