A Novel 3D Twofold Zn(Ⅱ) Coordination Polymer Constructed by Mixed Flexible Ligands: Synthesis,Crystal Structure and Fluorescence Property

A new Zn(Ⅱ) coordination polymer, {[Zn(1,3-bip)(oba)]·0.5H_2O}n(1),1,3-bip =1,3-bis(imidazole)propane, H_2oba=4,4?-oxybis(benzoate)), have been synthesized and characterized by single-crystal X-ray diffraction, powder XRD, FTIR, TGA and elemental analysis techniques. The single-crystal X-ray diffraction reveals that complex 1 shows a 3D→3D twofold interpenetrating network that can be described as a 4-connected uninodal net with(65.8) topology. In addition, the photoluminescence property of complex 1 was also investigated at room temperature.     

Synthesis,Crystal Structure,and Luminescence of a 1D Chain Cd(Ⅱ) Polymerwith 3,3?,5,5?-Benzene-1,3-biyl-tetrabenzoic Acid

A new Cd(Ⅱ) coordination polymer, [Cd(H_2btb)(bpy)]_n(1, H_4btb = 3,3?,5,5?-benzene-1,3-biyl-tetrabenzoic acid, bpy = 2,2?-bipyridine), has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric(TG) analyses and single-crystal X-ray diffraction techniques. Complex 1 belongs to monoclinic system, C2/c space group. In 1, two carboxylate groups of the H_4btb ligand adopt bidentate chelating and μ_2-η~1:η~1 coordination modes, respectively, bridging the Cd(Ⅱ) atoms to generate a 1D polymeric ribbon. In addition, the photoluminescence property of complex 1 has also been studied.     

Two Co(Ⅱ) Complexes Constructed from 1-(3,5-Dicarboxybenzyl)-3,5-pyrazole Dicarboxylic Acid:Syntheses,Structures and Magnetic Properties

Two new complexes[Co_2(L)(4,4′-bip)(H_2O)_3]_n (1) and{[Co(L′)_2(phen)]·2H_2O)}_n (2)(H_4L=1-(3,5-dicarboxybenzyl)-3,5-pyrazole dicarboxylic acid,H_3L′=1-(3,5-dicarboxybenzyl)-3-pyrazole carboxylic acid,4,4′-bip=4,4′-bis(1-imidazolyl)biphenyl,phen=1,10-phenanthroline) were synthesized.Complexes 1 and 2have been characterized by IR spectrography,X-ray single-crystal diffraction,elemental analysis and thermogravimetry.1 crystallizes in monoclinic system,space group P2_1/c.Complex 2 crystallizes in monoclinic system,space group I2/a.It is remarkable that in situ hydrothermal decarboxylation was observed during preparing complex 2.In addition,magnetic analysis indicates that antiferromagnetic interaction exists among Co(Ⅱ) ions in complexes 1 and 2.     

Auxiliary Ligand-tuned Structural Variation of Cd(Ⅱ) Coordination Polymers: Synthesis,Crystal Structures and Luminescent Properties

Two new Cd(Ⅱ) coordination polymers, [Cd(PT)(1,4-BDC)0.5]_n(1) and [Cd(PT)(1,3-BDC)0.5]_n(2)(HPT = 3-(pyridin-2-yl)-1,2,4-triazole, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid, 1,3-H2 BDC = 1,3-benzenedicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Complexes 1 and 2 are both three-dimensional coordination polymers with two-dimensional sheet structures bridged by the deprotonated carboxylate ligands. In 1, 1,4-BDC~(2-) bridges the layered network to generate a quadrangular framework, and 2 owns a sexangular framework, which was caused by the different steric hindrance between 1,4-BDC~(2-) and 1,3-BDC~(2-). Their thermal stabilities and photoluminescent properties have been also investigated.     

Synthesis,Crystal Structure and Magnetic Behavior of a Novel Cd(Ⅱ) Complex with Four Nitroxide Radicals

A novel diamagnetic-metal Cd(Ⅱ) complex with four nitroxide radicals[Cd(IM4Py)4Cl2](IM4Py=2-(4'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl) was synthesized and characterized by elemental analyses,IR spectra,UV-Vis spectra and X-ray single crystal diffraction.The complex crystallized in triclinic space group P1 with a=0.93285(14) nm,b=1.16827(18) nm,c=1.3660(2) nm,α=112.759(2)°,β=104.524(2)°,γ=92.008(3)°,V= 1.3143(3) nm3,Z=1,Dc=1.335 g/cm3,the final R1=0.0423 and wR2=0.1009.In the title complex,each Cd(Ⅱ) ion adopting a distorted octahedral geometry is coordinated by two Cl-anions and four pyridyl-N atoms from four IM4Py ligands.The magnetic measurements show the weak antiferromagnetic interactions between the nitroxide radicals.     

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, Structure and Thermochromic Properties of a Copper(Ⅱ) Complex Based on Naphthyl Carboxylate and Benzimidazolyl Ligands

One novel copper(Ⅱ) complex, [Cu(NAA)2(bim)2]·H2O (1, HNAA = a-naphthylacetic acid, bim = benzimidazole) has been synthesized and characterized by X-ray single-crystal diffraction analysis, elemental analysis, and IR spectrum. It crystallizes in monoclinic, space group C2/c with a = 1.15969(12), b = 1.9757(2), c = 1.45763(16) nm, β = 104.712(2)°, V = 3.2298(6) nm3, Z = 4, C38H32N4O5Cu, Mr = 688.22, Dc = 1.418 g/cm-3, μ = 0.729 mm-1, S = 1.039, F(000) = 1428, the final R = 0.0380 and wR = 0.0912 for 2849 unique reflections. In 1, two carboxylate and two benzimidazole ligands coordinate to the central Cu(Ⅱ) atom by a bidentate chelate mode. Interesting, reversible thermochromic properties of 1 can be observed and investigated by thermal analysis method.     

Synthesis,Crystal Structure,Fluorescent Property and DFT Calculations of a New Zn(Ⅱ) Complex Based on 3-(2-Pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole

A new coordination compound Zn(2,4?-bpt)2(H_2O)(1) based on the versatile ligand 2,4?-Hbpt(2,4?-Hbpt = 3-(2-pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole) was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a = 23.877(3), b = 0.7483(9), c = 1.2492(2) ?, b = 92.681(2)°, V = 2230.6(4) ?3, Z = 4, Dc = 1.572 g/cm~3, m = 1.143 mm~(-1), Mr = 527.85 and F(000) = 1080. The final R = 0.0581 and w R = 0.0898 with I 2s(I). 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory(DFT) were employed in order to explicate the stability and chemical reactivity of 2,4?-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.     

Solvothermal Synthesis,Crystal Structure and Luminescent Property of a Two-dimensional Lead(Ⅱ) Compound:[Pb(bmzbc)_2]_n

A two-dimensional coordination polymer, [Pb(bmzbc)_2]_n(1)(Hbmzbc =4-benzimidazole-1-yl-benzoic acid), has been synthesized by the solvothermal reaction of Pb(NO_3)_2 with Hbmzbc at 120 ℃ in ethanol solvent. Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the orthorhombic system, space group Pccn, with a = 12.5801(7), b = 20.0795(11), c = 9.1830(6) ?, V = 2319.6(2) ?~3, Z = 4, C_(28)H_(18)N_4O_4Pb, M_r = 681.65, D_c = 1.952 g/cm~3, μ = 7.319 mm~(-1), F(000) = 1312, the final R = 0.0336 and wR = 0.0965 for 1699 observed reflection with I 2σ(I). In 1, the bmzbc~– ligands bridge the Pb(Ⅱ) ions to generate a 2-D sheet with(4, 4) topology. The complex exhibits turquoise photoluminescent emission with a maximum at 480 nm upon excitation at 300 nm.     

A Cd(Ⅱ) Coordination Polymer with cds Topology Constructed by Polycarboxylate and Imidazole-containing Ligand

A new Cd(Ⅱ) coordination polymer,{[Cd(pda)(bimb)]·(H_2O)_(0.5)}_n(1,H_2pda=1,3-phenylenediacetic acid,bimb = 4,4-bis(1-imidazolyl)biphenyl),has been synthesized and characterized by elemental analysis,IR spectroscopy,powder X-ray diffraction(PXRD) analyses and single-crystal X-ray diffraction techniques. Complex 1 shows a 4-connected two-fold interpenetrated three-dimensional(3-D) cds topology. In additional,photoluminescent properties of 1 and its dehydrated product have also been studied.     

Synthesis,Structure and Highly Enhanced Phosphorescence of a Cadmium (Ⅱ) Coordination Polymer Assembled with 1,4-Naphthalenedicarboxylic Acid and 2-Propylimidazole

One cadmium(Ⅱ)coordination polymer[Cd(1,4-NDC)(PPIM)₂]_n(1,1,4-H₂NDC=1,4-na-phthalenedicarboxylic acid,PPIM=2-propylimidazole),has been synthesized under hydrothermal conditions and structurally characterized by elemental analysis,TGA and X-ray single-crystal diffraction.Complex 1 crystallizes in monoclinic with space group P2₁/n,a=8.8292(2),b=16.6936(4),c=16.7869(4)?,β=99.701(2)°,V=2438.86(10)?³,Z=4,Dc=1.489 Mg/m³,F(000)=1112,μ=0.932 mm^–1,S=1.076,the final R=0.0360 and wR=0.0850.In 1,the 1,4-NDC ligand bridges the Cd(Ⅱ)to form a 1D infinite chain,which are connected through N–H···O hydrogen bond to form a 2D layer then to an overall 3D supramolecular structure.The time-resolved measurements indicate that 1 shows highly prolonged phosphorescent lifetime about 452 times in comparison with that of pristine PPIM ligand.Single-crystal analysis and theory calculations indicate that strong coordination bonds and complete separation of HOMOs and LUMOs in the rigid matrix of 1 promote the long-last phosphorescence emission.     

Hydrothermal Synthesis and Crystal Structure of a New 2D Zinc（Ⅱ） Coordination Polymer with 2-Aminoethanesulfonic Acid

A new 2D Zn(Ⅱ) coordination polymer [Zn(TAU)2]n (1, HTAU=2-aminoethane- sulfonic acid) constructed by 2-aminoethanesulfonic acid ligand has been hydrothermally synthesized by the reaction of Zn(CH3COO)2 and 2-aminoethanesulfonic acid with a 1:2 mole ratio and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. Crystal structural analysis reveals it crystallizes in monoclinic, space group P21/c with a=8.672(4), b=6.523(3), c=9.134(5) , β=115.441(5)°, V=466.6(4) 3, Mr=313.65, Z=2, Dc=2.232 Mg·m-3, F(000) =320, μ(MoKα)=3.091 mm-1, the final R=0.0358 and wR=0.0919 for 2026 observed reflections with Ⅰ > 2σ(Ⅰ). In the structure, each zinc(Ⅱ) ion is coordinated in a slightly distorted octahedron, and each μ3-TAU– acts as a bridge to bond three neighboring Zn(Ⅱ) ions to form an infinite 2D network structure.     

Synthesis, Characterization and Crystal Structure Determination of a Thiocyanato Bridged One-dimensional Polymeric Complex of Cadmium(Ⅱ)

A new one-dimensional polymeric complex [Cd(SCN)2(H2O)]L (L = N,N?-bis(furan- 2-ylmethylene)hydrazine) has been synthesized and characterized by IR, UV spectra, TG-DTA technique and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, pace group P1 with a = 5.9268(8), b = 10.8678(15), c = 13.3671(19) , α = 109.295(2), β = 95.092(2), γ = 97.8580(10)°, V = 796.70(19) 3, Z = 2, C12H10CdN4O3S2, Mr = 434.76, μ = 1.648 mm–1, Dc = 1.812 g/cm3, F(000) = 428, R = 0.0308 and wR = 0.0769. The crystal structure reveals that the structure of [Cd(SCN)2(H2O)]n features di-μ-1,3-thiocyante bridges and 1D chains. The octahedrally coordinated Cd atom is surrounded by one oxygen atom from water molecule, three S atoms and two Natoms from five di-μ-1,3 thiocyanato bridges. The Cd atoms are connected by two di-μ-1,3 thiocyanato bridges with the Cd(1)…Cd(1A) separation of 4.239(1)  and Cd(1)…Cd(1B) of 5.852(1). In addition, the one-dimensional straight chain structure is further connected by multiform intermolecular N-H…O hydrogen bonds and π…π interactions to form a three-dimensional supramolecular structure.     

A New Cd(Ⅱ) Coordination Polymer Constructed by 3-(2-Pyridyl)pyrazole and 5-Nitroisophthalic Acid:Synthesis,Crystal Structure and Theoretical Calculations

A new coordination polymer, [Cd_2(NIPH)(L)_2(H_2O)]n(1, HL = 3-(2-pyridyl)pyrazole and H_2NIPH = 5-nitroisophthalic acid), has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis, thermogravimetric analysis and fluorescence spectrum analysis. Complex 1 belongs to the triclinic system, space group P1 with a = 8.9539(6), b = 11.6252(8), c = 12.2472(8) ?, α = 80.011(2), β = 80.3850(10), γ = 86.773(2)°, V = 1237.37(14) ?~3, Z = 2, D_c = 1.987 g/cm~3, μ = 1.780 mm~(-1), M_r = 740.25, F(000) = 724, the final R = 0.0295 and wR = 0.1015 with I 2σ(I). Two H_2NIPH as monodentate and bidentate ligands and two L ligands link four Cd(Ⅱ) ions to form a tetranuclear subunit. Each pair of the tetranuclear subunits is bridged by NIPH ligands to yield a one-dimensional double-chain structure. Furthermore, the 1D chains are linked into a 3D supramolecular framework with hydrogen bonds and π-π interactions. In addition, we analyzed Natural Bond Orbital(NBO) in using the PBE0/LANL2DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Cd(Ⅱ) ion.     

Hydrothermal Synthesis and Crystal Structure of a Novel Binuclear Cd(Ⅱ) Coordination Polymer Based on 1,2-Benzenedicarboxylate and Imidazole

The hydrothermal reaction of Cd(OAc)2·H2O with 1,2-benzenedicarboxylate(1,2-BDC),imidazole and H2O resulted in the formation of a binuclear polymeric Cd(Ⅱ) complex {[Cd2(1,2-BDC)2(Im)4]·(H2O)}n which was then characterized by elemental analyses and single-crystal X-ray diffraction analysis.The crystal is of monoclinic system,space group P21/c with a = 14.6455(3),b = 9.3530(2),c = 23.7838(5) ,β = 106.6290(10)°,C112H104Cd8N32O36,Mr = 3373.47,V = 3121.64(11) 3,Dc = 1.795 g/cm3,F(000) = 1672,μ = 1.428 cm-1 and Z = 1.The final R = 0.0316 and wR = 0.0687 for 5045 reflections with I > 2σ(I).In the title complex,the two Cd(Ⅱ) ions are in different coordination environments with distorted octahedral and pengonal bipyramidal geometries,respectively.Two Cd polyhedra are linked together through one μ2-η1:η1 and one μ2-η1:η2 carboxylate groups from different 1,2-BDC ligands,giving rise to a binuclear Cd(Ⅱ) cluster,and such clusters are connected by bridged 1,2-BDC ligands to form a 2-D structure along the c axis.The inter-and intermolecular hydrogen bonds further connect the 2-D structures into a 3-D supramolecular network.     

Syntheses,Crystal Structures,and Photoluminescent Properties for One New Cd(Ⅱ) CP Based on 3,5-Bis(4?-carboxy-phenyl)-1,2,4-triazole and 1,4-Bis(imidazol-1-ylmethyl)benzene

One new coordination polymer(CP) [Cd(bct)(bib)]·2(H_2O)(1), based on 3,5-bis(4?-carboxy-phenyl)-1,2,4-triazole(H2 bct) and 1,4-bis(imidazol-1-ylmethyl)benzene(bib), has been synthesized by hydrothermal method, and its structure was determined and characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR spectroscopy, and thermogravimetric analysis. The crystal structure of CP 1 is a three-dimensional framework with(3,5)-connected topology, where the bct ligands adopt a μ3-kO,kO,kO coordination mode connecting with three Cd centers and the bib ligands adopt a μ2-k N,k N coordination mode bridging two Cd ions. It crystallizes in monoclinic system, space group C2/c, with a = 2.6838(4), b = 1.24221(17), c = 1.8011(2) nm, β = 102.939(2)o, V = 5.8522(13) nm3, Z = 8, C30 H27 CdN7O6, Mr = 694.00, Dc = 1.566 g/cm~3, F(000) = 2784, S = 1.055, R = 0.0294 and wR = 0.0731. Furthermore, solid-state photoluminescence measurements show that CP 1 produces strong emissions at room temperature.     

Synthesis,Structure and Photochromism of a New Diarylethene and Its Ag(Ⅰ) Complex

A new symmetric diarylethene containing cyano group was synthesized and structurally characterized by elemental analysis,IR,1 H NMR and X-ray single-crystal diffraction.It belongs to the monoclinic system,space group C2/c with a = 18.848(6),b = 8.561(2),c = 16.875(5) ?,β = 100.398(6)o,V = 1344.6(11) ?~3,Z = 4,μ = 0.262 mm~(-1),Dc = 1.415 g/cm~3,M_r = 570.56,F(000) = 1160,the final R = 0.0808 and wR = 0.2107 with I 2σ(I).The two thienyls adopt reactive anti-parallel conformation and the carbon distance of photocyclization is 3.57 ?.The neighboring molecules are stacked closely with C–H…F hydrogen bonding.In addition,the photochromism of the new compound was investigated in solvents with different polarity and PMMA film.The alternative photo-irradiation of 254 nm light and ≥550 visible light can induce the reversible photo-cyclization and photo-reversion with the color interconversion between colorlessness and blue.In THF solution,the λ_(max) of diarylethene in PSS in visible band is 585 nm.The diarylethene further reacted with AgBF_4 in benzene to give rise to complex 1,which was structurally characterized by elemental analysis,IR,ESI-MS and TG.1 demonstrated reversible photochromism in both solution and PMMA film.The complexation of metal ions with diarylethene leads to a minor red-shift of the λ_(max) of 1 in THF in PSS to 590 nm.     

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.     

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.     

Synthesis, Crystal Structure and Magnetic Properties of a New 3D Cobalt Vanadate

A new cobalt vanadate compound 1 [Co^Ⅱ(H2O)2V2^VO6] has been hydrothermally synthesized and characterized by the elemental analyses and the single crystal X-ray diffraction analysis. Compound 1 crystallizes in the orthorhombic system, space group Pinna, with a=0.55646, b=1.06900, c=1.18452 nm, and Z=4. The magnetic susceptibility of the cobalt vanadate has been measured and indicates possible antiferromagnetic coupling between adjacent cobalt (Ⅱ) (0.5432—0.5697 nm) through bond or space.