TY - JOUR

T1 - Self-assembly patterns of non-metalloid silver thiolates: Structural, HR-ESI-MS and stability studies

AU - Chupina, Anastasia V.

AU - Yanshole, Vadim V.

AU - Sulyaeva, Veronica S.

AU - Kokovkin, Vasily V.

AU - Abramov, Pavel A.

AU - Sokolov, Maxim N.

N1 - Funding Information: This work was supported by the grant of the President of the Russian Federation for young scientists – Doctors of sciences MD-396.2021.1.3. VY thanks the Ministry of Science and Higher Education of RF for access to MS equipment. The NIIC team thanks the Ministry of Science and Higher Education of RF for an access to SEM and XRD facilities. The authors thank Dr V. Komarov (NIIC SB RAS) for the help with X-ray powder diffraction experiments. Authorship agreed by all authors. Publisher Copyright: © The Royal Society of Chemistry.

PY - 2022/1/14

Y1 - 2022/1/14

N2 - Screening of AgNO3/AgStBu solutions in DMF, DMSO and NMP resulted in the isolation of three novel nanosized silver/thiolate complexes with a torus-like {Ag20(StBu)10} core. The structures of [NO3@Ag20(StBu)10(NO3)9(DMF)6] (1) and [NO3@Ag20(tBuS)10(NO3)8(NMP)8][NO3@Ag19(tBuS)10(NO3)8(NMP)6]2(NO3) (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@Ag16(StBu)8(NO3)5(DMF)3](NO3)2 (3), which is the one of the few genuine host-guest complexes in the silver/thiolate systems. Solutions of the individual complexes in CH3CN were studied by HR-ESI-MS techniques, which revealed a dynamic behavior for each complex, driven by a redistribution of the {AgNO3} 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 Ag2S with a porous morphology, as observed using the SEM technique. The electrocatalytic HER activity of such a material was studied. This journal is

AB - Screening of AgNO3/AgStBu solutions in DMF, DMSO and NMP resulted in the isolation of three novel nanosized silver/thiolate complexes with a torus-like {Ag20(StBu)10} core. The structures of [NO3@Ag20(StBu)10(NO3)9(DMF)6] (1) and [NO3@Ag20(tBuS)10(NO3)8(NMP)8][NO3@Ag19(tBuS)10(NO3)8(NMP)6]2(NO3) (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@Ag16(StBu)8(NO3)5(DMF)3](NO3)2 (3), which is the one of the few genuine host-guest complexes in the silver/thiolate systems. Solutions of the individual complexes in CH3CN were studied by HR-ESI-MS techniques, which revealed a dynamic behavior for each complex, driven by a redistribution of the {AgNO3} 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 Ag2S with a porous morphology, as observed using the SEM technique. The electrocatalytic HER activity of such a material was studied. This journal is

UR - http://www.scopus.com/inward/record.url?scp=85122757293&partnerID=8YFLogxK

U2 - 10.1039/d1dt02398e

DO - 10.1039/d1dt02398e

M3 - Article

C2 - 34913941

AN - SCOPUS:85122757293

VL - 51

SP - 705

EP - 714

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 2

ER -