Synthesis, crystal structure, DFT (B3LYP/LanL2DZ) and photoluminescence study of new stanate (IV) based inorganic-organic hybrid

Abstract

A novel interesting metal hybrid compound, named as hexachlorostanate (II) 4.4′ bipyridinium and formulated as (C10H10N2) SnCl6, was synthesized at room temperature by slow evaporation and then characterized by a single X-ray diffraction, spectroscopic measurements, Scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and photoluminescence technique. It crystallizes in the space group C2/c with the following unit cell parameters: a = 17.9611 (13) Å, b = 12.9274 (5) Å, c = 7.6305 (6) Å and β = 117.860 (10) °. The structure can be described by the alternation of two different cationic-anionic layers. It consists of isolated [SnCl6]2- octahedral anions and 4.4′ bipyridinium (C10H10N2) cations, which are connected via N-H⋯Cl hydrogen bonds forming a chain network. The Hirshfeld surface analysis was conducted to investigate intermolecular interactions and associated 2D fingerprint plots, revealing the relative contribution of these interactions in the crystal structure quantitatively. The optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of the present compound were theoretically examined by the DFT/B3LYP method with the LanL2DZ basis set. The X-ray powder is in agreement with the X-ray structure. 13C NMR spectrum shows three signals, confirming the solid state structure determined by X-ray diffraction. Photoluminescence measurements showed a strong emission line at 2.95 eV associated with radiative recombinations of excitons confined within the [SnCl6]2- which were investigated at room temperature.