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

•Tripodal alcohols provide versatile coordination modes for transition metal ions.•Spontaneous polyalcohol deprotonation leads to binuclear MIII complexes.•The versatile tripodal ligands confer notable robustness to the binuclear aggregates.•Products are formed in air or inert atmosphere and non-pro...

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Bibliographic Details
Published in:	Journal of molecular structure Vol. 1274; p. 134360
Main Authors:	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., Soares, Jaísa F.
Format:	Journal Article
Language:	English
Published:	Elsevier B.V 15-02-2023
Subjects:	Binuclear Early transition metal Intermolecular interactions Polyalcohol Spontaneous deprotonation Tripodal Intermolecular interactions Tripodal Polyalcohol Spontaneous deprotonation Binuclear Early transition metal
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Summary:	•Tripodal alcohols provide versatile coordination modes for transition metal ions.•Spontaneous polyalcohol deprotonation leads to binuclear MIII complexes.•The versatile tripodal ligands confer notable robustness to the binuclear aggregates.•Products are formed in air or inert atmosphere and non-protic or protic media.•Metal ion oxidation or solvent loss does not lead to product decomposition. 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. [Display omitted]
ISSN:	0022-2860 1872-8014
DOI:	10.1016/j.molstruc.2022.134360