Rare‐Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox‐Switchable Single‐Molecule Magnets
Jian Su, Shuai Yuan, Jing Li, Hai‐Ying Wang, Jing‐Yuan Ge, Hannah F. Drake, Chanel F. Leong, Fei Yu, Deanna M. D’Alessandro, Mohamedally Kurmoo, Jing‐Lin Zuo, Hong‐Cai Zhou
Abstract
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), [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) were constructed. 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 = 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.