Rare-Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox-Switchable Single-Molecule Magnets

Abstract

Using the redox-active tetrathiafulvalene tetrabenzoate (TTFTB^4- ) 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 TTFTB^4- 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.

Keywords: metal-organic frameworks; rare-earth clusters; redox switchable molecules; single-molecule magnets.