• Journal of the Korean Chemical Society
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• v.35 no.4
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• pp.379-388
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• 1991

We synthesized the binuclear Tetradentate Schiff base cobalt (II) complexes; [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] (where, SMPD: N,N'-bis(salicylaldehyde)-m-phenylenediimine, SPPD: N,N'-bis(salicylaldehyde)-p-phenylenediimine, L: Py, DMSO and DMF). We identified the binuclear structure of these complexes by elemental analysis, IR-spectrum, and T. G. A. According to the results of cyclic voltammetry and DPP measurements in aprotic solvents containing 0.1M TEAP as supporting electrolyte, it was found that diffusionally controlled redox process of two step for one electron was reversible or quasi reversible process in 0.1M TEAP-pyridine and 0.1M TEAP-DMSO solution at mononuclear complexes; [Co(II)(SOPD)(L)$_2$]. But, we knew that diffusionally controlled reduction processes of four steps with one electron for binuclear [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] complexes was Co(III)$_2\;{\longrightarrow^e}$ Co(III)Co(II) ${\longrightarrow^e}$ Co(II)$_2\;{\longrightarrow^e}$ Co(II)Co(I) ${\longrightarrow^e}$ Co(I)$_2$ in aprotic solvents.

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.509-519
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• 1987

The tetradentate Schiff base ligand, 3,4-bis(salicylidene diimine) toluene, have been prepared by the reaction of salicylaldehyde with 3,4-diaminotoluene by Duff method. The Schiff base ligand reacts with Ni(II), Co(II), and Cu(II) ions to form new complexes, [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)$], and [Cu(o-BSDT)]. It seems that Ni(II) and Ni(II) complexes are hexacoordinated with the Schiff base ligand and two molecules of water, while the Cu(II) complexes are tetracoordinated with the Schiff base. The mole ratio of tetradentate Schiff base ligand to metals was found to be 1 : 1. The redox chemistry of these complexes was investigated by polarography and cyclic voltammetry with glassy carbon electrode in DMSO with 0.1M TEAP${\cdot}$[Ni(o-BSDT)${\cdot}(H_2O)_2$] hav EC reaction mechanisms which undergo a irreversible electron transfer followed by a fast chemical reaction. [Co(o-BSDT)${\cdot}(H_2O)_2$] undergoes a reduction of Co(II) to Co(I) and a oxidation of Co(II) to Co(III), and [Cu(o-BSDT)] undergoes a reduction of Cu(II) to Cu(I).

• Journal of the Korean Electrochemical Society
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• v.19 no.2
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• pp.29-38
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• 2016

Screen printed carbon electrodes (SPCEs) with immobilized osmium-based hydrogel redox polymer, uricase and PEGDGE can be used to apply uric acid electrochemical detecting. The osmium redox complexes were synthesized by the coordinating pyridine group having different functional group at 4-position with osmium compounds. The synthesized poly-osmium hydrogel complexes are described as PAA-PVI-$[Os(dCl-bpy)_2Cl]^{+/2+}$, PAA-PVI-$[Os(dme-bpy)_2Cl]^{+/2+}$, PAA-PVI-$[Os(dmo-bpy)_2Cl]^{+/2+}$. The different concentrations of uric acid were measured by cyclic voltammetry technique using enzyme-immobilized SPCEs. The prepared SPCEs using PAA-PVI-$[Os(dme-bpy)_2Cl]^{+/2+}$ showed no interference from common physiologic interferents such as ascorbic acid (AA) or glucose. The resulting electrical currents at 0.33 V vs. Ag/AgCl displayed a good linear response with uric acid concentrations from 1.0 to 5.0 mM. Therefore, this approach allowed the development of a simple, point of care in the medical field, disposable electrochemical uric acid biosensor.

• Journal of Electrochemical Science and Technology
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• v.6 no.3
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• pp.106-110
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• 2015

This study investigates Cu(II) complexes of cyclam, propylene cross-bridged cyclam (PCB-cyclam), and propylene cross-bridged cyclam diacetate (PCB-TE2A) as homogeneous electrocatalysts for CO₂ reduction in comparison with Ni(II)-cyclam. It is found that Cu(II)-cyclam can catalyze CO₂ reduction at the potential close to its thermodynamic value (0.75 V vs. Ag/AgCl) in tris-HCl buffer (pH 8.45) on a glassy carbon electrode. Cu(II)-cyclam, however, suffers from severe demetalation due to the insufficient stability of Cu(I)-cyclam. Cu(II)-PCB-cyclam and Cu(II)-PCB-TE2A are revealed to exhibit much less demetalation behavior, but poor CO₂ reduction activities as well. The inferior electrocatalytic ability of Cu(II)-PCB-cyclam is ascribed to its redox potential that is too high for CO₂ reduction, and that of Cu(II)-PCB-TE2A to the steric hindrance preventing facile contact with CO₂ molecules. This study suggests that in addition to the redox potential and chemical stability, the stereochemical aspect has to be considered in designing efficient electrocatalysts for CO₂ reduction.

• Journal of the Korean Chemical Society
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• v.39 no.3
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• pp.198-203
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• 1995

The Mo(V) $di-\mu-oxo$ type $(Mo_2O_4(H_2O)_2L)$ complexes $(L:\;C_3H_7CH(SCH_2COOH)_2,\;C_6H_5CH(SCH_2COOH)_2,\;CH_3OC_6H_4CH(SCH_2COOH)_2,\;C_5H_{10}C(SCH_2COOH)_2,\;C_3H_7C(CH_3)(SCH_2COOH)_2,\;C_3H_7CH(SCH_2CH_2COOH)_2,\;C_6H_5CH(SCH_2CH_2COOH)_2)$ have been prepared by the reaction of $[Mo_2O_4(H_2O)_6]^{2+}$ with a series of dithiodicarboxy ligands. These complexes are completed by two terminal oxygens arranged trans to one another and each ligand forms a chelate type between two molybdenum. In $Mo_2O_4(H_2O)_2L$, two $H_2O$ coordinated at trans site of terminal oxygens. The prepared complexes have been characterized by elemental analysis, infrared spectra, electronic spectra, and nuclear magnetic resonance spectra. In the potential range -0.00 V to -1.00 V at a scan rate of 20 $mVs^{-1}$, a cathodic peak at -0.50∼-0.58 V (vs. SCE) and an anodic peak at -0.40∼-0.43 V (vs. SCE) have been observed in aquous solution. The ratio of the cathodic to anodic current ($I_{pc}/I_{pa}$) is almost 1, we infer that redox is reversible reaction.

• Bulletin of the Korean Chemical Society
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• v.26 no.10
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• pp.1525-1528
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• 2005

The synthesis and characterization of ${K_3[Ru(C_2O_4)3]{\cdot}4H_2O\;(C_2O_4}^{2-}$ = oxalato anoin) complex are described, and its redox properties (in buffer solution of pH = 12) have been investigated. This complex is used for in situ generation of oxoruthenates complexes which have been characterized by electronic spectroscopy. Reaction of ${K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${S_2O_8}^{2-}$ in molar KOH generates trans-${[RuO_3(OH)_2]^{2-}/S_2O_8}^{2-}$ reagent while with excess ${BrO_3}^-$ in molar $Na_2CO_3$ generates ${[RuO_4]^-/BrO_3}^-$ reagent. Avoiding the direct use of [$RuO_4$] the organic-soluble $(n-Pr_4N)^+[RuO_4]^-$, (TPAP) has been isolated by reaction of $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${BrO_3}^-$ in molar carbonate and n-$Pr_4$NOH. In a mixture of $H_2O/CCl_4$ ruthenium tetraoxide can be generated by reaction of $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${IO_4}^-$. The catalytic activities of oxoruthenates that have been made from $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ towards the oxidation of benzyl alcohol, piperonyl alcohol, benzaldehyde and benzyl amine at room temperature have been studied.

• Journal of the Korean Chemical Society
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• v.37 no.12
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• pp.1053-1059
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• 1993

The determination of iron(Ⅱ), iron(Ⅲ) and total iron was studied by differential-pulse and Tast polarography in 0.1 M acetate buffer solution at pH 4.60, Half wave potentials of iron(Ⅱ)-DTPA and iron(Ⅲ)-DTPA complexes were -0.150V vs. SCE reference electrode. In the presence of DTPA the redox process of iron(Ⅱ) and iron(Ⅲ) was reversible. Linear calibration plots were obtained for iron(Ⅱ) and iron(Ⅲ) concentration of 0.2∼1.0 mM. The detection limits of iron(Ⅱ) and iron(Ⅲ)by Tast polarographic method were 0.05 mM and 0.07 mM, respectively.

• Journal of the Korean Applied Science and Technology
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• v.20 no.2
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• pp.125-129
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• 2003

The effects of molecular structure on the redox properties of the organic electroluminescent materials (Ir$(ppy)_3$ Ir$(m-ppy)_3$ Ir$(p-toly)_3$) were studied using cyclic voltammetry and spectroscopy. These iridium complexes show reversible oxidation and reduction on the electrode, which produce the symmetric cyclic voltammogram. It indicates that these materials are very stable under repetitive oxidation/reduction cycles. The electrochemically determined ionization potentia/electron affinity values are 5.4OeV/3.02eV for Ir$(ppy)_3$, 5.36eV/2.96eV for Ir$(m-ppy)_3$, and 5.35eV/2.97eV for Ir$(p-toly)_3$ from the SCE(Standard Calomel Electrode). The electrically determined band gaps are 2.38eV (521nm), Ir$(ppy)_3$, 2.4OeV (517nm), Ir$(m-ppy)_3$, and 2.38eV (521nm). Ir$(p-toly)_3$, which are similar with the optical band gaps. The position of methyl group on 2-phenylpyridine (ppy) effects do not influence much on the ionization potential, electron affinity, and band gap of Ir$(ppy)_3$ derivatives.

• Bulletin of the Korean Chemical Society
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• v.8 no.4
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• pp.225-230
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• 1987

The redox properties of 2-mercaptopyridine N-oxide (mpno) and its oxovanadium complex, $VO (mpno)_2$ have been studied by the use of polarography and cyclic voltammetry. The radical anion of mpno is generated in acetone and is adsorbed to the electrode to form an adsorption wave at -0.21 V vs Ag/AgCl electrode. The normal wave appeared at -0.50 V is attributed to the formation of radical anion. The $VO (mpno)_2$ exhibits one oxidation wave at +0.57 V, and two reduction waves at -1.07 V and -1.76 V vs. Ag/AgCl electrode; the oxidation is fully reversible one-electron process ($VO (mpno)_2\;{\leftrightarrow}\;VO(mpno)_2^+ + e).$ The reduction wave at -1.07 V is quasireversible and is arised from the formation of $VO (mpno)_2^-.$ The second reduction wave at -1.76 V is irreversible and this reduction process consists of two one-electron steps. The sulfur containing ligands seem to enhance the stability of lower oxidation state of vanadium while the oxygen or nitrogen donor of the ligands stabilize the higher oxidation state of vanadium when comparisons are made among several oxovanadium complexes.

• Journal of the Korean Electrochemical Society
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• v.17 no.1
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• pp.30-36
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• 2014

Redox complexes to transport electrons from enzyme to electrodes are very important part in glucose sensor. Pentacyanoferrate-bound aniline ($Fe(CN)_5$-aminopyridine), was prepared as a potential redox mediator in a glucose dehydrogenase (GDH)-glucose sensor. The synthesized pyridyl-$NH_2$ to pentacyanoferrate was characterized by the electrochemical and spectroscopic methods. A amperometric enzyme-linked electrode was developed based on GDH, which catalyses the oxidation of glucose. Glucose was detected using GDH that was co-immobilized with an $Fe(CN)_5$-aminopyridine and gold nano-particles (AuNPs) on ITO electrodes. The $Fe(CN)_5$-aminopyridine and AuNPs immobilized onto ITO electrodes provided about a two times higher electrochemical response compared to that of a bare ITO electrode. As glucose was catalyzed by wired GDH, the electrical signal was monitored at 0.4 V versus Ag/AgCl by cyclic voltammetry. The anode currents was linearly increased in proportion to the glucose concentration over the 0~10 mM range.