TY - JOUR

T1 - A novel silver(I) di-iso-butyldithiocarbamate: Unusually complicated 1-D polymeric structure, multiple ligand-supported Ag–Ag interactions and its capability to bind gold(III). Preparation, structural organisation and (13C, 15N) CP-MAS NMR of [Ag6(S2CNiBu2)6]n and [Au(S2CNiBu2)2][AgCl2]

AU - Korneeva, Eugenia V.

AU - Smolentsev, Anton I.

AU - Antzutkin, Oleg N.

AU - Ivanov, Alexander V.

N1 - Funding Information: The authors are grateful to the Knut and Alice Wallenberg Foundation (NMR for Life program), SciLifeLab Laboratory, and personally to Dr. Tobias Sparrman (Umeå University, Sweden) for his assistance in recording some of 13 C CP-MAS NMR spectra. The Foundation in memory of J. C. and Seth M. Kempe is acknowledged for grants, from which NMR probes and a Bruker Ascent Aeon 400 MHz NMR spectrometer at LTU were purchased. OA’s salary is partially covered from the REFIT project (EM16-0013) on ionic materials funded by The Swedish Foundation for Strategic Research (SSF). Publisher Copyright: © 2021 Elsevier B.V. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/9/24

Y1 - 2021/9/24

N2 - We have synthesised three new complexes of [Ag6{S2CN(iso-C4H9)2}6]n (1), [Au{S2CN(iso-C4H9)2}2][AgCl2] (2) and [Au{S2CN(iso-C4H9)2}2][Ag0.69Au0.31Cl2] (3), chemically identified these compounds using solution (1H, 13C) and solid-state (13C, 15N) CP-MAS NMR and FT-IR spectroscopy, and structurally characterised them by single-crystal X-ray diffraction analysis. There are six structurally inequivalent silver(I) centres in the former compound, whose unusually complicated, monodimensional polymeric structure is generally stabilised by six unequal iBuDtc ligands acting as bridges, along with numerous ligand-supported Ag–Ag interactions. Studying the capability of the precipitated AgiBuDtc to bind gold(III) from a [AuCl4]–/5.15 M NaCl solution, the double pseudo-polymeric heterometallic dithiocarbamato-chlorido complexes 2 and 3 were successfully obtained as individual fixation modes of gold to the solid phase. In the self-assembly of a bidimensional supramolecular structure of the latter two compounds, numerous interionic secondary bonds (Au···S, Ag···S and S···Cl), the anagostic H–C···Ag interactions and the Cl···H–C hydrogen bonds play a key role. To study the thermal behaviour of crystalline compounds 1 and 2, we additionally used simultaneous thermal analysis (STA). During the thermolysis of 1/2, the formation of Ag2S/AgCl,Au0 was supported, respectively, by energy dispersive X-ray (EDX) spectroscopy, while the dispersity and morphology of residual substances were studied using scanning electron microscopy.

AB - We have synthesised three new complexes of [Ag6{S2CN(iso-C4H9)2}6]n (1), [Au{S2CN(iso-C4H9)2}2][AgCl2] (2) and [Au{S2CN(iso-C4H9)2}2][Ag0.69Au0.31Cl2] (3), chemically identified these compounds using solution (1H, 13C) and solid-state (13C, 15N) CP-MAS NMR and FT-IR spectroscopy, and structurally characterised them by single-crystal X-ray diffraction analysis. There are six structurally inequivalent silver(I) centres in the former compound, whose unusually complicated, monodimensional polymeric structure is generally stabilised by six unequal iBuDtc ligands acting as bridges, along with numerous ligand-supported Ag–Ag interactions. Studying the capability of the precipitated AgiBuDtc to bind gold(III) from a [AuCl4]–/5.15 M NaCl solution, the double pseudo-polymeric heterometallic dithiocarbamato-chlorido complexes 2 and 3 were successfully obtained as individual fixation modes of gold to the solid phase. In the self-assembly of a bidimensional supramolecular structure of the latter two compounds, numerous interionic secondary bonds (Au···S, Ag···S and S···Cl), the anagostic H–C···Ag interactions and the Cl···H–C hydrogen bonds play a key role. To study the thermal behaviour of crystalline compounds 1 and 2, we additionally used simultaneous thermal analysis (STA). During the thermolysis of 1/2, the formation of Ag2S/AgCl,Au0 was supported, respectively, by energy dispersive X-ray (EDX) spectroscopy, while the dispersity and morphology of residual substances were studied using scanning electron microscopy.

KW - Heteronuclear (C, N) CP-MAS NMR

KW - Ligand-supported argentophilic interaction

KW - Polymeric silver(I) di-iso-butyldithiocarbamate

KW - Pseudo-polymer gold(III)-silver(I) complex

KW - Supramolecular self-assembly

UR - http://www.scopus.com/inward/record.url?scp=85109449668&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2021.120383

DO - 10.1016/j.ica.2021.120383

M3 - Article

AN - SCOPUS:85109449668

VL - 525

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

M1 - 120383

ER -