Polar Phosphorus Chalcogenide Cage Molecules: Enhancement of Nonlinear Optical Properties in Adducts. (2nd February 2023)

• Record Type: Journal Article
• Authors: Yang, Shunda; Lin, Chensheng; Fan, Huixin; Chen, Kaichuang; Zhang, Ge; Ye, Ning; Luo, Min
• Is Part Of: Angewandte Chemie. Volume 135:Number 11(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-02-02
• Subjects: Inorganic Adducts -- Nonlinear Optics -- Phosphorus Chalcogenides -- Second Harmonic Generation; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202218272
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Inorganic adducts are an emerging class of infrared nonlinear optical (NLO) materials. However, although the reported NLO adducts have sufficient birefringences and significant laser‐induced damage thresholds (LIDTs), they commonly suffer from weak second harmonic generation (SHG) responses. In this work, a series of polar phosphorus chalcogenide cage molecules with strong hyperpolarizabilities were theoretically screened out to enhance the SHG responses of adducts. Accordingly, (CuI)3 (P4 S4 ), (CuI)3 (P4 Se4 ), (CuBr)7 (P4 S3 )3 and (CuBr)7 (P4 Se3 )3 with target polar cage molecules were successfully synthesized. As expected, they exhibit enhanced SHG responses while keeping moderate birefringences and high LIDTs. Notably, (CuBr)7 (P4 Se3 )3 possesses the largest SHG response (3.5×AGS@2.05 μm) among the known inorganic NLO adducts. Our study confirms that introducing NLO‐active cage molecules into adducts is an efficient strategy for high‐performance NLO materials. Abstract : Polar phosphorus chalcogenide cages (β‐P4 S3, β‐P4 S4, β‐P4 Se3, β‐P4 Se4 ) with strong hyperpolarizabilities as functional molecules are introduced into inorganic adducts, resulting in four high‐performance IR nonlinear optical materials. Among them, (CuBr)7 (P4 Se3 )3 exhibits the largest second harmonic generation response (3.5×AGS @ 2 μm) in inorganic adducts.