Substitution effects on the frontier orbitals of 3,4,9,10-perylene bis(dicarboximide). A computational quantum chemistry study with insights into the electronic properties of organic semiconductors

Quantum chemical (semiempirical and density functional theory) calculations have been performed on the 3,4,9,10-perylene-bis(dicarboximide) (PCI) molecule and fifteen of its N-alkyl or N-aryl derivatives. Electron-attractive substituents have the effect of lowering the energies of both frontier orbitals of PCI while electron-donative substituents exert the opposite effect. These observations should be useful in the design of novel perylene-based molecules for applications in the field of organic electronics.