From Cd(SCN)2(CH4N2S)2 to Cd(SCN)2(C4H6N2)2: Controlling Sulfur Content in Thiocyanate Systems Significantly Improves the Overall Performance of UV Nonlinear Optical Materials

Abstract Combining a strong second‐order nonlinear optical (NLO) effect (>1×KH 2 PO 4 (KDP)), a large band gap (>4.2 eV), and a moderate birefringence in ultraviolet (UV) NLO crystals remains a formidable challenge. Herein, Cd(SCN) 2 (C 4 H 6 N 2 ) 2 , the first example of a thiocyanate capable of realizing a phase‐matched UV NLO crystal material, is obtained by reducing the sulfur (S) content in the centrosymmetric (CS) structure of Cd(SCN) 2 (CH 4 N 2 S) 2 . Compared to the “shoulder‐to‐shoulder” one‐dimensional (1D) chain of Cd(SCN) 2 (CH 4 N 2 S) 2 , Cd(SCN) 2 (C 4 H 6 N 2 ) 2 has a different sawtooth 1D chain structure. Cd(SCN) 2 (CH 4 N 2 S) 2 has second harmonic generation (SHG) inertia with a band gap of 3.90 eV and a UV cutoff edge of 342 nm, however, it possesses a large birefringence (0.35@546 nm). In contrast, the symmetry center breaking of Cd(SCN) 2 (C 4 H 6 N 2 ) 2 leads to remarkably strong SHG intensity (10 times that of KDP). Furthermore, it has a wide band gap (4.74 eV), short UV cutoff edge (234 nm), and moderate birefringence capable of phase matching (0.17@546 nm). This research indicates that thiocyanates are a promising class of UV NLO crystal materials, and that modulation of the sulfur content of CS thiocyanates is an effective strategy for the development of UV NLO crystals with excellent overall performances.