Bridging the Gap between Pentacene and Perfluoropentacene: Synthesis and Characterization of 2,3,9,10-Tetrafluoropentacene in the Neutral, Cationic, and Dicationic States

The Journal of Organic Chemistry
Bin ShenHolger F Bettinger

Abstract

The thermal and photochemical syntheses of 2,3,9,10-tetrafluoropentacene (F4PEN) from 6,13-etheno bridged precursors were investigated computationally and experimentally. A computational study of the retro-Diels-Alder reaction to give 2,3,9,10-tetrasubstituted pentacenes and pyridazine revealed a linear correlation between barrier height and substituent constant (σp) indicative of an electronic effect that could diminish the yield of electron-poor 2,3,9,10-tetrasubstituted pentacenes in this reaction. The photochemical route from the corresponding bridged α-diketone yields F4PEN, which was characterized photophysically, electrochemically, and structurally. The compound crystallizes in a herringbone motif with quite short intermolecular F-F contacts that are, however, only very weakly bonding according to computations. The electrochemical and photophysical data show that the HOMO-LUMO gap of F4PEN is increased compared to that of PEN. This is due to an increase of the oxidation potential of F4PEN by 0.18 V in combination with an essentially unchanged reduction potential. The radical cation and dication of F4PEN could be generated in oxidizing solvents and characterized by optical spectroscopy and ESR or NMR, respectively. Both c...Continue Reading

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Citations

Apr 27, 2019·Chemical Communications : Chem Comm·Yanwei GuJishan Wu
Sep 21, 2019·Chemistry : a European Journal·Gaozhan XieUwe H F Bunz
Jun 9, 2020·Angewandte Chemie·Ulrich KoertSergei Ivlev
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Sep 26, 2020·Beilstein Journal of Nanotechnology·Qi WangSteffen Duhm
Aug 3, 2021·The Journal of Physical Chemistry Letters·Clemens ZeiserKatharina Broch

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