Influence of Guest Exchange on the Magnetization Dynamics of Dilanthanide Single‐Molecule‐Magnet Nodes within a Metal–Organic Framework |
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| Authors: | Xuejing Zhang Veacheslav Vieru Xiaowen Feng Jun‐Liang Liu Dr. Zhenjie Zhang Dr. Bo Na Prof. Dr. Wei Shi Prof. Dr. Bing‐Wu Wang Prof. Dr. Annie K. Powell Prof. Dr. Liviu F. Chibotaru Prof. Dr. Song Gao Prof. Dr. Peng Cheng Prof. Dr. Jeffrey R. Long |
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| Affiliation: | 1. Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), State Key Laboratory of Elemento‐Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071 (P. R. China);2. Theory of Nanomaterials Group and INPAC—Institute of Nanoscale Physics and Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, 3001 Heverlee (Belgium);3. Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA);4. Beijing National Laboratory of Molecular Science, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (P. R. China);5. Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstrasse 15, 76131 Karlsruhe (Germany) |
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| Abstract: | Multitopic organic linkers can provide a means to organize metal cluster nodes in a regular three‐dimensional array. Herein, we show that isonicotinic acid N‐oxide (HINO) serves as the linker in the formation of a metal–organic framework featuring Dy2 single‐molecule magnets as nodes. Importantly, guest solvent exchange induces a reversible single‐crystal to single‐crystal transformation between the phases Dy2(INO)4(NO3)2?2 solvent (solvent=DMF (Dy2‐DMF), CH3CN (Dy2‐CH3CN)), thereby switching the effective magnetic relaxation barrier (determined by ac magnetic susceptibility measurements) between a negligible value for Dy2‐DMF and 76 cm?1 for Dy2‐CH3CN. Ab initio calculations indicate that this difference arises not from a significant change in the intrinsic relaxation barrier of the Dy2 nodes, but rather from a slowing of the relaxation rate of incoherent quantum tunneling of the magnetization by two orders of magnitude. |
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| Keywords: | ab initio calculations host– guest systems lanthanides metal– organic frameworks single‐molecule magnets |
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