XAFS study of copper(II) complexes with square planar and square pyramidal coordination geometries

• Published in: Journal of molecular structure Vol. 1118; pp. 212 - 218
• Main Authors: Gaur, A., Klysubun, W., Nitin Nair, N., Shrivastava, B.D., Prasad, J., Srivastava, K.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15.08.2016
• Subjects: Ab-initio calculations; Absorption; Acetates; Copper; EXAFS; Ligands; Mathematical models; Phenyls; Square planar; Square pyramidal; X-rays; XANES; Square pyramidal; Square planar; XANES; EXAFS; Ab-initio calculations
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2016.04.008

X-ray absorption fine structure of six Cu(II) complexes, Cu2(Clna)4 2H2O (1), Cu2(ac)4 2H2O (2), Cu2(phac)4 (pyz) (3), Cu2(bpy)2(na)2 H2O (ClO4) (4), Cu2(teen)4(OH)2(ClO4)2 (5) and Cu2(tmen)4(OH)2(ClO4)2 (6) (where ac, phac, pyz, bpy, na, teen, tmen = acetate, phenyl acetate, pyrazole, bipyridine, nicotinic acid, tetraethyethylenediamine, tetramethylethylenediamine, respectively), which were supposed to have square pyramidal and square planar coordination geometries have been investigated. The differences observed in the X-ray absorption near edge structure (XANES) features of the standard compounds having four, five and six coordination geometry points towards presence of square planar and square pyramidal geometry around Cu centre in the studied complexes. The presence of intense pre-edge feature in the spectra of four complexes, 1–4, indicates square pyramidal coordination. Another important XANES feature, present in complexes 5 and 6, is prominent shoulder in the rising part of edge whose intensity decreases in the presence of axial ligands and thus indicates four coordination in these complexes. Ab initio calculations were carried out for square planar and square pyramidal Cu centres to observe the variation of 4p density of states in the presence and absence of axial ligands. To determine the number and distance of scattering atoms around Cu centre in the complexes, EXAFS analysis has been done using the paths obtained from Cu(II) oxide model and an axial Cu-O path from model of a square pyramidal complex. The results obtained from EXAFS analysis have been reported which confirmed the inference drawn from XANES features. Thus, it has been shown that these paths from model of a standard compound can be used to determine the structural parameters for complexes having unknown structure. •XANES features of the standard compounds used to detect square planar and square pyramidal geometry in the Cu complexes.•Using Ab initio calculations, variation of p-DOS is correlated to axial ligation for five and four coordinated centers.•For complexes having known/unknown structures, EXAFS analysis was performed using paths from models of standard compounds.