Syntheses, structures, photoluminescence, and magnetic properties of (3,6)- and 4-connected lanthanide metal-organic frameworks with a semirigid tricarboxylate ligand

Lanthanide coordination polymers [LnL(DMF)(2)]·0.25H(2)O [Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), and Tm (12)], and [GdL(H(2)O)(3)] (7') (H(3)L = 5-(4-carboxy-2-nitrophenoxy)-isophthalic acid), have been synthesized under hydro- and solvothermal conditions, respectively. Compounds 1-12 exhibit the same three-dimensional (3D) architecture, which is built up from binuclear paddle-wheel building blocks, and their resulting frameworks can be rationalized as rarely reported flu-3,6-C2/c topology. Compound 7' crystallizes in the monoclinic system, space group P2(1)/c. The ligands (L) bridge the Gd(III) centers to form 3D frameworks featuring a zeolite BCT topology, which have been unreported based on rare earth metals until now. Moreover, compound 6 exhibits characteristic red luminescent properties of Eu(III) complexes. The magnetic susceptibilities, over a temperature range of 2.0-300 K, of 7 and 7' have also been investigated.     

Structures and properties of porous coordination polymers based on lanthanide carboxylate building units

A series of 3-D lanthanide porous coordination polymers, [Ln(6)(BDC)(9)(DMF)(6)(H(2)O)(3)·3DMF](n) [Ln = La, 1; Ce, 2; Nd, 3], [Ln(2)(BDC)(3)(DMF)(2)(H(2)O)(2)](n) [Ln = Y, 4; Dy, 5; Eu, 6], [Ln(2)(ADB)(3)(DMSO)(4)·6DMSO·8H(2)O](n) [Ln = Ce, 7; Sm, 8; Eu, 9; Gd, 10], {[Ce(3)(ADB)(3)(HADB)(3)]·30DMSO·29H(2)O}(n) (11), and [Ce(2)(ADB)(3)(H(2)O)(3)](n) (12) (H(2)BDC = benzene-1,4-dicarboxylic acid and H(2)ADB = 4,4'-azodibenzoic acid), have been synthesized and characterized. In 1-3, the adjacent Ln(III) ions are intraconnected to form 1-D metal-carboxylate oxygen chain-shaped building units, [Ln(4)(CO(2))(12)](n), that constructed a 3-D framework with 4 × 7 ? rhombic channels. In 4-6, the dimeric Ln(III) ions are interlinked to yield scaffolds with 3-D interconnecting tunnels. Compounds 7-10 are all 3-D interpenetrating structures with the CaB6-type topology structure. Compound 11 is constructed by ADB spacers and trinulcear Ce nodes with a NaCl-type topology structure and a 1.9-nm open channel system. In 12, the adjacent Ce(III) ions are intraconnected to form 1-D metal-carboxylate oxygen chain-shaped building units, [Ln(4)(CO(2))(12)](n), and give rise to a 3-D framework. Moreover, 6 exhibits characteristic red luminescence properties of Eu(III) complexes. The magnetic susceptibilities, over a temperature range of 1.8-300 K, of 3, 6, and 7 have also been investigated; the results show paramagnetic properties.     

Syntheses, structures, luminescence, and magnetic properties of one-dimensional lanthanide coordination polymers with a rigid 2,2'-bipyridine-3,3',6,6'-tetracarboxylic acid ligand

A series of novel one-dimensional (1-D) lanthanide coordination polymers (CPs), with the general formula {[Ln(bptcH)(H(2)O)(2)]·H(2)O}(n) (Ln = Nd(III) (1), Eu(III) (2), Gd(III) (3), Tb(III) (4), Dy(III) (5), Ho(III) (6), or Er(III) (7)) have been synthesized by the solvothermal reactions of the corresponding lanthanide(III) picrates and 2,2'-bipyridine-3,3',6,6'-tetracarboxylic acid (bptcH(4)). These polymers have been structurally characterized by single-crystal X-ray diffraction, IR, PXRD, thermogravimetric (TGA), and elemental analysis. Coordination polymers 1-7 are isostructural; they possess the same 3D supramolecular architectures and crystallize in triclinic space group P1?. The frameworks constructed from dinuclear lanthanide building blocks exhibit one-dimensional double-stranded looplike chain architectures, in which the bptcH(3-) ions adopted hexadentate coordination modes. The Eu(III) (2) and Tb(III) (4) polymers exhibit characteristic photoluminescence in the visible region. The magnetic properties of polymers 2, 3, and 5 have been investigated through the measurement of their magnetic susceptibilities over the temperature range of 1.8-300 K.     

Synthesis, structure, and luminescent properties of microporous lanthanide metal-organic frameworks with inorganic rod-shaped building units

A series of microporous lanthanide metal-organic frameworks, Tb3(BDC)(4.5)(DMF)2(H2O)3.(DMF)(H2O) (1) and Ln3(BDC)(4.5)(DMF)2(H2O)3.(DMF)(C2H5OH)(0.5)(H2O)(0.5) [Ln = Dy (2), Ho (3), Er (4)], have been synthesized by the reaction of the lanthanide metal ion (Ln3+) with 1,4-benzenedicarboxylic acid and triethylenetetramine in a mixed solution of N,N'-dimethylformamide (DMF), water, and C(2)H(5)OH. X-ray diffraction analyses reveal that they are extremely similar in structure and crystallized in triclinic space group P. An edge-sharing metallic dimer and 4 metallic monomers assemble with 18 carboxylate groups to form discrete inorganic rod-shaped building units [Ln6(CO2)18], which link to each other through phenyl groups to lead to three-dimensional open frameworks with approximately 4 x 6 A rhombic channels along the [0,-1,1] direction. A water sorption isotherm proves that guest molecules in the framework of complex 1 can be removed to create permanent microporosity and about four water molecules per formula unit can be adsorbed into the micropores. These complexes exhibit blue fluorescence, and complex 1 shows a Tb3+ characteristic emission in the range of 450-650 nm.     

Luminescence tuning of imidazole-based lanthanide(III) complexes [Ln = Sm, Eu, Gd, Tb, Dy

To tune the lanthanide luminescence in related molecular structures, we synthesized and characterized a series of lanthanide complexes with imidazole-based ligands: two tripodal ligands, tris{[2-{(1-methylimidazol-2-yl)methylidene}amino]ethyl}amine (Me(3)L), and tris{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(3)L), and the dipodal ligand bis{[2-{(imidazol-4-yl)methylidene}amino]ethyl}amine (H(2)L). The general formulas are [Ln(Me(3)L)(H(2)O)(2)](NO(3))(3)·3H(2)O (Ln = 3+ lanthanide ion: Sm (1), Eu (2), Gd (3), Tb (4), and Dy (5)), [Ln(H(3)L)(NO(3))](NO(3))(2)·MeOH (Ln(3+) = Sm (6), Eu (7), Gd (8), Tb (9), and Dy (10)), and [Ln(H(2)L)(NO(3))(2)(MeOH)](NO(3))·MeOH (Ln(3+) = Sm (11), Eu (12), Gd (13), Tb (14), and Dy (15)). Each lanthanide ion is 9-coordinate in the complexes with the Me(3)L and H(3)L ligands and 10-coordinate in the complexes with the H(2)L ligand, in which counter anion and solvent molecules are also coordinated. The complexes show a screw arrangement of ligands around the lanthanide ions, and their enantiomorphs form racemate crystals. Luminescence studies have been carried out on the solid and solution-state samples. The triplet energy levels of Me(3)L, H(3)L, and H(2)L are 21?000, 22?700, and 23?000 cm(-1), respectively, which were determined from the phosphorescence spectra of their Gd(3+) complexes. The Me(3)L ligand is an effective sensitizer for Sm(3+) and Eu(3+) ions. Efficient luminescence of Sm(3+), Eu(3+), Tb(3+), and Dy(3+) ions was observed in complexes with the H(3)L and H(2)L ligands. Ligand modification by changing imidazole groups alters their triplet energy, and results in different sensitizing ability towards lanthanide ions.     

Amine-templated polymeric lanthanide formates: synthesis, characterization, and applications in luminescence and magnetism

The novel polymeric formates of general formula [(Fmd)Ln(III)(HCOO)(4)](∞) (Fmd(+) = NH(2)-CH(+)-NH(2); Ln = Eu (1), Gd (2), Tb (3), Dy (4)] were synthesized through solvothermal methods in formamide solutions. The compounds are isotructural; they crystallize in the orthorhombic C222(1) chiral space group. The coordination geometry at the metal centers is square antiprismatic (coordination number eight), with each formate ligand bridging adjacent lanthanide ions. The overall negative three-dimensional (3D) framework charge is balanced by the formamidinium cations sitting inside the channels along the a axis, forming extensive N-H···O hydrogen bonding with the surrounding cage. All the compounds have been characterized through single-crystal/powder X-ray diffraction, IR spectroscopy, and TG-MS analysis. Finally, their luminescence and magnetic properties have been assessed, leading to remarkable emission intensities, especially for the Tb(III) compound (Φ = 0.83), with corresponding lifetime decays in the micro (Dy) and millisecond (Tb, Eu) time scale. A weak but sizable antiferromagnetic interaction has been observed for the Gd(III) derivative.     

Diverse lanthanide coordination polymers tuned by the flexibility of ligands and the lanthanide contraction effect: syntheses, structures and luminescence

Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L(I)) and 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L(II)). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2?:?3. L(I), as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)](∞) (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln(2)(NO(3))(6)(L(I))(3)·nCH(3)OH](∞) (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L(II), two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln(2)(NO(3))(6)(L(II))(3)·2C(4)H(8)O(2)](∞) (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)·nCH(3)OH](∞) (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.     

Two- and three-dimensional lanthanide complexes: synthesis, crystal structures, and properties

3,5-pyrazoledicarboxylic acid (H3L) reacts with nitrate salts of lanthanide(III) (Ln=Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er) under hydrothermal conditions to form a series of lanthanide polymers 1-9. These nine polymers have the same crystal system of monoclinic, but they exhibit three different kinds of metal-organic framework structures. The complexes {[Ln2(HL)3(H2O)4].2H2O}n (Ln=Pr (1), Nd (2), and Sm (3)) were isostructural and exhibited porous 3D frameworks with a Cc space group. The complexes {[Ln2(HL)3(H2O)3].3H2O}n (Ln=Eu (4), Gd (5), and Tb (6)) were isostructural and built 2D double-decker (2DD) frameworks with a P21/c space group. The complexes {[Ln(HL)(H2L)(H2O)2]}n ((Ln=Dy (7), Ho (8), and Er (9)) were also isostructural and formed 2D monolayer (2DM) frameworks with a P21/n space group. The structure variation from the 3D porous framework to the 2D double-decker to the 2D monolayer is attributed to the lanthanide contraction effect. Notably, six new coordination modes of 3,5-pyrazoledicarboxylic acid were observed, which proved that 3,5-pyrazoledicarboxylic acid may be used as an effective bridging ligand to assemble lanthanide-based coordination polymers. The photophysical and magnetic properties have also been investigated.     

Synthesis, structure and magnetic properties of a novel family of heterometallic nonanuclear Na(I)2Mn(III)6Ln(III) (Ln = Eu, Gd, Tb, Dy) complexes

The structures and magnetic properties of four isomorphous nonanuclear heterometallic complexes [Na(2){Mn(3)(III)(μ(3)-O(2-))}(2)Ln(III)(hmmp)(6)(O(2)CPh)(4)(N(3))(2)]OH·0.5 CH(3)CN·1.5H(2)O are reported, where Ln(III) = Eu (1), Gd (2), Tb (3) and Dy (4), H(2)hmmp = 2-[(2-hydroxyethylimino)methyl]-6-methoxyphenol. Complexes 1-4 were prepared by the reactions of hmmpH(2) with a manganese salt and the respective lanthanide salt together with NaO(2)CPh and NaN(3). Single-crystal X-ray diffraction analyses reveal that the six Mn(III) and one Ln(III) metal topology in the aggregate can be described as a bitetrahedron. The two peripheral [Mn(III)(3)(μ(3)-O(2-))](7+) triangles are each bonded to a central Ln(III) ion with rare distorted octahedral geometry. The magnetic properties of all the complexes were investigated using variable temperature magnetic susceptibility and both antiferromagnetic and ferromagnetic interactions exist in the [Mn(III)(3)(μ(3)-O(2-))](7+) triangle. Weak ferromagnetic exchange between the Ln(III) and Mn(III) ions has been established for the corresponding Gd derivative. The Gd, Tb and Dy complexes show no evidence of slow relaxation behaviour above 2.0 K.     

Three-dimensional open-frameworks based on Ln(III) ions and open-/closed-shell PTM ligands: synthesis, structure, luminescence, and magnetic properties

A series of isostructural open-framework coordination polymers formulated as [Ln(dmf)(3)(ptmtc)] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5); PTMTC = polychlorotriphenylmethyl tricarboxylate) and [Ln(dmf)(2)H(2)O(αH-ptmtc)] (Ln = Sm (1'), Eu (2'), Gd (3'), Tb (4'), Dy (5')) have been obtained by treating Ln(III) ions with PTMTC ligands with a radical (PTMTC(3-)) or a closed-shell character (αH-PTMTC(3-)). X-ray diffraction analyses reveal that these coordination polymers possess 3D architectures that combine large channels and fairly rare lattice complex T connectivity. In addition, these compounds show selective framework dynamic sorption properties. For both classes of ligands, the ability to act as an antenna in Ln sensitization processes has been investigated. No luminescence was observed for compounds 1-5, and 3' because of the PTMTC(3-) ligand and/or Gd(III) ion characteristics. Conversely, photoluminescence measurements show that 1', 2', 4', and 5' emit dark orange, red, green, and dark cyan metal-centered luminescence. The magnetic properties of all of these compounds have been investigated. The nature of the {Ln-radical} exchange interaction in these compounds has been assessed by comparing the behavior of the radical-based coordination polymers 1-5 with those of the compounds with the diamagnetic ligand set. While antiferromagnetic {Sm-radical} interactions are found in 1, ferromagnetic {Ln-radical} interactions propagate in the 3D architectures of 3, 4, and 5 (Ln = Gd, Tb, and Dy, respectively). This procedure also provided access to information on the {Ln-Ln} exchange existing in these magnetic systems.     

4-[(1,3-二氧代丁基)氨基]苯甲酸稀土配合物的合成、表征及发光性质

在乙醇体系中,由主配体4-[(1,3-二氧代丁基)氨基]苯甲酸(H2L,C11H11NO4)、稀土硝酸盐及辅助配体邻菲啰啉(phen)反应合成了两个系列8个配合物[Ln2(L)3(H2O)4]n(Ln=Sm(1),Eu(2),Tb(3),Dy(4));[Ln2(NO3)2(L)2(phen)2]n(Ln=Sm(5),Eu(6),Tb(7),Dy(8))。用元素分析、红外光谱、摩尔电导、热重分析进行表征,确定了产物的化学组成,推断了相应的结构。测定了室温时固体产物的激发和发射光谱,结果表明:由主辅配体共同配位的三元配合物的发光强度好于无辅助配体参与的二元配合物。测定了三元配合物的荧光寿命,其中铕和铽配合物显示较长的荧光寿命。     

(2-羧基苯氧基)苯-1,2-二羧酸构筑的镧系配合物对苯甲醛和阳离子的荧光传感

采用水热法合成了5个稀土配合物[Sm₂(bdbc)₂(phen)₄](1)和[Ln(bdbc)(phen)(H₂O)][Ln=Eu(2), Gd(3), Tb(4), Dy(5), bdbc=(2-羧基苯氧基)苯-1,2-二羧酸根, phen=1,10-邻菲啰啉]. 配合物1是双核分子, 通过氢键和C—H…π作用进一步构筑成一维超分子结构; 配合物2~5是同构的一维双螺旋结构, 通过氢键和C—H…π作用进一步构筑成三维超分子结构. 配合物1, 2, 4和5呈现了Sm³⁺, Eu³⁺, Tb³⁺和Dy³⁺离子的特征发射, 分别对应于Sm³⁺离子的⁴G_5/2→⁶H_J/2(J=5, 7, 9)、 Eu³⁺离子的⁵D₀→⁷F_J(J=1—4)、 Tb³⁺离子的⁵D₄→⁷F_J(J=6, 5, 4, 3)和Dy³⁺离子的⁴F_5/2→⁶H_J/2(J=15, 13)跃迁. 对配合物4的荧光性质进行了表征, 结果表明, 配合物4可用作荧光探针以检测阳离子和苯甲醛.     

Synthesis of Highly Luminescent LnMOFs through Structural Regulation

Two series of three dimensional（3D） lanthanide metal-organic frameworks（LnMOFs） of [Ln（tftpa）_1.5（phen）(H₂O)]_n（Ln = Sm 1a, Eu 1b, Tb 1c, Dy 1d, H2tftpa = tetrafluoroterephthalic acid, phen = 1,10-phenanthrolin） and [Ln（tftpa）1.5（bpy）(H₂O)]_n（Ln = Sm 2a, Eu 2b, Tb 2c, Dy 2d, bpy = 2,2’-bipyridine） are obtained by structural regulation. Results reveal that the 3D LnMOFs show high water-and thermal-stability. Interestingly, through selecting the ...     

Trinuclear lanthanide complexes of a compartmental ligand N,N'-bis(2-pyridinyl)-2,6-pyridinedicarboxamide: a spectroscopic investigation

Trinuclear lanthanide complexes of the formula [Ln(3)(PPDA)(NO(3))(6)(H(2)O)(2)].NO(3).2H(2)O where Ln=La(III), Pr(III), Sm(III), Nd(III), Eu(III) Gd(III) Tb(III), Dy(III) and Y(III); H(2)PPDA=N,N'-bis(2-pyridinyl)-2,6-pyridinedicarboxamide, have been isolated. The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibility measurements and spectral (IR, NMR, UV-vis, fluorescence, FAB and EPR) and thermal studies.     

A family of 13 tetranuclear zinc(II)-lanthanide(III) complexes of a [3+3] Schiff-base macrocycle derived from 1,4-diformyl-2,3-dihydroxybenzene

A family of thirteen tetranuclear heterometallic zinc(II)-lanthanide(III) complexes of the hexa-imine macrocycle (L(Pr))(6-), with general formula Zn(II)(3)Ln(III)(L(Pr))(NO(3))(3)·xsolvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), were prepared in a one-pot synthesis using a 3:1:3:3 reaction of zinc(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene (H(2)L(1)) and 1,3-diaminopropane. A hexanuclear homometallic zinc(II) macrocyclic complex [Zn(6)(L(Pr))(OAc)(5)(OH)(H(2)O)]·3H(2)O was obtained using a 2:0:1:1 ratio of the same reagents. A control experiment using a 1:0:1:1 ratio failed to generate the lanthanide-free [Zn(3)(L(Pr))] macrocyclic complex. The reaction of H(2)L(1) and zinc(II) acetate in a 1:1 ratio yielded the pentanuclear homometallic complex of the dialdehyde H(2)L(1), [Zn(5)(L(1))(5)(H(2)O)(6)]·3H(2)O. An X-ray crystal structure determination revealed [Zn(3)(II)Pr(III)(L(Pr))(NO(3))(2)(DMF)(3)](NO(3))·0.9DMF has the large ten-coordinate lanthanide(III) ion bound in the central O(6) site with two bidentate nitrate anions completing the O(10) coordination sphere. The three square pyramidal zinc(II) ions are in the outer N(2)O(2) sites with a fifth donor from DMF. Measurement of the magnetic properties of [Zn(II)(3)Dy(III)(L(Pr))(NO(3))(3)(MeOH)(3)]·4H(2)O with a weak external dc field showed that it has a frequency-dependent out-of-phase component of ac susceptibility, indicative of slow relaxation of the magnetization (SMM behaviour). Likewise, the Er and Yb analogues are field-induced SMMs; the latter is only the second example of a Yb-based SMM. The neodymium, ytterbium and erbium complexes are luminescent in the solid phase, but only the ytterbium and neodymium complexes show strong lanthanide-centred luminescence in DMF solution.     

Synthesis, structure, and luminescent and magnetic properties of novel lanthanide metal-organic frameworks with zeolite-like topology

A series of microporous lanthanide metal-organic frameworks [Ln(BTC)(DMF)(2) x H(2)O, Ln = Tb (1), Dy (2), Ho (3), Er (4), Tm (5), Yb (6); DMF = N,N'-dimethylformamide] with 4 x 4 x 4 x 6 x 6 x 8 topology, which is very common in the zeolite topologies, have been synthesized under mild conditions. The single-crystal X-ray diffraction analysis reveals that they exhibit the same three-dimensional (3D) architecture and crystallize in monoclinic symmetry space group C2/c. Organic and inorganic four-connected nodes link each other to form a 3D open framework. The framework contains approximate 13 Angstrom x 7 Angstrom rectangle channels along the [1,1,0] and [1,-1,0] directions, respectively. The luminescent properties of these complexes have been studied, and complex 1 shows a Tb(3+) characteristic emission in the range of 450-650 nm at room temperature. Complexes 1-5 exhibit antiferromagnetic interaction between Ln(3+) ions. The water sorption isotherm shows that about 15 water molecules per unit cell can be adsorbed into the micropores of dehydrated complex 4.     

Salen-based coordination polymers of iron and the rare earth elements

Reaction of N,N'-bis(4-carboxysalicylidene)ethylenediamine (H(4)L) with iron(III) chloride and lanthanide nitrates resulted in the coordination polymers of composition {[Ln(2)(FeLCl)(2)(NO(3))(2)(DMF)(5)]·(DMF)(4)}(n) (Ln = Y, Eu, Gd, Tb, Dy). The polymers consist of iron-salen-based moieties having carboxylate linkers connected to rare earth atoms in a 1D chain structure. Thus, the iron-salen complex acts as a "metalloligand". Because of the twisting of the chains, porous structures are formed and possess large free void space. The magnetic studies of selected compounds exhibit weak intramolecular antiferromagnetic interactions of Ln-Ln. At 3, 30, and 80 K, the M?ssbauer spectra of the iron-dysprosium compound show a strongly asymmetric quadrupole doublet with isomer shift and quadrupole splitting values typical for Fe(III) ions in high spin state. In addition, an anomalous temperature dependence of both isomer shift and quadrupole splitting has been observed.     

Solvothermal synthesis, crystal structure, and properties of lanthanide-organic frameworks based on thiophene-2,5-dicarboxylic acid

A series of lanthanide-organic framework coordination polymers, {[La(2)(TDC)(2)(NO(3))(H(2)O)(4)](OH)·5H(2)O}(n) (1) and [Ln(TDC)(NO(3))(H(2)O)](n) (TDC = thiophene- 2, 5- dicarboxylic acid; Ln = Nd(2), Sm(3), Eu(4), Gd(5), Tb(6), Dy(7), Ho(8), Er(9), Yb(10)) have been synthesized by solvothermal reaction and characterized by elemental analysis, FT-IR, TG analysis, single-crystal X-ray diffraction and power X-ray diffraction. The single-crystal X-ray diffraction analysis results show that 1 displays a 3-D porous framework with (3,7)-connected {4(10).6(11)}{4(3)} topology. The compounds 2-10 crystallized in the same P2(1)/c space group and exhibits a (3,6)-connected {4.6(2)}(2){4(2).6(10).8(3)} topology, Right-handed and left-handed helical chains coexist in the 2-D layer structure. The luminescence properties of 2-10 and the magnetic properties of 5,7,8,9 were investigated.     

Heterometallic cubanes: syntheses, structures, and magnetic properties of lanthanide(III)-nickel(II) architectures

Reactions of lanthanide(III) perchlorate (Ln = Dy, Tb, and Gd), nickel(II) acetate, and ditopic ligand 2-(benzothiazol-2-ylhydrazonomethyl)-6-methoxyphenol (H(2)L) in a mixture of methanol and acetone in the presence of NaOH resulted in the successful assembly of novel Ln(2)Ni(2) heterometallic clusters representing a new heterometallic 3d-4f motif. Single-crystal X-ray diffraction reveals that all compounds are isostructural, with the central core composed of distorted [Ln(2)Ni(2)O(4)] cubanes of the general formula [Ln(2)Ni(2)(μ(3)-OH)(2)(OH)(OAc)(4)(HL)(2)(MeOH)(3)](ClO(4))·3MeOH [Ln = Dy (1), Tb (2), and Gd (3)]. The magnetic properties of all compounds have been investigated. Magnetic analysis on compound 3 indicates ferromagnetic Gd···Ni exchange interactions competing with antiferromagnetic Ni···Ni interactions. Compound 1 displays slow relaxation of magnetization, which is largely attributed to the presence of the anisotropic Dy(III) ions, and thus represents a new discrete [Dy(2)Ni(2)] heterometallic cubane exhibiting probable single-molecule magnetic behavior.     

A Terbium Metal–Organic Framework for Highly Selective and Sensitive Luminescence Sensing of Hg2+ Ions in Aqueous Solution

A series of isomorphic lanthanide metal–organic frameworks (MOFs) Ln(TATAB)?(DMF)₄(H₂O)(MeOH)_0.5 (LnTATAB, Ln=Eu, Tb, Sm, Dy, Gd; H₃TATAB=4,4′,4′′‐s‐triazine‐1,3,5‐triyltri‐p‐aminobenzoic acid) have been solvothermally synthesized and structurally characterized. Among these MOFs, TbTATAB exhibits good water stability and a high fluorescence quantum yield. Because mercury ions (Hg²⁺) have a high affinity to nitrogen atoms, and the space between multiple nitrogen atoms from triazine and imino groups is suitable for interacting with Hg²⁺ ions, TbTATAB shows highly selective and sensitive detection of Hg²⁺ in aqueous solution with a detection limit of 4.4 nm . Furthermore, it was successfully applied to detect Hg²⁺ ions in natural water samples.