• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1615-1620
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• 2010

Bis-[dipyrido[3,2-$\alpha$:2',3'-c]phenazine)$_2$(1,10-phenanthroline)$_2Ru_2$]$^{2+}$ complexes (bis-Ru(II) complexes) tethered by linkers of various lengths were synthesized and their binding properties to DNA investigated by normal absorption and linear dichroism spectra, and fluorescence techniques in this study. Upon binding to DNA, the bis-Ru(II) complex with the longest linker (1,3-bis-(4-pyridyl)-propane), exhibited a negative $LD^r$ signal whose intensity was as large as that in the DNA absorption region, followed by a complicate $LD^r$ signal in the metal-to-ligand charge transfer region. The luminescence intensity of this bis-Ru(II) complex was enhanced. The observed $LD^r$ and luminescence results resembled that of the [Ru(1,10-phenanthroline)$_2$ dipyrido[3,2-$\alpha$:2',3'-c]phenazine]$^{2+}$ complex, whose dipyrido[3,2-$\alpha$:2',3'-c]phenazine (dppz) ligand has been known to intercalate between DNA bases. Hence, it is conclusive that both dppz ligands of the bis-Ru(II) complex intercalate. The binding stoichiometry, however, was a single intercalated dppz per ~ 2.3 bases, which violates the "nearest binding site exclusion" model for intercalation. The length between the two Ru(II) complexes may be barely long enough to accommodate one DNA base between the two dppz ligands, but not for two DNA bases. When the linker was shorter (4,4'-bipyridine or 1,2-bis-(4-pyridyl)-ethane), the magnitude of the LD in the dppz absorption region, as well as the luminescence intensity of both bis-Ru(II) complexes, was half that of the bis-Ru(II) complex bearing a long linker. This observation can be elucidated by a model whereby one of the dppz ligands intercalates while the other is exposed to the aqueous environment.

• Bulletin of the Korean Chemical Society
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• v.27 no.1
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• pp.99-105
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• 2006

Polyamine dendrimers functionalized with electrochemiluminescent (ECL) polypyridyl Ru(II) complexes, dend-$[CO-(CH_2)_3-mbpy{\cdot}Ru(L)_2]_3(PF_6)_6$ (dend: N$(CH_2CH_2NH)_3$-, L: bpy, o-phen, phen-Cl, DTDP), were synthesized through the complexation of dendritic polypyridyl ligands to Ru(II) complexes. Their electrochemical redox potentials, photoluminescence (PL), and relative ECL intensities were studied. The ECL emissions produced by the reaction between the electro-oxidized $Ru^{3+}$ species of polyamine dendrimers and tripropylamine as a coreactant were measured in a static system with potential cycles between 0.8 and 1.3 V or through flow injection analysis with a potential of +1.3 V, and were compared to that of $[Ru(o-phen)_3](PF_6)_2{\cdot}Dend-[CO-(CH_2)_3-mbpy{\cdot}Ru(bpy)_2]_3(PF_6)_6$ showed an ECL intensity that was two-fold greater than that of the reference complex $[Ru(o-phen)_3](PF_6)_2$.

• Journal of the Korean Chemical Society
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• v.56 no.3
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• pp.313-315
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• 2012

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.663-665
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• 2014

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1200-1204
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• 1999

The reactions of Ru(tpy)Cl3 (tpy = 2,2';6',2"-terpyridine) with new N,N,C-terdentate ligands, 3,2'-annulated-6-(2"-pyridyl)-2-phenylpyridines (1, HL) and the properties of their Ru(II) complexes are described. The distribution ratio of the two possible Ru(II) complexes, a pentaaza-coordinated complex [Ru(tpy)(1-N,N')Cl]+ and a cycloruthenated complex [Ru(tpy)(La-N,N',C)]+ are highly dependent on the length of the polymethylene unit. The trimethylene bridge of the N,N,C-terdentate in pentaaza-coordinated complex is rigid enough to induce an asymmetry in the complex.

• 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.

• 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.57 no.6
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• pp.726-730
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• 2013

Complexes synthesized by reacting alkyl and aryl phosphines with different transition metals are of great interest due to their catalytic properties. Many of the phosphine complexes are soluble in polar solvents as a result they find applications in homogeneous catalysis. In our present work we report, four transition metal complexes of Ni(II), Pd(II), Pt(II) and Ru(II) with an asymmetrical ditertiaryphosphine ligand. The synthesized ligand bears a less electronegative substituent such as methyl group on the aromatic nucleus hence makes it a strong ${\sigma}$-donor to form stable complexes and thus could effectively used in catalytic reactions. The complexes have been completely characterized by elemental analyses, FTIR, $^1HNMR$, $^{31}PNMR$ and FAB Mass Spectrometry methods. Based on the spectroscopic evidences it has been confirmed that Ni(II), Pd(II) and Pt(II) complexes with the ditertiaryphosphine ligand showed cis whereas the Ru(II) complex showed trans geometry in their molecular structure.

• Journal of the Korean Chemical Society
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• v.51 no.6
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• pp.526-535
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• 2007

Ru(II)-terpyridine complexes (8, 9, 11) linked with adamantyl or β-cyclodextrin moieties were synthesized and characterized based on their 1H and 13C NMR spectra as well as MS spectra. Ru(II)-terpyridine complexes (8, 11) linked with adamantyl moiety were readily dissolved in aqueous solution via encapsulation by β-cyclodextrin when they were mixed with an equimolar amount of β-cyclodextrin. In the similar way, the adamantane guest of the Ru(II)-terpyridine complexes (8, 11) were encapsulated by β-cyclodextrin moiety of the ruthenium complex 9 to afford supramolecular assemblies in aqueous environment. Formation of assemblies was corroborated by 1H NMR spectroscopy.

• Rapid Communication in Photoscience
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• v.3 no.3
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• pp.42-47
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• 2014

Development of molecular and supramolecular systems showing efficient photoinduced energy or electron transfer are of current research interest due to their applications in various chemical and biological processes. Various polypyridine metal complexes including Ru(II), Ru(III), Os(II), Pt(II), Fe(II), Re(I), Ir(III) and so on as a metal center introduce for expanding some more understanding of molecular-scale photoelectronics. Their complexes are concisely classified by the types of relay ligands as follows; (a) metal-direct ligand-metal system; dinuclear or trinuclear systems, (b) metal-nonconjugated ligand-metal system and metal-nonconjugated ligand system having flexible/rigid ligand, (c) metal-conjugated ligand-metal system, and (d) conjugated ligand-metal-conjugated ligand system and metal-self assembly ligand-metal system. It is pointed out that the role played by the relay ligands is important in constructing the metal complexes.