Improved Synthesis of (TBA)2[W6Br14] Paving the Way to Further Study of Bromide Cluster Complexes

Darya V Evtushok, Taisiya S Sukhikh, Anton A Ivanov, Yakov M Gayfulin, Ilia V Eltsov, Dmitri V Stass, Alexey A Ryadun, Anna P Zubareva, Michael A Shestopalov

Результат исследования: Научные публикации в периодических изданияхстатьярецензирование


Octahedral cluster complexes of molybdenum and tungsten, [M6X8Y6]n- (M = Mo, W; X, Y = Cl, Br, I), are promising active components in various fields, including biomedicine and solar energy. Cluster complexes draw considerable attention due to their X-ray opacity, red/near-IR luminescence, and ability to convert triplet molecular oxygen to active singlet oxygen under UV and visible irradiation. Among the octahedral cluster complexes of molybdenum and tungsten, compounds with a {W6Br8}4+ core are the least studied. There are only a few examples of compounds with substituted terminal ligands, and their properties are not well understood. Among other things, this is due to more labor-intensive and expensive methods for obtaining the starting compounds in comparison with molybdenum counterparts. In this paper, we describe the synthesis of an octahedral cluster complex, (TBA)2[W6Br14] (TBA+ = tetrabutylammonium), in gram quantities, starting from simple substances─W, Br2, and Bi─in 70% yield. The formation of pentanuclear tungsten cluster complexes was recorded as a byproduct. Compounds with substituted terminal ligands (TBA)2[W6Br8Y6] (Y = NO3, Cl, I) were obtained. We also discuss the instability of (TBA)2[W6Br8(NO3)6] under light exposure, the optical properties of a series of compounds (TBA)2[W6Br8Y6] (Y = Cl, Br, I), and the effect of terminal ligands on the chemical shifts in 183W NMR spectra in dimethyl sulfoxide-d6. The presented approach to the synthesis of one of the main precursors of various bromide cluster complexes on a gram scale can stimulate the study of their properties and development of new functional materials based on them.

Язык оригиналаанглийский
ЖурналInorganic Chemistry
СостояниеЭлектронная публикация перед печатью - 15 мар. 2023

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