Nature of intermolecular interaction in squaraine dimers

Squaraine dyes are known for their particular optical properties. They exhibit intense photochemically stable fluorescence in usually (near) infra red region that can be quenched by intermolecular interactions. Moreover, even the centrosymmetric dyes feature non-zero second harmonic generation upon aggregation. Therefore, the detailed knowledge of the squaraine dye interaction nature both in homogenic aggregates and with other species present in the environment can be of importance for the design of new materials of desired properties. In the present study, interaction in squaraine dimers is investigated with quantum chemistry tools. Four structures: two stacked and two hydrogen-bonded are analyzed in terms of supermolecular approach and symmetry-adapted perturbation theory. MP2C/aug-cc-pVTZ supermolecular calculations confirm the particular stability of the stacked dimers and the favoured dispersion attraction for the long-displaced system.