Core Halogenation as a Construction Principle in Tuning the Material Properties of Tetraazaperopyrenes

• Published in: Chemistry : a European journal Vol. 21; no. 49; pp. 17691 - 17700
• Main Authors: Hahn, Lena, Maaß, Friedrich, Bleith, Tim, Zschieschang, Ute, Wadepohl, Hubert, Klauk, Hagen, Tegeder, Petra, Gade, Lutz H.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.12.2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: Chemistry; cyclic voltammetry; density functional calculations; Derivatives; Electron energy loss spectroscopy; Fluorescence; Glass substrates; Halogenation; material science; Molecular orbitals; Thin film transistors; Voltammetry; X-rays; density functional calculations; halogenation; cyclic voltammetry; electron energy loss spectroscopy; material science
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201503484

A detailed study on the effects of core halogenation of tetraazaperopyrene (TAPP) derivatives is presented. Its impact on the solid structure, as well as the photophysical and electrochemical properties, has been probed by the means of X‐ray crystallography, UV/Vis and fluorescence spectroscopy, high‐resolution electron energy loss spectroscopy (HREELS), cyclic voltammetry (CV), and DFT modeling. The aim was to assess the potential of this approach as a construction principle for organic electron‐conducting materials of the type studied in this work. Although halogenation leads to a stabilization of the LUMOs compared to the unsubstituted parent compound, the nature of the halide barely affects the LUMO energy while strongly influencing the HOMO energies. In terms of band‐gap engineering, it was demonstrated that the HOMO–LUMO gap is decreased by substitution of the TAPP core with halides, the effect being found to be most pronounced for the iodinated derivative. The performance of the recently reported core‐fluorinated and core‐iodinated TAPP derivatives in organic thin‐film transistors (TFTs) was investigated on both a glass substrate, as well as on a flexible plastic substrate (PEN). Field‐effect mobilities of up to 0.17 cm2 Vs−1 and on/off current ratio of >106 were established. A detailed study on the effects of core halogenation of tetraazaperopyrene (TAPP) derivatives is presented. Its impact on the solid structure, as well as the photophysical and electrochemical properties, has been probed by the means of X‐ray crystallography, UV/Vis and fluorescence spectroscopy, high‐resolution electron energy loss spectroscopy, cyclic voltammetry, and DFT modeling (see scheme).