Rare-Earth Metal Tetrathiafulvalene Carboxylate Frameworks as Redox-Switchable Single-Molecule Magnets |
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| Authors: | Jian Su Shuai Yuan Jing Li Hai-Ying Wang Jing-Yuan Ge Hannah F. Drake Chanel F. Leong Fei Yu Prof. Dr. Deanna M. D'Alessandro Prof. Dr. Mohamedally Kurmoo Prof. Dr. Jing-Lin Zuo Prof. Dr. Hong-Cai Zhou |
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| Affiliation: | 1. State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210093 P.R. China;2. Department of Chemistry, Texas A&M University, College Station, TX, 77843 USA;3. School of Chemistry, The University of Sydney, Sydney, New South Wales, 2006 Australia;4. Institut de Chimie de Strasbourg, CNRS-UMR7177, Université de Strasbourg, 4 rue Blaise Pascal, Strasbourg, 67000 France |
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| Abstract: | 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)(H2O)9(TTFTB)3] ( 1-RE , where RE=Y, Sm, Gd, Tb, Dy, Ho, and Er) were constructed. The RE9(μ3-OH)13(μ3-O) (H2O)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= 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. |
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| Keywords: | metal–organic frameworks rare-earth clusters redox switchable molecules single-molecule magnets |
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