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Hybrid Molecular Magnets with Lanthanide- and Countercation-Mediated Interfacial Electron Transfer between Phthalocyanine and Polyoxovanadate

  • Irina Werner
    Irina Werner
    Leibniz Institute of Surface Engineering (IOM), Permoserstr. 15, Leipzig04318, Germany
    More by Irina Werner
  • Jan Griebel
    Jan Griebel
    Leibniz Institute of Surface Engineering (IOM), Permoserstr. 15, Leipzig04318, Germany
    More by Jan Griebel
  • Albert Masip-Sánchez
    Albert Masip-Sánchez
    Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo 1, Tarragona43007, Spain
  • Xavier López*
    Xavier López
    Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo 1, Tarragona43007, Spain
    *Email: [email protected]
  • Karol Załęski
    Karol Załęski
    NanoBioMedical Centre, Adam Mickiewicz University in Poznań, Poznań61-614, Poland
  • Piotr Kozłowski*
    Piotr Kozłowski
    Institute of Spintronics and Quantum Information, Faculty of Physics, Adam Mickiewicz University in Poznań, ul. Uniwersytetu Poznańskiego 2, Poznań61-614, Poland
    *Email: [email protected]
  • Axel Kahnt
    Axel Kahnt
    Leibniz Institute of Surface Engineering (IOM), Permoserstr. 15, Leipzig04318, Germany
    More by Axel Kahnt
  • Martin Boerner
    Martin Boerner
    Leibniz Institute of Surface Engineering (IOM), Permoserstr. 15, Leipzig04318, Germany
    Institute of Inorganic Chemistry, Leipzig University, Johannisallee 29, Leipzig04103, Germany
  • Ziyan Warneke
    Ziyan Warneke
    Leibniz Institute of Surface Engineering (IOM), Permoserstr. 15, Leipzig04318, Germany
    Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, Leipzig University, Linnéstr. 2, Leipzig04103, Germany
  • Jonas Warneke
    Jonas Warneke
    Leibniz Institute of Surface Engineering (IOM), Permoserstr. 15, Leipzig04318, Germany
    Wilhelm-Ostwald-Institute for Physical and Theoretical Chemistry, Leipzig University, Linnéstr. 2, Leipzig04103, Germany
  • , and 
  • Kirill Yu. Monakhov*
    Kirill Yu. Monakhov
    Leibniz Institute of Surface Engineering (IOM), Permoserstr. 15, Leipzig04318, Germany
    *Email: [email protected]
Cite this: Inorg. Chem. 2023, 62, 9, 3761–3775
Publication Date (Web):December 19, 2022
https://doi.org/10.1021/acs.inorgchem.2c03599
Copyright © 2022 American Chemical Society

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    Abstract

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    A series of {V12}-nuclearity polyoxovanadate cages covalently functionalized with one or sandwiched by two phthalocyaninato (Pc) lanthanide (Ln) moieties via V–O–Ln bonds were prepared and fully characterized for paramagnetic Ln = SmIII–ErIII and diamagnetic Ln = LuIII, including YIII. The LnPc-functionalized {V12O32} cages with fully oxidized vanadium centers in the ground state were isolated as (nBu4N)3[HV12O32Cl(LnPc)] and (nBu4N)2[HV12O32Cl(LnPc)2] compounds. As corroborated by a combined experimental (EPR, DC and AC SQUID, laser photolysis transient absorption spectroscopy, and electrochemistry) and computational (DFT, MD, and model Hamiltonian approach) methods, the compounds feature intra- and intermolecular electron transfer that is responsible for a partial reduction at V(3d) centers from VV to VIV in the solid state and at high sample concentrations. The effects are generally Ln dependent and are clearly demonstrated for the (nBu4N)3[HV12O32Cl(LnPc)] representative with Ln = LuIII or DyIII. Intramolecular charge transfer takes place for Ln = LuIII and occurs from a Pc ligand via the Ln center to the {V12O32} core of the same molecule, whereas for Ln = DyIII, only intermolecular charge transfer is allowed, which is realized from Pc in one molecule to the {V12O32} core of another molecule usually via the nBu4N+ countercation. For all Ln but DyIII, two of these phenomena may be present in different proportions. Besides, it is demonstrated that (nBu4N)3[HV12O32Cl(DyPc)] is a field-induced single molecule magnet with a maximal relaxation time of the order 10–3 s. The obtained results open up the way to further exploration and fine-tuning of these three modular molecular nanocomposites regarding tailoring and control of their Ln-dependent charge-separated states (induced by intramolecular transfer) and relaxation dynamics as well as of electron hopping between molecules. This should enable us to realize ultra-sensitive polyoxometalate powered quasi-superconductors, sensors, and data storage/processing materials for quantum technologies and neuromorphic computing.

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    The fluorescence quantum yields should be considered as the upper limit, since already marginal residual amounts (<0.1%) of free base phthalocyanines from the syntheses may contribute substantially to the observed fluorescence.

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    • General methods, synthetic procedures, analytical and crystallographic data, computational study, and magnetochemical modeling (PDF)

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    CCDC 21442132144216 and 21531572153159 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.

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    Cited By

    This article is cited by 3 publications.

    1. Yue Cheng, Zi-Yi Chen, Yi-Fei Deng, Yuan-Zhu Zhang. 3 nm-wide Cyanometallate Fe–Co Tape Exhibiting Single-Chain Magnet Behavior. Inorganic Chemistry 2024, 63 (9) , 4063-4071. https://doi.org/10.1021/acs.inorgchem.3c03531
    2. Saurabh Soni, Irina Werner, Michael Aidi, Marco Moors, C. Lungani Mthembu, Michael Zharnikov, Remco W. A. Havenith, Kirill Yu. Monakhov, Ryan C. Chiechi. Influence of Polyoxovanadate and Phthalocyanine on 4f Electron Transfer in Gold-Confined Monolayers Probed with EGaIn Top Contacts. ACS Applied Nano Materials 2023, 6 (24) , 22643-22650. https://doi.org/10.1021/acsanm.3c05021
    3. Kirill Yu. Monakhov. Implication of counter-cations for polyoxometalate-based nano-electronics. Comments on Inorganic Chemistry 2022, , 1-10. https://doi.org/10.1080/02603594.2022.2157409