Chalcogenoviologen Enhanced Host–Guest Recognition  

作　　者：Yuanning Feng Xingang Zhao Daniel A.Appleton Han Han Ryan M.Young Wenqi Liu Christopher K.Lee Weixingyue Li Bai-Tong Liu Yong Wu Chun Tang Aspen X-Y.Chen Charlotte L.Stern Dong Jun Kim Michael R.Wasielewski Yunyan Qiu J.Fraser Stoddart 

机构地区：[1]Department of Chemistry and Biochemistry,The University of Oklahoma,Norman,Oklahoma 73019 [2]Weinberg College of Arts and Sciences,Northwestern University,Evanston,Illinois 60208 [3]Department of Chemistry,The University of Hong Kong,Hong Kong SAR 999077 [4]Paula M.Trienens Institute for Sustainability and Energy,Northwestern University,Evanston,Illinois 60208 [5]Department of Chemistry,University of South Florida,Tampa,Florida 33620 [6]School of Chemistry,University of New South Wales,Sydney,NSW 2052 [7]Department of Chemistry,National University of Singapore,Singapore 117543 [8]Center for Regenerative Nanomedicine,Northwestern University,Chicago,Illinois 60611 [9]Stoddart Institute of Molecular Science,Department of Chemistry,Zhejiang University,Hangzhou 310027 [10]ZJU-Hangzhou Global Scientific and Technological Innovation Center,Hangzhou 311215

出　　处：《CCS Chemistry》2024年第11期2679-2691,共13页中国化学会会刊（英文）

基　　金：supported by the US Department of Energy,Office of Science,Office of Basic Energy Sciences,under Award DE-FG02-99ER14999(M.R.W.);This research made use of the Integrated Molecular Structure Education and Research Center NMR,MS,and X-ray facility at NU,which receives support from the Soft and Hybrid Nanotechnology Experimental(SHyNE)Resource(NSF ECCS-2025633)and NU(C.L.S.).

摘　　要：In the field of supramolecular chemistry,cyclophanes with novel properties are highly sought after since they can be tailored to fulfill specific tasks.In this article,we incorporate chalcogenoviologen-based units into tetracationic cyclophanes,resulting in enhanced host–guest recognition.The cyclophanes can be tuned through the addition of chalcogen bridging atoms—S,Se,and Te—which enhance their rigidity,regulate bond rotation and introduce additional steric bulk.Three cyclophanes containing chalcogen bridging atoms were synthesized and characterized in both the solution and solid states.The energy barriers for their interconversion between syn-and anti-conformations in solution were found to be correlated with chalcogen atom size.The photophysical properties of the cyclophanes are strongly dependent on the chalcogen atomic number,with intersystem crossing rates increasing from S to Se to Te.UV–vis-NIR spectroscopic and fluorometric titrations revealed that the chalcogenoviologenbased cyclophanes exhibit significantly stronger binding with electron-rich guests compared to the well-known,unsubstituted cyclobis(paraquat-pphenylene).This enhancement in binding can be attributed to restricted rotation within the chalcogenoviologen units.This research provides insight into the rational design and tailored synthesis of cationic cyclophanes.

关 键 词：binding titrations CHALCOGENS host–guest systems molecular recognition supramolecular chemistry 

分 类 号：O62[理学—有机化学]