• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.709-719
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• 1992

We synthesized the binuclear tetradentate Schiff base cobalt(II), nickel(II) and copper(II) complexes such as [Co(II)_2(TSBP)(L)_4], [Ni(II)_2(TSBP)(II)_4] and [Cu(II)_2(TSBP)] (TSBP: 3,3',4,4'-tetra(salicylideneimino)-1,1'-biphenyl, L: Py, DMSO and DMF). We identified the binucleated structure of these complexes by elemental analysis, IR-spectrum, UV-visible spectrum, T.G.A. and D.S.C. According to the results for cyclic voltammogram and differential pulse polarogram of 1 mM complexes in nonaqueous solvents included 0.1M TEAP-L (L; Py, DMSO and DMF) as supporting electrolyte, it was found that diffusionally controlled redox processes of four steps through with one electron for binucleated Schiff base Cobalt(II) complex was Co(III)_2 {^\longrightarrow \\_\longleftarrow^e^-}Co(III)Co(II)_2{^\longrightarrow \\_\longleftarrow^e^-}Co(II){^\longrightarrow \\_\longleftarrow^e^-}Co(I){^\longrightarrow \\_\longleftarrow^e^-}Co(I)_2 and two steps with one electron for Nickel(II) and Copper(II) complexes were M(II)_2 {^\longrightarrow \\_\longleftarrow^e^-}M(I)M(I){^\longrightarrow \\_\longleftarrow^e^-}M(I)_2 (M; Ni and Cu) in nonaqueous solvents.

• Journal of the Mineralogical Society of Korea
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• v.24 no.2
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• pp.73-82
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• 2011

X-ray absorption spectroscopy (XAS) study was conducted using arsenite-sorbed two-line ferrihydrite to investigate the mechanism of surface interactions between two-line ferrihydrite and As(III) (arsenite) which are ubiquitous in nature. The two-line ferrihydrite used was synthesized in the laboratory and the study was undertaken at pHs 4 and 10 to compare the difference in mechanisms of surface interaction between acidic and alkaline environments. The effect of arsenite-adsorbed concentrations on surface complexation was investigated at each pH condition as well. From the results of XAS analyses, the structural parameters of arsenite in the EXAFS revealed that the coordination number and distanceof As-O were 3.1~3.3 and 1.74~1.79 ${\AA}$, respectively, which indicate that the unit structure of arsenite complex formed on the surface of two-line ferrihydrite is $AsO_3$. The dominant structures of As(III)-Fe complex were examined to be bidentate binuclear comer-sharing ($^2C$) and the mixture of bidentate mononuclear edge sharing ($^2E$) and $^2C$ appeared as well. At pH 4, arsenite complex showed different structures on the surface of two-line ferrihydrite, depending on the adsorbed concentrations. At pH 10, on the contrary, the surface structures of arsenite complexes were interpreted to be almost identical, irrespective of the adsorbed concentrations of arsenite. Consequently, this microscopic XAS results support the results of macroscopic adsorption experiments in which the surface interaction between arsenite and two-line ferrihydrite is significantly influenced by pH conditions as well as arsenite concentrations.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.2117-2124
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• 2013

The binding properties and sequence selectivities of ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ (bip = 4,4'-biphenylene (imidazo [4,4-f][1,10]phenanthroline) complexes with $poly[d(A-T)_2]$ and $poly[d(G-C)_2]$ were investigated using conventional spectroscopic methods. When bound to $poly[d(A-T)_2]$, a large positive circular dichroism (CD) spectrum was induced in absorption region of the bridging moiety for both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes, which suggested that the bridging moiety sits in the minor groove of the polynucleotide. As luminescence intensity increased, decay times became longer and complexes were well-protected from the negatively charged iodide quencher compared to that in the absence of $poly[d(A-T)_2]$. These luminescence measurements indicated that Ru(II) enantiomers were in a less polar environment compared to that in water and supported by minor groove binding. An angle of $45^{\circ}$ between the molecular plane of the bridging moiety of the ${\Delta}{\Delta}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex and the local DNA helix axis calculated from reduced linear dichroism ($LD^r$) spectrum further supported the minor groove binding mode. In the case of ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex, this angle was $55^{\circ}$, suggesting a tilt of DNA stem near the binding site and bridging moiety sit in the minor groove of the $poly[d(A-T)_2]$. In contrast, neither ${\Delta}{\Delta}$-nor ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complex produced significant CD or $LD^r$ signal in the absorption region of the bridging moiety. Luminescence measurements revealed that both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes were partially accessible to the $I^-$ quencher. Furthermore, decay times became shorter when bis-Ru(II) complexes bound to $poly[d(G-C)_2]$. These observations suggest that both the ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ complexes bind at the surface of $poly[d(G-C)_2]$, probably electrostatically to phosphate group. The results indicate that ${\Delta}{\Delta}$- and ${\Lambda}{\Lambda}-[{\mu}-Ru_2(phen)_4(bip)]^{4+}$ are able to discriminate between AT and GC base pairs.

• Journal of the Korean Chemical Society
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• v.33 no.5
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• pp.484-495
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• 1989

Reactions of $(Et_4N)_2[MoOCl_5]$ with multidentate ligands containing nitrogen or/and oxygen donor atom (EDTA, DTPA, IDA, CyDTA, OX) produce a series of binuclear molybdate (V) complexes. The prepared Mo (V) complexes has been identified by Elemental Analysis, Infrared Spectra, Proton Magnetic Resonance Spectra, and Electronic Spectra. The electrochemical reduction mechanism has been studied by Cyclic voltammetry, Controlled Potential Coulometry, and Spectrophotometry in pH 3.571-10.375 acetate, borate, phosphate/sodium hydroxide, phosphate, ammonium/ammonia buffers. The cyclic voltammogram of the Mo-EDTA, DTPA, IDA, CyDTA complexes at pH < ca. 6.00 have shown two reduction waves. The first reduction wave shows two electron process and the second reduction wave shows two electron process. The cyclic voltammogram of the Mo-EDTA, DTPA, IDA, CyDTA complexes at pH < ca. 8.00 has shown one reduction wave. This reduction wave show four electron process. The cyclic voltammogram of the Mo-OX complex at pH < ca. 7.2 has shown one reduction wave. This reduction wave show four electron process.

• Journal of the Korean Chemical Society
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• v.55 no.1
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• pp.38-45
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• 2011

The complexation behavior of the $\alpha$-ketostabilized phosphorus ylides $Ph_3P$=CHC(O) $C_6H_4-X$ (X=Br, Ph) towards the transition metal ions mercury (II) and Silver (I) was investigated. The mercury(II) complex {$HgX_2$ [Y]} 2 ($Y_1$=4-bromo benzoyl methylene triphenyl phosphorane; X=Cl(1), Br(2), I(3), $Y_2$=4-phenyl benzoyl methylene triphenyl phosphorane; X=Cl(4), Br(5), I(6)) have been prepared from the reaction of $Y_1$ and $Y_2$ with $HgX_2$ (X=Cl, Br, I) respectively. Silver complexes [$Ag(Y_2)_2]$ X(X=$BF_4$(7), OTf(8)) of the $\alpha$-keto-stabilized phosphorus ylides ($Y_2$) were obtained by reacting this ylide with AgX (X=$BF_4$, OTf) in $Me_2CO$. The crystal structure of complexes (1) and (4) was discussed. These reactions led to binuclear complexes C-coordination of ylide and trans-like structure of complexes $[Y_1HgCl_2]_2$. $CHCl_3$ (1) and $[Y_2HgCl_2]_2$ (4) is demonstrated by single crystal X-ray analyses. Not only all of complexes have been studied by IR, $^1H$ and $^{31}P$ NMR spectroscopy, but also complexes 1-3 have been characterized by $^{13}$CNMR.