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The Mukherjee Group focuses on systematic development of synthetic coordination chemistry of transition metal ions with designed organic ligands to address diversified research problems. Emphasis is directed to bioinorganic modeling, metal-coordinated ligand radicals, coordination polymers, multi-metal clusters etc. Specific research themes include: (I) Bioinorganic synthetic model work: chemical modeling of tyrosinase and catechol oxidase [dioxygen activation and aromatic ring hydroxylation, phenoxo-/ hydroxo-bridged dicopper (II) systems]; bio-inspired synthesis of binuclear oxo-/acetate-bridged diiron (III) and dimanganese (III,III; III,IV; IV,IV) systems and reactivity studies of dimanganese(IV) complex with phenols of relevance to photosystem II; demonstration of hydrolysis of biologically-relevant substrates by phenoxo-bridged Mn(II)2, Co(II)2, Ni(II)2, Cu(II)2, and Zn(II)2 complexes (detailed kinetic investigations to throw light on the mechanistic aspects); stability and properties of metal-coordinated phenoxyl radical of relevance to galactose oxidase. Low-temperature absorption spectroscopic characteri-zation and reactivity studies of metal-O2 intermediates. (ii) Stabilization of nickel(III) and nickel(IV) states; Cobalt-coordinated C-S(thioether) bond cleavage and Co-C bond formation; Stabilization of iron(III)/ruthenium(III)-coordinated o-benzosemiquinonato radical by deprotonated pyridine amide ligands; Synthesis and properties of ligand-bridged six-coordinate cobalt(III) and four-coordinate cobalt(II) complexes and also a series of hetero-bimetallic complexes; Anion (bisulfate) recognition using ferrocene-appended amide groups; Assembly and properties of a discrete tetrairon(III) cluster and coordination polymers by pyridine amide ligands in their neutral form. (iii) Metal-coordinated ligand radicals: molecular and electronic structural investigation of metal-coordinated o-iminobenzosemiquinonato anion radical using non-innocent (redox active) ligands and formation of radical-based benzo-triazole ring formation. (iv) Discovery of a new class of Fe(II)N6 spin-equilibria systems, exhibiting interesting cooperativity phenomena (effect of counter-anion and solvate of crystallization). (v) Co-C bond formation [cobalt(III)-alkyl and cobalt(III)-dialkyl complexes] and investigation of their properties and stabilization of ligand-bridged dinickel(II), dicopper(II), nickel(II)-nickel(I) systems, supported by pyrazole-based chelating ligands. (vi) Magneto-structural studies of discrete binuclear, trinuclear, and oligonuclear transition metal compl-exes and coordination polymers. (vii) Synthesis of half-sandwich organometallic molecules and nucleophilic addition reactions onto the ruthenium(II)-coordinated benzene. (viii) Identification of non-covalent interactions with emphasis on C–H....Cl hydrogen-bonding.
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