Guanlei Gao,Si-Yu Xu,Xinghui Qi,Jie-Ru Yang,Peiqi Lin,Jin Chen,Xiao-Ying Huang,Ke-Zhao Du
The strategy of organic ligand exchange is proposed to tune the optical properties of organic–inorganic hybrid cuprous halides. In this work, the chiral ligand (S)-(−)-2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl ((S)-Tol-BINAP) and achiral triphenylphosphine (PPh3) are introduced into cuprous halides CuX-PPh3-[(S)-Tol-BINAP] (X = Cl, Br, I) through organic ligand exchange. As a result, the mixed organic ligands can enhance second harmonic generation (SHG) and aggregation-induced emission (AIE) optical properties. Moreover, the title compounds exhibit progressively enlarged SHG effects along with heavier halogen substitution due to their stronger polarizability. In the meantime, the reduced π–π stacking interaction of the organic ligand will improve their photoluminescence quantum yield. The experimental results combined with the theoretical calculation clarify the structure–property relationship well. Furthermore, the title compounds have been developed for the application of latent fingerprint detection.
Nonlinear optical (NLO) crystals demonstrate notable NLO effects, which are predominantly attributed to their anionic groups. However, the role of cations has long been overlooked. For the first time, S 2− , Cl − , and O 2− are successfully incorporated into two new salt-inclusion oxychalcogenides, namely, [La 4 Cl 3 S][GaGeS 6 O] ( 1 ) and [La 4 Cl 2 S 2 ][Ge 2 S 6 O] ( 2 ), which are characterized by highly distorted and polarizable polycations and anionic groups. Notably, they exhibit substantial second-harmonic generation (SHG) intensities of 2.7 and 3.8 × AgGaS 2 @1700 nm, respectively. To the best of knowledge, the latter represents the highest value recorded for all oxychalcogenides constructed from tetrahedral structural units. Crystal structure analysis and theoretical calculations reveal that the distorted tetrahedral units in the host lattice and the polyhedral units in the guest lattice considerably contributed to the SHG coefficients. Furthermore, compounds 1 and 2 display favorable laser-induced damage thresholds (4.4 and 7.2 × AgGaS 2 @1064 nm) along with expanded transparency windows. This finding underscores the potential of host–guest architectures with multiple anions for markedly enhancing SHG coefficients, which paves the way for the development of new NLO materials.
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