Broad-band luminescence involving fluconazole antifungal drug in a lead-free bismuth iodide perovskite: Combined experimental and computational insights

The synthesis and characterization of a lead-free perovskite-type material, (C₁₃H₁₄N₆F₂O)₂ Bi₂I₁₀ is reported. It exhibits a zero-dimensional (0D) Bi₂I₁₀ ⁴⁻ octahedral unit, surrounded by a flexible tripodal antifungal ligand (H₂Fluconazole)²⁺. The several intermolecular interactions of the independent cation and the bismuth iodide octahedra were tested via the Hirshfeld surface analysis. The detailed interpretation of the vibrational modes was carried out. The band gap (Eg) of 2.10 eV agrees with the theoretical values. Upon photoexcitation, the crystals exhibit a broadband green emission peaked at 534 nm, which originates from electronic transitions within the inorganic cluster [Bi₂I₁₀]⁴⁻. The theoretical calculations were carried out using DFT and TD-DFT methods to appraise the molecular geometry, vibrational spectra, electronic absorption spectra, frontier molecular orbitals (FOMs) and global reactivity descriptors. Calculations reveal that the energy gap (Eg) and other chemical reactivity descriptors are primarily linked to the inorganic anion and the triazolium rings (A and B) of the organic cation reflecting their importance in the activity and the antioxidant ability of the molecule.