R.K. Dani

Ni(II) and Co(III) complexes of 5-methyl-1,3,4-thiadiazole-2-thiol: syntheses, spectral, structural, thermal analysis, and DFT calculation

Two new complexes, [Ni(en)2(mtt)2] (1) and [Co(en)2(mtt)2](mtt) (2) (Hmtt = 5-methyl-1,3,4-thiadiazole-2-thiol and en = ethylenediamine), have been synthesized and characterized by various physicochemical techniques. Complexes 1 and 2 crystallize in monoclinic and orthorhombic system with space groups P 21/n and P 21 21 21, respectively. The molecular structures of 1 and 2 show that the metal ions are six-coordinate bonded through four equatorial nitrogens of two en and two axial nitrogens of mtt ligands. The crystal structures of the complexes reveal that mtt is present in thione form and bound to the metal ion through the thiadiazole nitrogen. The crystal structures of the complexes are stabilized by various intermolecular hydrogen bonding providing supramolecular architecture. Complex 2 is also stabilized by weak π···π interactions occurring between two thiadiazole rings. The bioefficacies of the ligand and complexes have been examined against the growth of bacteria to evaluate their antimicrobial potential. The biological results suggest that 2 is more active than the ligand and 1 against the tested bacteria. The geometries of the ligand and the complexes have been optimized by the DFT method and the results are compared with the X-ray diffraction data. The Co(III) complex exhibits an irreversible Co(III)/Co(II) process while the Ni(II) complex displays quasi-reversible Ni(II)/Ni(III) redox processes with large peak separation as compared to that expected for a one electron process which is thought to be coupled with some chemical reaction. Graphical abstract

Surface enhanced Raman scattering investigation of two novel piperazine carbodithioic acids adsorbed on Ag and ZnO nanoparticles

In this work piperazine-1-carbodithioic acid (PZCDT) and piperazine-1,4-dicarbodithioic acid (PZbCDT) were synthesized. These analytes PZCDT and PZbCDT have chair conformations, which is expected to give specific surface-enhanced Raman scattering (SERS) effects on individual bands. SERS, UV-Visible, TEM and DFT methods have proved that the dithiocarbamate moiety is a potential and suitable functional group for silver and ZnO nanoparticles (AgNPs and ZnONPs). The enhancement mechanism and enhancement factors in both SERS@AgNPs and SERS@ZnONPs are also discussed. Two new strong bands appear at 1630, 1286 cm−1 with very large intensity in SERS@AgNPs, which signifies the conversion of the C–N bond of the dithiocarbamate moiety into CN bonds. The SERS signatures that are observed are quite different in SERS@AgNPs and SERS@ZnONPs.

Vibrational and quantum chemical investigation of cyclization of thiosemicarbazide group in 1-benzoyl-4-phenyl-3-thiosemicarbazide

1-Benzoyl-4-phenyl-3-thiosemicarbazide (H3bpt) was treated with acid - base in one sequence and base - acid in other sequence, both of which lead to ring formation of thiosemicarbazide group, giving N-phenyl-5-phenyl-1,3,4-thiadiazol-2-amine (Hppta) in the first case and 4,5-diphenyl-2,4-dihydro-1,2,4-triazole-3-thione (Hdptt) in the second case. The primary (H3bpt) as well as the resulting compounds (Hppta & Hdptt) has been characterized by elemental analyses, NMR, FTIR and Raman spectroscopic techniques. The quantum chemical calculations of the compounds are performed using DFT/B3LYP/6311G(d,p) method for geometry optimizations and also for prediction of the molecular properties. The cyclization is confirmed by disappearance of many bands belonging to the open chain subgroups of H3bpt such as; NH stretching, NH bending, CN stretching, NH puckering, CO stretching etc. The ring formation of 1-benzoyl-4-phenyl-3-thiosemicarbazide (H3bpt) has been further confirmed by the appearance of many bands belonging to the closed ring of thiosemicarbazide in the resulting compounds Hppta and Hdptt.