New Organic-Inorganic Salt Based on Fluconazole Drug: TD-DFT Benchmark and Computational Insights into Halogen Substitution.

In this study, we report the synthesis of a new organic-inorganic molecular salt of the clinically used antifungal drug fluconazole, (H2Fluconazole).SnCl6.2H2O. By detailed investigation and analysis of its structural properties, we show that the structure represents a 0D structure built of alternating organic and inorganic zig-zag layers along the crystallographic c-axis and the primary supramolecular synthons in this salt are hydrogen bonding, F···π and halogen bonding interactions. Magnetic measurements reveal the co-existence of weak ferromagnetic behavior at low magnetic field and large diamagnetic contributions, indicating that the synthesized material behaves mainly as a diamagnetic material, with very low magnetic susceptibility and with a band gap energy of 3.6 eV, and the salt is suitable for semiconducting applications. Extensive theoretical study is performed to explain the acceptor donor reactivity of this compound and to predict the Cl-substitution effect by F, Br and I. The energy gap, frontier molecular orbitals (FMOs) and the different chemical reactivity descriptors were evaluated at a high theoretical level. Calculations show that Cl substitution by Br and I generates compounds with more important antioxidant ability and the intramolecular charge transfer linked to the inorganic anion.

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) Bi2I104- 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.