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.