Zhu Qingwen, Tao Yong, Yang Can, Gou Jie, Zhu Yaolong, Wang Xuefei, Wu Qi
State Key Laboratory of New Textile Materials and Advanced Processing Technologies, Wuhan Textile University, Wuhan 430200, China.
No.11 Middle School of Wuhan, Wuhan 430030, China.
Inorg Chem. 2024 Nov 25;63(47):22620-22627. doi: 10.1021/acs.inorgchem.4c04326. Epub 2024 Nov 12.
Developing approaches to induce noncentrosymmetric (NCS) frameworks through atomic-scale structural optimizations is crucial due to the growing need for new ultraviolet (UV) nonlinear optical (NLO) materials. Herein, the first two new NCS pyridine carboxylates, ZnBr(CHFNO) () and Cd(CHFNO)(HO) (), were successfully synthesized using centrosymmetric (CS) templates and rational structural reconstructions induced by different ionic radius. Both compounds crystallize in the orthorhombic system and feature metal-centered zero-dimensional (0D) isolated clusters. Substituting the [ZnONO] pyramid in the CS pyridine carboxylate with the [ZnONBr] pyramid in compound breaks the centrality, leading to an NCS framework with a second harmonic generation (SHG) response of 1.7 × KHPO (KDP). Introducing a larger Cd cation results in a -to- transition of the [MON] (M = Zn, Co, and Ni in CS templates, Cd in ) octahedra, forming a wing-shaped asymmetric 0D cluster with an SHG response of 2.1 × KDP. These findings indicate an approach that can effectively induce NCS structures of 0D organic-inorganic hybrid materials.
由于对新型紫外（UV）非线性光学（NLO）材料的需求不断增长，通过原子尺度结构优化来开发诱导非中心对称（NCS）框架的方法至关重要。在此，使用中心对称（CS）模板和由不同离子半径诱导的合理结构重构，成功合成了前两种新型NCS吡啶羧酸盐，即ZnBr(CHFNO) （）和Cd(CHFNO)(HO) （）。这两种化合物均结晶于正交晶系，并具有以金属为中心的零维（0D）孤立簇。用化合物中的[ZnONBr]金字塔取代CS吡啶羧酸盐中的[ZnONO]金字塔会破坏中心对称性，从而导致具有1.7×KHPO（KDP）二次谐波产生（SHG）响应的NCS框架。引入更大的Cd阳离子会导致[MON]（CS模板中的M = Zn、Co和Ni，中的M = Cd）八面体发生从到的转变，形成具有2.1×KDP的SHG响应的翼状不对称0D簇。这些发现表明了一种可以有效诱导0D有机-无机杂化材料NCS结构的方法。
