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The Separation of the Mn₁₂ Single-Molecule Magnets onto Spherical Silica Nanoparticles.

ABSTRACT: The Mn₁₂ single-molecule magnets (SMMs) could be attached to the surface of spherical silica for the first time with a high probability. This allowed separation of the individual molecular magnets and direct microscopic observation of the SMMs. We described in detail how to fabricate such a composite material. The synthesis procedure proposed here is simple and efficient. We confirmed the efficiency of the method by transmission electron microscopy (TEM): single-molecule magnets were visible at the surface of a silica substrate. Based on TEM observation, we described how the molecules anchor to the surface of silica (the geometry of the magnetic molecule in regard to the surface of the substrate). The SQUID magnetometry showed that single-molecule magnet behaviour is kept intact after grafting. The attachment of the single-molecule magnets to the surface of silica allows to investigate their properties as separate molecules. This is particularly important in the analysis of magnetic properties such as magnetic states of the separated SMMs, their mutual interactions, and the influence of a silica support.

SUBMITTER: Laskowski L

PROVIDER: S-EPMC6567163 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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The Separation of the Mn<sub>12</sub> Single-Molecule Magnets onto Spherical Silica Nanoparticles.

Laskowski Lukasz L Kityk Iwan I Konieczny Piotr P Pastukh Oleksandr O Schabikowski Mateusz M Laskowska Magdalena M

Nanomaterials (Basel, Switzerland) 20190518 5

The Mn<sub>12</sub> single-molecule magnets (SMMs) could be attached to the surface of spherical silica for the first time with a high probability. This allowed separation of the individual molecular magnets and direct microscopic observation of the SMMs. We described in detail how to fabricate such a composite material. The synthesis procedure proposed here is simple and efficient. We confirmed the efficiency of the method by transmission electron microscopy (TEM): single-molecule magnets were ...[more]

PMID: 31109066

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Project description:Similar synthetic schemes yield two different metallacrown (MC) complexes: bis-(μ-3-chloro-benzoato)hexa-kis-(di-methyl-formamide)-tetra-kis-(μ4-N,2-dioxido-benzene-1-carboximidato)tetra-manganese(III)disodium(I), [Mn4Na2(C7H4ClO2)2(C7H4NO3)4(C3H7NO)6] or Na2(3-chloro-benzoate)2[12-MCMn(III)N(shi)-4](DMF)6, 1, and tetra-μ-aqua-tris-(μ-3-chloro-benzoato)(di-methyl-formamide)-tetra-kis-(μ4-N,2-dioxido-benzene-1-carboximidato)penta-manganese(III)sodi-um(I) di-methyl-formamide tetra-solvate 0.72-hydrate, [Mn5Na(C7H4ClO2)3(C7H4NO3)4(C3H7NO)(H2O)4]·4C3H7NO·0.718H2O or MnNa(3-chloro-benzo-ate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O, 2, where shi3- is salicyl-hydrox-imate and DMF is N,N-di-methyl-formamide. Both complexes have the same framework consisting of four MnIII ions in the MC ring and four shi3- ligands, resulting in an overall square-shaped mol-ecule. The MnIII ions are either five- or six-coordinate with elongated bond lengths in the apical or axial direction, respectively. The structure of 1 is nearly planar, and the MC binds two Na+ ions on opposite faces of the MC central cavity. The 3-chloro-benzoate anions also bind on opposite faces of the MC and form bridges between the central Na+ ions and the ring MnIII ions. For 1 the metallacrown mol-ecule, except for the central Na+ ion, exhibits whole mol-ecule disorder over two sets of sites. Both moieties are centrosymmetric and are related to each other by a pseudo-mirror operation with opposite sense of rotation around the Na⋯Na axis. The occupancy ratio of the main disorder of the metallacrown mol-ecules and 3-chloro-benzoate anions refined to 0.9276 (9):0.0724 (9). The structure of 2 is slightly domed, and the MC binds both an MnII ion and an Na+ ion in the MC central cavity. The MnII ion is located on the convex side of the MC, while the Na+ ion binds to the concave side. Complex 2 represents the first instance of a [12-MCMn(III)N(shi)-4] mol-ecule binding both 3d transition metal and alkali metal ions in the central cavity. In addition, three 3-chloro-benzoate anions bind on the convex side of the MC and connect the MnII ion to three of the ring MnIII ions.

Dataset Information

The Separation of the Mn12 Single-Molecule Magnets onto Spherical Silica Nanoparticles.

Publications

The Separation of the Mn<sub>12</sub> Single-Molecule Magnets onto Spherical Silica Nanoparticles.

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The Separation of the Mn₁₂ Single-Molecule Magnets onto Spherical Silica Nanoparticles.