One-dimensional Bi-Br pyrazinamide-based hybrid halide perovskite: crystal architecture, intermolecular interactions, and structure-optical properties relationship.
Alibi Amin A, Elleuch Nour N, Khdhiri Emna E, Shova Sergiu S et al.
A one-dimensional bismuth bromide organic-inorganic hybrid halide perovskite based on protonated pyrazinamide cations, (C5H6N3O)2·[BiBr5], is reported and comprehensively investigated. Single-crystal X-ray diffraction reveals a perovskite-related architecture built from corner-sharing [BiBr6] octahedra forming one-dimensional chains, stabilized by a dense network of N-H⋯Br and N-H⋯O hydrogen bonds together with significant π-π stacking interactions. Hirshfeld surface analysis quantitatively confirms the dominance of halogen-mediated hydrogen bonding in governing the supramolecular organization. Diffuse reflectance spectroscopy establishes the material as a direct-band-gap semiconductor with an optical gap of ∼2.8 eV, supported by a sharp absorption edge, low Urbach energy, and consistent threshold wavelength analysis. Photoluminescence measurements reveal a single intense phosphorescent emission centered at 540 nm, with CIE coordinates located in the yellowish-green region. Density functional theory calculations, including DOS, PDOS, ELF, LOL, and NCI-RDG analyses, provide microscopic insight into the electronic structure and intermolecular interactions, highlighting charge-transfer contributions from the inorganic sublattice to the organic moiety near the band edges. The combined results establish clear structure-property correlations in this lead-free Bi-based hybrid system and underline its relevance within the broader family of perovskite-inspired semiconductors.