EXAFS study of mixed ligand copper complexes having nicotinic acid as one of the ligands

Abstract

Copper K-edge EXAFS spectra of the copper (II) complexes [Cu3(NA)4(dca)2(H2O)8].2H2O (1) and [Cu2(2,2'-bipy)(NA)2](ClO4)2.H2O (2) (where NA = Nicotinic acid; dca = dicyanamide anion; 2,2'-bipy = 2-2' bipyridine) having different coordination environments and geometries have been investigated. The complex 1 is supposed to have six coordinated geometry and complex 2 five coordinated geometry. EXAFS has been recorded at the K-edge of copper in the complex at the dispersive EXAFS beamline at 2 GeV Indus-2 synchrotron source at RRCAT, Indore, India. Theoretical models have been generated for both the complexes separately using their reported crystal structures. These theoretical models have been fitted to the respective experimental EXAFS data and the structural parameters, which include bond lengths, coordination numbers and thermal disorders, have been determined. The results obtained have been found to be comparable with those reported using crystallography. The coordination geometry about the copper (II) ion has been depicted for both the complexes. Further, copper has been found to be in +2 oxidation state in both the complexes. The study shows that the dispersive EXAFS beamline can be used to obtain information about the coordination geometry of a sample, though the beamline provides limited range of EXAFS data.