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This study investigates the impacts of structure and composition on the optical and electronic properties of a series of pyridinium-based bismuth iodide complexes. Organic substrates with various functional groups, such as 4-aminopyridine (4-Ampy), 4-methylpyridine (4-Mepy), 4-dimethylaminopyridine (4-Dmapy), and 4-pyridinecarbonitrile (4-CNpy) with different electron-donating and electron-withdrawing groups at the para position of the pyridine ring were employed. Crystallographic analysis reveals various bismuth iodide structures, including 1D chains and discrete 0D motifs. The optical band gap of these materials, identified via diffuse reflectance spectroscopy (DRS) and verified with density functional theory (DFT) calculations, is influenced by the crystal packing and stabilising interactions. Through a comprehensive analysis, including Hirshfeld surface (HS) and void assessment, the study underscores the influence of noncovalent intermolecular interactions on crystal packing. Spectroscopic evaluations provide insights into electronic interactions, elucidating the role of electron donor and acceptor substituents within the lattice. Thermogravimetric differential thermal analysis (TG–DTA) indicates structural stability up to 250 °C. Linear sweep voltammetry (LSV) reveals significant conductivity in the range of 10–20 mS per pixel at 298.15 K. X-ray absorption spectroscopy (XAS) at the Bi L3 edge indicates a similar oxidation state and electronic environment across all samples, underscoring the role of bismuth centres surrounded by iodides. [ABSTRACT FROM AUTHOR]

This review focuses on the synthesis, properties and selected applications of heavy pnictogen chalcohalides, i.e. compounds of the MQX stoichiometry, where M = As, Sb, and Bi; Q = O, S, Se, and Te; and X = F, Cl, Br and I. The first section focuses on their synthesis and crystal structures, and the second section discusses the electronic structure on the basis of quantum chemical modelling and selected experimental data. Finally, the third section discusses their electrical, photoelectrochemical and photocatalytic properties and applications. In contrast to perovskites, chalcopyrites and kesterites, chalcohalides have attracted relatively less attention, but their structure and properties are well suited for numerous applications. [ABSTRACT FROM AUTHOR]