The effects of alkyl substitution on the aggregation of π-conjugated dyes: spectroscopic study and modelling

A family of dithienosilole-based dyes with alternating donor and acceptor conjugated groups, decorated with linear or branched alkyl chains at different positions on the backbone, have been obtained and investigated in different aggregation states. These dyes are characterized by almost panchromatic absorption and by near-IR emission, with good quantum yields in a variety of solvents with different polarity. We demonstrate that the nature and position of the alkyl substituents strongly govern the self-assembly of the dyes, whose packing is also sensitive to external stimuli, such as grinding and water addition. Thanks to computational results and theoretical modelling, we are able to interpret the results based on two possible preferential packings, characterized by distinct spectroscopic behaviour, whose abundance can be tuned according to the nature and position of the alkyl chains, as well as via external stimuli.