title: 2H-Tetrakis(3,5-di-tert-butyl)phenylporphyrin on a Cu(110) Surface: Room-Temperature Self-Metalation and Surface-Reconstruction-Facilitated Self-Assembly.
abstract: The adsorption behavior of 2H-tetrakis(3,5-di-tert-butyl)phenylporphyrin (2HTTBPP) on Cu(110) and Cu(110)-(2×1)O surfaces have been investigated by using variable-temperature scanning tunneling microscopy (STM) under ultrahigh vacuum conditions. On the bare Cu(110) surface, individual 2HTTBPP molecules are observed. These molecules are immobilized on the surface with a particular orientation with respect to the crystallographic directions of the Cu(110) surface and do not form supramolecular aggregates up to full monolayer coverage. In contrast, a chiral supramolecular structure is formed on the Cu(110)-(2×1)O surface, which is stabilized by van der Waals interactions between the tert-butyl groups of neighboring molecules. These findings are explained by weakened molecule-substrate interactions on the Cu(110)-(2×1)O surface relative to the bare Cu(110) surface. By comparison with the corresponding results of Cu-tetrakis(3,5-di-tert-butyl)phenylporphyrin (CuTTBPP) on Cu(110) and Cu(110)-(2×1)O surfaces, we find that the 2HTTBPP molecules can self-metalate on both surfaces with copper atoms from the substrate at room temperature (RT). The possible origins of the self-metalation reaction at RT are discussed. Finally, peculiar irreversible temperature-dependent switching of the intramolecular conformations of the investigated molecules on the Cu(110) surface was observed and interpreted.
authors.affiliation: Lehrstuhl für Physikalische Chemie II, Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany.|Interdisciplinary Center for Molecular Materials (ICMM), Universität Erlangen-Nürnberg, Germany.
authors.forename: Liang
authors.initials: L
authors.lastname: Zhang
authors.affiliation: Lehrstuhl für Physikalische Chemie II, Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany.|Interdisciplinary Center for Molecular Materials (ICMM), Universität Erlangen-Nürnberg, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Lepper
authors.affiliation: Lehrstuhl für Physikalische Chemie II, Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany.|Interdisciplinary Center for Molecular Materials (ICMM), Universität Erlangen-Nürnberg, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Stark
authors.affiliation: Lehrstuhl für Physikalische Chemie II, Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany.|Interdisciplinary Center for Molecular Materials (ICMM), Universität Erlangen-Nürnberg, Germany.
authors.forename: Ralf
authors.initials: R
authors.lastname: Schuster
authors.affiliation: Interdisciplinary Center for Molecular Materials (ICMM), Universität Erlangen-Nürnberg, Germany.|Lehrstuhl für Organische Chemie II, Universität Erlangen-Nürnberg, Henkestrasse 42, 91054, Erlangen, Germany.
authors.forename: Dominik
authors.initials: D
authors.lastname: Lungerich
authors.affiliation: Interdisciplinary Center for Molecular Materials (ICMM), Universität Erlangen-Nürnberg, Germany.|Lehrstuhl für Organische Chemie II, Universität Erlangen-Nürnberg, Henkestrasse 42, 91054, Erlangen, Germany.
authors.forename: Norbert
authors.initials: N
authors.lastname: Jux
authors.affiliation: Lehrstuhl für Physikalische Chemie II, Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany.|Interdisciplinary Center for Molecular Materials (ICMM), Universität Erlangen-Nürnberg, Germany.
authors.forename: Hans-Peter
authors.initials: HP
authors.lastname: Steinrück
authors.affiliation: Lehrstuhl für Physikalische Chemie II, Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058, Erlangen, Germany. hubertus.marbach@fau.de.|Interdisciplinary Center for Molecular Materials (ICMM), Universität Erlangen-Nürnberg, Germany. hubertus.marbach@fau.de.
authors.forename: Hubertus
authors.initials: H
authors.lastname: Marbach
keywords: adsorption; porphyrinoids; scanning tunneling microscopy; self-assembly; surfaces and interfaces