Thiacalix[4]arene-protected alkynyl Ag ( = 9, 18) nanoclusters: syntheses, structural characterizations, photocurrent responses and fluorescence properties

• Published in: Dalton transactions : an international journal of inorganic chemistry 2023-09, Vol.52 (37), p.1345-13412
• Main Authors: Xie, Wen-Xuan, Xue, Chun-Hui, Liu, Meng, Zhou, Kun, Gu, Hui-Hao, Ji, Jiu-Yu, Chen, Bao-Kuan, Liu, Na, Bi, Yan-Feng
• Format: Article
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d3dt02285d

Two thiacalix[4]arene-protected silver( i ) alkynyl nanoclusters, [Na 2 (H 2 O) 2 ][Ag 9 (TC4A)( t BuC&z.tbd;C) 4 (CH 3 OH) 2 (SbF 6 ) 0.5 (OH) 2.5 ]·3.5H 2 O·CH 3 OH ( 1 , abbreviated as Ag 9 ) and [Ag 9 (TC4A)( t BuC&z.tbd;C) 4 (CF 3 COO)] 2 ·4CH 3 OH ( 2 , abbreviated as Ag 18 ), were synthesized by the reaction of [ t BuC&z.tbd;CAg] n , p-tert -butylthiacalix[4]arene (H 4 TC4A), NaBH 4 , and AgSbF 6 or CF 3 COOAg in the mixed solvent of methanol-trichloromethane-toluene under solvothermal conditions, respectively. Driven by SbF 6 − and CF 3 COO − with different coordination properties, the structural unit [Ag 9 (TC4A)( t BuC&z.tbd;C) 4 ] + in both the compounds migrated in different modes, accompanied by distinct Ag Ag distances. Ag 9 and Ag 18 exhibit similar UV-Vis absorption and diffuse reflection spectra along with contrary tendency between photocurrent responses and solid-state fluorescence. The solution stability of Ag 9 and Ag 18 was demonstrated by 1 H NMR and MALDI-TOF mass spectrometry. The fluorescence responses of Ag 9 and Ag 18 towards different organic molecules were also investigated, which indicated that the polarity of solvent has a certain effect on the emission intensities of Ag 9 and Ag 18 . This study provides a positive guide for the controlled synthesis and further study of the structure-activity relationship of thiacalix[4]arene-protected silver alkynyl nanoclusters. Ag 9 and Ag 18 were obtained, characterized, and studied for photocurrent responses and fluorescence properties, providing a guide for controlled synthesis and studying the structure-activity relationship of calixarene-protected alkynyl Ag clusters.