• Title/Summary/Keyword: Redox complexes

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Synthesis and Electrochemical Studies of Cu(II) and Ni(II) Complexes with Tetradentate Schiff Base Ligands

  • 조기형;정병구;김정희;전승원;임채평;최용국
    • Bulletin of the Korean Chemical Society
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    • v.18 no.8
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    • pp.850-856
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    • 1997
  • A series of tetradentate Schiff-base ligands; 1,3-bis(salicylideneimino) propane, 1,4-bis(salicylideneimino)butane, and 1,5-bis(salicylideneimino)pentane, and their Cu(Ⅱ) and Ni(Ⅱ) complexes have been synthesized. The properties of ligands and complexes have been characterized by elemental analysis, IR, NMR, UV-Vis spectra, molar conductance, and thermogravimetric anaylsis. The mole ratio of Schiff base to metal at complexes was found to be 1 : 1. All complexes were four-coordinated configuration and non-ionic compound. The electrochemical redox processes of the ligands and their complexes in DMF solution containing 0.1 M TEAP as supporting electrolyte have been investigated by cyclic voltammetry, chronoamperometry, differential pulse voltammetry at glassy carbon electrode, and by controlled potential coulometry at platinum gauze electrode. The redox process of the ligands was highly irreversible, whereas redox process of Cu(Ⅱ) and Ni(Ⅱ) complexes was observed as one electron transfer process of quasi-reversible and diffusion-controlled reaction. Also the electrochemical redox potentials of complexes were affected by chelate ring size of ligands. The diffusion coefficients of Cu(Ⅱ) and Ni(Ⅱ) complexes in DMF solution were determined to be 4.2-6.6×10-6 cm2/sec. Also the exchange rate constants were determined to be 3.6-9.7×10-2 cm/sec.

Synthesis of Several Osmium Redox Complexes and Their Electrochemical Characteristics in Biosensor (오스뮴 착물들의 합성 및 전기화학적인 특성에 관한 연구)

  • Kim, Hyug-Han;Choi, Young-Bong;Tae, Gun-Sik
    • Journal of the Korean Electrochemical Society
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    • v.11 no.3
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    • pp.176-183
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    • 2008
  • Redox complexes to transport electrodes from bioreactors to electrodes are very important part in electrochemical biosensor industry. A novel osmium redox complexes were synthesized by the coordinating pyridine group having different functional group at 4-position with osmium metal. Newly synthesized osmium complexes are described as ${[Os(dme-bpy)}_2{(ap-im)Cl]}^{+/2+}$, ${[Os(dme-bpy)}_2{(ap-im)Cl]}^{+/2+}$, ${[Os(dmo-bpy)}_2{(ap-im)Cl]}^{+/2+}$, ${[Os(dcl-bpy)}_2{(ap-im)Cl]}^{+/2+}$. We have been studied the electrochemical characteristics of these osmium complex with electrochemical techniques such as cyclic voltammetry and chronoamperommetry. Osmium redox complexes were immobilized on the screen printed carbon electrode(SPE) with deposited gold nanoparticles. The electrical signal converts the osmium redox films into an electrocatalyst for glucose oxidation. Each catalytic currents were related with the potentials of osmium complexes.

Synthesis and Electrochemical Studies of Ni(Ⅱ) Complexes with Tetradentate Schiff Base Ligands

  • 정병구;임채평;국성근;조기형;최용국
    • Bulletin of the Korean Chemical Society
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    • v.17 no.2
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    • pp.173-179
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    • 1996
  • A series of tetradentate Schiff base ligands; [1,2-bis(naphthylideneimino)ethane, 1,3-bis(naphthylideneimino)propane, 1,4-bis(naphthylideneimino)butane, and 1,5-bis(naphthylideneimino)pentane] and their Ni(Ⅱ) complexes have been synthesized. The properties of these ligands and their Ni(Ⅱ) complexes have been characterized by elemental analysis, IR, NMR, UV-vis spectra, molar conductance, and thermogravimetric analysis. The mole ratio of Schiff base to Ni(Ⅱ) metal was found to be 1:1. The electrochemical redox process of the ligands and their Ni(Ⅱ) complexes in DMF and DMSO solution containing 0.1 M tetraethyl ammonium perchlorate (TEAP) as a supporting electrolyte have been investigated by cyclic voltammetry, chronoamperometry, differential pulse voltammetry, and controlled potential coulometry at glassy carbon electrode. The redox process of the ligands was highly irreversible, whereas redox process of Ni(Ⅱ) complexes were observed as one electron transfer process in quasi-reversible and diffusion-controlled reaction. The electrochemical redox potentials of the Ni(Ⅱ) complexes were affected by the chelate ring size of ligands. The diffusion coefficients of Ni(Ⅱ) complexes containing 0.1 M TEAP in DMSO solution were determined to be 5.7-6.9 × 10-6 cm2/sec. Also the exchange rate constants were determined to be 1.8-9.5 × 10-2 cm2/sec. These values were affected by the chelate ring size of ligands.

Synthesis and Characterization of Schiff Base-Cu(II) Complexes Derived from 2-Hydroxy-1-Naphthaldehyde and Aliphatic Diamines

  • 정병구;임채령;채희남;조기형;남계춘;최용국
    • Bulletin of the Korean Chemical Society
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    • v.17 no.8
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    • pp.688-693
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    • 1996
  • Tetradentate Schiff base ligands derived from 2-hydroxy-1-naphthaldehyde and aliphatic diamine have been synthesized. Cu(Ⅱ) complexes of Schiff base ligands have been synthesized from the free ligands and copper acetate. The mole ratio of ligand to copper was identified to be 1:1 by the result of elemental analysis and Cu(Ⅱ) complexes were in a four-coordinated configuration. The electrochemical redox process of Cu(Ⅱ) complexes in a DMF solution has been investigated by cyclic voltammetry, chronoamperometry, differential pulse voltammetry, and controlled potential coulometry. The redox process of Cu(Ⅱ) complexes is one electron transfer process in quasi-reversible and diffusion-controlled reaction. The electrochemical redox potentials and the kinetic parameters of Cu(Ⅱ) complexes are affected by the chelate ring of Schiff base ligands.

A Study on the Electronic Properties and Redox Reaction of Palladium(Ⅱ) and Platinum(Ⅱ) Alkylsulfoxide Complexes in Aprotic Solvent [Ⅱ] (비양성자성 용매속에서 Pd(Ⅱ)와 Pt(Ⅱ) 알킬슬폭사이드 착물에 대한 전자적 성질과 산화 · 환원반응에 관한 연구 [Ⅱ])

  • Choe, Chil Nam;Son, Hyo Youl;Kim, Se Bong
    • Journal of the Korean Chemical Society
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    • v.40 no.10
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    • pp.649-655
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    • 1996
  • The chemical behaviour of Pt(Ⅱ) and Pd(Ⅱ) complexes with the organic ligand tetramethylenesulfoxide(TMSO) has been investigated by UV/vis-spectrophotometric, magnetic, and electrochemical methods. Two energy absorption bands are observed in the spectra of these complexes. The crystal field splitting energy, spin pairing energy, and bond strength were obtained from the spectra of the complexes. The electronic properties of the complexes are found to be delocalized, and low-spin state. The correlation between ligand and metals were strong bonding strength. These complexes are diamagnetics. The redox reaction processes of the complexes were investigated by cyclic voltammetry in an aprotic solvent. The redox processes of complexes turned out to be respect to one-electrton one step. These complexes were considerably diffusion and reaction controlled.

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Electrochemical Properties of Oxygen Adducts Tetradentate Schiff Base Cobalt (II) Complexes in Pyridine (Ⅲ) (Pyridine 용액에서 네자리 Schiff Base Cobalt (II) 착물들의 산소첨가 생성물에 대한 전기화학적 성질 (제 3 보))

  • Ky Hyung Cho;Seong Seob Seo;Dong Chul Chon
    • Journal of the Korean Chemical Society
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    • v.33 no.3
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    • pp.295-303
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    • 1989
  • Tetradentate Schiff base cobalt(II) complex; Co(SND) and Co(SOPD) were synthesized, and these complexes were allowed to react with dry oxygen to form oxygen adducts cobalt(III) complexes such as $[Co(SND)(Py)]_2O_2$ and $[Co(SOPD)(Py)]_2O_2$ in pyridine. These complexes have been identified by IR specta, T.G.A., magnetic susceptibilities measurements and elemental analysis. It has been found that the oxygen adducts coblat(III) complexes have hexacoordinated octahedral configuration with tetradentate Schiff base cobalt(II), pyridine and oxygen, and the mole ratio of oxygen to cobalt(II) complexes are 1;2. The redox reaction processes of $Co(SND)(Py)_2$ and $Co(SOPD)(Py)_2$ complexes were investigated by cyclic voltammetry with glassy carbon electrode in 0.1M TEAP pyridine. The result of redox reaction processes of Co(III)/Co(II) and Co(II)/Co(I) for $Co(SND)(Py)_2$ and $Co(SOPD)(Py)_2$ complexes are reversible or quasi reversible process but oxygen adducts complexes are irreversible processes. Redox process for oxygen of oxygen adducts complexes was quasi reversible and redox range of potential was $E_{pc}\;=\;-0.96{\sim}-1.03V$ and $E_{pa}\;=\;-0.78{\sim}-0.80V.$

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A Study on the Electronic Properties and Redox Reaction of Europium(Ⅲ) Complexes in Aprotic Solvent (반 양성자성 용매속에서 Europium(Ⅲ) 착물에 대한 전자적 성질과 산화 · 환원 반응에 관한 연구)

  • Choe, Chil Nam;Son, Hyo Youl;Kim, Se Bong
    • Journal of the Korean Chemical Society
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    • v.40 no.1
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    • pp.65-71
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    • 1996
  • The chemical behaviour of the Eu(Ⅲ) complexes with organic ligands(tris[3-(trifluoromethylhydroxymethylene-camphorato)]) and tris[3-heptafluoropropylhydroxymethylene-camphorato)] has been investigated by the UV/vis-spectrophotometric, magnetic, and electrochemcial methods. The two or three energy absorption bands are observed by the spectra of these complexes. The magnitude of crystal field splitting energy, the spin pair energy and strength were obtained from the spectra of the complexes. These complexes are found to be delocalization, low-spin state, and strong bonding strenth of electron configuration. The magnetic dipolemoment are found to be diamagnetic. The redox reaction processes of complexes were investigated by cyclic voltammetry in aprotic solvent. The redox reaction processes of complexes are turned out to be single or double reaction with respect to one electron diffusion current.

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Synthesis of Osmium Redox Complex and Its Application for Biosensor Using an Electrochemical Method (오스뮴 착물 합성과 전기화학적인 방법을 이용한 바이오센서에 관한 연구)

  • Choi, Young-Bong;Kim, Hyug-Han
    • Journal of the Korean Electrochemical Society
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    • v.10 no.2
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    • pp.150-154
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    • 2007
  • Redox complexes to transport electrodes from biomaterial to electrodes are very important part in commercial biosensor industry. A novel osmium redox complex was synthesized by the coordinating pyridine group with osmium metal. A novel osmium complex is described as $[Os(dme-bpy)_2(ap-im)Cl]^{+/2+}$. We have been studied the electrochemical characteristics of this osmium complex with electrochemical techniques such as cyclic voltammetry and chronoamperommetry. In order to immobilize osmium redox complexes on the electrode, we deposited gold nano-particles on screen printed carbon electrode(SPE). The electrical signal converts the osmium redox films into an electrocatalyst for glucose oxidation. The catalytic currents were monitored that the catalytic currents were linearly increased from 1 mM to 5 mM concentrations of glucose.

Electrochemical Behaviors of Sparteine-Copper (II) Dihalide

  • Sung-Nak Choi;Jin-Hyo Park;Young-In Kim;Yoon-Bo Shim
    • Bulletin of the Korean Chemical Society
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    • v.12 no.3
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    • pp.276-281
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    • 1991
  • Electrochemical behaviors of optically active sparteine-Cu(II) dihalide complexes were investigated by polarography and cyclic voltammetry (CV). These Cu(II) complexes are rather easier to be reduced to Cu(I) states when comparison is made with other nonplaner copper complexes, We have assigned the CV peaks and polarographic waves related to the redox processes for these complexes. We could also observe the exchange reaction of Cu(II) ion in the complex with mercury metal in the cell having mercury pool. The redox mechanism of these complelxes is as follows; The 1st wave appeared at +0.47 V/+0.65 V corresponds to the reaction of $SpCuX_2+ e{\rightleftarrow}SpCuX_{2^-}$ and the 2nd one at +0.26 V/+0.21 V does the reaction of $SpCuX_{2 ^-} +e{\rightleftarrow}SpCuX_2^{2-}$. The 3rd one at -0.35 V/-0.27 V is dueto the reduction of mercury complex formed via exchange reaction. Where, X is chloride ion.