Luminescent chains formed from neutral, triangular gold complexes sandwiching TlI and AgI. Structures of (Ag([Au(mu-C2,N3-bzim)]3)2)BF4.CH2Cl2, (Tl([Au(mu-C2,N3-bzim)]3)2)PF(6).0.5THF (bzim = 1-benzylimidazolate), and (Tl([Au(mu-C(OEt)=NC6H4CH3)]3)2)PF6.THF, with MAu6 (M = Ag+, Tl+) cluster cores

It has been found that several trinuclear complexes of AuI interact with silver and thallium salts to intercalate Ag+ and Tl+ cations, thereby forming chains. The resulting sandwich clusters center the cations between the planar trinuclear moieties producing structures in which six AuI atoms interact with each cation in a distorted trigonal prismatic coordination. The resultant (B3AB3B3AB3)infinity pattern of metal atoms also shows short (approximately 3.0 A) aurophilic interactions between BAB molecular centers. These compounds display a strong visible luminescence, under UV excitation, which is sensitive to temperature and the metal ion interacting with the gold. X-ray crystal structures are reported for Ag([Au(mu-C2,N3-bzim)]3)2BF4CH2Cl2 (P1, Z = 2, a = 14.4505(1) A; b = 15.098(2)A; c = 15.957(1)A; alpha = 106.189(3) degrees; beta = 103.551(5) degrees; gamma = 101.310(5) degrees); Tl([Au(mu-C2,N3-bzim)]3)2PF(6)05C4H8O (P1, Z = 2, a = 15.2093(1)A; b = 15.3931(4)A; c = 16.1599(4)A; alpha = 106.018(1) degrees; beta = 101.585(2) degrees; gamma = 102.068(2) degrees); and Tl([Au(mu-C(OEt)=NC6H4CH3)]3)2PF6.C4H8O (P2(1)/n, Z = 4, a = 16.4136(3)A; b = 27.6277(4)A; c = 16.7182(1)A; beta = 105.644(1) degrees). Each compound shows that the intercalated cation, Ag+ or Tl+, coordinates to a distorted trigonal prism of six AuI atoms. The counteranions reside well apart from the cations between the cluster chains.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O and [La(DMSO)4(H2O)3Co(CN)6]·H2O (DMSO = Dimethylsulfoxide)

Two new bimetallic cyano-bridged complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O 1 and [La(DMSO)4(H2O)3Co(CN)6]·H2O 2 have been prepared by the ball milling reaction method and structurally characterized by X-ray single-crystal structure analyses. Crystallographic data for 1:C14H32CeFeN6O8S4, Mr = 736.67, monoclinic, space group P21/n, a = 14.952(1), b =13.7276(9), c = 15.392(1) (A), β = 108.288(1)°, V = 2999.6(4) (A)3, Z = 4, Dc= 1.631 g/cm3,μ =2.304 mm-1, F(000) = 1480, R = 0.0593 and wR = 0.1611; and those for 2: C14H32CoLaN6O8S4,Mr=738.54, monoclinic, space group P21/n, a = 14.945(3), b = 13.731(3), c = 15.300(3) (A), β=107.806(1)°, V= 2989.3(11) (A)3, Z = 4, Dc = 1.641 g/cm3,μ = 2.288 mm-1, F(000) = 1480, R =0.0383 and wR = 0.1132. In both complexes the lanthanide ion is eight-coordinated in a square antiprism arrangement, and the Fe(Ⅲ) or Co(Ⅲ) ion in a nearly regular octahedral environment.The [LnM(CN)6(DMSO)4(H2O)3]·H2O (Ln = Ce and M = Fe for 1; Ln = La and M = Co for 2)species are held together via hydrogen bonds by coordinated water molecules, lattice water molecules and nitrogen atoms of cyanide groups to form a three-dimensional framework.     

新型三维开放骨架稀土硫酸盐[Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4(Ln=Gd,Eu)的合成、结构及荧光性质

以哌嗪为模板剂,在水-乙醇混合溶剂体系中溶剂热合成了两个具有三维开放骨架结构的稀土硫酸盐[Ln4(H2O)4(SO4)10](C4N2H12)4(H2O)4（Ln = Gd,化合物1和Eu,化合物2）,并对其进行了结构表征、热重以及荧光光谱分析. 单晶结构解析表明,化合物1和2属于同构异质,均结晶于单斜晶系,P21/c空间群,化合物1,a = 19.691(3) ?,b = 19.249(3) ?,c = 13.186(2) ?,β = 92.33(0)o,V = 4993.5(1) ?3, Z =4. 化合物2,a = 19.7233(8) ?,b = 19.2791(8) ?,c = 13.2095(5) ?,β = 92.329(1)o,V = 5018.7(3) ?3, Z =4. 两个化合物在ab平面上由SO4,GdO8和GdO9多面体共边或共角交错连接形成含有八元环和十六元环的二维层状结构,该二维层沿c方向平行排列,相邻层通过SO4四面体相连形成具有孔道的三维开放骨架结构,其孔道之中包含平衡骨架负电荷的质子化哌嗪分子. 化合物2的固体荧光光谱分析显示其在397nm激发波长下,表现出典型的Eu3+发光性质.       

Ferromagnetism in malonato-bridged copper(II) complexes. Synthesis,crystal structures,and magnetic properties of [[Cu(H2O)3][Cu(mal)2(H2O)]]n and [[Cu(H2O)4]2[Cu(mal)2(H2O)]][Cu(mal)2(H2O)2][[Cu(H2O)4][Cu(mal)2(H2O)2][(H2mal = malonic acid)

Three malonato-bridged copper(II) complexes of the formulas [[Cu(H2O)3][Cu(C3H2O4)2(H2O)]]n (1), [[Cu(H2O)4]2[Cu(C3H2O4)2(H2O)]] [Cu(C3H2O4)2(H2O)2][[Cu(H2O)4][Cu(C3H2O4)2(H2O)2]] (2), and [Cu(H2O)4][Cu(C3H2O4)2(H2O)2] (3) (C3H2O4 = malonate dianion) have been prepared, and the structures of the two former have been solved by X-ray diffraction methods. The structure of compound 3 was already known. Complex 1 crystallizes in the orthorhombic space group Pcab, Z = 8, with unit cell parameters of a = 10.339(1) A, b = 13.222(2) A, and c = 17.394(4) A. Complex 2 crystallizes in the monoclinic space group P2/c, Z = 4, with unit cell parameters of a = 21.100(4) A, b = 21.088(4) A, c = 14.007(2) A, and beta = 115.93(2) degrees. Complex 1 is a chain compound with a regular alternation of aquabis(malonato)copper(II) and triaquacopper(II) units developing along the z axis. The aquabis(malonato)copper(II) unit acts as a bridging ligand through two slightly different trans-carboxylato groups exhibiting an anti-syn coordination mode. The four carboxylate oxygens, in the basal plane, and the one water molecule, in the apical position, describe a distorted square pyramid around Cu1, whereas the same metal surroundings are observed around Cu2 but with three water molecules and one carboxylate oxygen building the equatorial plane and a carboxylate oxygen from another malonato filling the apical site. Complex 2 is made up of discrete mono-, di-, and trinuclear copper(II) complexes of the formulas [Cu(C3H2O4)2(H2O)2]2-, [[Cu(H2O)4] [Cu(C3H2O4)2(H2O)2]], and [[Cu(H2O)4]2[Cu(C3H2O4)2(H2O)]]2+, respectively, which coexist in a single crystal. The copper environment in the mononuclear unit is that of an elongated octahedron with four carboxylate oxygens building the equatorial plane and two water molecules assuming the axial positions. The neutral dinuclear unit contains two types of copper atoms, one that is six-coordinated, as in the mononuclear entity, and another that is distorted square pyramidal with four water molecules building the basal plane and a carboxylate oxygen in the apical position. The overall structure of this dinuclear entity is nearly identical to that of compound 3. Finally, the cationic trimer consists of an aquabis(malonato)copper(II) complex that acts as a bismonodentate ligand through two cis-carboxylato groups (anti-syn coordination mode) toward two tetraaqua-copper(II) terminal units. The environment of the copper atoms is distorted square pyramidal with four carboxylate oxygens (four water molecules) building the basal plane of the central (terminal) copper atom and a water molecule (a carboxylate oxygen) filling the axial position. The magnetic properties of 1-3 have been investigated in the temperature range 1.9-290 K. Overall, ferromagnetic behavior is observed in the three cases: two weak, alternating intrachain ferromagnetic interactions (J = 3.0 cm-1 and alpha J = 1.9 cm-1 with H = -J sigma i[S2i.S2i-1 + alpha S2i.S2i+1]) occur in 1, whereas the magnetic behavior of 2 is the sum of a magnetically isolated spin doublet and ferromagnetically coupled di- (J3 = 1.8 cm-1 from the magnetic study of the model complex 3) and trinuclear (J = 1.2 cm-1 with H = -J (S1.S2 + S1.S3) copper(II) units. The exchange pathway that accounts for the ferromagnetic coupling, through an anti-syn carboxylato bridge, is discussed in the light of the available magneto-structural data.     

Cluster-type basic lanthanide iodides [M6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 (M = Nd, Eu, Tb, Dy)

Ln6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)(8) (Ln = Nd, Eu, Tb, Dy) compounds are obtained as the final hydrolysis products of lanthanide triiodides in an aqueous solution. Their X-ray crystal structure features a body-centered arrangement of oxygen-centered {Ln6X8}8+ cluster cores: [Nd6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1310.4(3) pm, b = 1502.1(3) pm, c = 1514.9(3) pm, 3384 reflections with I0 > 2sigma(I0), R1 = 0.0340, wR2 = 0.0764, GOF = 1.022, T = 298(2) K], [Eu6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1306.6(2) pm, b = 1498.15(19) pm, c = 1499.41(18) pm, 4262 reflections with I0 > 2sigma(I0), R1 = 0.0540, wR2 = 0.0860, GOF = 0.910, T = 298(2) K], [Tb6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1296.34(5) pm, b = 1486.13(7) pm, c = 1491.88(6) pm, 4182 reflections with I0 > 2sigma(I0), R1 = 0.0395, wR2 = 0.0924, GOF = 1.000, T = 298(2) K], and [Dy6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1296.34(5) pm, b = 1486.13(7) pm, c = 1491.88(6) pm, 3329 reflections with I0 > 2sigma(I0), R1 = 0.0389, wR2 = 0.0801, GOF = 0.992, T = 298(2) K.     

Syntheses, structures and properties of seven isomorphous 1D Ln3+complexes Ln(BTA)(HCOO)(H2O)3 (H2BTA = bis(tetrazoly)amine, Ln = Pr, Gd, Eu, Tb, Dy, Er, Yb) and two 3D Ln3+ complexes Ln(HCOO)3 (Ln = Pr, Nd)

Seven isomorphous 1D chain Ln3+ complexes Ln(BTA)(HCOO)(H2O)3 (Ln = Pr (1), Gd (2), Eu (3), Tb (4) Dy (5), Er (6) and Yb (7)), and two formate coordinating and bridging 3D Ln3+ complexes Ln(HCOO)3 (Ln = Pr (8) and Nd (9)) have been synthesized and characterized by single crystal X-ray diffraction analysis. Although the Ln3+ ions in 1-7 have different radius, the trivalent lanthanide ions in 1-7 show the same coordinated environment. The well-defined single crystal structures of 8 and 9 are first samples for formate-bridged Ln3+ metallic complexes. The luminescent properties of solid samples of 2-5 at room temperature and the magnetic property of 2 have been also reported and discussed in this paper.     

Structure-based description of a step-by-step synthesis of homo- and heterodinuclear (4f, 4f ') lanthanide complexes

The stepwise course of the synthesis of homo- (4f, 4f) and heterodilanthanide (4f, 4f ') complexes has been investigated through structural determination of the intermediate and final products occurring in the process. In the first step, the tripodal ligand H(3)L is reacted with Ln(NO(3))(3) x 5H(2)O to give a complex (H(3)L)Ln(NO(3))(3) in which the ligand does exist in a zwitterionic form. This unexpected feature has been definitely supported by a structural determination performed on a closely related complex (HL')(3)Ln(NO(3))(3) (1). These species are fairly stable and may be isolated. In basic medium, (H(3)L)Ln(NO(3))(3) is deprotonated to yield a neutral LLn complex crystallized as LLnNaClO(4) (2), the lanthanide ion being linked to the inner N(4)O(3) coordination site of the ligand. Finally, addition of Ln'(NO(3))(3) x 5H(2)O (Ln' being similar or different from Ln) to the LLn complex yields the desired homo- or heterodinuclear LLnLn'(NO(3))(3) complex 3, where the Ln' ion is coordinated to the outer O(3)O(3) coordination site of the tripodal ligand. Complex 1 (Ln = La) crystallizes in the triclinic space group P1 (No. 2): a = 11.1883(7) A, b = 11.8993(9) A, c = 16.4197(10) A, alpha = 81.900 (6) degrees, beta = 79.406(5) degrees, gamma = 79.470(6) degrees, V = 2099.5(2) A(3), Z = 2. Complex 2 (Ln = Eu) crystallizes in the monoclinic space group P2(1)/n (No. 14): a = 13.6333(13) A, b = 15.3799(12) A, c = 17.1473(13) A, beta = 111.283(10) degrees, V = 3350.2(5) A(3), Z = 4. Complex 3 (Ln = Ln' = Dy) crystallizes in the trigonal space group R3 (No. 148) with a = b = 23.847(3) A, c = 42.982(2) A, V = 21168(4) A(3), Z = 18. Complex 3 possesses a Dy(O(phenoxo))(3)Dy core, and a nitrato anion has been replaced by a eta(2)-chelated o-vanillin anion. We did not succeed in obtaining crystals of any of the heterodinuclear LLnLn'(NO(3))(3) entities, but their existence was unambiguously confirmed by positive fast atom bombardment mass spectrometry experiments.     

Layered Lanthanum Complex with 3-Nitrophthalic Acid Assembled via Hydrogen Bonds-Synthesis, Structure and Characterization of [LaL(HL)(H2O)3]2·2H2O (H2L = 3-NO2C6H3(CO2H)2)

A new dinuclear centrosymmetric complex [LaL(HL)(H2O)3]2(2H2O (H2L = 3-nitrophthalic acid, NPA) was synthesized in water/ethanol solution and characterized by X-ray diffraction, IR spectrum and TGA-DTA. The complex crystallizes in triclinic system, space group P-1 with a = 8.1549(16), b = 8.8856(18), c = 15.277(3)(A),α= 100.93(3),α= 90.81(3), γ= 104.56(3)°, V = 1049.8(4)(A)3, Z = 1,μ= 2.125 mm-1, Dc＝1.994 g/cm3, R = 0.0259 and wR = 0.0679. Two 3-nitrophthalates(2-) coordinate with the La3 ions in a bridging mode, and two monohydrogen- 3-nitrophthates(1-) and three waters in terminal ways, respectively. Each La3 ion is nine-coordinated to exhibit a distorted tricapped trigonal prism coordination polyhedron. Both the coordinated and crystal waters are involved in the inter- and intramolecular hydrogen bonds. The dinuclear units are linked into a 2D network structure in the ab plane via intermolecular hydrogen bonds along the axes a and b. Two crystal waters fill each rhombic pore of the network. The networks are further packed along the c axis forming a layered supramolecular structure through the C-H…O weak forces between the adjacent sheets. TGA analysis shows the complex undergoes the loss of waters of crystallization and coordination and the decomposition of ligands sequentially.     

Hydrothermal Synthesis and Crystal Structure of a New Phosphonate： {[Cu（1,10-phen）]2-（H2O3PCH2C6H4C6H4CH2PO3H）2-（HO3PCH2C6H4C6H4CH2PO3H） }n

1 INTRODUCTION Metal organophosphonates have attracted considerable attention for over three decades due to their potential or practical applications, include- ing ion exchanges[1, 2], molecular sensors[3] and optics[4, 5]. Recently, a number of porous m…     

Solid-state and solution structure of lanthanide complexes of a new nonadentate tripodal ligand containing phenanthroline binding units

The new nonadentate tripodal ligand trenphen (tris[(1,10-phenanthroline-2-carboxamido)-ethyl]amine) has been synthesized by condensation of tren [tris(2-aminoethyl)amine] with an excess of 1,10-phenanthroline-2-carboxylic acyl chloride. The ligand trenphen and its lanthanide complexes (Sm, Nd, Eu, Tb, and Lu) have been structurally characterized by single-crystal X-ray diffractometry. Crystals of trenphen.H2O.CH3CN, 1, are monoclinic, space group P2(1)/n, a = 14.9923(8) A, b = 17.4451(10) A, c = 17.1880(10) A, beta = 114.8290(10) degrees, V = 4079.9(4) A3, Z = 4. The solid-state crystal structures of the isostructural [Ln(trenphen)](OTf)3.yH2O.xEt2O.zCH3CN (OTf = CF3SO3) (Ln = Nd, y = 0.5, x = 1, z = 3 (2); Ln = Sm, y = 0.5, x = 1, z = 3 (3); Ln = Eu, y = 0.5, z = 3 (4); Ln = Tb, y = 0.5, x = 1, z = 1.5 (5); Ln = Lu, y = 0.5, x = 1, z = 1.5 (6)) (trigonal, P-3, Z = 2) show that the covalent tripod trenphen undergoes a rearrangement in the presence of lanthanide ions yielding three tridentate binding units which encapsulate the nine-coordinated lanthanide ion with a slightly distorted, tricapped, trigonal prismatic coordination geometry. The correlation observed between the decrease of Ln-N distances and the metal ionic radius indicates that trenphen, although containing rigid bidentate phenanthroline units, is sufficiently flexible to self-organize without steric constraints around lanthanide ions of different size. Solution-state NMR studies show that complexes 2-6 exist in acetonitrile solution as discrete rigid C3-symmetric species retaining the triple-helical structure observed in the solid state. NMR and ES-MS titration show the formation of bimetallic and trimetallic species in the presence of an excess of metal, whereas mononuclear bistrenphen complexes are obtained in the presence of an excess of ligand.     

Hydrogen-bonded Three-Dimensional Networks Encapsulating One-dimensional Covalent Chains: [Cu(3-ampy)(H2O)4](SO4)·(H2O) (3-ampy = 3-Aminopyridine)

A three-dimensional complex [Cu(3-ampy)(H2O)4](SO4)·(H2O) (3-ampy = 3-aminopyridine) has been synthesized. Crystallographic data: C5H16CuN2O9S, Mr = 343.80, triclinic, space group P, a = 7.675(2), b = 8.225(3), c = 10.845(3) (A), α= 86.996(4), β = 76.292(4),γ = 68.890(4)°, V = 620.0(3) (A)3, Z = 2, Dc = 1.841 g/cm3, F(000) = 354 and μ = 1.971 mm-1. The structure was refined to R = 0.0269 and wR = 0.0659 for 1838 observed reflections (I ＞ 2σ(Ⅰ)). The structure consists of [Cu(3-ampy)(H2O)4]2 cations, SO42- anions and lattice water molecules. 3-Ampy acting as a bidentate bridging ligand generates a 1D covalent chain. A supramolecular 2D framework is formed through π-π stacking of pyridine rings. The lattice water molecules and SO42- anions are located between the adjacent 2D frameworks. The hydrogen bonding interactions from lattice water molecules and SO42- anions to coordinate water extend the 2D framework into a 3D network.     

CRYSTAL STRUCTURES OF Ln(o-ClC_6H_4CO_2)_3(H_2O)[Ln = Tb(Ⅲ) , Nd(Ⅲ)]

<正> Ln(o-ClC6H4CO2)3 (H2O) (Ln = Tb,Nb) ,Mr = 643. 62[628. 89]**, monoclinic,space group P21/n,a=12. 360(2)[12. 373(5)],b=6. 908(0)[7. 021(2)], c = 25. 936(6) [26. 086(9)] A ,β= 101. 30(2) [101. 71 (3)]°,Z= 4,V = 2171. 5(6) [2219(1)] A3,Dc=1. 97[1. 88]g·cm-3,μ= 37. 5[27. 5]em-1 (MoKa) ,F(000) = 1248[1228]. The two compounds are isomorphous,they show infinite chain structure.     

Synthesis, structure, and characterization of novel two- and three-dimensional vanadates: Ba2.5(VO2)3(SeO3)4.H2O and La(VO2)3(TeO6).3H2O

Two new vanadates, Ba(2.5)(VO2)3(SeO3)4.H2O and La(VO2)3(TeO6).3H2O, have been synthesized by hydrothermal methods using BaCO3, Ba(OH)2.H2O, La(NO3)3.6H2O, V2O5, TeO2, and H2SeO3 as reagents. The structures were determined by single-crystal X-ray diffraction. Ba(2.5)(VO2)3(SeO3)4.H2O exhibits a two-dimensional layered structure consisting of VO(5) square pyramids and SeO3 polyhedra, whereas La(VO2)3(TeO6).3H2O has a three-dimensional framework structure composed of VO(4) tetrahedra and TeO6 octahedra. Infrared and Raman spectroscopy, UV-vis diffuse reflectance spectroscopy, and thermogravimetric analysis are also presented. Crystal data: Ba(2.5)(VO2)3(SeO3)4.H2O, trigonal, space group P (No. 147) with a = b = 12.8279(15) A, c = 7.2631(9) A, V = 1035.1(2) A(3), and Z = 2; La(VO2)3(TeO6).3H2O, trigonal, space group R3c (No. 161) with a = b = 9.4577(16) A, c = 23.455(7) A, V = 1816.9(7) A3, and Z = 6.     

{Ln(III)[mu(5)-kappa(2),kappa(1),kappa(1),kappa(1),kappa(1)-1,2-(CO2)(2)C6H4][isonicotine][H2O]}(2)Cu(I) x X (Ln = Eu, Sm, Nd; X = ClO4-, Cl-): a new pillared-layer approach to heterobimetallic 3d-4f 3d-network solids

A new series of heterometallic lanthanide(III)-copper(I) coordination polymers Ln2(bdc)2(ina)2(H2O)2Cu x X (Hina = isonicotinic acid; H2bdc = 1,2-benzenedicarboxylic acid; Ln = Eu (1), Sm (2), Nd (3), X = ClO4-; Ln = Nd (4), X = Cl-) have been hydrothermally synthesized in the presence/absence of HClO4. Both compounds are isostructural and contained two distinct units of 2D Ln-bdc layers and linear [Cu(ina)2]-. The linear [Cu(ina)2]- complexes act as pillars and further link the Ln-bdc layers resulting in four heterometallic metal-organic frameworks, which represent the first pillared-layer 3d-4f framework with two distinct types of channels along the b and c axes. The compounds can be specified by the Schl?fli symbol (47.63)(47.68) as a novel 3D (5,6)-connected net. Furthermore, the IR, TGA, PXRD, and UV-vis spectral and luminescent properties of 1-4 were also studied.     

The solution structure of rhombic lanthanide complexes analyzed with a Model-free and crystal-field independent paramagnetic NMR method: application to nonaxial trimetallic complexes [LnxLu(3-x)(TACI-3H)2(H2O)6]3+ (x = 1-3)

The model-free approach has been extended with the derivation of a novel three-nuclei crystal-field independent method for investigating isostructurality in nonaxial (i.e., rhombic) complexes along the lanthanide series. Application of this technique to the heterotrimetallic sandwich complexes [LnLu2(TACI-3H)2(H2O)6]3+, which possess a single C2v-symmetrical paramagnetic center, unambiguously evidences isostructurality for Ln = Pr-Yb, while the variation of the second-rank crystal-field parameters and along the series prevents reliable structural analyses with the classical one-nucleus equation. Extension toward polymetallic magnetically noncoupled rhombic lanthanide complexes in [Ln2Lu(TACI-3H)2(H2O)6]3+ (two paramagnetic centers with Cs microsymmetry) and [Ln3(TACI-3H)2(H2O)6]3+ (three paramagnetic centers with C2v microsymmetry) requires only minor modifications of the original three-nuclei equation. Isostructurality characterizes [Ln2Lu(TACI-3H)2(H2O)6]3+ (Ln = Pr-Yb), while [Ln3(TACI-3H)2(H2O)6]3+ exhibit a structural change between Eu and Tb which results from the concomitant contraction of the three metallic centers. Particular attention has been focused on (i) the stepwise increase of contact (i.e., through-bond) and pseudocontact (i.e., through-space) contributions when the number of paramagnetic centers increases, (ii) the assignment of 13C resonances in the strongly paramagnetic complexes [Ln3(TACI-3H)2(H2O)6]3+ (Ln = Tb-Yb) for which reliable T1 measurements and [1H-13C] correlation spectra are not accessible, and (iii) the combination of crystal-field dependent and independent methods for analyzing the paramagnetic NMR spectra of axial and nonaxial lanthanide complexes.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)_4(H_2O)_3Fe(CN)_6]·H_2O and [La(DMSO)_4(H_2O)_3Co(CN)_6]·H_2O(DMSO = Dimethylsulfoxide)

1INTRODUCTION Recently,cyano-bridged lanthanide-transition me-tal complexes have been extensively investigateddue to their potential applications as precursors in the preparation of rare earth orthoferrites,fluores-cent and magnetic materials[1].Various complexes of this system have been obtained in order to ex-plore the relations between structures and pro-perties by using different ligands,such as DMF,4,4?-bipy,and so on,to fill the coordination sites of lanthanide ions[2～9].But up to…     

Copper(I) complexes of tripodal tris(imidazolyl) ligands: potential mimics of the Cu(A) site of hydroxylase enzymes

Copper(I) complexes of tripodal tris(N-methyl-4,5-diphenyl-imidazolyl)methane ligands, N3CR (1a-c, R = OH, OMe, H), have been prepared as models for the Cu(A) site of copper hydroxylase enzymes. In the absence of additional donors, the ligands 1 react with [Cu(CH3CN)4]PF6 (2) to produce dinuclear complexes [(N3CR)2Cu2](PF6)2 (3) in which the tripodal ligands bridge two trigonal Cu centers; the structures of 3b and 3c are established by X-ray diffraction. Mononuclear adducts [(N3CR)CuL]Z are produced with L = acetonitrile (4), carbon monoxide (5), and t-BuNC (6, 7). The carbonyl complexes 5 are in dynamic equilibrium with the dimeric complexes 3, but 5c (R = H) can be isolated. The structures of the isocyanide derivatives depend critically on the tripod methane substituent, R. Thus, the X-ray structures of 6 (R = OMe) and 7 (R = H) show trigonal and tetrahedral geometries, respectively, with bi- or tridentate coordination of the tripod. A trinuclear complex [Cu3(N3COH)2(t-BuNC)2](PF6)3 (8) is formed from N3COH (1a) which features both three-coordinate and two-coordinate Cu atoms and bidentate tripod coordination. Reactions of dioxygen with dinuclear 3c or mononuclear [(N3CR)CuL]Z are sluggish, producing from the latter in acetone [(N3CH)CuII(L)(L')](PF6)2 (9, L = acetone, L' = H2O).     

Crystal Structure of[PrAl(CF3COO)2(CF3CHOO)(C2H5)2(C4H8O)2]2

[PrAl(CF3COO)2(CF3CHOO)(C2H5)2(C4H8O)2]2 Mr=1420.56, monoclinic, P21/n, a=10.651(6), b=24.276(9), c=11.110(5)(), β=107.650(4)°, V=2737.4(1)()3, Z=2, Dc=3.45 g/cm3, F(000)=2816, T=233K, MoKα radiation (λ=0.71069()), μ(MoKα)=38.017 cm-1, R=0.048 for 2847 observed reflections (I≥3σ(I)). It is isostructural with [LnAl(CF3COO)2(CF3CHOO)-R2(C4H8O)2]2 (Ln=Ho, R=Et; Ln=Nd, Y, R=iBu). Pr3+ is coordinated by eight oxygen atoms from five bridging ligands and two THF forming a distorted bicap-prism.     

CRYSTAL STRUCTURES OF Ln(o-HOC_6H_4CO_2)_3 (H_2O)_2·2H_2O [Ln =Tb,Ho]

<正> Ln(o-HOC6H4CO2)3(H2O)2·2H2O [Ln = Tb, Ho], Mr = 642. 32 (648. 33 )**,monoclinic, space group Cc,a=16. 280(4)(16. 217 (2)) ,b= 14. 889(3) (14. 877(2)),c = 9.867(1)(9. 835(2)) A,β=101.49(1)(101. 46(1))°,Z= 4,V= 2343. 8(7)(2325. 3(6)) A3,Dc=1. 8(1. 85)g·cm-3,μ=31. 6(36. 1)cm-1(MoKa), F(000) = 1272(1280).The final R=0. 031(0. 031),Rw = 0. 029(0. 031). There is no discrete molecules of the compounds in the crystal structures. The compounds are in linear polymeric arrangements, each metal ion is bridged to the next by two bridging carboxyl groups from salicylato ions.     

New lanthanide-containing polytungstates derived from the cyclic P8W48 Anion: {Ln4(H2O)28[K subset P8W48O184(H4W4O12)2Ln2(H2O)10]13-}x, Ln = La, Ce, Pr, Nd

The reaction of K28Li5H7[P8W48O184].92H2O with early lanthanides under hydrothermal and conventional conditions yields novel structures of the molecular formula Ln4(H2O)28K6Li7[K subsetP8W48O184(H4W4O12)2Ln2(H2O)10] congruent with 57H2O, Ln = La (1), Ce (2, 2a), Pr (3), Nd (4), in which the central cavity of the precursor anion is occupied by lanthanide cations and H4W4O12 moieties. The new heteropolyanions were characterized by elemental analysis, infrared spectroscopy, 31P NMR, and X-ray crystallography. All of the crystals are monoclinic, space group C2/m, with lattice constants (A, Epsilon) a = 33.061(3), b = 30.986(3), c = 15.1649(13), beta = 103.607(2), (1); a = 33.0577(16), b = 31.0562(15), c = 15.2320(7), beta = 104.015(2), (2); a = 33.0577(16), b = 31.0562(15), c = 15.2320(7), beta = 104.015(2), (2a); a = 33.007(2), b = 31.060(2), c = 15.2129(10), beta = 104.0140(10), (3); a = 32.913(19), b = 31.155(18), c = 15.135(9), beta = 103.495(11), (4); and Z = 2.