Visible-Light-Mediated Synthesis of AzaBenzannulated Perylenediimide-Based Light-Harvesting Dyads

Intramolecular imine photocyclization has been explored for grafting on the bay region of perylenediimide (PDI) different electro- and photoactive chromophores to achieve new AzaBenzannulated-PDI (AzaBPDI) dyads. Triphenylamine (TPA), fluorene (Fl), perylenemonoimide (PMI), and perylenediimide (PDI) units have been successfully assembled to AzaBPDI using this straightforward one-pot synthesis starting from the easily accessible 1-aminoPDI. This original procedure was compared to the well-known Pictet-Spengler reaction and appears to be an attractive alternative in terms of versatility and efficiency with higher yields obtained. The optical and electrochemical properties of these molecular systems demonstrated large absorption capabilities in the visible range, good accepting abilities with low LUMO levels, and efficient electronic interactions between chromophoric units such as energy or electron transfers. In addition, with their large dihedral angle estimated by theoretical calculations, those dyads should present interesting applications in various organic optoelectronic devices. In particular, the PMI-AzaBPDI and PDI-AzaBPDI dyads presenting low LUMO levels, a broad absorption in the visible range, and a twisted conformation make them good candidates as non-fullerene acceptors in organic solar cells.