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Title

Stimuli Responsive Hybrid Magnets: Tuning the Photoinduced Spin-Crossover in Fe(III) Complexes Inserted into Layered Magnets

Authors
Clemente-León, Miguel
Coronado, Eugenio
López-Jordà, Maurici
Waerenborgh, João C.
Desplanches, Cédric
Wang, Hongfeng
Létard, Jean-François
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Published in Journal of the American Chemical Society. 2013, vol. 135, no. 23, p. 8655-8667
Abstract The insertion of a [Fe(sal2-trien)]+ complex cation into a 2D oxalate network in the presence of different solvents results in a family of hybrid magnets with coexistence of magnetic ordering and photoinduced spin-crossover (LIESST effect) in compounds [FeIII(sal2-trien)][MnIICrIII(ox)3]·CHCl3 (1·CHCl3), [FeIII(sal2-trien)][MnIICrIII(ox)3]·CHBr3 (1·CHBr3), and [FeIII(sal2-trien)][MnIICrIII(ox)3]·CH2Br2 (1·CH2Br2). The three compounds crystallize in a 2D honeycomb anionic layer formed by MnII and CrIII ions linked through oxalate ligands and a layer of [Fe(sal2-trien)]+ complexes and solvent molecules (CHCl3, CHBr3, or CH2Br2) intercalated between the 2D oxalate network. The magnetic properties and Mössbauer spectroscopy indicate that they undergo long-range ferromagnetic ordering at 5.6 K and a spin crossover of the intercalated [Fe(sal2-trien)]+ complexes at different temperatures T1/2. The three compounds present a LIESST effect with a relaxation temperature TLIESST inversely proportional to T1/2. The isostructural paramagnetic compound, [FeIII(sal2-trien)][ZnIICrIII(ox)3]·CH2Cl2 (2·CH2Cl2) was also prepared. This compound presents a partial spin crossover of the inserted FeIII complex as well as a LIESST effect. Finally, spectroscopic characterization of the FeIII doped compound [Ga0.99Fe0.01(sal2trien)][MnIICrIII(ox)3]·CH2Cl2 (3·CH2Cl2) shows a gradual and complete thermal spin crossover and a LIESST effect on the isolated FeIII complexes. This result confirms that cooperativity is not a necessary condition to observe the LIESST effect in an FeIII compound.
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Structures
Research group Groupe Hauser
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CLEMENTE-LEÓN, Miguel et al. Stimuli Responsive Hybrid Magnets: Tuning the Photoinduced Spin-Crossover in Fe(III) Complexes Inserted into Layered Magnets. In: Journal of the American Chemical Society, 2013, vol. 135, n° 23, p. 8655-8667. doi: 10.1021/ja402674x https://archive-ouverte.unige.ch/unige:28703

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Deposited on : 2013-06-26

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