Electronic, Crystal Chemistry, and Nonlinear Optical Property Relationships in the Dugganite A3B3CD2O14 Family

A family of six nonlinear optical (NLO) materials, A3B3CD2O14 (A = Sr, Ba, or Pb; B = Mg or Zn; C = Te or W; and D = P or V), has been synthesized and characterized. In addition to the synthesis and crystal structures, comprehensive characterization of these compounds includes second harmonic generation (SHG) measurements, theoretical calculations, infrared and diffuse reflectance spectroscopies, and thermogravimetric measurements. We find that all of the reported materials are SHG-active at 1064 nm, with responses ranging from 2.8 to 13.5 × KDP, and exhibit absorption edges in the mid- to deep-ultraviolet regime. By systematically replacing the A, B, C, and D cations, we are able to tune these properties and investigate the role of different NLO-active structural units in producing the SHG responses. Specifically, our electronic structure calculations reveal that the presence of Pb2+ on the A-site and Te6+ on the C-site is critical for generating a large SHG response. The synthesis and structure–property relationships described in this family of materials will enable the design and discovery of new NLO materials.本研究合成并表征了一类共6种非线性光学（NLO）材料，其通式为A₃B₃CD₂O₁₄，其中A可选Sr、Ba或Pb，B可选Mg或Zn，C可选Te或W，D可选P或V。除合成与晶体结构解析外，对该系列化合物的全面表征还涵盖二次谐波产生（SHG）测试、理论计算、红外光谱与漫反射光谱分析，以及热重分析。研究发现，所有报道的材料在1064 nm波长下均表现出SHG活性，其响应强度介于2.8至13.5倍磷酸二氢钾（KDP）之间，且吸收边位于中紫外至深紫外区间。通过系统性替换A、B、C、D位阳离子，我们可调控该类材料的相关性能，并探究不同NLO活性结构单元对二次谐波响应的贡献机制。具体而言，电子结构计算结果表明，A位引入Pb²+、C位引入Te⁶+是实现高强SHG响应的关键因素。本系列材料的合成方法与构效关系研究，将为新型NLO材料的设计与发掘提供重要指导。