▎ 摘　　要

The rectification properties of porphyrin-graphene nanoflake complexes and endohedral complexes of C28 fullerene with metal atoms have been studied using the fully ab initio method. D3 dispersion-corrected PBE/-def2-SVP model was used for the optimisations and the electronic energy evaluation. In porphyrin-graphene nanoflake complexes dispersion dominates, while in the endohedral complexes of C28 dispersion does not play an important role. All studied systems do rectify. In the case of fullerenes, the rectification is possible due to the reduction in the molecular symmetry of the fullerene caused by the interaction with electrodes and the endohedral complex formation. The origin of the rectification is the asymmetrical deformation of the electron density under direct and inverse voltages which creates different currents in opposite directions. It seems that peculiar geometry of Au-TPP-Cd/NF diode is responsible for its high rectification ratio. The Cd ion is notably out of the porphyrin plane making close contact with the neighbouring electrode, increasing the asymmetry of the diode compared to other TPP/NF complexes.