Chirality Transfer to the Magnetic Sublattice in the Hybrid Perovskite (R)-/(S)-3-Fluoropyrrolidinium Copper(II) Chloride

Abstract

Incorporating chiral organic cations into organic-inorganic hybrid materials has been shown to enable the inorganic sublattice to display chiroptical properties. We report a new two-dimensional magnetic ($S=1/2$) chiral metal halide perovskite, (R)- and (S)-$(C_4{H}_{9}FN{)}_{2}CuC{l}_4$ (where $(C_4{H}_{9}FN{)}^{+}$ is 3-fluoropyrrolidinium), which consists of Cu-Cl inorganic layers separated by $(C_4{H}_{9}FN{)}^{+}$ organic cations. The presence of the chiral $(C_4{H}_{9}FN{)}^{+}$ organic cation induces formation of chiral magnetic order, even though the inorganic sublattice itself is nearly structurally centrosymmetric. We also report the racemic variant, containing an equal amount of (R)- and (S)- cations, which shows no evidence of chiral magnetic order. When the magnetic susceptibility is measured perpendicular to inorganic Cu-Cl layer propagation direction, an antiferromagnetic phase transition at Néel temperature $T_N=2.23K$ is observed in both the chiral and racemic materials, and the existence of the magnetic phase transition is supported by specific heat capacity measurements. Field-induced magnetic chirality is observed through the existence of a second-order magnetoelectric effect in the chiral variant, while no magnetoelectric signal is observed for the racemic material, indicating the absence of magnetic chirality. Our findings demonstrate that materials exhibiting chiral magnetic order can be created through the incorporation of a chiral cation into an organic-inorganic hybrid magnetic material, potentially allowing for the design of tailored materials that combine chiral magnetism with other desirable optical and electronic properties that come from structural chirality.

Version of record. Main text is 10 pages containing 7 figures. The Supporting Information is an additional 13 pages with 11 supplementary figures. Crystallographic data can be obtained from via the joint Cambridge Crystallographic Data Centre (CCDC) and Fachinformationszentrum Karlsruhe Access Structures service at https://ccdc.cam.ac.uk/structures under Deposition Numbers 2543946-2543948

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