TY - JOUR

T1 - Improved Synthesis of (TBA)2[W6Br14] Paving the Way to Further Study of Bromide Cluster Complexes

AU - Evtushok, Darya V

AU - Sukhikh, Taisiya S

AU - Ivanov, Anton A

AU - Gayfulin, Yakov M

AU - Eltsov, Ilia V

AU - Stass, Dmitri V

AU - Ryadun, Alexey A

AU - Zubareva, Anna P

AU - Shestopalov, Michael A

N1 - Acknowledgments: This research was funded by The Council for Grants of the President of the Russian Federation (Grant MK-87.2022.1.3). The authors gratefully acknowledge the Ministry of Science and Higher Education of the Russian Federation (Nos. 121031700321-2, 121031700321-3, and 121031700313-8), thank Prof. E. Cadot and Dr. C. Falaise (Versailles, France) for providing access to a Bruker AXS D8 VENTURE single-crystal X-ray diffractometer to collect the data for the cluster complexes obtained, thank the Collective Center of NIIC, SB RAS (http://www.niic.nsc.ru/institute/tskp), thank the XRD Facility of NIIC, SB RAS, and personally thank V. Y. Komarov and D. A. Piryazev for data collection.

PY - 2023/3/27

Y1 - 2023/3/27

N2 - 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.

AB - 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.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85150375102&origin=inward&txGid=26c5a3a95a3b4c04f74b271c0fbf3e62

UR - https://www.mendeley.com/catalogue/986e030a-697d-3846-ba2e-0325727ba7da/

U2 - 10.1021/acs.inorgchem.2c04426

DO - 10.1021/acs.inorgchem.2c04426

M3 - Article

C2 - 36920338

VL - 62

SP - 4934

EP - 4946

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 12

ER -