• Title/Summary/Keyword: Coordination polymers

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Lanthanide-Oxalate Coordination Polymers Formed by Reductive Coupling of Carbon Dioxide to Oxalate: [Ln2(3,5-pdc)2(C2O4)(H2O)4]·2H2O (Ln = Eu, Sm, Ho, Dy; pdc = Pyridinedicarbox

  • Huh, Hyun-Sue;Lee, Soon W.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1839-1843
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    • 2006
  • Hydrothermal reactions of $Ln(NO_3)_3{\cdot}5H_2O $ (Ln = Eu (1), Sm (2), Ho (3), Dy (4)) with 3,5-pyridinedicarboxylic acid (3,5-pdcH2) in the presence of 4,4'-bipyridine led to the formation of the 3-D Ln(III)-coordination polymers with a formula unit of $[Ln_2(3,5-pdc)_2(C_2O_4)(H_2O)_4]{\cdot}2H_2O$. These polymers contain a bridging oxalate ligand ($C_2O_4\;^2$). On the basis of GCMS study of the mother liquor remaining after the reaction, we proposed that the $C_2O_4\;^2$ formation proceeds in three steps: (1) Ln(III)-mediated decarboxylation of $3,5-pdcH_2$ to give $CO_2$, (2) the reduction of $CO_2$ to $CO_2\;^{\cdot}$ by the Ln(II) species, and (3) the reductive coupling of the two $CO_2\;^{\cdot}$ radicals to the oxalate ($C_2O_4\;^2$) ion. All polymers were structurally characterized by X-ray diffraction.

Two-Dimensional Nickel Coordination Polymers: Ni(OBC)(bipyen)]·H2O and [Ni(NDC)(bipyen)(H2O)] (NDC = 2,6-Naphthalenedicarboxylate; OBC = 4,4'-Oxybis(benzoate); bipyen = trans-1,2-Bis(4-pyridyl)ethylene)

  • Lee, Yeon-Kyoung;Lee, Soon W.
    • Bulletin of the Korean Chemical Society
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    • v.24 no.7
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    • pp.906-910
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    • 2003
  • Hydrothermal reactions of Ni(NO₃)₂· 6H₂O with trans-1,2-bis(4-pyridyl)ethylene (bipyen), in the presence of a linear 2,6-naphthalene dicarboxylic acid (NDCH₂) and a bent 4,4'-oxybis(benzoic acid) (OBCH₂), gave a 2-D coordination polymer [Ni(NDC)(bipyen)(H₂O)] (1) and also a 2-D coordination polymer [Ni(OBC)(bipyen)]· H₂O (2), respectively. A reversible de-coordination and re-coordination of an aqua ligand was observed for polymer 1. Polymer 2 has an undulated 2-D network based on 50-membered rectangular grids, each of which has the dimension of 13.61 × 13.17 Å.

Preparation and Pore-Characteristics Control of Nano-Porous Materials using Organometallic Building Blocks

  • Oh, Gyu-Hwan;Park, Chong-Rae
    • Carbon letters
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    • v.4 no.1
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    • pp.1-9
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    • 2003
  • Recently, the control of pore-characteristics of nano-porous materials has been studied extensively because of their unique applications, which includes size-selective separation, gas adsorption/storage, heterogeneous catalysis, etc. The most widely adopted techniques for controlling pore characteristics include the utilization of pillar effect by metal oxide and of templates such as zeolites. More recently, coordination polymers constructed by transition metal ions and bridging organic ligands have afforded new types of nano-porous materials, porous metal-organic framework(porous MOF), with high degree and uniformity of porosity. The pore characteristics of these porous MOFs can be designed by controlling the coordination number and geometry of selected metal, e.g transition metal and rare-earth metal, and the size, rigidity, and coordination site of ligand. The synthesis of porous MOF by the assembly of metal ions with di-, tri-, and poly-topic N-bound organic linkers such as 4,4'-bipyridine(BPY) or multidentate linkers such as carboxylates, which allow for the formation of more rigid frameworks due to their ability to aggregate metal ions into M-O-C cluster, have been reported. Other porous MOF from co-ligand system or the ligand with both C-O and C-N type linkage can afford to control the shape and size of pores. Furthermore, for the rigidity and thermal stability of porous MOF, ring-type ligand such as porphyrin derivatives and ligands with ability of secondary bonding such as hydrogen and ionic bonding have been studied.

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Molecular Switching Coordination Polymers. 4.4'-Chalcogenobispyridine Bridged Cobalt Benzoquinone Complexes

  • 조두환;정종화;여환진;손윤수;정옥상
    • Bulletin of the Korean Chemical Society
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    • v.16 no.6
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    • pp.504-507
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    • 1995
  • The reaction of Co2(CO)8 with 3,6-di-tert-butyl-1,2-benzoquinone in the presence of the respective 4,4'-chalcogenobispyridine results in the coordination polymers of [CoⅢ(4,4'-X(Py)2)(DBSQ)(DBCat)]n (X=S, Se, Te; Py=pyridine; DBSQ=3,6-di-tert-butylsemiquinone; DBCat=3,6-di-tert-butylcatechol). The title compounds undergo an intramolecular Cat → Co electron transfer, and thus change toward the [CoⅡ(4,4'-X(Py)2)(DBSQ)2]n at elevated temperature. The temperature-switching properties of the compounds directly depend upon the electronegativity of the chalcogen atom of the 4,4'-chalcogenobispyridine coligands. The spectroscopic data disclose that the properties of [CoⅢ(4,4'-S(Py)2)(DBSQ)(DBCat)]n and [CoⅢ(4,4'-Se(Py)2)(DBSQ)(DBCat)]n are similar each other in contrast to those of [CoⅢ(4,4'-Te(Py)2)(DBSQ)(DBCat)]n.

3-Dimensional Terbium Coordination Polymers: [Tb4(NDC)6(H2O)5]·2H2O and [Tb2(BPDC)3(H2O)3]·H2O(NDC = 2,6-Naphthalenedicarboxylate; BPDC = 2,2'-Bipyridine-4,4'-dicarboxylate)

  • Min, Dong-Won;Lee, Soon-W.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.7
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    • pp.948-952
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    • 2002
  • Three-dimensional terbium coordination polymers with the formulas of [Tb4(NDC)6(H2O)5]${\cdot}$2H2O (1) and [Tb2(BPDC)3(H2O)3]${\cdot}$H2O (2) (NDC = 2,6-naphthalenedicarboxylate; BPDC = 2,2'-bipyridine-4,4'-dicarboxy-late) were prepared by hydrothermal reactions. Both compounds were structurally characterized by X-ray diffraction. Compound 1 has a polymeric structure that contains four distinct Tb metals. Three Tb metals have a square-antiprismatic structure, and the remaining one has a 9-coordinate, triply capped trigonal-prismatic structure. Compound 2 is also a polymer with two distinct Tb metals, both of which have a square-antiprismatic structure. The pyridine nitrogen atoms of the BPDC 2- ligand do not coordinate to the metal centers in compound 2.

Copper(II) Coordination Polymers Assembled from 2-[(Pyridin-3-ylmethyl)amino]ethanol: Structure and Magnetism

  • Han, Jeong-Hyeong;Shin, Jong-Won;Min, Kil-Sik
    • Bulletin of the Korean Chemical Society
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    • v.30 no.5
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    • pp.1113-1117
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    • 2009
  • The one-dimensional coordination polymers, $[Cu^{II}(L)(NO_3)_2]_n$ (1) and {$[Cu^{II}(L)(NO_3)]{\cdot}2H_2O}_{2n} (2), were synthesized from $Cu(NO_3)_2{\cdot}3H_2O$ and 2-[(pyridin-3-ylmethyl)amino]ethanol (L, PMAE) in methanol by controlling the molar ratio of copper(II) salt. Copper(II) ion in 1 has one pyridine group of PMAE whose an aminoethanol group coordinates adjacent copper(II) ion. As the pyridine group is bonded to neighboring copper(II) ion, 1 becomes a one-dimensional chain. Contrary to 1, the structure of 2 shows that the oxygen atom of ethoxide group is bridged between two copper(II) ions, which forms a dinuclear complex. Additionally, the pyridine group of PMAE included one dinuclear unit is coordinated to the other dimeric one each other, which leads to a one-dimensional polymer. Due to the structural differences, 1 exhibits weak antiferromagnetic interaction, while 2 shows strong antiferromagnetic interaction. Due to direct spin exchange via oxygen of PMAE 2 has a much strong spin coupling than 1.