Na₁₀Zn(NO₃)₄(SO₃S)₄: a nonlinear optical crystal combining inorganic π-conjugated and non-π-conjugated heteroanion groups

Abstract

Combining non-π-conjugated heteroanionic groups and π-conjugated groups is an effective strategy for obtaining crystals with excellent optical properties.

Two Acentric Zn-Based l-Tartrates with Moderate Second Harmonic Generation Responses and Large Birefringence

“…Figures S8 and S9 present the IR spectra of the two title compounds. Both of them display broad absorption peaks near 3200 cm –1 associated with water molecules. , The absorption bands from 1238 to 1585 cm –1 could be assigned to the asymmetric stretching of CO and C–O bonds. , The IR spectrum of Zn-LTS shows the asymmetric and symmetric stretching vibrations of [SO 4 ] group near 1293 cm –1 . − The absorption bands in the range of 780–516 cm –1 can be assigned to the vibration of Zn–O bonds. − …”

(C5H12N2S)Hg(NO3)2: A Mercury Nitrate Nonlinear Optical Crystal Motivated by Heteroatom Coordination Strategy

“…In recent years, researchers have successfully synthesized compounds with excellent NLO properties by combining d 10 metals with π-conjugated anions of triangular planar geometry, especially in borate and carbonate systems, such as AZn 2 (BO 3 )Si 2 O 5 (A = Rb, Cs), Cd 4 BiO(BO 3 ) 3 , CsZn 2 BO 3 X 2 (X 2 = F 2 , Cl 2 , and FCl), LiZn(OH)CO 3 , Ba 5 Zn 4 (BO 3 ) 6 , and KCdCO 3 F. ,− However, the d 10 metal nitrate NLO crystals have shown very limited reports. Only A 2 Hg(NO 3 ) 4 (A = K, Rb), Na 10 Zn(NO 3 ) 4 (SO 3 S) 4 , Na 10 Cd(NO 3 ) 4 (SO 3 S) 4 and PbCdF(SeO 3 )(NO 3 ) exhibit SHG effects. ,,, Prominently, A 2 Hg(NO 3 ) 4 (A = K, Rb) demonstrate strong SHG effects of 8.8–9.2 times than that of KDP . Note that Hg 2+ ions can adopt multiple coordination configurations, including linear, trigonal planar, and tetrahedral units, which contribute to the diversity of structural variations.…”

“…Only A 2 Hg(NO 3 ) 4 (A = K, Rb), Na 10 Zn(NO 3 ) 4 (SO 3 S) 4 , Na 10 Cd(NO 3 ) 4 (SO 3 S) 4 and PbCdF(SeO 3 )(NO 3 ) exhibit SHG effects. 33,35,52,53 Prominently, A 2 Hg(NO 3 ) 4 (A = K, Rb) demonstrate strong SHG effects of 8.8−9.2 times than that of KDP. 52 Note that Hg 2+ ions can adopt multiple coordination configurations, including linear, trigonal planar, and tetrahedral units, which contribute to the diversity of structural variations.…”

“…We have found that replacing O with S atoms having high polarizability is particularly favorable for achieving larger effects in NLO oxysulfide crystals. 33,35 Additionally, controlling the sulfur content is also very important, because it contributes to structural transformation and enhances the SHG effect, which can be exemplified (C 5 H 12 N 2 S)Hg(NO 3 ) 2 belongs to the orthorhombic crystal system P2 1 2 1 2 1 space group (No. 19).…”

“…Therefore, in the development of second-order NLO materials, it is crucial to strategically control the structural units and their arrangements for the effective design of NCS structures. Recently, a heteroatom substitution strategy has been proved to be an effective route to designing NCS compounds via regulating the polarizability of structural units, which can be exemplified by the change from PO 4 to PO 3 NH 3 and PO 3 F; from SO 4 to SO 3 S and NH 2 SO 3 ; from BO 4 to BO 3 F, BO 2 F 2 , and from SiO 6 to SiO 5 F and SiO 2 F 4 , resulting in the formation of NCS NaPO 3 NH 3 , Rb(NO 3 )(SO 3 NH 3 ), [C(NH 2 ) 3 ] 2 SO 3 S, Na 10 Cd(NO 3 ) 4 (SO 3 S) 4 , M(NH 2 SO 3 ) 2 (M = Sr, Ba), Na 10 Zn(NO 3 ) 4 (SO 3 S) 4 , K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ), SrB 5 O 7 F 3 , M 2 B 10 O 14 F 6 (M = Ca, Sr), AB 4 O 6 F (A = NH 4 , Na, K, Rb, Cs), K 3 Ba 3 Li 2 Al 4 B 6 O 20 F, and CsSiP 2 O 7 F. − …”