| Institution: | 1. Laboratorium für Organische Chemie, ETH Zurich, Zurich, Switzerland), Fax: (+41)?44-632-1109;2. Institute of Nano Science and Technology, Habitat Centre, Sector-64, Phase-X, Mohali, India;3. Departamento de Química Física, Facultad de Ciencias, Universidad de Zaragoza, Zaragoza, Spain), Fax: (+34)?976-761-202;4. Instituto de Ciencia de Materiales de Aragón (ICMA), Universidad de Zaragoza-CSIC, Zaragoza, Spain;5. Instituto de Nanociencia de Aragón (INA) and Laboratorio de Microscopias Avanzadas (LMA), Edificio i+d. Campus Rio Ebro, Universidad de Zaragoza, C/Mariano Esquillor, s/n, Zaragoza, Spain;6. Instituto de Microelectrónica de Barcelona (IMB-CNM, CSIC), Campus UAB, Bellaterra, Spain;7. Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, Institut de Chimie-UMR 7177, C.N.R.S., Université de Strasbourg, Strasbourg Cedex, France;8. Laboratory of Physical Chemistry, ETH Zurich, Zurich, Switzerland |
| Abstract: | The design and synthesis of Aviram–Ratner‐type molecular rectifiers, featuring an anilino‐substituted extended tetracyanoquinodimethane (exTCNQ) acceptor, covalently linked by the σ‐spacer bicyclo2.2.2]octane (BCO) to a tetrathiafulvalene (TTF) donor moiety, are described. The rigid BCO spacer keeps the TTF donor and exTCNQ acceptor moieties apart, as demonstrated by X‐ray analysis. The photophysical properties of the TTF‐BCO‐exTCNQ dyads were investigated by UV/Vis and EPR spectroscopy, electrochemical studies, and theoretical calculations. Langmuir–Blodgett films were prepared and used in the fabrication and electrical studies of junction devices. One dyad showed the asymmetric current–voltage (I–V) curve characteristic for rectification, unlike control compounds containing the TTF unit but not the exTCNQ moiety or comprising the exTCNQ acceptor moiety but lacking the donor TTF part, which both gave symmetric I–V curves. The direction of the observed rectification indicated that the preferred electron current flows from the exTCNQ acceptor to the TTF donor. |
