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Magnetic Hysteresis at 10 K in Single Molecule Magnet Self‐Assembled on Gold
2021, Chen, Chia-Hsiang, Spree, Lukas, Koutsouflakis, Emmanouil, Krylov, Denis S., Liu, Fupin, Brandenburg, Ariane, Velkos, Georgios, Schimmel, Sebastian, Avdoshenko, Stanislav M., Federov, Alexander, Weschke, Eugen, Choueikani, Fadi, Ohresser, Philippe, Dreiser, Jan, Büchner, Bernd, Popov, Alexey A.
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.
Robust Single Molecule Magnet Monolayers on Graphene and Graphite with Magnetic Hysteresis up to 28 K
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
Cell Adhesion on Dynamic Supramolecular Surfaces Probed by Fluid Force Microscopy-Based Single-Cell Force Spectroscopy
2017, Sankaran, Shrikrishnan, Jaatinen, Leena, Brinkmann, Jenny, Zambelli, Tomaso, Vörös, Janos, Jonkheijm, Pascal
Biomimetic and stimuli-responsive cell-material interfaces are actively being developed to study and control various cell-dynamics phenomena. Since cells naturally reside in the highly dynamic and complex environment of the extracellular matrix, attempts are being made to replicate these conditions in synthetic biomaterials. Supramolecular chemistry, dealing with noncovalent interactions, has recently provided possibilities to incorporate such dynamicity and responsiveness in various types of architectures. Using a cucurbit[8]uril-based host−guest system, we have successfully established a dynamic and electrochemically responsive interface for the display of the integrin-specific ligand, Arg-Gly-Asp (RGD), to promote cell adhesion. Due to the weak nature of the noncovalent forces by which the components at the interface are held together, we expected that cell adhesion would also be weaker in comparison to traditional interfaces where ligands are usually immobilized by covalent linkages. To assess the stability and limitations of our noncovalent interfaces, we performed single-cell force spectroscopy studies using fluid force microscopy. This technique enabled us to measure rupture forces of multiple cells that were allowed to adhere for several hours on individual substrates. We found that the rupture forces of cells adhered to both the noncovalent and covalent interfaces were nearly identical for up to several hours. We have analyzed and elucidated the reasons behind this result as a combination of factors including the weak rupture force between linear Arg-Gly-Asp and integrin, high surface density of the ligand, and increase in effective concentration of the supramolecular components under spread cells. These characteristics enable the construction of highly dynamic biointerfaces without compromising cell-adhesive properties.