Abstract
Nonlinear optical (NLO) crystals featuring a strong second-harmonic generation (SHG) response and suitable birefringence to achieve phase-matching are in urgent demand in industrial and commercial applications. Based on the substitution strategy, two new NLO lead-iodide formates, K(2)[PbI(2)(HCOO)(2)] and Rb(2)[PbI(2)(HCOO)(2)], have been successfully synthesized using a moderate mixed-solvothermal method. K(2)[PbI(2)(HCOO)(2)] and Rb(2)[PbI(2)(HCOO)(2)] exhibit strong phase-matching SHG responses of 8 and 6.8 × KDP, respectively, a suitable birefringence and transparent window covering most of the visible light and mid-IR region. Crystal structures and theoretical calculations unveil that the origins of the strong SHG response and suitable birefringence can be credibly attributed to the oriented arrangement of the highly distorted [PbI(2)O(4)] hexa-coordinated polyhedra, which are consistent in their local dipole moments, as well. This research provides a new strategy to explore high-performance NLO crystals.