Chen Jin, Hu Chun-Li, Lin Yi-Lin, Chen Yan, Chen Qian-Qian, Mao Jiang-Gao
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou 350002 P. R. China
College of Chemistry and Materials Science, Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University Fuzhou 350007 P. R. China.
Chem Sci. 2021 Dec 6;13(2):454-460. doi: 10.1039/d1sc06026k. eCollection 2022 Jan 5.
The combination of d transition metal oxofluorides with iodate anions helps to synthesize polar crystals. Herein, a novel polar crystal, KVOF(IO), which is the first metal vanadium iodate with two types of V-centered polyhedra (VOF octahedron and VOF trigonal bipyramid), has been prepared hydrothermally. It crystallizes in the polar space group of 2 and its structure displays an unprecedented 0D [VOF(IO)] anion, which is composed of Λ-shaped -[VOF(IO)] and [VOF(IO)] anions interconnected the corner-sharing of one oxo anion. The synergy gained from the VOF, VOF and IO groups resulted in KVOF(IO) exhibiting both a strong second-harmonic generation (SHG) response (1.3 × KTiOPO) under 2050 nm laser irradiation and a large birefringence (0.158 @ 2050 nm). This study provides a facile route for designing SHG materials by assembling various vanadium oxide-fluoride motifs and iodate anions into one compound.
d 过渡金属氧氟化物与碘酸根阴离子的结合有助于合成极性晶体。在此，一种新型极性晶体KVOF(IO)通过水热法制备而成，它是首例具有两种以钒为中心的多面体（VOF 八面体和 VOF 三角双锥）的金属钒碘酸盐。它结晶于极性空间群 2，其结构呈现出前所未有的 0D [VOF(IO)] 阴离子，该阴离子由 Λ 形的 -[VOF(IO)] 和 [VOF(IO)] 阴离子通过一个氧阴离子的角共享相互连接而成。VOF、VOF 和 IO 基团之间的协同作用使得 KVOF(IO) 在 2050 nm 激光照射下表现出强烈的二次谐波产生（SHG）响应（1.3 × KTiOPO）以及较大的双折射（在 2050 nm 处为 0.158）。本研究为通过将各种钒氧化物 - 氟化物基序和碘酸根阴离子组装成一种化合物来设计 SHG 材料提供了一条简便途径。
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