• Bulletin of the Korean Chemical Society
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• v.16 no.7
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• pp.619-624
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• 1995

Oxidation of triphenylphosphine to triphenylphosphine oxide by [(tpy)(bpy)Ru(O)]2+ (tpy is 2,2':6',2"-terpyridine and bpy is 2,2'-bipyridine) in CH3CN has been studied. Experiments with the 18O-labeled oxo complex show that transfer of oxygen from [(tpy)(bpy)RuⅣ=O]2+ to triphenylphosphine is quantitative within experimental error. The reaction is first order in each reactant with k (25.3 ℃)=1.25 × 106 M-1s-1. The inital product, [(tpy)(bpy)RuⅡ-OPPh3]2+, is formed as an observable intermediate and undergoes slow k (25 ℃)=6.7 × 10-5 s-1 solvolysis. Activation parameters for the oxidation step are ΔH≠=3.5 kcal/mol and ΔS≠=-23 eu. The geometry at ruthenium in the complex cation, [(tpy)(bpy)RuⅡ(OH2)]2+, is approximately octahedral with the ligating atoms being the three N atoms of the tpy ligand, the two N atoms of the bpy ligand, and the oxygen atom of the aqua ligand. The Ru-O bond length is 2.136(5) Å.

• Bulletin of the Korean Chemical Society
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• v.6 no.5
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• pp.287-291
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• 1985

The addition of poly(styrenesulfonate) (PSS) to $Ru(bpy)_3^{2+}$ solutions shifted the emission peak by 3 nm to red, and increased emission intensity by 1.8 times. By contrast, poly(vinylsulfonate) (PVS) had little effect on the fluorescence spectrum. The effects of PSS on the spectral properties of $Ru(bpy)_3^{2+}$, were attributed to the presence of a hydrophobic phenyl group in PSS, which interact with $Ru(bpy)_3^{2+}$ by, at least in part, hydrophobic effect. The binding constant of $Ru(bpy)_3^{2+}$ to PSS in 0.1 M NaCl was $6{\times}10^4\;M^{-1}$, and this value was about $10^3$ times higher than those of methyl viologen ($MV^{2+}$) and $Cu^{2+}$. The Stern-Volmer constants of emission quenching of $Ru(bpy)_3^{2+}$ by $MV^{2+}$ and $Cu^{2+}$ in 0.1 M NaCl solutions were 426 and 40 $M^{-1}$, which correspond to second order rate constants($k_q$) of $1.1{\times}10^9\;and\; 1.0{\times}10^8\;M^{-1}s^{-1}$, respectively. The presence of PSS enhanced $K_{SV's}\;by\;{\sim}50$ times, whereas PVS increased the values only 1-4 times. The large enhancing effect of PSS, despite of lower charge density than PVS, was explained in terms of longer life-time of photoexcited $Ru(bpy)_3^{2+}$ bound to PSS and strong association of $Ru(bpy)_3^{2+}$ to PSS due to a specific interaction involving hydrophobic effect. The variation of $K_{SV's}$ on the concentrations of PVS and PSS were also investigated for $Ru(bpy)_3^{2+}-MV^{2+}\;and \;Ru(bpy)_3^{2+}-Cu^{2+}$ photoredox systems.

• Bulletin of the Korean Chemical Society
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• v.14 no.6
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• pp.682-686
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• 1993

The syntheses and reactivities with olefins of $[Ru^{II}(L_3)(L_2)OH_2]^{2+}$ $[L_3$= 2,6-bis(N-pyrazolyl)pyridine(bpp), 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine $(Me_4bpp);\;L_2$= 2,2'-bipyridine(bpy), 4,4'-dimethyl-2,2'-bipyridine $(Me_2bpy)$] are described. Their spectral and redox properties in aqueous solution were investigated. Evidence for each one electron redox process for the $Ru^{IV}-Ru^{III}$ and $Ru^{III}-Ru^{II}$ couples has been obtained. Oxidation of $[Ru^{II}(bpp)(bpy)OH_2]^{2+}$ with $Ce^{IV}$ gave $[Ru^{IV}(bpp)(bpy)O]^{2+}$. The $[Ru^{IV}$= 0 complex is paramagnetic $({\mu}_{eff}=2.82)$ and the complexes $[Ru(L_3)(L_2)OH_2]^{2+}$ are robust catalysts for the oxidation of styrene, cyclohexene, and cyclooctene with cooxidant such as NaOCl. Product distributions and selectivities are discussed by varying the number of the substituted-methyl group in the ring.

• Proceeding of EDISON Challenge
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• 2014.03a
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• pp.251-262
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• 2014

최근 유기 발광 다이오드(Organic Light Emitting Diodes; OLED)가 각광받고 있어 이를 개발하기 위한 좀 더 효율적이고 실용적인 OLED 구조의 예측이 필요해지고 있다. 본 연구는 가장 기초적인 OLED dye의 형태인 $Ru(bpy){_3}^{2+}$와 그와 유사한 구조의 발광 물질이 전기화학발광(ECL) 현상을 통해 방출하는 빛의 특성을 계산하는 것을 목적으로 한다. EDISON 화학 서버의 GAMESS 프로그램을 사용하여 $Ru(bpy){_3}^{2+}$와 유도체들의 바닥상태(ground state)와 첫 번째 들뜬 상태(first excited state)를 계산하였다. Basis set으로는 MINI와 3-21G 혹은 SBKJC를 사용하였다. 들뜬 상태 계산은 configuration interaction with single excitation(CIS)을 이용하여 단일항(singlet)과 삼중항(triplet) 상태에서 바닥과 들뜬 상태의 최적 구조에 대한 계산을 수행하였다. 다양한 방법으로 방출 파장을 계산한 결과를 바탕으로 $Ru(bpy){_3}^{2+}$와 다양한 유도체들의 에너지 계산에 어떤 방법이 효율적으로 적용될 수 있을지 탐색하였다. 같은 계산방법들이 중심 금속이 이리듐(Ir)인 분자에도 적용이 될 수 있을지 알아보기 위해 $lr(mppy)_3$에도 적용하였다. 본 연구를 통하여 얻어진 방식은 시간을 절약하고 더 효율적인 $Ru(bpy){_3}^{2+}$ 유도체 계산에도 사용할 수 있을 것이다.

• Polymer(Korea)
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• v.25 no.6
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• pp.782-788
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• 2001

The $[Ru(v-bpy)_3]^{2+}$ and vinylbenzoic acid (vba) were electrochemically copolymerized to afford electrodes modified with dopamine to study their properties such as electropolymerization rate, redox process, and electron transfer. The optimum mole ratio of the monomers was 5:2, which gave $1.84{ imes}10^{-2}s^{-1}$ of rate constant for first order reaction, while the ratio of the substances on the copolymeric film produced was 5:1.68. The formal potential produced from the hydroquinone=quinone+$2H^+2e^-$reaction at the electrode of GC/p- $[Ru(v-bpy)_3]^{2+}$/vba-dopamine was 0.17 V in phosphate buffer (pH=7.10). The electrocatalytic rate was $2.58{ imes}10^5cms^{-1}$;2.41 times faster than that of non-modified one. The mass change measured by EQCM was $3.28{ imes}10^3$$gmol^{-1}$ which is larger than that of non-modified one.

• Journal of the Korean Chemical Society
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• v.44 no.1
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• pp.17-23
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• 2000

Electrodes of the polycationic film with electropolymerized $[Ru(v-bpy)_3]^{2+}$ having about 1:1 ratio of $PF6^-/ClO_4^-$as the doped counter ions, were modified with xylenol orange and diethylditbiocarbamate by ion exchange which had stability constant as 38.6 and 17.5 respectively. These electrodes were employed in the quantitative multiple determination of U(W) in solution. The working electrode of electrochemical cell for the analytical signal was Pt/p-$[Ru(v-bpy)_3]^{2+}$, ligand, U(VI) with Ag/AgCl reference elecrode. In the stripping voltammetry. electrode process was electron transfer controlled one and calibration curves at the ranges of $1.0{\times}10^{-3}{\sim}1.0{\times}10^{-7}$ M had excellent relationship as 0.99 and relative standard deviation as 5${\sim}$8%.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1314-1318
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• 2010

The $[Ru(tpy)_2]Cl_2$ (tpy:2,2':6',2"-terpyridine) complex was synthesized and its structure was confirmed by $^1H$-NMR and elemental analysis. Its binding mode toward DNA was compared with the well-known $[Ru(bpy)_3]Cl_2$ (bpy:2,2-bipyridyl), using isotropic absorption, linear dichroism(LD) spectroscopy, and an energy minimization study. Compared to $[Ru(bpy)_3]^{2+}$, the $[Ru(tpy)_2]^{2+}$ complex exhibited very little change in its absorption pattern, especially in the MLCT band, upon binding to DNA. Furthermore, upon DNA binding, both Ru(II) complexes induced a decrease in the LD magnitude in the DNA absorption region. The $[Ru(tpy)_2]^{2+}$ complex produced a strong positive LD signal in the ligand absorption region, which is in contrast with the $[Ru(bpy)_3]^{2+}$ complex. Observed spectral properties led to the conclusion that the interaction between the ligands and DNA bases is negligible for the $[Ru(tpy)_2]^{2+}$ complex, although it formed an adduct with DNA. This conclusion implies that both complexes bind to the surface of DNA, most likely to negatively charged phosphate groups via a simple electrostatic interaction, thereby orienting to exhibit the LD signal. The energy minimization calculation also supported this conclusion.

• Bulletin of the Korean Chemical Society
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• v.19 no.1
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• pp.86-93
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• 1998

Trans-4-(9-anthrylethenyl)-4'-methyl-2,2'-bipyridine(t-aemb) and its bipyridyl Ru complex $[Ru(bpy)_2(t-aemb)](PF_6)_2$ (bpy=2,2'-bipyridine) 1 have been prepared and their excited state properties have been studied. t-Aemb exhibits solvent-dependent fluorescence and efficient trans→cis photoisomerization. 1 shows very weak fluorescence and its photochemically reactive. Fluorescence is wavelength-dependent. While the excitation into the MLCT band makes the complex fluorescent, direct absorption by the t-aemb ligand leads to the photoreaction of t-aemb ligand and no fluorescence is observed. 1 is considered to behave in part as bichromophoric molecule in which $[Ru(bpy)_3](PF_6)_2$ and anthryl group are covalently linked by ethenyl linkage. Because anthryl moiety is not effectively conjugated with bipyridylethenyl moiety due to steric hindrance, weak fluorescence can be explained due to the efficient energy or electron transfer.

• Journal of Photoscience
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• v.6 no.3
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• pp.91-96
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• 1999

Zeolites and microporouos materials continue to attract attention as novel hosts for photochemical reactions. Zeolities are attractive because of their ability to selectivity exchange and incorporate species within the void spaces and interconnecting channels, providing a spatial arrangement of molecules. Our research has primarily focused on intrazeolitic electron transfer from excited Ru(bpy)32+ in supercages of zeolite Y to a series of bipyridinium ions. In the Ru(bpy)32+ viologen-zeolite Y samples, the slowing of the back electron transfer from the bipyridinium radical cation to Ru(bpy)32+ allows for charge propagation via self exchange between diquat molecules. This provides an opportunity for permanent charge separation. When the migrating charge on the diquat radical within the zeolite reaches the surface, it can be transferred to a neutral viologen (PVS) in solution, resulting in permanent charge separation. The advantage of long-lived charge separation can be exploited for useful chemistry if suitable catablysts can be assembled on the zeolities. We have studied Ru(bpy)2 as water oxdiation catalysts. We have demonstrated that synthesis of RuO2 fibers on a zeolite via thermal decomposition of Ru3(CO)12 leads to the most active water decomposition catalyst reported to date. Because of the extensive interest of photochemical water reduction to H2, much is known about catalytic systems usin gone electron catalyst, and even more importantly, that no reaction of viologen occurred with H2 over this catalyst. The present challenge is to incorporate all these elements of the system into an architecture and we are examining zeolite membranes for this purpose.

• Journal of the Korean Chemical Society
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• v.49 no.4
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• pp.343-348
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• 2005