M2As2Q5 (M = Ba, Pb; Q = S, Se) have been screened out by combined experiments and theoretical calculations as a new source of IR NLO materials. Interestingly, they exhibit excellent overall performance activated by multiple discrete arsenate anions.

Non-centrosymmetric (NCS) Bi-based oxides with giant second-harmonic generation (SHG) responses have been widely studied as UV–visible nonlinear optical (NLO) materials over the past few decades. However, high-performance Bi-based NLO chalcogenides in the infrared (IR) region have rarely been reported. Herein, a novel NCS Bi-based thiophosphate RbBiP2S6 (P21) has been successfully designed by the aliovalent substitution of centrosymmetric Rb4P2S6 (P21/c). Notably, this compound affords a record-high SHG intensity (11.9 × AgGaS2 @ 2.05 μm) ever reported for IR-NLO sulfides. Moreover, detailed structure analysis and theoretical studies indicate that the superior IR-NLO performance can be attributed to the highly polarizable [BiS7] units together with the favorable alignment of ethane-like [P2S6] units. This discovery offers an excellent candidate for IR-NLO applications and suggests that aliovalent substitution is a promising way to search for unknown high-performance NLO materials.