We describe the aggregate formation and optical properties of a star-shaped hexaarylbenzene with six squaraine chromophores (=hexasquarainyl benzene). Comprehensive concentration-dependence studies in acetone/CHCl3 mixtures reveal a strong propensity to form discrete dimeric aggregates with a high binding constant in excess of 106 m-1 . In this context, a large hypsochromic shift of almost 2700 cm-1 was found in the absorption spectrum, indicating H-type exciton coupling. The aggregate band is characterised by a very small band width of only 560 cm-1 , probably caused by exchange narrowing. Both experimental and computational methods were used to elucidate the supramolecular aggregate structure, which is assumed to consist of two stacked hexasquarainyl benzene monomers.
Keywords: dyes/pigments; exchange narrowing; exciton coupling; noncovalent interactions; self-assembly.
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.