• Title/Summary/Keyword: Coordination chemistry

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Preparation and Crystal Structures of Silver(I), Mercury(II), and Lead(II) Complexes of Oxathia-Tribenzo-Macrocycles

  • Siewe, Arlette Deukam;Ju, Huiyeong;Lee, Shim Sung
    • Bulletin of the Korean Chemical Society
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    • v.34 no.3
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    • pp.725-730
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    • 2013
  • An investigation of the coordination behavior of sulfur-containing mixed-donor tribenzo-macrocycles $L^1-L^3$ ($L^1$: 20-membered $O_3S_2$, $L^2$: 20-membered $O_2S_3$, and $L^3$: 23-membered $O_4S_2$) with $d^{10}$-metal ($Ag^+$, $Hg^{2+}$, and $Pb^{2+}$) salts is reported. The X-ray structures of five complexes (1-5) with different structural types and stoichiometries, including mono- to dinuclear species have been determined. Reactions of $L^2$ and $L^3$ with the silver(I) salts ($PF_6{^-}$ and $SCN^-$) afforded two dinuclear 2:2 (metal-to-ligand) complexes with different arrangements: a sandwich-type cyclic dinuclear complex $[Ag_2(L^2)_2](PF_6)_2{\cdot}3CH_2Cl_2$ (1) and a linear dinuclear complex $[Ag_2(L^3)_2(SCN)_2]$ (2), in which two monosilver(I) complex units are linked by an Ag-Ag contact. Reactions of $L^1$ and $L^2$ with mercury(II) salts ($SCN^-$ and $Cl^-$) gave a mononuclear 1:1 complexes $[Hg(L^1)(SCN)_2]$ (3) and $[Hg(L^2)Cl_2]$ (4) with anion coordination in both cases. $L^2$ reacts with lead(II) perchlorate to yield a mononuclear sandwich-type complex $[Pb(L^2)_2(ClO_4)_2]$ (5), giving an overall metal coordination geometry of eight with a square antiprism arrangement. From these results, the effects of the donor variation and the anioncoordination ability on the resulting topologies of the soft metal complexes are discussed.

Cadmium-Substituted Concanavalin A and Its Trimeric Complexation

  • Park, Yeo Reum;Kim, Da Som;Lee, Dong-Heon;Kang, Hyun Goo;Park, Jung Hee;Lee, Seung Jae
    • Journal of Microbiology and Biotechnology
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    • v.28 no.12
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    • pp.2106-2112
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    • 2018
  • Concanavalin A (ConA) interacts with carbohydrates as a lectin, and recent reports proposed its application for detecting a diversity of viruses and pathogens. Structural studies have detailed the interaction between ConA and carbohydrates and the metal coordination environment with manganese and calcium ions (Mn-Ca-ConA). In this study, ConA was crystallized with a cadmium-containing precipitant, and the refined structure indicates that $Mn^{2+}$ was replaced by $Cd^{2+}$ (Cd-Ca-ConA). The structural comparison with ConA demonstrates that the metal-coordinated residues of Cd-Ca-ConA, that is Glu8, Asp10, Asn14, Asp19, and His24, do not have conformational shifts, but residues for sugar binding, including Arg228, Tyr100, and Leu99, reorient their side chains, slightly. Previous studies demonstrated that excess cadmium ions can coordinate with other residues, including Glu87 and Glu183, which were not coordinated with $Cd^{2+}$ in this study. The trimeric ConA in this study coordinated $Cd^{2+}$ with other residues, including Asp80 and Asp82, for complex generation. The monomer does not have specific interaction near interface regions with the other monomer, but secondary cadmium coordinated with two aspartates (Asp80 and Asp82) from monomer 1 and one aspartate (Asp16) from monomer 2. This study demonstrated that complex generation was induced via coordination with secondary $Cd^{2+}$ and showed the application potential regarding the design of complex formation for specific interactions with target saccharides.

Spectral and Geometrical Study of Two Cadmium Complexes, mer-R,S-[Cd(aepn)2]X2 (X: I-, Cl-, aepn: N-(2-Aminoethyl)-1,3-propanediamine) Supported by Solution Experiments

  • Hakimi, Mohammad;Mardani, Zahra;Moeini, Keyvan
    • Journal of the Korean Chemical Society
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    • v.57 no.4
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    • pp.447-454
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    • 2013
  • In this research, two new complexes of N-(2-aminoethyl)-1,3-propanediamine (aepn), $[Cd(aepn)_2]I_2$ (1) and $[Cd(aepn)_2]Cl_2{\cdots}H_2O$ (2), were prepared and identified by elemental analysis, FT-IR, Raman spectroscopy and single-crystal X-ray diffraction. Geometry around the cadmium atom in two complexes by coordination of six nitrogen atoms of two aepn is distorted octahedral. If distortion in the mer-$[Cd(aepn)_2]^{2+}$ cation is disregarded, it has a $C_2$ axis and $C_2$ symmetry. The cyclic voltammetry experiments were carried out to study the complexation process. Two structural surveys on coordination modes and complexes of aepn are presented. A study was carried out using CSD data to estimate the averages of bond lengths for different types of the Cd-N bonds. It was found that the intermolecular $N-H{\cdots}I$, $C-H{\cdots}I$ hydrogen bonds in 1 and $N-H{\cdots}Cl$, $N-H{\cdots}O$, $C-H{\cdots}O$, $O-H{\cdots}Cl$ in 2 stabilized the crystal networks.

A Two-dimensional Supramolecular Network Built through Unique π-πStacking: Synthesis and Characterization of [Cu(phen)2(μ-ID A)Cu(phen)·(NO3)](NO3)·4(H2O)

  • Lin, Jian-Guo;Qiu, Ling Qiu;Xu, Yan-Yan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.5
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    • pp.1021-1025
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    • 2009
  • A novel supramolecular network containing binuclear copper unit $[Cu(phen)_{2}({\mu}-ID\;A)Cu(phen){\cdot}(NO_{3})](NO_{3}){\cdot}4(H_{2}O)$ (1) was synthesized through the self-assembly of iminodiacetic acid ($H_2IDA$) and 1,10-phenanthroline (phen) in the condition of pH = 6. It has been characterized by the infrared (IR) spectroscopy, elemental analysis, single crystal X-ray diffraction, and thermogravimetric analysis (TGA). 1 shows a 2-D supramolecular structure assembled through strong and unique $\pi-\pi$ packing interactions. Density functional theory (DFT) calculations show that theoretical optimized structures can well reproduce the experimental structure. The TGA and powder X-ray diffraction (PXRD) curves indicate that the complex 1 can maintain the structural integrity even at the loss of free water molecules. The magnetic property is also reported in this paper.

Preparation and characterization of boron-nitrogen coordination phenol resin/SiO2 nanocomposites

  • Gao, J.G.;Zhai, D.;Wu, W.H.
    • Advances in materials Research
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    • v.3 no.1
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    • pp.259-269
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    • 2014
  • The boron-nitrogen-containing phenol-formaldehyde resin (BNPFR)/$SiO_2$ nanocomposites (BNPFR/$SiO_2$) were synthesized in-situ, and structure of BNPFR/$SiO_2$ nanocomposites was characterized by FTIR, XRD and TEM. The loss modulus peak temperature $T_p$ of BNPFR/$SiO_2$ nanocomposites cured with different nano-$SiO_2$ content are determined by torsional braid analysis (TBA). The thermal degradation kinetics was investigated by thermogravimetric analysis (TGA). The results show that nano-$SiO_2$ particulate with about 50 nm diameter has a more uniformly distribution in the samples. The loss modulus peak temperature $T_p$ of BNPFR/$SiO_2$ nanocomposite is $214^{\circ}C$ when nano-$SiO_2$ content is 6 wt%. The start thermal degradation temperature $T_{di}$ is higher about $30^{\circ}C$ than pure BNPFR. The residual rate (%) of nanocomposites at $800^{\circ}C$ is above 40 % when nano-$SiO_2$ content is 9 %. The thermal degradation process is multistage decomposition and following first order.

Study on the Coordination Polymers of Metal (II) Ions with 2,5-Diamine 1,4-Dihydroxybenzene (2,5-Diamine 1,4-Dihydroxybenzene과 금속 (II) 이온이 만드는 Coordination Polymer에 관하여)

  • Joon Suk Oh;Kyun Ok Cho
    • Journal of the Korean Chemical Society
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    • v.13 no.4
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    • pp.309-312
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    • 1969
  • A series of metal ion-2, 5-diamine 1, 4-dihydroxybenzene polymers containing copper(II), nickel(II) or cobalt (II) have been prepared. The structure was postulated on the basis of elementary analysis of polymers. It was found that copper polymer is most likely the coordination polymers by X-ray powder pattern studies. The thermal stability of the polymers was also studied by a simple method, utilizing a thermogravimetric balance. The order of thermal stabilities is Cu(II) > Ni(II) > Co(II). The polymers start to decompose at a relatively low temperature.

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Construction of a 2D Co(II) Coordination Polymer with (4,4)-Connected Topology: Synthesis, Crystal Structure, and Surface Photo-electric Property

  • Li, Jia-Ming
    • Bulletin of the Korean Chemical Society
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    • v.35 no.4
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    • pp.1177-1181
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    • 2014
  • A 2D grid-like (4, 4)-connected topology coordination polymer, $[Co(BTA)_2(H_2O)_2]_n$ (1), where HBTA = 2-(1H-benzotriazol-1-yl)acetic acid, has been synthesized by hydrothermal method and characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and surface photovoltage spectroscopy (SPS). X-ray diffraction analyses indicated that 1 displays octahedral metal centers with secondary building units (SBUs) [$Co(BTA)_2(H_2O)_2$] bridged by the $BTA^-$ ligands. In the crystal, the 2D supramolecular architecture is further supported by $O-H{\cdots}O$, $O-H{\cdots}N$, $C-H{\cdots}O$ hydrogen bonds and ${\pi}{\cdots}{\pi}$ stacking interactions. The SPS of polymer 1 indicates that there are positive response bands in the range of 300-600 nm showing photo-electric conversion properties. There are good relationships between SPS and UV-Vis spectra.