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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 -, 期 -, 页码 -出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c12525
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Hybrid organic-inorganic perovskites (HOIPs) are promising stimuli-responsive materials (SPMs) with the capability to undergo structural changes and exhibit unique properties upon mechanical deformation. It has been discovered that chirality of the organic cations plays a significant role in strain-induced phase conversion. By applying mechanical strain, chiral halide pseudo-perovskite single crystals can undergo a crystal-to-crystal conversion from a 0D structure to a 1D structure, accompanied by the incorporation of new interactions that affect the band gap and magnetic properties.
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 pseudo-perovskite single crystals (R/S)-(FE)(2)CuCl4 (FE = (4-Fluorophenyl)ethylamine) from a 0D isolated CuCl4 tetrahedral to 1D corner-sharing CuFCl5 octahedral framework via the incorporation of CumiddotmiddotmiddotF interaction and N-HmiddotmiddotmiddotF hydrogen bonding. This strain-induced crystal-to-crystal conversion involves the connection of neighboring 0D CuCl4 tetrahedra via Cu2+-Cl--Cu2+ linkages as well as the incorporation of a F-terminated organic cation as one of the X atoms in BX6 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. [GRAPHICS]
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