Dehydration Induced a Structural Transformation into a One-Dimensional Hybrid Perovskite with Second Harmonic Generation and Dual Dielectric Switching

Abstract

Hybrid organic–inorganic perovskites with structural transformation have garnered continued interest in recent years for their potential as multifunctional materials in the field of optoelectronics and smart devices. Herein, we report a novel hybrid organic–inorganic halide, [C5NOH12]2[Cd1.5Cl5(H2O)] (1). Remarkably, the centrosymmetric compound 1 undergoes a structural transformation to a novel noncentrosymmetric hybrid perovskite [C5NOH12][CdCl3] (2) after dehydration. Accompanied by the chemical bond cleavage and reorganization, the zero-dimensional (0D) trinuclear cluster in compound 1 transforms into an intriguing one-dimensional (1D) hexagonal perovskite structure in compound 2, generating multiple optoelectronic switching behaviors. It is worth mentioning that compound 2 demonstrates successive structural phase transitions at 353 and 405 K, resulting in switchable second harmonic generation (SHG) and a dual dielectric response. In addition, compounds 1 and 2 both feature blue-light luminescence, with respective photoluminescence lifetimes of 0.73 and 1.42 ns. This work will offer a pioneering approach and expansive potential for the preparation and development of hybrid organic–inorganic perovskite materials with superior properties.

Successive high-temperature phase transitions triggered dielectric switching in a one-dimensional hybrid perovskite with blue emission

“…The results revealed a prolonged average lifetime of 9.94 ns, surpassing that of the majority of reported organic–inorganic hybrid metal halides exhibiting blue-light emission. 41,42…”

“…The results revealed a prolonged average lifetime of 9.94 ns, surpassing that of the majority of reported organic-inorganic hybrid metal halides exhibiting blue-light emission. 41,42 To further understand the optical properties of compound 1, as depicted in Fig. 5d, the solid ultraviolet-visible (UV-vis) spectrum was carried out at room temperature, with an absorption edge at about 240 nm.…”

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

“…This will further lead to the development of smart phase-transition materials with different T c values for applications in various challenging temperature environments. However, there are rare studies and reports on how to effectively regulate T c so far, which will make it difficult to help people in the preparation of smart switches and sensors with specific T c . − Dielectric materials, as a type of temperature-responsive smart material, exhibit a sudden change in their dielectric constant near the T c , imparting switch-like characteristics. As a highly promising switching material, more and more reports on its properties and applications are being published. − …”

Second-Order Nonlinear Switching and Photoluminescence Properties of Cd-Based Hybrid Perovskite with High-Temperature Phase Transition

“…Organic–inorganic hybrid perovskites, noted for their remarkable optoelectronic properties and propensity for structural phase transitions, are prime candidates for developing efficient switchable NLO materials. − Hybrid perovskites are characterized by a distinctive crystalline structure, generally represented by the formula ABX 3 , where A represents an organic cation, B denotes a metal cation, and X corresponds to a halide anion. Due to the size tunability and flexibility, the organic cations can easily distort or reorient within the inorganic lattice, inducing structural phase transitions that often result in substantial alterations in the material’s optical and electronic properties, which are conducive to promoting NLO switching applications. , Consequently, achieved by incorporating flexible linear or cyclic cations into rigid inorganic frameworks, numerous hybrid perovskites, such as [(CH 3 ) 3 NCH 2 I]PbCl 3 and [C 5 NOH 12 ]CdCl 3 , , have been effectively developed as NLO switching materials, capable of undergoing reversible phase transitions facilitated by the dynamic order–disorder motion of organic cations. Similar to the hybrid Pb-based halide perovskites, Cd-based hybrid perovskites are often equipped with one- or two-dimensional anionic structures based on a basic CdX 6 octahedron.…”