RESUMEN
Crystal structures and magnetic properties of three one-dimensional (1D) azido-bridged cobalt(II) chains with different amide ligands (L), [Co2(N3)4(DMF)3] (1), [Co4(N3)8(DEF)5] (2), and [Co2(N3)4(DIPF)2] (3) (DMF = N,N-dimethylformamide, DEF = N,N-diethylformamide, and DIPF = N,N-diisopropylformamide), are reported to investigate the influence of L on their structures and magnetic properties. Single-crystal X-ray crystallographic analysis revealed that, although 1-3 all consist of cobalt chains bridged by end-on (EO) azides, the coordination geometry of the CoII ions and the repeating units of the 1D structures are quite different. As the size of L increases, the ratio of L to CoII decreases from 6:4 in 1 to 5:4 and 4:4 in 2 and 3, respectively. In 1, two [CoN5O1] and two [CoN4O2] distorted octahedra form the {[CoN5O1][CoN4O2]2[CoN5O1]} tetramers (denoted as Co4A), which are linked to each other by sharing the N-N edge to form the chain. Similarly, the chain structure of 3 is constructed from a similar tetramer unit {[CoN5][CoN4O2]2[CoN5]} (denoted as Co4B), where half of the CoII centers are in the [CoN5] trigonal bipyramid because of the larger steric effect of the DIPF ligand, while, for compound 2 of the medium-sized amide, it has the transition structure between those of 1 and 3. The chain is composed of two different repeating units: Co4A unit similar to that in 1 and Co4B unit similar to that in 3. Because of their similar structures, compounds 1-3 exhibit analogical magnetic properties. Direct-current magnetic measurements demonstrated that all compounds show intrachain ferromagnetic coupling through the EO azides and interchain anti-ferromagnetic interactions. Alternating-current data revealed the slow magnetic relaxation in the anti-ferromagnetic ordered phases. While compound 1 exhibits spin glass behavior, compounds 2 and 3 behave as the single-chain magnets. This difference might come from the interference of the anti-ferromagnetic ordering on the magnetic dynamic of the magnetic chain.
RESUMEN
Two cyanide-bridged compounds based on the FeII cation and the anisotropic [MoIII(CN)7]4- anion, namely, {Fe2(H2O)5[Mo(CN)7]·5H2O}n (1) and {[NH2(CH3)2]2Fe5(H2O)10[Mo(CN)7]3·8H2O}n (2), have been prepared. Single crystal X-ray analyses revealed that their structures exhibit different three-dimensional topologies as a result of the addition of [NH2(CH3)2]+ during the synthesis of 2. For both 1 and 2, the geometry of the [Mo(CN)7]4- unit is a slightly distorted capped trigonal prism; all FeII centers are hexacoordinate and adopt a distorted octahedral configuration. Compound 1 is a three-nodal 3,4,7-connected net with the point symbol of {4.62}{45.6}{46.612.83}, while compound 2 is a five-nodal 4,4,4,6,7-connected net with the point symbol of {44.62}{45.6}4{46.67.82}{49.611.8}2. Magnetic studies revealed that both compounds exhibit magnetic ordering below 65 K. Apart from the plethora of MnII-[Mo(CN)7]4- compounds documented in the literature, these two FeII-[Mo(CN)7]4- compounds are the only other [Mo(CN)7]4- extended structures to be characterized by single crystal structures to date.
RESUMEN
Four 2p-4f LnIII-radical complexes, [(NIT-2-Pm)Ln(hfac)3]·0.5C7H16 (NIT-2-Pm = 2-pyrimidyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxy-3-oxide, hfac = hexafluoroacetylacetonato, Ln = Tb (1), Dy (2), Ho (3) and Er (4)), and four 4f-2p-4f LnIII-radical-LnIII complexes, [(µ-NIT-2-Pm)Ln2(hfac)6(H2O)2]·0.5C7H16 (Ln = Tb (5), Dy (6), Ho (7) and Er (8)) have been synthesized and characterized structurally and magnetically. These compounds can be selectively obtained by controlling the reaction ratio of Ln(hfac)3·2H2O to the radical ligand NIT-2-Pm. The crystal structures show that in the former four complexes 1-4, the NIT-2-Pm radical acts as a terminal bidentate ligand chelating to one LnIII ion, while in 5-8, the NIT-2-Pm acts as a bridging ligand linking two LnIII ions to form a binuclear three-spin system. Magnetic studies revealed that complexes 1-4 and 6 show frequency-dependent ac magnetic susceptibilities, suggesting a possible single-molecule magnet behavior. To the best of our knowledge, complexes 3 and 4 are the first Ho-NIT and Er-NIT compounds showing slow magnetic relaxation. Compounds 5-8 represent a rare family of compounds showing the NIT bridged 4f-2p-4f three-spin motif, while complex 6 is a rare NIT bridged multinuclear lanthanide compound possessing SMM-like behaviour. Ab initio calculations were performed on all these complexes. The fitting of the magnetic susceptibilities of these compounds suggests weak antiferromagnetic coupling between the LnIII and NIT radical in 1-8 and weak ferromagnetic LnIII-LnIII interactions in 5-8.