期刊
INORGANICA CHIMICA ACTA
卷 443, 期 -, 页码 251-266出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2016.01.008
关键词
Polymeric polymorphs; Azido bridges; Crystal structures; Halogen interaction; Solvatochromism
资金
- UGC, New Delhi, India
- Cochin University of Science and Technology, Kochi, India
In the present investigation, copper(II) complexes of tridentate 2,4-dichlorido-6-((2-(dimethylamino) ethylimino) methyl) phenol] (HL) Schiff base system incorporating azido [Cu(L)(N-3)](n) (1a and 1b) and cyanato groups [Cu(L)(NCO)] (2) are prepared and characterized by elemental analysis, IR, UV-Vis and single crystal X-ray diffraction studies. While the polymeric polymorphs, 1a and 1b have a square-pyramidal geometry for the basic unit, complex 2 exhibits square planar topology. The polymorphs are one-dimensional helical coordination polymers with azido group in single asymmetric equatorial-axial end-on bridging mode. The interestingly different combinations of intermolecular interactions have resulted in polymorphs 1a and 1b. Based on the angular preference, intermolecular distance and the size of Cl atom, type I halogen interactions which is rather rarely observed is also discussed. Solvent effect on the charge-transfer bands and d-d bands were analyzed and the former exhibits negative solvatochromic effect while latter a positive effect with increasing polarity of solvents. Solid and solution state optical emission properties are analyzed. All the copper complexes emit in the blue region. Thermal analyses have been performed in order to understand the thermal decomposition pattern of the complexes. Spin Hamiltonian and bonding parameters have been calculated from EPR analysis. The g values, calculated for the complexes 1a, 1b in frozen DMF, indicate the presence of the unpaired electron in the d(x)(2)-(2)(y) orbital consistent with a square pyramidal topology whereas that of complex 2 corresponds to a rhombic symmetry. (C) 2016 Elsevier B.V. All rights reserved.
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