Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics

Abstract The search of new borates with improved functional properties has attracted considerable attention. Herein, a new polar fluorooxoborate, NaB 4 O 6 F (NBF) was prepared by high‐temperature solid‐state reaction. NBF belongs to the AB 4 O 6 F family (A=alkali metal or ammonium), a series of compounds that undergoes significant cation‐dependent structural changes. NBF is of particular interest owing to the special cation position. Temperature‐dependent ionic conductivity measurements show that NBF is a solid ionic conductor, and it has the lowest active energy of 32.5 kJ mol −1 of fluorooxoborates. NBF also shows a second‐harmonic generation (SHG) response of 0.9×KH 2 PO 4 and 0.2×β‐BaB 2 O 4 , at 1064 and 532 nm, respectively, and it has a short UV cutoff edge below 180 nm. Based on bond valence (BV) concepts, symmetry analysis, and the first principles calculation, the unique [B 4 O 6 F] ∞ layer can be regarded as the “multifunctional unit”, which is responsible for the observed properties of NBF.