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RAS Chemistry & Material ScienceЖурнал неорганической химии Russian Journal of Inorganic Chemistry

  • ISSN (Print) 0044-457X
  • ISSN (Online) 3034-560X

Crystal polymorphism of the double pseudopolymeric gold(III)-thallium(III) dithiocarbamato-chlorido complex of [Au(SCNPr)][TlCl]: preparation, self-assembly of supramolecular architectures, and thermal behavior

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PII
S3034560XS0044457X25080091-1
DOI
10.7868/S3034560X25080091
Publication type
Article
Status
Published
Authors
O.A. Bredyuk
  • Affiliation: Institute of Geology and Nature Management, Far Eastern Branch of the Russian Academy of Sciences
S.V. Zinchenko
  • Affiliation: Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences
A.I. Smolentsev
  • Affiliation: Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences
A.V. Ivanov
  • Affiliation: Institute of Geology and Nature Management, Far Eastern Branch of the Russian Academy of Sciences
Volume/ Edition
Volume 70 / Issue number 8
Pages
1051-1064
Abstract
The interaction of thallium(I) N,N-dipropyldithiocarbamate with [AuCl] anions in a 2M HCl medium was studied. The heterogeneous reaction of gold(III) binding from solution to the solid phase, including the redox process, results in the formation of a double dithiocarbamato-chlorido complex of [Au(SCNPr)][TlCl]. The crystals of the obtained compound are characterized by their ability to polymorphism: at 220 K the complex exists in the form of the α-modification (α-I), while at 296 K the β-modification (β-I) is stable. The α-I/β-I structures include 4/2 nonequivalent square-planar cations of [Au(SCNPr)] (A, 2 B, C/A, B) and 2/1 distorted tetrahedral anions [TlCl]. Self-assembly of these structural units, which are combined due to interionic secondary interactions (the most important of which are chalcogen bonds S···Cl), leads to the formation of the complicated supramolecular architectures such as cation-anionic pseudo-polymeric ribbons. Alternating along the edges of these ribbons and acting as double linkers, thallium(III) anions pairwise combine neighboring iso- meric complex cations of [Au(SCNPr)], which are localized in the central part of the ribbons. When studying the thermal behavior of the complex, TlCl and elemental gold were identified as individual thermolysis products, which are quantitatively reduced and crystallized under low-temperature conditions (up to 300°C).
Keywords
двойные дитиокарбаматно-хлоридные комплексы Au(III)-Tl(III) полиморфизм супрамолекулярная самоорганизация межионные вторичные связи термолиз
Date of publication
09.12.2025
Year of publication
2025
Number of purchasers
0
Views
16

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