Systematic Investigation of Controlled Nanostructuring of Mn 12 Single-Molecule Magnets Templated by Metal–Organic Frameworks
[2];
[1]
- Department of Chemistry &, Biomolecular Science, Clarkson University, Potsdam, New York 13699, United States
- Department of Chemistry, Texas A&,M University, College Station, Texas 77845, United States
- Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
- X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States
This is the first systematic study exploring metal–organic frameworks (MOFs) as platforms for the controlled nanostructuring 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 Mn12 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.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 1410806
- Journal Information:
- Inorganic Chemistry, Vol. 56, Issue 12; ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
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