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Hybrid halide perovskites containing small organic cations continue to attract attention as semiconducting materials for optoelectronic applications, which make them promising candidates for next-generation photovoltaic and optoelectronic devices. Among them, aziridinium-based perovskites represent an emerging class of compounds with distinctive structural and optoelectronic properties, enabling the formation of stable three-dimensional perovskite frameworks.[1, 2] In the present work, a series of germanium-based hybrid perovskites with the general formula (AzrH)GeX3 (X = Cl, Br) were synthesized and comprehensively studied. Single-crystal X-ray diffraction analysis revealed that (AzrH)GeCl3 crystallizes in the Pnma space group and (AzrH)GeBr3 crystallizes in R3m space group at room temperature and are characterized by a non-centrosymmetric crystal structure – a distinctive feature that may open opportunities for nonlinear optical applications. Differential scanning calorimetry (DSC) and variable-temperature X-ray diffraction measurements indicate the presence of temperature-induced phase transitions. Optical diffuse reflectance spectroscopy was used to determine the band gap values by the Kubel’ka-Munk method, which were found to be 3.18 eV for (AzrH)GeBr3 and 3.87 eV for (AzrH)GeCl3. These results allow us to classify the materials as wide-band-gap semiconductors. The obtained data extend the family of aziridinium-based perovskites and demonstrate that germanium substitution leads to significant changes in the structure and electronic characteristics compared to their lead and tin analogues.
- Petrosova, H. R. et al. Chem. Commun. 2022, 58, 5745–5748.
- Kucheriv, O. I. et al. Inorg. Chem. Front. 2023, 10, 6953–6963.
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