Dissymmetric Bay-Functionalized Perylenediimides

We report the synthesis of perylenediimide (PDI)-based donor-acceptor hybrids through dissymmetric bay functionalization of PDIs. The dissymmetric bay-functionalized di- and trisubstituted PDIs were characterized by using one-and two-dimensional NMR spectroscopy. Density functional theory calculations revealed (i) an energy gap between the HOMO and LUMO in the range 2.14-2.34 eV, beneficial for charge-transfer properties; and (ii) a twist angle between the two naphthalene units in the range 17-26 degrees, which might be beneficial for disruption of co-facial stacking of the PDI.