A. V. Konkova, D. V. Evtushok, Y. A. Vorotnikov, I. V. Eltsov, V. V. Yanshole, A. A. Ivanov, M. A. Shestopalov
{"title":"Tetrabutylammonium Salts of [Mo12O28(μ-L)8]4– Polyoxometal Clusters with Pyrazolate and Triazolate Ligands","authors":"A. V. Konkova, D. V. Evtushok, Y. A. Vorotnikov, I. V. Eltsov, V. V. Yanshole, A. A. Ivanov, M. A. Shestopalov","doi":"10.1134/s0022476624030156","DOIUrl":null,"url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The metathesis of ammonium cations in (NH<sub>4</sub>)<sub>4</sub>[Mo<sub>12</sub>O<sub>28</sub>(μ-L)<sub>8</sub>] (L = pz (pyrazolate) and trz (1,2,4-triazolate)) with tetrabutylammonium is performed under boiling in an aqueous solution with Bu<sub>4</sub>NOH. The substitution of cations and the preservation of the anionic cluster fragment are confirmed by a number of physicochemical methods such as XRD, <sup>1</sup>H NMR, and mass spectrometry. The resulting compounds are soluble and stable in organic solvents, so their redox properties are studied. According to the cyclic voltammetry data, the compounds exhibit reversible oxidation with <i>E</i><sub>1/2</sub> = 0.26 V and 0.61 V for L = pz and trz respectively. The electronic structure is studied by quantum chemical calculations. It is shown that the frontier molecular orbitals of these compounds are mainly composed of molybdenum <i>d</i>-orbitals.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.2000,"publicationDate":"2024-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1134/s0022476624030156","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
The metathesis of ammonium cations in (NH4)4[Mo12O28(μ-L)8] (L = pz (pyrazolate) and trz (1,2,4-triazolate)) with tetrabutylammonium is performed under boiling in an aqueous solution with Bu4NOH. The substitution of cations and the preservation of the anionic cluster fragment are confirmed by a number of physicochemical methods such as XRD, 1H NMR, and mass spectrometry. The resulting compounds are soluble and stable in organic solvents, so their redox properties are studied. According to the cyclic voltammetry data, the compounds exhibit reversible oxidation with E1/2 = 0.26 V and 0.61 V for L = pz and trz respectively. The electronic structure is studied by quantum chemical calculations. It is shown that the frontier molecular orbitals of these compounds are mainly composed of molybdenum d-orbitals.
期刊介绍:
Journal is an interdisciplinary publication covering all aspects of structural chemistry, including the theory of molecular structure and chemical bond; the use of physical methods to study the electronic and spatial structure of chemical species; structural features of liquids, solutions, surfaces, supramolecular systems, nano- and solid materials; and the crystal structure of solids.