화학공학소재연구정보센터
Inorganic Chemistry, Vol.56, No.12, 6965-6972, 2017
Systematic Investigation of Controlled Nanostructuring of Mn-12 Single-Molecule Magnets Templated by Metal-Organic Frameworks
This is the first systematic study exploring metal organic frameworks (MOTs) as platforms for the controlled nanostructuririg of molecular magnets. We report the incorporation of seven single-molecule magnets (SMMs) of general composition Mn12O12(O2CR)(16)(OH2)(4)], with R = CF3 (1), (CH3)CCH2 (2), CH2Cl (3), CH2Br(4), CHCl2 (5), CH2But (6), and C6H5 (7), into the hexagonal channel pores of a mesoporous MOF host. The resulting nanostructured composites combine the key SMM properties with the functional properties of the MOF. Synchrotron based powder diffraction with difference envelope density analysis, physisorption analysis (surface area and pore size distribution), and thermal analyses reveal that the well-ordered hexagonal structure of the host framework is preserved, and magnetic measurements indicate that slow relaxation of the magnetization, characteristic of the corresponding Mn-12 derivative, guests, occurs inside the MOF pores. Structural host guest correlations including the bulkiness and polarity of peripheral SMM ligands are discussed as fundamental parameters influencing the global SMM@MOF loading capacities. These results demonstrate that employing MOFs as platforms for the nanostructuration of SMMs is not limited to a particular host guest system but potentially applicable to a multitude of other molecular magnets. Such fundamental findings will assist in paving the way for the development of novel advanced spintronic devices.