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

Using the redox-active tetrathiafulvalene tetrabenzoate (TTFTB 4- ) as the linker, we constructed a series of stable and porous rare-earth metal-organic frameworks (RE-MOFs), [RE 9 (μ 3 -OH) 13 (μ 3 -O)(H 2 O) 9 (TTFTB) 3 ] ( 1-RE , where RE = Y, Sm, Gd, Tb, Dy, Ho, and Er). The RE 9 (μ 3 -OH) 13 (μ 3 -O) (H 2 O) 9 ](CO 2 ) 12 clusters within 1-RE act as segregated single-molecule magnets (SMMs) displaying slow relaxation. Interestingly, upon oxidation by I 2 , the S = 0 TTFTB 4- linkers of 1-RE were converted into S = ½ TTFTB •3+ radical linkers which introduced exchange-coupling between SMMs and modulated the relaxation. Furthermore, the SMM property can be restored by the reduction in N, N -dimethylformamide. These results highlight the advantage of MOFs in the construction of redox-switchable SMMs.

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