• 제목/요약/키워드: Coordination polymers

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Bulk Coordination Polymerization of Dicyclopentadiene (DCPD) by Pd Complexes Containing β-Ketoiminate or β-Diketiminate Ligands

  • Lee, Eung Jun;Kim, Ho Sup;Lee, Byoung Ki;Hwang, Woon Sung;Sung, Ik Kyoung;Lee, Ik Mo
    • Bulletin of the Korean Chemical Society
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    • v.33 no.12
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    • pp.4131-4136
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    • 2012
  • Several palladium complexes containing ${\beta}$-ketoiminate and ${\beta}$-diketiminate ligands successfully produced poly(DCPD) possibly via vinyl addition. It was found that catalysts with ${\beta}$-diketiminate ligands containing bulkier aryl substituents showed the highest activity in the presence of MAO as a cocatalyst. Purity of DCPD is quite essential for the higher activity and small amount of organic solvent such as $CH_2Cl_2$ and toluene is required to reduce the viscosity of the reactant mixture for the higher activity. $^1H$ NMR spectra of produced polymers with N,N-dimethylanilinium tetra(pentafluorophenyl)borate (N,N-DAPFAr"$_4$) show that 5,6-double bond of DCPD is removed with 2,3-double bond remaining. Produced poly(DCPD) with MAO cocatalyst is quite rigid and insoluble in common organic solvents but rather brittle.

Perpendicular Interpenetration of Independent Square Grid Sheets. Synthesis and Structural Properties of $[Co(NCS)_2(Py_2L)_2]_n$($Py_2L$=trans-1,2-Bis(4-pyridyl)ethylene, 1,2-Bis(4-pyridyl)ethane)

  • 박성호;김관묵;이상기;정옥상
    • Bulletin of the Korean Chemical Society
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    • v.19 no.1
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    • pp.79-82
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    • 1998
  • Novel coordination polymers of general form $[Co(NCS)_2(Py_2L)_2]_n\; (Py_2L=trans-1,2-bis(4-pyridyl)ethylene$ (bpee), 1; 1,2-bis(4-pyridyl)ethane (bpea), 2) have been synthesized by slow diffusion of aqueous solution of $Co(NCS)_2$ with ethanolic solution of appropriate spacer ligand, $Py_2L$, in a mole ratio of 1 : 2. X-ray analyses on both 1 and 2 have provided similar unit and infinite structures with space group Ibam. The local geometry around the cobalt(Ⅱ) atoms is an octahedral arrangement with two NCS groups in trans position (N-Co-N, 180.0° (1); 180.0°(2)) and four pyridine units in propeller fashion. Each spacer ligand connects two cobalt(Ⅱ) ions defining the edges of a $[Co(II)]_4$ rhombus. The most fascinating feature is the occurrence of perpendicular interwoven of independent square grid sheets: this is, one molecular network is perpendicularly interpenetrated through the centers of the $[Co(II)]_4$ rhombuses of another independent network with all of the cobalt(Ⅱ) atoms in a coplanar sheet. The physicochemical properties of the present unique structures were studied.

Preparation and Characterization of Palladium Nanoparticles Supported on Nickel Hexacyanoferrate for Fuel Cell Application

  • Choi, Kwang-Hyun;Shokouhimehr, Mohammadreza;Kang, Yun Sik;Chung, Dong Young;Chung, Young-Hoon;Ahn, Minjeh;Sung, Yung-Eun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.4
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    • pp.1195-1198
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    • 2013
  • Nickel hexacyanoferrate supported palladium nanoparticles (Pd-NiHCF NPs) were synthesized and studied for oxygen reduction reactions in direct methanol fuel cell. The NiHCF support was readily synthesized by a comixing of $Ni(OCOCH_3)_2$ and equimolar $K_3[Fe(CN)_6]$ solution into DI water under rigorous stirring. After the preparation of NiHCF support, Pd NPs were loaded on NiHCF via L-ascorbic acid reduction method at $80^{\circ}C$. Pd-NiHCF NPs were electrochemically active for oxygen reduction reaction in 0.1 M $HClO_4$ solution. X-ray absorption near edge structure analysis was conducted to measure the white line intensity of Pd-NiHCF to verify the OH adsorption. As a comparison, carbon supported Pd NPs exhibited same white line intensity. This study provides a general synthetic approach to easily load Pd NPs on porous coordination polymers such as NiHCF and can provide further light to load Pd based alloy NPs on NiHCF framework.

Anions as Connectors for Higher Dimensions. Silver(I) Trifuoracetate with 3,3'-Oxybispyridine vs 3,3'-Thiobispyridine

  • Kim, Yun-Ju;Yoo, Kyung-Ho;Park, Ki-Min;Hong, Jong-Ki;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.23 no.12
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    • pp.1744-1748
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    • 2002
  • Trifluoroacetate anion as a connector has been studied on $AgCF_3CO_2$ with 3,3'-$Py_2X$(X=O vs S) produces 1 : 1 adducts of [Ag($CF_3CO_2$)(3,3'-$Py_2X<$)]. Crystallographic characterization of [Ag($CF_3CO_2$)(3,3'-$Py_2X$)](monoclinic $P2_1$a=7.383(1)$\AA$b=19.801(3)$\AA$c=9.297(3)$\AA$,$\beta$=$100.26(2)^{\circ}$,V=1337.4(5) $\AA^3$, Z=2, R=0.0386) reveals that the 3,3'-$Py_2O$ spacer connects two silver ions to give a single strand and that the single strands are linked via the trifluoroacetate anions in an "up and down even-bridge" to give an elegant molecular grid. The framework of [$Ag(CF_3CO_2)(3,3'-Py_2X)$](monoclinic $P2_1/c$a=8.331(2)$\AA$b=14.010(2)$\AA$,c=11.926(3 $\AA$$\beta$=$93.70(2)^{\circ}$=1385.1(6)$\AA^3$, Z=4, R=0.0589) is a single-strand. The single strands are connected via the trifluoroacetate anions in a double-bridge, resulting in a typical molecular chicken-wire. The trifluoroacetate anion as a connector appears to be primarily associated with its moderately coordinating ability. Their structural features have been discussed based on the anion exchangeability. Thermal analyses indicate that the compounds are stable up to approximately $200^{\circ}C$.

Adhesion Properties between Polyimide Film and Copper by Ion Beam Treatment and Imidazole-Silane Compound (이온빔 및 이미다졸-실란 화합물에 의한 폴리이미드 필름과 구리의 접착 특성)

  • Kang, Hyung Dae;Kim, Hwa Jin;Lee, Jae Heung;Suh, Dong Hack;Hong, Young Taik
    • Journal of Adhesion and Interface
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    • v.8 no.1
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    • pp.15-27
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    • 2007
  • Polyimide (PI) surface modification was carried out by ion-beam treatment and silane-imidazole coupling agent to improve the adhesion between polyimide film and copper. Silane-imidazole coupling agent contains imidazole functional groups for the formation of a complex with copper metal through a coordination bonding and methoxy silane groups for the formation of siloxane polymers. The PI film surface was first treated by argon (Ar)/oxygen ($O_2$) ion-beam, followed by dipping it into a modified silane-imidazole coupling agent solution. The results of X-ray photoelectron spectroscopy (XPS) spectra revealed that the $Ar/O_2$ plasma treatment formed oxygen functional groups such as hydroxyl and carbonyl groups on the polyimide film surface and confirmed that the PI surface was modified by a coupling reaction with imidazole-silane coupling agent. Adhesion between copper and the treated PI film by ion-beam and coupling agent was superior to that with untreated PI film. In addition, adhesion of PI film treated by an $Ar/O_2$ plasma to copper was better than that of PI film treated by a coupling agent. The peeled-off layers from the copper-PI film joint were completely different in chemical composition each other. The layer of PI film side showed similar C1s, N1s, O1s spectra to the original Upilex-S and no Si and Cu atoms appeared. On the other hand the layer of copper side showed different C1s and N1s spectra from the original PI film and many Si and Cu atoms appeared. This indicates that the failure occurs at an interface between the imidazole-silane and PI film layers rather than within the PI layers.

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Spectroscopic, Thermal and Biological Studies on Newly Synthesized Cu(II), Ni(II) and Co(II) Complexes with 3-N-2-hydroxyethylamine Benzanthrone and 3-N-2-aminoethylamine Benzanthrone (3-N-2-hydroxyethylamine benzanthrone 및 3-N-2-aminoethylamine benzanthrone에 대한 Cu(II), Ni(II) 및 Co(II) 착물의 분광학, 열 및 생물학적 연구)

  • Refat, Moamen S.;Megahed, Adel S.;El-Deen, Ibrahim M.;Grabchev, Ivo;El-Ghol, Samir
    • Journal of the Korean Chemical Society
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    • v.55 no.1
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    • pp.28-37
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    • 2011
  • Spectroscopic (infrared, electronic and $1^H$-NMR), elemental analyses CHN, molar conductivity, thermogravimetric analyses (TGA/DTG) and biological studies, of both benzanthrone derivatives 3-N-2-hydroxy ethylamine benzanthrone (HEAB) and 3-N-2-amino ethylamine benzanthrone (AEAB) with Cu(II), Co(II) and Ni(II) chlorides were discussed herein. Based on the above studies, HEAB ligand was suggested to be coordinated to each metal ions via hydroxo and amino groups to form [Cu(HEAB)$(Cl)_2$].$2H_2O$, [Co(HEAB)$(Cl)_2(H_2O)_2$].$8H_2O$ and [Ni(HEAB)$(Cl)_2(H_2O)_2$].$7H_2O$ coordinated complex. On the other hand, AEAB has an octahedral coordinated feature with formulas [Cu(AEAB)$(Cl)_2(H_2O)_2$].$2H_2O$, [Co(AEAB)$(Cl)_2(H_2O)_2$].$4H_2O$ and [Ni(AEAB)$(Cl)_2(H_2O)_2$]. $6H_2O$. The molar conductance values at $25{\circ}C$ for all complexes in DMF are slightly higher than free ligands; this supported the presence of chloride ions inside the coordination sphere. Both benzanthrone ligands and their complexes have been screened against different kinds of bacteria.