Shivnath Mazumder

Ligand Transformations and Efficient Proton/Water Reduction with Cobalt Catalysts Based on Pentadentate Pyridine‐Rich Environments

A series of cobalt complexes with pentadentate pyridine-rich ligands is studied. An initial Co(II) amine complex 1 is prone to aerial oxidation yielding a Co(III) imine complex 2 that is further converted into an amide complex 4 in presence of adventitious water. Introduction of an N-methyl protecting group to the ligand inhibits this oxidation and gives rise to the Co(II) species 5. Both the Co(III) 4 and Co(II) 5 show electrocatalytic H2 generation in weakly acidic media as well as in water. Mechanisms of catalysis seem to involve the protonation of a Co(II)-H species generated in situ.

The Mechanisms of Rectification in Au|Molecule|Au Devices Based on Langmuir–Blodgett Monolayers of Iron(III) and Copper(II) Surfactants†

Langmuir-Blodgett films of metallosurfactants were used in Au|molecule|Au devices to investigate the mechanisms of current rectification.

Effects of Methyl Substitution in Ruthenium Tris(2-pyridylmethyl)amine Photocaging Groups for Nitriles

Four complexes of the general formula [Ru(L)(CH3CN)2](PF6)2, [L = TPA (5), MeTPA (6), Me2TPA (7), and Me3TPA (8)] [TPA = tris[(pyridin-2-yl)methyl]amine, where methyl groups were introduced consecutively onto the 6-position of py donors of TPA, were prepared and characterized by various spectroscopic techniques and mass spectrometry. While 5 and 8 were isolated as single stereoisomers, 6 and 7 were isolated as mixtures of stereoisomers in 2:1 and 1.5:1 ratios, respectively. Steric effects on ground state stability and thermal and photochemical reactivities were studied for all four complexes using (1)H NMR and electronic absorption spectroscopies and computational studies. These studies confirmed that the addition of steric bulk accelerates photochemical and thermal nitrile release.

Distinct Proton and Water Reduction Behavior with a Cobalt(III) Electrocatalyst Based on Pentadentate Oximes.

A new pentadentate oxime has been designed to drive the preferential coordination favored by Co(I) in catalysts used for proton/water reduction. The ligand incorporates water upon metal coordination and is water soluble. This Co(III) species is doubly reduced to Co(I) and exhibits H(+) reduction activity in the presence of weak acids in MeCN and evolves H2 upon protonation suggesting that the ligand design increases catalyst effectiveness. Superior catalysis is observed in water with a turnover number (TON) of 5700 over 18 h. However, the catalyst yields Co-based nanoparticles, indicating that the solvent media may dictate the nature of the catalyst.

Efficient electro/photocatalytic water reduction using a [NiII(N2Py3)]2+ complex

The pyridine-rich complex [NiII(LN2Py3)(MeCN)](ClO4)2 (1) acts as an efficient electro- and photocatalyst in the generation of H2 from water. Observed TONs reach 1050 for electrocatalysis and a remarkable 3500 for photocatalysis. Experimental and DFT data support the ligand-reduced [NiIL˙] as the catalytically active species, contrasting with the [CoIL] observed for cobalt catalysts.

Electronic Modulation of the SOMO‐HOMO Energy Gap in Iron(III) Complexes towards Unimolecular Current Rectification

Amphiphilic five-coordinate iron(III) complexes with {N2 O2 Cl} and {N2 O3 } coordination spheres are studied to elucidate the roles of electronic structure on the mechanisms for current rectification. The presence of an apical chlorido or phenolato ligand plays a crucial role, and the [Fe(III) {N2 O2 Cl}] species supports an asymmetric mechanism while its [Fe(III) {N2 O3 }] counterpart seems to allow for unimolecular mechanism. The effects of electron-donating and electron-withdrawing substituents in the ligand frameworks are also considered.