Engineering Multiple Hydrogen‐Bond Sites With D‐π‐A Motifs for Strong Optical Nonlinearity and Giant Birefringence in Organic‐Inorganic Halides
Abstract
ABSTRACT Organic‐inorganic metal halides (OIMHs) have emerged as promising nonlinear optical (NLO) materials, but simultaneously achieving large birefringence (Δ n ) and strong second‐harmonic generation (SHG) remains challenging owing to the propensity of π‐conjugated organic motifs to favor centrosymmetric packing. Herein, we develop a molecular design strategy by constructing a donor‐π‐acceptor (D‐π‐A) long‐chain cation, [DA7ClQ] 2+ , featuring multiple hydrogen‐bonding sites. Hybridization with inorganic [Sb 2 Cl 9 ] 3− anions yields the non‐centrosymmetric crystal (DA7ClQ)SbCl 5 , which exhibits a record birefringence of 0.46 at 550 nm among OIMHs‐based NLO crystals, coupled with a robust SHG response of 0.4 × KTP at 1550 nm and exceptional thermal and environmental stability. Theoretical calculations reveal that the D‐π‐A motif possesses superior first‐order hyperpolarizability (12.1 × 10 −29 esu) and polarizability anisotropy (739 a.u.), while a robust hydrogen‐bond network locks the acentric alignment. This work establishes that engineering extended π‐conjugated systems with augmented asymmetry and precise orientational control provides a versatile pathway toward advanced hybrid NLO materials.
Article Details
Authors (15)
Yangkai Zhang
Yuchao Li
Yuekai Wu
College of Physics Qingdao Key Laboratory of Ultrabroadband Terahertz Crystals and System Applications Qingdao Broadband Terahertz Spectroscopy Technology Engineering Research Center Qingdao University Qingdao People's Republic of China
Bing Teng
College of Physics Qingdao Key Laboratory of Ultrabroadband Terahertz Crystals and System Applications Qingdao Broadband Terahertz Spectroscopy Technology Engineering Research Center Qingdao University Qingdao People's Republic of China
Hongting Lu
Xingxing Jiang
Technical Institute of Physics and Chemistry
Shijia Sun
College of Physics Qingdao Key Laboratory of Ultrabroadband Terahertz Crystals and System Applications Qingdao Broadband Terahertz Spectroscopy Technology Engineering Research Center Qingdao University Qingdao People's Republic of China
Chen Hu
Division of Quantitative Sciences Sidney Kimmel Comprehensive Cancer Center Johns Hopkins University School of Medicine Baltimore Maryland USA
Dongwei Zhai
College of Physics Qingdao Key Laboratory of Ultrabroadband Terahertz Crystals and System Applications Qingdao Broadband Terahertz Spectroscopy Technology Engineering Research Center Qingdao University Qingdao People's Republic of China
Lifeng Cao
College of Physics Qingdao Key Laboratory of Ultrabroadband Terahertz Crystals and System Applications Qingdao Broadband Terahertz Spectroscopy Technology Engineering Research Center Qingdao University Qingdao People's Republic of China
Jinkang Ma
College of Physics Qingdao Key Laboratory of Ultrabroadband Terahertz Crystals and System Applications Qingdao Broadband Terahertz Spectroscopy Technology Engineering Research Center Qingdao University Qingdao People's Republic of China
Run Li
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering
Degang Xu
Institute of Laser and Optoelectronics School of Precision Instrument and Optoelectronics Engineering Tianjin University Tianjin People's Republic of China
Zheshuai Lin
Technical Institute of Physics and Chemistry
Degao Zhong
College of Physics Qingdao Key Laboratory of Ultrabroadband Terahertz Crystals and System Applications Qingdao Broadband Terahertz Spectroscopy Technology Engineering Research Center Qingdao University Qingdao People's Republic of China