• Title/Summary/Keyword: N,O-ligand

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Synthesis and Crystal Structure of 13-Membered Tetraaza Macrocyclic Cobalt(III) Complex with Azido Ligand (Azido 리간드가 포함된 13변 테트라아자 거대고리 코발트(III) 착물(錯物)의 합성(合成) 및 결정구조(結晶構造))

  • Choi, Ki-Young
    • Korean Journal of Crystallography
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    • v.17 no.2
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    • pp.41-45
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    • 2006
  • The complex $cis-[Co(13-aneN_4)(N_3)_2]Cl\cdot H_2O$ (1) (13-ane$N_4$ = 1,4,7,10-tetraazacyclotridecane) has been synthesized and structurally characterized by X-ray crystalloaraphy. It crystallizes in the orthorhombic system Pbca, a = 7.8282(4) ${\AA}$, b = 14.3197(7) ${\AA}$, c = 29.9021(15) ${\AA}$, V = 3351.9(3) ${\AA}^3$, Z = 8. The cobalt(III) ion in 1 is coordinated to four nitrogen atoms from the macrocycle and two azide ligands of cis position in a distorted octahedral environment, which forms the 1D polymer through hydrogen bonding contacts involving the cation, chloride anion and solvent water molecules.

Metal-Dinitrosyl Complexes(III) : Synthesis and Structural Study of Homo-, Hetero-dinuclear Molybdenum and Tungsten Complexes, $[Cl(phen)(NO)_2M({\mu}-pyz)M'(NO)_2(phen)Cl][ClO_4]_2 $(phen = 1,10-phenanthroline, pyz = pyrazine) (금속-디니트로실 착물 (제 3 보) : 몰리브덴과 텅스텐의 호모 및 헤테로 이핵 착물, $[Cl(phen)(NO)_2M({\mu}-pyz)M'(NO)_2(phen)Cl][ClO_4]_2 (phen=1,10-phenanthroline,\;pyz=pyrazine)$의 합성 및 구조에 대한 연구)

  • Sang-Oh Oh;Seong-Jong Mo
    • Journal of the Korean Chemical Society
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    • v.37 no.7
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    • pp.655-661
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    • 1993
  • The neutral monomeric compounds $[Mo(NO)_2Cl_2(phen)]$ and $[W(NO)_2Cl_2(phen)]$ (phen= 1,10-phenanthroline) have been prepared by reactions of polymeric compounds $[{Mo(NO)_2Cl_2}n],\;[{W(NO)_2Cl_2}n]$ with chelate ligands. Additions of one equivalent of silver(I) perchlorate to these cis-dinitrosyl compounds in acetone solution produce $[Mo(NO)_2(phen)(S)Cl][ClO_4]\;and\;[W(NO)_2(phen)(S)Cl][ClO_4]$ (S = acetone). The homo- and hetero-dinuclear complexes, $[Cl(phen)(NO)_2M(pyz)M'(NO)_2(phen)Cl][ClO_4]_2$ (M = Mo, W) and $[Cl(phen)(NO)_2M(pyz)M'(NO)_2(phen)Cl][C1O_4]_2$ (M = Mo, M' = W) have been prepared by these monocationic complexes with pyrazine ligand respectively. These complexes characterized by elemental analysis, $1^H-\;and\;^{13}C-NMR$, infrared, and UV-visible spectroscopy are reported. The spectral data indicate that homo- and hetero-dinuclear complexes were symmetrical structures of $C_{2v}$.

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Synthesis, Structure and Biological Properties of a Novel Copper (II) Supramolecular Compound Based on 1,2,4-Triazoles Derivatives

  • Qiu, Guang-Mei;Wang, Cui-Juan;Zhang, Ya-Jun;Huang, Shuai;Liu, Xiao-Lei;Zhang, Bing-Jun;Zhou, Xian-Li
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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    • pp.2603-2608
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    • 2012
  • A novel mononuclear supramolecule of copper(II) has been synthesized with Ippyt ligand (Ippyt=3-(4'-imidazole phenyl)-5-(pyrid-2''-yl)-1,2,4-triazole) (1). Compound 1, namely [$Cu(Ippyt)_2(H_2O)_2$], has been characterized by single-crystal X-ray diffraction, IR spectrum, elemental analysis and thermogravimetric analysis. Structure determination reveals that the elongated-octahedral geometry is formed in the vicinity of the copper (II) atom being coordinated by four nitrogen atoms from two Ippyt ligands occupying the equatorial position and two oxygen atoms from two coordinated water molecules in the axial position, which together form the $N_4O_2$ donor set. Hydrogen bonding interactions between nitrogen and oxygen atoms result in the set up of a supramolecular network architecture. Biological properties including antibacterial activity and superoxide dismutase (SOD) mimetic activity of compound 1 have been investigated by agar diffusion method and the modified Marklund method, respectively. The results indicate that compound 1 exhibits a stronger antibacterial efficiency than the parent ligand and it also has a certain radical-scavenging activity.

Dynamic Rapid Synthesis of Bis(2,2'-bipyridine)nitrato Zinc (II) Nitrate Using a Microwave Method and its Application to Dye-Sensitized Solar Cells (DSSC)

  • Kim, Young-Mi;Kim, Su-Jung;Nahm, Kee-Pyung;Kang, Mi-Sook
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2923-2928
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    • 2010
  • This study examined the synthesis of the crystal structure of bis(2,2'-bipyridine)nitrato zinc (II) nitrate, $[Zn(bipy)_2(NO_3)]^+NO_3^-$ using a microwave treatment at 300 W and 60 Hz for the application to dye-sensitized solar cells. The simulated complex structure of the complex was optimized with the density functional theory calculations for the UV-vis spectrum of the ground state using Gaussian 03 at the B3LYP/LANL2DZ level. The structure of the acquired complex was expected a penta-coordination with four nitrogen atoms of bipyridine and the oxygen bond of the $NO_3^-$ ion. The reflectance UV-vis absorption spectra exhibited two absorptions (L-L transfers) that were assigned to the transfers from the ligand ($\sigma$, $\pi$) of $NO_3$ to the ligand ($\sigma^*$, $\pi^*$) of pyridine at around 200 - 350 nm, and from the non-bonding orbital (n) of O in $NO_3$ to the p-orbital of pyridine at around 450 - 550 nm, respectively. The photoelectric efficiency was approximately 0.397% in the dye-sensitized solar cells with the nanometer-sized $TiO_2$ at an open-circuit voltage (Voc) of 0.39 V, a short-circuit current density (Jsc) of $1.79\;mA/cm^2$, and an incident light intensity of $100\;mW/cm^2$.

Selective Deprotonation and Decarbonylation from Hydridocarbonyl-iridium(III) Compounds with Trimethylamine N-oxide

  • 천청식;오문현;원경식;조해연;신동찬
    • Bulletin of the Korean Chemical Society
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    • v.20 no.1
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    • pp.85-88
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    • 1999
  • Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0.1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, C1O4-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (lb) to give IrCl(CO)(PPh3)2 (2b) is first order in both lb and Me3NO. The rate law d[2b]/dt=kobs[lb]=k2[lb][Me3NO] suggests the formation of (PPh3)2(CI)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis liaand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, C1O4-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-lr(H)(-CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.

X-ray crystal structure of two-dimensional bimetallic host clathrate with 2-aminoethanol, [Cd{NH2CH2CH2OH}2Ni(CN)4]·3C6H5NH2·H2O

  • Kim, Chong-Hyeak;Moon, Hyoung-Sil;Lee, Sueg-Geun
    • Analytical Science and Technology
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    • v.21 no.6
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    • pp.562-568
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    • 2008
  • A novel two-dimensional cadmium(II)-nickel(II) bimetallic host clathrate, $[Cd{NH_2CH_2CH_2OH}_2Ni(CN)_4]{\cdot}3C_6H_5NH_2{\cdot}H_2O$, 1, has been synthesized and structurally characterized by X-ray single crystallographic method. The clathrate 1 crystallizes in the monoclinic system, space group $P2_1/c$ with a = 14.370(3), b = 7.728(1), c = 28.172(4) ${\AA}$, ${\beta}=97.58(1)^{\circ}$, V = 3101.1(9) ${\AA}^3$, Z = 4. The host framework of the clathrate 1 is built of the cyanide bridges between octahedral Cd(II) atom and square planar Ni(II) atom. The octahedral Cd atoms ligated by two 2-aminoethanol molecules and four cyanide ligands bridged with square planar Ni atoms. The Ni atoms bridges to four Cd atoms via cyanides is made up of puckered quadrangles of composition $\{CdNi(CN)_2\}_2$, all edges are shared. This cyanide bridges form an infinite two-dimensional host networks stacking along b axis. 2-Aminoethanol ligands bond to Cd atom through N atom as a monodentate ligand in the axial position and four cyanides take an equatorial plane with all in trans-configurations. The aniline guest molecules and water molecules are located in between the host layer sheets, respectively.

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.

The Synthesis and Antispectrum of Alkylene Bisthioureido $\beta$-tactam Derivatives of Cefadroxil. (Cefadroxil을 사용한 Alkylene Bisdithioureido $\beta$-Lactam 유도체의 합성 및 항균작용)

  • 이기홍;김돈기;김지한;성동호;유주현
    • Microbiology and Biotechnology Letters
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    • v.17 no.3
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    • pp.193-197
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    • 1989
  • The three new Alkylene bisdithionreido $\beta$-lactam derivatives were synthesized and evaluated for antimicrobial activities. Treatment of cefadroxil.2DMF with alkylene diisothiocyanate which was obtained by the reaction of alkylene diamine with carbon disulfide, sodium hydroxide and ethyl chloroformate afforden alkylene bisdithioureido $\beta$ -lactam derivatiives. The antimicrobial activities of the compounds synthesized were ethylene bisdithioureido $\beta$-lactam derivative lost the sensitivity against Escherichia coli but showed potent antimicrobial activity against $\beta$-lactams Escherichia coli, but, tetramethylene bisdithioureido $\beta$-lactam derivative and hexamethylene bisdithioureido $\beta$ -lactam derivative compounds showed diminished or no antimicrobial activities.

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Flexible quantum dot solar cells with PbS-MIx/PbS-BuDT bilayers

  • Choe, Geun-Pyo;Yang, Yeong-U;Yun, Ha-Jin;Im, Sang-Gyu
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.347.2-347.2
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    • 2016
  • Recently, in order to improve the performance of the colloidal quantum dot solar cells (CQDSCs), various efforts such as the modification of the cell architecture and surface treatment for quantum dot (QD) passivation have been made. Especially, the incorporation of halides into the QD matrix was reported to improve the performances significantly via passivating QD trap states that lower the life-time of the minority-carrier. In this work, we fabricated a lead sulfide (PbS) QD bilayer treated with different ligands and utilized it as a photoactive layer of the CQDSCs. The bottom and top PbS layer was treated using metal iodide ($MI_x$ and butanedithiol (BuDT), respectively. All the depositions and ligand treatments were carried out in air using layer-by-layer spin-coating process. The fabrication of the active layers as well as the n-type zinc oxide (ZnO) layer was successfully carried out on the bendable indium-tin-oxide (ITO)-coated polyethylene terephthalate (PET) substrate, which implies that this technique can be applied to the fabrication of flexible and/or wearable solar cells. The power conversion efficiency (PCE) of the CQDSCs with the architecture of $PET/ITO/ZnO/PbS-MI_x/PbS-BuDT/MoO_x/Ag$ reached 4.2 %, which is significantly larger than that of the cells with single QD (PbS-BuDT) layer.

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Synthesis, Physico-Chemical and Biological Properties of Complexes of Cobalt(II) Derived from Hydrazones of Isonicotinic Acid Hydrazide (Isonicotinic Acid Hydrazide의 Hydrazone으로부터 유도된 코발트(II) 착물의 합성, 물리-화학 및 생물학적 성질)

  • Prasad, Surendra;Agarwal, Ram K.
    • Journal of the Korean Chemical Society
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    • v.53 no.1
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    • pp.17-26
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    • 2009
  • Hydrazones of isonicotinic acid hydrazide, viz., N-isonicotinamido-furfuralaldimine (INH-FFL), N-isonicotnamido-cinnamalidine (INH-CIN) and N-isonicotnamido-3',4',5'-trimethoxybenzaldimine (INH-TMB) were prepared by reacting isonicotinic acid hydrazide with respective aromatic aldehydes, i.e., furfural, cinnamaldehyde or 3,4,5-trimethoxy-benzaldehyde. A new series of fifteen complexes of cobalt(II) with these new hydrazones, INH-FFL, INH-CIN and INH-TMB, were synthesized by their reaction with cobalt(II) salts. The infrared spectral data reveal that hydrazone ligands behave as a bidentate ligand with N, O donor sequence towards the $Co^{2+}$ ion. The complexes were characterized on the basis of elemental analysis, magnetic susceptibility, conductivity, infrared and electronic spectral measurements. Analytical data reveal that the complexes have general composition [Co($L)_2X_2]\;and\;[Co(L)_3](ClO_4)_2$ where L= INH-FFL, INH-CIN or INH-TMB and X = $Cl^-,{NO_3}-,\;NCS^-\;or\;CH_3COO^-.$ The thermal behaviour of the complexes were studied using thermogravimetrictechnique. Electronic spectral results and magnetic susceptibility measurements are consistent with the adoption of a six-coordinate geometry for the cobalt(II) chelates. The antimicrobial properties of cobalt(II) complexes and few standard drugs have revealed that the complexes have very moderate antibacterial activities.