Cucurbit[8]uril-regulated face-to-face dimerization assembly enhanced photosensitization and photocatalysis

作     者：Haigen Nie Die Hu Zhiyao Zeng Yan Fan Yaxin Zhai Xin-Long Ni 

作者机构：Key Laboratory of Chemical Biology and Traditional Chinese MedicineMinistry of Educational of ChinaKey Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan ProvinceCollege of Chemistry and Chemical EngineeringHunan Normal UniversityChangsha 410081China Key Laboratory of Low-Dimensional Quantum Structures and Quantum Control of Ministry of EducationDepartment of PhysicsHunan Normal UniversityChangsha 410081China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2024年第67卷第5期

页      面：1605-1612页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 081705[工学-工业催化] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China (22271090  12204167) 

主　　题：host-guest interaction dimerization macrocycles photosensitization 

摘      要：In water, N,N′-diarylpyridinium thiazolo[5,4-d]thiazole guests(G1–G3) were encapsulated by cucurbit[8]uril(Q[8]) to construct Q[8]_(3)/G_(2) complexes, in which the encapsulated G molecules exist as an exact face-to-face dimer. These complexation behaviors have been indicated by proton nuclear magnetic resonance(~1H NMR) spectroscopy and isothermal titration calorimetry(ITC),and have been confirmed by X-ray single crystal structural analysis of Q[8]_(3)/G2_(2). While free guests G1–G3 have no ability to sensitize singlet oxygen, they all become effective singlet oxygen sensitizers when complexed with Q[8]. By irradiation of white light, Q[8]_(3)/G_(2) complexes induced selective oxidation of aryl sulfide to aryl sulfoxide in good yields and selective oxidation of dimethyl sulfide(DMS) to dimethyl sulfoxide(DMSO) in excellent yields without over-oxidation to dimethyl sulfone(DMSO_(2))even for elongated irradiation. High-yield photo-oxidation of DMS to DMSO_(2) was only achieved by irradiation of blue light in the presence of Q[8]_(3)/G1_(2), which was also effective in photobleaching of Rhodamine B in water. The higher photo-oxidation power of Q[8]_(3)/G1_(2) has been ascribed to an additional generation of reactive oxygen species besides singlet oxygen.