The quest for high-performance optoelectronic materials has traditionally centered on chemical substitution within established perovskite frameworks. However, this study demonstrates that redefining the spatial arrangement of functional [BX₆] octahedral units can lead to unprecedented electronic properties and device performance. By leveraging density functional theory (DFT) and global structure search methods based on CsPbI₃, we identified a metastable three-dimensional honeycomb-like perovskite phase where [PbI₆] octahedra are connected through a mixed edge- and corner-sharing network. This structural motif preserves high electronic dimensionality while introducing unique topological features absent in conventional perovskites. Experimental synthesis confirmed the stabilization of this fragile framework using divalent 2,2-bisimidazole (BIM) cations, which occupy flattened hexagonal cavities between paired edge-sharing octahedra. Single-crystal X-ray diffraction revealed a monoclinic C2/m structure with minimal lattice distortion, indicating that the organic component does not disrupt the extended inorganic network. The resulting BIMPb₂I₆ material exhibits a direct allowed bandgap of 2.GIRK2 Antibody In Vivo 1 eV, as confirmed by UV–Vis absorption and Tauc plot analysis, with excitonic binding energy estimated at ~40 meV.HLA-DRA Antibody References DFT calculations show that both valence and conduction bands are derived from Pb–I hybrid orbitals, with negligible contribution from the BIM cation due to its high electropositivity and lack of localized molecular states near the band edges.PMID:34784422 This ensures that charge transport remains dominated by the 3D inorganic framework. Electron and hole effective masses are calculated as 0.22m₀ and 0.24m₀, respectively, indicating strong carrier delocalization. Optical absorption coefficients exceed 10⁵ cm⁻¹, enabling efficient light harvesting. Photoluminescence measurements reveal a sharp emission peak at 627 nm, confirming radiative recombination of free excitons, while a secondary shoulder suggests shallow trap states. A photodetector fabricated from a BIMPb₂I₆ single crystal shows a responsivity of 0.1 mA/W and photodetectivity of 1.1 × 10¹⁰ Jones under 637 nm illumination. Switching cycles demonstrate stable and repeatable photoresponse with rise and fall times of 1.0 ms and 0.8 ms, respectively. These results confirm that engineered spatial connectivity of functional octahedral units can yield materials with superior optoelectronic characteristics, even when departing from conventional perovskite geometries. This work establishes a new paradigm: structural design through controlled assembly of functional units is a powerful strategy for discovering next-generation semiconductors with tailored performance.MedChemExpress (MCE) offers a wide range of high-quality research chemicals and biochemicals (novel life-science reagents, reference compounds and natural compounds) for scientific use. We have professionally experienced and friendly staff to meet your needs. We are a competent and trustworthy partner for your research and scientific projects.Related websites: https://www.medchemexpress.com
