title: Design and Synthesis of Aviram-Ratner-Type Dyads and Rectification Studies in Langmuir-Blodgett (LB) Films.
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 bicyclo[2.2.2]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.
authors.affiliation: Laboratorium für Organische Chemie, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland), Fax: (+41) 44-632-1109.|Institute of Nano Science and Technology, Habitat Centre, Sector-64, Phase-X, Mohali, India.
authors.forename: Govindasamy
authors.initials: G
authors.lastname: Jayamurugan
authors.affiliation: Laboratorium für Organische Chemie, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland), Fax: (+41) 44-632-1109.
authors.forename: Vijayendran
authors.initials: V
authors.lastname: Gowri
authors.affiliation: Departamento de Química Física, Facultad de Ciencias, Universidad de Zaragoza, 50009, Zaragoza, Spain), Fax: (+34) 976-761-202.
authors.forename: David
authors.initials: D
authors.lastname: Hernández
authors.affiliation: Departamento de Química Física, Facultad de Ciencias, Universidad de Zaragoza, 50009, Zaragoza, Spain), Fax: (+34) 976-761-202.|Instituto de Ciencia de Materiales de Aragón (ICMA), Universidad de Zaragoza-CSIC, 50009, Zaragoza, Spain.
authors.forename: Santiago
authors.initials: S
authors.lastname: Martin
authors.affiliation: 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, 50017, Zaragoza, Spain.
authors.forename: Alejandro
authors.initials: A
authors.lastname: González-Orive
authors.affiliation: Laboratorium für Organische Chemie, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland), Fax: (+41) 44-632-1109.
authors.forename: Cagatay
authors.initials: C
authors.lastname: Dengiz
authors.affiliation: Laboratorium für Organische Chemie, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland), Fax: (+41) 44-632-1109.
authors.forename: Oliver
authors.initials: O
authors.lastname: Dumele
authors.affiliation: Instituto de Microelectrónica de Barcelona (IMB-CNM, CSIC), Campus UAB, 08193, Bellaterra, Spain.
authors.forename: Francesc
authors.initials: F
authors.lastname: Pérez-Murano
authors.affiliation: Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, Institut de Chimie-UMR 7177, C.N.R.S., Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081, Strasbourg Cedex, France.
authors.forename: Jean-Paul
authors.initials: JP
authors.lastname: Gisselbrecht
authors.affiliation: Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, Institut de Chimie-UMR 7177, C.N.R.S., Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081, Strasbourg Cedex, France.
authors.forename: Corinne
authors.initials: C
authors.lastname: Boudon
authors.affiliation: Laboratorium für Organische Chemie, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland), Fax: (+41) 44-632-1109.
authors.forename: W Bernd
authors.initials: WB
authors.lastname: Schweizer
authors.affiliation: Laboratorium für Organische Chemie, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland), Fax: (+41) 44-632-1109.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Breiten
authors.affiliation: Laboratorium für Organische Chemie, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland), Fax: (+41) 44-632-1109.
authors.forename: Aaron D
authors.initials: AD
authors.lastname: Finke
authors.affiliation: Laboratory of Physical Chemistry, ETH Zurich, Vladimir-Prelog-Weg 2, 8093, Zurich, Switzerland.
authors.forename: Gunnar
authors.initials: G
authors.lastname: Jeschke
authors.affiliation: Laboratorium für Organische Chemie, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland), Fax: (+41) 44-632-1109.
authors.forename: Bruno
authors.initials: B
authors.lastname: Bernet
authors.affiliation: Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, Institut de Chimie-UMR 7177, C.N.R.S., Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081, Strasbourg Cedex, France.
authors.forename: Laurent
authors.initials: L
authors.lastname: Ruhlmann
authors.affiliation: Departamento de Química Física, Facultad de Ciencias, Universidad de Zaragoza, 50009, Zaragoza, Spain), Fax: (+34) 976-761-202. pilarcea@unizar.es.|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, 50017, Zaragoza, Spain. pilarcea@unizar.es.
authors.forename: Pilar
authors.initials: P
authors.lastname: Cea
authors.affiliation: Laboratorium für Organische Chemie, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland), Fax: (+41) 44-632-1109. diederich@org.chem.ethz.ch.
authors.forename: François
authors.initials: F
authors.lastname: Diederich
keywords: Aviram-Ratner dyad; Langmuir-Blodgett films; [2+2] cycloaddition-retroelectrocyclization; charge transfer; molecular electronics materials