Chlorocobaloxime containing N -(4-pyridylmethyl)-1,8-naphthalamide peripheral ligands: synthesis, characterization and enhanced electrochemical hydrogen evolution in alkaline medium.

Two new discrete cobaloxime based complexes with the general formula [ClCo(dioxime) 2 L] (1 and 2), L1 = N -(4-pyridylmethyl)-1,8-naphthalamide, L2 = 4-bromo- N -(4-pyridylmethyl)-1,8-naphthalamide have been synthesized and characterized by various spectroscopic techniques such as FT-IR, 1 H, 13 C{ 1 H} NMR and PXRD. The molecular structures of both complexes have also been determined using single crystal X-ray crystallography. The solid state molecular structures revealed distorted octahedral geometry around the Co(III) central metal ion with two dioximes in the equatorial plane and axial positions are occupied by chloro and pyridine nitrogen of N -(4-pyridylmethyl)-1,8-naphthalamide ligands. Both complexes exhibit weaker non-covalent interactions (C-H⋯O, C-H⋯Cl and C-H⋯π(Centroid) in complex 1 whereas C-H⋯O and C-H⋯Br in complex 2) resulting in the formation of dimeric and 1D supramolecular structures. Furthermore, these complexes are immobilized onto the surface of activated carbon cloth (CC) and their electrocatalytic performance for the hydrogen evolution reaction (HER) has been investigated in alkaline and acidic media as well as buffer solution. In alkaline medium, we found that complex 2 exhibited impressive electrocatalytic HER activity and produced a current density of -10 mA cm -2 at an overpotential of 260 mV, whereas complex 1 produced the same current density at an overpotential of 334 mV. An electrochemical impedance spectroscopy (EIS) spectral study revealed the faster charge transfer kinetics of complex 2 than that of complex 1. Similarly, the low Tafel slope (100 mV dec -1 ) for the HER with complex 2 indicates faster HER kinetics compared to complex 1. The chronoamperometric study showed that complex 2 is stable under electrocatalytic HER conditions for 5 h without losing the initial current density and it has also been established that the complex structure is retained after electrocatalysis.