Influence of Guest Exchange on the Magnetization Dynamics of Dilanthanide Single-Molecule-Magnet Nodes within a Metal-Organic Framework

Xuejing Zhang; Veacheslav Vieru; Xiaowen Feng; Jun-Liang Liu; Zhenjie Zhang; Bo Na; Wei Shi; Bing-Wu Wang; Annie K Powell; Liviu F Chibotaru; Song Gao; Peng Cheng; Jeffrey R Long

doi:10.1002/anie.201503636

Influence of Guest Exchange on the Magnetization Dynamics of Dilanthanide Single-Molecule-Magnet Nodes within a Metal-Organic Framework

Angew Chem Int Ed Engl. 2015 Aug 17;54(34):9861-5. doi: 10.1002/anie.201503636. Epub 2015 Jun 26.

Authors

Xuejing Zhang¹, Veacheslav Vieru², Xiaowen Feng³, Jun-Liang Liu³, Zhenjie Zhang¹, Bo Na¹, Wei Shi⁴, Bing-Wu Wang⁵, Annie K Powell⁶, Liviu F Chibotaru⁷, Song Gao⁸, Peng Cheng¹, Jeffrey R Long⁹

Affiliations

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 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). shiwei@nankai.edu.cn.
⁵ 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).
⁶ Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstrasse 15, 76131 Karlsruhe (Germany).
⁷ Theory of Nanomaterials Group and INPAC-Institute of Nanoscale Physics and Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, 3001 Heverlee (Belgium). Liviu.Chibotaru@chem.kuleuven.be.
⁸ 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). gaosong@pku.edu.cn.
⁹ Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720 (USA). jrlong@berkeley.edu.

PMID: 26119180
DOI: 10.1002/anie.201503636

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.

Keywords: ab initio calculations; host-guest systems; lanthanides; metal-organic frameworks; single-molecule magnets.