摘要: Diamond-like AgGaS2 (DL AGS), as the typical infrared nonlinear optical (IR NLO) material, has suffered from its intrinsic drawbacks like narrow band gap (Eg) and low laser-induced damage threshold (LIDT). In this work, by first introducing [NaS8] polyhedral unit into the A2IQVI-Ag2QVI-C2IIIQ3VI system, a new Ag-based sulfide NaAg3Ga8S14 with diamond-like framework (DLF) has been successfully synthesized via a high-temperature solid-state method in experiment. The compound shows a wide Eg (∼3.0 eV), high LIDT (3.0 × AGS) and moderate phase-matching NLO response (∼0.7 × AGS), effectively balancing the Eg (≥ 3.0 eV) and NLO response (≥ 0.5 × AGS), demonstrating its promise for IR NLO applications. Theoretical calculations elucidate the orbital hybridization between Na 3s, Ag 4d5s and S 3p enhances Eg, and the aligned NLO-active units ([AgS4] and [GaS4]) induce moderate NLO response in the compound. These findings not only expand the chemical and structural diversities of Ag-based chalcogenides, but also provide effective strategies for designing DLF functional materials derived from diamond-like structures.