[Ag(4，4′-bpy)]+及[Zn(phen)2(H2O)2]2+两种配合物的合成、结构与荧光性质

用水热法和溶液法分别合成了2个新的配合物{[Ag(4,4′-bpy)]·3-HSBA.H2O}n(1)和[Zn(phen)2(H2O)2]·(A-2,5-DSA)·3H2O(2)(3-HSBA=3-羧基苯磺酸根,A-2,5-DSA=苯氨-2,5-二磺酸根,4,4′-bpy=4,4′-联吡啶,phen=1,10-邻菲咯啉),用X-射线单晶衍射结构分析方法测定了其晶体结构。配合物1是一维链状结构。在1个不对称单元中包含1个[Ag(4,4′-bpy)]+阳离子,1个3-羧基苯磺酸根阴离子和1个晶格水分子。Ag髣离子与2个4,4′-联吡啶的2个氮原子配位。配合物2是单核结构。在1个不对称单元中包含1个[Zn(phen)2(H2O)2]2+阳离子,1个苯氨-2,5-二磺酸根阴离子和3个晶格水分子。Zn髤离子与2个1,10-邻菲咯啉的4个氮原子和2个水氧原子配位。配合物1和2中,配位阳离子、抗衡阴离子以及晶格水分子之间存在丰富的氢键,进而构筑成超分子网络结构。配合物的荧光均来自于配体的π-π*电子跃迁。     

Synthesis and physical properties of K4[Fe(C5O5)2(H2O)2](HC5O5)2·4H2O (C5O5(2-) = croconate): a rare example of ferromagnetic coupling via H-bonds

The reaction of the croconate dianion (C(5)O(5))(2-) with a Fe(III) salt has led, unexpectedly, to the formation of the first example of a discrete Fe(II)-croconate complex without additional coligands, K(4)[Fe(C(5)O(5))(2)(H(2)O)(2)](HC(5)O(5))(2)·4H(2)O (1). 1 crystallizes in the monoclinic P2(1)/c space group and presents discrete octahedral Fe(II) complexes coordinated by two chelating C(5)O(5)(2-) anions in the equatorial plane and two trans axial water molecules. The structure can be viewed as formed by alternating layers of trans-diaquabis(croconato)ferrate(II) complexes and layers containing the monoprotonated croconate anions, HC(5)O(5)(-), and noncoordinated water molecules. Both kinds of layers are directly connected through a hydrogen bond between an oxygen atom of the coordinated dianion and the protonated oxygen atom of the noncoordinated croconate monoanion. A H-bond network is also formed between the coordinated water molecule and one oxygen atom of the coordinated croconate. This H-bond can be classified as strong-moderate being the O···O bond distance (2.771(2) ?) typical of moderate H-bonds and the O-H···O bond angle (174(3)°) typical of strong ones. This H-bond interaction leads to a quadratic regular layer where each [Fe(C(5)O(5))(2)(H(2)O)(2)](2-) anion is connected to its four neighbors in the plane through four equivalent H-bonds. From the magnetic point of view, these connections lead to an S = 2 quadratic layer. The magnetic properties of 1 have been reproduced with a 2D square lattice model for S = 2 ions with g = 2.027(2) and J = 4.59(3) cm(-1). This model reproduces quite satisfactorily its magnetic properties but only above the maximum. A better fit is obtained by considering an additional antiferromagnetic weak interlayer coupling constant (j) through a molecular field approximation with g = 2.071(7), J = 2.94(7) cm(-1), and j = -0.045(2) cm(-1) (the Hamiltonian is written as H = -JS(i)S(j)). Although this second model might still be improved since there is also an extra contribution due to the presence of ZFS in the Fe(II) ions, it confirms the presence of weak ferromagnetic Fe-Fe interactions through H-bonds in compound 1 which represents one of the rare examples of ferromagnetic coupling via H-bonds.     

Synthesis and Crystal Structure of an Unusual Dodecacoordinated Lanthanum Complex by Phenanthroline and Nitrate （phenH）_2[La（NO_3）_5（phen）]·CH_3OH

Lanthanum complex (phenH)2[La(NO3)5(phen)]·CH3OH (1, phen=phenanthroline) was synthesized and characterized by single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/c with a=20.3040(3), b=10.7091(1), c=19.0771(2), β=102.090(1)°, V=4056.07(8)3, Z=4, Dc=1.676 g/cm3, μ= 1.142 mm-1, F(000)=2056, the final R=0.0346 and wR=0.0793 for 9981 (Rint=0.0358) independent reflections. The mononuclear complex 1 consists of four parts: two phenH+ cations formed by the protonation of phen, one complex anion [La(NO3)5(phen)]2-, and one solvent methanol molecule. The complex anion contains one phen and five nitrate ligands which both chelate the center La(III) ion, adopting a distorted twelve-coordinated icosahedral geometry. The cations, anion and solvent molecule are linked together by hydrogen bonds. One of the protonated phenanthrolines (phenH+) acting as cation connects to the anion via N–H…O hydrogen bond directly, and the other one links to the anion through an intermediate solvent CH3OH via N–H…O and O–H…O hydrogen bonds. By the plentiful additional weak C–H…O intermolecular hydrogen bonds, the compound molecules construct a two-dimensional layer structure.     

含三脚架配体及吡啶甲酸根的锰(Ⅱ)配合物的合成及结构表征

本文合成了2种含有吡啶甲酸根的三(2-苯并咪唑亚甲基)胺合锰配合物,并对其进行了红外,元素分析和X-射线单晶衍射测定。结果表明,单核配合物1和2分别具有三角双锥和扭曲八面体的几何构型。在配合物1中,烟酸根阴离子利用一个羧基氧原子和锰离子配位;在配合物2中,邻吡啶甲酸根阴离子采取N,O螯合的配位方式。由于烟酸根和邻吡啶甲酸根的配位方式不同,导致配合物晶体结构中存在不同类型的氢键。配合物1形成了由氢键连接的二维网状结构,而配合物2只能形成由氢键连接成的一维链状结构。     

Mono- and dinuclear iron complexes of bis(1-methylimidazol-2-yl)ketone (bik): structure, magnetic properties, and catalytic oxidation studies

The newly synthesized dinuclear complex [Fe(III)(2)(μ-OH)(2)(bik)(4)](NO(3))(4) (1) (bik, bis(1-methylimidazol-2-yl)ketone) shows rather short Fe···Fe (3.0723(6) ?) and Fe-O distances (1.941(2)/1.949(2) ?) compared to other unsupported Fe(III)(2)(μ-OH)(2) complexes. The bridging hydroxide groups of 1 are strongly hydrogen-bonded to a nitrate anion. The (57)Fe isomer shift (δ = 0.45 mm s(-1)) and quadrupole splitting (ΔE(Q) = 0.26 mm s(-1)) obtained from Mo?ssbauer spectroscopy are consistent with the presence of two identical high-spin iron(III) sites. Variable-temperature magnetic susceptibility studies revealed antiferromagnetic exchange (J = 35.9 cm(-1) and H = JS(1)·S(2)) of the metal ions. The optimized DFT geometry of the cation of 1 in the gas phase agrees well with the crystal structure, but both the Fe···Fe and Fe-OH distances are overestimated (3.281 and 2.034 ?, respectively). The agreement in these parameters improves dramatically (3.074 and 1.966 ?) when the hydrogen-bonded nitrate groups are included, reducing the value calculated for J by 35%. Spontaneous reduction of 1 was observed in methanol, yielding a blue [Fe(II)(bik)(3)](2+) species. Variable-temperature magnetic susceptibility measurements of [Fe(II)(bik)(3)](OTf)(2) (2) revealed spin-crossover behavior. Thermal hysteresis was observed with 2, due to a loss of cocrystallized solvent molecules, as monitored by thermogravimetric analysis. The hysteresis disappears once the solvent is fully depleted by thermal cycling. [Fe(II)(bik)(3)](OTf)(2) (2) catalyzes the oxidation of alkanes with t-BuOOH. High selectivity for tertiary C-H bond oxidation was observed with adamantane (3°/2° value of 29.6); low alcohol/ketone ratios in cyclohexane and ethylbenzene oxidation, a strong dependence of total turnover number on the presence of O(2), and a low retention of configuration in cis-1,2-dimethylcyclohexane oxidation were observed. Stereoselective oxidation of olefins with dihydrogen peroxide yielding epoxides was observed under both limiting oxidant and substrate conditions.     

Antimonato polyoxovanadates with structure directing transition metal complexes: pseudopolymorphic {Ni(dien)2}3[V15Sb6O42(H2O)]·nH2O compounds and {Ni(dien)2}4[V16Sb4O42(H2O)

Three new poloxovanadates were synthesized under solvothermal conditions and were structurally characterized. The two compounds with composition {Ni(dien)(2)}(3)[V(15)Sb(6)O(42)(H(2)O)]·nH(2)O (n = 12 and 8; dien = bis(2-aminoethyl)amine or diethylenetriamine) are pseudopolymorphs crystallizing in different space groups. The compounds were obtained by applying identical reaction slurries but using different reaction temperatures. Both compounds feature the [V(15)Sb(6)O(42)(H(2)O)](6-) anion which is the antimony analogue to the single molecule magnet [V(15)As(6)O(42)(H(2)O)](6-). Crystal data: 1 tetragonal space group P4, a = 46.9378(3), c = 16.51300(10) ? and V = 36380.7(4) ?(3). 2 rhombohedral space group R3c with a = 23.0517(4), c = 28.6216(5) ? and V = 13171.3(4) ?(3). In 1 several unusual short inter-cluster Sb···O contacts lead to the formation of three different super-clusters with composition V(60)Sb(24)O(168). The 12 unique {Ni(dien)(2)}(2+) complexes adopt all three possible configurations. In 2 the special arrangement of the {Ni(dien)(2)}(2+) complexes around the cluster anion prevents inter-cluster Sb···O contacts. The main structural motif of the third compound {Ni(dien)(2)}(4)[V(16)Sb(4)O(42)(H(2)O)] (3) is the [V(16)Sb(4)O(42)(H(2)O)](8-) cluster anion consisting of two perpendicular eight-membered rings of VO(5) pyramids. Two additional VO(5) polyhedra are located on opposite sides. Crystal data: 3 triclinic space group P1 = 13.5159(4), b = 14.2497(5), c = 14.9419(4) ?, α = 98.322(2), β = 114.080(2), γ = 110.130(2)° and V = 2326.35(12) ?(3).     

Synthesis and characterization of thorium(IV) sulfates

Three Th(IV) sulfates, two new and one previously reported, have been synthesized from aqueous solution. In all of the compounds, the sulfate anions coordinate the Th(4+) metal center(s) in a monodentate manner with Th-S distances of 3.7-3.8 ?. Th(SO(4))(2)(H(2)O)(7)·2(H(2)O) (1; P2(1)/m, a = 7.224(1) ?, b = 12.151(1) ?, c = 7.989(1) ?, ss =98.289(2)°) and Th(4)(SO(4))(7)(H(2)O)(7)(OH)(2)·H(2)O (2; Pnma, a = 18.139(2) ?, b = 11.173(1) ?, c = 14.391(2) ?) each contain 9-coordinate monomeric (1,2) and dimeric (2) Th(IV) cations in monocapped square antiprism geometry. Alternatively, Th(OH)(2)SO(4) (3; Pnma, a = 11.684(1) ?, b = 6.047(1) ?, c = 7.047(1) ?) is built from chains of hydroxo-bridged, 8-coordinate Th(4+) centers. Whereas 1 adopts a molecular structure, 2 and 3 both exhibit 3D architectures. Differences in the dimensionality and the topology of 1-3 are manifested in the local coordination environment about the Th(IV) centers, the formation of oligomeric Th(4+) species, and the extended connectivity of the sulfate ligands. Herein, we report the syntheses and characterization of 1-3 as well as the atomic correlations of 1 in solution, as determined by high-energy X-ray scattering (HEXS).     

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) ?, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) ?(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) ?, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) ?(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not significantly couple with the S = 1/2 vanadyl groups. The susceptibility data can be successfully reproduced assuming a distorted ligand field for the Co(2+) ions (1) and an O(h)-symmetric Ni(2+) ligand field (2).     

Reactions of an osmium-hexahydride complex with Cytosine, deoxycytidine, and cytidine: the importance of the minor tautomers

Complex OsH(6)(P(i)Pr(3))(2) (1) deprotonates cytosine to give molecular hydrogen and the d(4)-trihydride derivative OsH(3)(cytosinate)(P(i)Pr(3))(2) (2), which in solution exists as a mixture of isomers containing κ(2)-N1,O (2a) and κ(2)-N3,O (2b) amino-oxo and κ(2)-N3,N4 (2c) imino-oxo tautomers. The major isomer 2b associates with the minor one 2c through N-H···N and N-H···O hydrogen bonds to form [2b·2c](2) dimers, which crystallize from saturated pentane solutions of 2. Complex 1 is also able to perform the double deprotonation of cytosine (cytosinate') to afford the dinuclear derivative (P(i)Pr(3))(2)H(3)Os(cytosinate')OsH(3)(P(i)Pr(3))(2) (3), where the anion is coordinated κ(2)-N1,O and κ(2)-N3,N4 to two different OsH(3)(P(i)Pr(3))(2) metal fragments. The deprotonation of deoxycytidine and cytidine leads to OsH(3)(deoxycytidinate)(P(i)Pr(3))(2) (4) and OsH(3)(cytidinate)(P(i)Pr(3))(2) (5), respectively, containing the anion κ(2)-N3,N4 coordinated. Dimer [2b·2c](2) and dinuclear complex 3 have been characterized by X-ray diffraction analysis.     

Octa-membered Water Ring Chain Based on Sulfonic Group in Ni(Ⅱ) Complex with 2-[(E)-(2-Oxidophenyl)methyleneamino]Ethanesulfonato and 2,2''-Bipyridinyl

The title compound, [Ni(tssb)(2,2-bipy)2]·5(H2O) 1 (tssbH2 =2-[(E)-(2-oxido-phenyl)methyleneamino]ethanesulfonato, 2,2-bipy = 2,2'-bipyridinyl), belongs to orthorhombic,space group Pbcn with a = 20.3983(18), b = 17.6929(15), c = 17.0897(15) nm, V = 6167.8(9) nm3,Mr= 688.38, Z = 8, Dc = 1.481 g·cm-3, F(000) = 2880, μ = 0.758 mm-1 and S =1.099. Each NiⅡ atom is six-coordinated by one N and one O atoms from one tssb2- anion and four N atoms from two 2,2-bipy ligands to give a distorted octahedral geometry. Noticeably, there exists a rare octa-membered water ring which presents a 1D chain by sulfonic group.     

Photogeneration of reactive oxygen species and photoinduced plasmid DNA cleavage by novel synthetic chalcones

This paper describes the synthesis and photodynamic properties of six different chalcone derivatives. Using N,N-dimethyl-4-nitrosoaniline (RNO) bleaching assay, the singlet oxygen generating efficiencies of these chalcones are determined relative to rose bengal (RB). Superoxide dismutase (SOD) inhibitable cytochrome c reduction assay and electron magnetic resonance (EMR) spin trapping techniques are used to determine the superoxide anion radical (O?·?) yield upon photoirradiation. Photoinduced DNA scission studies show that O?·? is involved in the DNA strand break. In addition, antimicrobial activity of these chalcones is also investigated. Structure activity relationship accounts for the difference in the photogeneration of reactive oxygen species (ROS) by these sensitizers. Presence of electron releasing -OCH? groups enhances the photogeneration of ROS. Cyclic voltammetry studies indicate a correlation between enzymatic O?·? generation efficiency and redox potential of chalcones. Both O?·? (Type I) and 1O? (Type II) paths are involved in the photosensitization of chalcones. The LUMO energies obtained by molecular modeling correlate with the one-electron reduction potentials.     

Syntheses and Crystal Structures of Ternary Complexes of Zinc(Ⅱ) and Cadmium(Ⅱ) with 3-Aminobenzoic Acid and 1,10-Phenanthroline

Two new ternary complexes [Zn(3-aba)2(phen)](2.58H2O 1 and {[Cd(3-aba)- (phen)2]·(NO3)·(1.5H2O)}n 2 (3-aba = 3-aminobenzoic acid anion, phen = 1,10-phenanthroline) were synthesized and characterized by elemental analysis, IR, UV spectrum and X-ray diffraction. Complex 1 crystallizes in the rhombohedral system, space group R with a = 3.5733(3), b = 3.5733(3), c = 1.1231(2) nm, V = 12.419(3) nm3, C26H25.17N4O6.58Zn, Mr = 564.37, Z = 18, F(000) = 5253, μ = 0.937 mm-1, Dc = 1.358 g/cm3, R = 0.0668 and wR = 0.1690 for 2424 observed reflections (I > 2σ(I)). Complex 2 belongs to the tetragonal system, space group P4/ncc with a = 2.88451(10), b = 2.88451(10), c = 1.55571(11) nm, V = 12.9441(11) nm3, C31H25CdN6O6.50, Mr = 697.97, Z = 16, F(000) = 5648, μ = 0.727 mm-1, Dc = 1.433 g/cm3, R = 0.0607 and wR = 0.1742 for 3468 observed reflections (I > 2σ(I)). Complex 1 displays a mononuclear structure. The carboxylate group of 3-aminobenzoic acid anion coordinates to Zn(Ⅱ) in a chelating bidentate mode, and the nitrogen atom of the ligand does not involve in coordination. Complex 2 exhibits a one-dimensional chain structure with 3-aminobenzoic acid anion coordinating to Cd(Ⅱ) in a μ2-bridging mode through its nitrogen atom and one of its oxygen atoms.     

Synthesis and Crystal Structure of One-dimensional Chain Zinc(II) Coordination Polymer:{Na[ZnL(H2O)2]}n(L=2-Hydroxyl-2-hydroxylate-malonate Trivalent Anion)

1 INTRODUCTION For a long time much research interest has been focused on coordination polymers because such new coordination polymers may afford new materials with useful properties such as catalytic activity, mi- croporosity, electrical conductivity, …     

气相中烯丙基负离子与N2O反应机理

采用二阶微扰理论的MP2/6-31G(d,p)方法对气相中烯丙基负离子与N2O的反应机理进行了理论计算研究, 并在相同基组下进一步用CCSD(T)方法进行了单点能的校正. 计算结果表明, 该反应存在三条反应通道, 产物分别为cis-CH2CHCNN-+H2O, trans-CH2CHCNN-+H2O和CH2CCH-+N2+H2O, 其中生成cis-CH2CHCNN-和trans-CH2CHCNN-的两条通道为相互竞争的主反应通道, 计算结果与实验相吻合. 同时利用传统的过渡态理论, 计算了各反应通道在298 K时, 速控步骤的反应速率常数k(T).     

Hydrothermal Synthesis and Structural Characterization of two Hybrid Keggin-based Polyoxometalates

Two new hybrid polyoxotungstates, [Co（2,2＇-bipy）3][a-H5PW11CoO40]-3H2O 1 and [Fe（2,2＇-bipy）3]2[a-HBW12O40]-2.5H2O 2 （2,2＇-bipy = 2,2＇-dipyridyl）, have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray structural analyses. The results of X-ray crystallography analyses exhibit that 1 consists of one a-Keggin anion [a-H5PW11CoO40]2- and one isolated [Co（2,2＇-bipy）3]2＋ complex, while 2 is constructed from one a-Keggin anion [a- HBW12O40]4- and two isolated [Fe（2,2＇-bipy）3]2＋ cations. The data for 1： orthorhombic system, space group Pbcn, a = 16.062（6）, b = 27.278（10）, c = 16.951（6）A, V = 7427（5）A3 and Z = 4; and those for 2： triclinic system, space group P1, a = 13.787（3）, b = 17.857（5）, c = 18.918（5）A, a = 88.009（12）, β = 72.768（10）, γ = 74.935（10）°, V = 4291（2）A3 and Z = 2.     

以7H-苯并[c，g]卡唑-4，10-二磺酸为构筑块原位合成具有晶体学特征的二维层状锶配位聚合物

2，2′-二甲酰胺-1,1′-联二奈-5，5-二磺酸(H₂DCS)和SrCl₂·2H₂O反应生成了一个从未有过的二维层状配位聚合物{Sr₂[(DCS)₂ (H₂O)₂]·H₂O·C₂H₅OH}_n (1)(DCS=7H-苯并[c，g]卡唑-4，10-二磺酸阴离子)，其中配体DCS是通过原位合成的。另外，1在室温下显示了很强的蓝色荧光(445 nm)。晶体结构分析表明，化合物1的晶体属三斜晶系，空间群为P1(a=1.169 3(2) nm，b=1.299 1(3) nm，c=1.629 2(3) nm，α=97.606(4)°，β=107.691(4)°，γ=114.536(4)°，V=2.047 2(7) nm³，Z=2，M=1 126.19，D_c=1.827 Mg·m^-3)。     

1-D Selenidoindates {[In2Se5]}∞ directed by chiral metal complex cations of 1,10-phenanthroline

Two 1-D selenidoindates {[M(phen)(3)]In(2)Se(5)·H(2)O}(n) (M = Ni, Fe) were synthesized by a solvothermal method. The 1-D {[In(2)Se(5)](2-)}(n) anion is a new type of single 1-D structure constituted by an alternately fused four-membered In(2)Se(2) ring and five-membered In(2)Se(3) ring. The chalcogenoindates were separated as mechanical racemic mixtures of single enantiomer crystals, in which the R-helix of 1-D InSe anion is directed by the related clockwise (Δ) cations of [M(phen)(3)](2+) or the L-helix of 1-D anion is directed by the related anticlockwise (Λ) cation. The π···π, C···Se, and C-H···Se oriented interactions of metal complex cations with selenidoindate anions play an important role in the formation of the chiral crystals. The embedded [M(phen)(3)](2+) cations improve the optical absorption of the 1-D semiconductor materials.     

Sr(3)Co(2)O(4.33)h(0.84): an extended transition metal oxide-hydride

Reaction of the n = 2 Ruddlesden-Popper oxide Sr(3)Co(2)O(5.80) with CaH(2) yields an extended oxide-hydride phase: Sr(3)Co(2)O(4.33)H(0.84). Neutron powder diffraction data reveal the material adopts a body-centered orthorhombic structure (Immm: a = 3.7551(5) ?, b = 3.7048(4) ?, c = 21.480(3) ?) in which the hydride ions are accommodated within disordered CoO(1.16)H(0.46) layers. Low temperature neutron powder diffraction data show no evidence for long-range magnetic order, suggesting the chemical disorder in the anion lattice of the material leads to magnetic frustration.     

Study and fabrication of europium picrate triethylene glycol complex

A mononuclear of [Eu(NO3)(Pic)(H2O)2(EO3)](Pic)·(0.73)H2O complex, where EO3=trietraethylene glycol and Pic=picrate anion, shows a red emission when used as an active layer in a single layer of ITO/EO3-Eu-Pic/Al configuration. The crystal structure of the complex consists of [Eu(NO3)(Pic)(H2O)2(EO3)]+ cation and [Pic]- anion. The Eu(III) ion is coordinated to the 10 oxygen atoms from one EO3 ligand, one Pic anion, one nitrate anion, and two water molecules. The complex is crystallized in triclinic with space group P-1. The hybrids in thin films I and II were prepared in the respective order solution concentrations of 15 and 20 mg/mL the emissive center. Comparing the photoluminescence (PL) and electroluminescence (EL) spectra, we can find that all emissions come from the characteristic transitions of the Eu(III) ion. The EL spectra of both thin films showed the occurrence of the most intense red-light emission around at 612 nm. Comparison of organic light-emitting device (OLED) current intensity characteristics as a function of voltage (I-V) show that the thin film I is better than those found for the thin film II. The thickness of the emitting layer is an important factor to control the current-voltage curve. The sharp and intense emission of the complex at low voltage indicates that the complex is a suitable and promising candidate for red-emitting materials.     

Synthesis, structural, and photoluminescence studies of Gd(terpy)(H2O)(NO3)2M(CN)2 (M = Au, Ag) complexes: multiple emissions from intra- and intermolecular excimers and exciplexes

The highly luminescent bimetallic cyanide materials, Gd(terpy)(H(2)O)(NO(3))(2)M(CN)(2) (M = Au, Ag; GdAu and GdAg, respectively) are quick and easy to synthesize under ambient conditions. A characteristic feature exhibited by both solid-state compounds is an intense red emission when excited with UV light. Additionally, GdAu exhibits a broad-band green emission upon excitation in the near UV region. A combination of structural and spectroscopic results for the compounds helps explain the underlying conditions responsible for their unique properties. Single-crystal X-ray diffraction experiments expose their structural features, including the fact that they are isostructural. Crystallographic data for the representative GdAu compound (Mo K(α), λ = 0.71073 ?, T = 290 K): triclinic, space group P ?1, a = 7.5707(3) ?, b = 10.0671(4) ?, c = 15.1260(4) ?, α = 74.923(3)°, β = 78.151(3)°, γ = 88.401(3)°, V = 1089.04(7) ?(3), and Z = 2. Although the compounds crystallize as dimers containing M···M distances smaller than the sum of their van der Waals radii, the Au···Au (3.5054(4) ?) and/or the Ag···Ag (3.6553(5) ?) interactions are relatively weak and are not responsible for the low energy red emission. Rather, the green emission in GdAu presumably originates from the [Au(CN)(2)(-)](2) dimeric excimer, while the [Ag(CN)(2)(-)](2) dimers in GdAg do not display visible emission at either 290 or 77 K. The unusual red emission exhibited by both compounds likely originates from the formation of an excited state exciplex that involves intermolecular π-stacking of 2,2':6',2"-terpyridine ligands. The room-temperature and low-temperature steady-state photoluminescent properties, along with detailed time-dependent, lifetime, and quantum yield spectroscopic data provide evidence regarding the sources of the multiple visible emissions exhibited by these complexes.