ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

On-Surface Synthesis of Square-Type Porphyrin Tetramers with Central Antiaromatic Cyclooctatetraene Moiety

  • Eduardo Corral Rascon
    Eduardo Corral Rascon
    Physics Department E20, Technical University of Munich, James-Franck Str. 1, 85748 Garching, Germany
  • Alexander Riss
    Alexander Riss
    Physics Department E20, Technical University of Munich, James-Franck Str. 1, 85748 Garching, Germany
  • Adam Matěj
    Adam Matěj
    Institute of Physics, Czech Academy of Sciences, 162 00 Prague, Czech Republic
    Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute (CATRIN), Palacky University in Olomouc, 779 00 Olomouc, Czech Republic
    Department of Physical Chemistry, Faculty of Science, Palacky University in Olomouc, 779 00 Olomouc, Czech Republic
    More by Adam Matěj
  • Alissa Wiengarten
    Alissa Wiengarten
    Physics Department E20, Technical University of Munich, James-Franck Str. 1, 85748 Garching, Germany
  • Pingo Mutombo
    Pingo Mutombo
    Institute of Physics, Czech Academy of Sciences, 162 00 Prague, Czech Republic
  • Diego Soler
    Diego Soler
    Institute of Physics, Czech Academy of Sciences, 162 00 Prague, Czech Republic
    More by Diego Soler
  • Pavel Jelinek*
    Pavel Jelinek
    Institute of Physics, Czech Academy of Sciences, 162 00 Prague, Czech Republic
    Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute (CATRIN), Palacky University in Olomouc, 779 00 Olomouc, Czech Republic
    *Email: [email protected]
  • , and 
  • Willi Auwärter*
    Willi Auwärter
    Physics Department E20, Technical University of Munich, James-Franck Str. 1, 85748 Garching, Germany
    *Email: [email protected]
Cite this: J. Am. Chem. Soc. 2023, 145, 2, 967–977
Publication Date (Web):December 29, 2022
https://doi.org/10.1021/jacs.2c10088
Copyright © 2022 American Chemical Society

    Article Views

    2753

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    The synthesis of two-dimensionally extended polycyclic heteroatomic molecules keeps attracting considerable attention. In particular, frameworks bearing planar cyclooctatetraenes (COT) moieties can display intriguing properties, including antiaromaticity. Here, we present an on-surface chemistry route to square-type porphyrin tetramers with a central COT ring, coexisting with other oligomers. This approach employing temperature-induced dehydrogenative porphyrin homocoupling in an ultrahigh vacuum environment provides access to surface-supported, unsubstituted porphyrin tetramers that are not easily achievable by conventional synthesis means. Specifically, monomeric free-base (2H-P) and Zn-metalated (Zn-P) porphines (P) were employed to form square-type free-base and Zn-functionalized tetramers on Ag(100). An atomic-level characterization by bond-resolved atomic force microscopy and scanning tunneling microscopy and spectroscopy is provided, identifying the molecular structures. Complemented by density functional theory modeling, the electronic structure is elucidated, indeed revealing antiaromaticity induced by the COT moiety. The present study thus gives access, and insights, to a porphyrin oligomer, representing both a model system for directly fused porphyrins and a potential building block for conjugated, extended two-dimensional porphyrin sheets.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c10088.

    • Additional experimental AFM and dI/dV data, simulated AFM images, ACID plot, and calculated orbitals (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 4 publications.

    1. Zhiwen Zhu, Jiayi Lu, Shaoxuan Yuan, Yu He, Fengru Zheng, Hao Jiang, Yuyi Yan, Qiang Sun. Automated Generation and Analysis of Molecular Images Using Generative Artificial Intelligence Models. The Journal of Physical Chemistry Letters 2024, 15 (7) , 1985-1992. https://doi.org/10.1021/acs.jpclett.3c03504
    2. Binbin Liu, Meng Chen, Xinyue Liu, Ruihua Fu, Yubo Zhao, Yuxiao Duan, Lei Zhang. Bespoke Tailoring of Graphenoid Sheets: A Rippled Molecular Carbon Comprising Cyclically Fused Nonbenzenoid Rings. Journal of the American Chemical Society 2023, 145 (51) , 28137-28145. https://doi.org/10.1021/jacs.3c10303
    3. Nicolas Néel, Jörg Kröger. Orbital and Skeletal Structure of a Single Molecule on a Metal Surface Unveiled by Scanning Tunneling Microscopy. The Journal of Physical Chemistry Letters 2023, 14 (16) , 3946-3952. https://doi.org/10.1021/acs.jpclett.3c00460
    4. Aleksandr Baklanov, Johannes T. Küchle, David A. Duncan, Paul T. P. Ryan, Reinhard J. Maurer, Martin Schwarz, Eduardo Corral Rascon, Ignacio Piquero-Zulaica, Huynh Thien Ngo, Alexander Riss, Francesco Allegretti, Willi Auwärter. Zinc-Porphine on Coinage Metal Surfaces: Adsorption Configuration and Ligand-Induced Central Atom Displacement. The Journal of Physical Chemistry C 2023, 127 (15) , 7501-7512. https://doi.org/10.1021/acs.jpcc.3c00232

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect