Framework robustness in early d-block metal complexes with tripodal polyalcohol ligands

Krupczak, Carla, Stoeberl, Bruno J., Westrup, Kátia C. M., Tesi, Lorenzo, Santana, Francielli S., Giese, Siddhartha O. K., Yokaichiya, Fabiano, Costa, Daniel da S., Missina, Juliana M., Stinghen, Danilo, Hughes, David L., Sessoli, Roberta, Nunes, Giovana G., Reis, Dayane M. and Soares, Jaísa F. (2023) Framework robustness in early d-block metal complexes with tripodal polyalcohol ligands. Journal of Molecular Structure, 1274 (Part 1). ISSN 0022-2860

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While performing our research on the tetranuclear "star-shaped" complexes formulated as [M3M'(LR)2(dpm)6], where M, M' are first-row d-block metals; H3LR is a tripodal alcohol, RC(CH2OH)3, with R = Et, Me or Ph; and Hdpm = dipivaloylmethane, we isolated a series of binuclear, alkoxide-bridged chelate complexes of titanium and chromium upon spontaneous deprotonation of the polyalcohol. In the titanium system, both [TiIII2Cl4(H2LEt)2]·4thf and [TiIV2Cl4(HLEt)2]·2thf were identified; they present analogous binuclear frameworks but distinct metal oxidation states and polyalcohol deprotonation degrees. Four similar CrIII2 compounds were also isolated, differing in the tripodal R groups and cocrystallized solvent or proligand molecules. The products were characterized by single-crystal X-ray diffraction analysis and spectroscopic, thermogravimetric and magnetic measurements. Cocrystallization influences the nature, strength and pattern of intermolecular interactions. Among the binuclear MIII products, all those containing solvating tetrahydrofuran, [M2Cl4(H2LR)2]·x thf (R = Et, Ph; x = 4 or 5 respectively), lose solvent upon gradual polyalcohol deprotonation, mild heating or vacuum drying. The versatile tripodal skeleton assembles the alkoxide-bridged M2 units (M = TiIII/IV or CrIII) in various experimental conditions, including air or inert atmosphere and non-protic or protic media, and confers remarkable robustness to the final binuclear aggregates.

Item Type: Article
Additional Information: Author acknowledgements: Authors are grateful to Brazilian CNPq [Conselho Nacional de Desenvolvimento Científico e Tecnológico, grants 308426/2016–9 and 314581/2020–0], CAPES [Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, Finance Code 001] and PrInt/CAPES-UFPR Internationalization Program for scholarships and financial support. This work has also been supported by Italian MIUR [Project PRIN 2015-HYFSRT and Progetto Dipartimenti di Eccellenza 2018–2022, ref B96C1700020008]. We are very grateful to the technical staff from the Department of Chemistry/UFPR and Department of Chemistry and Biology/UTFPR, particularly Dr. Rubia Camila R. Bottini and Mr. Angelo Roberto dos Santos Oliveira, for performing the metal and thermogravimetric analyses. The access to the LAMAQ/UTFPR (Multi-User Laboratory of Chemical Analysis) is also appreciated.
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 18 Oct 2022 14:32
Last Modified: 17 Oct 2023 01:38
DOI: 10.1016/j.molstruc.2022.134360


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