scholarly journals Tuning 1-D Pb(II) Coordination Polymers by Flexible and Semirigid Dicarboxylates: Synthesis, Structure and Properties

2012 ◽  
Vol 67 (3) ◽  
pp. 185-191 ◽  
Author(s):  
Guo-Cheng Liu ◽  
Zhi-Chao Guo ◽  
Xiu-Li Wang ◽  
Yun Qu ◽  
Song Yang ◽  
...  

Two new one-dimensional (1-D) Pb(II) coordination polymers, namely, [Pb(3-pdip)(L1)]·H2O (1) and [Pb(3-pdip)(L2)] (2) [L1H2 = 1,6-hexanedioic acid, L2H2 = homophthalic acid, 3-pdip = 2-(3-pyridyl)imidazo[4,5-f]1,10-phenanthroline] have been obtained from hydrothermal reactions of Pb(II) nitrate with the phenanthroline derivative and the two dicarboxylic acids. Single-crystal X-ray diffraction analysis reveals that compound 1 is a staircase-like double-chain coordination polymer constructed from binuclear [Pb2N4O8] subunits and pairs of [L1]2− anions. Compound 2 is a linear coordination polymer connected via two μ2-η2:η1 carboxylate groups from [L2]2− anions. Furthermore, adjacent chains of 1 and 2 are extended into 3-D supramolecular networks by hydrogen bonds and π-π stacking interactions. The organic carboxylic acids with different flexibility determine the structures of the coordination polymers. Moreover, the thermal stabilities and photoluminescence properties of compounds 1 and 2 were investigated.

2018 ◽  
Vol 74 (11) ◽  
pp. 1434-1439
Author(s):  
Hong-Tao Zhang ◽  
Xiao-Long Wang

In recent years, much initial interest and enthusiasm has focused on the self-assembly of coordination polymers due to the aesthetics of their crystalline architectures and their potential applications as new functional materials. As part of an exploration of chiral coordination polymers, a new twofold interpenetrated two-dimensional (2D) coordination polymer, namely, poly[[tetraaquabis[μ3-(2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)dipropionato-κ5 O,O′:O′′,O′′′:O′′]dicadmium(II)] trihydrate], {[Cd2(C14H14N2O6)2(H2O)4]·3H2O} n , has been synthesized by the reaction of Cd(CH3COO)2·2H2O with the designed ligand (2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)dipropionic acid (H2 L). The compound has been structurally characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analysis. In the crystal structure, each CdII cation binds to three carboxylate groups from two crystallographically independent L 2− dianions. Four carboxylate groups link two crystallographically independent cadmium cations into a 4,4-connected secondary building unit (SBU). The resulting SBUs are extended into a two-dimensional folding sheet via the terephthalamide moiety of the ligand as a spacer, which can be simplified as a (4,4)-connected 4,4L15 net with the point symbol (3.53.62)(32.52.62). In the lattice, two independent folding sheets interpenetrate each other to yield a double-sheet layer. The resulting 2D layers pack in parallel arrays through intermolecular hydrogen bonds and interlayer π–π interactions. The thermal stability and photoluminescence properties of the title compound have been investigated and it exhibits an enhanced fluorescence emission and a longer lifetime compared with free H2 L.


1997 ◽  
Vol 52 (1) ◽  
pp. 125-134 ◽  
Author(s):  
Rolf W. Saalfrank ◽  
Roland Harbig ◽  
Oliver Struck ◽  
Frank Hampel ◽  
Eva Maria Peters ◽  
...  

Reaction of a methanolic copper(II) acetate solution with tetrazolyl enol derivatives 2a or 2b leads to the formation of the corresponding lD-coordination polymer 1∞[CuL2] 3a and pseudo 1D-coordination polymer [CuL2]2 3b, respectively. On the contrary, reaction of 2c with methanolic copper(II) acetate solution yields OH-bridged 1D-coordination polymer 1∞[CuL2(MeOH)2 3c. Single-crystal X-ray diffraction of the supramolecular species 3 established unequivocally the structures of the stairlike coordination compounds. Reaction of a methanolic copper(II) acetate solution with amidotetrazole derivative 6 leads to the formation of the lD-coordination polymer 1∞ [CuL2] 7. The structure of 7 has been established by X-ray structure analysis


Molecules ◽  
2021 ◽  
Vol 26 (17) ◽  
pp. 5400
Author(s):  
Roman D. Marchenko ◽  
Taisiya S. Sukhikh ◽  
Alexey A. Ryadun ◽  
Andrei S. Potapov

Coordination polymers with a new rigid ligand 1,3-bis(1,2,4-triazol-1-yl)adamantane (L) were prepared by its reaction with cadmium(II) or silver(I) nitrates. Crystal structure of the coordination polymers was determined using single-crystal X-ray diffraction analysis. Silver formed two-dimensional coordination polymer [Ag(L)NO3]n, in which metal ions are linked by 1,3-bis(1,2,4-triazol-1-yl)adamantane ligands, coordinated by nitrogen atoms at positions 2 and 4 of 1,2,4-triazole rings. Layers of the coordination polymer consist of rare 18- and 30-membered {Ag2L2} and {Ag4L4} metallocycles. Cadmium(II) nitrate formed two kinds of one-dimensional coordination polymers depending on the metal-to-ligand ratio used in the synthesis. Coordination polymer [Cd(L)2(NO3)2]n was obtained in case of a 1:2 M:L ratio, while for M:L = 2:1 product {[Cd(L)(NO3)2(CH3OH)]·0.5CH3OH}n was isolated. All coordination polymers demonstrated ligand-centered emission near 450 nm upon excitation at 370 nm.


2018 ◽  
Vol 74 (6) ◽  
pp. 734-741 ◽  
Author(s):  
Olga Drath ◽  
Robert W. Gable ◽  
Colette Boskovic

The combination of cobalt, 3,5-di-tert-butyldioxolene (3,5-dbdiox) and 1-hydroxy-1,2,4,5-tetrakis(pyridin-4-yl)cyclohexane (tpch) yields two coordination polymers with different connectivities, i.e. a one-dimensional zigzag chain and a two-dimensional sheet. Poly[[bis(3,5-di-tert-butylbenzene-1,2-diolato)bis(1,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-yl-3-olato)[μ4-1-hydroxy-1,2,4,5-tetrakis(pyridin-4-yl)cyclohexane]cobalt(III)]–ethanol–water 1/7/5], {[Co2(C14H20O2)4(C26H24N4O)]·7C2H5OH·5H2O} n or {[Co2(3,5-dbdiox)4(tpch)}·7EtOH·5H2O} n , is the second structurally characterized example of a two-dimensional coordination polymer based on linked {Co(3,5-dbdiox)2} units. Variable-temperature single-crystal X-ray diffraction studies suggest that catena-poly[[[(3,5-di-tert-butylbenzene-1,2-diolato)(1,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-yl-3-olato)cobalt(III)]-μ-1-hydroxy-1,2,4,5-tetrakis(pyridin-4-yl)cyclohexane]–ethanol–water (1/1/5)], {[Co(C14H20O2)2(C26H24N4O)]·C2H5OH·5H2O} n or {[Co(3,5-dbdiox)2(tpch)]·EtOH·5H2O} n , undergoes a temperature-induced valence tautomeric interconversion.


1999 ◽  
Vol 54 (9) ◽  
pp. 1129-1132 ◽  
Author(s):  
Julia A. Rusanova ◽  
Philip J. Squattrito ◽  
Vera V. Ponomareva ◽  
Konstantin V. Domasevitch ◽  
Volodimir N. Kokozay

The new macrocyclic dicyanoargentate complex Cs(dibenzo-24-crown-8)[Ag(CN)2] has been prepared and studied by means of X-ray diffraction (monoclinic, space group P21/a, with a = 12.730(3), b = 15.443(3), c = 15.323(3) Å, V = 3005(1) Å3, Z = 4, R1 = 0.041; wR2 = 0.048 for 5488 unique reflections with I > 3σ(I)). The lattice consists of complex Cs(db- 24-crown-8)+ cations (as an example of the “wrap-around” structure) and [Ag(CN)2]- anions forming a one-dimensional polymeric structure. The caesium atoms are coordinated with 8 oxygen atoms of the macrocycle and two nitrogen atoms of the dicyanoargentate groups, bonding to the cation on both sides of the crown-ether. It is the first structure of a dibenzo-24-crown-8 complex with a large metal cation such as Cs+.


Author(s):  
Huang-Huang Liu ◽  
Chu-Heng Liang ◽  
Yan Liu ◽  
Hong-Tao Zhang

A new two-dimensional (2D) coordination polymer, namely, poly[[diaqua-[μ4-2,2′-[terephthaloylbis(azanediyl)]diacetato]calcium(II)] monohydrate], {[Ca(C12H10N2O6)(H2O)2]·H2O} n , (I), has been synthesized by the reaction of CaCl2 with 2,2′-[terephthaloylbis(azanediyl)]diacetic acid (H2 L). The title compound was structurally characterized by single-crystal X-ray diffraction analysis, elemental analysis and IR spectroscopy. In the crystal structure of (I), each CaII cation binds to six carboxylate groups from four symmetry-related L 2− dianions. The hexadentate L 2− ligand links four symmetry-related calcium cations into a 2D layer-like structure, which can be simplified as a uninodal SP 2-periodic (3,6)III net with the point symbol (43·63). In the lattice, all layers pack in parallel arrays through weak interlayer hydrogen bonding and π–π interactions. The thermal stability and photoluminescence properties of (I) have been investigated. Thermogravimetric analysis reveals the different thermal stabilities of the two coordinated water molecules due to their different hydrogen-bonding interactions. The title coordination polymer exhibits an excitation-wavelength-dependent fluorescence in the solid state.


Author(s):  
Ranjan Patra ◽  
Israel Goldberg

5-[(Imidazol-1-yl)methyl]benzene-1,3-dicarboxylic acid (H2L) was synthesized and the dimethylformamide- and dimethylacetamide-solvated structures of its adducts with CuII, namelycatena-poly[[copper(II)-bis[μ-3-carboxy-5-[(imidazol-1-yl)methyl]benzoato]] dimethylformamide disolvate], {[Cu(C12H9N2O4)2]·2C3H7NO}n, (I), andcatena-poly[[copper(II)-bis[μ-3-carboxy-5-[(imidazol-1-yl)methyl]benzoato]] dimethylacetamide disolvate], {[Cu(C12H9N2O4)2]·2C4H9NO}n, (II), the formation of which are associated with mono-deprotonation of H2L. The two structures are isomorphous and isometric. They consist of one-dimensional coordination polymers of the organic ligand with CuIIin a 2:1 ratio, [Cu(μ-HL)2]n, crystallizing as the dimethylformamide (DMF) or dimethylacetamide (DMA) disolvates. The CuIIcations are characterized by a coordination number of six, being located on centres of crystallographic inversion. In the polymeric chains, each CuIIcation is linked to four neighbouring HL−ligands, and the organic ligand is coordinatedviaCu—O and Cu—N bonds to two CuIIcations. In the corresponding crystal structures of (I) and (II), the coordination chains, aligned parallel to thecaxis, are further interlinked by strong hydrogen bonds between the noncoordinated carboxy groups in one array and the coordinated carboxylate groups of neighbouring chains. Molecules of DMF and DMA (disordered) are accommodated at the interface between adjacent polymeric assemblies. This report provides the first structural evidence for the formation of coordination polymers with H2Lviamultiple metal–ligand bonds through both carboxylate and imidazole groups.


Chemistry ◽  
2020 ◽  
Vol 3 (1) ◽  
pp. 1-12
Author(s):  
Chia-Jou Chen ◽  
Chia-Ling Chen ◽  
Yu-Hsiang Liu ◽  
Wei-Te Lee ◽  
Ji-Hong Hu ◽  
...  

Reactions of the semi-rigid N,N′-bis(3-pyridyl)terephthalamide (L) with divalent metal salts in the presence of dicarboxylic acids afforded [Cd(L)0.5(1,2-BDC)(H2O)]n (1,2-H2BDC = benzene-1,2-dicarboxylic acid), 1, {[Cd(L)1.5(1,3-BDC)(H2O)]·5H2O}n (1,3-H2BDC = benzene-1,3-dicarboxylic acid), 2a, {[Cd(1,3-BDC)(H2O)3]·2H2O}n, 2b, {[Cd(L)0.5(1,4-BDC)(H2O)2]·H2O}n (1,4-H2BDC = benzene-1,4-dicarboxylic acid), 3, and [Cu(L)0.5(5-tert-IPA)]n (5-tert-IPA = 5-tert-butylbenzene-1,3-dicarboxylic acid), 4, which have been structurally characterized by single crystal X-ray diffraction. Complexes 1 and 3 are two-dimensional (2D) layers with the bey and the hcb topologies, and 2a and 2b are one-dimensional (1D) ladder and zigzag chain, respectively, while 4 shows a 3-fold interpenetrated three-dimensional (3D) net with the cds topology. The structures of these coordination polymers containing the semi-rigid L ligands are subject to the donor atom positions and the identity of the dicarboxylate ligands, which are in marked contrast to those obtained from the flexible bis-pyridyl-bis-amide ligands that form self-catenated nets. The luminescence of 1 and 3 and thermal properties of complexes 1, 3, and 4 are also discussed.


Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1101
Author(s):  
Anirban Karmakar ◽  
Anup Paul ◽  
Elia Pantanetti Sabatini ◽  
M. Fátima C. Guedes da Silva ◽  
Armando J. L. Pombeiro

The new coordination polymers (CPs) [Zn(μ-1κO1:1κO2-L)(H2O)2]n·n(H2O) (1) and [Cd(μ4-1κO1O2:2κN:3,4κO3-L)(H2O)]n·n(H2O) (2) are reported, being prepared by the solvothermal reactions of 5-{(pyren-4-ylmethyl)amino}isophthalic acid (H2L) with Zn(NO3)2.6H2O or Cd(NO3)2.4H2O, respectively. They were synthesized in a basic ethanolic medium or a DMF:H2O mixture, respectively. These compounds were characterized by single-crystal X-ray diffraction, FTIR spectroscopy, thermogravimetric and elemental analysis. The single-crystal X-ray diffraction analysis revealed that compound 1 is a one dimensional linear coordination polymer, whereas 2 presents a two dimensional network. In both compounds, the coordinating ligand (L2−) is twisted due to the rotation of the pyrene ring around the CH2-NH bond. In compound 1, the Zn(II) metal ion has a tetrahedral geometry, whereas, in 2, the dinuclear [Cd2(COO)2] moiety acts as a secondary building unit and the Cd(II) ion possesses a distorted octahedral geometry. Recently, several CPs have been explored for the cyanosilylation reaction under conventional conditions, but microwave-assisted cyanosilylation of aldehydes catalyzed by CPs has not yet been well studied. Thus, we have tested the solvent-free microwave-assisted cyanosilylation reactions of different aldehydes, with trimethylsilyl cyanide, using our synthesized compounds, which behave as highly active heterogeneous catalysts. The coordination polymer 1 is more effective than 2, conceivably due to the higher Lewis acidity of the Zn(II) than the Cd(II) center and to a higher accessibility of the metal centers in the former framework. We have also checked the heterogeneity and recyclability of these coordination polymers, showing that they remain active at least after four recyclings.


2004 ◽  
Vol 2004 (14) ◽  
pp. 2943-2949 ◽  
Author(s):  
Dejana Vujovic ◽  
Helgard G. Raubenheimer ◽  
Luigi R. Nassimbeni

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