Photoluminescent tetrahedral d(10)-metal Schiff base complexes exhibiting highly ordered mesomorphism

TitlePhotoluminescent tetrahedral d(10)-metal Schiff base complexes exhibiting highly ordered mesomorphism
Publication TypeJournal Article
Year of Publication2016
AuthorsChakraborty, S, Purkayastha, DDhar, Das, G, Bhattacharjee, CR, Mondal, P, S. Prasad, K, Rao, DSShankar
JournalPolyhedron
Volume105
Pagination150-158
Date PublishedFEB
ISSN0277-5387
KeywordsDensity functional theory, Luminescence, Mesophase, Schiff base, X-ray diffraction
Abstract

A series of four-coordinate d(10)-metal complexes of the type [ML2] {M = Zn, Cd, Hg; L = 4-nitro-2-((octadecylimino)methyl)phenol}, incorporating a new N-alkylated bidentate [N,O]-donor salicylaldimine Schiff base ligand, has been synthesized and characterized by elemental analyses, FT-IR, UV-Vis, H-1 NMR and FAB-mass spectroscopies. The ligand is non-mesomorphic and devoid of any photoluminescence. The zinc(II) and cadmium(II) complexes displayed highly ordered mesophases reminiscent of soft crystals. The phases have been characterized by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD) studies. The complex of mercury(II) decomposed prior to melting. An orthogonal symmetry with a `herringbone' array for the zinc complex and a primitive triclinic symmetry (p(1)) for the cadmium complex, respectively, has been proposed. The complexes exhibited fluorescence at room temperature, both in the solution and in the solid state, with emission maxima in the blue region. Density functional theory (DFT) calculations carried out using the GAUSSIAN 09 program at the B3LYP level revealed a distorted tetrahedral geometry around the metal center in all the complexes. Natural bond orbital (NBO) analysis suggested appreciable charge transfer from the ligand to the metal center in the complexes. (C) 2015 Elsevier Ltd. All rights reserved.

DOI10.1016/j.poly.2015.11.053
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)2.108
Divison category: 
Polymer Science & Engineering