LAUSR

A wide bandgap is an essential requirement for a nonlinear optical (NLO) material. However, it is very challenging to simultaneously engineer a wide bandgap and a strong second-harmonic generation (SHG) response, particularly in NLO materials containing second-order Jahn–Teller (SOJT) distorted units. Herein, we employ a bandgap engineering strategy that involves the dual fluorination of two different types of SOJT distorted units to realize remarkably wide bandgaps in the first examples of 5d0-transition metal (TM) fluoroiodates. Crystalline A2WO2F3(IO2F2) (A = Rb (RWOFI) and Cs (CWOFI)) exhibit the largest bandgaps yet observed in d0-TM iodates (4.42 (RWOFI) and 4.29 eV (CWOFI)), strong phase-matching SHG responses of 3.8 (RWOFI) and 3.5 (CWOFI) × KH2PO4, and wide optical transparency windows. Computational studies have shown that the excellent optical responses result from synergism involving the two fluorinated SOJT distorted units ([WO3F3]3− and [IO2F2]−). This work provides not only an efficient strategy for bandgap modulation of NLO materials, but also affords insight into the relationship between the electronic structure of the various fluorinated SOJT distorted units and the optical properties of crystalline materials.