TY - JOUR

T1 - Iodide-to-DMSO substitution in [{M6I8}I6] (M = Mo, W) clusters: NMR-resolved isomeric pathway and isolation of early adducts

AU - Petunin, Anton A.

AU - Evtushok, Darya V.

AU - Vegner, Margarita V.

AU - Berezin, Alexey S.

AU - Sukhikh, Taisiya S.

AU - Eltsov, Ilia V.

AU - Shestopalov, Michael A.

AU - Vorotnikov, Yuri A.

N1 - The study was funded by the Ministry of Science and Higher Education of the Russian Federation within the governmental order (№ 125020401317–8). NIIC team thank the Ministry of Science and Higher Education of the Russian Federation. The authors thank XRD Facility of NIIC SB RAS and personally thank to V. Y. Komarov and D. V. Kochelakov for the crystal data collection.

PY - 2026/9/15

Y1 - 2026/9/15

N2 - Due to a unique set of properties, octahedral cluster complexes of molybdenum and tungsten [{M6I8}L6]n are promising for various applications. However, the majority of studies focus on homoleptic compounds, while heteroleptic analogues remain largely unexplored. This work examines the interaction of iodide cluster complexes (Bu4N)2[{M6I8}I6] (M = Mo, W) with dimethyl sulfoxide, resulting in the synthesis and structural characterization of four new heteroleptic complexes (Bu4N)[{M6I8}(DMSO)I5] and cis-[{M6I8}(DMSO)2I4] (M = Mo, W). Using 1H NMR spectra to monitor reaction mixtures and varying the synthetic conditions (including I2 addition), we tracked the formation of deeper substitution products, up to the homoleptic [{M6I8}(DMSO)6](I3)4 (M = Mo, W), previously reported by us. This study allowed us to identify the most stable products under synthesis conditions and elucidate the isomeric pathway of the substitution process. The optical and luminescent properties of the new heteroleptic complexes were studied. Partial substitution of terminal ligands was shown to significantly reduce the photophysical characteristics.

AB - Due to a unique set of properties, octahedral cluster complexes of molybdenum and tungsten [{M6I8}L6]n are promising for various applications. However, the majority of studies focus on homoleptic compounds, while heteroleptic analogues remain largely unexplored. This work examines the interaction of iodide cluster complexes (Bu4N)2[{M6I8}I6] (M = Mo, W) with dimethyl sulfoxide, resulting in the synthesis and structural characterization of four new heteroleptic complexes (Bu4N)[{M6I8}(DMSO)I5] and cis-[{M6I8}(DMSO)2I4] (M = Mo, W). Using 1H NMR spectra to monitor reaction mixtures and varying the synthetic conditions (including I2 addition), we tracked the formation of deeper substitution products, up to the homoleptic [{M6I8}(DMSO)6](I3)4 (M = Mo, W), previously reported by us. This study allowed us to identify the most stable products under synthesis conditions and elucidate the isomeric pathway of the substitution process. The optical and luminescent properties of the new heteroleptic complexes were studied. Partial substitution of terminal ligands was shown to significantly reduce the photophysical characteristics.

KW - Cluster complexes

KW - Crystal structure

KW - Dimethyl sulfoxide

KW - Heteroleptic complexes

KW - Luminescence

KW - Molybdenum

KW - Tungsten

UR - http://scopus.com/pages/publications/105037975721

UR - https://www.mendeley.com/catalogue/634f4c1a-4927-332b-ae6b-720f2f69ab54/

U2 - 10.1016/j.molstruc.2026.146446

DO - 10.1016/j.molstruc.2026.146446

M3 - Article

VL - 1370

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

M1 - 146446

ER -