Photomagnetic properties of an Fe(ii) spin-crossover complex of 6-(3,5-diamino-2,4,6-triazinyl)-2,2'-bipyridine and its insertion into 2D and 3D bimetallic oxalate-based networks.
The Fe(ii) complex of the L1ligand (L1= 6-(3,5-diamino-2,4,6-triazinyl)-2,2'-bipyridine) has been used as a templating cation for the growth of oxalate-based networks. The magnetic characterization of the [FeII(L1)2](ClO4)2·CH3CN (1) precursor in the solid state has been performed for the first time showing that the low-spin (LS) state is predominating from 2 to 400 K with 10% of Fe(ii), which undergoes a gradual and irreversible spin-crossover above 350 K. 1 presents the LIESST effect with a photo-conversion close to 25% and a T(LIESST) of 49 K. During the preparation of 1, a secondary product of the formula [FeII(L1)(CH3CN)2(H2O)](ClO4)2·CH3CN (2) has been obtained. The magnetic characterization of 2 shows that it contains high-spin (HS) Fe(ii). 1 has afforded two novel oxalate-based compounds, the 2D compound of the formula [FeII(L1)2][MnIICrIII(ox)3]2·(CH3NO2)6·(CH3OH)·(H2O)2(3) and the 3D compound of the formula [FeII(L1)2][MnIICrIII(ox)3]2·(CH3CN)3(4), which have been obtained by changing the synthetic conditions. The magnetic properties show that in 3 the inserted Fe(ii) cation remains in the LS state from 2 to 340 K and presents a partial and irreversible spin-crossover of ∼20% at higher temperatures. In 4, most of the Fe(ii) complexes remain in the LS state from 2 to 230 K and present a partial and irreversible spin-crossover of ∼50% from 230 to 400 K. 3 and 4 do not present the LIESST effect.
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán 2, 46980 Paterna, Spain. miguel.clemente@uv.es.
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Sánchez-Sánchez
CNRS, Univ Bordeaux, ICMCB UPR 9048, F-33608 Pessac, France.
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Desplanches
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán 2, 46980 Paterna, Spain. miguel.clemente@uv.es.
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Clemente-Juan
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán 2, 46980 Paterna, Spain. miguel.clemente@uv.es.
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http://orcid.org/0000-0003-3868-1078
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Clemente-León
Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, C/Catedrático José Beltrán 2, 46980 Paterna, Spain. miguel.clemente@uv.es.
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Coronado