First chiral fluorinated lead vanadate selenite Pb2(V2O4F)(VO2)(SeO3)3 with five asymmetric motifs and large optical properties.

Lin Lin,Lin Lin,Lin Lin,Lin Lin,Zheshuai Lin,Zheshuai Lin,Zheshuai Lin,Zheshuai Lin,Zheshuai Lin,Lin Lin,Mark G Humphrey,Mark G Humphrey,Mark G Humphrey,Mark G Humphrey,Chao Wu,Chao Wu,Chao Wu,Chao Wu,Chao Wu,Xingxing Jiang,Xingxing Jiang,Xingxing Jiang,Xingxing Jiang,Xingxing Jiang,Zhipeng Huang,Zhipeng Huang,Zhipeng Huang,Zhipeng Huang,Zhipeng Huang,Chi Zhang,Chi Zhang,Chi Zhang,Chi Zhang,Chi Zhang

doi:10.1039/d1dt00536g

Abstract

The first fluorinated lead vanadate selenite Pb2(V2O4F)(VO2)(SeO3)3 (PVOFS) was successfully synthesized via a mild hydrothermal method. This compound crystallizes in the chiral space group P212121 of the orthorhombic system and it is the first noncentrosymmetric structure in the PbII-VV-SeIV-O-F system. PVOFS is composed of five kinds of second-order Jahn-Teller susceptible asymmetric motifs, including three distinct types of vanadium-centered polyhedral units ([VO5F], [VO6] and [VO5]), [SeO3] pyramids and Pb2+ cations. It features a unique three-dimensional open framework structure displaying three types of tunnels (10-, 8- and 7-membered rings), which enriches the structural diversity for fluorinated vanadate selenite systems. Optical property studies revealed that PVOFS shows a second-harmonic generation response of 0.3 times that of the commercial KH2PO4 with phase matching behavior, a wide transparent region covering IR windows, an optical band gap of 2.35 eV, a high laser damage threshold of 61 times that of AgGaS2, and a large birefringence of 0.105 at 1064 nm. Theoretical calculations have been performed to clarify the correlation between the molecular structure and the optical properties of PVOFS.

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