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2D Chiral Ag(I) Complexes with A-π-A- and D-π-A-Type Dicarboxylic Acid Ligands: Presenting Significant Differences in
Congli Gao1, Xiaoyu Cai1, Jinying Huang1
1Henan Provincial Key Laboratory of Surface and Interface Science, Zhengzhou University of Light Industry, Zhengzhou 450002, P. R. China.
Abstract:
Three two-dimensional (2D) chiral Ag(I) complexes with formulas [Ag4(L)4(5-nipa)2] (1), [Ag4(L)4(5-nipa)2] (2), and {[Ag4(L)4(5-hipa)2]·2H2O} (3) were prepared through the reactions of Ag2O with enantiopure bis-monodentate N-donors (L/L) and different dicarboxylic acids bearing A (acceptor)-π-A- and D (donor)-π-A-type structural features, where L/L = (-)/(+)-2-(4'-pyridyl)-4,5-pinene-pyridine, 5-H2nipa = 5-nitroisophthalic acid, and 5-H2hipa = 5-hydroxyisophthalic acid. A study of their nonlinear optical responses reveals that chiral 1 and 2 enantiomeric pairs with the A-π-A-type dicarboxylic acid ligand simultaneously display second- and third-harmonic generation (SHG and THG) responses, while chiral 3 containing the D-π-A-type dicarboxylic acid ligand only exhibits a very strong THG response. The THG intensity of 3 is 451 × α-SiO2, being about 27 and 24 times larger than those of 1 and 2, respectively.
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