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A SIM‐MOF: Three‐Dimensional Organisation of Single‐Ion Magnets with Anion‐Exchange Capabilities
Author(s) -
Baldoví José J.,
Coronado Eugenio,
GaitaAriño Alejandro,
Gamer Christoph,
GiménezMarqués Mónica,
Mínguez Espallargas Guillermo
Publication year - 2014
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.201402255
Subject(s) - lanthanide , magnet , trifluoromethanesulfonate , ion , metal organic framework , relaxation (psychology) , chemistry , crystallography , ion exchange , materials science , chemical physics , nanotechnology , physics , catalysis , organic chemistry , social psychology , psychology , adsorption , quantum mechanics
Abstract The formation of a metal–organic framework (MOF) with nodes that have single‐molecule magnet (SMM) behaviour has been achieved by using mononuclear lanthanoid analogues, also known as single‐ion magnets (SIMs), which enormously simplifies the challenging issue of making SMM‐MOFs. Here we present a rational design of a family of MOFs, [ Ln(bipyNO) 4 ](TfO) 3 ⋅ x solvent (Ln=Tb ( 1 ); Dy ( 2 ); Ho ( 3 ); Er ( 4 ); TfO=triflate), in which the lanthanoid centres have an square‐antiprismatic coordination environment suitable for SIM behaviour. Magnetic measurements confirm the existence of slow magnetic relaxation typical of SMMs, which has been rationalised by means of a radial effective charge model. In addition, we have explored the incorporation of bulky polyoxometalates (POMs) into the cavities of the SIM‐MOF by anion exchange, finding that they do not interfere with the slow magnetic relaxation. This demonstrates the robustness of the frameworks and opens the possibility of incorporating non‐innocent anions.