Huang Yu, Li Bing-Xuan, Hu Chun-Li, Yang Bing-Ping, 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.
State Key Laboratory of Material Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, Hubei 430074, China.
Inorg Chem. 2023 Feb 27;62(8):3343-3348. doi: 10.1021/acs.inorgchem.3c00189. Epub 2023 Feb 15.
A new polar hafnium iodate, CsHfF(IO), was successfully designed and synthesized by integrating fluorinated hafnium-oxygen polyhedra (HfFO) and IO anionic functional groups. Owing to the weak electronic effect of Hf and the bond-network-induced out-of-center distortion of the HfFO dodecahedra, CsHfF(IO) achieves a good balance between a strong second-harmonic-generation effect (3.5 × KHPO) and a rather large band gap (4.47 eV), which is the largest among the d transition-metal iodates. In addition, CsHfF(IO) possesses a wide transparent region (0.27-9.9 μm), a large birefringence for phase-matching (0.161), and a high laser-induced damage threshold (55.41 MW cm, 26 × AgGaS) and is nonhygroscopic. This work indicates that the integration of mixed-ligand acentric coordination polyhedra and functional groups containing lone electron pairs is an effective strategy for developing novel inorganic nonlinear-optical materials with balanced overall properties.
通过整合氟化铪 - 氧多面体（HfFO）和IO阴离子官能团，成功设计并合成了一种新型极性碘酸铪CsHfF(IO)。由于铪的电子效应较弱以及HfFO十二面体的键网络诱导的中心外畸变，CsHfF(IO)在强二次谐波产生效应（3.5×KHPO）和相当大的带隙（4.47 eV）之间实现了良好的平衡，这在d过渡金属碘酸盐中是最大的。此外，CsHfF(IO)具有宽透明区域（0.27 - 9.9μm）、用于相位匹配的大双折射（0.161）和高激光诱导损伤阈值（55.41 MW cm，26×AgGaS），并且不吸湿。这项工作表明，混合配体非中心配位多面体与含孤电子对官能团的整合是开发具有平衡综合性能的新型无机非线性光学材料的有效策略。
