• Title/Summary/Keyword: Bridging ligand

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Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part II); Synthesis and Characterization of Cr(III)-Citrato Macrocyclic Complex

  • Byun, Jong-Chul;Park, Yu-Chul;Youn, Jeung-Su;Han, Chung-Hun;Lee, Nam-Ho
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.634-640
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    • 2005
  • The reaction of cis-[Cr([14]-decane)(OH$_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = citrate(cit)} leads to a new dimeric complex cis-[{Cr([14]-decane)($\mu$-cit)}$_2](ClO_4)_2$. This binuclear complex has been structurally characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[{Cr([14]-decane)($\mu$-cit)})($_2]^+$ reveals that each chromium has a distorted octahedral coordination environment and citrato ligands are monodentate to the two chromium atoms via the carboxyl groups. For dimeric complex the bridging geometry is as follows: Cr$\ldots$Cr = 7.361 $\AA$; Cr-O(average) = 1.958 (8) $\AA$; Cr-N range = 2.108 (9)-2.147(9) $\AA$; N(1)-Cr-N(3) (equatorial position) = 98.0(4)$^{\circ}$; N(2)-Cr-N(4) (axial position) = 166.4(4)$^{\circ}$; O(1)-Cr-N(2) = 98.1(4)$^{\circ}$; O(3)-Cr-N(4) = 96.6(3)$^{\circ}$; O(1)-Cr-O(3) = 90.4$^{\circ}$. The FAB mass spectrum of the dimeric complex displays peak due to the molecular ions cis-[{Cr([14]-decane)($\mu$-cit)})($_2]^+$ at m/z 1053.

Anion Effects on Crystal Structures of CdII Complexes Containing 2,2'-Bipyridine: Photoluminescence and Catalytic Reactivity

  • Park, Hyun-Min;Hwang, In-Hong;Bae, Jeong-Mi;Jo, Young-Dan;Kim, Cheal;Kim, Ha-Yeong;Kim, Young-Mee;Kim, Sung-Jin
    • Bulletin of the Korean Chemical Society
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    • v.33 no.5
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    • pp.1517-1522
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    • 2012
  • Anion effects on structures of $Cd^{II}$ complexes containing 2,2'-bipyridine (2,2'-bpy) ligands have been studied, and compared with $Zn^{II}$-(2,2'-bpy) complexes. For each anion, different structures have been obtained in both $Zn^{II}$-(2,2'-bpy) and $Cd^{II}$-(2,2'-bpy). Polymeric structures of $Cd^{II}$-2,2'-bpy complexes can be produced by hydrogen bonding interactions as shown in $Zn^{II}$-2,2'-bpy complexes. In addition, the bigger size of a $Cd^{II}$ ion gives higher coordination numbers forming variety of structures, and it makes that chlorides can act as bridging ligands to form a one-dimensional structure. The compound $\mathbf{5}$ catalyzed efficiently the transesterification of a variety of esters with methanol, while the rest of the compounds have displayed very slow conversions. In addition, the emission bands of complexes $\mathbf{1}$, $\mathbf{2}$, $\mathbf{4}$, and $\mathbf{6}$ are blue-shifted compared to the corresponding ligand 2,2'-bpy, whereas $\mathbf{3}$ and $\mathbf{5}$ showed the similar emission observed for the ligand.

Syntheses of Polysiloxane-Bridged Dinuclear Metallocenes and Their Catalytic Activities

  • 노석균;김수찬;이동호;윤근병;이훈봉
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.618-622
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    • 1997
  • The polysiloxane-bridged dinuclear metallocenes $[(SiMe_2O)_n-SiMe_2(C_5H_4)_2][(C_9H_7)ZrCl_2]_2$ (n=1 (7), 2 (8), 3 (9)) have been generated as a model complex for the immobilized metallocene at silica surface by treating the respective disodium salts of the ligands with 2 equivalents of $(C_9H_7)ZrCl_3$ in THF. All three complexes are characterized by $^1H$ NMR and measurement of metal content through ICP-MS. It turned out that the values of ${\Delta}{\delta}=[{\delta}_d-{\delta}_p]$, the chemical shift difference between the distal $({\delta}_d)$ and proximal $({\delta}_p)$ protons, for the produced dinuclear compounds (0.47 for 7, 0.49 for 8, and 0.5 for 9) were larger than the Δδ value of the known ansa-type complex holding the same ligand as a chelating one, that is just the opposite to the normal trend. In order to compare polymerization behavior of the dinuclear metallocene with the corresponding mononuclear metallocene, (Cp)$(C_9H_7)ZrCl_2$ was separately prepared. To investigate the catalytic properties of the dinuclear complexes and mononuclear metallocenes ethylene polymerization has been conducted in the presence of MMAO. The polymerization results display the typical activity dependence on polymerization temperature for all complexes. The most important feature is that the polymers from the dinuclear metallocenes represent enormously improved molecular weight compared with the polymer from the corresponding mononuclear metallocene. In addition, the influence of the nature of the bridging ligand upon the reactivities of the dinuclear metallocenes has also been observed.

Structure of an Organotitanoxane Containing a Tetrahedral $Ti_{4}O_{6}$ Cage, $C_{40}H_{60}O_{6}Ti_{4}$

  • Kim, Young-Sang;Ko, Jae-Jung;Kang, Sang-Ook;Kim, Tae-Jin;Han, Won-Sik;Suh, Il-Hwan
    • Korean Journal of Crystallography
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    • v.16 no.2
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    • pp.102-106
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    • 2005
  • The crystal structure of the title compound has been analyzed by single crystal X-ray diffraction method. The compound crystallized in the triclinic space group $P\bar{1}$ with a=11.300(6) ${\AA}$, c=18.716(10) ${\AA}$, ${\alpha}=82.833(10)^{\circ}$, ${\beta}=83.042(11)^{\circ}$, ${\gamma}=66.139(10)^{\circ}$, $V=2162(2)\;{\AA}^{3}$, Z=2 and R1=0.661 for 10578 unique reflections. The four $C_{5}Me_{5}$ planar groups from a tetrahedron with a mean dihedral angle $70.92(9)^{\circ}$ among them and the $Ti_{4}O_{6}$ cage sits at the center of the tetrahedron. Each Ti atom in the $Ti_{4}O_{6}$ cage is bonded by three bridging oxygen atoms and coordinated by a $C_{5}Me_{5}$ ligand with a mean distance $2.067{\AA}$ from Ti atoms to the centroids of the four five-membered rings. Two oxygen atoms facing each other in $Ti_{4}O_{6}$ cage are $4.051(3){\AA}$ away in average.

Crystal Structures and Thermal Properties of Two Binuclear Cd(II) Supramolecular Complexes Based on Quinolinecarboxylate Ligand

  • Hao, Hu-Jun;Yin, Xian-Hong;Lin, Cui-Wu;Wei, Shui-Qiang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3255-3260
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    • 2011
  • Two novel binuclear metal-organic coordination complexes $[Cd_2(L)_2(bpy)_2(H_2O)_2]{\cdot}6H_2O$ (1), $[Cd_2(L)_2(phen)_2-(H_2O)_2]{\cdot}2H_2O$ (2) (where L = 2-methylquinoline-3,4-dicarboxylate dianion, bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) have been synthesized under hydrothermal conditions and characterized by single crystal Xray diffraction, spectral method (IR), elemental analysis and thermal gravimetric analysis (TGA). Both 1 and 2 consist of two Cd(II) atoms bridged by two monoatomic bridging carboxylate groups from two L ligands, and the second carboxylate group of each L is monodentately coordinated to Cd(II), creating a sevenmembered chelating ring. The coordination at each metal nucleus is completed by a water molecule and a chelating bidentate molecule. The 3D structures of the complexes are stabilized by ${\pi}-{\pi}$ stacking interactions and hydrogen-bonds.

Synthesis, Structure, and Magnetic Properties of 1D Nickel Coordination Polymer Ni(en)(ox)·2H2O (en = ethylenediamine; ox = oxalate)

  • Chun, Ji-Eun;Lee, Yu-Mi;Pyo, Seung-Moon;Im, Chan;Kim, Seung-Joo;Yun, Ho-Seop;Do, Jung-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1603-1606
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    • 2009
  • A new 1D oxalato bridged compound Ni(en)(ox)-2$H_2$O, (ox = oxalate; en = ethylenediamine) has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum, TG analysis, and magnetic measurements. In the structure the Ni atoms are coordinated with four oxygen atoms in two oxalate ions and two nitrogen atoms in one ethylenediamine molecule. The oxalate anion acts as a bis-bidentate ligand bridging Ni atoms in cis-configuration. This completes the infinite zigzag neutral chain, [Ni(en)(ox)]. The interchain space is filled by water molecules that link the chains through a network of hydrogen bonds. Thermal variance of the magnetic susceptibility shows a broad maximum around 50 K characteristic of one-dimensional antiferromagnetic coupling. The theoretical fit of the data for T > 20 K led to the nearest neighbor spin interaction J = -43 K and g = 2.25. The rapid decrease in susceptibility below 20 K indicate this compound to be a likely Haldane gap candidate material with S = 1.

One-Pot Synthesis, Crystal Structures and Thermal Properties of Two Three-Dimensional Cobalt(II) Complexes

  • Tao, Bo;Lei, Wen;Cheng, Feiran;Xia, Hua
    • Bulletin of the Korean Chemical Society
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    • v.33 no.6
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    • pp.1929-1933
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    • 2012
  • Two cobalt(II) compounds $[Co(2,2{^\prime}-bipy)(H_2O)_2(SO_4)]_n$ (1) and $[Co_2(2,2^{\prime}-bipy)_2(btec)(H_2O)_6]{\cdot}2H_2O$ (2) (2,2'-bipy = 2,2'-bipyridine, $H_4btec$ = 1,2,4,5-benzenetetracarboxylic acid), have been simultaneously synthesized by a one-pot slow solvent evaporation reaction. Their structures were determined by single-crystal X-ray diffraction and further characterized by X-ray powder diffraction (XRPD), IR, elemental and thermogravimetric analysis (TGA). The structural analysis reveals that compound 1 exhibits an infinite 1D chain structure with the octahedral Co(II) centers bridging by the tetrahedral ${\mu}_2-SO{_4}^{2-}$ ligands, while compound 2 possesses a dinuclear $Co_2(2,2^{\prime}-bipy)_2(btec)(H_2O)_6$ unit and the two adjacent octahedral Co(II) ions are linked by the bismonodentately coordinated btec ligand. Additionally, compound 2 exhibits blue fluorescent emission in the solid state at room temperature.

Synthesis, Structures and Properties of Two Metal-organic Frameworks Derived from 3-Nitro-1,2-benzenedicarboxylic Acid

  • Xu, Wen-Jia;Zhang, Ling-Yu;Tang, Jin-Niu;Wang, Dai-Yin;Pan, Gang-Hong;Feng, Yu
    • Bulletin of the Korean Chemical Society
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    • v.34 no.8
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    • pp.2375-2380
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    • 2013
  • Two metal-organic frameworks based on the connectivity co-effect between rigid benzenedicarboxylic acid and bridging ligand have been synthesized $[Zn_2(3-NO_2-bdc)_2(4,4'-bpy)_2H_2O]_n$ (1), $[Co(3-NO_2-bdc)(4,4'-bpy)H_2O]_n$ (2) (where $3-NO_2-bdcH_2$ = 3-nitro-1,2-benzenedicarboxylic acid, 4,4'-bpy = 4,4'-bipyridine). The two novel complexes were characterized by IR spectrum, elemental analysis, fluorescent properties, thermogravimetric analysis, single-crystal X-ray diffraction and powder X-ray diffraction (PXRD). X-ray structure analysis reveals that 1 and 2 are two-dimensional (2D) network structures. Complex 1 and complex 2 belong to triclinic crystal with P-1 space group. The luminescence measurements reveal that two complexes exhibit good fluorescent emissions in the solid state at room temperature. Also, thermal decomposition process and powder X-ray diffraction of complexes were investigated.

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.

Anti-adherence of Antibacterial Peptides and Oligosaccharides and Promotion of Growth and Disease Resistance in Tilapia

  • Peng, K.S.;She, R.P.;Yang, Y.R.;Zhou, X.M.;Liu, W.;Wu, J.;Bao, H.H.;Liu, T.L.
    • Asian-Australasian Journal of Animal Sciences
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    • v.20 no.4
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    • pp.569-576
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    • 2007
  • Four hundred and fifty tilapias ($6.77{\pm}0.23$ g) were assigned randomly to six groups to evaluate the feasibility of the tested antibacterial peptides (ABPs) and oligosaccharides as substitutes for antibiotics. The control group was fed with a commercial tilapia diet; other five groups were fed with the same commercial diet supplemented with konjac glucomannan (KGLM), cluster bean galactomannan (CBGAM), and three animal intestinal ABPs derived from chicken, pig and rabbit at 100 mg/kg respectively. After 21 days of feeding, growth, disease resistance, and in vivo anti-adherence were determined. Furthermore, the inhibitory effect of tested agents on adhesion of Aeromonas veronii biovar sobria (A.vbs) strain BJCP-5 to tilapia enteric epithelia in vitro was assessed by cell-ELISA system. As a result, the tested agents supplemented at 100 mg/kg show significant benefit to tilapia growth and disease resistance (p<0.05), and the benefit may be correlated with their interfering in the contact of bacteria with host mucosal surface. Although none of the tested agents did inhibit the growth of BJCP-5 in tryptic soy broth at $100{\mu}g/ml$, all of them did inhibit the adhesion of A.vbs to tilapia enteric epithelia in vivo and in vitro. In vitro mimic assays show that three ABPs at low concentrations of $25{\mu}g/ml$ and $2.5{\mu}g/ml$ have the reciprocal dose-dependent anti-adherence effect. The inhibition of ABPs may be correlated with a cation bridging and/or receptor-ligand binding, but not with hydrophobicity. The KGLM and CBGAM inhibited the adherence of BJCP-5 to tilapia enteric epithelia with dose-dependent manner in vitro, and this may be through altering bacterial hydrophobicity and interfering with receptor-ligand binding. Our results indicate that the anti-adherence of the tested ABPs and oligosaccharides may be one of the mechanisms in promoting tilapia growth and resistance to A.vbs.