A conformationally adaptive macrocycle: conformational complexity and host-guest chemistry of zorb[4]arene.
A conformationally adaptive macrocycle: conformational complexity and host-guest chemistry of zorb[4]arene.
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构象自适应大环：zorb[4]芳烃的构象复杂性和主客体化学
DOI：
10.3762/bjoc.14.134
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发表时间：
2018
影响因子：
2.7
通讯作者：
Jiang W
中科院分区：
文献类型：
--
作者：
Yang LP;Lu SB;Valkonen A;Pan F;Rissanen K;Jiang W
大幅度构象变化是生物分子识别的特征之一，也是功能生物系统中变构效应和信号转导的基础。然而，具有可控构象变化的合成受体是罕见的。本文对一种构象自适应的大环化合物--全乙氧基唑[4]芳烃（ZB 4）的主客体化学进行了深入的研究。与全-O-乙氧基氧杂[4]芳烃类似，ZB 4能够容纳广泛的有机阳离子。然而，ZB 4对客体上的电子取代基没有表现出大幅度的构象响应。ZB 4遵循抛物线自由能关系，而不是线性自由能关系。这是通过调用二级C-H···O氢键对初级阳离子···π相互作用的影响来解释的，基于从四个代表性晶体结构获得的信息。此外，热容量变化（ΔCp）和熵-熵补偿现象都表明在结合过程中还涉及溶剂重组。该研究进一步加深了我们对ZB 4结合行为的认识，为构建以ZB 4为主要成分的刺激响应材料奠定了基础。
Large amplitude conformational change is one of the features of biomolecular recognition and is also the basis for allosteric effects and signal transduction in functional biological systems. However, synthetic receptors with controllable conformational changes are rare. In this article, we present a thorough study on the host–guest chemistry of a conformationally adaptive macrocycle, namely per-O-ethoxyzorb[4]arene (ZB4). Similar to per-O-ethoxyoxatub[4]arene, ZB4 is capable of accommodating a wide range of organic cations. However, ZB4 does not show large amplitude conformational responses to the electronic substituents on the guests. Instead of a linear free-energy relationship, ZB4 follows a parabolic free-energy relationship. This is explained by invoking the influence of secondary C–H···O hydrogen bonds on the primary cation···π interactions based on the information obtained from four representative crystal structures. In addition, heat capacity changes (ΔCp) and enthalpy–entropy compensation phenomena both indicate that solvent reorganization is also involved during the binding. This research further deepens our understanding on the binding behavior of ZB4 and lays the basis for the construction of stimuli-responsive materials with ZB4 as a major component.
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