Rare‐Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox‐Switchable Single‐Molecule Magnets Academic Article uri icon


  • Using the redox-active tetrathiafulvalene tetrabenzoate (TTFTB4- ) as the linker, a series of stable and porous rare-earth metal-organic frameworks (RE-MOFs), [RE9 (μ3 -OH)13 (μ3 -O)(H2 O)9 (TTFTB)3 ] (1-RE, where RE=Y, Sm, Gd, Tb, Dy, Ho, and Er) were constructed. The RE9 (μ3 -OH)13 (μ3 -O) (H2 O)9 ](CO2 )12 clusters within 1-RE act as segregated single-molecule magnets (SMMs) displaying slow relaxation. Interestingly, upon oxidation by I2 , the S=0 TTFTB4- linkers of 1-RE were converted into S= 1 / 2 TTFTB.3- radical linkers which introduced exchange-coupling between SMMs and modulated the relaxation. Furthermore, the SMM property can be restored by reduction in N,N-dimethylformamide. These results highlight the advantage of MOFs in the construction of redox-switchable SMMs.

author list (cited authors)

  • Su, J., Yuan, S., Li, J., Wang, H., Ge, J., Drake, H. F., ... Zhou, H.

publication date

  • January 1, 2020 11:11 AM