A New centrosymmetric supramolecular Hybrid Antimony (III)-based material :X-ray characterization, vibrational studies, theoretical (DFT and TD-DFT) studies, thermal behavior, opto-electric properties and atomic Hirshfeld surface analysis.

Abstract

The new centrosymmetric hybrid material (C8H12N)4[SbCl5]2 has been successfully elaborated at room temperature by slow evaporation in the centrosymmetric monoclinic space group P21/c with the following parameters: a = 29.0349(16) Å, b = 13.1241(7) Å, c = 12.0278(7) Å, β = 95.567(2) ° Z = 4 and V = 4561.7(4) Å3. The asymmetric unit consists of two isolated [Sb2Cl10]4- dimers and four protonated cations (C8H12N)+ was optimized d by density functional theory (DFT) using the B3LYP method. The cohesion of this supramolecular material was ensured by the means of N—H…Cl hydrogen-bonding interactions yield a three-dimensional network. The infrared IR and Raman studies which were performed at room temperature charge in the 4000–400 cm -1 and 10- 3000 cm -1 frequency regions, respectively, displayed the existence of vibrational modes that correspond to the organic and inorganic groups. The assignment of wavenumbers which were based on potential energy distribution (PED), were performed using Vibrational Energy Distribution Analysis (VEDA) software. Actually, the values obtained by the B3LYP/LanL2MB are in good agreement with the experimental data.Moreover, the Hirschfeld surfaces analysis which was employed to identify the different intermolecular interactions, showed that predominate interactions were H…Cl. The Thermogravimetric analysis (TGA) reveals the decomposition of the compound remains stable above 175 °C that confirms its great thermal stability. Furthermore, the optical property of the 0D hybrid Sb(III) based halide was studied with a focus on the band gap. Theoretical investigations on the electronic structure, Simulated UV–Visible spectrum, band gap, and frontier molecular orbitals (FMOs) were undertaken using density functional theory (DFT) and time-dependent DFT (TD-DFT). Therefore, our results indicate an acceptable consistency was found between calculations and experimental results leading to consistent vibrational and optical features assignments as well as the energy gap (Eg) and the chemical reactivity descriptors which are primarily linked to the ring of the organic cation and the inorganic anion.