Chiral 2D Cu(I) Halide Frameworks

Ji，Xiaoqin1; Geng，Shining2; Zhang，Shuai3; Gong，Yaping4; Zhang，Xuanyu5; Li，Ruiqian1; Liu，Yang1; Chen，Jian1; Chen，Rui5; Xiao，Zewen2; Mao，Lingling1

2022

10.1021/acs.chemmater.2c01729

CHEMISTRY OF MATERIALS   Impact Factor & Quartile

0897-4756

1520-5002

Hybrid multifunctional materials have great potential in a wide variety of applications due to their flexible combination of organic and inorganic components. Introducing chiral organic modules into the metal halide frameworks can effectively generate multifunctional materials, achieving new functionalities with noncentrosymmetric structures. Here, by incorporating (R)- or (S)-piperidine-3-carboxylic acid (R/S-PCA) as the templating cation, we report the synthesis and characterization of three pairs of new 2D chiral hybrid Cu(I) halides, namely, (R/S-PCA)CuBr2, (R/S-PCA)CuBr2·0.5H2O, and (R/S-PCA)CuI2. These chiral Cu(I) halides crystallize in the noncentrosymmetric space group C2 and belong to a new structural type similar to layered silicates. The optical absorption edges of these chiral materials can be tuned by changing the halide or upon the absorption of water and range from 2.70 to 3.66 eV. A dynamic conversion between (R/S-PCA)CuBr2 and (R/S-PCA)CuBr2·0.5H2O occurs through exposure to moisture or vacuum drying along with changes in the reversible bandgap and photoluminescence. Chiroptical properties such as circular dichroism, circular polarized light emission, and second harmonic generation are investigated. Density functional theory calculations (DFT) show the indirect and direct bandgap natures of these Cu(I) halides and reveal the mechanism for the broadband self-trapped exciton emission at the excited state. The fascinating structural type, chiroptical properties, and reversible hydrochromic behavior of these Cu(I)-based halides make them viable candidates for next-generation multifunctional optoelectronic materials.

EI ; SCI

English

First ; Corresponding

SUSTech startup grant[Y01216150]

Chemistry ; Materials Science

Chemistry, Physical ; Materials Science, Multidisciplinary

WOS:000877358600001

AMER CHEMICAL SOC

20223812756617

Density functional theory ; Energy gap ; Excited states ; Excitons ; Light absorption ; Metal halides ; Nonlinear optics ; Silicates ; Transition metals ; Water absorption

Metallurgy and Metallography:531 ; Light/Optics:741.1 ; Nonlinear Optics:741.1.1 ; Chemical Operations:802.3 ; Chemical Products Generally:804 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

MATERIALS SCIENCE

2-s2.0-85137857389

Scopus

1.Department of Chemistry,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China
2.Wuhan National Laboratory for Optoelectronics,Huazhong University of Science and Technology,Wuhan,Hubei,430074,China
3.State Key Laboratory of Luminescent Materials and Devices,Guangdong Provincial Key Laboratory of Fiber Laser Materials and Applied Techniques,South China University of Technology,Guangzhou,Guangdong,510641,China
4.MOE,Key Laboratory of Bioinorganic and Synthetic Chemistry,School of Chemistry,Sun Yat-Sen University,Guangzhou,Guangdong,510275,China
5.Department of Electrical and Electronic Engineering,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China

Ji，Xiaoqin,Geng，Shining,Zhang，Shuai,et al. Chiral 2D Cu(I) Halide Frameworks[J]. CHEMISTRY OF MATERIALS,2022.

Ji，Xiaoqin.,Geng，Shining.,Zhang，Shuai.,Gong，Yaping.,Zhang，Xuanyu.,...&Mao，Lingling.(2022).Chiral 2D Cu(I) Halide Frameworks.CHEMISTRY OF MATERIALS.

Ji，Xiaoqin,et al."Chiral 2D Cu(I) Halide Frameworks".CHEMISTRY OF MATERIALS (2022).