Cycloalkane and alicyclic heterocycle complexation by new switchable resorcin[4]arene-based container molecules: NMR and ITC binding studies.
Cycloalkane and alicyclic heterocycle complexation by new switchable resorcin[4]arene-based container molecules: NMR and ITC binding studies.
复制标题
新型可切换间苯二酚[4]芳烃基容器分子与环烷烃和脂环族杂环络合：NMR 和 ITC 结合研究。
作者：
J. Hornung;Daniel Fankhauser;L. D. Shirtcliff;Antonia Praetorius;W. Schweizer;F. Diederich
报道了一种新型的“分子篮”桥联空穴的合成和结构表征。基于间苯二酚[4]芳烃的容器分子具有定义明确的空穴，这些空穴结合了各种环烷烃和脂环杂环。用核磁共振氢谱和恒温滴定热法测定了1：1包合物的缔合常数K(A)。均三甲苯的K(A)值从环庚烷的1.7×10(2)M(-1)到吗啉的1.7×10(7)M(-1)。分子篮的主客体络合作用一般是由分散相互作用、客体与空腔芳香壁的C-H···π相互作用和最佳空腔填充驱动的。核磁共振结构数据和结合亲和力的相关性支持复杂的杂环客体经历额外的极性C-O···C=O，N-H···π和S···π相互作用。报道了基于空穴的分子篮的第一个晶体结构，提供了关于固态内腔的几何和体积的精确信息。分子动力学(MD)模拟提供了有关包裹客体存在时空腔的大小和构象预组织的信息。当空洞填充体积为63±9%时，杂环客体与宿主发生极性相互作用，结合力最强。
The synthesis and structural characterization of novel, "molecular basket"-type bridged cavitands is reported. The resorcin[4]arene-based container molecules feature well-defined cavities that bind a wide variety of cycloalkanes and alicyclic heterocycles. Association constants (K(a)) of the 1:1 inclusion complexes were determined by both (1)H NMR and isothermal titration calorimetry (ITC). The obtained K(a) values in mesitylene ranged from 1.7×10(2) M(-1) for cycloheptane up to 1.7×10(7) M(-1) for morpholine. Host-guest complexation by the molecular baskets is generally driven by dispersion interactions, C-H···π interactions of the guests with the aromatic walls of the cavity, and optimal cavity filling. Correlations between NMR-based structural data and binding affinities support that the complexed heterocyclic guests undergo additional polar C-O···C=O, N-H···π, and S···π interactions. The first crystal structure of a cavitand-based molecular basket is reported, providing precise information on the geometry and volume of the inner cavity in the solid state. Molecular dynamic (MD) simulations provided information on the size and conformational preorganization of the cavity in the presence of encapsulated guests. The strongest binding of heterocyclic guests, engaging in polar interactions with the host, was observed at a cavity filling volume of 63 ± 9%.
影响因子：
15
作者：
Sessler, Jonathan L.;Gross, Dustin E.;Gale, Philip A.
通讯作者：
Gale, Philip A.
影响因子：
15
作者：
Hooley, RJ;Van Anda, HJ;Rebek, J
通讯作者：
Rebek, J
影响因子：
7.4
作者：
Freire, Ernesto
通讯作者：
Freire, Ernesto