Homoatomic Polychalcogenide Nonlinear Optical Anionic Groups with Ultra-Large Optical Anisotropy.

Functional assembly of nonlinear optical (NLO) motifs with a large optical anisotropy is vital to the development of advanced NLO and birefringent materials. In this work, we highlight that, in addition to heteroatomic NLO motifs, homoatomic anionic clusters formed by aggregated anions (S, Se, Te) exhibit diverse chain-, ring-, and cage-like chemical structures as well as one-, two-, and three-dimensional motif alignments. The rich structural chemistry enables homoatomic polychalcogenides (HAPCs) to exhibit asymmetric structural features and anisotropic optical properties, with great potential for NLO and birefringent performance. Focusing on totally 55 binary HAPCs AQ ( = 2, 3, 4, 5; A = Na, K, Rb, Cs; Q = S, Se, Te) and their ternary analogues, we employ the state-of-the-art first-principles approach to systematically investigate the modulation evolution of their NLO and birefringent properties. Remarkably, RbTe and NaTeSe exhibit rarely colossal birefringence (>1.0@10 μm) and NLO effects (>20 × AgGaS), much larger than conventional NLO chalcogenides. NaTe presents the largest birefringence to date (∼3.48@1, 2.72@2, 2.34@10 μm), indicating the unique structural superiority of HAPC in terms of ultra-large birefringence. By mining the intrinsic mechanism, the HAPC anionic groups are identified as novel mid-infrared NLO "material genes", furnishing unique NLO and birefringent performance for the design of novel optoelectronic materials.