Supramolecular Terbium-SIP Complex Pillared by 4,4'-Bipyridyl,{[Tb(SIP)(H_2O)_5]_2(bpy)_3(H_2O)}n:Synthesis,Crystal Structure and Photoluminescence

The supramolecular terbium complex, {[Tb(SIP)(H2O)5]2(bpy)3(H2O)}n (NaH2SIP= 5-sulfoisophthalic acid monosodium salt and bpy=4,4'-bipyridyl), has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a= 30.6840(1), b=10.9206(2), c=17.4967(3), β=111.931(1)o, V=5438.65(14)3, Z=4, C46H52N6O25S2Tb2, Mr=1470.90, Dc=1.796 g/cm3, μ=2.747 mm-1, F(000)=2928, the final R= 0.0654 and wR=0.1322 for 3806 observed reflections with I > 2σ(I). In the neutral [Tb(SIP)(H2O)5]2 motif, the Tb(III) ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H···N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.     

A Dinuclear Dysprosium-2-quinolinecarboxylate-1,10-Phenanthroline Compound:Crystal Structure and Magnetism

A dinuclear dysprosium(III) compound,[Dy_2(μ_2-OH)_2(QLC)_4(1,10-phen)_2]·4H_2O(1)(QLC-= 2-quinolinecarboxylate and 1,10-phen = 1,10-phenanthroline),was synthesized and structurally and magnetically characterized.Compound 1 crystallizes in triclinic system,space group P1 with a = 10.9439(3),b = 11.2823(3),c = 12.2323(4) ?,α = 107.446(3),β = 91.700(3),γ = 91.511(2)°,V = 1439.25(8) ?~3,Z = 1,C_(64)H_(50)N_8O_(14)Dy_2,Mr = 1480.12,Dc = 1.708 g/cm3,μ = 2.653 mm-1 and F(000) = 734.The final R = 0.0366 and w R = 0.0736 for 5816 observed reflections with I 2σ(I).Compound 1 contains the mononuclear [Dy(QLC)_2(1,10-phen)] subunit formed from one 1,10-phen and two QLC-ligands chelating Dy(III) ion.Two mononuclear [Dy(QLC)_2(1,10-phen)] subunits are bridged by a pair of μ_2-OH groups to give a centrosymmetric dinuclear [Dy_2(μ2-OH)_2(QLC)4(1,10-phen)_2] with each Dy(III) ion being eight-coordinated.Detailed susceptibility measurements revealed that compound 1 does not show slow magnetic relaxation under zero direct-current field but exhibits field-induced slow magnetic relaxation under 2 kOe applied field.     

[Et_4N]_2[Zn_2(OPh)_2Cl_4]的合成和晶体结构

ZnCl2, PhONa和Et4NCl稨2O在乙腈溶剂中反应合成了一种二核锌配合物[Et4N]2[Zn2(OPh)2Cl4]。X射线衍射结果表明,晶体属单斜晶系,C2/m空间群,晶胞参数 a = 14.1366(2), b=13.6985(5), c=9.3308(3)牛?107.851(2)o, V=1719.92(9)?,C28H50O2N2Zn2Cl4,Mr=721.24,Z=2,Dx=1.393g/cm3,μ(MoKα)=1.732mm—1,F(000)=756, R=0.0552, wR=0.1534, S=1.027。 配合物是由2个阳离子Et4N+和1个阴离子[Zn2(OPh)2Cl4]2—组成。阴离子[Zn2(OPh)2Cl4]2—包含着1个中心Zn2O2菱形平面。配合物中的2个锌原子通过2个苯酚中的氧原子桥连,每个锌原子还与2个氯原子配位形成变形四面体结构。     

A Luminescent Tb(Ⅲ)-4,4’,4’’-nitrilotribenzoate Compound with a Three-dimensional Structure

A coordination polymer of [Tb(ntb)]n(1) based on 4,4’,4’’-nitrilotribenzoate ligand(ntb3–) was synthesized. Compound 1 crystallizes in monoclinic system, space group C2/c with a = 13.7318(4), b = 27.5628(9), c = 5.4046(2) ?, β = 111.142(3)°, V = 1907.88(12) ?3, Z = 4, C21H12NO6Tb, Mr = 533.24, Dc = 1.856 g/cm3, μ = 3.745 mm–1, F(000) = 1032, the final R = 0.0184 and wR = 0.0456 for 1883 observed reflections with Ⅰ > 2s(Ⅰ). In compound 1, the eight-coordinated Tb(III) atoms are bridged by carboxylate groups of ntb3– ligands to generate a one-dimensional Tb-carboxylate chain, which is further linked by the ntb3– ligands to form a three-dimensional structure. Compound 1 exhibits characteristic Tb(Ⅲ) luminescent emissions in the solid state.     

Conformation Diversity of Complexes Constructed by N-（2-Pyridylmethyl）-phenylalanine and Zn（Ⅱ）

Four configurationally and conformationally related Zn（II） complexes with a tridentate ligand namely, N-（2-pyridylmethyl）-phenylalanine （Hpmpa）, have been synthesized by hydrothermal reactions. [Zn（L-α-pmpa）2·HaO] 1： orthorhombic, space group P21212 with a = 15.1091（7）, b = 16.2417（8）, c = 5.9972（3） A, V= 1471.70（12）A^3, Z = 2, Mr = 593.97, Dc = 1.340 g/cm^3,μ = 0.879 mm^-1, F（000） = 620, Rint= 0.0205, R = 0.0450 and wR = 0.1578 for 3102 observed reflections with I 〉 2σ（I）; [Zn（D-α-pmpa）2·2H2O] 2： orthorhombic, space group P21212 with a = 15.1023（6）, b = 16.2516（7）, c = 6.0024（2）A, V= 1473.21（10）A^3, Z = 2, Mr = 611.98, Dc = 1.380 g/cm^3,μ = 0.882 mm^-1, F（000） = 640, Rint= 0.0337, R = 0.0484 and wR = 0.1435 for 2408 observed reflections with I 〉 2σ（I）; [Zn（L-β-pmpa）2] 3： monoclinic, space group C2/c with a = 27.8667（5）, b = 5.60350（10）, c = 19.9636（2）A β = 120：2210（10）°, V = 2693.66（7）A^3, Z = 4, Mr = 575.95, De= 1.420 g/cm^3,μ = 0.955 mm^-1, F（000） = 1200, Rint= 0.0345, R = 0.0358 and wR = 0.1135 for 2251 observed reflections with I 〉 2σ（I）; and [Zn（D-β-pmpa）2] 4. They are all mononuclear discrete structures. The influence of temperature and pH on the conformation of structures has been investigated. Moreover, the photoluminescent properties of compounds 1 and 3 are also reported.     

In Situ Hydrothermal Synthesis of a Mononuclear Copper（Ⅱ） Complex： Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-Hydroxyl-5-sulfoisophthalic Acid）

The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.     

Synthesis and Crystal Structure of a Novel Two-dimensional Layered Polymer

The title complex [Zn(μ-O2CCH=CHCO2)(C3H4N2)(H2O)]n was prepared by the reaction of zinc carbonate with maleic acid and imidazole in an aqueous-alcohol solution at 333 K, and its crystal structure has been solved by single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group Pc with a = 5.3858(7), b = 22.685(3), c =7.6782(1) A, β = 92.261(2)°, V = 937.4(2) A3, Z = 1, C14H16N4O10Zn2, Mr= 531.05, Dc= 1.882g/cm3,μ = 2.623 mm-1, F(000) = 532, the final R = 0.0372 and wR = 0.0930 for 1926 observed reflections with I＞2σ(I). The central zinc atom is five-coordinated in a distorted square pyramidal environment to three oxygen atoms of two different maleate ligands, a nitrogen atom of the imidazole ligand and an oxygen atom of water. In the complex two carboxylate groups of the maleate ligands have two coordination modes. One acts as a bidentate chelate ligand and the other a monoatomic monodentate ligand to bridge two zinc centers. As a result, 1-D infinite polymeric coordination water OH groups and carboxylate oxygen atoms to construct a 2-D layered polymer,and the layer structure is stabilized by π-π stacking of the imidozel ligands.     

Ionothermal Syntheses and Crystal Structures of Two Cobalt（Ⅱ） Compounds：Co（2,2＇-bpy）_2Br_2 and Co（1,10-phen）_2Br_2

Two cobalt(Ⅱ) compounds,Co(2,2-bpy) 2 Br 2 (1,2,2-bpy=2,2-bipyridyl) and Co(1,10-phen) 2 Br 2 (2,1,10-phen=1,10-phenanthroline),have been prepared under ionothermal reactions using the 1-propyl-3-methylimidazolium bromide ionic liquid solvent.Single-crystal X-ray analyses reveal that 1 crystallizes in a monoclinic space group P2 1 /c,with a=8.5509(13),b=14.804(2),c=15.650(2),β=97.119(2) o,V=1965.8(5) 3,Z=4,C 20 H 16 Br 2 N 4 Co,M r=531.12,D c=1.795 g/cm 3,μ=4.950 mm-1,F(000)=1044,the final R=0.0467 and wR=0.0736 for 2291 observed reflections with I > 2σ(Ⅰ).Complex 2 crystallizes in a monoclinic space group P2 1 /n,with a=10.4237(8),b=16.8657(12),c=12.4945(9)b,β=102.110(1) o,V=2147.7(3) 3,Z=4,C 24 H 16 Br 2 N 4 Co,M r=579.16,D c=1.791 g/cm 3,μ=4.540 mm-1,F(000)=1140,the final R=0.0431 and wR=0.1042 for 3470 observed reflections with I > 2σ(Ⅰ).The mononuclear molecules of 1 are linked by the C-H···Br hydrogen bonds and π-π interactions to form a three-dimensional supramolecular framework structure.The C-H···Br hydrogen bonds and π-π interactions link the mononuclear molecules of 2 to give a two-dimensional layer structure.     

Synthesis, Crystal Structure and Photoluminescent Property of a Novel Silver(I) Compound {[Ag(bpp)]_2(Hphth)(NO_3)·(H_2O)_2}_n

Self-assembly of Ag(I) nitrate, 1,3-bis(4-pyridyl)propane (bpp) and phthalic acid monopotassium salt (KHphth) in CH3OH-H2O solution produced the title complex, {[Ag(bpp)]2(Hphth)(NO3)·(H2O)2}n, which was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, and photoluminescent spectrum. Single-crystal X-ray analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, with a = 15.4174(5), b = 8.6398(2), c = 25.2466(8) , β = 91.072(1)o, V = 3362.34(17) 3, Z = 4, C34H37N5O9Ag2, Mr = 875.43, Dc = 1.729 g/cm3, μ = 1.228 mm-1, F(000) = 1768, the final R = 0.0749 and wR = 0.1580 for 5754 reflections with I > 2σ(I). The Ag atom is coordinated by two N atoms from two bpp molecules in an approximately linear geometry. The Ag(I) ions are linked by the bpp molecules to form one-dimensional zigzag chains propagating along the c axis. The Hphth- and nitrate counter-ions are bridged by solvent water molecules through hydrogen bonds to generate a one-dimensional chain extending along the b axis. Electrostatic interactions between cations and anions, extensive hydrogen bonds and π-π interactions are responsible for the three-dimensional supramolecular structure. In the solid state, the compound exhibits blue photoluminescence with the maximum at 436 nm upon excitation at 344 nm.     

Synthesis and Structural Characterization of Co( Ⅱ ) Coordination Polymer [Co(μ-phth)(imi)2]n

A new cobalt( Ⅱ ) complex [Co(μ-phth)(imi)2]n (phth = o-phthalato, imi = imidazole)has been synthesized by the reaction of CoCl2 with disodium o-phthalate and imidazole. The crystal structure of the compound has been determined by single-crystal X-ray diffraction. The crystal is of monoclinic system, space group Pn with a = 8.405(1), b = 9.995(1), c = 9.996(2) (A),β= 104.479(2),V= 813.0(2) (A)3, Dc= 1.467 g/cm3, C14H12N4O4Co, Mr= 359.21, F(000) = 366,μ = 1.079 mm-1, Z = 2, R = 0.0483 and wR = 0.1209 for 1583 observed reflections (Ⅰ＞ 2σ(Ⅰ)). In the title complex, the Co(Ⅱ) ions are bridged by o-phthalate ligands in a bidentate mode, producing a zigzag infinite chain structure. Each four-coordinated cobalt( Ⅱ ) center was coordinated by two oxygen atoms and two nitrogen atoms to give a distorted tetrahedral geometry. The chains are linked by hydrogen bonds between oxygen atoms belonging to carboxylate groups and hydrogen atoms of imidazole molecules, forming an unusual two-dimensional coordination polymer.