SYNTHESIS, CRYSTAL STRUCTURE, AND SUPRAMOLECULAR INTERACTIONS IN A BIS(TETRACHLOROCATECHOLATE) CHELATED MANGANESE(III) C
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SYNTHESIS, CRYSTAL STRUCTURE, AND SUPRAMOLECULAR INTERACTIONS IN A BIS(TETRACHLOROCATECHOLATE) CHELATED MANGANESE(III) COMPLEX G. Mahata1 and A. Panja1,2*
A mononuclear manganese(III) complex [DABH2][Mn2(Cl4Cat)2(H2O)2]⋅4DMF (1) (DAB = 1,4-diaminobutane, Cl4CatH2 = tetrachlorocatechol) is synthesized by a one-pot reaction involving manganese(II) chloride tetrahydrate and tetrachlorocatechol in a 1:2 molar ratio in the presence of 1,4-diaminobutane in a DMF-water mixture under aerobic conditions, and is structurally characterized. X-ray crystallography reveals that the complex anion is constructed with two tetrachlorocatecholate ligands coordinated to the manganese(III) center in equatorial positions, and two axial positions are occupied by two water molecules. The crystal packing of 1 is stabilized by complex networks of hydrogen bonding interactions in which oxygen atoms of coordinated tetrachlorocatecholate ligands and lattice DMF molecules serve as hydrogen bond acceptors, while the axially coordinated water molecules together with doubly protonated 1,4diaminobutane act as hydrogen bond donors. The solid state packing of 1 is further stabilized by Cl⋯Cl halogen bonding interactions within tetracholorocatecholate units and the C–H⋯π and π⋯π interactions involving DMF solvates and aromatic rings of the tetracholorocatecholate ligands. The complex is further characterized by IR spectroscopy and cyclic voltammetry, and the results are analyzed. DOI: 10.1134/S0022476620090164 Keywords: manganese(III) complex, redox active ligand, crystal structure, hydrogen and halogen bonding, C–H⋯π and π⋯π interactions, cyclic voltammetry.
INTRODUCTION Transition metal complexes with redox active organic ligands have attracted considerable attention because of their application in various fields, including bioinspired catalysis, C–H bond activation, and C–C cross coupling [1-7]. Furthermore, these compounds display several closely associated electronic states because of their close energy levels of the d and π orbitals of metal and the redox non-innocent ligand, respectively. These so called valence tautomeric compounds can be switched by the influence of external stimuli such as heat and light, and therefore, these bistable materials are considered as potential candidates for the fabrication of memory storage devices [8-19]. Apart from the material perspective, several 1st row transition metal complexes with non-innocent ligands, such as dioxolenes, dithiolenes, and benzoquinonediimines, were synthesized for structural and/or functional models for various metallo-oxidases [20-25].
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Department of Chemistry, Gokhale Memorial Girls' College, Kolkata, Republic of India; *[email protected]. Postgraduate Department of Chemistry, Panskura Banamali College, Panskura, Republic of India. Original article submitted January 24, 2020; revised February 3, 2020; accepted February 3, 2020.
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0022-4766/20/6109-1475 © 2020 by Pleiades Publishing, Ltd.
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Weak non-covalent interactions, popularly known as supramolecular interactions, pla
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