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Rare‐Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox‐Switchable Single‐Molecule Magnets
Author(s) -
Su Jian,
Yuan Shuai,
Li Jing,
Wang HaiYing,
Ge JingYuan,
Drake Hannah F.,
Leong Chanel F.,
Yu Fei,
D'Alessandro Deanna M.,
Kurmoo Mohamedally,
Zuo JingLin,
Zhou HongCai
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202004883
Subject(s) - redox , tetrathiafulvalene , metal organic framework , single molecule magnet , carboxylate , molecule , metal , linker , molecular magnets , chemistry , crystallography , magnetic relaxation , dimethylformamide , materials science , inorganic chemistry , stereochemistry , organic chemistry , magnetization , adsorption , physics , quantum mechanics , solvent , magnetic field , computer science , operating system
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 = 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.