Research output: Contribution to journal › Article › peer-review
Iodide-to-DMSO substitution in [{M6I8}I6] (M = Mo, W) clusters: NMR-resolved isomeric pathway and isolation of early adducts. / Petunin, Anton A.; Evtushok, Darya V.; Vegner, Margarita V. et al.
In: Journal of Molecular Structure, Vol. 1370, 146446, 15.09.2026.Research output: Contribution to journal › Article › peer-review
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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 -
ID: 77726604