Premium
Influence of Guest Exchange on the Magnetization Dynamics of Dilanthanide Single‐Molecule‐Magnet Nodes within a Metal–Organic Framework
Author(s) -
Zhang Xuejing,
Vieru Veacheslav,
Feng Xiaowen,
Liu JunLiang,
Zhang Zhenjie,
Na Bo,
Shi Wei,
Wang BingWu,
Powell Annie K.,
Chibotaru Liviu F.,
Gao Song,
Cheng Peng,
Long Jeffrey R.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201503636
Subject(s) - single molecule magnet , magnetization , chemistry , relaxation (psychology) , quantum tunnelling , lanthanide , single crystal , solvent , molecule , magnet , oxide , metal , cluster (spacecraft) , crystallography , metal organic framework , crystal (programming language) , isonicotinic acid , condensed matter physics , ion , magnetic field , adsorption , physics , organic chemistry , psychology , social psychology , quantum mechanics , computer science , programming language , hydrazide
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 Dy 2 single‐molecule magnets as nodes. Importantly, guest solvent exchange induces a reversible single‐crystal to single‐crystal transformation between the phases Dy 2 (INO) 4 (NO 3 ) 2 ⋅2 solvent (solvent=DMF (Dy 2 ‐DMF), CH 3 CN (Dy 2 ‐CH 3 CN)), thereby switching the effective magnetic relaxation barrier (determined by ac magnetic susceptibility measurements) between a negligible value for Dy 2 ‐DMF and 76 cm −1 for Dy 2 ‐CH 3 CN. Ab initio calculations indicate that this difference arises not from a significant change in the intrinsic relaxation barrier of the Dy 2 nodes, but rather from a slowing of the relaxation rate of incoherent quantum tunneling of the magnetization by two orders of magnitude.