• Journal of the Korean Ceramic Society
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• v.35 no.8
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• pp.783-790
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• 1998

The characterization of the complexation reaction of PVA and Al(III) ion at different pH and the sint-ering behaviour of UO2 containing the PVA-Al(III) complexes were investigated. Compared with pure PVA powder the complexed PVA-Al(III) powder had compacter shape and lower decomposition temperature The major phase of PVA-Al(III) complex decomposed at 90$0^{\circ}C$ was $\alpha$-Al2O3 The PVA-Al(III) complex formed at pH 9 had the lowest relative viscosity the highest Al content of 36% and the smallest particle size of 19${\mu}{\textrm}{m}$ While the pure UO2 pellet appeared with bimodal one. The grain size of the pure UO2 pellet was 7${\mu}{\textrm}{m}$ but that of the PVA-Al(III) complex added UO2 pellet was increased up to 36${\mu}{\textrm}{m}$ The largest grain size was ob-tained when the PVA-Al(III) complex formed at pH9 was added and the PVA-Al(III) complex formed at pH 11 had the greatest effect on increasing pore size.

• Journal of the Korean Ceramic Society
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• v.36 no.8
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• pp.782-790
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• 1999

The compressibility sinterability sintering behaviour and thermal stability of AlOOH added UO2 pellt and PVA-Al(III) complex added UO2 pellet were investigated respectively. Compared with characteristics of AlOOH added UO2 pellet the green density and the sintered density of PVA-Al(III) complex added UO2 pellet were lowered but the grain size and the pore size of that were more increased in accordance with higher compacting pressure. The AlOOH added UO2 pellet had the grain size of about 14${\mu}{\textrm}{m}$ with monomodal pore size distribution while the PVA-Al(III) complex added UO2 pellet had the grain size of about 42 ${\mu}{\textrm}{m}$ with bimodal pore size distribution. The PVA-A(III) complex added UO2 pellet had a similiar open porosity to the AlOOH added UO2 pellet and a lower resintered density change than the AlOOH added UO2 pellet.

• Bulletin of the Korean Chemical Society
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• v.21 no.1
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• pp.65-68
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• 2000

A $\mu-oxo$ diiron(III) complex and two bis( $\mu-alkoxo)$ diiron(III) complexes with biomimetic tripodal ligand containing mixed N/O donor atoms were synthesized using a mononuclear iron(III) complex as starting material. Depending on the amounts and kinds of bases used, we obtained various kinds of diiron (III) complexes. The reaction of $[$Fe^{III}$(Hbbea)Cl_2]Cl$, 1, with an equivalent amount of $KO_2$ or NaOAc produced $[$Fe^{III}$_2O(Hb-bea)_2Cl_2]Cl_2$, 2. An additional equivalent amount of NaOBz or NaOAc converts complex 2 to complex 3 or complex 4 depending on the base used. The addition of two equivalent amounts of NaOBz orNaOAc directly converts complex 1 to $[$Fe^{III}$_2(bbea)_2(OBz)_2]Cl_2$, 3, or $[$Fe^{III}$_2(bbea)_2(OAc)_2]Cl_2$, 4, depending on the base used. Crystal data are as follows: [$Fe^{III}_2O(Hbbea)_2Cl_2]Cl_2$, 2: monoclinic space group $$P2_1/n$$, a = 8.421 (1) $\AA$, b = 18.416 (2) $\AA$, c = 13.736 (1) $\AA$, $\beta$ = 104.870 $(7)^{\circ}$, V = 2058.9 (4) $\AA^3$, Z = 2, R1 = 0.0469 and wR2 = 0.1201 for reflections with I > 2 ${\sigma}$(I).

• Bulletin of the Korean Chemical Society
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• v.19 no.6
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• pp.654-660
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• 1998

$[Fe^{II}Fe^{III}BPLMP(OAc)_2](BPh_4)_2$ (1), a new model for the reduced form of the purple acid phosphatases, has been synthesized by using a dinucleating ligand, 2,6-bis[((2-pyridylmethyl)(6-methyl-2-pyridylmethyl)amino) methyl]-4-methylphenol (HBPLMP). Complex I has been characterized by X-ray diffraction method as having (μ-phenoxo)bis(acetato)diiron core. Complex 1 was crystallized in the monoclinic space group C2/c with the following cell parameters: a=41.620(6) Å, b=14.020(3) Å, c=27.007(4) Å, β=90.60(2)°, and Z=8. The iron centers in the complex 1 are ordered as indicated by the difference in the Fe-O bond lengths which match well with typical $Fe^{III}-O\; and\; Fe^{II}-O$ bond lengths. Complex 1 has been studied by electronic spectral, NMR, EPR, SQUID, and electochemical methods. Complex 1 exhibits strong bands at 592 nm, 1380 nm in $CH_3CN$ (ε = 1.0 × 103 , 3.0 × 102). These are assigned to $phenolate-to-Fe^{III}$ and intervalence charge-transfer transitions, respectively. Its NMR spectrum exhibits sharp isotropically shifted resonances, which number half of those expected for a valence-trapped species, indicating that electron transfer between $Fe^{II}\;and\;Fe^{III}$ centers is faster than NMR time scale. This complex undergoes quasireversible one-electron redox processes. The $Fe^{III}_2/Fe^{II}Fe^{III}\;and\;Fe^{II}Fe^{III}/Fe^{II}_2$ redox couples are at 0.655 and -0.085 V vs SCE, respectively. It has $K_{comp}=3.3{\times}10^{12}$ representing that BPLMP/bis(acetate) ligand combination stabilizes a mixed-valence $Fe^{II}Fe^{III}$ complex in the air. Complex 1 exhibits a broad EPR signal centered near g=1.55 which is a characteristic feature of the antiferromagnetically coupled high-spin $Fe^{II}Fe^{III}$ system $(S_{total}=1/2)$. This is consistent with the magnetic susceptibility study showing the weak antiferromagnetic coupling $(J= - 4.6\;cm^{-1},\; H= - 2JS_1{\cdot}S2)$ between $Fe^{II}\; and \;Fe^{III}$center.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.923-928
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• 2000

[FeIII(BBA)DBC]ClO4 as a new functional model for catechol dioxygenases has been synthesized, where BBA is a bis(benzimidazolyl-2-methyl)amine and DBC is a 3,5-di-tert-butylcatecholate dianion.The BBA complex has a structuralfeature that iron cent er has a five-coordinate geometry similar to that of catechol dioxygenase-substrate complex.The BBA complex exhibits strong absorptionbands at 560 and 820 nm in CH3CN which are assigned to catecholate to Fe(III) charge transfer transitions. It also exhibits EPR signals at g = 9.3 and 4.3 which are typical values for the high-spin FeIII (S = 5/2) complex with rhombicsymmetry. Interestingly, the BBA complex reacts with O2 within an hour to afford intradiol cleavage (35%) and extradiol cleavage (60%) products. Surprisingly, a green color intermediate is observed during the oxygenation process of the BBA com-plex in CH3CN. This green intermediate shows a broad isotropic EPR signal at g = 2.0. Based on the variable temperature EPR study, this isotropic signalmight be originated from the [Fe(III)-peroxo-catecholate] species havinglow-spin FeIII center, not from the simple organic radical. Consequently,it allows O2 to bind to iron cen-ter forming the Fe(III)-superoxide species that converts to the Fe(III)-peroxide intermediate. These present data can lead us tosuggest that the oxygen activation mechanism take place for the oxidative cleavingcatechols of the five-coordinate model systems for catechol dioxygenases.

• 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.

• YAKHAK HOEJI
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• v.40 no.6
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• pp.670-678
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• 1996

The combinations of N-4-salicyloamido-2-amino-6-piperidinopyrimidine 3-oxide (Salmi) and two transitional metals were colored. Among metals, Fe(III) made a distinct colored comp lex with Salmi. The mole ratio of Salmi and Fe(III) in the complex was 1:1. This Salmi-Fe(III) complex was recrystallized in Hexane/Acetone(=10/1, v/v) and investigated its physicochemical properties. The color of this complex was changed by pH.; deep violet pink in acids, orange in neutral, and yellow in bases. The range of color change was approximately 0.7 pH unit. Acid-base titration of various acidic or basic drugs using Salmi-Fe(III) complex as an indicator showed good accuracy and reproducibility.

• Analytical Science and Technology
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• v.9 no.2
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• pp.139-144
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• 1996

The spectrophotometric determination method of scandium with eriochrome cyanine R(ECR) and the composition ratio of the complex were investigated in the presence of surfactants. The absorbance increase and red shift of maximum adsorption wavelength of Sc(III)-ECR complex were observed in cetyltrimethylammonium bromide (CTMAB), but those changes were not observed in the sodium dodecyl sulfate(SDS) and Triton X-100. A volume of 5ml of $1{\times}10^{-3}M$ ECR and 10ml of $2{\times}10^{-4}M$ CTMAB are necessary for the determination of $1{\times}10^{-7}{\sim}3.0{\times}10^{-6}M$ Sc(III) at pH 6.5. The apparent molar absorption coefficient of the Sc(III)-ECR-CTMAB, temary complex at 610nm is $5.6{\times}10^5mol^{-1}cm^{-1}L$ and its detection limit is $1.0{\times}10^{-7}M$. The binary complex composition of Sc(III)-ECR is 1:2 and the ternary complex composition of Sc(III)-ECR-CTMAB is 1:3:1.

• Korean Journal of Materials Research
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• v.10 no.1
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• pp.55-61
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• 2000

The sintering characteristics of PVA-Al(III) complex added $UO_2$ pellet and AlOOH added $UO_2$pellet were compared. The major phase of PVA-Al(III) complex and AlOOH decomposed at $1000^{\circ}C$ in $H_2$atmosphere was $\theta-Al_2O_3$. Compared with the apparent density of pure $UO_2$, that of AlOOH added $UO_2$ powder was higher but that of PVA-Al(III) complex was lower. the densification of AlOOH added $UO_2$ pellet was initiated at about $800^{\circ}C$, the densification of PVA-Al(III) complex added $UO_2$ pellet was initiated at about $900^{\circ}C$ respectively. In a view of pore size distribution, the PVA-Al(III) complex added $UO_2$ pellet appeared as monomodal type, whereas the AlOOH added $UO_2$ pellet appeared as bimodal type. The grain size of AlOOH added $UO_2$ pellet was about $13\mu\textrm{m}$ but the grain size of PVA-Al(III) complex added $UO_2$ pellet was increased up to about $36\mu\textrm{m}$.

• Bulletin of the Korean Chemical Society
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• v.21 no.10
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• pp.969-972
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• 2000

[Fe II Fe III $BPLNP(OAc)_2](BPh_4)_2$ (1), a new model for the reduced form of the purple acid phosphatases, has been synthesized by using a dinucleating ligand, 2,6-bis[((2-pyridylmethyl)(6-methyl-2-pyridylmethyl)ami-no)methyl]-4-nitrophenol (HBPLNP) . Complex 1 has been studied by electronic spectral, NMR, EPR, SQUID, and electrochemical methods. Complex 1 exhibits two strong bands at 498 nm $(\varepsilon=$ 2.6 ${\times}10^3M-^1cm-^1)$ and 1363 nm $(\varepsilon=$ 5.7 ${\times}10^2M-^1cm-^1)$ in $CH_3CN.$ These are assigned to phenolate-to-FeIII and intervalence charge-transfer transitions, respectively. NMR spectrum of complex 1 exhibits sharp isotropically shifted resonances, which number is half of those expected for a valence-trapped species, indicating that electron transfer between FeⅡ and FeⅢ centers is faster than NMR time scale at room temperature. Complex 1 undergoes quasireversible one-electron redox processes. The $FeIII_2/FeIIFeIII$ and $FeIIFeIII/FeII_2$ redox couples are at 0.807 and 0.167 V ver-sus SCE, respectively. It has Kcomp = 5.9 ${\times}$10 1s(acetato) ligand combination sta-bilizes a mixed-valence FeIIFeIII complex in the air. Interestingly, complex 1 exhibits intense EPR signals at g = 8.56, 5.45, 4.30 corresponding to mononuclear high-spin FeⅢ species, which suggest a very weak magnetic coupling between the iron centers. Magnetic susceptibility study shows that there is a very weak antiferromag-netic coupling (J = $-0.78cm-^1$, H = $-2JS_1${\times}$S_2)$ between FeII and FeIII centers. Thus, we can suggest that complex 1 has a very weak antiferromagnetic coupling between the iron centers due to the electronic effect of the nitro group in the bridging phenolate ligand.