ACS Publications. Most Trusted. Most Cited. Most Read
Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn2+, Zn2+, and Mixed-Valence Fe2+/3+

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2024, 63, 1, 129-140
    Article

    Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn2+, Zn2+, and Mixed-Valence Fe2+/3+
    Click to copy article linkArticle link copied!

    • Margit Aust
      Margit Aust
      Chair of Inorganic and Metal−Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany
      More by Margit Aust
    • Marina I. Schönherr
      Marina I. Schönherr
      Department of Chemistry and Center for NanoScience (CeNS), Ludwig-Maximilians-Universität (LMU), Butenandtstraße 11, 81377 Munich, Germany
      More by Marina I. Schönherr
    • Dominik P. Halter
      Dominik P. Halter
      Chair of Inorganic and Metal−Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany
      More by Dominik P. Halter
      Orcidhttps://orcid.org/0000-0003-0733-8955
    • Lena Schröck
      Lena Schröck
      Chair of Inorganic and Metal−Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany
      More by Lena Schröck
    • Thomas Pickl
      Thomas Pickl
      Chair of Inorganic and Metal−Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany
      More by Thomas Pickl
    • Simon N. Deger
      Simon N. Deger
      Chair of Inorganic and Metal−Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany
      More by Simon N. Deger
    • Mian Z. Hussain
      Mian Z. Hussain
      Chair of Inorganic and Metal−Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany
      More by Mian Z. Hussain
    • Andreas Jentys
      Andreas Jentys
      Chair of Industrial Chemistry and Heterogeneous Catalysis, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany
      More by Andreas Jentys
    • Raphael Bühler
      Raphael Bühler
      Chair of Inorganic and Metal−Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany
      More by Raphael Bühler
    • Zihan Zhang
      Zihan Zhang
      Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstr. 1, 91058 Erlangen, Germany
      More by Zihan Zhang
    • Karsten Meyer
      Karsten Meyer
      Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstr. 1, 91058 Erlangen, Germany
      More by Karsten Meyer
      Orcidhttps://orcid.org/0000-0002-7844-2998
    • Matthias Kuhl
      Matthias Kuhl
      Walter Schottky Institute, Physics Department, TUM School of Natural Sciences, Technical University of Munich, 85747 Garching, Germany
      More by Matthias Kuhl
    • Johanna Eichhorn
      Johanna Eichhorn
      Walter Schottky Institute, Physics Department, TUM School of Natural Sciences, Technical University of Munich, 85747 Garching, Germany
      More by Johanna Eichhorn
    • Dana D. Medina
      Dana D. Medina
      Department of Chemistry and Center for NanoScience (CeNS), Ludwig-Maximilians-Universität (LMU), Butenandtstraße 11, 81377 Munich, Germany
      More by Dana D. Medina
    • Alexander Pöthig*
      Alexander Pöthig
      Chair of Inorganic and Metal−Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany
      *Email: [email protected]
      More by Alexander Pöthig
      Orcidhttps://orcid.org/0000-0003-4663-3949
    • Roland A. Fischer*
      Roland A. Fischer
      Chair of Inorganic and Metal−Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany
      *Email: [email protected]
      More by Roland A. Fischer
      Orcidhttps://orcid.org/0000-0002-7532-5286
    Other Access OptionsSupporting Information (2)

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2024, 63, 1, 129–140
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.3c02471
    Published December 18, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Three new coordination polymers (CPs) constructed from the linker 1,4-di(dithiocarboxylate) (BDDTC2–)─the sulfur-analog of 1,4-benzenedicarboxylate (BDC2–)─together with Mn-, Zn-, and Fe-based inorganic SBUs are reported with description of their structural and electronic properties. Single-crystal X-ray diffraction revealed structural diversity ranging from one-dimensional chains in [Mn(BDDTC)(DMF)2] (1) to two-dimensional (2D) honeycomb sheets observed for [Zn2(BDDTC)3][Zn(DMF)5(H2O)] (2). Gas adsorption experiments confirmed a 3D porous structure for the mixed-valent material [Fe2(BDDTC)2(OH)] (3). 3 contains a 1:1 ratio of Fe2+/3+ ions, as evidenced by 57Fe Mössbauer, X-band EPR, and X-ray absorption spectroscopy. Its empirical formula was established by elemental analysis, thermal gravimetric analysis, infrared vibrational spectroscopy, and X-ray absorption spectroscopy in lieu of elusive single-crystal X-ray diffraction data. In contrast to the Mn- and Zn-based compounds 1 and 2, the Fe2+/3+ CP 3 showed remarkably high electrical conductivity of 5 × 10–3 S cm–1 (according to van der Pauw measurements), which is within the range of semiconducting materials. Overall, our study confirms that sulfur derivatives of typical carboxylate linkers (e.g., BDC) are suitable for the construction of electrically conducting CPs, due to acceptedly higher covalency in metal–ligand bonding compared to the electrically insulating carboxylate CPs or metal-organic frameworks. At the same time, the direct comparison between insulating CPs 1 and 2 with CP 3 emphasizes that the electronic structure of the metal is likewise a crucial aspect to construct electrically conductive materials.

    Copyright © 2023 American Chemical Society

    Subjects

    what are subjects

    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. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02471.

    • Experimental infrared spectra, thermogravimetric analysis data, solid-state UV/VIS-NIR spectra, PXRD studies for air stability, SQUID magnetometry spectra, EXAFS analysis data, XPS spectra and analysis, scanning electron microscopy images and structural details, tables for comparison of coordination motifs and electrical conductivities, and crystallographic information (PDF)

    • Adsorption information (PDF)

    Accession Codes

    CCDC 2249203–2249205 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

    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

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 1 publications.

    1. Farzaneh Afshariazar, Ali Morsali. Mixed-valence metal–organic frameworks: concepts, opportunities, and prospects. Chemical Society Reviews 2025, 54 (3) , 1318-1383. https://doi.org/10.1039/D4CS01061B
    Download PDF
    Go to Inorganic Chemistry
    Get e-Alerts
    Get e-Alerts

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2024, 63, 1, 129–140
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.3c02471
    Published December 18, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

    Article Views

    799

    Altmetric

    -

    Citations

    1
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.