• Title/Summary/Keyword: Donor ligand

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Electronic Spectroscopy and Ligand Field Analysis of mer-[Cr(progly)(2,2-tri)]$CIO_4$

  • Park, Jong-Ha
    • Journal of Photoscience
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    • v.9 no.3
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    • pp.51-55
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    • 2002
  • The 77 K emission and excitation spectra, and 298 K infrared and absorption spectra of [Cr(progly)(2,2-tri)]CIO$_4$[progly=prolylglycinate,2,2-tri=N-(2-aminoethyl)-1,2-ethanediamine] have been measured. The vibrational intervals of the electronic ground state are extracted from emission and infrared spectra. The twelve electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using the observed electronic transitions, a ligand field analysis was performed to determine the metaligand bonding properties for the coordinated atoms. It is found that the carboxylate oxygen of the progly is a strong $\sigma$-and $\pi$-donor while the peptide nitrogen has weak $\pi$-donor property toward chromium(III) ion.

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Electronic Structure and Chemical Reactivity of Transition Metal Complexes (Part 16). A Spectroscopic Study on the Electronic Structure of cis-[Cr(cyclam)$Cl_2$]Cl (전이금속 착물의 전자 구조 및 화학적 반응성 (제 16 보). cis-[Cr(cyclam)$Cl_2$]Cl의 전자 구조에 관한 분광학적 연구)

  • Choi, Jong-Ha
    • Journal of the Korean Chemical Society
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    • v.39 no.7
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    • pp.501-507
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    • 1995
  • The electronic structure of cis-$[Cr(cyclam)Cl_2]Cl$ has been investigated by the emission and excitation spectroscopy at 77K, and infrared and visible spectroscopy at room temperature. The ten electronic transitions due to spin-allowed and spin-forbidden are assigned. The zero-phonon line in the excitation spectrum splits into two components by $139\;cm^{-1}$, and it can be reproduced by modern ligand field theory. According to the results of ligand field analysis, we can confirm that nitrogen atoms of the cyclam ligand have a strong ${\sigma}$-donor character, but chloride ligand has weak ${\sigma}-$ and ${\pi}-$donor properties toward chromium(III) ion.

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Theoretical Study of the Conformation of Cis Carbene-Olefin Transition Matal Complexes (시스 카벤-올레핀 전이금속 착물들의 형태에 대한 이론적 연구)

  • Seong-Kyu Park;Ill-Doo Kim;Joon-Tae Kim;Chang-Jin Choi;Young-Gu Cheun
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.802-811
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    • 1992
  • The conformations of several carbene-olefin-transition metal complexes[$(CO)_4M$-(CHX)olefin] (X: $OCH_3,\;NHCH_3,\;SCH_3$, M: C, Mo, W) have been studied by means of Extend Huckel calculations. In the case of $d^6$ transition metal octahedral complexes, it is shown that the two main factors which determine the optimal conformation are metal-to-ligand back-donation and direct ligand-ligand interaction at the metal, but the ligand-ligand interaction dominates the situation for a metal that is coordinated to $\pi$ acceptor ligands and to $\pi$ donor group on the carbene. The relative amounts of both factors depend strongly on the electronic nature of the ligands at the metal. The greater electron donating ability of nitrogen stabilizes amino-substituted carbene complexes compared with their alkoxyl substituted analogues. This interaction is optimal when the $\pi$ systems of the carbene and olefin are coplanar. The introduction of the $\pi$ donor group on the carbene carbon increases also the importance of the ligand-ligand interaction.

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Spectroscopic, Redox and Biological Studies of Push-Pull Porphyrins and Their Metal Complexes

  • Rajesh, K.;Rahiman, A. Kalilur;Bharathi, K. Shanmuga;Sreedaran, S.;Gangadevi, V.;Narayanan, V.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.9
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    • pp.2656-2664
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    • 2010
  • We have synthesized a series of push-pull porphyrins containing both donor and acceptor substituents at the mesopositions and have examined their spectral and biological properties. The push-pull porphyrins containing both strong donor $NH_2$ and acceptor $NO_2$ at meso-positions, in which donor group condensed with the ligand, (2,6-bis(4-methylpiperazine-1-yl-methyl)-4-formlyphenol (L) to form imine linkages with porphyrin. The Schiff base ligand 5-[4-(2,6-bis(4-methylpiperazine-1-yl-methyl)-4-iminomethylphenol)phenyl]-10,15,20-tris(4-nitrophenyl) porphyrin [$an_3$(TPP)L] can be synthesized from 2,6-bis(4-methylpiperazine-1-yl-methyl)-4-formylphenol (L) and 5-(4-aminophenyl)-10, 15,20-tris(4-nitrophenyl)porphyrin. The push-pull porphyrin [$an_3$(TPP)L] was metallated to get copper, nickel and zinc complexes. The spectral, electrochemical, antibacterial, antifungal and cytotoxicity properties of all the donor- acceptor push-pull porphyrins and their complexes were characterized and studied.

Oxovanadium(IV) Complexes Containing VO(ONS) Basic Core: Synthesis, Structure, and Spectroscopic Properties

  • Jang, Yoon-Jung;Lee, Uk;Koo, Bon-Kweon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.1
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    • pp.72-76
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    • 2005
  • Some mononuclear oxovanadium(IV) complexes having the general formula [VOL(bidentate)] (1-4) of which L is tridentate ONS-donor salicylaldehyde S-methyldithiocarbazate (sal-mdtc$^{2-}$) or salicylaldehyde 4- phenylthiosemicarbazate (sal-phtsc$^{2-}$) and bidentate stands for 2,2'-bipyridyl (bpy) or 1,10-phenanthroline (phen) have been synthesized. The complexes were characterized by elemental analyses, FAB mass, UV, IR spectroscopy, and cyclic voltammetry. Two of the complexes [VO(sal-mdtc)(bpy)] (1) and [VO(sal-mdtc) (phen)] (2) were crystallographically characterized. The structures revealed that vanadium atom is octahedrally coordinated by the O, N, and S donor atoms of the tridentate ligand, the two N atoms of bidentate ligand, and the oxo atom. The oxygen donor, occupying an apical position has a trans-labilizing effect, resulting in elongation of the V-N bond. The cyclic voltammograms of the complexes exhibited one cathodic response in the range −d1.45 $\sim$ −f1.52 V due to the reduction of V(IV) to V(III).

Spectroscopic Properties and Ligand Field Analysis of cis-Dinitrato(1,4,8,11-tetraazacyclotetradecane)chromium(III) Nitrate

  • 최종하
    • Bulletin of the Korean Chemical Society
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    • v.18 no.8
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    • pp.819-823
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    • 1997
  • The luminescence and photoexcitation spectra of cis-[Cr(cyclam)(NO3)2]NO3·½ H2O (cyclam=1,4,8,11-tetraazacyclotetradecane) taken at 77 K are reported. The infrared and visible spectra at room-temperature are also measured. The vibrational intervals of the electronic ground state are extracted from the far-infrared and emission spectra. The ten electronic bands due to spin-allowed and spin-forbidden transitions are assigned. With observed transitions, a ligand field analysis has been performed to determine the bonding property of nitrate group in the chromium(Ⅲ) complex. According to the results, it is found that nitrate ligand has weak σ- and π-donor properties toward chromium(Ⅲ).

Electronic Spectroscopy and Ligand Field Analysis of trans-[CrX2([15]aneN4)]+(X=F,CI) (trans-[CrX2([15]aneN4)]+(X=F,CI)의 전자분광학과 리간드장 해석)

  • Jong-Ha Choi;In-Gyung Oh;Sang Hak Lee;Yu Chul Park
    • Journal of the Korean Chemical Society
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    • v.47 no.2
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    • pp.109-114
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    • 2003
  • The electronic absorption spectra of trans-$[CrX_2([15]aneN_4)]ClO_4\;([15]aneN_4$=1,4,8,12-tetraazacyclopentadecane; X=F, Cl) complexes have been interpreted using the ligand field theory. An AOMX program is used to optimize the differences between the calculated and the observed positions for the spin-allowed transition bands. The crystal field theory(CFT) parameter is directly related to the angular overlap model(AOM), normalized spherical harmonic hamiltonians(NSH), and semiempirical parameters. The various ligand field parameters are discussed in terms of their chemical significances. According to the ligand field analysis, we can confirm that the fluoride ligand is a very strong ${\sigma}-$ and ${\pi}-$donor while the chloride has weak ${\sigma}-$ and ${\pi}-$donor properties toward chromium(III) ion.

EuIII-1-Naphthoate Complex with N-Donor Ligand as a New White Luminescent Single Molecular Material

  • Eom, Yu Kyung;Biju, Silvanose;Kim, Hwan Kyu
    • Rapid Communication in Photoscience
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    • v.2 no.1
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    • pp.34-37
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    • 2013
  • Two novel antenna complexes of $Eu^{III}$ with 1-naphthoic acid (NA) as primary ligand and two aromatic N-donor ligands namely N-hexyl-N-(pyridin-2-yl) pyridin-2-amine (1) and 4-((dipyridin-2-ylamino)methyl)benzoic acid (2) have been synthesized and characterized by various spectroscopic techniques. The room-temperature (298 K) photoluminescence spectrum of $Eu^{III}$ complexes composed of typical line like emissions, assigned to transitions between the first excited state $^5D_0$ to the $^7F_J$ (J = 0-4), resulting in red emission along with the residual emission from the 1-naphthoic acid moiety in the blue region. The determined CIE color coordinate value for the complex 2 is (x = 0.36, y = 0.34), which is in white region.

Synthesis and Crystal Structures of Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) Metal Complexes with NNO Functionalized Ligands

  • Jang, Yoon-Jung;Lee, Uk;Koo, Bon-Kweon
    • Bulletin of the Korean Chemical Society
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    • v.26 no.6
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    • pp.925-929
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    • 2005
  • Some new metal(II) complexes, $M^{II}L_2$ [M = Mn (1), Co (2), Ni (3), Cu (4), and Zn (5)] of 2-acetylpyridine benzoylhydrazone ligand (HL) containing trifunctional NNO-donor system have been synthesized and crystallographically characterized for the complex 1 and 5. The complexes consist of two ligands to give sixcoordinate, which are bonded to the metal atom on a meridional plane through acetylpyridine ring nitrogen, azomethine nitrogen, and benzoyl oxygen atoms, respectively. The coordination geometry for other complexes was identified on the basis of the physicochemical data by elemental analyses, FAB -MS, IR, $^1H$ NMR, and electronic spectral measurements. The resulting data indicated that the complexes are accordance with the above formulation.

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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