The influence of charge-transfer interactions on solid and cholesteric liquid crystalline mixtures of cholesteryl anthraquinone-2-carboxylate and cholesteryl 9,10-dimethoxyanthracene-2-carboxylate

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Abstract
The phase behaviour of 3beta-cholesteryl 9,10-anthraquinone-2-carboxylate (CAQ, an excellent electron acceptor) and 3beta-cholesteryl 9,10-dimethoxyanthracene-2-carboxylate (CMAQ, an excellent electron donor) have been investigated neat and as mixtures by a variety of techniques. Both molecules form thermotropic cholesteric phases. UV-Vis absorption spectra of CAQ:CMAQ mixtures provide strong evidence for the formation of charge-transfer (CT) complexes in the solid state. DSC thermograms of the mixtures reveal several transitions, only some of which are observable by optical microscopy. The mesophase range of CAQ is increased by c. 40 upon addition of as little as 10 wt% of CMAQ as a consequence of increased attractive forces in the CT complexes. X-ray powder diffraction patterns confirm that CAQ forms different crystalline phases upon being cooled from the mesophase and by recrystallization from solvents. The 5:5 mixture can be supercooled to a glass from its cholesteric phase. Some of the phase behaviour of the CAQ:CMAQ mixtures is explained with a model that includes selective crystallization of the two components into eutectics from supercooled liquid crystalline matrices.