Xenon Induces Its Own Preferred Heterochiral Host from Exclusive Homochiral Assembly

作者：Shi‐Xin Nie, Teng-Yu Huang, Hao Guo, Lixia Wang, Jie Cui, Junfeng Xiang, Yu‐Fei Ao, De‐Xian Wang, Qi‐Qiang Wang · 发表于：Journal of the American Chemical Society · 年份：2022 · DOI：10.1021/jacs.2c12202 · 被引用次数：8 · 研究领域：Supramolecular Chemistry and Complexes、Advanced NMR Techniques and Applications、Crystallography and molecular interactions

Xenon binding represents a formidable challenge, and efficient hosts remain rare. Here we report our findings that while enantiomeric bis(urea)–bis(thiourea) macrocycles form exclusive homochiral dimeric assemblies, xenon is able to overcome the narcissism and induces an otherwise-nonobservable heterochiral assembly as its preferred host. An experimental approach and fitting model were developed to obtain binding constants associated with the invisible assembly species. The determined xenon binding affinity with the heterochiral capsule reaches 1600 M –1, which is 15 times higher than that with the homochiral capsule and represents the highest record for an assembled host. The origin of the large difference in xenon affinity between the two subtle diastereotopic assemblies was revealed by single-crystal analysis. In the heterochiral capsule with S 4 symmetry, the xenon atom is more tightly enclosed by van der Waals surroundings of the four thiourea groups arranged in a spherical cross-array, superior to the antiparallel array in the homochiral capsule with D 2 symmetry.