(R)- and (S)-SbF(3)(C(8)H(9)NO(3)): Chiral Antimony-Based Hybrid Materials with Enhanced Second-Harmonic Generation and Birefringence

(R)-和(S)-SbF(3)(C(8)H(9)NO(3)):具有增强的二次谐波产生和双折射的手性锑基杂化材料

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Abstract

Noncentrosymmetric (NCS) materials have garnered significant attention due to their unique second-harmonic generation (SHG) properties, which are crucial for nonlinear optical (NLO) applications. However, achieving optimal SHG efficiency and birefringence remains challenging for Sb(3)⁺-based hybrid materials, which are being actively explored as potential alternatives to toxic Pb(2)⁺-based systems. In this study, we successfully synthesized two novel chiral NCS compounds, (R)-SbF₃(C₈H₉NO₃) [(R)-Sb] and (S)-SbF₃(C₈H₉NO₃) [(S)-Sb], by incorporating the stereochemically active lone pair cation Sb(3)⁺, highly electronegative F⁻ anions, and the chiral zwitterionic 4-hydroxyphenylglycine. The compounds crystallize in the polar noncentrosymmetric space group, P2(1) (No. 4), featuring [SbOF₃] polyhedra that form hydrogen bonds with 4-hydroxyphenylglycine. Notably, the Sb(3)⁺ lone pairs align along the b-axis, resulting in enhanced polar characteristics. These structural features endow the compounds with outstanding NLO properties, including an SHG response 2.6 times greater than that of KH(2)PO(4), a wide band gap of 4.19 eV, and suitable birefringence (0.184@546.1 nm). This work contributes to the expanding research on chiral hybrid materials and underscores the potential of Sb(3)⁺-based systems for advanced optical applications.

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