Synthesis of Molecular Dyads and Triads Based Upon N‐Annulated Perylene Diimide Monomers and Dimers

The synthesis of N‐annulated perylene diimides (NPDIs) with grafted electron donating phenothiazine (PTZ) groups is presented. The synthetic strategy takes advantage of the N‐annulation at the PDI bay position, which allows for the facile installation of the pendant donors. Three new molecular materials are reported, a dyad consisting of an NPDI monomer tethered to a PZT unit (4), a dyad consisting of an NPDI dimer with one PZT unit tethered (9), and a triad consisting of an NPDI dimer with two PTZ units tethered (10). The PTZ and NPDI were “clicked” together using copper catalyzed alkyne–azide cycloaddition chemistry. Analysis of optical absorption/emission spectra and electrochemical data reveal that the electronic structure of each individual aromatic system remains distinct, but through‐space interactions occur, as is evident by fluorescence quenching in both solution and the solid state. Synthesis of monomeric and dimeric perylene diimide dyads and triads via N‐annulation at the bay position, by a strategy suitable for the facile installation of the pendant donors, is reported.