The 6,6‐Dicyanopentafulvene Core: A Template for the Design of Electron‐Acceptor Compounds |
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Authors: | Dr Aaron D Finke Dr Burkhard O Jahn Dr Anas Saithalavi Dr Christian Dahlstrand Dr Djawed Nauroozi Sophie Haberland Dr Jean‐Paul Gisselbrecht Prof?Dr Corinne Boudon Dr Edgar Mijangos Dr W Bernd Schweizer Dr Sascha Ott Dr Henrik Ottosson Prof?Dr François Diederich |
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Institution: | 1. Laboratorium für Organische Chemie, ETH Zurich, Vladimir‐Prelog‐Weg 3, 8093 Zurich (Switzerland), Fax: (+41)?44‐632‐1109;2. Department of Chemistry, BMC, Uppsala University, Box 576, 751 23 Uppsala (Sweden), Fax: (+46)?18‐471‐3818;3. Department of Chemistry, ?ngstr?m Laboratory, Uppsala University, Box 523, 751 20 Uppsala (Sweden);4. Laboratoire d'Electrochemie et de Chimie Physique du Corps Solide, Institut de Chimie, UMR 7177, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex (France) |
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Abstract: | The electron‐accepting ability of 6,6‐dicyanopentafulvenes (DCFs) can be varied extensively through substitution on the five‐membered ring. The reduction potentials for a set of 2,3,4,5‐tetraphenyl‐substituted DCFs, with varying substituents at the para‐position of the phenyl rings, strongly correlate with their Hammett σp‐parameters. By combining cyclic voltammetry with DFT calculations ((U)B3LYP/6‐311+G(d)), using the conductor‐like polarizable continuum model (CPCM) for implicit solvation, the absolute reduction potentials of a set of twenty DCFs were reproduced with a mean absolute deviation of 0.10 eV and a maximum deviation of 0.19 eV. Our experimentally investigated DCFs have reduction potentials within 3.67–4.41 eV, however, the computations reveal that DCFs with experimental reduction potentials as high as 5.3 eV could be achieved, higher than that of F4‐TCNQ (5.02 eV). Thus, the DCF core is a template that allows variation in the reduction potentials by about 1.6 eV. |
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Keywords: | computational chemistry density functional calculations electron acceptors molecular materials reduction potentials |
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