ABSTRACT
Two ion-pair Fe(iii) complexes (PPh4)[FeIII(HATD)2]·2H2O (1, H3ATD = azotetrazolyl-2,7-dihydroxynaphthalene) and [FeII(phen)3][FeIII(HATD)2]2·3DMA·3.5H2O (2, phen = 1,10-phenanthroline, DMA = N,N-dimethylformamide) were synthesized by employing the tridentate ligand H3ATD. Crystal structure analyses reveal that complexes 1 and 2 consist of FeIII ions in an octahedral environment where a FeIII ion is coordinated by two HATD2- ligands forming the [FeIII(HATD)2]- core. The shortest cationanion distance between the phosphorus ion of the (PPh4)+ cation and the ferric ion of the [FeIII(HATD)2]- anion is 13.190 Å in complex 1, whereas that between the ferrous ion of the [FeII(Phen)3]2+ cation and the ferric ion of the [FeIII(HATD)2]- anion is 7.821 Å in complex 2. C-HC and C-HO hydrogen interactions between the [FeII(phen)3]2+ cation and the [FeIII(HATD)2]- anion are observed in 2. Face-to-face π-π stacking interactions between naphthalene rings with the separated interplanar center to center distances of 3.421-3.680 Å were observed, which result in a one-dimensional supramolecular chain in complexes 1 and 2. Magnetic measurements show that complex 1 is in the low-spin (LS) state below 500 K, whereas 2 undergoes a high temperature spin crossover (SCO) between 360 and 500 K. Magneto-structural relationship studies reveal that π-stacking, hydrogen interactions and Coulomb interactions between the [FeIII(HATD)2]- anion and the [FeII(phen)3]2+ cation play a crucial role in the high temperature Fe(iii) SCO behaviour of complex 2.
ABSTRACT
By employing the ligand azotetrazolyl-2,7-dihydroxynaphthalene (H3ATD), two linear trinuclear mixed-valence cobalt complexes [CoIICoIII2(HATD)4(H2O)4]·4DMA·3H2O (1, DMA = N,N-dimethylacetamide) and [CoIICoIII2(HATD)4(DMF)2(H2O)2]·2DMF·2H2O (2, DMF = N,N-dimethylformamide) were synthesized. Two [2 × 2] grid-like tetranuclear ion-pair complexes [CoII2CoIII2(HATD)4(bpp)2(H2O)2][CoIII(HATD)2]2·8DMF·6H2O (3, bpp = 2,6-di(pyrazol-1-yl)pyridine) and [CoII2CoIII2(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
The unique electronic configurations of lanthanide(III) ions generate abundant electronic energy levels, resulting in the fantastic magnetic and optical multifunctional properties of lanthanide complexes. Here, 2-hydroxy-3-methoxybenzoic acid (H2MBA) was used to construct four Dy(III) and Tb(III) complexes containing two isostructural dinuclear complexes of [Ln2(HMBA)2(MBA)2(DMF)2(H2O)2]·6H2O [Ln = Dy (1), Tb (2); DMF = N,N-dimethylformamide] and two other isostructural beltlike one-dimensional-chain complexes of [NH4][Ln(HMBA)4] [Ln = Dy (3), Tb (4)]. Fluorescence measurements reveal that H2MBA can sensitize Dy(III) and Tb(III) characteristic luminescence. Furthermore, complex 3 can emit white light under UV-light irradiation originating from a dichromatic mixture of a blue emission of H2MBA and a dominating yellow emission of Dy3+ ions. Magnetic susceptibility measurements show that two Dy(III) complexes are single-molecule magnets with anisotropy barriers of 90(2) and 31(5) cm-1 for 1 and 3, respectively. The magnet-luminescence-structure correlations as well as relaxation pathways are investigated by ab initio calculations and fluorescent spectrometry.
ABSTRACT
One-dimensional zig-zag chain and two-dimensional network dysprosium(iii) single-molecule toroics with anisotropy barriers of about 5 and 31 cm-1 under a zero dc field are reported. These are the first one- and two- dimensional homometallic single-molecule toroics reported to date. Furthermore, the two complexes also display white-light emission under UV-light irradiation.
