Intramolecular electron-transfer of C60-oligoaniline leucoemeraldine conjugates upon photoactivation

Conductive starburst C-60-derived macromolecules were synthesized using C-60(NO2)(6) as a precursor intermediate for linking pi-conjugate oligomers, such as tetraaniline and hexadecaaniline, directly onto the fullerene cage. Subsequent phenylhydrazine reduction of the resulting hexa(tetra-anilino)[60]fullerene and hexa(hexadecaanilino)[60]fullerene emeraldines produced the corresponding leucoemeraldine donors. Photoexcitation of these hexa(oligoanilino)[60]fullerene leucoemeraldines under N-2 induced intramolecular electron-transfer from benzenoid moieties of oligoaniline arms to the C-60 cage, that regenerated the emeraldine structure in oligoaniline arms. Proceeding on the number of electrons transferred was followed and estimated by in situ chemical trapping method on the reaction of electrophiles with fullerenic anions generated. That substantiated the capability of the fullerene cage to accept multiple electrons during the irradiation process.