Photoluminescence and Nonlinear Optical Properties of Two Terpyridine-Based Hybrid Zn/Cd Halides

Sihan Wang; Zhengli Liang; Xinluan Song; Xin Huang; Lehui Liu; Xingxing Jiang; Zheshuai Lin; Hongming Liu

doi:10.1021/acs.inorgchem.3c03596

Photoluminescence and Nonlinear Optical Properties of Two Terpyridine-Based Hybrid Zn/Cd Halides

Inorg Chem. 2023 Dec 25;62(51):21451-21460. doi: 10.1021/acs.inorgchem.3c03596. Epub 2023 Dec 12.

Authors

Sihan Wang¹, Zhengli Liang², Xinluan Song¹, Xin Huang¹, Lehui Liu³, Xingxing Jiang², Zheshuai Lin², Hongming Liu¹

Affiliations

¹ Guangxi Key Laboratory of Electrochemical Energy Materials, School of Chemistry and Chemical Engineering, Guangxi University, Nanning, Guangxi 530004, China.
² Functional Crystals Lab, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
³ Key Laboratory of Optoelectronic Materials Chemistry and Physics Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.

PMID: 38085670
DOI: 10.1021/acs.inorgchem.3c03596

Abstract

Hybrid metal halides (HMHs) with low-dimensional structures have attracted increasing attention due to their striking optical properties. Herein, two new zero-dimensional HMHs have been fabricated by CdCl₂/ZnCl₂ and 4'-(4-pyridyl-phenyl)-2,2':6',2″-terpyridine (Tpy), including (TpyH₃)[CdCl₄][Cl] (Tpy-Cd) and (TpyH₃)[ZnCl₄][Cl] (Tpy-Zn). Their structures are consisted of a [TpyH₃]³⁺ organic cation, an inorganic [ZnCl₄] or [CdCl₄] tetrahedron, and one isolated Cl^- anion. Tpy-Cd crystallizes to a noncentrosymmetric structure and possesses a moderate second harmonic response of 0.72 × KH₂PO₄, while Tpy-Zn features a centrosymmetric space group. Though Tpy-Cd and Tpy-Zn crystallize into space groups of completely different symmetry due to distinct connection mode and molecular distortion, they display quite similar photoluminescence of bright green light emission under ultraviolet excitation, nearly identical in Stokes shift, photoluminescence quantum yield, decay lifetime, and energy. The photoluminescence quantum yields of green light emission were measured to be nearly 25%, outperforming most of the Cd/Zn low-dimensional HMHs.