期刊
DALTON TRANSACTIONS
卷 46, 期 8, 页码 2680-2689出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6dt04900a
关键词
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资金
- EU
- Spanish MINECO [CTQ2014-52758-P, MAT-2014-56143-R]
- Unidad de Excelencia Maria de Maeztu [MDM-2015-0538]
- Generalitat Valenciana (Prometeo)
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 [Fe-II(L-1)(2)](ClO4)(2 center dot)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 [Fe-II(L-1)(CH3CN)(2)(H2O)](ClO4)(2)center dot 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 [Fe-II(L-1)(2)][(MnCrIII)-Cr-II(ox)(3)](2)center dot(CH3NO2)(6 center dot)(CH3OH)center dot(H2O)(2) (3) and the 3D compound of the formula [Fe-II(L-1)(2)][(MnCrIII)-Cr-II(ox)(3)](2)center dot(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 similar to 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 similar to 50% from 230 to 400 K. 3 and 4 do not present the LIESST effect.
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