H/F Substitution on the Spacer Cations Leads to 1D-to-2D Increment of the Pyrrolidinium-Containing Lead Iodide Hybrid Perovskites.

Hybrid organic-inorganic perovskites (HOIPs) have emerged as multifunctional materials with remarkable optical and electronic properties. In particular, 2D-layered lead iodide-based HOIPs possess great practical application potential in the photoelectric field. In this work, we report H/F substitution-induced 1D-to-2D increment of lead iodide HOIPs. The enantiomeric HOIPs, S- and R-FPPbI3 (FP = 3-fluoropyrrolidinium), were achieved by monofluoride substitution on the spacer cations of the parent HOIP, PyPbI3 (Py = pyrrolidinium), showing mirror image structural relationship and reversible solid-state phase transition. A 2D-layered HOIP, (DFP)2PbI4 (DFP = 3,3-difluoropyrrolidinium), was achieved with a low band gap of 2.09 eV through difluoride substitution, thanks to the expansion of the Pb-I network from 1D to 2D. This work highlights the exploration of 1D chiral and 2D-layered HOIP materials with reversible phase transitions through H/F substitution strategies.

Room-Temperature Phase Transition Material with Switchable Second-Order Nonlinear Optical Properties.

Phase transition materials with switchable second-order nonlinear optical (NLO) properties have attracted extensive attention because of their great application potential in photoelectric switches, sensors, and modulators, while metal-free organics with NLO switchability near room temperature remain scarce. Herein, we report a hydrogen-bonded metal-free organic crystal, 2-methylpropan-2-aminium 2,2-dimethylpropanoate (1), exhibiting a room-temperature phase transition and favorable NLO switchability. Through investigations on its thermal anomalies, dielectric properties, and crystal structures, we uncover that 1 holds a near-room-temperature phase transition at 303 K from noncentrosymmetric point group C2v to centrosymmetric one D2h, which is attributed to the order-disorder transformations of both tert-butylamine cations and dimethylpropionic acid anions. Accompanied by symmetry change during the phase transition, 1 exhibits reversible and repeatable NLO "on-off" switchability with a desirable switching contrast ratio of ca. 19 between high and low NLO states. This discovery demonstrates a metal-free organic crystal with NLO switching behavior near room temperature, serving as a promising candidate in smart and ecofriendly photoelectric functional materials and devices.