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    Robust Single Molecule Magnet Monolayers on Graphene and Graphite with Magnetic Hysteresis up to 28 K
    (Weinheim : Wiley-VCH, 2021) Spree, Lukas; Liu, Fupin; Neu, Volker; Rosenkranz, Marco; Velkos, Georgios; Wang, Yaofeng; Schiemenz, Sandra; Dreiser, Jan; Gargiani, Pierluigi; Valvidares, Manuel; Chen, Chia-Hsiang; Büchner, Bernd; Avdoshenko, Stanislav M.; Popov, Alexey A.
    The chemical functionalization of fullerene single molecule magnet Tb2@C80(CH2Ph) enables the facile preparation of robust monolayers on graphene and highly oriented pyrolytic graphite from solution without impairing their magnetic properties. Monolayers of endohedral fullerene functionalized with pyrene exhibit magnetic bistability up to a temperature of 28 K. The use of pyrene terminated linker molecules opens the way to devise integration of spin carrying units encapsulated by fullerene cages on graphitic substrates, be it single-molecule magnets or qubit candidates. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
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    Substrate-Independent Magnetic Bistability in Monolayers of the Single-Molecule Magnet Dy2ScN@C80 on Metals and Insulators
    (Weinheim : Wiley-VCH, 2020) Krylov, Denis S.; Schimmel, Sebastian; Dubrovin, Vasilii; Liu, Fupin; Nguyen, T.T. Nhung; Spree, Lukas; Chen, Chia-Hsiang; Velkos, Georgios; Bulbucan, Claudiu; Westerström, Rasmus; Studniarek, Michał; Dreiser, Jan; Hess, Christian; Büchner, Bernd; Avdoshenko, Stanislav M.; Popov, Alexey A.
    Magnetic hysteresis is demonstrated for monolayers of the single-molecule magnet (SMM) Dy2ScN@C80 deposited on Au(111), Ag(100), and MgO|Ag(100) surfaces by vacuum sublimation. The topography and electronic structure of Dy2ScN@C80 adsorbed on Au(111) were studied by STM. X-ray magnetic CD studies show that the Dy2ScN@C80 monolayers exhibit similarly broad magnetic hysteresis independent on the substrate used, but the orientation of the Dy2ScN cluster depends strongly on the surface. DFT calculations show that the extent of the electronic interaction of the fullerene molecules with the surface is increasing dramatically from MgO to Au(111) and Ag(100). However, the charge redistribution at the fullerene-surface interface is fully absorbed by the carbon cage, leaving the state of the endohedral cluster intact. This Faraday cage effect of the fullerene preserves the magnetic bistability of fullerene-SMMs on conducting substrates and facilitates their application in molecular spintronics. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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    Magnetic hysteresis and strong ferromagnetic coupling of sulfur-bridged Dy ions in clusterfullerene Dy2S@C82
    (Cambridge : RSC, 2020) Krylov, Denis; Velkos, Georgios; Chen, Chia-Hsiang; Büchner, Bernd; Kostanyan, Aram; Greber, Thomas; Avdoshenko, Stanislav M.; Popov, Alexey A.
    Two isomers of metallofullerene Dy2S@C82 with sulfur-bridged Dy ions exhibit broad magnetic hysteresis with sharp steps at sub-Kelvin temperature. Analysis of the level crossing events for different orientations of a magnetic field showed that even in powder samples, the hysteresis steps caused by quantum tunneling of magnetization can provide precise information on the strength of intramolecular Dy⋯Dy interactions. A comparison of different methods to determine the energy difference between ferromagnetic and antiferromagnetic states showed that sub-Kelvin hysteresis gives the most robust and reliable values. The ground state in Dy2S@C82 has ferromagnetic coupling of Dy magnetic moments, whereas the state with antiferromagnetic coupling in Cs and C3v cage isomers is 10.7 and 5.1 cm-1 higher, respectively. The value for the Cs isomer is among the highest found in metallofullerenes and is considerably larger than that reported in non-fullerene dinuclear molecular magnets. Magnetization relaxation times measured in zero magnetic field at sub-Kelvin temperatures tend to level off near 900 and 3200 s in Cs and C3v isomers. These times correspond to the quantum tunneling relaxation mechanism, in which the whole magnetic moment of the Dy2S@C82 molecule flips at once as a single entity. © the Partner Organisations.