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The 6,6‐Dicyanopentafulvene Core: A Template for the Design of Electron‐Acceptor Compounds
Author(s) -
Finke Aaron D.,
Jahn Burkhard O.,
Saithalavi Anas,
Dahlstrand Christian,
Nauroozi Djawed,
Haberland Sophie,
Gisselbrecht JeanPaul,
Boudon Corinne,
Mijangos Edgar,
Schweizer W. Bernd,
Ott Sascha,
Ottosson Henrik,
Diederich François
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500379
Subject(s) - solvation , chemistry , absolute deviation , cyclic voltammetry , core electron , ring (chemistry) , computational chemistry , reduction (mathematics) , acceptor , electron , atomic physics , molecular physics , molecule , electrochemistry , physics , electrode , quantum mechanics , mathematics , statistics , geometry , organic chemistry
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 σ p ‐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 F 4 ‐TCNQ (5.02 eV). Thus, the DCF core is a template that allows variation in the reduction potentials by about 1.6 eV.