• Bulletin of the Korean Chemical Society
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• v.22 no.12
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• pp.1316-1322
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• 2001

Transition metal complexes of novel mono- and di-ferrocene-substituted porphyrins have been synthesized and characterized by structural and electrochemical methods. The X-ray structures of Mn(FPTTP)Cl and Mn(DFTTP)Cl showed the distorted square pyramidal coordination geometry with syn configuration of chloride and ferrocenyl substituents. The electrochemistry of ferrocene-substituted porphyrins and their metal complexes has been determined to elucidate the ${\pi}-conjugation$ effect of the porphyrin ring. The ferrocenyl group of H2FPTTP underwent a reversible one-electron transfer process at 0.30 V, indicating the good electron donating effect of the phorphyrin ring to the ferrocene substituent. The redox potential of the ferrocenyl subunit and porphyrin ring was affected by the central metal ions of the metalloporphyrins, that is, Zn(II) and Ni(II) made the oxidation of ferrocene much easier and Mn(III) made it harder. The ferrocene subunits of H2DFTTP interacted electrochemically with each other with peak splitting of 0.21 V. The strength of the electrochemical interactions between the two ferrocenyl substituents can be controlled by central metal ions of metalloporphyrins.

• Journal of the Korean Chemical Society
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• v.57 no.6
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• pp.721-725
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• 2013

Reaction between 2-pyridinecarboxylic acid (Hpic) and $K_3[Cr(O_2)_4]$ give complex $[Cr(pic)_3].H_2O$ (1) which is characterized by elemental analysis and spectroscopic methods (FT-IR, Raman) and X-ray crystallography. In the crystal structure of 1, chromium atom with coordinated by three nitrogen and three oxygen atoms has a distorted octahedral geometry. Also a water molecule is incorporated in crystal network. Each water molecule acts as hydrogen bond bridging and connects two adjacent complexes by two $O-H{\cdots}O$ hydrogen bonds.

• 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.

• Journal of the Korean Chemical Society
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• v.31 no.3
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• pp.250-257
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• 1987

The electrical conductances for the thorium (IV) complexes with crown ethers have been measured in DMSO, and water solvents, and the oxidation-reduction reaction mechanisms, electron number and diffusion coefficients in the reversible reduction process have been examined by polarography and cyclic voltammography. The dissociation mole ratio of $Th^{4+}$ and nitrate ion are 1:1 and in aprotic solvent, and 1:4 in protic solvent like as water. The limiting molar conductances of all complexes in aprotic solvent have been found to be in the range of $92.2{\times}159$ $ohm^{-1}cm^2mol^{-1}$. In aprotic solvent, DMSO, the reduction of each complex is reversible by one electron reduction of one step, and the range of diffusion coefficients is obserbed to be $5.83\;10^{-6}{\sim}6.90{\times}10^{-6}$. The complexes which have reduction step were hydrolyzed above at 1.8volt with reference saturated calomel electrode, generating the hydrogen gas. The reaction mechanisms of thorium (IV)-crown ether complexes appear as follows. ${Th_m(IV)L_n(H_2O)_x(NO_3)_{4y}}_=^{DMSO} {\overline{{Th_m(IV)L_n(H_2O)_x(NO_3)_{4y-1}}}^+ + NO_3-$

• Nuclear Engineering and Technology
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• v.42 no.5
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• pp.552-561
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• 2010

This study investigates the solubility of neptunium (Np) in the deep natural groundwater of the Korea Atomic Energy Research Institute Underground Research Tunnel (KURT). According to a Pourbaix diagram (pH-$E_h$ diagram) that was calculated using the geochemical modeling program PHREEQC 2.0, the redox potential and the carbonate ion concentration both control the solubility of neptunium. The carbonate effect becomes pronounced when the total carbonate concentration is higher than $1.5\;{\times}\;10^{-2}$ M at $E_h$ = -200 mV and the pH value is 10. Given the assumption that the solubility-limiting stable solid phase is $Np(OH)_4(am)$ under the reducing condition relevant to KURT, the soluble neptunium concentrations were in the range of $1\;{\times}\;10^{-9}$ M to $3\;{\times}\;10^{-9}$ M under natural groundwater conditions. However, the solubility of neptunium, which was calculated with the formation constants of neptunium complexes selected in an OECD-NEA TDB review, strongly deviates from the value measured in natural groundwater. Thus, it is highly recommended that a prediction of neptunium solubility is based on the formation constants of ternary Np(IV) hydroxo-carbonato complexes, even though the presence of those complexes is deficient in terms of the characterization of neptunium species. Based on a comparison of the measurements and calculations of geochemical modeling, the formation constants for the "upper limit" of the Np(IV) hydroxo-carbonato complexes, namely $Np(OH)_y(CO_3)_z^{4-y-2z}$, were appraised as follows: log $K^{\circ}_{122}\;=\;-3.0{\pm}0.5$ for $Np(OH)_2(CO_3)_2^{2-}$, log $K^{\circ}_{131}\;=\;-5.0{\pm}0.5$ for $Np(OH)_3(CO_3)^-$, and log $K^{\circ}_{141}\;=\;-6.0{\pm}0.5$ for $Np(OH)_4(CO_3)^{2-}$.

• Journal of the Korean Chemical Society
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• v.38 no.2
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• pp.160-168
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• 1994

Pentadentate Schiff base molybdenum(Ⅴ) complexes such as [Mo(Ⅴ)O(Sal-DET)(NCS)] and [Mo(Ⅴ)O(Sal-DPT)(NCS)] were synthesized by Sabat method. The structure of these complexes were identified by elemental analysis, spectroscopy, and thermogravimetric analysis(T.G.A.). It was found that the mole ratio of Schiff base ligand to the complexes was found to be 1 : 1. The redox processes of the complexes were investigated by cyclic voltammetric and differential pulse polarographic technique in nonaqueous solvent containing 0. 1 M tetraethyl ammonium perchlorate(TEAP) as supporting electrolyte at glassy carbon electrode. It was found that diffusion controlled reduction processes of four steps with one electron were 2Mo(Ⅴ)$\rightleftarrow^{e-}$ Mo(Ⅴ)Mo(Ⅳ) $\longrightarrow^{e-}$ 2Mo(Ⅳ), Mo(Ⅳ) $\longrightarrow^{e-}$ Mo(Ⅲ) $\longrightarrow^{e-}$ Mo(Ⅱ)

• Analytical Science and Technology
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• v.15 no.2
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• pp.97-101
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• 2002

Co(II) complexes with tridentate Schiff base-NOIPH and tetradentate Schiff base-$NOTDH_2$ and $TNBPH_4$ were synthesized. The redox process of the complexes in DMF solution containing 0.1M TBAP was investigated at glassy carbon electrode by cyclic voltammetry and differential pulse voltammetry techniques. Reduction step of [Co(II)$(NOIP)_2$] and [Co(II)$(H_2O)_2$] complexes were observed in two step as one electron process of irreversible or quasi-reversible and diffusion-controlled reaction. [$Co(II)_2$(TNBP)] complex was observed in one step as one electron process of quasi-reversible and diffusion-controlled reaction.

• Analytical Science and Technology
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• v.13 no.5
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• pp.558-564
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• 2000

Mononuclear schiff base ligand N,N'-bissalicylidene-1,2-phenylenediamine(BSPD) and binuclear schiff base ligands N,N',N',N'''-tetrasalicylidene-3,3',4,4'-tetraaminodiphenyl-methane (TSTM), N,N',N'',N'''-tetrasalicylidene-3,3'-diaminobenzidine (TSDB) have been synthesized. Proton dissociation constants of the ligands were determined by potentiometric method. The synthesized ligands and complexes formed with Cu(II) ion. These complexes were investigated by cyclic voltammetry and differential pulse voltammetry. The results revealed two step diffusion controlled redox process. The mononuclear complex Cu(II)-BSPD and binuclear complexes $Cu(II)_2$-TSDB and $Cu(II)_2$-TSTM were used in the oxidation reaction of ascorbic acid. The reaction rates were in the order of $Cu(II)_2$-TSTM>$Cu(II)_2$-TSDB>Cu(II)-BSPD, indicating that the binuclear $Cu(II)_2$-TSTM complex had the fastest values.

• Journal of the Korean Chemical Society
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• v.39 no.1
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• pp.47-56
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• 1995

Tridentate Schiff base molybdenum(V) complexes such as [Mo(Ⅴ)2O(SOHB)4], [Mo(Ⅴ)2O3(SOIP)2(NCS)2] and [Mo(Ⅴ)2O3(SOTB)2(H20)2](SOHB: Salicylidene-o-imino hydroxybenzene, SOIP; Salicylidene-o-imino pyridine, SOTB; Salicylidene-o-imino thiolbenzene) were synthesized and identified by elemental analysis, spectroscopy, and thermogravimetric analysis (TGA). It was found that the mole ratio of Schiff base ligand to the metal in these complexes is 1 : 1 or 1 : 2. The redox processes of the complexes were investigated by cyclic voltammetric and differential pulse polarographic techniques in nonaquous solvent containing 0.1 M tetraethylammonium perchlorate (TEAP) as supporting electrolyte at glassy carbon electrode. It was found that diffusion controlled reduction processes with one electron were Mo(Ⅴ)Mo(Ⅴ)e-→ Mo(Ⅴ)Mo(Ⅳ)e-→Mo(Ⅳ)Mo(Ⅳ)e-→Mo(Ⅳ)Mo(Ⅲ).

• Analytical Science and Technology
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• v.8 no.4
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• pp.887-894
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• 1995

Toward the development of universal, sensitive, and convenient method of DNA (or RNA) detection, two kinds of electrochemically active DNA ligands. acridine - viologen and oligonucleotide - ferrocene conjugate, were prepared. Thermodynamic and electrochemical study revealed that these probes bound strongly to DNA, and showed a typical cyclic voltammograms, indicating a potential for use as a reversible electrochemical labelling agent for DNA. Especially, using the electrochemically active oligonucleotide, we have been able to demonstrate the detection of DNA at femtomole levels by HPLC equipped with ordinary electrochemical detector (ECD). These results lead to the conclusion that the redox-active probes are very useful for the microanalysis of nucleic acid due to the stabilily of the complexes, high detection sensitivity, and wide applicability to the target structures (single- and double strands) and sequences.