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.