• Title/Summary/Keyword: Coordination polymers

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A Novel Linking Schiff-Base Type Ligand (L: py-CH=N-C6H4-N=CH-py) and Its Zinc Coordination Polymers:Preparation of L, 2-Pyridin-3-yl-1H-benzoimidazol, trans-[Zn(H2O)4L2].(NO3)2.(MeOH)2[Zn(NO3)(H2O)2(L)].(NO3).(H2O)2 and [Zn(L)(OBC)(H2O)] (OBC = 4,4'-Oxybis(benzoate))

  • Kim, Han-Na;Lee, Hee-K.;Lee, Soon-W.
    • Bulletin of the Korean Chemical Society
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    • v.26 no.6
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    • pp.892-898
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    • 2005
  • A long, bis(monodentate), linking Schiff-base ligand L (py-CH=N-$C_6H_4$-N=CH-py) was prepared from 1,4-phenylenediamine and 3-pyridinecarboxaldehyde by the Schiff-base condensation. Ligand L has two terminal pyridyl groups capable of coordinating to metals through their nitrogen atoms. In contrast, the same reaction between 1,2-phenylenediamine and 3-pyridinecarboxaldehyde produced a mixture of imidazol isomers (2-pyridin-3-yl-1H-benzoimidazole), which are connected to one another by the N-H…N hydrogen bonding to form a tetramer. From Zn($NO_3)_2{\cdot}6H_2O$ and ligand L under various conditions, one discrete molecule, trans- [Zn($H_2O)_4L_2]{\cdot}(NO_3)_2{\cdot}(MeOH)_2$, and two 1-D zinc polymers, [Zn$(NO_3)(H_2O)_2(L)]{\cdot}(NO_3){\cdot}(H_2O)_2$ and [Zn(L) (OBC)($H_2O$)], were prepared. In ligand L, the N$\ldots$N separation between the terminal pyridyl groups is 13.994 $\AA$, with their nitrogen atoms at the meta positions (3,3’) in a trans manner. The corresponding N$\ldots$N separations in its compounds range from 13.853 to 14.754 $\AA$.

Cesium separation from radioactive waste by extraction and adsorption based on crown ethers and calixarenes

  • Wang, Jianlong;Zhuang, Shuting
    • Nuclear Engineering and Technology
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    • v.52 no.2
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    • pp.328-336
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    • 2020
  • Cesium is a major product of uranium fission, which is the most commonly existed radionuclide in radioactive wastes. Various technologies have been applied to separate radioactive cesium from radioactive wastes, such as chemical precipitation, solvent extraction, membrane separation and adsorption. Crown ethers and calixarenes derivatives can selectively coordinate with cesium ions by ion-dipole interaction or cation-π interaction, which are promising extractants for cesium ions due to their promising coordinating structure. This review systematically summarized and analyzed the recent advances in the crown ethers and calixarenes derivatives for cesium separation, especially focusing on the adsorbents based on extractants for cesium removal from aqueous solution, such as the grafting coordinating groups (e.g. crown ether and calixarenes) and coordinating polymers (e.g. MOFs) due to their unique coordination ability and selectivity for cesium ions. These adsorbents combined the advantages of extraction and adsorption methods and showed high adsorption capacity for cesium ions, which are promising for cesium separation The key restraints for cesium separation, as well as the newest progress of the adsorbents for cesium separation were also discussed. Finally, some concluding remarks and suggestions for future researches were proposed.

Cyanide- and Phenoxo-Bridged Heterobimetallic Fe(III)-Mn(III) Coordination Polymer: Synthesis, Crystal Structures and Magnetic Properties

  • Zhang, Daopeng;Kong, Lingqian;Li, Yueyun;Wang, Ping;Chen, Xia
    • Bulletin of the Korean Chemical Society
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    • v.35 no.9
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    • pp.2684-2688
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    • 2014
  • Two two-dimensional cyanide- and phenoxo-bridged heterometallic M(II)-Mn(III) (M = Ni, Pd) coordination polymers $\{[Mn(saltmen)]_4[Ni(CN)_4]\}(ClO_4)_2{\cdot}CH_3OH{\cdot}H_2O$ (1) and $\{[Mn(saltmen)]_4[Pd(CN)_4]\}(ClO_4)_2{\cdot}CH_3CN{\cdot}H_2O$ (2) ($saltmen^{2-}$ = N,N'-(1,1,2,2-tetramethylethylene)bis(salicylideneaminato)dianion) have been obtained by using $K_2[M(CN)_4]$ as building blocks and a salen-tpye Schiff-base manganese(III) compound as assembling segment. Single X-ray analysis reveals their isostrutural cyanide-bridged $MMn_4$ pentanuclear cationic structure. The four Schiff base manganese units of the pentanuclear entity are self-complementary through the phenoxo oxygen atoms from the neighboring complex, therefore forming cyanide- and phenoxo-bridged 2D sheet-like structure. Investigation over magnetic susceptibilities reveals the overall ferromagnetic coupling between the adjacent Mn(III) ions bridged by the phenoxo oxygen atoms with J = 2.13 and $2.21cm^{-1}$ for complexes 1 and 2, respectively.

Novel Linking Ligand Containing Sulfur-Donor Atoms and Its Compounds of Palladium and Silver

  • Lee, Hee-K.;Lee, Soon-W.
    • Bulletin of the Korean Chemical Society
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    • v.28 no.3
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    • pp.421-426
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    • 2007
  • A linking ligand containing sulfur donor atoms in the terminal thiophene rings, 1,2-bis(thiophen-2-ylmethylene) hydrazine (L), was prepared by Schiff-base condensation. Ligand L reacted with [PdCl2(NCPh)2] to produce a molecular Pd compound [PdL2Cl2] (1). On the other hand, it reacted with AgNO3 and AgClO4 to produce a 2-D network [AgL0.5(NO3)] (2) and a 1-D polymer [AgL]ClO4 (3), respectively, whose structures are based on secondary intermolecular forces such as H-bonding, van der Waals interaction, and π-π stacking. Polymer 2 exhibited photoluminescence at room temperature in the solid state.

Synthesis of Terpolymers and Dependence of Their Characteristics on Types and Content of High α-olefin

  • Kim, Jung Soo;Kim, Dong Hyun
    • Elastomers and Composites
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    • v.55 no.4
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    • pp.263-269
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    • 2020
  • Novel flexible terpolymers with a reactive moiety were synthesized by coordination polymerization with a metallocene catalyst and a cocatalyst system. C2-symmetric rac-Et(Ind)2ZrCl2 and tri-iso-butylaluminum/dimethylanilinium tetrakis (pentafluorophenyl) borate were employed as the catalyst and cocatalyst, respectively. We synthesized reactive terpolymers consisting of ethylene, a high α-olefin content (1-hexene, 1-octene, 1-decene, and 1-dodecene), and divinylbenzene. The structure and composition of the terpolymers were characterized by 1H-nuclear magnetic resonance analysis. The catalytic activity, polymer yield, molecular weight, and molecular weight distribution were measured as functions of the chain length and high content of α-olefins. Furthermore, the thermal properties and crystallinity of the terpolymers were determined by differential scanning calorimetry and wide-angle X-ray scattering.

Hydrothermal Synthesis, Crystal Structure of Four Novel Complexes Based on Thiabendazole Ligand

  • Wei, Shui-Qiang;Lin, Cui-Wu;Yin, Xian-Hong;Huang, Yue-Jiao;Luo, Pei-Qi
    • Bulletin of the Korean Chemical Society
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    • v.33 no.9
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    • pp.2917-2924
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    • 2012
  • Four novel metal-organic complexes $[Cd_2(IP)_2(TBZ)_2(H_2O)_2]{\cdot}(H_2O)$ (1), $[Zn_4(IP)_4(TBZ)_4]{\cdot}2(H_2O)$ (2), $[Zn_2(BTC)(TBZ)_2(CO_2H)]$ (3), [Co(PDC)(TBZ)] (4) (where IP = isophthalate; TBZ = thiabendazole; BTC = 1,3,5-benzenetricarboxylate; PDC = pyridine-3,4-dicarboxylate) have been prepared and characterized by IR spectrum, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. X-ray structure analysis reveals that 1, 2, and 3 are one-dimensional chain polymers, while 4 is a two-dimensional network polymer. The TBZ acts as a typical chelating ligand coordinated to the metal center in all complexes. The 1D chain architecture of 1 is constructed from isophthalates and cadmium atoms. A simultaneous presence of chelating, monodentate and bidentate coordination modes of IP ligands is observed in complex 2. In complex 3, the 16-membered rings are alternately arranged forming an infinite 1D double-chain structure. The 2D skeleton of 4 is formed by cobalt ions as nodes and PDC dianions as spacers, through coordination bonds. The hydrogen bonds and ${\pi}-{\pi}$ stacking play important roles in affecting the final structure where complexes 1 and 3 have 2D supramolecular networks, while complexes 2 and 4 have 3D supramolecular architectures.

One-step Fabrication of a Tannic Acid-Transition Metal-Polymer Gel as a Pressure-Sensitive Adhesive (타닌산-전이 금속-고분자로 구성된 젤의 단일 단계 합성과 점착제로의 이용)

  • Lee, Jaehong;Lee, Kyoungmun;Choi, Siyoung Q.
    • Korean Chemical Engineering Research
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    • v.58 no.2
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    • pp.176-183
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    • 2020
  • In this study, synthesis of a hydrogel consisted of a coordination bond network between small organic molecules and transition metals had been carried out. By adding a tackifying material to the gel, the potential of the gel to be used as an adhesive material had been also confirmed. Synthesis of the adhesive had been done with simple mixing of 3 components: tannic acid, transition metal, and polymer. The tannic acid molecule possesses multiple hydroxyl groups that can form coordination bonds with the transition metals and hydrogen bonds with the hydrophilic polymers. Due to the morphology of the metal-organic complex and polymer dispersed in water, the fabricated material exhibited high adhesiveness and cohesiveness. Optimizing the rheological property had been conducted for use in adhesive by the synthesis with varying the transition metal (Fe3+, Ti4+), polymer, and treatment conditions. Rheological measurement results demonstrate the promising potential of the material as a bio-compatible and versatile pressure-sensitive adhesive with both high adhesiveness and cohesiveness.

Molecular Strands and Related Properties of Silver(Ⅰ) Triflate with 3,3'-Oxybispyridine vs 3,3'-Thiobispyridine

  • Kim, Yu-Ju;Lee, Young-A;Park, Ki-Min;Chae, Hee K.;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.23 no.8
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    • pp.1106-1109
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    • 2002
  • Studies on subtle spacer ligand effects of AgCF3SO3 with 3,3'-Py2X (X = O vs S) have been carried out. The reaction of AgCF3SO3 with 3,3'-Py2O and 3,3'-Py2S produces [Ag(CF3SO3)(3,3'-Py2O)] and [Ag(3,3'-Py2S)] (CF3SO3), respectively. Crystallographic characterization of [Ag(CF3SO3)(3,3'-Py2O)] (monoclinic P1, a =8.405(2) $\AA$, b = 10.714(2) $\AA$, c = 18.031(2) $\AA$, $\alpha=$ 77.36(2), $\beta=107.83(2)^{\circ}$, $\gamma=$ 66.92(2), V = 1438.0(5) $\AA3$ , Z =2,R = 0.0486) reveals that the skeletal structure is an anion-bridged double-strand. The double-strands are packed like a plywood. The framework of [Ag(3,3'-Py2S)](CF3SO3) (orthorhombic Pcab, a = 17.330(2) $\AA$, b = 8.640(1) $\AA$, c = 19.933(6) $\AA$, V = 2985(1) $\AA3$ , Z =8, R = 0.0437) is a sinusoidal single-strand. The formation of each coordination polymer appears to be primarily associated with the donating ability and the confor ma-tional energy barrier of the spacer ligands. Thermal analyses indicate that [Ag(CF3SO3)(3,3'-Py2O)] and [Ag(3,3'-Py2S)](CF3SO3) are stable up to 250 $^{\circ}C$ and 210 $^{\circ}C$, respectively. For the anion exchangeability, the nature of the spacer ligand is more significant factor than the distance of silver(Ⅰ)···triflate.

1D and 2D Cobalt(II) Coordination Polymers, Co(ox)(en): Synthesis, Structures and Magnetic Properties

  • Kang, Jaeun;Lee, Yumi;Kim, Seungjoo;Yun, Hoseop;Do, Junghwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.11
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    • pp.3244-3248
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    • 2014
  • Two ethylenediamine cobalt(II) oxalate complexes Co(ox)(en), 1 and $Co(ox)(en){\cdot}2H_2O$, 2 have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum, TG analysis, and magnetic measurements. In 1, Co atoms are coordinated by two bis-bidentate oxalate ions in transconfiguration to form Co(ox) chains, which are further bridged by ethylenediamine molecules to produce 2D grid layers, Co(ox)(en). In 2, Co atoms are coordinated by bridging oxalate ions in cis-configuration to form Co(ox) chains, and the additional chelation of ethylenediamine to Co atoms completes 1D zigzag chain, Co(en)(ox). Two lattice water molecules stabilize the chains through hydrogen bonding. Magnetic susceptibility measurements indicate that both complexes exhibit weak antiferromagnetic coupling between cobalt(II) ions with the susceptibility maxima at 23 K for 1 and 20 K for 2, respectively. In 1 and 2, the oxalate ligands afford a much shorter and more effective pathway for the magnetic interaction between cobalt ions compared to the ethylenediamine ligands, so the magnetic behaviors of both complexes could be well described with 1D infinite magnetic chain model.

Synthesis, Structures and Properties of Three Metal-organic Frameworks Based on 3-(4-((1H-imidazol-1-yl)methyl)phenyl)acrylic Acid

  • Liang, Peng;Ren, Tian-Tian;Tian, Wei-Man;Xu, Wen-Jia;Pan, Gang-Hong;Yin, Xian-Hong
    • Bulletin of the Korean Chemical Society
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    • v.35 no.1
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    • pp.182-188
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    • 2014
  • Three new transition metal complexes based on Ozagrel $[Cu(Ozagrel)]_n$ (1), $[Zn(Ozagrel)(Cl)]_n$ (2), ${[Mn_2-(Ozagrel)(1,4-ndc)_2]{\cdot}(H_2O)}_n$ (3), (Ozagrel = 3-(4-((1H-imidazol-1-yl)methyl)phenyl)acrylic acid; 1,4-ndc = 1,4-Naphthalenedicarboxylic acid) have been hydrothermally synthesized and characterized by elemental analyse, IR, TG, PXRD, electrochemical analysis and single crystal X-ray diffraction. X-ray structure analysis reveals that 1 and 3 are 3D coordination polymers, while complex 2 is a two-dimensional network polymer, the 2D layers are further packed into 3D supramolecular architectures that are connected through hydrogen bonds. The electrochemistry of 1-3 was studied by cyclic voltammetry in methanol and water using a glassy carbon working electrode. Also, thermal decomposition process and powder X-ray diffraction of complexes were investigated.