Competition between the Photothermal Effect and Emission in Potential Phototherapy Agents

Planar donor-acceptor-donor (D-A-D) organic molecules have been highlighted as promising photothermal agents due to their good light-to-heat conversion ratio, easy degradation, and chemical tunability. Very recently, it has been demonstrated that their photothermal conversion can be boosted by appending rather long alkyl chains. Despite this behavior being tentatively associated with the population of a nonradiative twisted intramolecular charge transfer (TICT) state driven by an intramolecular motion, the precise mechanisms and the role played by the environment, and most notably aggregation, still remain elusive. In this context, we carried out a series of time-dependent density functional theory (TD-DFT) calculations combined with molecular dynamics (MD) simulations to achieve a realistic description of the isolated and aggregated systems. Our theoretical models unambiguously evidence that the population of CT states is very unlikely in both cases, whereas the light-triggered heat dissipation can be ascribed to the activation of specific vibrational degrees of freedom related to the relative motion of the peripheral chains. Overall, our results clearly corroborate the active role played by the alkyl substituents in the photothermal conversion through vibrational motion, while breaking from the conventional picture, which invokes the formation of dark TICT states in loosely packed aggregates.