title: Self-assembly of partially fluorinated hexabenzocoronene derivatives in the solid state.
abstract: We report on the synthesis and structural characterization of novel, partially fluorinated hexabenzocoronene (HBC) derivatives. The fluorination of polycyclic aromatic hydrocarbons (PAHs) is a well-established method to enhance the stability of organic semiconductors (OSCs) and render them n-type. For HBC it has been observed that fluorination leads to a modification of the molecular packing motif from a herringbone arrangement to a parallel-packed motif. Here, we study whether this transformation of the molecular packing is also found for the partially fluorinated HBCs 2,5-difluoro-hexa-peri-hexabenzocoronene (F2HBC) and 2,5,8,11-tetrafluoro-peri-hexabenzocoronene (F4HBC). Combining powder diffraction and NEXAFS dichroism measurements, we reveal that indeed all partially fluorinated compounds adopt a parallel molecular packing, hence maximizing their intermolecular contact area. We identify fluorine-hydrogen bonds as the mediating driving force to specifically stabilize this molecular arrangement and direct self-assembly. Furthermore, we show that the relative orientation of the HBCs on the underlying surface can be precisely controlled by varying the substrate materials. Finally, the energetic states of the compounds are analyzed using photoelectron spectroscopy, optical spectroscopy and density functional theory to identify the effects of fluorination on these fundamental electronic characteristics.
authors.affiliation: Fachbereich Physik, Universität Marburg, Renthof 7, 35032 Marburg, Germany. tobias.breuer@physik.uni-marburg.de.
authors.forename: Tobias
authors.identifier: http://orcid.org/0000-0002-9962-9444
authors.initials: T
authors.lastname: Breuer
authors.affiliation: Fachbereich Physik, Universität Marburg, Renthof 7, 35032 Marburg, Germany. tobias.breuer@physik.uni-marburg.de.
authors.forename: Michael
authors.initials: M
authors.lastname: Klues
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin, 12489 Berlin, Germany.
authors.forename: Pauline
authors.initials: P
authors.lastname: Liesfeld
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin, 12489 Berlin, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Viertel
authors.affiliation: Fachbereich Chemie, Universität Marburg, Hans-Meerwein-Str. 4, 35032 Marburg, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Conrad
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin, 12489 Berlin, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Hecht
authors.affiliation: Fachbereich Physik, Universität Marburg, Renthof 7, 35032 Marburg, Germany. tobias.breuer@physik.uni-marburg.de.
authors.forename: Gregor
authors.initials: G
authors.lastname: Witte