Structural Optimization and Property Tunability by Halogen Regulation in Zero-Dimensional Zinc Halide Organic–Inorganic Hybrid Materials

Abstract

Low-dimensional hybrid materials show great structural flexibility and adjustability in photoelectric properties compared with high-dimensional (such as three-dimensional (3-D)) hybrid materials. To investigate the effect of halogen substitution on low-dimensional materials, three zero-dimensional (0-D) organic−inorganic hybrids, [BMPD] 2 ZnX 4 (BMPD = 1-butyl-1-methylpiperidine cation, X = I, Br, and Cl), were synthesized. The phase transition temperature (T c ) increased gradually after changing I to Cl. Interestingly, the halogen regulation method induced the bright blue luminescence of [BMPD] 2 ZnBr 4 with a quantum yield of 9.62% and the nonlinear optical properties of [BMPD] 2 ZnCl 4 . Thus, multiproperties are achieved by the above strategy. This work presented a method for discovering and application of new organic−inorganic hybrid multifunctional optoelectronic materials.

Tuning and Enhancing Nonlinear Optical Behavior in Hybrid Arylammonium Perrhenate Salts through Halogen Substitution

“…The SHG intensity of (4-Br-BTAB)­ReO 4 is always close to three times that of KDP. Through previous literature research, − organic–inorganic salt NLO materials featured by halogen substitution with SHG switches and phase transition temperature are shown in the Figure e and compared with this work. Compound (4-X-BTAB)­ReO 4 (X = F, Cl, Br) has outstanding properties.…”

Tin-based organic–inorganic metal halides with a reversible phase transition and thermochromic response

“…[24][25][26][27][28][29][30] Compared with high-dimensional hybrid phase transition materials with limited organic ammonium species, the structures of low-dimensional compounds are more flexible and diverse. [31][32][33][34] Meanwhile, low-dimensional materials can provide a large degree of freedom for organic ammonium, thereby triggering the order-disorder phase transition. [35][36][37][38] As an example, Zou et al…”

“…24–30 Compared with high-dimensional hybrid phase transition materials with limited organic ammonium species, the structures of low-dimensional compounds are more flexible and diverse. 31–34 Meanwhile, low-dimensional materials can provide a large degree of freedom for organic ammonium, thereby triggering the order–disorder phase transition. 35–38 As an example, Zou et al reported a zero-dimensional organic–inorganic hybrid single crystal (TMA) 2 SbCl 5 -DMF (TMA = (CH 3 ) 3 NH + , DMF = HCON(CH 3 ) 2 ) with a high quantum yield of 67.2%.…”

High-Symmetry Structural Phase Transition Triggers a Triple Switch Based on Dielectric, Nonlinear Optics, and Photoluminescence

“…At the same time, materials with nonlinear optical (NLO) properties exhibiting a reversible switch in second-harmonic generation (SHG) also play a significant role in the areas of optoelectronic and electronic devices, showing tremendous vitality in application prospects. 47 Wang et al 48 prepared an organic− inorganic hybrid material with both dielectric dual switching and NLO properties through the halogen substitution strategy to effectively modify and regulate molecular structures. Zhang et al 49 synthesized an unconventional two-step "off−on−off" SHG transition material.…”