Singlet Fission in Colloidal Nanoparticles of Amphipathic Diketopyrrolopyrrole Derivatives: Probing the Role of the Charge Transfer State.

To evaluate the role of the charge transfer (CT) state in the singlet fission (SF) process, we prepared three 3,6-bis(thiophen-2-yl)diketopyrrolopyrrole (TDPP) derivatives with zero (Ph2TDPP), one (Ph2TDPP-COOH), and two (Ph2TDPP-(COOH)2) carboxylic groups, respectively. Their colloidal nanoparticles were also prepared by a simple precipitation method. The SF dynamics and mechanism in these colloid nanoparticles were investigated by using steady-state/transient absorption and fluorescence spectroscopy. Steady-state absorption spectra reveal that the strength of the CT resonance interactions between the adjacent DPP units is increased gradually from Ph2TDPP to Ph2TDPP-COOH and then to Ph2TDPP-(COOH)2. Fluorescence and transient absorption spectra demonstrate that SF is proceeded via a CT-assisted superexchange mechanism in these three nanoparticles. Furthermore, SF rate and yield are enhanced gradually with the increase of the number of the carboxylic group, which may be attributed to the enhancement of the CT coupling strength. The result of this work not only provides a better understanding of the SF mechanism especially for the role of the CT state but also gives some new insights for the design of efficient SF materials based on DPP derivatives.