Hybrid organic-inorganic perovskites (HOIPs) are promising stimuli-responsive materials (SPMs) owing to their molecular softness and tailorable structural dimensionality. The design of mechanically responsive HOIPs requires an in-depth understanding of how lattice strain induces intermolecular rearrangement that impacts physical properties. While chirality transfer from an organic cation to an inorganic lattice is known to influence chiral-optical properties, its effect on strain-induced phase conversion has not been explored. As opposed to achiral or racemic organic cations, chiral organic cations can potentially afford a new dimension in strain-responsive structural change. Herein, we demonstrate that mechanical strain induces a solid phase crystal conversion in chiral halide -perovskite single crystals (/)-(FE)CuCl (FE = (4-Fluorophenyl)ethylamine) from a 0D isolated CuCl tetrahedral to 1D corner-sharing CuFCl octahedral framework via the incorporation of Cu···F interaction and N-H···F hydrogen bonding. This strain-induced crystal-to-crystal conversion involves the connection of neighboring 0D CuCl tetrahedra via Cu-Cl-Cu linkages as well as the incorporation of a F-terminated organic cation as one of the X atoms in BX octahedra, leading to a reduced band gap and paramagnetic-to-ferromagnetic conversion. Control experiments using nonchiral or racemic perovskite analogs show the absence of such solid phase conversion. To demonstrate pressure-sensitive properties, the 0D phase is dispersed in water-soluble poly(vinyl alcohol) (PVA) polymer, which can be applied to a large-scale pressure-induced array display on fibrous Spandex substrates via a screen-printing method.
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http://dx.doi.org/10.1021/jacs.2c12525 | DOI Listing |
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