• 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.

• Journal of the Korean Chemical Society
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• v.41 no.12
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• pp.639-644
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• 1997

Novel carbonylruthenium (Ⅲ) complex Cp*Ru(CO)Cl2(2, Cp*=η5-C5Me5) was synthesized by the reaction of [Cp*RuCl2]2(1) with CO in toluene. The effective magnetic moment (Veff=1.81 B.M.) derived from the magnetic susceptibility measurement of the complex (2) was consistent with the presence of one "single" unpaired electron. Dibromocarbonylruthenium (Ⅲ) complex Cp*Ru(CO)Br2(3) was obtained by the reaction of complex (2) with KBr in toluene. Complex (2) was easily reduced by the reaction with phosphine in toluene to give the corresponding Ru (Ⅱ) complex Cp*Ru(CO)(PR3)Cl (4a∼4e, PR3=PMe3, PEt3, PMePh2, PPh3, PCy3).

• 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.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.32 no.4
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• pp.1341-1345
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• 2011

A novel ruthenium(II) complex, [$RuCl_2(DMSO)_2$(PhenTPy)] has been synthesized by the condensation of $RuCl_2(DMSO)_4$ with (1-(1,10-phenanthrolinyl)-2,5-di(2-thienyl)-1H-pyrrole)[PhenTPy] in $CHCl_3$ solution. The [$RuCl_2(DMSO)_2$(PhenTPy)] complex modified electrode was fabricated through the electropolymerization of the monomer in a 0.1 M tetrabutylammonium perchlorate (TBAP)/$CH_2Cl_2$ solution, to take advantage of the electronic communication between metal ion center by the conjugated backbone. The UV-visible spectroscopy (UV), mass spectrometry (MS), and cyclic voltammetry (CV) were employed to characterize the [$RuCl_2(DMSO)_2$(PhenTPy)] complex and its polymer (poly-Ru(II)Phen complex). The poly-Ru(II)Phen complex modified electrode exhibited an electrocatalytic activity to the oxidation of acetaminophen and the catalytic property was used for the analysis of acetaminophen at the concentration range between 0.09 and 0.01 mM in a phosphate buffer solution (pH 7.0).

• 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.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.

• Bulletin of the Korean Chemical Society
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• v.28 no.6
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• pp.965-969
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• 2007

The spectral properties, namely the circular dichroism, electric absorption and luminescence properties, of Λ- and Δ-[Ru(II)(1,10-phenanthroline)2benzodipyrido[b:3,2-h:2',3'-j]phenazine]2+ ([Ru(phen)2BDPPZ]2+) in the presence and absence of single stranded poly(dA) and poly(dT) were compared in this work. In the presence of single stranded DNAs, hypochromism in the absorption spectrum and significant changes in the circular dichroism spectrum in the ligand absorption band were apparent, indicating the strong interaction of the [Ru(phen)2BDPPZ]2+ complex with the single stranded DNAs. The luminescence intensity of the Ru(II) complex decreased stoichiometrically with increasing concentrations of the single stranded DNAs. All of these spectral changes were independent of the configuration of the Ru(II) complex and the nature of the DNA bases. Therefore, it is conceivable that both enantiomers of the [Ru(phen)2BDPPZ]2+ complex interact electrostatically with the negatively charged phosphate groups of DNA. However, the spectral properties of [Ru(II)(1,10-phenanthroline)3]2+ were not altered even in the presence of single stranded DNAs. Therefore, the size of the ligand involved in the interaction of the metal complex with the phosphate group of DNA may play an important role, even when the nature of the interaction is electrostatic.

• Bulletin of the Korean Chemical Society
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• v.9 no.2
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• pp.84-87
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• 1988

The Photophysical and photochemical properties of Ruthenium bipyridine with two long hydrocarbon chains, $[Ru(bipy)_2(dhbipy)]^{2+}$ and transient phenothiazine derivative cation radical $(PTD^+)$ in the cationic vesicle were studied. Transient absorption spectra of cation radical of phenothiazine derivative in the vesicle system containing the $Ru^{2+}$ complex, $[Ru(bipy)_2(dhbipy)]^{2+}$, (1) as sensitizer and phenothiazine derivative as electron donor was observed by XeCl excimer laser photolysis system. Thus the excited ruthenium complex would be quenched by phenothiazine derivative(PTD) reductively in the vesicle system. The quenching rate constant($K_Q$) of $Ru^{2+}$ with two long hydrocarbon chains in the vesicle by PTD was $9.6{\times}10^8M^{-1}S^{-1}$. The absorption decay kinetics showed that lifetime of phenothiazine derivative cation radical is a value in the 4-8m sec range.

• Bulletin of the Korean Chemical Society
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• v.18 no.2
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• pp.174-179
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• 1997

The synthesis and electronic as well as redox properties of four Ru(Ⅱ) complexes based on the ligand 4'-(4-pyridyl)-3,3';5',3"-bis-dimethylene-2,2';6',2"-terpyridine are reported. Each new complex is of the type [Ru(L)2]n+ and [Ru(tpy)(L)]n+, where L is the terdentate ligand with extra pyridine ring at 4'-position or is a N-methylated ligand and n=2, 3, or 4. Cyclic voltammetry indicates that the first electron added to the complex enters the viologen-type acceptor in N-methylated ligand.