Synthesis of Precisely Functionalized Nano-confinement: a Bottom-up Approach to the Evolution of Selective Molecular Receptors

{"title":"Synthesis of Precisely Functionalized Nano-confinement: a Bottom-up Approach to the Evolution of Selective Molecular Receptors","authors":"Ya-Mei Tan, Lu-Mei Zhang, Qixia Bai, Zhe Zhang, Pingshan Wang, Qi Zhang","doi":"10.1039/d4sc08176e","DOIUrl":null,"url":null,"abstract":"<strong>Abstract</strong>: Precise molecular recognition depends on the delicate interplay between a guest molecule and a host possessing complementary functional groups. De novo design of selective artificial receptors remains a formidable challenge, given the complexity of predicting these interactions. We present herein a bottom-up approach to the evolution of selective molecular receptor through precise endo-functionalization of a supramolecular cage. Internal functional groups were introduced within the heteroleptic palladium coordination cage in a site-precise fashion. With just five different functional groups, we successfully created a library of 32 isoreticular nano-cages, each featuring unique micro-environments, by varying the nature, location and combination of endo-functional groups. The nano-cage exhibited adaptive recognition ability towards guest molecules of distinct geometries and hydrogen bonding capabilities. Titration experiments demonstrated that the binding affinity for a specific guest can be finely tuned and optimized by changing the endo-functional groups. As a proof of principle, by strategically screening our nano-cage library, we identified a receptor with high affinity and specificity for the dihydrogen phosphate guest. X-ray analysis and DFT calculation highlighted the pivotal role of the synergistic interactions among distinct endo-functional groups in achieving high-fidelity molecular recognition. This study is expected to provide a versatile solution for the bottom-up construction of tailor-made molecular receptors.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"198 1","pages":""},"PeriodicalIF":7.6000,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4sc08176e","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}