• Title/Summary/Keyword: donor atoms

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Spectroscopic Properties and Ligand Field Analysis of Tris[($\pm$)-trans-1,2-cyclohexanediamine]chromium(Ⅲ) Chloride$^1$

  • Jong-Ha Choi
    • Bulletin of the Korean Chemical Society
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    • v.15 no.2
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    • pp.145-150
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    • 1994
  • The low temperature luminescence and excitation, room-temperature UV-visible and infrared spectra of [Cr(${\pm})chxn_3]Cl_3$ (chxn=trans-1,2-cyclohexanediamine) have been measured. It is found that the zero-phonon line in the excitation spectrum splits into two components by $47\;cm^{-1}$. The eight electronic transitions due to spin-allowed and spin-forbidden are assigned. As expected, nitrogen atoms of chxn ligand have strong ${\sigma}-donor $properties toward chromium(Ⅲ). The positions and splittings of sharp-line transitions are analyzed as a function of the Cartesian bite (${\alpha}$) and twist (${\beta}$) angles to predict the metal-ligand geometry.

The Crystal and Molecular Structures of Sulfametrole

  • Koo Chung Hoe;Chung Yong Je;Shin Hyun So;Suh Jung Sun
    • Bulletin of the Korean Chemical Society
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    • v.3 no.1
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    • pp.9-13
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    • 1982
  • Sulfametrole, $C_9H_{10}N_4O_3S_2$, crystallizes in the monoclinic system, space group $P2_1/n$ , with a = 8.145(2), b = 16.505(4), c = 9.637(1)${\AA},{\beta}=103.72(1)^{\circ},D_m=1.52gcm^{-3}$,Z=4.Intensities for 3594(2143 observed) unique reflections were measured on a four-circle diffractometer with Mo $K{\alpha}$ radiation $({\lambda}=0.71069{\AA})$. The structure was solved by direct method and refined by full-matrix least squares to a final R of 0.070. The geometrical features of the thiadiazole ring indicate some ${pi}$-electron delocalization inside the ring. The least squares planes defined by the benzene and thiadiazole rings are nearly perpendicular to each other(dihedral angle; $93.9^{\circ}$ ). All the potential hydrogen-bond donor atoms in the molecule, N(1) and N(2), are included in the hydrogen bonding. The molecules through hydrogen bonding form three dimensional network.

Magnetic and Spectroscopic Studies of some Oxovanadium(IV) Complexes having O = V(O)$_4$ Chromophore

  • Choi, Sung-Nak;Kim, Young-Inn;Shim, Yoon-Bo;Choo, Hi-Shik;Kim, Young-Jin
    • Bulletin of the Korean Chemical Society
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    • v.10 no.2
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    • pp.138-142
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    • 1989
  • Three oxovanadium(IV) complexes with bidentate ligands having only oxygen donor atoms, benzohydroxamic acid (Hben), 8-hydroxyquinoline-N-oxide(Hhqno) and picolinic acid-N-oxide (Hpicn) are prepared and magnetic and spectroscopic properties are investigated for the complexes $VO(ben)_2,\;VO(hqno)_2\;and \;VO(picn)_2.$ Magnetic data together with IR results strongly indicate that dimeric intermolecular interaction is significant in $VO(ben)_2$ while the presence of polymeric V-O${\cdot}{\cdot}$V-O interaction is suggestive in $VO(picn)_2$. For all three complexes, three electronic d-d transitions were observed; extremely strong optical absorption of these bands of $VO(ben)_2$ in DMSO are supposed to be arised from a great metal-ligand covalency. Some fundamental vibration modes of oxovanadium(IV) complexes were empirically assigned from the differences in the spectrum of metal complexes with free ligand.

Fluorescence Intensity Changes for Anthrylazacrown Ethers by Paramagnetic Metal Cations

  • 장정호;김해중;박중희;신영국;정용석
    • Bulletin of the Korean Chemical Society
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    • v.20 no.7
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    • pp.796-800
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    • 1999
  • Three anthrylazacrown ethers in which the anthracene fluorophore π system is separated from the electron donor atoms by one methylene group were synthesized, and their photophysical study was accomplished. These fluorescent compounds showed a maximum fluorescence intensity at pH=5 in aqueous solutions and a decrease in fluorescence intensity upon binding of paramagnetic metal cations (Mn 2+ (d 5 ), Co 2+ (d 7 ), Cu 2+ (d 9 )). The decrease in fluorescence intensity may be attributed to the paramagnetic effect of metal cations to deactivate the excited state by the nonradiative quenching process. The benzylic nitrogen was found to play an important role in changing fluorescence intensity. From the observed linear Stern-Volmer plot and the fluorescence lifetime independence of the presence of metal ions, it was inferred that the chelation enhanced fluorescence quenching (CHEQ) mechanism in the system is a ground state static quenching process. Enhanced fluorescence was also observed when an excess Na + ion was added to the quenched aqueous solution, and it was attributed to cation displacement of a complexed fluorescence quencher.

Synthesis and Characterization of Molybdenum(V) Complexes with Tridentate Schiff Bases

  • Jung Sook Kim;Bon Kweon Koo
    • Bulletin of the Korean Chemical Society
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    • v.13 no.5
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    • pp.507-511
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    • 1992
  • Six-coordinate molybdenum(V) complexes X[MoO$(NCS)_2$(L)], where X=$PyH^+$, $Me_4N^+$, $Et_4N^+$, n-$Bu_4N^+$, and L= the tridentate schiff base dianions derived from the condensation reaction between various salicylaldehydes and 2-aminophenol have been synthesized. The complexes have been characterized by elemental analysis, conductivity, UV-visible, IR, $^1H$-NMR, and mass spectroscopy. The coordination around the molybdenum appears to be distorted octahedral. A tridentate ligand containing the ONO donor atoms occupies meridional positions with the N atom trans to the terminal oxo group. Two NCS ligands bond to the molybdenum through the N atom and are cis to the Mo = $O_t$ group. The electrochemical behaviors of the complexes have also been investigated by cyclic voltammetry in dimethylsulfoxide.

5-Bromo-Ph4-BTPhen Ligand for Selective Removal of Strontium and Cobalt From Water

  • Jang, Jiseon;Harwood, Laurence M.;Cowell, Joe;Afsar, Ashfaq;Lee, Dae Sung
    • Proceedings of the Korean Radioactive Waste Society Conference
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    • 2018.05a
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    • pp.183-183
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    • 2018
  • In this study, 5-bromo-2,9-bis(5,6-diphenyl-1,2,4-triazin-3-yl)-1,10-phenanthroline (5-bromo-Ph4-BTPhen) was synthesized and evaluated for its ability to remove major radionuclides ($Cs^+$, $Sr^{2+}$, and $Co^{2+}$). The synthesized ligand removed both $Sr^{2+}$ and $Co^{2+}$ from $1mg\;L^{-1}$ aqueous solutions with extraction efficiencies of up to 99% at neutral and alkaline pH. The $Sr^{2+}$ and $Co^{2+}$ removal efficiencies decreased as a consequence of the higher bonding strengths of competing metal ions to the N-donor atoms in the cavity of the ligand; competing divalent ions affected the $Sr^{2+}$ and $Co^{2+}$ removal efficiencies more than monovalent ions.

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Syntheses and Spectroscopic properties of Palladium(II) Complexes with Bidentate Aminophosphine of N,N-Dialkyl-N'-diphenylphosphinodiaminoethane

  • Doh, Myung-Ki;Kim, Bong-Gon
    • Bulletin of the Korean Chemical Society
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    • v.9 no.4
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    • pp.198-202
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    • 1988
  • Several new palladium(II) complexes of aminophosphines, $(Pd(L)X_2)$, (L = $Ph_2PNH$ ++ $NR_2$; R = $CH_3(L_1)$, $C_2H_5(L_2)$ : X = Cl, Br, I, and NCS) that contain two different donor atoms of nitrogen and phosphorus as ${\pi}$-electron acceptor, were synthesized and characterized by conductivity measurement, ir, and UV/Vis-spectra. For the dithiocyanatopalladium(II) complexes with aminophosphines, it was confirmed that the thiocyanate group trans to phosphorus is coordinated as Pd-NCS mode and the one trans to nitrogen as Pd-SCN mode, and the aminophosphines form six-membered chelate ring. The spectra of dihalogenopalladium(II) complexes with aminophosphines show that the band maxima are shifted to the short wavelengths as the concentration is decreased.

Alanine and S-Methylcysteine Cobalt (III) Complexes of Ethylenediamine-N,N'-di-${\alpha}$-butyric Acid

  • Moo-Jin Jin;Jio Woo Cheon;Sung Rack Choi
    • Bulletin of the Korean Chemical Society
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    • v.11 no.3
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    • pp.251-253
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    • 1990
  • L-Alanine(L-ala) and S-methyl-L-cysteine(L-mcy) cobalt(III) complexes of a flexible $N_2O_2$-type tetradentate ligand ethylenediamine-N,N'-di- -butyric acid(eddb), s-cis-[Co(eddb)(L-ala)] and s-cis-[Co(eddb)(L-mcy), have been prepared via the substitution reactions of the s-cis-$[Co(eddb)Cl_2]$-complex with, respectively, L-alanine and S-methyl-L-cysteine. Both L-alanine and S-methyl-L-cysteine are found to coordinate to the cobalt(III) ion via the nitrogen and oxygen donor atoms to give the meridional s-cis isomer. Electronic absorption, ir and pmr spectra are used to characterize the complexes obtained in this work along with elemental analysis data.

Synthesis and Characterization of 14-Membered Tetraaza Macrocycles with N-Ethyl Groups and their Nickel(Ⅱ) and Copper(Ⅱ) Complexes

  • Kang Shin-Geol;Kweon Jae Keun
    • Bulletin of the Korean Chemical Society
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    • v.13 no.3
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    • pp.256-259
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    • 1992
  • The 14-membered tetraaza macrocyclic ligand 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradeca-4,11-diene(B) can be synthesized as its dihydroperchlorate salt by the one-pot reaction of 2-ethylaminoethylamine, methylvinyl ketone, and perchloric acid in absolute ethanol. The reaction of Ni(II) or Cu(II) ion and the salt yields $[M(B)]^{2+}$ (M = Ni(II) or Cu(II)), which reacts with $NaBH_4$ to produce $[M(D)]^{2+}$ (D = 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradecane). The complexes $[M(L)]^{2+}$ (L = B or D) have planar geometry and contain two ethyl groups at the donor nitrogen atoms of the ligands. The red solids $[Cu(B)](X)_2(X)$ = $ClO_4-$ or $PF_6^-$) react with water molecules of atmospheric moisture to produce the purple solids in which water molecules are coordinated to the metal ion. Synthesis, characterization, and the properties of the new N-ethylated macrocyclic ligands and their Ni(II) and Cu(II) complexes are reported.

Dichloro, Alanine and S-Methylcysteine Cobalt (III) Complexes of Ethylenediamine-N,N$^\prime$-di-$\alpha$-isobutyric Acid

  • Jun, Moo-Jim;Park, Chang-Woo;Park, Youn-Bong;Cheon, Jin-Woo;Choi, Sung-Rack
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.354-357
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    • 1990
  • Synthesis of dichloro cobalt (Ⅲ) complexes of a flexible $N_2O_2-type$ tetradentate ligand, ethylenediamene-N,N'-di-${\alpha}$-isobutyric acid (eddib), has yielded two geometrical isomers, s-cis-$(Co(eddib)Cl_2)- and uns-cis-(Co(eddib)Cl_2)-.$ A series of substitution reactions, $(Co(eddib)Cl_2)^- {\to} (CO(eddib)Cl H_2O) {\to} (Co(eddib)CO_3)^- {\to} (Co(eddib(H_2O)_2)^+$ have been run for each of the two geometrical isomers. The reaction between the s-cis-(Co(eddib)Cl_2)^-$ complex and L-alanine (L-als) or S-methyl-L-cysteine (L-mcy) gave the meridional s-cis-[Co(eddib)(aa)) (aa = L-ala or L-mcy) complex. The S-methyl-L-cysteine was found to coordinate to cobalt (Ⅲ) ion via the nitrogen and oxygen donor atoms.