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.     

Heterometallic cubane-like {M2Ln2} (M = Ni, Zn; Ln =, Gd, Dy) and {Ni2Y2} aggregates. Synthesis, structures and magnetic properties

The syntheses, structural determinations and magnetic studies of tetranuclear M(II)Ln(III) complexes (M = Ni, Zn; Ln = Y, Gd, Dy) involving an in situ compartmentalized schiff base ligand HL derived from the condensation of o-vanillin and 2-hydrazinopyridine as main ligand are described. Single-crystal X-ray diffraction reveals that all complexes are closely isostructural, with the central core composed of distorted {M(2)Ln(2)O(4)} cubes of the formulas [Ni(2)Ln(2)(μ(3)-OH)(2)(L)(2)(OAc)(4)(H(2)O)(3.5)](ClO(4))(2)·3H(2)O (Ln = Y 1 and Gd 2), [Ni(2)Dy(2)(μ(3)-OH)(2)(L)(2)(OAc)(5)(EtOH)(H(2)O)(1.5)](ClO(4))·EtOH·H(2)O (3) and [Zn(2)Ln(2)(μ(3)-OH)(2)(L)(2)(OAc)(5)(EtOH)(H(2)O)](ClO(4))·2EtOH·1.5H(2)O (Gd 4 and Dy 5). The Ln(III) ions are linked by two hydroxo bridges and each M(II) ion is also involved in a double phenoxo-hydroxo bridge with the two Ln(III) ions, so that each hydroxo group is triply linked to the two Ln(III) and one M(II) ions. The magnetic properties of all complexes have been investigated. Ni(2)Y(2) (1) has a ferromagnetic Ni(II)Ni(II) interaction. A weak ferromagnetic Ni(II)Ln(III) interaction is observed in the Ni(2)Ln(2) complexes (Ln = Gd 2, Dy 3), along with a weak antiferromagnetic Ln(III)Ln(III) interaction, a D zero-field splitting term for the nickel ion and a ferromagnetic Ni(II)Ni(II) interaction. The isomorphous Zn(2)Ln(2) (Ln = Gd 4, Dy 5) does confirm the presence of a weak antiferromagnetic Ln(III)Ln(III) interaction. The Ni(2)Dy(2) complex (3) does not behave as a SMM, which could result from a subtractive combination of the Dy and Ni anisotropies and an increased transverse anisotropy, leading to large tunnel splittings and quantum tunneling of magnetization. On the other hand, Zn(2)Dy(2) (5) exhibits a possible SMM behavior, where its slow relaxation of magnetization is probably attributed to the presence of the anisotropic Dy(III) ions.     

Using the flexible ligand bis(2-hydroxyethyl)amino-tris (hydroxymethyl)methane ("bis-tris") to access a family of 3d-4f Mn(III)4Ln4 complexes

A series of isostructural 3d-4f coordination clusters (CCs) [Mn(4)Ln(4)(OH)(6)(H(2)L)(2)(H(3)L)(2)(PhCO(2))(2)(N(3))(2)(MeOH)(4)]Cl(1.6)(N(3))(0.4)(NO(3))(2)·2.4H(2)O·1.6MeOH where Ln = Gd, Tb, Dy, Ho and Er and H(5)L = bis(2-hydroxyethyl)amino-tris(hydroxymethyl)methane (bis-tris) has been synthesised and structurally characterised. The paramagnetic metal ions within the clusters are weakly antiferromagnetically coupled, with the Tb and Dy compounds displaying slow relaxation of their magnetisation. This is the first report of this versatile ligand being used to target 3d-4f CCs.     

Lanthanoid-containing open Wells-Dawson silicotungstates: synthesis, crystal structures, and properties

Five novel lanthanoid-containing silicotungstates with polymeric crystal structures [Ln(2)(H(2)O)(7)Si(2)W(18)O(66)](n)(10n-) [Ln = Gd(III) (Gd-1 and Gd-2), Tb(III), Ho(III)] and [Dy(2)(H(2)O)(6.5)(C(2)H(4)O(2))(0.5)Si(2)W(18)O(66)](n)(10n-) were obtained from the one-step reaction of Na(10)[SiW(9)O(34)]·nH(2)O with Ln(NO(3))(3)·nH(2)O in a sodium acetate buffer. The compounds were characterized by single-crystal X-ray diffraction and a wide range of analytical methods, including FT-IR, UV/vis, and photoluminescence spectroscopy as well as electrochemistry and thermogravimetric analysis. This new polyoxotungstate series is the first example of lanthanoids embedded in the open Wells-Dawson silicotungstate anion [α-Si(2)W(18)O(66)](16-). The lanthanoid-containing Wells-Dawson-type polyoxoanions [Ln(2)(H(2)O)(7)Si(2)W(18)O(66)](10-) [Ln = Gd(III) (Gd-1 and Gd-2), Tb(III), Ho(III)] and [Dy(2)(H(2)O)(6.5)(C(2)H(4)O(2))(0.5)Si(2)W(18)O(66)](10-) are linked by Ln(3+) cations to form 3D architectures for Gd-1 or 2D frameworks for the isostructural compounds Tb-2, Dy-2, Ho-2, and Gd-2. The structure-directing influence of the lanthanoid cation on the local structure of the dimeric building blocks and on the crystal packing motifs is investigated in detail. The photoluminescence properties of Tb-2 and Dy-2 were investigated at room temperature, and Ho-2 exhibits an interesting photochromic behavior. The magnetic susceptibility of Gd-1 and Gd-2 was studied in the temperature range between 2 and 300 K for its effective magnetic moment.     

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.     

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.     

Cobalt-lanthanide coordination polymers constructed with metalloligands: a ferromagnetic coupled quasi-1D Dy3+ chain showing slow relaxation

Four types of cobalt-lanthanide heterometallic compounds based on metalloligand Co(2,5-pydc)(3) (3-) (2,5-H(2)pydc=pyridine-2,5-dicarboxylate acid), [Ln(2)Co(2)(2,5-pydc)(6)(H(2)O)(4)](n) 2n H(2)O (1) (Ln=Tb, Dy for 1 a, 1 b respectively), [Tb(2)Co(2)(2,5-pydc)(6)(H(2)O)(4)](n)3n H(2)O (2), [Tb(2)Co(2)(2,5-pydc)(6)(H(2)O)(9)](n)4n H(2)O (3), and [LaCo(2,5-pydc)(3)(H(2)O)(2)](n)2n H(2)O (4) have been synthesized. Compound 1 has a layer structure with well-isolated carboxylate-bridged Ln(3+) chains, compound 2 is a three-dimensional (3D) porous network with Tb(3+) chains that are also well isolated and carboxylate bridged, 3 is a layer structure based on dinuclear units, and 4 is a 3D network with boron nitride (BN) topology. DC magnetic studies reveal ferromagnetic coupling in all the carboxylate-bridged Ln(3+) chains in 1 a, 1 b, and 2. Compared to the silence of the out-of-phase ac susceptibility of 2, above 1.9 K the magnetic relaxation behavior of both 1 a and 1 b is slow like that of a single-chain magnet.     

Diversity of lanthanide(iii)-2,5-dihydroxy-1,4-benzenedicarboxylate extended frameworks: syntheses, structures, and magnetic properties

Six lanthanide(iii)-2,5-dihydroxy-1,4-benzenedicarboxylate frameworks, namely, [Ln(H(2)-DHBDC)(1.5)(H(2)O)(2)](n) (Ln = La (1) and Pr (2); H(4)-DHBDC = 2,5-dihydroxy-1,4-benzenedicarboxylic acid), {[Nd(H(2)-DHBDC)(1.5)(H(2)O)(3)](H(2)O)}(n) (3), {[Eu(H(2)-DHBDC)(NO(3))(H(2)O)(4)](H(2)O)(2)}(n) (4), and {[Ln(2)(H(2)-DHBDC)(2)(DHBDC)(0.5)(H(2)O)(3)](H(2)O)(4)}(n) (Ln = Gd (5) and Dy (6)), with four different structural types ranging from 1D chain, 2D layer to 3D networks have been synthesized and structurally characterized. Compounds La (1) and Pr (2) are isomorphous and exhibit 3D frameworks with the unique 1D tubular channels. Compounds Nd (3) and Eu (4) are 2D layer and 1D zigzag chain, respectively, which are further extended to 3D supramolecular frameworks through extensive hydrogen bonds. Isomorphous compounds of Gd (5) and Dy (6) are 3D frameworks constructed from secondary infinite rod-shaped metal-carboxylate/hydroxyl building blocks. While the hydroxyl groups as secondary functional groups in the 1D chain of Eu (4) and 2D layer of Nd (3) are not bonded to the lanthanide centers, the hydroxyl groups in the 3D frameworks of La (1), Pr (2), Gd (5), and Dy (6) participate in coordinating to lanthanide centers and thus modify the structural types of theses compounds. The magnetic data of compounds Pr (2), Nd (3), Gd (5), and Dy (6) have been investigated in detail. In addition, elemental analysis, IR spectra, powder X-ray diffraction (PXRD) patterns and thermogravimetric analysis of these compounds are described.     

Anion dependant self-assembly and the first X-ray structure of a neutral homoleptic lanthanide salen complex Tb4(salen)6

Reaction of H(2)salen (H(2)L) with Tb(OAc)(3).4H(2)O (3 : 2) in MeOH-MeCN under reflux gave homoleptic Tb(4)L(6) (1) in 40% yield; in contrast, similar reactions of Tb(NO(3))(3).6H(2)O and LnCl(3).6H(2)O (Ln = Tb, Nd and Yb) gave [TbL(NO(3))(MeOH)](2)(micro-H(2)L) (2) and [LnL(Cl)(MeOH)](2)(micro-H(2)L) (Ln = Tb (3), Nd (4) and Yb (5); H(2)L = N,N'-ethylenebis(salicylideneimine)).     

Novel polyoxometalate hybrids consisting of copper-lanthanide heterometallic/lanthanide germanotungstate fragments

Three organic-inorganic hybrid copper-lanthanide heterometallic germanotungstates, {[Cu(en)(2)(H(2)O)] [Cu(3)Eu(en)(3)(OH)(3)(H(2)O)(2)](α-GeW(11)O(39))}(2)·11H(2)O (1), {[Cu(en)(2)(H(2)O)][Cu(3)Tb(en)(3)(OH)(3)(H(2)O)(2)](α-GeW(11)O(39))}(2)·11H(2)O (2) and {[Cu(en)(2)(H(2)O)][Cu(3)Dy(en)(3)(OH)(3)(H(2)O)(2)](α-GeW(11)O(39))}(2)·10H(2)O (3) and three polyoxometalate hybrids built by lanthanide-containing germanotungstates and copper-ethylendiamine complexes, Na(2)H(6)[Cu(en)(2)(H(2)O)](8){Cu(en)(2)[La(α-GeW(11)O(39))(2)](2)}·18H(2)O (4), K(4)H(2)[Cu(en)(2)(H(2)O)(2)](5)[Cu(en)(2)(H(2)O)](2)[Cu(en)(2)](2){Cu(en)(2)[Pr(α-GeW(11)O(39))(2)](2)}·16H(2)O (5) and KNa(2)H(7)[enH(2)](3)[Cu(en)(2)(H(2)O)](2)[Cu(en)(2)](2){Cu(en)(2)[Er(α-GeW(11)O(39))(2)](2)}·15H(2)O (6) (en = ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, IR spectra, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. 1-3 are essentially isomorphous and their main skeletons display the interesting dimeric motif {[Cu(3)Ln(en)(3)(OH)(3)(H(2)O)(2)](α-GeW(11)O(39))}(2)(4-), which is constructed from two {Cu(3)LnO(4)} cubane anchored monovacant [α-GeW(11)O(39)](8-) fragments through two W-O-Ln-O-W linkers. The primary backbones of 4-6 exhibit the tetrameric architecture {Cu(en)(2)[Ln(α-GeW(11)O(39))(2)](2)}(24-) built by two 1?:?2-type [Ln(α-GeW(11)O(39))(2)](13-) moieties and one [Cu(en)(2)](2+) bridge, albeit they are not isostructural. To our knowledge, 1-6 are rare polyoxometalate derivatives consisting of copper-lanthanide heterometallic/lanthanide germanotungstate fragments. 1 exhibits antiferromagnetic coupling interactions within the {Cu(3)EuO(4)} cubane units, while 2 and 3 display dominant ferromagnetic interactions between the Tb(III)/Dy(III) and Cu(II) cations. The room-temperature solid-state photoluminescence properties of 1-3 have been investigated.     

[PMo_(12)O_(40)]~(3-)模板导向合成含螺旋链的新颖二维层状Dy(Ⅲ)化合物

在水热条件下,以[PMo_(12)O_(40)]~(3-)为模板,合成了一个例新型二维层状化合物[Dy(BMBCP)(H_2O)_4]·[PMo(12)O_(40)]·2.75H_2O[HNU-7,H_2BMBCP·Cl_2=1,4-双(4-羧酸吡啶基-1-亚甲基)苯二氯],并通过X射线单晶结构解析、红外光谱(IR)、电感耦合等离子体光谱(ICP)、X射线粉末衍射(XRD)和荧光光谱对该化合物结构进行表征.由于客体分子[PMo_(12)O_(40)]~(3-)与配体BMBCP中的N+之间存在静电吸引力,导致了-Dy2簇-BMBCP-Dy2簇-交替排列的螺旋链的形成.左手螺旋链和右手螺旋链通过共同的Dy2簇进一步构筑成层状的4,4-网格结构.     

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.     

A family of three-dimensional 3d-4f and 4d-4f heterometallic coordination polymers based on mixed isonicotinate and 2-sulfobenzoate ligands: syntheses, structures and photoluminescent properties

Hydrothermal reactions of isonicotinic acid (Hina), 2-sulfobenzoic acid (H(2)sba), d-block metal salts and lanthanide oxides/hydroxides yielded 17 three-dimensional (3D) 3d-4f and 4d-4f heterometallic coordination polymers (HCPs). They are formulated as [LaAg(sba)(ina)(2)](n) (1), [Ln(2)Ag(2)(sba)(2)(ina)(4)(H(2)O)(2)](n) [Ln = Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Ho (9), Er (10)] and [Ln(2)Cu(2)(sba)(2)(ina)(4)(H(2)O)(2)](n) [Ln = La (11), Pr (12), Nd (13), Sm (14), Eu (15), Gd (16), Tb (17)]. Their structures were characterized by single crystal X-ray diffraction, powder X-ray diffraction (XRD), infrared (IR) spectroscopy, elemental analysis (EA), and thermogravimetric analysis (TGA). It reveals that they represent two structural types of 3D HCPs. Furthermore, the investigations of their solid-state photoluminescent (PL) property demonstrate the extraordinary emission behaviors. HCP 1(La-Ag) exhibits tunable blue-to-green PL emissions by variation of excitation light. HCPs 6(Gd-Ag), 11(La-Cu), 12(Pr-Cu) and 16(Gd-Cu) show d(10)-metal-based ligand-to-metal charge transfer (LMCT) or metal-to-ligand charge transfer (MLCT) emissions. HCPs 3(Nd-Ag), 4(Sm-Ag), 5(Eu-Ag), 7(Tb-Ag), 8(Dy-Ag), 13(Nd-Cu), 14(Sm-Cu), 15(Eu-Cu) and 17(Tb-Cu) display characteristic PL emissions of the corresponding Ln(III) ions, while both d(10)-metal-based and 4f-metal-centered emissions are observed in the emission spectra of 4(Sm-Ag), 8(Dy-Ag), 14(Sm-Cu) and 17(Tb-Cu).     

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.     

Diversity of lanthanide(III)-organic extended frameworks with a 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid ligand: syntheses, structures, and magnetic and luminescent properties

A sulfonate-carboxylate ligand, 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid (H(4)-DSNDA), and eight new lanthanide coordination polymers {[Pr(4)(OH)(4)(DSNDA)(2)(H(2)O)(12)](H(2)O)(10)}(n) (1), [Ln(H(2)-DSNDA)(0.5)(DSNDA)(0.5)(H(2)O)(5)](n) (Ln = La(2), Nd(3), Sm(4), Eu(5), Gd(6), and Dy(7)), and {[Er(H-DSNDA)(H(2)O)(4)](H(2)O)}(n) (8) have been synthesized. Detailed crystal structures of these compounds have been investigated. Compound 1 has a 3D framework featuring the unique cubane-shaped [Pr(4)(μ(3)-OH)(4)] clusters and is a binodal 4,8-connected network with (4(16)·6(12))(4(4)·6(2))(2) topology. Compounds 2-7 are isostructural and have 2D layered structures. Compound 8 is also a 2D layer but belongs to different structural types. The luminescence behavior of compound Eu(5) shows that the π-rich aromatic organic ligands efficiently transfer the absorbed light energy to the Eu(III) ions, thus enhancing the overall luminescent properties of compound Eu(5). The magnetic properties of all compounds except for the diamagnetic La(2) compound have been investigated. In addition, elemental analysis, IR spectra, and thermogravimetric analysis of these compounds are also described.     

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.     

A series of luminescent lanthanide-cadmium-organic frameworks with helical channels and tubes

Lanthanide (Ln) oxides and cadmium (Cd) salts as sources of metals provided the first series of luminescent Ln-Cd-organic frameworks, [LnCd(imdc)(SO4)(H2O)3].0.5H2O (Ln = Tb, Eu, Dy, Gd, Er, Yb, Y, Nd, Pr; H3imdc = 4,5-imidazoledicarboxylic acid), in which the Ln atoms are linked by imdc ligands with skew coordination orientation, resulting in novel hetero-metallic-organic frameworks with left-/right-handed helical tubes (L1/R1) and channels (L2/R2) along the b axis.     

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.     

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 ...     

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.