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- Krylov, Denis S., et al.
(författare)
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Substrate-Independent Magnetic Bistability in Monolayers of the Single-Molecule Magnet Dy2ScN@C80 on Metals and Insulators
- 2020
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Ingår i: Angewandte Chemie - International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 59:14, s. 5756-5764
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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2. |
- Martinez, Valentina, et al.
(författare)
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Tunable Fulleretic Sodalite MOFs : Highly Efficient and Controllable Entrapment of C-60 Fullerene via Mechanochemistry
- 2020
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 0897-4756 .- 1520-5002. ; 32:24, s. 10628-10640
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Tidskriftsartikel (refereegranskat)abstract
- Encapsulation and confinement of fullerene guests in metal-organic frameworks (MOFs) lead to a novel class of crystalline fulleretic materials with unique physicochemical properties and a broad field of potential applications. The control over the amount of target guests confined in the MOF structure remains a significant challenge, which is particularly pronounced in the confinement of hardly accessible fullerene derivatives. The main strategies used in constructing fulleretic composites are limited by the solubility of components used and solvent versus guest competition for inhabitation of the framework voids. As mechanochemical procedures often overcome these issues, we developed here solvent-free processing by ball milling to gain control over the encapsulation of bulky and rigid C-60-fullerene into a sodalite MOF with large cages and narrow cage-apertures. A rapid, green, efficient, and stoichiometry-controlled mechanochemical processing afforded four model C-60@zeolitic-imidazolate framework 8 (ZIF-8) crystalline materials containing target 15, 30, 60, and 100 mol % of fullerene entrapped in the accessible cages of the model sodalite zeolitic-imidazolate framework 8 (ZIF-8), in stark contrast to the solution-based strategies that resulted in almost no loading. Varying the fullerene content affects the framework's vibrational properties, color and luminescence of the composites, and the electron-dose radiation stability. The computational and spectroscopic studies show that the fullerene is accommodated in the cage's center and that the cage-to-cage transport is a hardly feasible and energetically unfavored process. However, the fast release of C-60 molecules from ZIF-8 can be effectively controlled by the pH. The entrapment of fullerene molecules in ZIF-8 resulted in their effective isolation even in higher loadings, paving the way to other tunable porous fulleretics containing single-molecule magnets or nanoprobes available on low scales.
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3. |
- Westerström, Rasmus, et al.
(författare)
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Precise measurement of angles between two magnetic moments and their configurational stability in single-molecule magnets
- 2021
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Ingår i: Physical Review B. - 2469-9950. ; 104:22
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Tidskriftsartikel (refereegranskat)abstract
- A key parameter for the low-temperature magnetic coupling of in dinuclear lanthanide single-molecule magnets (SMMs) is the barrier UFA resulting from the exchange and dipole interactions between the two 4f moments. Here we extend the pseudospin model previously used to describe the ground state of dinuclear endofullerenes to account for variations in the orientation of the single-ion anisotropy axes and apply it to the two SMMs Dy2ScN@C80 and Dy2TiC@C80. While x-ray magnetic circular dichroism (XMCD) indicates the same Jz=15/2 Dy ground state in both molecules, the Dy-Dy coupling strength and the stability of magnetization is distinct. We demonstrate that both the magnitude of the barrier UFA and the angle between the two 4f moments are determined directly from precise temperature-dependent magnetization data to an accuracy better than 1. The experimentally found angles between the 4f moments are in excellent agreement with calculated angles between the quantization axes of the two Dy ions. Theory indicates a larger deviation of the orientation of the Dy magnetic moments from the Dy bond axes to the central ion in Dy2TiC@C80. This may explain the lower stability of the magnetization in Dy2TiC@C80, although it exhibits a ∼49% stronger exchange coupling than in Dy2ScN@C80.
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