Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence

Considerable effort has been invested in the development of non-centrosymmetric (NCS) inorganic solids for ferroelectricity-, piezoelectricity- and, particularly, optical nonlinearity-related applications. While great progress has been made, a persistent problem is the difficulty in constructing NCS materials, which probably stems from non-directionality and unsaturation of the ionic bonds between metal counter-cations and covalent anionic modules. We report herein a secondary-bond-driven approach that circumvents the cancellation of dipole moments between adjacent anionic modules that has plagued second-harmonic generation (SHG) material design, and which thereby affords a polar structure with strong SHG properties. The resultant first NCS counter-cation-free iodate, VO