Structural characterization, Hirshfeld surface analysis, vibrational (FT-IR and Raman) and optical properties of the tris (4-Bromo-N, N-dimethylanilinium) hexachlorobismuthate (III)

A novel interesting hybrid organic-inorganic compound with the formula [C8H11BrN]3BiCl6. Tris(4-Bromo-N, N-dimethylanilinium) hexachlorobismuthate (III) was grown by the slow evaporation technique at ambient temperature. It is structurally characterized by vibrational spectroscopy, Hirshfeld surface analyses, Solid state 13C NMR, UV-Visible absorption and photoluminescence measurements. A preliminary single crystal X-ray diffraction study revealed that the title compound crystallizes in the non-centrosymmetric (space group P212121) with crystallographic parameters: a = 9.2820(3) Å,b = 13.7960(5) Å, c = 27.4298(12) Å, v = 3512.5(2) Å3 with Z = 4. The Crystal structure composed of discrete [BiCl6]3- anions surrounded by three [C8H11BrN]+cations, which are connected via N-H⋯Cl and C-H⋯Cl hydrogen bonds arranged in a three dimensional network. The Hirshfeld surface analysis associated with 2D fingerprint plots were used to visualize and explore the significant intermolecular interactions in the crystal structure quantitatively.13C Nuclear Magnetic Resonance (NMR) spectrum is in agreement with the X-ray structure. Furthermore, the optical absorption and photoluminescence measurements, exhibit a strong purple photoluminescence emission located at 2.92 eV and observed at room temperature.This work is support by the “Department of Chemistry, Faculty of Sciences of Sfax, University of Sfax, BP 1171, 3038 Sfax, Tunisia”, Spanish MINECO (MAT2016-78155-C2-1-R) and Gobierno del Principado de Asturias (GRUPIN-ID2018-170)

Crystal structure, Hirshfeld surface analysis, vibrational and optical properties of organic-inorganic hybrid compound (C13H16N2)5(BiCl6)3•Cl

A novel hybrid material (C13H16N2)5(BiCl6)3•Cl has been successfully synthesized by slow evaporation at room temperature. The compound structure was determined by single-crystal X-ray diffraction and crystallized in the triclinic space group Pī (a = 14.7757(2) Å, b = 14.7799(2) Å, c = 23.1633(4) Å, α = 89.016(2)°, β = 84.0080(10)°, γ = 74.0400(10)° and v = 4836.57(13) Å3, Z = 2) at 296 K. The crystal packing consists of three isolated [BiCl6]3- octahedral anions and an isolated chloride ion Cl− surrounded by five crystallographically independent4,4′-Diaminiumdiphenylmethane cations. The organic layers are inserted between the inorganic ones and connected with N-H…Cl and C-H…Cl hydrogen bonds to build a three dimensional network. The vibrational spectrum measured at room temperature by FT-IR spectroscopy (4000-400 cm−1) on polycrystalline samples shows the presence of organic cation. The number of 13C CP-MAS NMR lines is in full agreement with the crystallographic data. The Hirshfeld surface analysis associated with 2D fingerprint plots visualizing the significant intermolecular interactions in the crystal structure have been used to examine molecular shapes. The optical and photoluminescence properties of the compound were investigated in the solid-state at room temperature.This work is support by the “Department of Chemistry, Faculty of Sciences of Sfax, University of Sfax, BP 1171, 3038 Sfax, Tunisia”, Spanish MINECO (MAT2016-78155-C2-1-R) and Gobiernodel Principado de Asturias (GRUPIN-ID2018-170).Peer reviewe

Synthesis, crystal structure, vibrational properties, optical properties and Hirshfeld surface analysis of a new Bi (III) halide complex: (C2H8N)3BiBr6 for optoelectronic devices

A new organic–inorganic material, dimethylaminium hexabromobismuthate (C2H8N)3BiBr6 was elaborated by the slow evaporation technique at room temperature. This compound is synthesized and characterized by X-ray diffraction, Raman spectroscopy scattering, Hirshfeld surface analysis, 13C NMR spectroscopy, photoluminescence and by UV–Vis spectroscopy. The crystal lattice is formed by discrete [BiBr6]3− anions surrounded by dimethylaminium cations. Besides, the title compound crystallizes in the space group R 3¯¯¯ of trigonal system. The unit cell parameters are a = 29.3387(9) Å, b = 29.3387(9) Å and c = 8.4642(3) Å. The Raman and infrared spectra recorded at room temperature were interpreted by analogy with homologous materials. The cohesion of the structure is ensured by a huge network of N–H…Br hydrogen bonds and van der Waals interaction (C–H….Cl). The UV–Vis measurements, performed from 200 to 2400 nm, show a direct and wide optical bandgap evaluated at (2.840 ± 0.005), (2.482 ± 0.004) and (2.805 ± 0.006) eV by different methods. The Urbach energy presents a low value estimated at (182 ± 3) meV confirming the high quality of our compound. In addition, the evolution of the extinction coefficient (ke) and the refractive index n with the wavelength λ were determined. Furthermore, we have demonstrated that n obeys to Cauchy relation. Other optical parameters such as the skin depth and the optical conductivity were calculated, and all obtained results were discussed. We have demonstrated, in addition, that the energy losses are mainly in the bulk rather than the surface of the studied material. Based on the Wemple–Di-Domenico model, the dispersion parameters E0 and Ed relative to the (C2H8N)3BiBr6 sample were calculated. These encouraging results such as the obtained high and direct optical bandgap value prompt us to propose this compound as a basic material for optoelectronic devices.This work is supported by the “Department of Chemistry, Faculty of Sciences of Sfax, University of Sfax, BP 1171, 3038 Sfax, Tunisia,” Spanish MINECO (MAT2016-78155-C2-1-R) and Gobierno del Principado de Asturias (GRUPIN-ID2018-170).Peer reviewe