Tremendous progress in the development of single molecule magnets (SMMs) raises the question of their device integration. On this route, understanding the properties of low‐dimensional assemblies of SMMs, in particular in contact with electrodes, is a necessary but difficult step. Here, it is shown that fullerene SMM self‐assembled on metal substrate from solution retains magnetic hysteresis up to 10 K. Fullerene‐SMM DySc2N@C80 and Dy2ScN@C80 are derivatized to introduce a thioacetate group, which is used to graft SMMs on gold. Magnetic properties of grafted SMMs are studied by X‐ray magnetic circular dichroism and compared to the films of nonderivatized fullerenes prepared by sublimation. In self‐assembled films, the magnetic moments of the Dy ions are preferentially aligned parallel to the surface, which is different from the disordered orientation of endohedral clusters in nonfunctionalized fullerenes. Whereas chemical derivatization reduces the blocking temperature of magnetization and narrows the hysteresis of Dy2ScN@C80, for DySc2N@C80 equally broad hysteresis is observed as in the fullerene multilayer. Magnetic bistability in the DySc2N@C80 grafted on gold is sustained up to 10 K. This study demonstrates that self‐assembly of fullerene‐SMM derivatives offers a facile solution‐based procedure for the preparation of functional magnetic sub‐monolayers with excellent SMM performance.

Realization of stable spin states in surface-supported magnetic molecules is crucial for their applications in molecular spintronic, memory storage or quantum information processing. In this work, we studied the surface...

Encapsulation of magnetic species within robust molecular containers is a natural route towards stable and processable single molecule magnets (SMMs). Air-stability, thermal stability, ability to form thin molecular layers on different substrates are among the critical issues to be addressed. Chemical and thermal stability of fullerenes makes them perfectly suitable for this goal. Fullerenes can encapsulate up to four metal atoms within their inner space, and a number of lanthanide EMFs was found to show SMM behavior.1-5 Besides, EMF-SMMs can form monolayers by sublimation6, 7 or by self-assembly from solution,8 and such monolayers retain their SMM properties on metallic substrates. In this contribution we will highlight recent developments in the field of lanthanide-EMFs with peculiar magnetic properties. 1. Spree, L.; Popov, A. A., Recent advances in single molecule magnetism of dysprosium-metallofullerenes. Dalton Trans. 2019, 48, 2861-2871. 2. Liu, F.; Spree, L.; Krylov, D. S.; Velkos, G.; Avdoshenko, S. M.; Popov, A. A., Single-Electron Lanthanide-Lanthanide Bonds Inside Fullerenes toward Robust Redox-Active Molecular Magnets. Acc. Chem. Res. 2019, 52, 2981-2993. 3. Liu, F.; Velkos, G.; Krylov, D. S.; Spree, L.; Zalibera, M.; Ray, R.; Samoylova, N. A.; Chen, C.-H.; Rosenkranz, M.; Schiemenz, S.; Ziegs, F.; Nenkov, K.; Kostanyan, A.; Greber, T.; Wolter, A. U. B.; Richter, M.; Büchner, B.; Avdoshenko, S. M.; Popov, A. A., Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal-metal bond. Nat. Commun. 2019, 10, 571. 4. Liu, F.; Krylov, D. S.; Spree, L.; Avdoshenko, S. M.; Samoylova, N. A.; Rosenkranz, M.; Kostanyan, A.; Greber, T.; Wolter, A. U. B.; Büchner, B.; Popov, A. A., Single molecule magnet with an unpaired electron trapped between two lanthanide ions inside a fullerene. Nat. Commun. 2017, 8, 16098. 5. Chen, C.-H.; Krylov, D. S.; Avdoshenko, S. M.; Liu, F.; Spree, L.; Yadav, R.; Alvertis, A.; Hozoi, L.; Nenkov, K.; Kostanyan, A.; Greber, T.; Wolter, A. U. B.; Popov, A. A., Selective arc-discharge synthesis of Dy2S-clusterfullerenes and their isomer-dependent single molecule magnetism. Chem. Sci. 2017, 8, 6451-6465. 6. Greber, T.; Seitsonen, A. P.; Hemmi, A.; Dreiser, J.; Stania, R.; Matsui, F.; Muntwiler, M.; Popov, A. A.; Westerström, R., Circular dichroism and angular deviation in x-ray absorption spectra of Dy2ScN@C80 single-molecule magnets on h-BN/Rh(111). Phys. Rev. Mater. 2019, 3, 014409. 7. Westerström, R.; Uldry, A.-C.; Stania, R.; Dreiser, J.; Piamonteze, C.; Muntwiler, M.; Matsui, F.; Rusponi, S.; Brune, H.; Yang, S.; Popov, A.; Büchner, B.; Delley, B.; Greber, T., Surface aligned magnetic moments and hysteresis of an endohedral single-molecule magnet on a metal. Phys. Rev. Lett. 2015, 114, 087201. 8. Chen, C. H.; Krylov, D. S.; Avdoshenko, S. M.; Liu, F.; Spree, L.; Westerström, R.; Bulbucan, C.; Studniarek, M.; Dreiser, J.; Wolter, A. U. B.; Büchner, B.; Popov, A. A., Magnetic hysteresis in self-assembled monolayers of Dy-fullerene single molecule magnets on gold. Nanoscale 2018, 10, 11287-11292.