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Electron donor-acceptor molecular charge transfer complexes (CTCs) formed by α-sexithiophene (6T) and tetrafluoro-tetracyano-quinodimethane (F 4 TCNQ) on a Au (111) surface are investigated by scanning tunneling microscopy, spectroscopy, and spectroscopic imaging at 6 K. New hybrid molecular orbitals are formed in the CTCs, and the highest occupied molecular orbital of the CTC is mainly located on the electron accepting F 4 TCNQ while the lowest unoccupied molecular orbital is predominantly positioned on the electron donating 6T. We observed the conductance switching of F 4 TCNQ inside CTCs, which may find potential applications in novel molecular device operations.