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

Two thiacalix[4]arene-protected silver(I) alkynyl nanoclusters, [Na 2 (H 2 O) 2 ][Ag 9 (TC4A)( t BuCC) 4 (CH 3 OH) 2 (SbF 6 ) 0.5 (OH) 2.5 ]·3.5H 2 O·CH 3 OH (1, abbreviated as Ag9) and [Ag 9 (TC4A)( t BuCC) 4 (CF 3 COO)] 2 ·4CH 3 OH (2, abbreviated as Ag18), were synthesized by the reaction of [ t BuC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C) 4 ] + in both the compounds migrated in different modes, accompanied by distinct Ag⋯Ag distances. Ag9 and Ag18 exhibit similar UV-Vis absorption and diffuse reflection spectra along with contrary tendency between photocurrent responses and solid-state fluorescence. The solution stability of Ag9 and Ag18 was demonstrated by 1 H NMR and MALDI-TOF mass spectrometry. The fluorescence responses of Ag9 and Ag18 towards different organic molecules were also investigated, which indicated that the polarity of solvent has a certain effect on the emission intensities of Ag9 and Ag18. 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.