Self-assembly patterns of non-metalloid silver thiolates: structural, HR-ESI-MS and stability studies.

Screening of AgNO 3 /AgS t Bu solutions in DMF, DMSO and NMP resulted in the isolation of three novel nanosized silver/thiolate complexes with a torus-like {Ag 20 (S t Bu) 10 } core. The structures of [NO 3 @Ag 20 (S t Bu) 10 (NO 3 ) 9 (DMF) 6 ] (1) and [NO 3 @Ag 20 ( t BuS) 10 (NO 3 ) 8 (NMP) 8 ][NO 3 @Ag 19 ( t BuS) 10 (NO 3 ) 8 (NMP) 6 ] 2 (NO 3 ) (2) were studied by single crystal X-ray diffraction (SCXRD). The self-assembly process leading to 1 can be switched to a different outcome using Br - , resulting in [Br@Ag 16 (S t Bu) 8 (NO 3 ) 5 (DMF) 3 ](NO 3 ) 2 (3), which is the one of the few genuine host-guest complexes in the silver/thiolate systems. Solutions of the individual complexes in CH 3 CN were studied by HR-ESI-MS techniques, which revealed a dynamic behavior for each complex, driven by a redistribution of the {AgNO 3 } units. This dynamics results in the appearance of both cationic and anionic species, based on unchanged silver-thiolate cores. Daylight causes degradation of 3 with the formation of a composite material based on defective orthorhombic Ag 2 S with a porous morphology, as observed using the SEM technique. The electrocatalytic HER activity of such a material was studied.