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An investigation into the coordination chemistry of tripodal “click” triazole ligands with Mn, Ni, Co and Zn ions

Chernobryva, Mariya; Motevalli, Majid; Hawes, Chris S.; Watkinson, Michael

Authors

Mariya Chernobryva

Majid Motevalli

Michael Watkinson



Abstract

The steric influences of the triazole side chains in two tripodal chelating ligands tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA) and tris[(1-phenyl-1H-1,2,3-triazol-4-yl)methyl]amine (TPTA) are explored through structural studies of four new mononuclear d-block metal complexes. The manganese(II) complex [Mn(TPTA)2](ClO4)2·H2O 1 includes two TPTA ligands each coordinated in a tridentate fashion to give an unusual trigonal prismatic coordination geometry with two non-coordinated pendant triazole groups which engage in weak hydrogen bonding interactions. [Ni(TBTA)(OH2)Cl]Cl·3H2O·MeCN 2 contains an octahedral nickel(II) centre bound by a tetradentate TBTA ligand along with aqua and chloride ligands, where the significant degree of lattice solvation leads to an extensive hydrogen bonding network linking complexes through hexa-aqua water clusters. The mononuclear copper(II) complex [Cu(TPTA)Cl2]·MeCN 3 contains no classical hydrogen bond donors but instead intermolecular aggregation takes place through chelating Csingle bondH···Cl hydrogen bonds involving the acidic triazole Csingle bondH groups which leads to close association of adjacent complexes. The zinc complex [Zn(TPTA)Cl]2[ZnCl4]·MeOH 4, in which cationic [Zn(TPTA)Cl]+ species are accompanied by tetrachlorozincate anions, exhibits a tris-triazole chelating coordination geometry for the TPTA ligand and associates through tetrameric p···p stacking interactions despite the positive charge present on each species. Structural analysis of these complexes, supported by solution-state mass spectrometry, NMR spectroscopic and magnetic susceptibility measurements, where applicable, provides new insights into the breadth of coordination geometries and intermolecular packing modes available to this important class of chelating ligand.

Journal Article Type Article
Acceptance Date Feb 27, 2022
Online Publication Date Mar 2, 2022
Publication Date Jul 5, 2022
Publicly Available Date May 30, 2023
Journal Journal of Molecular Structure
Print ISSN 0022-2860
Publisher Elsevier
Peer Reviewed Peer Reviewed
Volume 1259
Pages 132736 - 132736
DOI https://doi.org/10.1016/j.molstruc.2022.132736
Keywords Tripodal ligands; Click triazoles; Intermolecular interactions; d-block coordination compounds
Publisher URL https://www.sciencedirect.com/science/article/pii/S0022286022004094?via%3Dihub

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