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Synthesis, Ionisation Potentials and Electron Affinities of Hexaazatrinaphthylene Derivatives

Authors

  • Stephen Barlow Dr.,

    1. School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332, USA, Fax: (+1) 404-894-5909
    2. Department of Chemistry, University of Arizona, Tucson, AZ 85721, USA
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  • Qing Zhang Dr.,

    1. School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332, USA, Fax: (+1) 404-894-5909
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  • Bilal R. Kaafarani Dr.,

    1. School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332, USA, Fax: (+1) 404-894-5909
    2. Department of Chemistry, University of Arizona, Tucson, AZ 85721, USA
    3. Current address: Department of Chemistry, American University of Beirut, Beirut, Lebanon
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  • Chad Risko Dr.,

    1. School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332, USA, Fax: (+1) 404-894-5909
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  • Fabrice Amy Dr.,

    1. Department of Electrical Engineering, Princeton University, Princeton, NJ 08544, USA
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  • Calvin K. Chan,

    1. Department of Electrical Engineering, Princeton University, Princeton, NJ 08544, USA
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  • Benoit Domercq Dr.,

    1. School of Electrical and Computer Engineering and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332, USA
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  • Zoya A. Starikova Dr.,

    1. Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
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  • Mikhail Yu. Antipin Prof.,

    1. Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
    2. Department of Natural Sciences, New Mexico Highlands University, Las Vegas, NM 87701, USA
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  • Tatiana V. Timofeeva Prof.,

    1. Department of Natural Sciences, New Mexico Highlands University, Las Vegas, NM 87701, USA
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  • Bernard Kippelen Prof.,

    1. School of Electrical and Computer Engineering and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332, USA
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  • Jean-Luc Brédas Prof.,

    1. School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332, USA, Fax: (+1) 404-894-5909
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  • Antoine Kahn Prof.,

    1. Department of Electrical Engineering, Princeton University, Princeton, NJ 08544, USA
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  • Seth R. Marder Prof.

    1. School of Chemistry and Biochemistry and Center for Organic Photonics and Electronics, Georgia Institute of Technology, Atlanta, GA 30332, USA, Fax: (+1) 404-894-5909
    2. Department of Chemistry, University of Arizona, Tucson, AZ 85721, USA
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Abstract

Several hexaazatrinaphthylene derivatives and a tris(thieno)hexaazatriphenylene derivative have been synthesised by reaction of the appropriate diamines with hexaketocyclohexane. The crystal structure of 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazatrinaphthylene has been determined by X-ray diffraction; this reveals a molecular structure in good agreement with that predicted by density functional theory (DFT) calculations and π-stacking with an average spacing between adjacent molecular planes of 3.18 Å. Solid-state ionisation potentials have been measured by using UV photoelectron spectroscopy and fall in the range of 5.99 to 7.76 eV, whereas solid-state electron affinities, measured using inverse photoelectron spectroscopy, vary in the range −2.65 to −4.59 eV. The most easily reduced example is a tris(thieno)hexaazatriphenylene substituted with bis(trifluoromethyl)phenyl groups; DFT calculations suggest that the highly exothermic electron affinity is due both to the replacement of the outermost phenylene rings of hexaazatrinaphthylene with thieno groups and to the presence of electron-withdrawing bis(trifluoromethyl)phenyl groups. The rather exothermic electron affinities, the potential for adopting π-stacked structures and the low intramolecular reorganisation energies obtained by DFT calculations suggest that some of these molecules may be useful electron-transport materials.

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