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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 [Fe^III(sal₂-trien)][Mn^IICr^III(ox)₃]Â·CHCl₃ (1Â·CHCl₃), [Fe^III(sal₂-trien)][Mn^IICr^III(ox)₃]Â·CHBr₃ (1Â·CHBr₃), and [Fe^III(sal₂-trien)][Mn^IICr^III(ox)₃]Â·CH₂Br₂ (1Â·CH₂Br₂). The three compounds crystallize in a 2D honeycomb anionic layer formed by Mn^II and Cr^III 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 MÃ¶ssbauer 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 T_1/2. The three compounds present a LIESST effect with a relaxation temperature T_LIESST inversely proportional to T_1/2. The isostructural paramagnetic compound, [Fe^III(sal₂-trien)][Zn^IICr^III(ox)₃]Â·CH₂Cl₂ (2Â·CH₂Cl₂) was also prepared. This compound presents a partial spin crossover of the inserted Fe^III complex as well as a LIESST effect. Finally, spectroscopic characterization of the Fe^III doped compound [Ga_0.99Fe_0.01(sal₂trien)][Mn^IICr^III(ox)₃]Â·CH₂Cl₂ (3Â·CH₂Cl₂) shows a gradual and complete thermal spin crossover and a LIESST effect on the isolated Fe^III complexes. This result confirms that cooperativity is not a necessary condition to observe the LIESST effect in an Fe^III compound.

Stimuli Responsive Hybrid Magnets: Tuning the Photoinduced Spin-Crossover in Fe(III) Complexes Inserted into Layered Magnets M. Clemente-León, E. Coronado, M. López-Jordà, J.C. Waerenborgh, C. Desplanches, H. Wang, J.-F. Létard, A. Hauser and A. Tissot Journal of the American Chemical Society, 135 (23) (2013), p8655-8667 DOI:10.1021/ja402674x \| unige:28703 \| Abstract \| Article HTML \| Article PDF
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 [Fe^III(sal₂-trien)][Mn^IICr^III(ox)₃]Â·CHCl₃ (1Â·CHCl₃), [Fe^III(sal₂-trien)][Mn^IICr^III(ox)₃]Â·CHBr₃ (1Â·CHBr₃), and [Fe^III(sal₂-trien)][Mn^IICr^III(ox)₃]Â·CH₂Br₂ (1Â·CH₂Br₂). The three compounds crystallize in a 2D honeycomb anionic layer formed by Mn^II and Cr^III 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 MÃ¶ssbauer 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 T_1/2. The three compounds present a LIESST effect with a relaxation temperature T_LIESST inversely proportional to T_1/2. The isostructural paramagnetic compound, [Fe^III(sal₂-trien)][Zn^IICr^III(ox)₃]Â·CH₂Cl₂ (2Â·CH₂Cl₂) was also prepared. This compound presents a partial spin crossover of the inserted Fe^III complex as well as a LIESST effect. Finally, spectroscopic characterization of the Fe^III doped compound [Ga_0.99Fe_0.01(sal₂trien)][Mn^IICr^III(ox)₃]Â·CH₂Cl₂ (3Â·CH₂Cl₂) shows a gradual and complete thermal spin crossover and a LIESST effect on the isolated Fe^III complexes. This result confirms that cooperativity is not a necessary condition to observe the LIESST effect in an Fe^III compound.

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