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Synthesis, characterization, photoluminescent properties and supramolecular aggregations in diimine chelated cadmium dihalides

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A series of 12 new cadmium compounds, [Cd(X2)(L)] (4, 10), [Cd(X2)(L)(DMSO)] (9), [Cd(X2)(L)]2 (1–3, 5, 7, 8, 11, and 12), and [Cd(Cl2)2(L)]n (6) where X = chloride, bromide, and iodide, and diimine L = (E)-N-(pyridin-2-ylmethylidene)arylamine, were synthesized and characterized by elemental analyses. The spectroscopic properties were investigated by IR, UV–Vis, fluorescence, and 1H NMR studies. The solid-state structures of the 12 reaction products were studied by X-ray crystallography. A majority of the structures are binuclear with five-coordinate cadmium centers: dimerization occurs through μ2-bridging of the respective halides; the second halide is bound terminally. In the case of X = Br and I, dimerization is circumvented when L carries an additional donor capable of coordinating cadmium (4, 10) or when the additional donor is provided by coordinating solvent (9). A similar situation pertains in the CdCl2 analog (7). In the case where L strongly coordinates with cadmium, i.e. (6), an edge-shared polymeric chain and octahedrally coordinated cadmium are found as a result of μ2-bridging of both chloro ligands. An interesting feature of the crystal packing is the observation of rare C–H[Inline formula]π interactions where the π-system is a chelate ring or a Cd2Br2 unit.
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Keywords: (E)-N-(pyridin-2-ylmethylidene)arylamine; Cadmium; N,N-Donor ligands; Spectroscopy; Structure elucidation; Supramolecular aggregations

Document Type: Research Article

Affiliations: 1: Department of Chemistry, North-Eastern Hill University, Shillong, India 2: Department of Chemistry, University of Malaya, Kuala Lumpur, Malaysia 3: Department of Chemistry, University of Calcutta, Kolkata, India

Publication date: January 2, 2014

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