Molecular and excited state properties of photostable anthraquinone red and violet dyes for hydrophobic fibers

Abstract

The molecular, spectroscopic, and excited state properties of synthetic dyes for fiber-based outdoor materials continue to be of commercial interest. Early developments in this area were reported in the 1980s, when the need for dyes for polyester (PET)-based automobile interiors gave rise to commercially viable nitrodiphenylamine yellow, anthraquinone red and blue, and azo red dyes. To augment that initial knowledge base, the present study involved the use of experimental and theoretical methods to help establish the molecular structures and excited state properties of some more recent dyes for producing photostable colors on PET fibers. Having completed the characterization of present-day scarlet, blue, and yellow disperse dyes for PET-based fibers used outdoors, our attention turned to commercially available red and violet dyes. In this regard, HPLC analysis showed that the red product was a mixture containing four components, while the violet product contained only one component. Results from 1H NMR, HRMS, and single crystal X-ray diffraction analyses indicated that the principal components were dyes having a 1-amino-4-hydroxyanthraquinone base structure. The presence of an –OH group alpha to an anthraquinone C=O moiety provides for intramolecular H-bonding and a subsequent opportunity for intramolecular proton transfer in the excited state – as a photostabilizing mechanism. Further, for both dyes, results from the analysis of Frontier HOMO and LUMO isosurfaces indicated strong HOMO-LUMO overlap without molecular gaps and were consistent with strong excited state energy dissipation in a non-destructive way.