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A new compound of azotetrazole-3-hydroxy-2-naphthoic acid (H3ATNA) has been successfully synthesized and characterized. By controlling the ratio of metal ions to the ligand and the pH value of solution, mononuclear, dinuclear and tetranuclear dysprosium(III) complexes [Et3NH]3[Dy(HATNA)3]·5H2O (1), [Dy2(HATNA)3(DMF)(H2O)]·2DMF·CH3OH·2H2O (2) and [Et3NH]6[Dy4(ATNA)6(H2O)2]·DMF·2CH3CN·8H2O (3) were synthesized and characterized by X-ray diffraction crystallography (DMF = N,N-dimethylformamide). Crystallographic data demonstrate that the neutral H3ATNA exists as a hydrazone tautomer. Complex 1 is a mononuclear structure, in which the Dy(III) ion is a nine-coordinated ion surrounded by three tridentate HATNA− ligands. Complex 2 shows a dinuclear structure, which is bridged by three μ1,1-hydroxyl groups of three HATNA− ligands. In complex 2, the Dy(III)1 ion is a nine-coordinated ion surrounded by three tridentate HATNA− ligands, while Dy(III)2 is an eight coordinated atom with three tridentate HATNA− ligands, one DMF and one water molecule. Complex 3 displays a tetranuclear structure, which can be approximately considered as two μ1,3-carboxyl groups of ATNA3− ligands linking complex 2. The magnetic properties of 1–3 were investigated. Complexes 2 and 3 display slow magnetic relaxation in a zero dc field. [ABSTRACT FROM AUTHOR]

Two mixed-valence Co(II)/Co(III) complexes of [CoII(phen)3][CoIII(HATD)2]2·3DMA·3.5H2O (1), and [CoII(terpy)2][CoIII(HATD)2]2·4DMA·H2O (2), (phen = 1,10-phenanthroline, terpy = 2,2′:6′,2′′-terpyridine, H3ATD = azotetrazolyl-2,7-dihydroxynaphthalene, DMA = N,N-dimethylacetamide) were synthesized and their crystal structures were characterized. Crystal structure analyses reveal that complexes 1 and 2 consist of CoIII and CoII ions in an octahedral environment where the CoII ion is coordinated by three phen ligands and two terpy ligands, respectively. Magnetic measurements show that complex 1 displays field induced single-molecule magnet behavior, whereas 2 undergoes a gradual thermal spin crossover (SCO). [ABSTRACT FROM AUTHOR]

Three mononuclear, dinuclear and one-dimensional dysprosium(III) complexes based on 3-azotriazolyl-2,6-dihydroxybenzoic acid (H4ATB) of [Dy(H3ATB)3]·3H2O (1), [Dy2(H2ATB)2(H2DHB)2(H2O)4]·2CH3CN·5H2O (2), and [Dy2(H2ATB)2(DCB)(DMF)2(H2O)2]·4DMF (3) were synthesized and structurally characterized by X-ray single crystal diffraction (H3DHB = 2,6-dihydroxybenzoic acid, H2DCB = 1,4-dicarboxybenzene). Complex 1 was used as a precursor to synthesize complexes 2 and 3, and 2 was further used to synthesize 3. Complex 1 is a mononuclear complex, in which the Dy(III) ion is in a nine-coordinated structure surrounded by three tridentate chelate H3ATB− ligands. Complex 2 displays a dinuclear structure bridged by two μ2 carboxyl groups of two H2DHB− ligands and two μ1,1-O atoms from the phenolic hydroxyl groups of two H2ATB2− ligands. Complex 3 shows a one-dimensional structure formed by two bridging DCB2− ligands. The magnetic measurements were performed on three complexes 1–3, and they showed different magnetic behavior. Complex 1 shows a field-induced slow magnetic relaxation. Complexes 2 and 3 display distinct slow magnetic relaxation under zero dc field with energy barriers (Ueff) of 26(2) cm−1 and 11(1) cm−1, respectively. The magnetic behavior of three complexes 1–3 was investigated by ab initio calculations. [ABSTRACT FROM AUTHOR]

By employing the ligand azotetrazolyl-2,7-dihydroxynaphthalene (H3ATD), two linear trinuclear mixed-valence cobalt complexes [CoIICo III2 (HATD)4(H2O)4]·4DMA·3H2O (1, DMA = N,N-dimethylacetamide) and [CoIICo III2 (HATD)4(DMF)2(H2O)2]·2DMF·2H2O (2, DMF = N,N-dimethylformamide) were synthesized. Two [2 × 2] grid-like tetranuclear ion-pair complexes [Co II2 Co III2 (HATD)4(bpp)2(H2O)2][CoIII(HATD)2]2·8DMF·6H2O (3, bpp = 2,6-di(pyrazol-1-yl)pyridine) and [Co II2 Co III2 (HATD)4(bpp)2(H2O)2][CoIII(HATD)2]2·8DMSO·4MeOH (4, DMSO = dimethyl sulphoxide) were obtained by the reaction of complex 1/2 with tridentate-chelating bpp in DMF and DMSO, respectively. The single-crystal X-ray diffraction analysis indicated that complexes 1 and 2 have a similar core, in which the DMA in 1 acts as a guest molecule, and the DMF in 2 acts as a coordinated molecule and guest molecule. Complexes 3 and 4 are isostructural. All the Co(II) ions in 1–4 are present in a distorted octahedral geometry. The ac susceptibility measurements show that all complexes display frequency-dependent peaks in the out-of-phase (χm′′) component of the alternating-current (ac) magnetic susceptibility data, which is the characteristic behavior of single molecule magnets (SMMs). [ABSTRACT FROM AUTHOR]

A new salicylaldehyde-based azo dye 5-azotriazolyl-3-methoxysalicylaldehyde (H2TMSA) and its two Ln3+ complexes {[Ln(HTMSA)3(H2O)2][Ln(HTMSA)3(DMF)(H2O)]}·15H2O (Ln = Dy(1) and Tb(2)) have been synthesized and characterized by IR, Raman, 1H NMR and single-crystal X-ray diffraction techniques. H2TMSA shows an azo form in acidic (pH ＜ 5.05) and strong basic (pH ＞ 12.41) conditions, and a pH-dependent azo-hydrazone tautomerism in the range of pH 5.05 to 12.41, which is demonstrated by the time-dependent density functional theory (TD-DFT) calculations. Single-crystal X-ray diffraction reveals that 1 and 2 are isostructural complexes in which the Ln3+ ions are surrounded by six oxygen atoms from three dichelate HTMSA− ligands and two oxygen atoms from two solvent molecules forming a distorted square-antiprismatic geometry. Complex 1 shows distinct slow magnetic relaxation under a zero dc field, while 2 displays field-induced slow magnetic relaxation. Ab initio calculations were performed on the two complexes to understand their magnetic anisotropy and their different magnetic dynamics. [ABSTRACT FROM AUTHOR]