钳形酰腙类阴离子受体的合成及识别性质研究

Synthesis and Recognition Properties of Tweezer-Shaped Anion Receptors Based on Acylhydrazone Units

设计合成了基于吲哚酰腙单元的钳形阴离子受体(1),UV-Vis滴定实验表明,它在含1%DMSO的CH3CN溶液中能选择性识别具有重要生物学意义的F-、Ac O-和H2PO4-(结合比均为1∶1且Ka>104L/mol),但对Cl-、Br-、I-、NO3-、N3-、HSO4-和Cl O4-无识别作用。与它相比,端基为苯并呋喃的参照化合物2在同样溶剂中对上述3种阴离子的亲和性减弱,尤其是对H2PO4-。核磁滴定实验表明,受体1中的吲哚环NH和酰胺NH能产生协同效应,从而对阴离子产生了强效键合作用。

An indole-acylhydrazone-based tweezer-shaped anion receptor （1） was designed and synthesized, and it displayed a selective recognition for biologically important F- , AcO- and H2PO4 - （Ka 〉 104L/mol with a 1：1 stoichiometry） in CH3 CN containing 1 （vol） % DMSO. However, no binding interaction was observed for other anions such as Cl- , Br- , I- , NO3- , N3 - , HSO4 - and CIO4 -. Compared with 1, reference compound 2 （end groups were benzofuran） showed a decreased affinity towards the above three anions, especially for H2PO4 -. 1H NMR titration experiments indicated that cooperative utilization of indole NHs and amide NHs within 1 led to its strong binding with anions.