Issue 2, 2022

Distinct nonlinear optical responses in three pairs of 2D homochiral Ag(i) enantiomers modulated by dicarboxylic acid ligands

Abstract

Three pairs of homochiral Ag(I) enantiomers formulated as [Ag2(LR)(pa)]n/[Ag2(Ls)(pa)]n (R1/S1, H2pa = phthalic acid), [Ag2(LR)(tda)]n·H2O/[Ag2(Ls)(tda)]n·H2O (R2/S2, H2tda = 3,4-thiophene dicarboxylic acid), and [Ag4(LR)2(3-npa)2]n/[Ag4(Ls)2(3-npa)2]n (R3/S3, 3-H2npa = 3-nitrophthalic acid) were prepared by using different dicarboxylic acid coligands via the reactions of AgNO3 with enantiopure monobidentate N-donor heterocyclic ligands named (+)/(−)-4,5-pinenepyridyl-2-pyrazine (LS/LR), respectively. Investigations on the nonlinear optical (NLO) response suggest R1/S1 and R2/S2 enantiomers present very strong third-harmonic generation (THG) responses, and the lowest THG intensities of R1/S1 and R2/S2 are 244 and 142 times that of α-SiO2, respectively. However, R3/S3 enantiomers only exhibit mild second-harmonic generation (SHG) response (0.36 × KDP). A comparative study on the molecular structures of these Ag(I) enantiomeric pairs reveals that both the symmetry and degree of π-conjugation of the dicarboxylate ligands are mainly responsible for their different NLO responses. Our research result not only provides a feasible method of constructing coordination polymers (CPs) with strong THG response but also points out an effective strategy for switching NLO behaviors from THG to SHG response.

Graphical abstract: Distinct nonlinear optical responses in three pairs of 2D homochiral Ag(i) enantiomers modulated by dicarboxylic acid ligands

Supplementary files

Article information

Article type
Research Article
Submitted
19 okt 2021
Accepted
24 nov 2021
First published
24 nov 2021

Inorg. Chem. Front., 2022,9, 284-293

Distinct nonlinear optical responses in three pairs of 2D homochiral Ag(I) enantiomers modulated by dicarboxylic acid ligands

C. Gao, J. Zhou, M. Cui, D. Chen, L. Zhou, F. Li and X. Li, Inorg. Chem. Front., 2022, 9, 284 DOI: 10.1039/D1QI01321A

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