Planar tetranuclear Dy(III) single-molecule magnet and its Sm(III), Gd(III), and Tb(III) analogues encapsulated by salen-type and β-diketonate ligands

The syntheses, structures, and magnetic properties are reported for four new lanthanide clusters [Sm(4)(μ(3)-OH)(2)L(2)(acac)(6)]·4H(2)O (1), [Gd(4)(μ(3)-OH)(2)L(2)(acac)(6)]·4CH(3)CN (2), and [Ln(4)(μ(3)-OH)(2)L(2)(acac)(6)]·2H(2)L·2CH(3)CN (3, Ln = Tb; 4, Ln = Dy) supported by salen-type (H(2)L = N,N'-bis(salicylidene)-1,2-cyclohexanediamine) and β-diketonate (acac = acetylacetonate) ligands. The four clusters were confirmed to be essentially isomorphous by infrared spectroscopy and single-crystal X-ray diffraction. Their crystal structures reveal that the salen-type ligand provides a suitable tetradentate coordination pocket (N(2)O(2)) to encapsulate lanthanide(III) ions. Moreover, the planar Ln(4) core is bridged by two μ(3)-hydroxide, four phenoxide, and two ketonate oxygen atoms. Magnetic properties of all four compounds have been investigated using dc and ac susceptibility measurements. For 4, the static and dynamic data indicate that the Dy(4) complex exhibits slow relaxation of the magnetization below 5 K associated with single-molecule magnet behavior.     

Assembling process of charged nonanuclear cationic lanthanide(III) clusters assisted by dichromium decacarbonyl hydride

The reaction of Ln(acac)(3).3H(2)O (Ln = Sm, Eu, Gd, Dy, Yb) with K[Cr(2)(CO)(10)(micro-H)] at different molar ratios and solvents leads to the formation of nonanuclear lanthanide hydroxo acetylacetonate complexes of general formula [Ln(9)(OH)(10)(acac)(16)][HCr(2)(CO)(10)]. The compounds are isomorphous, and the common cationic cluster core consists of a novel square antiprismatic arrangement of nine Ln atoms connected by micro(3), micro(4) hydroxo bridges and/or by acetylacetonate ligands as it results from the single-crystal X-ray analysis of the Sm derivative for which the most suitable crystals were obtained.     

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 catalytic activity of alkali metal-free bent-sandwiched lanthanide amido complexes with calix[4]-pyrrolyl ligands

Simple silylamine elimination reactions of calix[4]-pyrrole [R(2)C(C(4)H(2)NH)](4) (R = Me (1), {-(CH(2))(5)-}(0.5) (2)) with 2 equiv. of [(Me(3)Si)(2)N](3)Ln(μ-Cl)Li(THF)(3) (Ln = Nd, Sm, Dy) in reflux toluene, afforded the novel dinuclear alkali metal-free trivalent lanthanide amido complexes (η(5):η(1):η(5):η(1)-R(8)-calix[4]-pyrrolyl){LnN(SiMe(3))(2)}(2) (R = Me, Ln = Nd (3), Sm (4), Dy (5); R = {-(CH(2))(5)-}(0.5), Ln = Nd (6), Sm(7)). The complexes were fully characterized by elemental analyses, spectroscopic analyses and single-crystal X-ray analyses. X-ray diffraction studies showed that each lanthanide metal was supported by bispyrrolyl anions in an η(5) fashion and along with three nitrogen atoms from N(SiMe(3))(2) and two other pyrroyl rings in η(1) modes formed the novel bent-sandwiched lanthanide amido bridged trivalent lanthanide amido complexes, similar to ansa-cyclopentadienyl ligand-supported lanthanide amides with respect to each metal center. The catalytic activities of these organolanthanide complexes as single component l-lactide polymerization catalysts were studied.     

Ligand field-tuned single-molecule magnet behaviour of 2p-4f complexes

Three new 2p-4f complexes of [Ln(acac)(3)(NIT-2Py)]·0.5NIT-2Py [Ln(III) = Gd(1), Dy(2)] and [Dy(tfa)(3)(NIT-2Py)]·0.5C(7)H(16) (3) (NIT-2Py = 2-(2'-pyridyl)- 4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide; acac = acetylacetonate and tfa = trifluoroacetylacetonate) have been synthesized, and structurally and magnetically characterized. The X-ray structural analysis exhibits that the three complexes show similar mononuclear structures, in which NIT-2Py radical chelates the Ln(III) ion through the oxygen atom of the NO group and the nitrogen atom from the pyridine ring. The static magnetic measurements on the three complexes exhibit ferromagnetic coupling between the lanthanide ion and the radical. Compared to the silence of the out-of-phase ac susceptibility of complex 3, the magnetic relaxation behavior of complex 2 is observed, suggesting single-molecule magnet behavior. The different magnetic relaxation behaviours of 2 and 3 are due to their slightly different crystal structure around the Dy(III) ions. It was demonstrated that the spin dynamic can be modified by the careful adjustment of the ligand field around the metal center.     

Defect-dicubane Ni2Ln2 (Ln = Dy, Tb) single molecule magnets

Two pairs of Ni(2)Dy(2) and Ni(2)Tb(2) complexes, [Ni(2)Ln(2)(L)(4)(NO(3))(2)(DMF)(2)] {Ln = Dy (1), Tb (2)} and [Ni(2)Ln(2)(L)(4)(NO(3))(2)(MeOH)(2)]·3MeOH {Ln = Dy (3), Tb (4)} (H(2)L is the Schiff base resulting from the condensation of o-vanillin and 2-aminophenol) possessing a defect-dicubane core topology were synthesized and characterized. All four complexes are ferromagnetically coupled, and the two Dy-analogues are found to be Single Molecule Magnets (SMMs) with energy barriers in the range 18-28 K. Compound 1 displays step-like hysteresis loops, confirming the SMM behavior. Although 1 and 3 show very similar structural topologies, the dynamic properties of 1 and 3 are different with blocking temperatures (3.2 and 4.2 K at a frequency of 1500 Hz) differing by 1 K. This appears to result from a change in orientation of the nitrate ligands on the Dy(III) ions, induced by changes in ligands on Ni(II).     

2D LnIII RuIII 2 compounds constructed from trans-[Ru(acac)2(CN)2]-. Syntheses, structures, and magnetic properties

A series of cyano-bridged Ln(III)Ru(III)2 coordination polymers, Ph4P{Ln(NO3)2[Ru(acac)2(CN)2]2} [Ln = Tb (1), Dy (2), Er (3), Gd (4); Hacac = acetylacetone] have been synthesized by the reaction of Ln(NO3)3 with trans-Ph4P[Ru(acac)2(CN)2] in methanol. X-ray crystallographic determination reveals that these compounds are isostructural and have a wavy (4,4) layer structure with the Ln3+ ions bridged by trans-[Ru(acac)2(CN)2]-. Magnetic studies shows that the magnetic coupling between the Ln(III) and Ru(III) ions through the cyano bridges in 1-4 is negligibly weak.     

Initial observation of magnetization hysteresis and quantum tunneling in mixed manganese-lanthanide single-molecule magnets

The preparation of a new family of mixed transition metal/lanthanide clusters is reported. The reaction of [Mn3O(O2CPh)6(py)2(H2O)] with Ln(NO3)3 (Ln = Nd, Gd, Dy, Ho, and Eu) in a 1:2 molar ratio in MeOH/MeCN (1:20 v/v) leads to dark crystals in 55-60% isolated yield of complexes all containing the [Mn11Ln4]45+ core. The Dy compound has been found to give out-of-phase AC susceptibility signals, suggesting it might be a single-molecule magnet (SMM). This was confirmed by the observation of magnetization hysteresis loops. An Arrhenius plot constructed from magnetization decay data gave a barrier to relaxation of 9.3 K and showed the temperature-independent relaxation at very low temperatures indicative of quantum tunneling of magnetization. This is the initial demonstration of hysteresis and quantum behavior in a mixed 3d/4f SMM.     

Synthesis, structures, and luminescence properties of lanthanide complexes with structurally related new tetrapodal ligands featuring salicylamide pendant arms

To explore the relationships between the structures of ligands and their complexes, we have synthesized and characterized a series of lanthanide complexes with two structurally related ligands, 1,1,1,1-tetrakis{[(2'-(2-benzylaminoformyl))phenoxyl]methyl}methane (L(I)) and 1,1,1,1-tetrakis{[(2'-(2-picolyaminoformyl))phenoxyl]methyl}methane (L(II)). A series of zero- to three-dimensional lanthanide coordination complexes have been obtained by changing the substituents on the Pentaerythritol. Our results revealed that, complexes of the L(I) ligand, {Ln(4)L(I)(3)(NO(3))(12).nC(4)H(10)O}(infinity) (Ln = Nd, Eu, Tb, Er, n = 3 or 6)] show the binodal 3,4-connected three-dimensional interpenetration coordination polymers with topology of a (8(3))(4)(8(6))(3) notation. Compared to L(I), complexes of L(II) present a cage-like homodinuclear [Ln(2)L(II)(2)(NO(3))(6).2H(2)O].nH(2)O (Ln = Nd, Tb, Dy, n = 0 or 1) or a helical one-dimensional coordination {[ErL(II)(NO(3))(3).H(2)O].H(2)O}(infinity) polymer. The luminescence properties of the resulting complexes formed with ions used in fluoroimmunoassays (Ln = Eu, Tb) are also studied in detail. It is noteworthy that subtle variation of the terminal group from benzene to pyridine not only sensibly affects the overall molecular structures but also the luminescence properties as well.     

不对称希夫碱卟啉及其稀土配合物的合成与表征

以二甲基甲酰胺为溶剂,5-对氨基苯基-10,15,20-三苯基卟啉与苯甲醛直接反应得到一种不对称希夫碱卟啉化合物,并合成了它的稀土配合物.用元素分析、紫外-可见光谱、红外光谱1、H核磁共振以及X射线光电子能谱对这些化合物进行了表征,推测了稀土乙酰丙酮卟啉配合物的结构,稀土离子与乙酰丙酮的两个O原子和卟啉的4个吡咯N原子配位,配位数为6,稀土离子位于卟啉平面的上方.     

A diabolo-shaped Dy9 cluster: synthesis, crystal structure and magnetic properties

The reaction of Dy(NO(3))(3)·6H(2)O with the ligand 2-((1-hydroxybutan-2-ylimino)methyl)phenol (H(2)L, ) generates the nonanuclear compound [Dy(9)L(8)(μ(3)-OH)(8)(μ(4)-OH)(2)(CH(3)OH)(8)](OH)(CH(3)OH)(3) (Dy(9)), whose single-crystal X-ray structure reveals the presence of two square pyramidal pentanuclear units assembled via the apical metal center. The square pyramidal core of a previously reported [Dy(5)(μ(4)-OH)(μ(3)-OH)(4)(μ-η(2)-Ph(2)acac)(4)(η(2)-Ph(2)acac)(6)] (Dy(5); Ph(2)acac = dibenzoylmethanide), is structurally related to those herein described; however, the magnetic properties of Dy(9) and Dy(5) are drastically different. Indeed, Dy(5) shows slow relaxation of magnetization while no out-of-phase ac signal is noticed for Dy(9). The underlying mechanism is not clear due to the complexity of such systems; however, the different anisotropy of the respective structures, which is dictated by the combination of the metal topology, the ligands involved and the structural parameters of the molecule, is mostly responsible for the distinctive relaxation dynamics observed.     

Single-molecule magnet behavior for an antiferromagnetically superexchange-coupled dinuclear dysprosium(III) complex

A family of five dinuclear lanthanide complexes has been synthesized with general formula [Ln(III)(2)(valdien)(2)(NO(3))(2)] where (H(2)valdien = N1,N3-bis(3-methoxysalicylidene)diethylenetriamine) and Ln(III) = Eu(III)1, Gd(III)2, Tb(III)3, Dy(III)4, and Ho(III)5. The magnetic investigations reveal that 4 exhibits single-molecule magnet (SMM) behavior with an anisotropic barrier U(eff) = 76 K. The step-like features in the hysteresis loops observed for 4 reveal an antiferromagnetic exchange coupling between the two dysprosium ions. Ab initio calculations confirm the weak antiferromagnetic interaction with an exchange constant J(Dy-Dy) = -0.21 cm(-1). The observed steps in the hysteresis loops correspond to a weakly coupled system similar to exchange-biased SMMs. The Dy(2) complex is an ideal candidate for the elucidation of slow relaxation of the magnetization mechanism seen in lanthanide systems.     

Diversity of crystal structure with different lanthanide ions involving in situ oxidation-hydrolysis reaction

A series of lanthanide and lanthanide-transition metal compounds with isonicotinic acid (Hina) and oxalate ligands have been synthesized under hydrothermal reactions. X-Ray crystal structure analyses reveal that they have a rich structural chemistry. Three distinct structure types were exhibited with decreasing lanthanide radii: [LnCu(ina)(2)(C(2)O(4))].H(2)O (Ln=La 1, Pr 2, Nd 3) for type I, [Ln(ina)(C(2)O(4))(H(2)O)(2)] (Ln=Sm 4, Eu 5, Gd 6) for type II, and [Ln(ina)(C(2)O(4))(0.5)(OH)] (Ln=Tb 7, Dy 8, Er 9) for type III. The structure of type I has a 3d-4f heterometallic structure and consists of 1D channels along the b axis, which filled with guest water molecules. They exhibit a first 3D uninodal eight-connected framework with a unique 3(6).4(18).5(3).6 topology. Type II has 2D Ln-ina-C(2)O(4) 4(4)-nets, the nitrogen donors of the ina ligand are not coordinated to any of the metal ions, inducing the lower dimensional networks. Type III consists of 2D Ln-C(2)O(4) layers pillared by ina ligands to form a pillared-layer framework. The structure evolution is due to the versatile coordination modes of ina and oxalate ligands as well as the lanthanide contraction effect. Notably, the oxalate ligand was in situ synthesized from orotic acid through an oxidation-hydrolysis reaction. The type III materials show high thermal stability; luminescence properties of Nd 3, Sm 4, Eu 5, Tb 7 are also investigated.     

Structural and photophysical properties of coordination networks combining [Ru(bipy)(CN)4]2- anions and lanthanide(III) cations: rates of photoinduced Ru-to-lanthanide energy transfer and sensitized near-infrared luminescence

Co-crystallization of K2[Ru(bipy)(CN)4] with lanthanide(III) salts (Ln = Pr, Nd, Gd, Er, Yb) from aqueous solution affords coordination oligomers and networks in which the [Ru(bipy)(CN)4]2- unit is connected to the lanthanide cation via Ru-CN-Ln bridges. The complexes fall into two structural types: [{Ru(bipy)(CN)4}2{Ln(H2O)m}{K(H2O)n}] x xH2O (Ln = Pr, Er, Yb; m = 7, 6, 6, respectively), in which two [Ru(bipy)(CN)4]2- units are connected to a single lanthanide ion by single cyanide bridges to give discrete trinuclear fragments, and [{Ru(bipy)(CN)4}3{Ln(H2O)4}2] x xH2O (Ln = Nd, Gd), which contain two-dimensional sheets of interconnected, cyanide-bridged Ru2Ln2 squares. In the Ru-Gd system, the [Ru(bipy)(CN)4]2- unit shows the characteristic intense (3)metal-to-ligand charge transfer luminescence at 580 nm with tau = 550 ns; with the other lanthanides, the intensity and lifetime of this luminescence are diminished because of a Ru --> Ln photoinduced energy transfer to low-lying emissive states of the lanthanide ions, resulting in sensitized near-infrared luminescence in every case. From the degree of quenching of the Ru-based emission, Ru --> Ln energy-transfer rates can be estimated, which are in the order Yb (k(EnT) approximately 3 x 10(6) sec(-1), the slowest energy transfer) < Er < Pr < Nd (k(EnT) approximately 2 x 10(8) sec(-1), the fastest energy transfer). This order may be rationalized on the basis of the availability of excited f-f levels on the lanthanide ions at energies that overlap with the Ru-based emission spectrum. In every case, the lifetime of the lanthanide-based luminescence is short (tens/hundreds of nanoseconds, instead of the more usual microseconds), even when the water ligands on the lanthanide ions are replaced by D2O to eliminate the quenching effects of OH oscillators; we tentatively ascribe this quenching effect to the cyanide ligands.     

Lanthanide diruthenium(II,III) compounds showing layered and PtS-type open framework structures

Two types of lanthanide diruthenium phosphonate compounds, based on the mixed-valent metal-metal bonded paddlewheel core of Ru(2)(hedp)(2)(3-) [hedp = 1-hydroxyethylidenediphosphonate, CH(3)C(OH)(PO(3))(2)], have been prepared with the formulas Ln(H(2)O)4[Ru(2)(hedp)(2)(H(2)O)2].5.5H(2)O (1.Ln, Ln = La, Ce) and Ln(H(2)O)4[Ru(2)(hedp)(2)(H(2)O)(2)].8H(2)O (2.Ln, Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er). In both types, each Ru(2)(hedp)2(H2O)23- unit is linked by four Ln(3+)ions through four phosphonate oxygen (OP) atoms and vice versa. The geometries of the {LnO(P4)} group, however, are different in the two cases. In 1.Ln, the geometry of {LnO(P4)} is closer to a distorted plane, and thus a square-grid layer structure is found. In 2.Ln, the geometry of {LnO(P4)} is better described as a distorted tetrahedron; hence, a unique PtS-type open-framework structure is observed. The channels generated in structures 2.Ln are filled with water aggregates with extensive hydrogen-bond interactions. The magnetic and electrochemical properties are also investigated.     

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.     

Synthesis, structures, and magnetic properties of three fluoride-bridged lanthanide compounds: effect of bridging fluoride ions on magnetic behaviors

A family of fluoride-bridged lanthanide compounds, [Dy(III)F(oda)(H(2)O)(3)] (1, oda = oxidiacetate) and [Ln(III)(2)F(2)(oda)(2)(H(2)O)(2)] (Ln = Tb(2) and Dy(3)), was synthesized and characterized. To investigate the effects of bridging ligands on magnetic behaviors, two hydroxyl-bridged complexes of formulas [Ln(III)(2)(OH)(2)(oda)(2)(H(2)O)(4)] (Ln = Tb(4) and Dy(5)) were also synthesized. Magnetic measurements show that the magnetic behaviors of the compounds are obviously distinct. Compounds 1, 2, and 3 show ferromagnetic interactions, while only antiferromagnetic interactions are observed in compounds 4 and 5. Among these compounds, 1 and 3 show frequency-dependent ac-susceptibility indicative of slow magnetic relaxation. Because the structures of Dy(2) cores are very similar in compounds 3 and 5, it may be inferred that the differences of bridging ligands are mainly responsible for the distinct magnetic exchange interactions and relaxation dynamics.     

A convenient route to lanthanide triiodide THF solvates. Crystal structures of LnI(3)(THF)(4) [Ln = Pr] and LnI(3)(THF)(3.5) [Ln = Nd, Gd, Y

The reaction between 1.5 equiv of elemental iodine and rare earth metals in powder form in THF at room temperature gives the rare earth triiodides LnI(3)(THF)(n)() in good yields. Purification by Soxhlet extraction of the crude solids with THF reliably gives the THF adducts LnI(3)(THF)(4) [Ln = La, Pr] and LnI(3)(THF)(3.5) [Ln = Nd, Sm, Gd, Dy, Er, Tm, Y] as microcrystalline solids. X-ray crystallography reveals that the early, larger lanthanide iodide PrI(3)(THF)(4) crystallizes as discrete molecules having a pentagonal bipyramidal structure, whereas the later, smaller lanthanide iodides LnI(3)(THF)(3.5) [Ln = Nd, Gd, Y] crystallize as solvent-separated ion pairs [LnI(2)(THF)(5)][LnI(4)(THF)(2)] in which the cations adopt a pentagonal bipyramidal geometry and the anions adopt an octahedral geometry in the solid state.     

In situ hydrothermal synthesis of dysprosium(III) single-molecule magnet with lanthanide salt as catalyst

A family of six dinuclear lanthanide complexes have been obtained via in situ hydrothermal synthesis with lanthanide ions as catalyst. These six complexes are formulated as [Ln(2)(3-Htzba)(2)(3-tzba)(2)(H(2)O)(8)]·4H(2)O [Ln = Gd, 1; Dy, 2; Eu, 3; Tb, 4; Sm, 5; Er, 6; 3-H(2)tzba = 3-(1H-tetrazol-5-yl)benzoic acid]. The magnetic investigations show that complex 2 behaves as a single-molecule magnet (SMM) with a quantum relaxation time of ~10(-2) s.     

New luminescent solids in the Ln-W(Mo)-Te-O-(Cl) systems

Solid-state reactions of lanthanide(III) oxide (and/or lanthanide(III) oxychloride), MoO3 (or WO3), and TeO2 at high temperature lead to eight new luminescent compounds with four different types of structures, namely, Ln2(MoO4)(Te4O10) (Ln = Pr, Nd), La2(WO4)(Te3O7)2, Nd2W2Te2O13, and Ln5(MO4)(Te5O13)(TeO3)2Cl3 (Ln = Pr, Nd; M = Mo, W). The structures of Ln2(MoO4)(Te4O10) (Ln = Pr, Nd) feature a 3D network in which the MoO4 tetrahedra serve as bridges between two lanthanide(III) tellurite layers. La2(WO4)(Te3O7)2 features a triple-layer structure built of a [La2WO4]4+ layer sandwiched between two Te3O72- anionic layers. The structure of Nd2W2Te2O13 is a 3D network in which the W2O108- dimers were inserted in the large tunnels of the neodymium(III) tellurites. The structures of Ln5(MO4)(Te5O13)(TeO3)2Cl3 (Ln = Pr, Nd; M = Mo, W) feature a 3D network structure built of lanthanide(III) ions interconnected by bridging TeO32-, Te5O136-, and Cl- anions with the MO4 (M = Mo, W) tetrahedra capping on both sides of the Ln4 (Ln = Pr, Nd) clusters and the isolated Cl- anions occupying the large apertures of the structure. Luminescent studies indicate that Pr2(MoO4)(Te4O10) and Pr5(MO4)(Te5O13)(TeO3)2Cl3 (M = Mo, W) are able to emit blue, green, and red light, whereas Nd2(MoO4)(Te4O10), Nd2W2Te2O13, and Nd5(MO4)(Te5O13)(TeO3)2Cl3 (M = Mo, W) exhibit strong emission bands in the near-IR region.