A Lead Mixed Halide with Three Different Coordinated Anions and Strong Second‐Harmonic Generation Response

Abstract

Nonlinear optical (NLO) crystals are widely applied in information technology, micro‐manufacturing and medical treatment. Herein, a new lead mixed halide with strong second‐harmonic generation (SHG) response, Cs3Pb2(CH3COO)2Br3I2, has been designed and rationally synthesized. Cs3Pb2(CH3COO)2Br3I2 represents the rare NLO crystal featuring that three different anions (I−, Br− and O2−) simultaneously coordinate the Pb(II) atom to form a severely distorted [PbBr2I2O2] polyhedron with a large polarizability. Remarkably, Cs3Pb2(CH3COO)2Br3I2 not only exhibits a very strong phase‐matching SHG response of 9×KH2PO4 (KDP), but also possesses a large birefringence (0.27@1064 nm) and high laser damage threshold (LDT). The strong SHG effect of Cs3Pb2(CH3COO)2Br3I2 mainly originates from the oriented arrangement of [Pb2Br3I2] chains. This study points out an effective strategy to develop new NLO crystals with strong SHG response.

APb2(C7H3NO4)2I (A = K, Rb, Cs): rare stable nonlinear optical crystals with second-harmonic generation response and highly distorted lead core coordination polyhedra

“…Notably, the Pb2(II) atom is simultaneously coordinated by three different kinds of atoms, which is rare in NLO crystals. [20][21][22][23][30][31][32][33] These distorted [PbNO 5 ] and [PbNO 4 I] coordination polyhedra are beneficial to the generation of the SHG response. Additionally, the 2,6-pyridinedicarboxylate groups display two different coordination modes.…”

“…Notably, the Pb2( ii ) atom is simultaneously coordinated by three different kinds of atoms, which is rare in NLO crystals. 20–23,30–33 These distorted [PbNO 5 ] and [PbNO 4 I] coordination polyhedra are beneficial to the generation of the SHG response.…”

SbI3·3S8: A Novel Promising Inorganic Adducts Crystal for Second Harmonic Generation

“…There are many standard DUV NLO crystals available, such as KH 2 PO 4 , KBe 2 BO 3 F 2 , KTiOPO 4 , BPO 4 , β-BaB 2 O 4 , and KLa(PO 3 ) 4 , which can satisfy basic necessity of the laser industry [ 6 , 16 , 17 , 18 , 19 ]. On the other hand, though the materials such as KBe 2 BO 3 F 2 , ZnGeP 2 , AgGaS 2 (AGS), and AgGaSe 2 (AGSe) have been used as DUV and MFIR NLO crystals, their ingrained obstructions harshly constrict their wide range of applications [ 20 , 21 ]. Among them, the most outstanding NLO crystal for MFIR is AGS and AGSe.…”

Metal oxyhalides: an emerging family of nonlinear optical materials

“…Pb 2 (CH 3 COO) 2 Br 3 I 2 . By the partial substitution of Br − anions in Cs 3 Pb 2 (CH 3 COO) 2 Br 5 for I − , a new isostructural compound, Cs 3 Pb 2 (CH 3 COO) 2 Br 3 I 2 , has been obtained under mixed-solvothermal conditions 66. Different from Cs 3 Pb 2 (CH 3 COO) 2 Br 5 with single halogen type, the structure of Cs 3 Pb 2 (CH 3 COO) 2 Br 3 I 2 contains rare Pb-mixed-oxyhalide polyhedra, [PbO 2 Br 2 I 2 ] (Fig.15), which are severely distorted and exhibiting a larger polarizability.…”