Three-Component Activation/Alkynylation/Cyclocondensation (AACC) Synthesis of Enhanced Emission Solvatochromic 3-Ethynylquinoxalines.
Chemistry
; 24(32): 8114-8125, 2018 Jun 07.
Article
em En
| MEDLINE
| ID: mdl-29425410
ABSTRACT
2-Substituted 3-ethynylquinoxaline chromophores can be readily synthesized by a consecutive activation-alkynylation-cyclocondensation (AACC) one-pot sequence in a three-component manner. In comparison with the previously published four-component glyoxylation starting from electron-rich π-nucleophiles, the direct activation of (hetero)aryl glyoxylic acids allows the introduction of substituents that cannot be directly accessed by glyoxylation. By introducing N,N-dimethylaniline as a strong donor in the 2-position, the emission solvatochromicity of 3-ethynylquinoxalines can be considerably enhanced to cover the spectral range from blue-green to deep red-orange with a single chromophore in a relatively narrow polarity window. The diversity-oriented nature of the synthetic multicomponent reaction concept enables comprehensive investigations of structure-property relationships by Hammett correlations and Lippert-Mataga analysis, as well as the elucidation of the electronic structure of the emission solvatochromic π-conjugated donor-acceptor systems by DFT and time-dependent DFT calculations with the PBEh1PBE functional for a better reproduction of the dominant charge-transfer character of the longest wavelength absorption band.
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MEDLINE
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En
Ano de publicação:
2018
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Article