Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 34, Pages 10695-10702Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201402255
Keywords
anions; magnetic properties; metal-organic frameworks; polyoxometalates; single-molecule studies
Categories
Funding
- European Union (ERC)
- Spanish MINECO [MAT2011-22785, CTQ2011-26507]
- Spanish MINECO (FEDER)
- Generalidad Valenciana (Prometeo Program)
- Generalidad Valenciana (ISIC-NANO Program)
- Spanish MECD for FPU
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The formation of a metal-organic framework (MOF) with nodes that have single-molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single-ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM-MOFs. Here we present a rational design of a family of MOFs, [Ln(bipyNO)(4)](TfO)(3)center dot xsolvent (Ln = Tb (1); Dy (2); Ho (3); Er (4); TfO = triflate), in which the lanthanoid centres have an square-antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM-MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non-innocent anions.
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