A new 3D terbium(Ⅲ)metal-organic network[Tb(HIMDC)(HCOO)(H_(2)O)]_(n)(complex 1)has been synthesized by Tb^(3+)ions coordinated with 4,5-imidazole dicarboxylic acid(H_(3)IMDC)and formic acid under solvothermal conditions with the mixed solvents of N,N-dimethylformamide(DMF)and H_(2)O.The unambiguous structural determination has been confirmed by single-crystal X-ray diffraction combined with elemental analysis,infrared(IR)spectrum,thermogravimetric analysis(TGA)and powder X-ray diffraction(PXRD).Complex 1crystallizes in orthorhombic Fdd2 space group with a=22.295(2),b=24.097(3),c=6.7256(6)?,V=3613.3?^(3),Z=16,D_(c)=2.765 g/cm^(3),F(000)=2816,μ=7.855 mm^(-1),the final R=0.0173(I≥2σ(I)),w R=0.0416(all data)and GOOF=1.068.In complex 1,the Tb^(3+)ions are connected by HIMDC^(2-)anions into 2D metal-organic layers which are further extended into a three-dimensional(3D)architecture through formic acid functional motif.In addition,complex 1 shows intense and characteristic green luminescence.
A new tetranuclear cuprous halide complex,(CuBr)_(4)(PN)_(2)(PN=2-(diphenylphosphaneyl)-6-methoxypyridine),was synthesized and fully characterized.In solid state,this complex exhibits efficient blue emission with a photoluminescence quantum yield of 43.3%and a decay time of 19μs at room temperature.The theoretical calculations,combined with the temperature dependence of spectroscopic properties and emission decay behaviors,indicate that the emission in the solid state originates from the ^(1,3)(MLCT+XLCT)excited states,which are in thermal equilibrium with a small energy gap of about 0.1 eV.
A novel compound, {[Y（HPIDC）（OX）1/2（H2O）]·2H2O}n （1, H3PIDC = 2-（pyridin-4- yl）-1H-imidazole-4,5-dicarboxylic acid, H2OX = oxalic acid）, has been synthesized under hydrothermal conditions and characterized by thermal analysis （TGA）, powder X-ray diffraction （PXRD）, and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic space group P21/c with a = 8.342（8）, b = 14.61（1）, c = 11.487（1）, β = 90.78（9）°, V = 1400.4（2）3, Z = 4, C11H11N3O9Y, Mr = 418.14, Dc = 1.983 g/cm3, F（000） = 836, Rint = 0.0509, T = 293（2） K, μ = 4.240 mm-1, the final R = 0.0477 and wR = 0.1125 for 2770 observed reflections with I 2σ（I）. Compound 1 exhibits a 3D framework and generates the 1D open channels filled with free water molecules. The structure of 1 can be rationalized as a diamondoid network when the atom yttrium is regarded as a 4-connected node linking four surrounding yttrium atoms. The luminescent property of compound 1 is also investigated.
The metal-organic framework（MOF）{[Cu（L1）_（0.5）（CN）]·4H_2O·3DMSO}_n（1） was assembled by 1,4-bis（3？,5？-dicyano-2？,6？-di（pyrid-4-yl）-1？,4？-dihydropyridyl）benzene（L1） together with copper cyanide at room temperature. In 1,the Cu~＋ ions are linked by CN-anions into a 1D helical chain,which is further fused together by tetradentate L1 ligands to build an extended 3D porous framework with two different types of functionalized channels. 1 crystallizes in the monoclinic,space group P21/c with a = 17.8729（6）,b = 8.7298（3）,c = 22.7524（9） ？,β = 96.072（4）o,V = 3530.1（2） ？~3,μ = 0.845 mm-1,Dc = 1.352 Mg/m^3,Z = 4,Mr = 718.35,F（000） = 1500,S = 1.081,the final R = 0.0877 and wR = 0.2275 for 6975 observed reflections with I 〉 2σ（I）.
A new luminescent Cd（Ⅱ） coordination polymer, [Cd（L）2（H2O）]n 1 （HL = xan-thene-9-carboxylic acid）, was synthesized hydrothermally and characterized by satisfactory elemental analysis, FT-IR spectra and single-crystal X-ray diffraction. The crystal is of orthorhombic system, space group P212121 with a = 6.4548（4）, b = 13.0876（12）, c = 27.466（2）, V = 2320.3（3）3, C28H20CdO7, Mr = 580.84, Z = 4, Dc = 1.663 g/cm3, F（000） = 1168, μ = 0.990 mm-1, Flack parameter = 0.00（2）, the final R = 0.0296 and wR = 0.0691 for 5301 observed reflections （I 2σ（I））. 1 features a one-dimensional （1D） carboxylate oxygen-bridged inorganic chain, which is further connected by intermolecular hydrogen bonds into a three-dimensional （3D） framework. Moreover, compound 1 exhibits strong photoluminescence in the solid state at room temperature.
Five new quaternary isostructural rare-earth sulfides, Al0.57Gd3(Si0.27Al0.73)S7 (1), Al0.55Dy3(Si0.34Al0.66)S7 (2), Al0.50Y3(Si0.50Al0.50)S7 (3), Al0.44Gd3(Si0.70Al0.30)S7 (4) and In0.33Sm3SiS7 (5), have been synthesized by facile solid-state reactions. They crystallize in the 3-D ALn3EQ7 structure type in the hexagonal chiral space group P63. The structures feature a 3-D host framework constructed by Ln-S bicapped trigonal prisms, in which the octahedral and tetrahedral interspaces are occupied by A and E atoms, respectively. The investigation of optical and magnetic properties of 4 indicates that it is a semiconductor and behaves antiferromagnetic-like interaction.
GUO ShengPing, GUO GuoCong & HUANG JinShun State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2]（ClO4）E·H2O 1 and [CoL2]（NO3）E·H2O 2 as isolatable products （L= N-（1- benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine）, where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1： monoclinic, space group P21/c, a = 11.9214（10）, b = 23.5828（17）, c = 14.0387（12）A, β = 135.219（4）°, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1（4） A^3 ,Z = 4, Dc = 1.625 g/cm^3,μ（MoKa） = 0.876 mm^-1, F（000） = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections （I 〉 2σ（I））. Crystal data for complex 2： monoclinic, space group P21/c, a = 18.2162（16）, b = 10.0610（6）, c = 18.593（2）A, β = 130.099（3）°, C22H30CoN10O7, Mr = 605.49, V = 2606.5（4） A3 Z = 4, Dc = 1.543 g/cm^3,μ（MoKa） = 0.722 mm^-1, F（000） = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4^- （or NO3^-） groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.
A new metal-organic coordination polymer, [Ag（L）（NO3）]H （1, L = β-amino-β- （pyrid-2-yl）acrylonitrile）, has been synthesized by solvent method at ambient temperature and characterized through single-crystal diffraction, Fourier transformed infrared spectrum （FTIR）, elemental analysis, thermogravimetry analysis （TGA） and fluorescent measurements. 1 crystallizes in the triclinic system, space group Pi with a = 7.3600（3）, b = 8.5095（17）, c = 9.2936（14） A, α= 66.65（6）, β = 70.56（7）, γ= 71.59（6）°, V = 492.4（4） A3, μ = 2.043 mm-1, Dc = 2.104 Mg/m3, Z = 2, Mr = 312.01, F（000） = 302, the final R = 0.0347 and wR = 0.0987 for 3924 observed reflections with I 〉 2σ（I）.
A binuclear cuprous complex [Cu（μ-I）（NPPh）]2（1,NPPh = 1-（2-（diphenylphosphanyl）phenyl）-3-phenyl-4,5-dihydro-1 H-pyrazole） was synthesized and characterized by elemental analysis,NMR and X-ray single-crystal structure analysis.It crystallizes in triclinic space group P2_1/n with a = 10.7520（3）,b = 18.1860（5）,c = 11.8487（3） ？,β = 91.864（2）,V = 2315.61（11） ？~3,Z = 4,Mr = 594.87,Dc = 1.706 g/cm^3,F（000） = 1176.0,μ = 12.582 mm（-1）,GOOF = 1.048,the final R = 0.0289 and wR = 0.0670 for 3787 observed reflections with I 〉 2σ（I）.The Cu atoms in the complex are four-coordinated and adopt distorted tetrahedral coordination geometry.In the solid state,the complex exhibits greenish yellow photoluminescence with a peak maximum of 533 nm,a decay time of 34 μs,and a photoluminescence quantum yield of 63.6% at room temperature,respectively.
A four-coordinate mononuclear cuprous complex oCBP-Cu-Pym(1, oCBP =1,2-bis(diphenylphosphine)-nido-carborane, Pym = 2-methyl-6-(1 H-pyrazol-1-yl)pyridine) was synthe-sized and characterized by elemental analysis, NMR, UV-Vis and X-ray single-crystal structure analysis. It crystallizes in monoclinic space group C2/c with a = 28.4182(8), b =16.2994(4), c = 22.2708(5) ?, β = 127.219(2)°, V = 8214.8(3) ?3, Z = 8, Mr = 766.92, ρcalc = 1.24 g/cm3, F(000) = 3160, μ = 2.30 mm–1, GOOF = 1.063, the final R = 0.0700 and wR = 0.1903 for7158 observed reflections with I > 2σ(I). The Cu(I) ion adopts a highly distorted tetrahedral geometry defined by two nitrogen and two phosphorous atoms. Under UV 365 nm at room temperature, this complex exhibits green emission with maximum emission peak at 516 nm,lifetime 32.4 μs and quantum yield(ф = 0.461) in the solid state. Photophysical investigation suggests that the emission of complex 1 at room temperature was attributed to TADF, which is strongly supported by theoretic calculation.
