Bifunctional Mixed-Lanthanide Cyano-Bridged Coordination Polymers Ln(0.5)Ln'(0.5)(H(2)O)(5)[W(CN)(8)] (Ln/Ln' = Eu(3+)/Tb(3+), Eu(3+)/Gd(3+), Tb(3+)/Sm(3+))

A new family of mixed-lanthanide cyano-bridged coordination polymers Ln(0.5)Ln'(0.5)(H(2)O)(5)[W(CN)(8)] (where Ln/Ln' = Eu(3+)/Tb(3+), Eu(3+)/Gd(3+), and Tb(3+)/Sm(3+)) containing two lanthanide and one transition metal ions were obtained and characterized by X-ray diffraction, photoluminescence spectroscopy, magnetic analyses, and theoretical computation. These compounds are isotypical and crystallize in the tetragonal system P4/nmm forming two-dimensional grid-like networks. They present a magnetic ordering at low temperature and display the red Eu(3+) ((5)D(0) → (7)F(0-4)) and green Tb(3+) ((5)D(4) → (7)F(6-2)) characteristic photoluminescence. The Tb(0.5)Eu(0.5)(H(2)O)(5)[W(CN)(8)] compound presents therefore green and red emission and shows Tb(3+)-to-Eu(3+) energy transfer.     

Photoluminescent layered lanthanide silicates

The hydrothermal synthesis and structural characterization of layered lanthanide silicates, K(3)[M(1-a)Ln(a)Si(3)O(8)(OH)(2)] (M = Y(3+), Tb(3+); Ln = Eu(3+), Er(3+), Tb(3+), and Gd(3+)), named AV-22 materials, are reported. The structure of these solids was elucidated by single-crystal (180 K) and powder X-ray diffraction and further characterized by chemical analysis, thermogravimetry, scanning electron microscopy, (29)Si MAS NMR, and photoluminescence spectroscopy. The Er-AV-22 material is a room-temperature infrared phosphor, while Tb- and Eu-AV-22 are visible emitters with output efficiencies comparable to standards used in commercial lamps. The structure of these materials allows the inclusion of a second (or even a third) type of Ln(3+) ion in the framework and, therefore, the fine-tuning of their photoluminescent properties. For the mixed Tb(3+)/Eu(3+) materials, evidence has been found of the inclusion of Eu(3+) ions in the interlayer space by replacing K+ ions, further allowing the activation of Tb(3+)-to-Eu(3+) energy transfer mechanisms. The occurrence probability of such mechanisms ranges from 0.62 (a = 0.05) to 1.20 ms(-1) (a = 0.1) with a high energy transfer efficiency (0.73 and 0.84, respectively).     

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.     

Novel microporous lanthanide silicates with tobermorite-like structure

The synthesis and structural characterization of microporous lanthanide silicates (Na(1.08)K(0.5)Ln(1.14)Si(3)O(8.5).1.78H(2)O, Ln = Eu, Tb, Sm, Ce) are reported. The structure of these solids is closely related with the structure of hydrated calcium silicate minerals known as tobermorites and was solved by powder X-ray diffraction ab initio (direct) methods and further characterized by chemical analysis, thermogravimetry, scanning electron microscopy, (23)Na and (29)Si MAS NMR and luminescence spectroscopy. These materials combine microporosity with interesting photoluminescence properties, and their structural flexibility allows fine-tuning of luminescence properties, by introducing a second type of lanthanide ion in the framework. Thus, they may find applications in new types of sensors.     

Synthesis and characterization of heterodinuclear Ln(3+)-Fe3+ and Ln(3+)-Co3+ complexes,bridged by cyanide ligand (Ln3+ = lanthanide ions). Nature of the magnetic interaction in the Ln(3+)-Fe3+ complexes

The reaction of Ln(NO3)3.aq with K3[Fe(CN)6] or K3[Co(CN)6] in N,N'-dimethylformamide (DMF) led to 25 heterodinuclear [Ln(DMF)4(H2O)3(mu-CN)Fe(CN)5].nH2O and [Ln(DMF)4(H2O)3(mu-CN)Co(CN)5].nH2O complexes (with Ln = all the lanthanide(III) ions, except promethium and lutetium). Five complexes (Pr(3+)-Fe3+), (Tm(3+)-Fe3+), (Ce(3+)-Co3+), (Sm(3+)-Co3+), and (Yb(3+)-Co3+) have been structurally characterized; they crystallize in the equivalent monoclinic space groups P21/c or P21/n. Structural studies of these two families show that they are isomorphous. This relationship in conjunction with the diamagnetism of the Co3+ allows an approximation to the nature of coupling between the iron(III) and the lanthanide(III) ions in the [Ln(DMF)4(H2O)3(mu-CN)Fe(CN)5].nH2O complexes. The Ln(3+)-Fe3+ interaction is antiferromagnetic for Ln = Ce, Nd, Gd, and Dy and ferromagnetic for Ln = Tb, Ho, and Tm. For Ln = Pr, Eu, Er, Sm, and Yb, there is no sign of any significant interaction. The isotropic nature of Gd3+ helps to evaluate the value of the exchange interaction.     

General synthesis and structural evolution of a layered family of Ln8(OH)20Cl4 x nH2O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y)

The synthesis process and crystal structure evolution for a family of stoichiometric layered rare-earth hydroxides with general formula Ln(8)(OH)(20)Cl(4) x nH(2)O (Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y; n approximately 6-7) are described. Synthesis was accomplished through homogeneous precipitation of LnCl(3) x xH(2)O with hexamethylenetetramine to yield a single-phase product for Sm-Er and Y. Some minor coexisting phases were observed for Nd(3+) and Tm(3+), indicating a size limit for this layered series. Light lanthanides (Nd, Sm, Eu) crystallized into rectangular platelets, whereas platelets of heavy lanthanides from Gd tended to be of quasi-hexagonal morphology. Rietveld profile analysis revealed that all phases were isostructural in an orthorhombic layered structure featuring a positively charged layer, [Ln(8)(OH)(20)(H(2)O)(n)](4+), and interlayer charge-balancing Cl(-) ions. In-plane lattice parameters a and b decreased nearly linearly with a decrease in the rare-earth cation size. The interlamellar distance, c, was almost constant (approximately 8.70 A) for rare-earth elements Nd(3+), Sm(3+), and Eu(3+), but it suddenly decreased to approximately 8.45 A for Tb(3+), Dy(3+), Ho(3+), and Er(3+), which can be ascribed to two different degrees of hydration. Nd(3+) typically adopted a phase with high hydration, whereas a low-hydration phase was preferred for Tb(3+), Dy(3+), Ho(3+), Er(3+), and Tm(3+). Sm(3+), Eu(3+), and Gd(3+) samples were sensitive to humidity conditions because high- and low-hydration phases were interconvertible at a critical humidity of 10%, 20%, and 50%, respectively, as supported by both X-ray diffraction and gravimetry as a function of the relative humidity. In the phase conversion process, interlayer expansion or contraction of approximately 0.2 A also occurred as a possible consequence of absorption/desorption of H(2)O molecules. The hydration difference was also evidenced by refinement results. The number of coordinated water molecules per formula weight, n, changed from 6.6 for the high-hydration Gd sample to 6.0 for the low-hydration Gd sample. Also, the hydration number usually decreased with increasing atomic number; e.g., n = 7.4, 6.3, 7.2, and 6.6 for high-hydration Nd, Sm, Eu, and Gd, and n = 6.0, 5.8, 5.6, 5.4, and 4.9 for low-hydration Gd, Tb, Dy, Ho, and Er. The variation in the average Ln-O bond length with decreasing size of the lanthanide ions is also discussed. This family of layered lanthanide compounds highlights a novel chemistry of interplay between crystal structure stability and coordination geometry with water molecules.     

Evolution of photoluminescence across dimensionality in lanthanide silicates

The dehydratation process of layered lanthanide silicates K3[LnSi3O8(OH)2], Ln = Y, Eu, Tb, and Er, and the structural characterization of the obtained small-pore framework K3LnSi3O9, Ln = Y, Eu, Tb, and Er solids, named AV-23, have been reported. The structure of AV-23 has been solved by single-crystal X-ray diffraction (XRD) methods and further characterized by chemical analysis, thermogravimetry, scanning electron microscopy, and 29Si MAS NMR. The photoluminescence (PL), radiance, and lifetime values of AV-23 have been studied and compared with those of AV-22. Both materials have a similar chemical makeup and structures sharing analogous building blocks, hence providing a unique opportunity for rationalizing the evolution of the PL properties of lanthanide silicates across dimensionality. Although Tb-AV-23 contains a single crystallographic Tb(3+) site, PL spectroscopy indicates the presence of Ln(3+) centers in regular framework positions and in defect regions. PL evidence suggests that Eu-AV-23 contains a third type of Ln(3+) environment, namely, Eu(3+) ions replacing K(+) ions in the micropores. The radiance values of the Tb-AV-22 and Tb-AV-23 samples are of the same order of magnitude as those of standard Tb(3+) green phosphors. For the samples K3(Y1-aEraSi3O9), a = 0.005-1, efficient emission and larger 4I13/2 lifetimes (ca. 7 ms) are detected for low Er(3+) content, indicating that the Er(3+)-Er(3+) interactions become significant as the Er(3)+ content increases.     

Synthesis and single-crystal x-ray diffraction examination of a structurally homologous series of tetracoordinate heteroleptic anionic lanthanide complexes: Ln[N[Si(CH3)2CH2CH2Si(CH3)2]]3(mu-Cl)Li(L)3 (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb; (L)3 =(THF)3, (Et2O)3, (THF)2(Et2O)

Anhydrous lanthanide(III) chlorides (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) react with 3 equiv of lithium 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentanide, Li[N[Si(CH3)2CH2Ch2Si(CH3)2]], in THF or Et(2)O to afford the monomeric four-coordinate heteroleptic ate complexes Ln[N[Si(CH3)2CH2CH2Si(CH3)2]]3(mu-Cl)Li(THF/Et2O)3 (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7), Tm (8), Yb (9)), whose solid-state structures were determined by the single-crystal X-ray diffraction technique. All complexes additionally were characterized by melting point determination, elemental analyses, and mass spectrometry.     

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.     

A series of novel lanthanide polyoxometalates: condensation of building blocks dependent on the nature of rare earth cations

A series of novel lanthanide polyoxomolybdates was synthesized by reaction of lanthanide cations with the Anderson type anion (TeMo(6)O(24))(6-). The polyoxometalates K(6n)(TeMo(6)O(24))(n)[(Ln(H(2)O)(7))(2)(TeMo(6)O(24))](n)[middle dot]16nH(2)O (Ln = Eu, Gd) and K(3n)[Ln(H(2)O)(5)(TeMo(6)O(24))](n)[middle dot]6nH(2)O (Ln = Tb, Dy, Ho, Er) were characterized by X-ray structure analysis, elemental analysis and IR spectroscopy. We found that the solid-state structures of Ln/(TeMo(6)O(24))(6-) compounds are strongly dependent on the lanthanide cations, and therefore represent a rare example for different arrangements of building units depending on the nature of the rare earth cations. While the Eu(3+) and Gd(3+) cations achieve ninefold coordination by seven water molecules and two terminal oxygen atoms of the (TeMo(6)O(24))(6-) anions, the Tb(3+), Dy(3+), Ho(3+) and Er(3+) cations are coordinated by five water molecules, two terminal oxygen atoms and one molybdenum-bridging oxygen atom belonging to the (TeMo(6)O(24))(6-) anion. The europium and gadolinium substituted compounds contain infinite one-dimensional [(Ln(H(2)O)(7))(2)(TeMo(6)O(24))](n) chains; the terbium, dysprosium, holmium and erbium compounds contain infinite one-dimensional [Ln(H(2)O)(5)(TeMo(6)O(24))](n)(3n-) chains.     

Synthesis, crystal structures, and luminescence of organic-lanthanide complexes with nicotinate and isonicotinate ligands

Six lanthanide coordination compounds with two isomeric carboxylic acids, nicotinic acid (HL(1)) and isonicotinic acid (HL(2)), [(L(1))3Ln(H2O)2]2 (Ln = Eu, 1; Gd, 2; Tb, 3) and [( L(2))2Ln(H2O)4][NO3] (Ln = Eu, 4; Gd, 5; Tb, 6), have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complexes 1-3 are dimeric whereas 4-6 are polymeric, all with 8-coordination of Ln(3+). The distinction between these lanthanide complexes is readily accomplished from the 10 K high resolution electronic emission spectra. Spectral interpretation is given for the Eu(3+) complexes 1, 4, whereas the spectra of 3 and 6 are more complex. The relationships between spectroscopic and crystallographic site symmetries are discussed. The calculated second rank crystal field strengths of Eu(3+) in 1 and 4 are intermediate in magnitude.     

Synthesis, structure, and thermally stable luminescence of Eu(2+)-doped Ba2Ln(BO3)2Cl (Ln = Y, Gd and Lu) host compounds

A new family of chloroborate compounds, which was investigated from the viewpoint of rare earth ion activated phosphor materials, have been synthesized by a conventional high temperature solid-state reaction. The crystal structure and thermally stable luminescence of chloroborate phosphors Ba(2)Ln(BO(3))(2)Cl:Eu(2+) (Ln = Y, Gd, and Lu) have been reported in this paper. X-ray diffraction studies verify the successful isomorphic substitution for Ln(3+) sites in Ba(2)Ln(BO(3))(2)Cl by other smaller trivalent rare earth ions, such as Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb. The detailed structure information for Ba(2)Ln(BO(3))(2)Cl (Ln = Y, Gd, and Lu) by Rietveld analysis reveals that they all crystallize in a monoclinic P2(1)/m space group. These compounds display interesting and tunable photoluminescence (PL) properties after Eu(2+)-doping. Ba(2)Ln(BO(3))(2)Cl:Eu(2+) phosphors exhibit bluish-green/greenish-yellow light with peak wavelengths at 526, 548, and 511 nm under 365 UV light excitation for Ba(2)Y(BO(3))(2)Cl:Eu(2+), Ba(2)Gd(BO(3))(2)Cl:Eu(2+), and Ba(2)Lu(BO(3))(2)Cl:Eu(2+), respectively. Furthermore, they possess a high thermal quenching temperature. With the increase of temperature, the emission bands show blue shifts with broadening bandwidths and slightly decreasing emission intensities. It is expected that this series of chloroborate phosphors can be used in white-light UV-LEDs as a good wavelength-conversion phosphor.     

Optimization of Pr3+, Tb3+, and Sm3+ co-doped (Y0.65Gd0.35)BO3:Eu0.05(3+) VUV phosphors through combinatorial approach

A combinatorial approach was used to systematically investigate the effect of trace Pr(3+), Tb(3+), or Sm(3+) on the VUV photoluminescence of Eu(3+) in the Pr(3+), Tb(3+), or Sm(3+) co-doped (Y(0.65)Gd(0.35))BO(3):E(3+)(0.05). We found that Pr(3+) and Tb(3+)increases the VUV photoluminescent efficiency, while Sm(3+) decreases the efficiency. The optimized composition was identified to be between 7 x 10(-6) and 3 x 10(-4), and the corresponding efficiency improvement is about 15%. Scale-up experiments confirmed the results in the combinatorial materials libraries.     

Zinc-adeninate metal-organic framework for aqueous encapsulation and sensitization of near-infrared and visible emitting lanthanide cations

Luminescent metal-organic frameworks (MOFs), Ln(3+)@bio-MOF-1, were synthesized via postsynthetic cation exchange of bio-MOF-1 with Tb(3+), Sm(3+), Eu(3+), or Yb(3+), and their photophysical properties were studied. We demonstrate that bio-MOF-1 encapsulates and sensitizes visible and near-infrared emitting lanthanide cations in aqueous solution.     

Encapsulation and Sensitization of UV-vis and Near Infrared Lanthanide Hydrate Emitters for Dual- and Bimodal-Emissions in Both Air and Aqueous Media Based on a Porous Heteroatom-Rich Cd(II)-Framework

A porous heteroatom-rich Cd(II)-polymeric framework which is generated from an ethylene glycol ether-bridging dicarboxylate ligand L, 4,4'-bipy and Cd(II) ion is reported. It contains one-dimensional tubes (9-11 ?) which are able to trap cationic lanthanide hydrates such as Eu(H(2)O)(8)(3+), Tb(H(2)O)(8)(3+), and Nd(H(2)O)(8)(3+) under ambient conditions to generate Ln(H(2)O)(8)(3+)-loaded materials. In addition, the heteroatom-rich host material can effectively protect and sensitize the encapsulated Ln(3+) emitters in their hydrate form in both air and aqueous media. Furthermore, the dual- and bimodal-emissions are successfully realized by intercalation of the different Ln(3+)-hydrates based on a guest-driven approach.     

Highly uniform and monodisperse Gd(2)O(2)S:Ln(3+) (Ln = Eu, Tb) submicrospheres: solvothermal synthesis and luminescence properties

Gd(2)O(2)S:Ln(3+) (Ln = Eu, Tb) submicrospheres were successfully prepared through a facile and mild solvothermal method followed by a subsequent heat treatment. X-ray diffraction (XRD) results demonstrate that all the diffraction peaks of the samples can be well indexed to the pure hexagonal phase of Gd(2)O(2)S. The energy dispersive spectroscopy (EDS), element analysis, and FT-IR results show that the precursors are composed of the Gd, Eu, O, S, C, H, and N elements. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show that these spheres are actually composed of randomly aggregated nanoparticles. The formation mechanism for the Gd(2)O(2)S:Ln(3+)(Ln = Eu, Tb) spheres has been proposed on an isotropic growth mechanism. Under ultraviolet excitation, Gd(2)O(2)S:Ln(3+)(Ln = Eu, Tb) spheres show red and green emission corresponding to the (5)D(0)→(7)F(2) transition of the Eu(3+) ions and the (5)D(4)→(7)F(5) transition of the Tb(3+) ions. Furthermore, this synthetic route may have potential applications for fabricating other lanthanide oxysulfides.     

Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with μ3-η2:η2:η2 bonding

A series of mononuclear lanthanide(III) complexes [Ln(LH(2))(H(2)O)(3)Cl](ClO(4))(2) (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand (LH(2)) in 95 : 5 (v/v) methanol-water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes [{Ln(LH(2))(H(2)O)Cl}(3)(μ(3)-CO(3))](ClO(4))(4)·nH(2)O. Under similar conditions, the mononuclear Y(III) complex forms the dimeric compound [{Y(LH(2))(H(2)O)Cl}(μ(2)-CO(3)){Y(LH(2))(H(2)O)(2)}](ClO(4))(3)·4H(2)O. These complexes have been characterized by their IR and NMR ((1)H, (13)C) spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of Nd(III), Gd(III) and Tb(III) and the dinuclear compound of Y(III). In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand (LH(2)) whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate μ(3)-η(2):η(2):η(2) fashion, while they are in bis-bidentate μ(2)-η(2):η(2) mode in the Y(III) complex. The magnetic properties of the Gd(III) complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = -0.042 cm(-1)) between the Gd(III) centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of Sm(III), Eu(III), and Tb(III) have been studied. The ligand LH(2) acts as a sensitizer for the metal ions in an acetonitrile-toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order Eu(3+) > Sm(3+) > Tb(3+).     

Lanthanide radii controlled one-dimensional polymer and dinuclear complexes and their fluorescent properties

A bi-phosphonate ligand tetraethyl-(2,3,5,6-tetramethyl-1,4-phenylene) bis(methylene)diphosphonate has been designed and synthesized. The bi-phosphonate as a bridging ligand reacts with lanthanide nitrates forming four different types of 1D coordination complexes: ribbon polymer (type I), semi-ribbon polymer (type II), zigzag polymer (type III), and dinuclear-triligand short chain (type IV), which changed according to the decrease of the radius of the lanthanide. They have been characterized by IR spectroscopy, elemental analysis, and X-ray diffraction spectroscopy. The photophysical properties of Sm(3+), Eu(3+), Tb(3+) and Dy(3+) complexes at room temperature were also investigated. They exhibit strong fluorescence by excitation of the Ln(3+) ion absorption bands and the quantum yield values of Eu(3+) and Tb(3+) complexes are no less than 20%.     

Interconvertable modular framework and layered lanthanide(III)-etidronic acid coordination polymers

Isostructural modular microporous Na2[Y(hedp)(H2O)0.67] and Na4[Ln2(hedp)2(H2O)2].nH2O (Ln = La, Ce, Nd, Eu, Gd, Tb, Er) framework-type, and layered orthorhombic [Eu(H2hedp)(H2O)2].H2O and Na0.9[Nd0.9Ge0.10(Hhedp)(H2O)2], monoclinic [Ln(H2hedp)(H2O)].3H2O (Ln = Y, Tb), and triclinic [Yb(H2hedp)].H2O coordination polymers based on etidronic acid (H5hedp) have been prepared by hydrothermal synthesis and characterized structurally by (among others) single-crystal and powder X-ray diffraction and solid-state NMR. The structure of the framework materials comprises eight-membered ring channels filled with Na+ and both free and lanthanide-coordinated water molecules, which are removed reversibly by calcination at 300 degrees C (structural integrity is preserved up to ca. 475 degrees C), denoting a clear zeolite-type behavior. Interesting photoluminescence properties, sensitive to the hydration degree, are reported for Na4[Eu2(hedp)2(H2O)2].H2O and its fully dehydrated form. The 3D framework and layered materials are, to a certain extent, interconvertable during the hydrothermal synthesis stage via the addition of HCl or NaCl: of the 3D framework Na4[Tb2(hedp)2(H2O)2].nH2O, affords layered [Tb(H2hedp) (H2O)].3H2O, whereas layered [Tb(H2hedp)(H2O)2].H2O reacts with sodium chloride yielding a material similar to Na4[Tb2(hedp)2(H2O)2].nH2O. In layered [Y(H2hedp)(H2O)].3H2O, noncoordinated water molecules are engaged in cooperative water-to-water hydrogen-bonding interactions, leading to the formation of a (H2O)13 cluster, which is the basis of an unprecedented two-dimensional water network present in the interlayer space.     

Hydrothermal synthesis, dimension evolution and luminescence properties of tetragonal LaVO4:Ln (Ln = Eu3+, Dy3+, Sm3+) nanocrystals

Well-defined 1D and 3D t-LaVO(4):Ln (Ln = Eu(3+), Dy(3+), Sm(3+)) nanocrystals with regular and uniform shapes were synthesized through a simple hydrothermal route assisted by disodium ethylenediaminetetraacetic acid (Na(2)EDTA). X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), as well as kinetic decay curves were employed to characterize the samples. The results show that the reaction time, pH value of the initial solution, and Na(2)EDTA/La(3+) molar ratio all have an important influence on the dimension and shapes of the final products. By introducing the "splitting mechanism" to the dimension and morphology evolution process from one-dimensional (1D) to three-dimensional (3D) t-LaVO(4) crystals, the nucleation and crystal growth processes were well demonstrated. The Ln(3+) ions doped t-LaVO(4) samples exhibit respective bright red, blue-white and orange luminescence of Eu(3+), Dy(3+), and Sm(3+) under ultraviolet excitation, and have potential application in the fields of colour display, UV laser and biomedicine. The results not only expand the knowledge of the properties of lanthanide orthovanadates luminescence, but also contribute to the principles of the crystal growth and dimension transition of this kind of inorganic material.