{[In₂S₇]^8–}_∞ Chain and Isolated HgS₄ Planar Unit Constructed One-Dimensional Pentanary Sulfide K₂Ba₇HgIn₄S₁₆ Exhibiting Nonlinear-Optical Activity

Hg-based chalcogenides possess diverse structures, large nonlinear-optical (NLO) responses, and suitable birefringences, making them potentially suitable for numerous crucial criteria of practical application as infrared (IR) NLO crystals. Here, a new pentanary Hg-based sulfide K₂Ba₇HgIn₄S₁₆ has been discovered by a high-temperature solid-state method. It crystallizes in the orthorhombic P2₁2₁2 space group, and its one-dimensional structure is constructed by {[In₂S₇]^8–}_∞ chains and isolated [HgS₄]^6– planar quadrilateral units located bewteeen the chains, representing a novel type of chalcogenide. K₂Ba₇HgIn₄S₁₆ exhibits a moderate NLO effect of 0.5 × AGS at 2.1 μm and a high laser-induced damage threshold of ∼5.8 × AGS, as well as a band gap of 2.98 eV, demonstrating that K₂Ba₇HgIn₄S₁₆ is a potential IR NLO material. This work enriches the structural chemistry of chalcogenides and the family of Hg-based IR NLO chalcogenides.