Aggregates of quadrupolar dyes for two-photon absorption: the role of intermolecular interactions

We present a theoretical investigation of small aggregates of quadrupolar (A-π-D-π-A or D-π-A-π-D) charge-transfer dyes, focusing the attention on the role of intermolecular interactions on optical properties. We tackle the theoretical issue adopting essential-state models (ESMs), that describe the isolated molecule in terms of a minimal number of electronic states, corresponding to the resonance structures. ESMs quite naturally describe intermolecular interactions relaxing the dipolar approximation and accounting for molecular polarizabilities. The approach is applied to curcuminoid and squaraine dyes, two families of chromophores with weak and strong quadrupolar character, respectively. The method is validated against experiment and for curcuminoids also against time-dependent density functional theory. ESMs rationalize the strong ultra-excitonic effects recurrently observed in experimental optical spectra of aggregates of highly polarizable quadrupolar dyes, offering a valuable tool to exploit the supramolecular design of material properties.