Hong-Ling Gao

Ligand Field Affected Single-Molecule Magnet Behavior of Lanthanide(III) Dinuclear Complexes with an 8-Hydroxyquinoline Schiff Base Derivative as Bridging Ligand

New dinuclear lanthanide(III) complexes based on an 8-hydroxyquinoline Schiff base derivative and β-diketonate ligands, [Ln2(hfac)4(L)2] (Ln(III) = Gd (1), Tb (2), Dy (3), Ho (4), Er (5)), [Ln2(tfac)4(L)2] (Ln(III) = Gd (6), Tb (7), Dy (8), Ho (9)), and [Dy(bfac)4(L)2·C7H16] (10) (L = 2-[[(4-fluorophenyl)imino] methyl]-8-hydroxyquinoline, hfac = hexafluoroacetylacetonate, tfac = trifluoroacetylacetonate, and bfac = benzoyltrifluoroacetone), have been synthesized. The single-crystal X-ray diffraction data show that complexes 1-10 are phenoxo-O-bridged dinuclear complexes; each eight-coordinated center Ln(III) ion is in a slightly distorted dodecahedral geometry with two bidentate β-diketonate coligands and two μ2-O bridging 8-hydroxyquinoline Schiff base derivative ligands. The magnetic study reveals that 1 and 6 display cryogenic magnetic refrigeration properties, whereas complexes 3, 8, and 10 show different SMM behaviors with energy barriers of 6.77 K for 3, 19.83 K for 8, and 25.65 K for 10. Meanwhile, slow magnetic relaxation was observed in 7, while no out-of-phase alternating-current signals were found for 2. The different dynamic magnetic behaviors of two Tb2 complexes and the three Dy2 complexes mainly derive from the tiny crystal structure changes around the Ln(III) ions. It is also proved that the β-diketonate coligands can play an important role in modulating magnetic dynamics of the lanthanide 8-hydroxyquinoline Schiff base derivative system.

Structures and Magnetic Properties of Ferromagnetic Coupling 2D Ln-M Heterometallic Coordination Polymers (Ln = Ho, Er; M = Mn, Zn)

Four new heterometallic coordination polymers have been successfully synthesized, namely, {[Ho(2)(HCAM)(6)Mn(3)(H(2)O)(12)].17.5H(2)O}(n) (1), {[Er(2)(HCAM)(6)Mn(3)(H(2)O)(12)].17.5H(2)O}(n) (2), {[Ho(2)(HCAM)(6)Zn(3)(H(2)O)(12)].26H(2)O}(n) (3), and {[Er(2)(HCAM)(6)Zn(3)(H(2)O)(12)].26H(2)O}(n) (4) (H(3)CAM = chelidamic acid). X-ray crystallographic studies reveal that coordination polymers 1-4 are isostructural and crystallized in the rhombohedral crystal system, space group R3. These compounds comprise a 2D honeycomb-type framework. A 2D water sheet is first found in 3 and 4, which exhibits a novel topological motif. The magnetic results for 1-4 show that ferromagnetic interactions take place between the Ho(3+)/Er(3+) and Mn(2+) ions within 1 and 2.

Modulating single-molecule magnet behaviour of phenoxo-O bridged lanthanide(III) dinuclear complexes by using different β-diketonate coligands

Three dinuclear Dy(III) complexes, [Dy2(tfa)4L2] (1), [Dy2(TTA)4L2] (2) and [Dy2(dbm)4L2·2CH3CN·0.5H2O] (3) (tfa = trifluoroacetylacetonate, TTA = 2-thenoyltrifluoroacetone, dbm = dibenzoylmethane and HL = 2-[((4-bromophenyl)-imino)methyl]-8-hydroxyquinoline, have been synthesized, and structurally and magnetically characterized. The Dy(III) ions are eight-coordinated with two bidentate β-diketonate and two μ2-O bridging 8-hydroxyquinoline Schiff base ligands. Magnetic studies reveal that 1–3 exhibit different magnetic relaxation behaviors with the anisotropic barriers of 9.61 K (1), 54.81 K (2) and 30.98 K (3), respectively. The different magnetic relaxation behaviors of the three Dy2 complexes originate from the different chemical environments of the central Dy3+ ions with different β-diketonate coligands.

Two three-dimensional lanthanide frameworks exhibiting luminescence increases upon dehydration and novel water layer involving in situ decarboxylation.

Two three-dimensional polymeric Tb(III) and Yb(III) frameworks, namely, {[Tb3(Hptc)(ptc)(pdc)(H2O)6]·2H2O}n (1) and {[Yb2(ptc)(ox)(H2O)5]·7H2O}n (2) (H4ptc = pyridine-2,3,5,6-tetracarboxylic acid, H2pdc = pyridine-3,5-dicarboxylic acid, ox = oxalate), have been synthesized by a hydrothermal method and characterized by infrared spectra, elemental analysis, powder X-ray diffraction, thermogravimetric analysis, and single-crystal X-ray diffraction. Framework 1 shows an interesting three-dimensional (8,8)-connected net with a Schläfli symbol of (3(3)·4(18)·5(5)·6(2))2(3(6)·4(14)·5(7)·6), while 2 exhibits an unusual (4,8)-connected sqc21 net with a Schläfli symbol of (3(2)·4(2)·5(2))(3(4)·4(8)·5(12)·6(4)). Luminescence studies of 1 reveal that the luminescence intensity increases when the framework is dehydrated.

Auxiliary ligand-assisted structural diversities of three metal–organic frameworks with potassium 1H-1,2,3-triazole-4,5-dicarboxylic acid: syntheses, crystal structures and luminescence properties

Three metal–organic frameworks (MOFs) with d10 metal ions, namely, {[Zn3(TDA)2(bpy)3]·(bpy)·10.5H2O}n (1), {[Zn3(TDA)2(azopy)2.5(H2O)]·4H2O}n (2) and {[Cd2K3(TDA)(HTDA)2(H2O)4]}n (3) (KH2TDA = potassium 1H-1,2,3-triazole-4,5-dicarboxylic acid, bpy = 4,4′-bipridine, azopy = 4,4′-azobispridine), have been successfully synthesized from KH2TDA with the aid of three different length-controllable auxiliary ligands and characterized by infrared spectra, elemental analysis, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction. MOF 1 shows an interesting three-dimensional (3D) (3,4,4,4)-connected KAVGAQ framework with a Schlafli symbol of {63}2{64·102}{64·82}2, which can be extended by 2D layers and bpy pillars. MOFs 2 and 3 also display 3D framework structures, corresponding to a 6-connected {44·611} net and a (6,12)-connected {312·430·520·64}{36·48·5} net, respectively. Moreover, a novel coordination mode of H3TDA is observed in 3. The luminescence properties of 1–3 are investigated.

Syntheses, structures, and photoluminescence of lanthanide coordination polymers with pyridine-2,3,5,6-tetracarboxylic acid

Six lanthanide(III) coordination polymers with the formulae {[Ln(Hpdtc)(H2O)3]·H2O}n [Ln = La (1), Ce (2), Pr (3)], {[Ln(Hpdtc)(H2O)2]·2H2O}n [Ln = Eu (4), Tb (5)] and {SmK(pdtc)(H2O)4}n (6) (H4pdtc = pyridine-2,3,5,6-tetracarboxylic acid) have been synthesized by reacting the corresponding rare earth salts or oxides with H4pdtc under hydrothermal conditions. In the three kinds of structure, H4pdtc displays three different coordination modes. H4pdtc is an elegant ligand with rich coordination sites and low symmetry, but has seldom been used to synthesize complexes. 1–6 are the first examples from lanthanide ions and H4pdtc. Furthermore, the novel wave-like T3(2)4(2)6(2) water tape with (H2O)4 as the substructure is present in complex 6. The two complexes of Eu(III) and Tb(III) exhibit the corresponding characteristic luminescence.

Novel lanthanide coordination polymers based on bis-tridentate chelator pyrazine-2,3,5,6-tetracarboxylate with nano-channels and water clusters

Three novel lanthanide coordination polymers with large channels and water clusters, [Yb2(pztc)1.5(H2O)6]·7H2O (1), [Lu2(pztc)1.5(H2O)6]·7.5H2O (2) and [Er2(pztc)1.5(H2O)6]·7H2O (3), have been synthesized by the reactions of pyrazine-2,3,5,6-tetracarboxylic acid (H4pztc) and Ln(III) salts in aqueous solution at room temperature or under hydrothermal conditions, and characterized by X-ray crystallography, elemental analysis, IR, UV-vis and thermal gravimetric analysis (TGA). Single crystal X-ray diffraction determination indicates that the Ln(III) ions were coordinated by three tridentate cheated pztc4− ligands and bis-tridentate cheated pztc4− ligands bridged Ln(III) ions to form hexanuclear metal ring structures with nano-channels which were filled with (H2O)14clusters.

Single-Molecule-Magnet Behavior and Fluorescence Properties of 8-Hydroxyquinolinate Derivative-Based Rare-Earth Complexes

Five tetranuclear rare-earth complexes, [RE4(dbm)4L6(μ3-OH)2] [HL = 5- (4-fluorobenzylidene)-8-hydroxylquinoline; dbm = 1,3-diphenyl-1,3-propanedione; RE = Y (1), Eu (2), Tb (3), Dy (4), Lu (5)], have been synthesized and completely characterized. The X-ray structural analyses show that each [RE4] complex is of typical butterfly or rhombus topology. Each RE(III) center exists in an eight-coordinated square-antiprism environment. Magnetic studies reveal that complex 4 displays single-molecule-magnet behavior below 10 K under a zero direct-current field, with an effective anisotropy barrier (ΔE/kB = 56 K). The fluorescence properties of complexes 1-5 were also investigated. Complexes 2-4 showed their characteristic peaks for the corresponding RE(III) center, while complexes 1 and 5 showed the same emission peaks with the ligand when they were excited at the same wavelength.

ds-Block metal ions catalyzed decarboxylation of pyrazine-2,3,5,6-tetracarboxylic acid and the complexes obtained from hydrothermal reactions and novel water clusters

The factors that influence the decarboxylation of pyrazine-2,3,5,6-tetracarboxylic acid (H4pztc) under hydrothermal conditions were investigated. Higher temperature and lower pH are very effective promoters for the decarboxylation of H4pztc in the presence of ds-block metal ions. Four novel complexes of H4pztc and four complexes from the decarboxylation of H4pztc, [Zn2(pz25dc)(phen)4](NO3)2·10H2O (1), [Zn2(pztc)(phen)4]·12H2O (2), {[Zn2(pztc)(bpy)2(H2O)2]·2H2O}n (3), [Cu2(pz25dc)(phen)4](NO3)2·10H2O (4), {[Cu2(pztc)(bpy)2 H2O]·4H2O}n (5), [Cu2(H2pztc)(bpy)2(H2O)2](NO3)2·2H2O (6), [Cd(pz26dc)(phen)(H2O)2] (7) and [Cd(pz26dc)(bpy)(H2O)2] (8) (pz25dc = pyrazine-2,5-dicarboxylate, pz26dc = pyrazine-2,6-dicarboxylate, phen = 1,10-phenanthroline, bpy = 2,2′-bipyridyl) have been synthesized and characterized by X-ray single crystal diffraction, elemental analysis, IR, thermal gravimetric analysis (TGA) and fluorescence measurement. 1, 2, 4 and 6 are dinuclear complexes bridged by pztc or pz25dc, 3 and 5 are 1D coordination polymers. In 6, the Cu(II) ions are bridged by bis-tridentate H2pztc2−. 7 and 8 are mononuclear Cd(II) complexes. The 2D or 3D supramolecular structures of 1–8 were built up by hydrogen bonds and π⋯π interactions. Notably, a novel T5(0)A0 water tape and a S-shaped (H2O)10cluster are observed in 2 and 5, respectively.

Syntheses and crystal structures of two new nickel(II) complexes with pyrazine-2,3,5,6-tetracarboxylate

Pyrazine-2,3,5,6-tetracarboxylic acid (H4pztc) reacted with Ni(ClO4)2·6H2O and 1,10-phenanthroline (phen) in aqueous solutions to form two different complexes, [Ni(H2pztc)(phen)H2O]·H2O (1), [Ni(phen)3](H2pztc)·10.5H2O (2), under hydrothermal conditions and at room temperature respectively. In 1, Ni(II) ion is coordinated by tridentate chelated H2pztc2−. The carboxyl and carboxylate groups of H2pztc2− are roughly coplanar with the pyrazine ring and form intramolecular hydrogen bonds. While in 2, H2pztc2− remains uncoordinated, the carboxyl and carboxylate groups of H2pztc2− are out of plane of the pyrazine ring and do not form intramolecular hydrogen bonds. H2pztc2− and water molecules form negatively-charged channels and the channels are filled with [Ni(phen)3]2+ in the 3D supramolecular structure of 2. In addition, a novel water tape is present in 2.