Wu Chao, Jiang Xingxing, Hu Yilei, Jiang Chunbo, Wu Tianhui, 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.
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
Angew Chem Int Ed Engl. 2022 Feb 1;61(6):e202115855. doi: 10.1002/anie.202115855. Epub 2021 Dec 23.
The targeted synthesis of deep-ultraviolet (deep-UV) nonlinear optical (NLO) materials, especially those with non-π-conjugated sulfates, has experienced considerable difficulties due to the need to reconcile the oft-competing requirements for deep-UV transparency and strong second-harmonic generation (SHG). We report herein the designed synthesis of the first rare-earth metal-based deep-UV sulfate La(NH )(SO ) by a double-salt strategy involving introduction of complementary cations, together with optical studies that reveal a short-wavelength deep-UV absorption edge (below 190 nm) and the strongest SHG response among deep-UV NLO sulfates (2.4×KDP). Theoretical calculations and crystal structure analysis suggest that the excellent balance between SHG response and deep-UV transparency can be attributed to a synergistic interaction of the hetero-cations La and [NH ] , which optimize alignment of the [SO ] tetrahedra and highly polarizable [LaO ] polyhedra.
深紫外（deep-UV）非线性光学（NLO）材料的定向合成，尤其是那些含有非π共轭硫酸盐的材料，由于需要协调深紫外透明度和强二次谐波产生（SHG）这两个经常相互矛盾的要求，一直面临着相当大的困难。我们在此报告通过一种涉及引入互补阳离子的复盐策略，首次设计合成了基于稀土金属的深紫外硫酸盐La(NH )(SO )，同时光学研究表明其具有短波长的深紫外吸收边（低于190 nm），并且在深紫外NLO硫酸盐中具有最强的SHG响应（2.4×KDP）。理论计算和晶体结构分析表明，SHG响应和深紫外透明度之间的优异平衡可归因于杂阳离子La和[NH ] 的协同相互作用，它们优化了[SO ]四面体和高极化率的[LaO ]多面体的排列。
