The everlasting pursuit of hybrid organic-inorganic lead-free semiconductors has directed the focus towards eco-friendly copper-based systems, perhaps because of the diversity in chemistry, controlling the structure-property relationship. In this work, we report single crystals of a Cu(i) halide-based perovskite-like organic-inorganic hybrid, (TMA)Cu2Br3, (TMA = tetramethylammonium), consisting of unusual one-dimensional inorganic anionic chains of -(Cu2Br3)-, electrostatically stabilized by organic cations, and the Cu(i)-Cu(i) distance of 2.775 Å indicates the possibility of cuprophilic interactions. X-ray photoelectron spectroscopy measurements further confirmed the presence of exclusive Cu(i) in (TMA)Cu2Br3 and electronic structure calculations based on density functional theory suggested a direct bandgap value of 2.50 eV. The crystal device demonstrated an impressive bulk photovoltaic effect due to the emergence of excitonic Cu(i)-Cu(i) interactions, as was clearly visualized in the charge-density plot as well as in the Raman spectroscopic analysis. The single crystals of a silver analogue, (TMA)Ag2Br3, have also been synthesized revealing a Ag(i)-Ag(i) distance of 3.048 Å (signature of an argentophilic interaction). Unlike (TMA)Cu2Br3, where more density of states from Cu compared to Br near the Fermi level was observed, (TMA)Ag2Br3 exhibited the opposite trend, possibly due to variation in the ionic potential influencing the overall bonding scenario.
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