Crystal Structure and Luminescence of a New Zn(Ⅱ) Complex [Zn(L)(IPP)(H_2O)]·2H_2O Based on Nicotinate Derivative and 1,10-Phenanthroline Derivative

A new Zn(Ⅱ) complex, [Zn(L)(IPP)(H2O)]·2H2O(1, H2 L = 3-carboxy-1-carboxymethyl-2-oxidopyridinium and IPP = 2-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol), was synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 8.5023(17), b = 9.945(2), c = 15.573(3) ?, α = 95.87(3), β = 102.56(3), γ = 100.73(3)o, V = 1248.7(4) ?3, Z = 2, C27H22N5O9 Zn, Mr = 625.87, Dc = 1.665 g/cm3, F(000) = 642, μ(Mo Ka) = 1.053 mm-1, R = 0.0474 and w R = 0.1352. In 1, one L2-, one IPP and one water molecule coordinate to the same Zn(II) atom to give a discrete complex with two lattice water molecules. Adjacent [Zn(L)(IPP)(H2O)]·2H2O molecules interact through π-π stacking between two IPP ligands to form a supramolecular chain. The N–H···O and O–H···N hydrogen bonds further stabilize the supramolecular chain structure of 1. The solid state luminescent property of 1 was also studied.     

Synthesis,Crystal Structure and Luminescence of a New Zn(Ⅱ) Dimer: [Zn(bpdc)(L)]_2·4H_2O

A new dimeric compound, [Zn(bpdc)(L)]2·4H2O(1, L = 11-fluoro-dipyrido[3,2-a:2',3'-c]phenazine and bpdc = 1,1'-biphenyl-2,2'-dicarboxylate), has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group C2/c with a = 23.671(5), b = 22.547(5), c = 13.741(3), β = 123.47(3)o, V = 6118(2) 3, Z = 4, C66H44Cl2F2N8O12Zn2, Mr = 1380.73, Dc = 1.499 g/cm3, F(000) = 2816, μ(MoKa) = 0.949 mm-1, R = 0.0572 and wR = 0.1620. In 1, Zn1 and the symmetry formed Zn1 ions are connected by four bridging bidentate carboxylate groups from two independent bpdc anions to yield a binuclear unit with the Zn···Zn separation by bpdc anions of 4.168. Two L ligands are located on both sides of the dimer in chelating bidentate modes. The lateral L ligands from neighboring dimers are paired through strong π-π interactions to result in a fascinating 1D ladder-like supramolecular array. In addition, neighboring supramolecular ladders are packed each other to yield a 3D supramolecular architecture with a 1D channel.     

Syntheses,Crystal Structures and DNA-binding Properties of Cd(Ⅱ), Co(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ) Complexes Containing Imidazolium Derivatives

Cd(Ⅱ), Co(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ) complexes(1~4) based on 2-(2-pyridyl)benzimidazole(pbm) and 4,4'-oxybisbenzoic acid(H2odc) were synthesized. The formulas of these complexes are [Cd(pbm)(odc)2](1), [Co(pbm)(odc)2](2), [Cu(pbm)(odc)2](3) and [Zn(pbm)(odc)2](4) confirmed by single-crystal X-ray diffraction analysis, which shows that complexes 1, 2 and 4 belong to monoclinic system with space group P21/n, while complex 3 belongs to monoclinic system with space group P21/c. The binding properties of complexes 1~4 with CT-DNA are evaluated by ultraviolet spectrum, fluorescence spectra and viscosity measurements. The results indicate that complexes 1~4 have strong interaction with CT-DNA binding. These complexes exhibit an electrostatic or groove mode in respect of binding with DNA, which can effectively destroy DNA. And this binding mode may be applied to the interaction between the complexes and cancer cell DNA. Therefore, we hope to provide a theoretical and scientific basis for the research of anti-cancer drugs.     

Structure and Fluorescence Property of a 2D Bilayer Cd(Ⅱ) Coordination Polymer Induced by H-bonding and π-π Interaction

Solvothermal reactions of 4,4'-oxybis(benzoic acid) (H2oba) with 1,3-dipyridyl benzene (1,3-dpb) produced a two-dimensional (2D) cadmium(Ⅱ) coordination polymer {[Cd(oba)(dpb)]·H2O}n (1). The complex was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 13.6692(9), b = 25.9647(17), c = 8.7912(6) , α = 125.0370(10), γ = 2544.7(3)°, V = 2544.7(3) 3, C30H22N2O6Cd, Mr = 618.91, Dc =1.609 g/cm3, F(000) = 1248, μ = 0.904 mm-1 and Z = 4. The neighboring Cd(Ⅱ) ions are linked by oba2-anions and 1,3-dpb to form an infinitely 2D wavelike sheet, and two such 2D sheets are interlocked with each other by H-bonding to form a 2D → 2D structure. The adjacent two groups of interlocked structures are further linked to form a bilayer 2D supramolecular network by π-π interactions. In addition, the fluorescence property of 1 was also studied.     

Synthesis,Crystal Structure and Luminescence of a New Zn(Ⅱ) Complex [Zn(1,2,3-HBTC)(L)]_2 Constructed by Mixed Ligands

A new Zn(Ⅱ) complex,[Zn(1,2,3-HBTC)(L)]2(1,L = 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline and 1,2,3-H3 BTC = 1,2,3-benzentricarboxylic acid),was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction.It crystallizes in triclinic,space group P1 with a = 10.455(2),b = 11.533(2),c = 12.499(3) ?,α = 116.97(3),β = 94.08(3),γ = 103.29(3)o,V = 1280.2(4) ?3,Z = 1,C56H28Cl2F2N8O12Zn2,Mr = 1244.50,Dc = 1.614 g/cm3,F(000) = 628,μ(Mo Ka) = 1.124 mm-1,R = 0.0502 and w R = 0.1417.In compound 1,two 1,2,3-HBTC anions bridge two Zn(Ⅱ) atoms to give a dimeric structure with Zn···Zn distance of 3.15 ?.Adjacent dimers interact through π-π stackings between two L ligands to result in a supramolecular layer.Moreover,N–H···O and O–H···N hydrogen bonds further stabilize the 2D supramolecular architecture of 1.In addition,the luminescent property of 1 has been studied.     

Synthesis and Structure of a La(Ⅲ) Complex of 1,10-Phenanthroline-2,9-dicarboxylate:a Three-dimensional Network via Hydrogen Bonding Interactions

A new La(Ⅲ) complex, {[La(L)(NO3)(H2O)3]·H2O}n (L = 1,10-phenanthroline- 2,9-dicarboxylate), has been synthesized and structurally determined by X-ray diffraction analysis. The complex crystallizes in the monoclinic system, space group P21/c with a = 7.7358(17), b = 8.1664(18), c = 28.271(6) , β = 95.184(4)°, V = 1778.6(7)3, Z = 4, C14H14LaN3O11, Mr = 539.19, Dc = 2.014 g/cm3, μ = 2.471 mm–1, F(000) = 1056, the final R = 0.0350 and wR = 0.0659. In this complex, each metal center adopts a ten-coordination geometry formed by two N atoms from a ligand L and eight O atoms from three H2O molecules, a nitrate ion and carboxylates of two ligands. Each ligand adopts a N2,O3-pentdentate coordination mode using two N and two O atoms chelating a La(III), and using another O atom of carboxylate to bridge another La(III) center resulting in a 1D helical chain molecule. Intermolecular strong O–H···O and weak C–H···O hydrogen bonds extend the 1D chain structure into a 3D supramolecular architecture.     

A New Cadmium(Ⅱ) Dimer Constructed by 1,10-Phenanthroline Derivative and Chlorine Anions: Syntheses,Crystal Structure and Photoluminescence

In this work, a new Cd(II) dimeric compound, [Cd(Cl)2(L)(H2O)]2(1, L = 2-(4-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline), has been achieved under hydrothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic, space group P21/c with a = 8.944(2), b = 18.781(5), c = 10.904(3), β = 91.392(4)°, V = 1831.2(8) 3, Z = 2, C38H26Cd2F2Cl4Cl4N8O2, Mr = 1031.27, Dc = 1.870 g/cm3, F(000) = 1016, μ(Mo Ka) = 1.513 mm-1, R = 0.0532 and w R = 0.1407. Each Cd(II) atom is in an octahedral coordination sphere, completed by two nitrogen atoms from one L ligand, two chlorine anions, and one water oxygen atom. Two chlorine anions bridge two Cd(II) atoms to give a dimer [Cd(Cl)2(L)(H2O)]2. Adjacent dimers are stacked by one type of π-π interactions among L ligands to generate a 1D supramolecular chain. Further, the 1D supramolecular chains are stacked by another type of π-π interactions among L ligands to give a 2D supramolecular layer. Finally, the luminescent property of 1 has been studied in solid state at room temperature.     

Synthesis and Crystal Structure of a Bimetallic Cyanide-bridged Complex Derived from Manganese(Ⅲ) Schiff-base Complex and Pentacyanidonitrosylferrate(Ⅱ) Building Blocks

A new cyanide-bridged bimetallic assembly [Mn(3-meosalpn)(H2O)]2[Fe(CN)5NO](1) was obtained by the reaction of [Fe(CN)5NO]2-with [Mn(3-meosalpn)]+,and characterized by elemental analysis,IR and single-crystal X-ray structure analysis.The complex crystallizes in the monoclinic system,space group P21/c with a = 12.992(5),b = 13.274(6),c = 14.644(6) ,β = 115.198(4)o,V = 2285.2(16)3,Z = 2,C43H44FeMn2N10O11,Mr = 1042.61,Dc = 1.515 g/cm3,F(000) = 1072,μ = 0.928 mm-1,S = 1.052,the final R = 0.0347 and wR = 0.0957 for 17377 observed reflections(Ⅰ 2σ(Ⅰ)).X-ray single-crystal diffraction analysis reveals that 1 has a trinuclear molecular structure,in which the two [Mn(3-meosalpn)(H2O)]+ cations are linked by the central [Fe(CN)5NO]2-anion via two trans CN-groups.Furthermore,the two [Mn(3-meo-salpn)(H2O)]+ cations and [Fe(CN)5NO]2-anion are connected into a one-dimensional zigzag chain through hydrogen bonding interactions.     

Synthesis,Structure and Characterization of a Cd(Ⅱ) Polymer Based on 6-Hydroxynicotinic Acid

A new 2D layered Cd(II) coordination polymer,[Cd(HnicO)(phen)(NO3)]n 1(H2nicO = 6-hydroxynicotinic acid,phen = 1,10-phenanthroline),has been hydrothermally synthesized and characterized by elemental analysis,IR,and single-crystal X-ray diffraction.It crystallizes in the monoclinic system,space group P21/c with a = 11.1107(2),b = 13.7639(2),c = 12.1457(4) ,β = 108.695(1)°,V = 1759.40(7) 3,Z = 4,Mr = 492.72,F(000) = 976,Dc = 1.860 g/cm3,μ = 1.289 mm-1,the final R = 0.0205 and wR = 0.0550 for 3663 observed reflections(I > 2σ(I)).X-ray single-crystal structural analyses reveal that in complex 1,the H2nicO ligands and Cd(II) nodes define the structure to be(4,4) 2D nets which are further assembled into the final 3D architecture via supramolecular interactions such as hydrogen bonds and aromatic interactions.Moreover,the solid-state luminescent study shows the title polymer possesses intense luminescent property at room temperature.     

Synthesis, Crystal Structure and Photoluminescent Property of a Novel Silver(Ⅰ) Compound {[Ag(bpp)]2(Hphth)(NO3)·(H2O)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 α =15.4174(5), b = 8.6398(2), c = 25.2466(8) (A), β = 91.072(1)°, V = 3362.34(17) (A)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, 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.     

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Polycarboxylate Ligand 5-(4-Hydroxypyridinium-1-ylmethyl)-isophthalic Acid: Synthesis,Structure, and Property

A Zn(Ⅱ) supramolecular coordination polymer, {[Zn_2(L)_2(m-bix)(H_2O)]·6 H_2O}n(1), with an interesting 1 D→2 D polythreading array from a flexible and angular organic aromatic polycarboxylate ligand 5-(4-hydroxypyridinium-1-ylmethyl)isophthalic acid(H2 L), and N-donor ligand 1,3-bis(imidazol-1-ylmethyl)benzene(m-bix), has been obtained under hydrothermal conditions and characterized by elemental analysis, powder X-ray diffraction(PXRD), IR, thermal gravimetric analyses(TGA) and single-crystal X-ray diffraction. In 1, the Zn(Ⅱ) center has two coordination geometries. One exhibits a trigonal bipyramidal coordination sphere, and the other is a tetrahedral geometry; L2-has two different coordination modes, with one connecting three Zn(Ⅱ) ions through two monodentate carboxylate groups and the monodentate hydroxyl group, and the other bridging two Zn(Ⅱ) ions through two carboxylate groups. The L2-anions connect the Zn(Ⅱ) centers forming an infinite 1 D tubular structure. These 1 D tubes are interconnected by the m-bix spacers to form a 2 D framework. Such 2 D layers are further assembled into a 3 D supramolecular network via hydrogen bonds. Meanwhile, the luminescent property of 1 has also been investigated in detail.     

Syntheses and Crystal Structures of Two Copper(Ⅱ) Coordination Polymers Derived from Aromatic Carboxylic Acids and Bis(imidazoles) Ligands

Two compounds have been obtained by the reaction of metal(Cu(II)), 4,4?-bis(imidazol-l-yl)diphenyl thioether(BIDPT) with two carboxylic acids, 4,4?-oxydibenzoic acid(H_2oba) and phthalic acid(H_2pht). The crystal structures of the resulting compounds, namely {[Cu(BIDPT)(oba)]·H2O}n(1) and {Cu(BIDPT)(pht)}n(2), have been determined by single-crystal X-ray diffraction analysis. Compound 1 is of orthorhombic system, space group Pbcn with a = 27.8310(3), b = 10.7791(1), c = 19.3913(2) ?, V = 5817.0(3) ?3 and Mr = 656.15. Compound 2 belongs to the monoclinic system, space group C2/c with a = 18.2678(2), b = 11.0259(1), c = 22.906(2) ?, β = 97.727(2)o, V = 4571.8(8) ?3 and Mr = 545.04. Structural analyses reveal that compounds 1 and 2 respectively exhibit two-dimensional(2D) wavy and corrugated layer structures. Through intermolecular hydrogen bonding, compound 1 is assembled into a 3D supramolecular structure. The thermal stability and ultraviolet spectroscopy properties of the two compounds are also investigated.     

Three 3D M~Ⅱ (M = Co,Ni, Zn) Supramolecular Polymers Constructed from O-vanillic Acid: Synthesis,Crystal Structure and TGA

The title compounds, [Co(H2O)6](OVA)2·2H2O 1, [Ni(H2O)6](OVA)2·2H2O 2 and [Zn(OVA)2·2H2O] 3 (HOVA = o-vanillic acid = 2-hydroxy-3-methoxybenzoate), were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR and TGA. Compounds 1 and 2 are both of triclinic with space group P1. The metal atom coordinated by six water molecules displays a slightly distorted octahedral configuration. Interestingly, the carboxyl group from HOVA ligand does not coordinate to the metal atom. Correspondingly, compound 3 belongs to the monoclinic system, space group C2/c. Each zinc(Ⅱ) atom exhibits a distorted four-coordinated tetrahedral geometry. Two monodentate carboxyl groups link one zinc(Ⅱ) atom to form a mononuclear molecule. The structure feature is different from that of compounds 1 and 2, which could be attributed to the different coordinated numbers and radii of Co(Ⅱ), Ni(Ⅱ) and Zn(Ⅱ) atoms.     

Construction of a 2D Cd(Ⅱ) Network with Homohelical Chains Based on 1,3-Dipyridyl Benzene(Dpb) and 4,4'-Sulfonyldibenzoic Acid(H_2sdb)

A two-dimensional(2D) coordination polymer {[Cd2(sdb)2(dpb)2]·3H2O}n(1) was prepared by solvothermal reaction of two types of V-shaped ligands: 1,3-dipyridyl benzene(dpb) and deprotonated 4,4'-sulfonyldibenzoic acid(H2sdb). It was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Complex 1 crystallizes in the monoclinic system, space group Fdd2 with a = 46.247(10), b = 9.994(2), c = 24.267(6) , V = 11216(4) 3, C60H46Cd2N4O15S2, Mr = 1387.97, Dc = 1.559 g/cm3, F(000) = 5296.0, μ = 0.902 mm-1 and Z = 8. Each [Cd(COO)]2 cluster links four sdb2- anions to form infinitely ABAB stacked 2D wave-like sheets, in which each sheet contains the same helical chains, and the helical directions of sheets A and B are reversed. Dpb links the rest coordinated sites of [(COO)Cd]2 cluster to form a 2D network. In addition, the solid fluorescence of 1 and dpb is also studied.     

Crystal Structure and Luminescent Properties of a Zn(Ⅱ) Coordination Polymer Assembled by Mixed-ligand

A Zn(Ⅱ) coordination polymer [Zn(NIP)(3,3'-bpt)]·H2O(1, NIP = 5-nitroisophthalate, 3,3'-bpt = 1H-3,5-bis(3-pyridyl)-1,2,4-triazolate) has been synthesized by the hydrothermal reaction at 140 ℃ and structurally characterized by IR spectroscopy, X-ray diffraction, thermal analysis, single-crystal X-ray diffraction and luminescent properties. In complex 1, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three H2 NIP and two nitrogen atoms from two 3,3'-bpt, respectively, forming a distorted trigonal bipyramidal geometry and showing a 1D chain structure, which is further bridged by NIP to form a 3D supramolecular network via self-assembly of hydrogen bonds.     

Two Coordination Polymers Constructed by Cd(Ⅱ) and Zn(Ⅱ) with in situ Generated 5-(3-Pyridyl)tetrazolate Ligand:Syntheses,Crystal Structures and Luminescence Properties

Hydrothermal reactions of 3-cyanopyridine and Na N3 with Zn Cl_2 or Cd Cl_2·5/2H_2 O in the presence of 1,4-benzenedicarboxylic acid(H2bdc) yielded two new coordination polymers,{[Zn(3-ptz)(bdc)_(0.5)(H_2O)_2]n·2H_2O}_n(1) and [Cd_2(3-ptz)_2Cl_2]_n(2),based on in situ synthesized 5-(3-pyridyl)tetrazolate(3-ptz-) organic ligand.They have been structurally characterized by elemental analysis(EA),infrared spectroscopy(IR) and single-crystal/powder X-ray diffraction(PXRD).In 1,two Zn(Ⅱ) ions are linked together through two μ_2-(3-ptz-) ligands to form a dimeric unit of [Zn(μ_2-3-ptz)(H_2O)_2]_2~(2+),which is further connected with other equivalent units by μ_2-bdc~(2-)spacers,resulting in an infinite 1D polymeric chain of [Zn_2(3-ptz)_2(H_2O)_2(bdc)]_n,and then strong hydrogen bonding interactions extend these 1D chains into a 3D supramolecular structure.In 2,the Cd(Ⅱ) ions are connected through μ_4-(3-ptz-) ligands and Cl-anions,leading to infinite 2D layers of [Cd_2(3-ptz)Cl_2]_n~(n+),which are further linked by another μ_4-(3-ptz-) pillared ligand to form a 3D layered-pillared framework architecture of [Cd)2(3-ptz))2Cl)2])n.Furthermore,thermal stability of these compounds was measured by thermogravimetric analysis(TGA) and their photoluminescent properties were also investigated in the solid state at room temperature.     

Syntheses,Structures and Properties of Two 2D Coordination Polymers from 5-（Pyridin-2-yl-methyl）aminoisophthalate

Hydrothermal reactions of 5-(pyridin-2-yl-methyl)aminoisophthalic acid(H2paip) with Mn(OAc)2·4H2O and Cu(NO3)2·3H2O produced two 2D complexes, [Mn(paip)]n·nH2O(1) and [Cu(paip)(H2O)]n(2). In complex 1, paip serves as a μ4-bridge, and its two carboxylate groups in μ2,η2-bridging and chelating modes connect Mn(Ⅱ) into 1D chains, which are further extended into a 2D layer through coordination of two chelating nitrogen atoms. However, paip in complex 2 acts as a μ3-bridge to link Cu(Ⅱ) into a 2D layer, in which two carboxylate groups function in a monodentate mode, and hydrogen bonds between the coordinated water and carboxylate oxygen atoms further extend the 2D layers into a 3D supramolecular network. The frameworks of complexes 1 and 2 are stable up to 470 and 250 ℃, respectively. Magnetic measurement shows that complex 2 possesses a weak antiferromagnetic interaction.     

Three New Polyoxometalates Derivatives Decorated by Phenanthroline and Transition-metal Cations(M=Zn~ⅡI,Co~Ⅱ , Ni~Ⅱ)

Three new Keggin polyoxometalates, [Zn(phen) 3 ] 2 [SiW 12 O 40 ]·5H 2 O(1), [Co(phen) 3 ] 2 [SiW 12 O 40 ](2) and [Ni(phen) 3 ] 2 [SiW 12 O 40 ]·2H 2 O(3)(phen=1,10′-phenanthroline) have been hydrothermally synthesized and characterized by elemental analysis, IR, crystal X-ray diffraction, thermogravimetric analyses(TGA) and fluorescence techniques. Complex 1, crystallized in the triclinic space group P1, consists of one [SiW 12 O 40 ] 4– anion, two discrete [Zn(phen) 3 ] 2+ cations and five crystal water molecules. Complexes 2 and 3 have the similar configuration to complex 1, but they crystallized in the monoclinic space group C2/c. Variable-temperature magnetic susceptibilities of complexess 2 and 3 reveal antiferromagnetism and ferromagnetism, respectively.     

A New Porous Cadmium(Ⅱ) Complex Based on 1,10-Phenanthroline Derivative and Dicarboxylate:Syntheses,Structure, Thermal Behavior and Luminescence

A new porous Cd(Ⅱ) coordination compound, namely, [Cd(bpdc)(L)2]·3H2O(1, L = 11-fluoro-dipyrido[3,2-a:2,3-c]phenazine and bpdc = 1,1-biphenyl-2,2-dicarboxylate) was synthesized under hydrothermal conditions, and characterized by single-crystal X-ray diffraction. It crystallizes in tetragonal, space group P4122 with a = 9.8486(4), b = 9.8486(4), c = 45.925(4)A, V = 4454.5(5) 3, Z = 4, C50H29 Cd F2N8O7, Mr = 1004.21, Dc = 1.497 g/cm3, F(000) = 2028, μ(Mo Ka) = 0.562 mm-1, R = 0.0566 and w R = 0.1585. Each Cd(Ⅱ) atom is coordinated by one bpdc anion and two L ligands to give a discrete molecule. Neighboring discrete molecules are stacked by π-π interactions among L ligands, resulting in an interesting 1D supramolecular chain. Moreover, the 1D supramolecular chains are packed with each other to give a porous structure, in which an infinite channel is filled with water molecules. In addition, the thermal behavior and luminescent property of 1 have also been studied.