Combination of N‑Arylstilbazolium Organic Nonlinear Optical Chromophores with Iodoargentates: Structural Diversities and Optical Properties
A combination of N-arylstilbazolium organic nonlinear optical chromophores with iodoargentates results in five new hybrids, i.e., [(DAST)(Ag2I3)] n (1), [(DMAQS)(Ag2I3)] n (2), [(DPAS)(Ag2I3)] n (3), [(DPTAS)2(Ag5I7)] n (4), and [(CEMAS)2(Ag5I7)] n (5). Among them, the former four are centrosym...
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Published in | Crystal growth & design Vol. 18; no. 7; pp. 3827 - 3840 |
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Main Authors | , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
American Chemical Society
05.07.2018
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Online Access | Get full text |
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Summary: | A combination of N-arylstilbazolium organic nonlinear optical chromophores with iodoargentates results in five new hybrids, i.e., [(DAST)(Ag2I3)] n (1), [(DMAQS)(Ag2I3)] n (2), [(DPAS)(Ag2I3)] n (3), [(DPTAS)2(Ag5I7)] n (4), and [(CEMAS)2(Ag5I7)] n (5). Among them, the former four are centrosymmetric, and 5 is non-centrosymmetrical (space group Pna21) with the introduction of a cyano group in an organic chromophore. The (Ag5I7) n 2n– chains in 4 and 5 are special, in which that of 4 is constructed from Ag5I10 building blocks with a μ6-I σ-bonding to six Ag ions, and that in 5 is the connection of a cubane-like Ag4I4 core with bridged AgI4 tetrahedra. UV/vis/near-IR adsorptions and near-IR photoluminescences have been observed. All the organic chromophores are stacked as head-to-tail arrangements, resulting in second harmonic generation (SHG) inactive in 1–4. But 5 is SHG active without J-aggregation of organic chromophore, whose symmetry break was driven by the formation of hydrogen bonds around the cyano group. The SHG activity of 5 originates from the polarizations of the asymmetric contribution of Ag5I9 4– unit mixing with non-centrosymmetrical (CEMAS)2 2+ pair. Theoretical calculations were carried out to disclose their electronic structures. |
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ISSN: | 1528-7483 1528-7505 |
DOI: | 10.1021/acs.cgd.8b00033 |