• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4321-4326
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• 2011

A new series of heteroleptic cyclometalated iridium(III) complexes has been synthesized and characterized by absorption, emission and cyclic voltammetry studies: $(pqx)_2Ir(acac)$ (1), $(dmpqx)_2Ir(acac)$ (2) and $(dfpqx)_2Ir(acac)$ (3) where pqx=2-phenylquinoxalinate, dmpqx=2-(2,4-dimethoxyphenyl)quinoxalinate, dfpqx=2-(2,4-difluorophenyl) quinoxalinate and acac=acetylacetonate anion. The reaction of excess acetylacetone with ${\mu}$-chloride-bridged dimeric iridium complex, $[(C\^N)_2Ir({\mu}-Cl)]_2$, gives a complex 1 and an unusual hydridoiridium(III) complex, $(pqx)IrH(acac)_2$ (4). The complex 1, 2 and 3 show their emissions in an orangered region (${\lambda}_{PL,max}$ = 583-616 nm), and the emission maxima can be tuned by the change of substituent at phenyl ring of 2-phenylquinoxaline ligand. The phosphorescent line shape indicates that the emissions originate predominantly from $^3MLCT$ states with little admixture of ligand-based $^3({\pi}-{\pi}^*)$ excited states. The structures of complex 3 and 4 are additionally characterized by a single crystal X-ray diffraction method. The complex 3 shows a distorted octahedral geometry around iridium(III) metal ion. A strong trans influence of the phenyl ring is examined. In complex 4, there are two discrete molecules which are mirror images each other at the ratio of 1:1 in an unit cell. We propose that the phosphorescent complex 1, 2 and 3 are possible candidates for the phosphors in OLEDs applications.

• Journal of the Korean Chemical Society
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• v.55 no.2
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• pp.199-203
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• 2011

The title one-dimensional hydrogen-bonded coordination compound $[Cu^{II}(C_{13}H_{17}N_3OBr)(C_8H_5O_4)]{\cdot}2H_2O.CH_3OH$ has been synthesized and characterized by single crystal X-ray diffraction study. The monomeric unit contains a square-planar $Cu^{II}$ centre. The four coordination sites are occupied by a tridentate anionic Schiff base ligand (4-bromo-2-[(2-piperazin-1-yl-ethylimino)-methyl]-phenol) which furnishes an $N_2O$-donor set, with the fourth position being occupied by the oxygen atom of an adjacent terephthalate unit. Two adjacent neutral molecules are linked through intermolecular N-H---O and O-H---N hydrogen bonds and generate a dimeric pair. Each dimeric pair is connected with each other via discrete water and methanol molecules by hydrogen bonding to form a one-dimensional supramolecular network.

• Journal of Powder Materials
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• v.30 no.1
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• pp.53-64
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• 2023

Atomic layer etching (ALE) is a promising technique with atomic-level thickness controllability and high selectivity based on self-limiting surface reactions. ALE is performed by sequential exposure of the film surface to reactants, which results in surface modification and release of volatile species. Among the various ALE methods, thermal ALE involves a thermally activated reaction by employing gas species to release the modified surface without using energetic species, such as accelerated ions and neutral beams. In this study, the basic principle and surface reaction mechanisms of thermal ALE?processes, including "fluorination-ligand exchange reaction", "conversion-etch reaction", "conversion-fluorination reaction", "oxidation-fluorination reaction", "oxidation-ligand exchange reaction", and "oxidation-conversion-fluorination reaction" are described. In addition, the reported thermal ALE processes for the removal of various oxides, metals, and nitrides are presented.

• Journal of the Korean Chemical Society
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• v.55 no.3
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• pp.418-429
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• 2011

Novel chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), ruthenium(III), and zirconyl(II) complexes of $N^1,N^2$-bis(3-((3-hydroxynaphthalen-2-yl)methylene-amino)propyl)phthalamide ($H_4L$, 1) have been synthesized and characterized by elemental, physical, and spectral analyses. The spectral data showed that the ligand behaves as either neutral tridentate ligand as in complexes 2-5 with the general formula $[H_4LMX_2(H_2O)]{\cdot}nH_2O$ (M=Cu(II), Ni(II), Co(II), X = Cl or $NO_3$), neutral hexadentate ligand as in complexes 10-12 with the general formula $[H_4LM_2Cl_6]{\cdot}nH_2O$ (M=Fe(III), Cr(III) or Ru(III)), or dibasic hexadentate ligand as in complexes 6-9 with the general formula $[H_2LM_2Cl_2(H_2O)_4]{\cdot}nH_2O$ (M = Cu(II), Ni(II), Co(II) or Mn(II), and 13 with general formula $[H_4L(ZrO)_2Cl_2]{\cdot}8H_2O$. Molar conductance in DMF solution indicated the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complexes 2, 5, and 6 showed $g_{\parallel}$ >g> $g_e$, indicating distorted octahedral structure and the presence of the unpaired electron in the $N^1,N^2$ orbital with significant covalent bond character. For the dimeric copper(II) complex $[H_2LCu_2Cl_2(H_2O)_4]{\cdot}3H_2O$ (6), the distance between the two copper centers was calculated using field zero splitting parameter for the parallel component that was estimated from the ESR spectrum. The antibacterial and antifungal activities of the compounds showed that, some of metal complexes exhibited a greater inhibitory effect than standard drug as tetracycline (bacteria) and Amphotricene B (fungi).

• Bulletin of the Korean Chemical Society
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• v.14 no.2
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• pp.195-200
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• 1993

The neutral, reduced, and oxidized 2,2-trans isomers of $Rh_2(ap)_4$ (ap=2-anilinopyridinate) were investigated with respect to dioxygen binding in $CH_2Cl_2$ containing 0.1 M tetrabutyl-ammonium perchlorate. $Rh_2(ap)_4$ binds dioxygen in nonaqueous media and forms a $Rh^{II}Rh^{III}$ superoxide complex, $Rh_2(ap)_4(O_2)$. This neutral species was isolated and is characterized by UV-visible and IR spectroscopy, mass spectrometry and cyclic voltammetry. It can be reduced by one electron at $E_{1/2}$ = -0.45 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^-$ as demonstrated by the ESR spectrum of a frozen solution taken after controlled potential reduction. The superoxide ion in ${[Rh_2(ap)_4(O_2)]}^-$ is axially bound to one of the two rhodium ions, both of which are in a +2 oxidation state. $Rh_2(ap)_4(O_2)$ can also be stepwise oxidized in two one-electron transfer steps at $E_{1/2}$ = 0.21 V and 0.85 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^+$ followed by ${[Rh_2(ap)_4(O_2)]}^{2+}$. ESR spectra demonstrate that the singly oxidized complex is best described as ${[Rh^{II}Rh^{III}(ap)_4(O_2)]}^+$ where the odd electron is delocalized on both of the two rhodium ions and the axial ligand is molecular oxygen.

• Journal of Korean Society of Environmental Engineers
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• v.31 no.5
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• pp.352-357
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• 2009

Due to rapid consumption of hydrogen peroxide, large amount of hydrogen peroxide is required when Fenton reaction is applied to the contaminated soil. In this study, acetate was employed as a ligand of $Fe^{2+}$ to enhance the efficiency of removal of phenanthrene by securing the stability of hydrogen peroxide. 0.5 ${\sim}$ 3 times of acetate (2${\sim}$12mM) was added to compare with molar concentration of $Fe^{2+}$. Low initial concentration of hydrogen peroxide was 0.7% to eliminate side effect of removal efficiency. The results showed that hydrogen peroxide lifetime was lasted up to 72 hours, or more than 50 times of normal lifetime. Phenanthrene removal efficiency was improved up to 70% due to stabilized hydrogen peroxide. Ferrous ion was oxidized to ferric ion and oxidation-reduction was repeated during the reaction. Finally ferric ion was reduced to ferrous by $HO_2$. It was confirmed that, due to the influence of hydrogen peroxide, pH was acid region and it remained at the range of 4 ${\sim}$ 5 when 8 mM or more of acetate was added. Acetate which was used as the ligand of Fe was also decomposed by Fenton reaction. The decomposition time of acetate was slower than phenanthrene. Therefore, it was able to come to the conclusion that phenanthrene was superior to acetate at the competition for decomposition. Through the results of this study, it was able to identify the possibilities to improve the efficiency of Fenton reaction in the contaminated soil and its economic feasibility, and to move to more realistic technique through research expanded to neutral pH region.

• Bulletin of the Korean Chemical Society
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• v.27 no.6
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• pp.899-902
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• 2006

The complexation of N,N'-4,5-(ethylenedioxy)benzenebis(salicylideneimine), (salphen$H_2$) with uranyl ion was studied in acetonitrile solution spectrophtometrically, and the formation constant of the resulting 1 : 1 complex was evaluated. The salphen$H_2$ ligand was used as an ionophore in plasticized poly(vinyl chloride) (PVC) matrix membrane sensor for uranyl ion. The prepared sensors exhibited a near Nernstian response, 28.0-30.9 mV/decade for uranyl ion over the concentration range $1.0\;{\times}\;10^{-2}$ to $1.0\;{\times}\;10^{-6}$M with a limit of detection of $3.2\;{\times}\;10^{-7}$ M. The proposed electrode could be used at a working pH range of 1.5 - 4.0.

• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3420-3424
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• 2013

The reaction of $LnCl_3{\cdot}7H_2O$ [Ln = La (1), Ce (2)] with salicylic acid (HL) and 1,10-phenanthroline (Phen) at $20^{\circ}C$ in $H_2O$/ethanol gave after work-up and recrystallization two novel lanthanide complexes with general formula $[Ln(Phen)_2(L)_3(HL)]{\cdot}H_2O$. Compounds 1 and 2 were characterized by IR and UV-Vis spectroscopy, TGA, CHN as well as by X-ray analysis. According to these results, compounds 1 and 2 are isostructural and contain $Ln^{3+}$ ions with coordination number nine. Complexes 1 and 2 consist of two Phen, one neutral HL and three L anions (two L anions act as monodentate ligands and the third one is chelating to $Ln^{3+}$). Thermal decomposition led to primary loss of the Phen molecules. Then HL molecules and finally L moieties left the material to give $Ln_2O_3$.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1603-1606
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• 2009

A new 1D oxalato bridged compound Ni(en)(ox)-2$H_2$O, (ox = oxalate; en = ethylenediamine) has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum, TG analysis, and magnetic measurements. In the structure the Ni atoms are coordinated with four oxygen atoms in two oxalate ions and two nitrogen atoms in one ethylenediamine molecule. The oxalate anion acts as a bis-bidentate ligand bridging Ni atoms in cis-configuration. This completes the infinite zigzag neutral chain, [Ni(en)(ox)]. The interchain space is filled by water molecules that link the chains through a network of hydrogen bonds. Thermal variance of the magnetic susceptibility shows a broad maximum around 50 K characteristic of one-dimensional antiferromagnetic coupling. The theoretical fit of the data for T > 20 K led to the nearest neighbor spin interaction J = -43 K and g = 2.25. The rapid decrease in susceptibility below 20 K indicate this compound to be a likely Haldane gap candidate material with S = 1.

• Bulletin of the Korean Chemical Society
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• v.13 no.5
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• pp.498-503
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• 1992

The protonation of RuH(NO)(Cyttp) resulted in the formation of $[RuH_2(NO)(Cyttp)]^+$ which is characterized as a classical cis-dihydried complex. This complex is fluxional and the intramolecular process involving a molecular hydrogen complex is proposed. This mechanism was further supported by the reactivity of this complex toward neutral 2-electron ligands. On the other hand, it failed to detect the existence of $[RuH_2(NO)(etp)]^+$ probably due to instability of the complex but the crystal structure of $[Ru(PMe_3)(NO)(etp)]^+$ formed by the protonation of RuH(NO)(etp) followed by the addition of $PMe_3$ was determined to have a trigonal bipyramidal structure with a linear NO in the equatorial plane and a facial etp ligand. The crystals are monoclinic, space group P21/n, with unit cell dimensions a = 14.130(2), b = 21.026 (3), c = 14.760 (1) ${\AA}$, ${\beta}$ = 97.88 $(l)^{\circ}$ V = 4344 ${\AA}^3$, Z = 4, R = 0.046 and $R_w$ = 0.056 for the 4779 intensities with $F_o^2 > 3{\sigma}(F_0^2)$ and the 440 variables.