Synthesis, Spatial Structure And Spectral Properties Of Pyrylo-4 (Thio) Squaraines Variously Substituted In Cyclobutene Moiety

Synthetic routes have been developed to a number of (thio) squaraine dyes containing the residues of CH-acids at the central cyclobutene ring. The electronic and spatial structure as well as the chemical conversions and optical behaviour of the compounds obtained have been studied both theoretically and by X-ray diffraction analysis, H-1 NMR and electronic spectroscopy. As shown, the electronic nature and sterical characteristics of the central ring substituents give rise to some general conformational features and crystal packing regularities and also govern the spectral position of the first pi-pi* absorption band. The structure-property relationships established in the study provide guidance for the purposeful design of deeply coloured (thio) squaraines. Copyright (C) 2015 John Wiley & Sons, Ltd.