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1.
Two lanthanide coordination polymers, {[La2(bpdc)3(H2O)4]·(H2O)4}n (1) and {[Sm2(bpdc)3(H2O)2]·(H2O)5}n (2) (H2bpdc = 2,2′-bipyridine-3,3′-dicarboxylic acid) have been obtained by hydrothermal synthesis. Single-crystal X-ray diffraction shows that 1 and 2 are two-dimensional network structures based on the zigzag chains which are linked by bpdc ligands, forming the first examples of binary lanthanide polymers with bpdc. It is unprecedented that the adjacent zigzag chains are symmetrical in mirror images with the arraying form of ?ABAB?. In 1 and 2, lanthanide ion are all nine-coordinate and bpdc ligands exhibit different kinds of coordination modes. The 1-D infinite water chain in 1 and pentameric water ring in 2 have been found between lattice water molecules. Thermo-gravimetric analyses of 1 and 2 display considerable thermal stability. Photoluminescent properties of 1 and 2 are discussed. 相似文献
2.
Two organic-inorganic hybrid polymers, {[Tb(μ2-bp3dc)(NO3)(H2O)4] · 2H2O}n (1) and {[Ni(μ2-η2-bp3dc)(H2O)3] · H2O}n (2) (bp3dc = 2,2′-bipyridine-3,3′-dicarboxylate) have been hydrothermally synthesized from 2,2′-bipyridine-3,3′-diformylhydrazide (bp3dh) and characterized by the elemental analyses, IR spectrum, TG analysis and the single crystal X-ray diffraction. Polymer 1 shows a 1D linear chain structure, in which extensive hydrogen bonding between the deprotonated carboxylates, nitrate ions, and coordinated water molecules result in a 3D network which also contains face-to-face π-π interactions between adjacent bp3dc ligands. Polymer 2 is a 1D helical chain, and the interchain hydrogen bonding interactions also contribute to the final 3D network. The bridging bp3dc ligands in 1 adopt the anti-bridging bidentate mode, while that in 2 adopt the chelating bridging tridentate mode. The solid-state magnetic properties of the Tb and Ni complexes demonstrated the presence of weak antiferromagnetic exchange interactions, caused by interaction between the neighbouring ions along the 2,2′-bipyridine-3,3′-dicarboxylate bridged chain. 相似文献
3.
Four structurally diverse complexes, [Cd(dppz)(bdoa)]n (1), [Zn(dppz)(bdoa)(H2O)]n (2), [Fe(dppz)2(bdoa)]n·2nH2O (3), and [Co2(dppz)2(bdoa)2(H2O)]n·3nH2O (4), where H2bdoa = benzene-1,4-dioxyacetic acid and dppz = dipyrido[3,2-a:2′,3′-c]phenazine, have been hydrothermally synthesized. Compounds 1-4 feature chain structures. There exist π-π interactions in the structures of 1, 2 and 4. Two neighboring chains of 1 are linked through the π-π interactions into a double chain supramolecular structure. The chains of 2 and 4 are further extended by the π-π interactions to form 3D and 2D supramolecular structures, respectively. The structural differences among such complexes show that the transition metals have important influences on their structures. The photoluminescent property of complex 2 and the magnetic property of complex 4 have also been investigated. 相似文献
4.
Montserrat Barquín Nerea Cocera Liher Larrínaga José M. Seco 《Inorganica chimica acta》2010,363(1):127-133
By the reactions of Cu(AcO)2·H2O and Cu(HCOO)2·4H2O with 4,4′-dimethyl-2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine the compounds [Cu(AcO)2(4,4′-Me2-2,2′-bipy)]·1/2H2O (1), [Cu(AcO)2(5,5′-Me2-2,2′-bipy)(H2O)] (2), [Cu(HCOO)(μ-HCOO)(4,4′-Me2-2,2′-bipy)]n·nH2O (3) and [Cu(HCOO)(μ-HCOO)(5,5′-Me2-2,2′-bipy)]n·2nH2O (4) were obtained. In the acetate complexes, 1 and 2, the geometry around copper is distorted octahedral and square pyramidal, respectively. Dimeric units of different geometry are formed in both cases through hydrogen bonds in which non-coordinated (in 1) and coordinated (in 2) water molecules are involved. The structures of 3 and 4 consist of polymeric monodimensional chains of square pyramidal copper units linked by axial-equatorial syn-anti (3) or anti-anti (4) bridging formate groups. Water molecules form hydrogen bonds with formate groups of the same chain in compound 3. In compound 4 the water molecules link the polymeric contiguous chains of complex through hydrogen bonds with oxygen atoms of formate groups and they are also linked between them, forming monodimensional water chains which run parallel to the complex chains. Sheets parallel to the ac plane are formed by alternating chains of water and polymeric complex. Magnetic properties and EPR spectra for these compounds have been studied. 相似文献
5.
Four lanthanide coordination polymers, [{Ln2(bpdc)3(phen)2(H2O)2} · (H2O)6]n (Ln = Sm (1); Eu (2); Gd (3), Tb (4)), were self-assembled from 2,2′-bipyridine-3,3′-dicarboxylic acid (H2bpdc),1,10-phenanthroline(phen) and corresponding lanthanide oxides by hydrothermal synthesis. Compounds 1-4 are found to be isomorphous and isostructural. Single-crystal X-ray diffraction studies show that compounds 1-4 are all of one-dimensional zigzag chain structures and extend to two-dimensional networks through π-π interactions and hydrogen bonds. The pyridyl nitrogen atoms of the 2,2′-bipyridyl unit in the bpdc ligand are uncoordinated in an anti-conformation along the central C-C bond of the ligand. Thermogravimetric analysis of 1-4 showed an obvious thermal stability indicating that the coordination habit of the metal ions with bpdc and phen has an effect on the overall framework. Photoluminescence measurement indicates that compound 2 and compound 4 are strong red and green emitters, respectively. 相似文献
6.
The reactions of 2,2′-bipyridyl-3,3′-dicarboxylic acid (H2bpdc) and 1,10-phenanthroline (phen) with lanthanide (III) salts in different concentrations under hydrothermal conditions formed two series of supramolecular isomers of 1D zigzag chains of [Ln(bpdc)1.5(phen)(H2O)]n·3nH2O (1Ln·3H2O), and 2D frameworks of [Ln(bpdc)1.5(phen)(H2O)]n (2Ln), (Ln = Ho, Er, Tm, and Yb). At lower concentrations, the supramolecular isomers of 1Ln were formed, in which each isomer has a dinuclear centrosymmetric dimeric unit of [Ln2(phen)2(H2O)2(μ2-bpdc)2]2+, and the dimeric units are alternately connected by μ2-bpdc2− to form a 1D zigzag chain of 1Ln. At higher concentrations, the supramolecular isomers of 2Ln were formed. All the compounds of 2Ln are isomorphous, in which two μ3-bpdc2− bridge two [Ln(phen)(H2O)]3+ units to yield a 1D double-chains of [Ln2(phen)2(H2O)2(bpdc)2]n2n+, and [Ln2(phen)2(H2O)2(bpdc)2]n2n+ chains are further connected by μ4-bpdc2− to form a 2D network of [Ln(bpdc)1.5(phen)(H2O)]n. The 2D sheets are combined through the intersheet π-π interactions between the adjacent phen molecules to form a 3D structure of 2Ln. The compounds of Er(III), and Yb(III) exhibit corresponding characteristic photoluminescence in the near-infrared (NIR) region, in which 1Ln and 2Ln show obviously different emission intensity due to their different structures. 相似文献
7.
Jun-Feng Lu Qiu-Xuan Zhou Jian-Mei Lu Xue-Wei Xia Yong Zhang 《Inorganica chimica acta》2009,362(10):3401-1003
The influence of coanion on self-assembly of CuSO4 and 4,4′-dipyridyl sulfide (dps) was studied in this paper. During the formation of Cu(II)/dps coordination polymers, coanions Cl−, SCN− and were added in the solution respectively. Three novel coordination polymers were obtained, {[Cu(dps)2 · (SO4)2][Cu(dps) · Cl · (H2O)2]2 · 12H2O}n (1 · 12H2O, a 3D network), {[Cu(SCN)2(dps)(CH3OH)2][Cu(dps)2 · SO4][Cu(dps)(CH3CH2OH)2 · SO4] · 5H2O}n (2 · 5H2O, a 3D network), and {[Cu(dps)2(H2O)2] · (PF6)2 · 3H2O}n (3 · 3H2O, a 2D lattice network). Different coanion shows different influence on framework construction. In 1 and 2, Cl− and SCN− act as terminal ligands and similar 3D frameworks were composed of [Cu(dps)] layer with larger cavity (ca. 400 Å) and sulfate bridge; in 3, replaces entirely and the 3D framework was broken due to the removal of bridging anions. However, a 2D [Cu(dps)]4 undulating grid was preserved in 3. 相似文献
8.
Bin Hu 《Inorganica chimica acta》2010,363(7):1348-6199
Four transition metal complexes of 3,8-di(thiophen-2′,2″-yl)-1,10-phenanthroline (dtphen), formulated as [Ni(dtphen)2(H2O)2]·(ClO4)2 (1), [Zn(dtphen)2(H2O)]·(ClO4)2 (2) [Cu(dtphen)2(H2O)]·(ClO4)2 (3), [Cu(dtphen)(phen)2]·(ClO4)2 (4) (phen = 1,10-phenanthroline) with different metal-to-ligand ratios, were synthesized and characterized herein. The X-ray single-crystal diffraction studies of 1-4 exhibit that different molecular configurations for the dtphen ligand can be observed where the side thiophene rings adopt the trans/trans, trans/cis, trans/disorder and cis/cis conformations relative to the central 1,10-phenanthroline unit in different compounds. Fluorescence emission spectra of 1-4 in methanol show that the fluorescence emission of 2 is much stronger than the other three metal complexes, which is mainly due to its full d10 electronic configuration of Zn(II) ion. 相似文献
9.
New ternary transition metal complexes of formulations [Ni(bpa)(p-AB)Cl]n · 3nH2O (bpa = 2,2′-bipyridylamine, p-AB = aminobenzenecarboxylic acid) (1), [Cu(bpa)(p-AB)Cl] · H2O (2), [Zn(bpa)(p-AB)2] · H2O (3) are prepared, their structural features are characterized by crystal structural studies, and their DNA binding propensity has been evaluated by fluorescence and viscosity method. In complex 2 and 3, both bpa and p-AB act as the bidentate N and O-donor ligand, respectively. While in complex 1, p-AB acts as a rare tridentate ligand. In the packing pattern of each complex, π-π interaction in their solid state is also described. The complexes show the competitive inhibition of ethidium binding to DNA, and the DNA binding propensity can be reflected as the relative order: 1 > 2 > 3. 相似文献
10.
Four new complexes, {[Mn(imH)2(pdc)]·H2O}n (1), [Zn2(pdc)2(H2O)5]·2H2O (2), [Zn(imH)2(pdc)]·H2O (3), {[Zn2(pdc)2(bpy)(H2O)2]·5H2O}n (4) [imH = imidazole pdc = pyridine 2,6-dicarboxylate, bpy = 4,4′-bipyridine] have been synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR, PXRD, single-crystal X-ray diffraction and thermogravimetric analyses. All the four complexes display a three-dimensional (3D) open framework with one-dimensional (1D) channels that are filled with lattice water molecules. Particularly, in 4, the lattice water molecules form an infinite water chain. Both 1 and 4 consist of 1D polymeric chains. While 2 contains a dinuclear Zn(II) unit, and 3 is a mononuclear complex. Further, the result of thermal analysis of 1 and 2 shows the robustness of the overall supramolecular three-dimensional architecture. Complexes 1, 3, and 4 exhibit strong fluorescent emissions in the solid state at room temperature and could be significant in the field of photoactive materials. 相似文献
11.
Hydrothermal synthesis has afforded five d10 configuration divalent metal diphenate coordination polymers containing pyridyl-piperazine type ligands, which were structurally characterized by single-crystal X-ray diffraction. {[Cd(diphenate)(3-bpmp)(H2O)]·0.5H2O}n (1, 3-bpmp = bis(3-pyridylmethyl)piperazine) has a double layer topology. Its perchlorate-containing analog {[Cd3(diphenate)4(H23-bpmp)(H3-bpmp)(H2O)2](ClO4)·7H2O}n (2) possesses a very rare 4-connected 658 dmp topology based on anionic trinuclear nodes. {[Cd(diphenate)(4-bpfp)]·H2O}n (3, 4-bpfp = bis(4-pyridylformyl)piperazine) manifests a non-interpenetrated diamondoid lattice, while the related compound [Cd(diphenate)(4-bpmp)(H2O)]n (4, 4-bpmp = bis(4-pyridylmethyl)piperazine) has a simple (4,4) grid topology. {[Zn(diphenate)(4-bpmp)]·0.5H2O}n (5) displays a 2-fold interpenetrated diamondoid lattice. Luminescent properties of these materials are also reported. 相似文献
12.
Jing Xu 《Inorganica chimica acta》2009,362(11):4002-4008
Three new coordination polymers {[Cu(HL)(H2O)]·H2O}n (1), [Ag(H2L)]n (2), and {[Co(HL)(phen)(H2O)]·8H2O}n (3) [H3L = 5-(1H-imidazol-4-ylmethyl)aminoisophthalic acid, phen = 1,10-phenanthroline] have been synthesized under hydrothermal conditions. The results of X-ray diffraction analysis revealed that complex 1 displays (3, 3)-connected 2D network with (4, 82) topology, while complexes 2 and 3 have infinite 1D chain structure, in which one of the two carboxylic groups of H2L−/HL2− is uncoordinated. The 2D layers of 1 or the 1D chains of 2 and 3 are further linked together by hydrogen bonds and π-π interactions to form 3D supramolecular frameworks. Moreover, the electrochemical properties of complexes 1 and 2 have been studied by modified glassy carbon electrodes of 1 (Cu-GCE) and 2 (Ag-GCE), and the results indicate that the Cu-GCE and Ag-GCE show one-electron redox peaks. In addition, both Cu-GCE and Ag-GCE have good electrocatalytic activities toward the reduction of H2O2 in phosphate buffer (pH 5.5) solution. 相似文献
13.
One-dimensional {[Cu2(dppa)2(4,4′-bipy)(CH3CN)2](BF4)2 · 2CH3CN}n (1), two-dimensional {[Cu2(dppa)(4,4′-bipy)2(CH3CN)2](BF4)2 · 4CH2Cl2 · 4H2O}n (2) and three-dimensional {[Cu2(dppa)(4,4′-bipy)3](BF4)2 · 2CH2Cl2 · 3CH3CN · 3H2O}n (3) polymeric complexes have been prepared by self-assembly of [Cu(MeCN)4]BF4, Ph2PCCPPh2 (dppa) and 4,4′-bipyridine (4,4′-bipy) in a 2:2:1, 1:1:1 and 2:2:3 molar ratio, respectively. The structures of 1-3, determined by an X-ray diffraction study, reveal a linear spring-like architecture for 1, a planar honeycomb grid for 2 and an interlocked adamantoid network for 3. 相似文献
14.
Four new fluconazole-bridged zinc(II) and cadmium(II) complexes with dicarboxylate co-ligands, namely [Zn(HFlu)(TPA)]n (1), {[Cd(HFlu)2(TPA)]·2CH3OH}n (2), [Zn(HFlu)2(Suc)(H2O)2]·H2O (3), and [Cd(HFlu)2(Suc)(H2O)2]·H2O (4), have been synthesized and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction (HFlu = 2-(2,4-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)-propan-2-ol, H2TPA = terephthalic acid, and H2Suc = succinic acid). Complex 1 displays a 2-D corrugated network with common (4,4) topology, in which two types of grids constructed by two bridging TPA dianions and two HFlu ligands are found. Complex 2 shows an unusual (3,6) coordination layer consisting of alternative PMPM Cd-HFlu helical chains in which the Cd(II) nodes are also fixed by terephthalate dianions in a cis fashion. The isostructural complexes 3 and 4 have 20-membered dimeric macrocyclic motifs with the Zn···Zn and Cd···Cd distances of 11.258(2) and 11.528(2) Å, respectively. The fluorescence and thermal stability of complexes 1-4 have also been investigated. 相似文献
15.
Jacqueline S. Lucas 《Inorganica chimica acta》2011,378(1):269-279
Hydrothermal synthesis has afforded cobalt 5-substituted isophthalate complexes with 4,4′-dipyridylamine (dpa) ligands, showing different dimensionalities depending on the steric bulk and hydrogen-bonding facility of the substituent. [Co(tBuip)(dpa)(H2O)]n (1, tBuip = 5-tert-butylisophthalate) is a (4,4) grid two-dimensional coordination polymer featuring 2-fold parallel interpenetration. [Co(MeOip)2(Hdpa)2] (2, MeOip = 5-methoxyisophthalate) is organized into 3-fold parallel interpenetrated (4,4) grids through strong N-H+?O− hydrogen bonding. {([Co(OHip)(dpa)(H2O)3])3·2H2O}n (3, OHip = 5-hydroxyisophthalate) possesses 1-D chain motifs. The 5-methyl derivative {[Co(mip)(dpa)]·3H2O}n (4, mip = 5-methylisophthalate) has a 3-D 658 cds topology. {[Co(H2O)4(Hdpa)2](nip)2·2H2O} (5, nip = 5-nitroisophthalate) and {[Co(sip)(Hdpa)(H2O)4]·2H2O} (6, sip = 5-sulfoisophthalate) are coordination complexes. Antiferromagnetic superexchange is observed in 1 and 4, with concomitant zero-field splitting. Thermal decomposition behavior of the higher dimensionality complexes is also discussed. 相似文献
16.
Ten transition metal coordination complexes [Cu2(phen)(p-tpha)(μ-O)]n1, [Cu(m-tpha)(imH)2]n2, [Ni(5-Haipa)2(H2O)2]n3, [Ni(phen)2(H2O)2]·btc·[Ni(H2O)6]0.5·9H2O 4, [Co(2,5-pdc)(H2O)2]n·nH2O 5, [Co2(2,5-pdc)2(H2O)6]n·2nH2O 6, [Fe(2,5-Hpdc)2(H2O)2]·H2O 7, [Co(C6H4NO2)3]·H2O 8, [Fe2(μ2-btec)(μ2-H2btec)(bipy)2(H2O)2]n9, [Mn(phen)(2,5-pdc)(H2O)2]·H2O 10 (H4btec = 1,2,4,5-benzenetetracarboxylic acid, phen = 1,10-phenanthroline, 2,5-H2pdc = 2,5-pyridine-dicarboxylic acid, p-tpha = p-phthalic acid, m-tpha = m-phthalic acid, bipy = 2,2′-bipyridine, 5-H2aipa = 5-aminoisophthalic acid, imH = imidazole, H3btc = 1,3,5-benzenetricarboxylic acid) were synthesized through hydrothermal method. They were characterized by UV-Vis absorption spectra, single-crystal X-ray diffraction and surface photovoltage spectra (SPS). Structural analysis indicated that the complexes 1, 2, 3, 5, 6 and 9 were linked into infinite structures bridged by organic acid ligands. The other four complexes were molecular complexes and further connected to 2D or 3D structures by the hydrogen bonds. The SPS of complexes 1-10 indicate that there are positive response bands in the range of 300-800 nm showing different levels of photo-electric conversion properties. The intensity, position, shape and the number of the response bands in SPS are obviously different since the structure, species, valence, dn electrons configuration and coordinated environment of the center metals are different. There are good relationships between SPS and UV-Vis spectra. 相似文献
17.
Four palladium(II) and platinum(II) complexes of 2,2′-dipyridylamine (dpya) with saccharinate (sac), cis-[Pd(dpya)(sac)2]·H2O (1), cis-[Pt(dpya)(sac)2]·H2O (2), [Pd(dpya)2](sac)2·2H2O (3) and [Pt(dpya)2](sac)2·2H2O (4), have been synthesized and characterized by elemental analysis, IR, NMR, TG-DTA and X-ray diffraction. In 1 and 2, the metal ions are coordinated by two N-bonded sac ligands, and two nitrogen atoms of dpya, resulting in a neutral square-planar coordination sphere, while in 3 and 4, the metal ions are coordinated by two dpya ligands to generate square-planar cationic species, which are stabilized by two sac counter-ions. The mononuclear species of 1 and 2 interact each other through weak intermolecular N-H?O, C-H?O and π?π interactions to form a three-dimensional network, while the ions of 3 and 4 are connected by N-H?N and OW-H?O hydrogen bonds into one-dimensional chains. On heating at 250 °C, the solid cationic complexes of 3 and 4 convert to corresponding anhydrous neutral complexes of 1 and 2 after elimination of a dpya ligand. In addition, all complexes 1-4 are luminescent at room temperature and their emissions seem to be attributed to the MLCT fluorescence. 相似文献
18.
Hirihattaya Phetmung Sukanya Wongsawat David J. Harding 《Inorganica chimica acta》2009,362(7):2435-3544
A metal organic-inorganic coordination framework formulated as {[Cu(4,4′-bipy)(H2O)3(SO4)] · 2H2O}n (1) (where 4,4′-bipy = 4,4′-bipyridine) has been successfully prepared by microwave synthesis. The title complex has been characterized by single crystal X-ray crystallography, FT-IR spectroscopy and thermal analysis. Complex (1) is an one-dimensional (1D) polymer in which 4,4′-bipy acts as a bridging ligand supporting the formation of infinite [Cu(4,4′-bipy)(H2O)3(SO4)] chains. The packing diagram shows that a 3D network is formed via hydrogen bonds. The infrared spectra and thermographic data are consistent with the chemical formula. 相似文献
19.
Sebastian Muthu 《Inorganica chimica acta》2005,358(3):595-605
Reactions of AgClO4, Zn(CH3COO)2 · H2O and CuI with the ligand 4,4′-dipyridylsulfide (dps) in 1:1 ratio give rise to coordination polymers 1-3 and 5, the structures of which were characterized by X-ray crystallography. Polymers [Ag2(dps)2](ClO4)2 · MeCN (1) and [Ag2(dps)2(μ2-MeCN)(MeCN)](ClO4)2 · MeCN · H2O (2) are pseudo-supramolecular isomers, differing from each other in the coordination geometry of silver atom and the packing pattern. Both 1 and 2 are zigzag coordination polymers bridged by weak Ag?Ag, Ag?S or Ag?NC-CH3 interactions to form double stranded coordination polymers. While [Zn(dps)(CH3COO)2] (3) is a zigzag single stranded coordination polymer, [Zn(dps)2(H2O)2](ClO4)2 · H2O (4) is an unusual mononuclear complex with a box-like structure. Interesting intermolecular hydrogen bonding present in the compounds 3 and 4 leads to 3D hydrogen-bonded network structure.Coordination polymer [Cu2I2(dps)2] (5) is a non-interpenetrating (4,4) net. Photoluminescence properties of the compounds 1-5 have been examined in solid states at room temperature. These compounds have been found to exhibit yellow and blue photoluminescence. 相似文献
20.
Four new cadmium(II) and zinc(II) coordination polymers {[Zn(btrp)(SIP)][Zn0.5(H2O)3]}n (1), {[Cd1.5(btrp)(SIP)(H2O)2]·2H2O}n (2), {[Cd1.5(btrb)(SIP)(H2O)3]·2H2O}n (3), {[Zn1.5(btrb)1.5(SIP)(H2O)2]·2H2O}n (4) (btrp = 1,3-bis(1,2,4-triazol-1-yl)propane, btrb = 1,3-bis(1,2,4-triazol-1-yl)butane, NaH2SIP = 5-sulfoisophthalic acid monosodium salt) have been synthesized under hydrothermal conditions and structurally characterized. Compound 1 possesses an infinite 1D ladder-like chain structure with [Zn(H2O)6]2+ trapped in the pores, which is further interconnected by π?π interactions to lead to a 2D supramolecular architecture. Compounds 2 and 3 features two similar 2D layer structures, and the resulting 2D structures are interconnected by hydrogen-bond interactions to lead to 3D supramolecular architectures. Compound 4 is a 2D parallel ladder structure, and through the interpenetrating btrb ligand, it constructs into 3D architectures. Luminescence analyses were performed on all the four compounds, which show strong fluorescent emissions in the solid state at room temperature. 相似文献