TY - JOUR

T1 - Evidences of the non-stoichiometry and control of the composition of the cluster-based solid solution K6[Re6-xMoxS8(CN)5] (x=2.75–3.63)

AU - Lappi, Tatiana I.

AU - Gaifulin, Yakov M.

AU - Yanshole, Vadim V.

AU - Cordier, Stephane

AU - Naumov, Nikolay G.

N1 - The reported study was funded by the Russian Science Foundation (project No 22-73-10181). The research was also supported by the Ministry of Science and Higher Education of the Russian Federation. Authors thank the Microscopic Centre of the Siberian Branch of the Russian Academy of Sciences and the Shared Equipment Center ‘‘Spectroscopy and Optics’’ of the Institute of Automation and Electrometry SB RAS for the provided instrumental support.

PY - 2023/3

Y1 - 2023/3

N2 - In this work, we investigated a high-temperature reaction between ReS2, MoS2 and KCN resulting in the formation of the cluster-based K6[Re6-xMoxS8(CN)5] solid solution. The crystal structure is based on chains of [Re6-xMoxS8(CN)6] cluster units. It was found that both the sintering temperature of starting sulfides and the reaction temperature with KCN have an influence on the composition of the product allowing x to be varied within the range x ​= ​2.75–3.63. The molar ration of ReS2:MoS2:KCN loaded composition is fixed to 3:3:14 in all experiments. Energy dispersive spectroscopy (EDS), powder X-ray diffraction (PXRD) and high-resolution electrospray (ESI) mass spectrometry were used to characterize the solid solution K6[Re6-xMoxS8(CN)5]. It was shown by mass spectrometry that the solid solution with fractional x contains anions based on the {Re4Mo2S8}, {Re3Mo3S8} and {Re2Mo4S8} cluster cores in different proportions depending on the above-mentioned factors. Particularly, the rise of the temperature of the synthesis or temperature of sintering of metal sulfides led to increase of the rhenium content in the solid solution.

AB - In this work, we investigated a high-temperature reaction between ReS2, MoS2 and KCN resulting in the formation of the cluster-based K6[Re6-xMoxS8(CN)5] solid solution. The crystal structure is based on chains of [Re6-xMoxS8(CN)6] cluster units. It was found that both the sintering temperature of starting sulfides and the reaction temperature with KCN have an influence on the composition of the product allowing x to be varied within the range x ​= ​2.75–3.63. The molar ration of ReS2:MoS2:KCN loaded composition is fixed to 3:3:14 in all experiments. Energy dispersive spectroscopy (EDS), powder X-ray diffraction (PXRD) and high-resolution electrospray (ESI) mass spectrometry were used to characterize the solid solution K6[Re6-xMoxS8(CN)5]. It was shown by mass spectrometry that the solid solution with fractional x contains anions based on the {Re4Mo2S8}, {Re3Mo3S8} and {Re2Mo4S8} cluster cores in different proportions depending on the above-mentioned factors. Particularly, the rise of the temperature of the synthesis or temperature of sintering of metal sulfides led to increase of the rhenium content in the solid solution.

KW - Metal sulfides

KW - Molybdenum

KW - Octahedral cluster

KW - Rhenium

KW - Solid state chemistry

UR - https://www.scopus.com/inward/record.url?eid=2-s2.0-85145181908&partnerID=40&md5=ac855c393b0f59e9d608089d4e3aea4d

UR - https://www.mendeley.com/catalogue/c11484eb-a35e-306c-a08d-6bc3c393fdca/

U2 - 10.1016/j.jssc.2022.123785

DO - 10.1016/j.jssc.2022.123785

M3 - Article

VL - 319

JO - Journal of Solid State Chemistry

JF - Journal of Solid State Chemistry

SN - 0022-4596

M1 - 123785

ER -