Magnetic study and DFT analysis of a doubly carboxylato-bridged Co(II) derivative anchored with a 'scorpionate' precursor as a potential electrocatalyst for heterogeneous H2 evolution.

A new doubly carboxylato-bridged Co(II) dinuclear complex, [Co(bdtbpza)(NCS)]2 (1), was obtained in a satisfactory yield by employing a 'scorpionate'-type precursor, bdtbpza {bis-(3,5-di-tert-butylpyrazol-1-yl)acetate}, and was then structurally characterized. Single-crystal X-ray diffraction analysis revealed that, in 1, each Co(II) is penta-coordinated, leading to a distorted trigonal-bipyramidal geometry within the coordination environment of N3O2. Weak antiferromagnetic coupling within the Co(II) ions in 1 was found based on the isotropic spin Hamiltonian H = -J(S1·S2) for the Si = 3/2 system. For evaluating the spin density distribution and the mechanism for the magnetic exchange coupling, DFT analysis was performed, with the calculated result agreeing the experimental magnetic data. A study into electrochemical H2 evolution, involving cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatographic (GC) analyses of the graphite electrode modified with the cobalt complex in a neutral aqueous solution revealed the high catalytic activity of the complex with a low overpotential toward H2O reduction. The faradaic efficiency of the catalyst was found to be 83.7% and the di-cobalt catalyst-modified electrode displayed quite an interesting H2-evolution activity compared with that of bare electrodes. These results are encouraging for the future potential application of 1 in water splitting.

Antibacterial activity of Cu(II) and Co(II) porphyrins: role of ligand modification.

In this study, we report antibacterial activity of metalloporphyrins; 5, 10, 15, 20-tetrakis (para-X phenyl)porphyrinato M (II) [where X = H, NH2 and COOMe for M = Cu and X = COOH and OMe for M = Co]. The activity study of the as-synthesized metalloporphyrins toward two Gram-positive (S. aureus and S. pyogenes) and two Gram-negative (E. coli and K. pneumoniae) bacteria showed a promising inhibitory activity. Among the complexes under study, the highest antibacterial activity is observed for 5, 10, 15, 20-tetrakis (p-carboxyphenyl)porphyrinato cobalt (II), with inhibition zone of 16.5 mm against Staphylococcus aureus (S. aureus). This activity could be attributed to the high binding ability of COOH group to cellular components, membranes, proteins, and DNA as well as the lipophilicity of the complex. Moreover, consistent with literature report, the study revealed that metalloporphyrins with electron withdrawing group at para-positions have better antibacterial activity than metalloporphyrin which possess electron donating group at para position.

EPR interpretation, magnetism and biological study of a Cu(II) dinuclear complex assisted by a schiff base precursor.

A new Cu(II) dinuclear complex, Cu2L2 (1) was afforded employing the potentially pentatentate Schiff base precursor H2L, a refluxed product of o-vanillin and diethylenetriamine in methanol. Complex 1 was systematically characterized by FTIR, UV-Vis, emission and EPR spectrometry. The single crystal X-ray diffraction analysis of 1 reveals that the copper atom exhibits a distorted square planar geometry, comprising two pairs of phenolato-O and imine-N donors from two different H2L ligands. The temperature dependent magnetic interpretation agrees with the existence of weak antiferromagnetic interactions between the bridging dinuclear Cu(II) ions. A considerable body of experimental evidence has been accumulated to elucidate the magneto-structural relationship in this dinuclear Cu(II) complex by DFT computation. Both the ligand and complex 1 exhibit anti-mycobacterial activity and considerable efficacy on M. tuberculosis H37Ra (ATCC 25177) and M. tuberculosis H37Rv (ATCC 25618) strains. The practical applicability of the ligand and complex 1 has been examined in living cells (African Monkey Vero Cells). The MTT assay proves the non-toxicity of the probe up to 100 mg mL-1. A new homometallic dinuclear Cu(II) complex is afforded with a tetradentate Schiff base precursor. EPR interpretation and temperature dependent magnetic studies show that complex 1 has weak antiferromagnetic coupling and DFT computation is governed to explain the magneto-structural correlation.

Highly efficient electrocatalytic hydrogen evolution from neutral aqueous solution by a water-soluble anionic cobalt(II) porphyrin.

We report the use of a water-soluble anionic cobalt(ii) tetrakis(p-sulfonatophenyl)porphyrin (CoTPPS) as a stable, active, and efficient catalyst for electrocatalytic H2 generation from neutral H2O without any organic additives. The molecule features nearly quantitative Faradaic efficiency with a turnover frequency of ∼1.83 s(-1) measured over 1 h and a turnover number of 1.9 × 10(4) moles of H2 per mole of catalyst with no loss of activity over 73 h at an applied potential of -1.29 V (vs. SHE) in neutral phosphate buffer solution.