Issue 8, 2017

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

Abstract

The Fe(II) complex of the L1 ligand (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.

Graphical abstract: 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

Supplementary files

Article information

Article type
Paper
Submitted
29 Dec 2016
Accepted
26 Jan 2017
First published
26 Jan 2017

Dalton Trans., 2017,46, 2680-2689

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

C. Sánchez-Sánchez, C. Desplanches, J. M. Clemente-Juan, M. Clemente-León and E. Coronado, Dalton Trans., 2017, 46, 2680 DOI: 10.1039/C6DT04900A

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