Collaborative enhancement from Pb²⁺ and F⁻ in Pb₂(NO₃)₂(H₂O)F₂ generates the largest second harmonic generation effect among nitrates

Abstract

The first metal nitrate fluoride nonlinear optical material, Pb(NO)(HO)F, was synthesized with the largest second harmonic generation (SHG) effect (12 × KHPO) among nitrates. Theoretical calculations revealed the synergistic effect of [NO], lone pair electrons in Pb, and F for the SHG effect. The F also promoted the blue-shift of the ultraviolet cut-off edge.

Sb6O7(SO4)2: A Promising Ultraviolet Nonlinear Optical Material with an Enhanced Second‐Harmonic‐Generation Response Activated by SbIII Lone‐Pair Stereoactivity

“…It is well known that the SHG responses or birefringence can be enhanced by introducing an additional distortive structural unit, that is, cations with a stereochemically active lone pair (SCALP). Typical examples include Bi 3 TeO 6 OH(NO 3 ) 2 , [33] Bi(IO 3 )F 2 , [34] Bi 3 (TeO 6 )(BO 3 ), [35] Pb 2 BO 3 I, [36] Pb 2 (NO 3 ) 2 (H 2 O)F 2 , [19] and Pb 2 B 5 O 9 I [37] . In comparison, it is noteworthy that antimony(III)‐based UV NLO materials are very limited [38–43] .…”

“…To further confirm the result, we also adopted the bond‐valence approach to investigate the microscopic structural origins for the macroscopic SHG behavior. The direction and magnitude of the dipole moments of all SbO 4 seesaws and SO 4 tetrahedra were studied [19, 34, 54–60] . The dipole moments for the three unsymmetrical SbO 4 seesaws and SO 4 unit are 9.28, 9.45, 9.88, and 1.97 D (D=Debye), respectively.…”

Giant Optical Anisotropy in the UV‐Transparent 2D Nonlinear Optical Material Sc(IO3)2(NO3)

“…Pb 2+ , Sn 2+ , Sb 3+ , etc. ); relevant examples include SbB 3 O 6 , [14a] Sn 2 B 5 O 9 Cl, [14b] and Pb 2 (NO 3 ) 2 (H 2 O)F 2 [14c] . The approaches to date have mainly focused on the combination of metal cation and single oxyanion; the combination of two types of oxyanions into the one structure to create new UV NLO materials with large birefringence is thus far underexploited because of the intricate multiple inter‐anion interactions.…”

Syntheses, Crystal Structures and Luminescent Properties of Two New Heterometallic Phosphates: Sn2Ge(PO4)2(OH)2 and Sn2Mn(PO4)2

“…It has been demonstrated that the ns 2 lone‐pair electrons are sensitive to the second order Jahn−Teller (JT) effect, hence the p‐block metal cations with a ns 2 stereo‐chemically active lone pairs usually tend to form a class of second‐order nonlinear optical materials with large second harmonic generation (SHG) responses, including 5 s 2 Sn 2+ and Sb 3+ and 6 s 2 Tl + , Pb 2+ , and Bi 3+ cations . For example, Pb 3 Zn 3 TeP 2 O 14 exhibits a large SHG response (13.5 × KH 2 PO 4 ), another single‐phased product of SnHPO 3 also exhibits a moderate SHG response (3 × KH 2 PO 4 ), and Sn 1−x Mn x HPO 3 show intrinsic white‐light emission and the doping of the Mn 2+ cation largely enhances the quantum efficiency of white luminescence .…”