Intermolecular Forces Regulating the Phase-Transition Temperatures in Organic-Inorganic Hybrid Materials

Organic-inorganic hybrid phase-transition materials have attracted widespread attention in energy storage and sensor applications due to their structural adaptability and facile synthesis. However, increasing the phase-transition temperature (T_c) effectively remains a formidable challenge. In this study, we employed a strategy to regulate intermolecular interactions (different types of hydrogen bonds and other weak interactions), utilizing bismuth chloride as an inorganic framework and azetidine, 3,3-difluoro azetidine, and 3-carboxyl azetidine as organic components to synthesize three compounds with different T_c values: [C₃H₈N]₂BiCl₅ (1, 234 K), [C₃H₆NF₂]₃BiCl₆ (2, 256 K), and [C₄H₈O₂N]₃BiCl₆ (3, 350 K). 1 is a one-dimensional chain structure and 2 and 3 are zero-dimensional structures. Analysis of the crystal structure and the Hirshfeld surface and 2D fingerprints further suggests that the intermolecular forces are efficiently modulated. These findings emphasize the efficacy of our strategy in enhancing T_c and may facilitate further research in this area.