Bunchuay Thanthapatra, Docker Andrew, Eiamprasert Utt, Surawatanawong Panida, Brown Asha, Beer Paul D
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, United Kingdom.
Department of Chemistry and Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of Science, Mahidol University, 272 Thanon Rama VI, Ratchathewi, Bangkok, 10400, Thailand.
Angew Chem Int Ed Engl. 2020 Jul 13;59(29):12007-12012. doi: 10.1002/anie.202001125. Epub 2020 May 12.
A series of heteroditopic receptors containing halogen bond (XB) and unprecedented chalcogen bond (ChB) donors integrated into a 3,5-bis-triazole pyridine structure covalently linked to benzo-15-crown-5 ether motifs exhibit remarkable cooperative recognition of halide anions. Multi-nuclear H, C, Te and F NMR, ion pair binding investigations reveal sodium cation-benzo-crown ether binding dramatically enhances the recognition of bromide and iodide halide anions, with the chalcogen bonding heteroditopic receptor notably displaying the largest enhancement of halide binding strength of over two hundred-fold, in comparison to the halogen bonding and hydrogen bonding heteroditopic receptor analogues. DFT calculations suggest crown ether sodium cation complexation induces a polarisation of the sigma hole of ChB and XB heteroditopic receptor donors as a significant contribution to the origin of the unique cooperativity exhibited by these systems.
一系列含有卤素键（XB）和前所未有的硫族元素键（ChB）供体的异二聚体受体，它们整合到与苯并-15-冠-5醚基序共价连接的3,5-双三唑吡啶结构中，对卤化物阴离子表现出显著的协同识别作用。多核氢、碳、碲和氟核磁共振以及离子对结合研究表明，钠阳离子与苯并冠醚的结合显著增强了对溴化物和碘化物卤化物阴离子的识别，与卤素键和氢键异二聚体受体类似物相比，硫族元素键异二聚体受体对卤化物结合强度的增强尤为显著，超过两百倍。密度泛函理论计算表明，冠醚与钠阳离子的络合诱导了硫族元素键和卤素键异二聚体受体供体的σ空穴极化，这是这些体系表现出独特协同作用的一个重要原因。
