Lin Lin, Jiang Xingxing, Wu Chao, Lin Zheshuai, Huang Zhipeng, Humphrey Mark G, Zhang Chi
China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China.
Key Lab of Functional Crystals and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Dalton Trans. 2021 Jun 1;50(21):7238-7245. doi: 10.1039/d1dt00536g.
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.
通过温和水热法成功合成了首例氟代钒酸铅亚硒酸盐Pb2(V2O4F)(VO2)(SeO3)3（PVOFS）。该化合物结晶于正交晶系的手性空间群P212121，是PbII-VV-SeIV-O-F体系中的首个非中心对称结构。PVOFS由五种二阶 Jahn-Teller 敏感不对称基序组成，包括三种不同类型的以钒为中心的多面体单元（[VO5F]、[VO6]和[VO5]）、[SeO3]金字塔和Pb2+阳离子。它具有独特的三维开放框架结构，呈现出三种类型的隧道（10元、8元和7元环），丰富了氟代钒酸铅亚硒酸盐体系的结构多样性。光学性质研究表明，PVOFS的二次谐波产生响应为商用KH2PO4的0.3倍，具有相位匹配行为，宽透明区域覆盖红外窗口，光学带隙为2.35 eV，激光损伤阈值为AgGaS2的61倍，在1064 nm处具有0.105的大双折射。已进行理论计算以阐明PVOFS分子结构与光学性质之间的相关性。
