Unlocking Giant Third‐Order Optical Nonlinearity in (MA)2CuX4 through Introducing Jahn‐Teller Distortion.

Nonlinear absorption coefficient and modulation depth stand as pivotal properties of nonlinear optical (NLO) materials, while the existing NLO materials exhibit limitations such as low nonlinear absorption coefficients and/or small modulation depths, thereby severely impeding their practical application. Here we unveil that introducing Jahn–Teller distortion in a Mott‐Hubbard system, (MA)2CuX4 (MA=methylammonium; X=Cl, Br) affords the simultaneous attainment of a giant nonlinear absorption coefficient and substantial modulation depth. The optimized compound, (MA)2CuCl4, demonstrates a nonlinear absorption coefficient of (1.5±0.08)×105 cm GW−1, a modulation depth of 60 %, and a relatively low optical limiting threshold of 1.22×10−5 J cm−2. These outstanding attributes surpass those of most reported NLO materials. Our investigation reveals that a more pronounced distortion of the [CuX6]4− octahedron emerges as a crucial factor in augmenting optical nonlinearity. Mechanism study involving structural and spectral characterization along with theoretical calculations indicates a correlation between the compelling performance and the Mott‐Hubbard band structure of the materials, coupled with the Jahn–Teller distortion‐induced d‐d transition. This study not only introduces a promising category of high‐performance NLO materials but also provides novel insights into enhancing the performance of such materials. [ABSTRACT FROM AUTHOR]