• Bulletin of the Korean Chemical Society
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• 제31권6호
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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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• 제31권12호
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• pp.3658-3662
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• 2010

A new bis-Ru(II) complex, in which two [Ru(1,10-phenanthroline)$_2$dipyrido[3,2-a:2',3'-c]phenazine]$^{2+}$ were tethered by a 1,3-bis(4-pyridyl)propane linker, was synthesized and its binding mode and stoichiometry to DNA was investigated by optical spectroscopy including linear dichroism (LD) and fluorescence intensity measurement. The magnitude of the negatively reduced LD signal of the bis-Ru(II) complex in the dipyrido[3,2-a:2',3'-c]phenazine (DPPZ) ligand absorption region appeared to be similar compared to that in the DNA absorption region, which is considered to be a diagnostic for DPPZ ligand intercalation. The binding stoichiometry measured from its LD magnitude and enhanced fluorescence intensity corresponds to one ligand per three DNA bases, effectively violating the nearest neighbouring site exclusion model for classical DNA intercalation. This observation is in contrast with monomer analogue [Ru(1,10-phenanthroline)$_2$dipyrido[3,2-a:2',3'-c]phenazine]$^{2+}$, which is saturated at the DPPZ ligand to DNA base ratio of 0.25, or one DPPZ ligand per four nucleobases.

• Bulletin of the Korean Chemical Society
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• 제14권6호
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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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• 제34권10호
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• pp.2895-2899
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• 2013

Direction of intercalation to DNA of the planar dipyrido[3,2-a:2',3'-c]phenazine ligands (dppz) of a bis-Ru(II) complex namely, $[Ru(1,10-phenanthroline)_2dipyrido[3,2-a:2^{\prime},3^{\prime}-c]phenazine]^{2+}$ linkered by a 1,3-bis(4-pyridyl)propane, was investigated by probing the behavior of 4',6-diamidino-2-phenylindole (DAPI) that bound deep in the minor groove. Bis-intercalation of DPPZ resulted in a little blue shift and hyperchromism in DAPI absorption band, and a large decrease in DAPI fluorescence intensity which accompined by an increase in the dppz emission intensity. Diminishing the intenisty of the positive induced circular dichroism (CD) and linear dichroism (LD) were also observed. These spectral changes indicated that insertion of dppz ligand caused the change of the binding mode of DAPI, which probably moved to the exterior of DNA from the minor groove and interacted with the phospghate groups of DNA by electrostatic interaction. At the surface of DNA, DAPI binds at the phosphate groups of DNA by electrostatic attraction. Consequently, this observation indicated that the dppz ligand intercalated from the minor groove.

• Bulletin of the Korean Chemical Society
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• 제18권2호
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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.

• Bulletin of the Korean Chemical Society
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• 제34권7호
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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.

• Bulletin of the Korean Chemical Society
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• 제24권9호
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• pp.1407-1409
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• 2003

• 한국전기전자재료학회논문지
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• 제29권3호
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• pp.192-197
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• 2016

A novel heteroleptic ruthenium(II) complex bearing a 4-picolinic acid unit as anchoring ligands (trans-dithiocyanato bis(4-picolinic acid)ruthenium(II) (trans-H1)) was synthesized and its chemical structure was identified by $^1H$-NMR, FT-IR and mass spectroscopy. The optical, thermal, electrochemical and dye adsorption properties of trans-H1 dye were investigated and compared with those of the gold standard ruthenium complex, Ru(4,4'-dicarboxy-2,2'-bipyridine)$_2cis(NCS)_2$ (N3). DSSCs based on trans-H1 dyes were examined under the illumination of AM 1.5 G, $100mWcm^{-2}$ and exhibited typical photovoltaic properties with an open-circuit voltage ($V_{OC}$) of 0.46 V, a short-circuit current ($J_{SC}$) of $4.10mA{\cdot}cm^{-2}$, a fill factor (FF) of 60.4%, and a conversion efficiency (PCE) of 1.14%.

• 대한화학회지
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• 제37권1호
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• pp.98-104
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• 1993

$[({\eta}^5-C_5Me_5)RuCl_2]_2$ (1)과 1당량의 포스핀을 반응시켜 새로운 상자기성 루테늄(Ⅲ) 착물 $({\eta}^5-C_5Me_5)RuCl_2(PR_3) (PR_3 = PMe_3,\;PEt_3,\;PiPr_3,\;PCy_3,\;PMe_2Ph,\;PMePh_2,\;PPh_3,\;P(p-C_6H_4CH_3)_3$, DPPE, DPPB, Py) (2a∼2k)를 합성하였다. 자기화율의 측정으로 부터 얻어진 착물 (2a∼2k)의 유효자기모멘트값(${\mu}_{eff} = 1.65∼2.07 B.M.$)은 분자내 짝을 이루지 않는 전자가 1개 있는 전자배치의 경우와 일치하였다. 디클로로루테늄(Ⅲ) 착물 ({\eta}^5-C_5Me_5)RuCl_2(PR_3)$ (2) 는 (ⅰ)아세톤 용매 중에서 KBr과 반응하여 디브로모루테늄(Ⅲ) 착물 $({\eta}^5-C_5Me_5)RuBr_2(PR_3) (PR_3 = PPh_3)$로 전환되었고, (ⅱ) 디에틸에테르 용매 중에서 Na/Hg과 반응하여 비스(포스핀) 유도체 $({eta}^5-C_5Me_5)RuCl(PR_3)_2 (PR_3 = PMe_3,\;PMePh_2)$로 환원되었으며, (iii) CO와 반응하여 카르보닐 유도체$({\eta}^5-C_5Me_5)RuCl(PR_3)(CO) (PR_3 = PMe_3,\;PPh_3)$를 생성하였다.

• 대한화학회지
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• 제55권3호
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• pp.418-429
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• 2011

[ $N^1,N^2$ ]bis(3-((3-hydroxynaphthalen-2-yl)methylene-amino)propyl)phthalamide ($H_4L$, 1) 의 새로운 크롬(III), 망간(II), 철(III), 코발트(II), 니켈(II), 구리(II), 루테늄(III) 및 산화 지르코늄(II) 착물을 합성하여 원소분석, 물리적 성질 및 분광학적으로 특성을 규명하였다. 분광학적 결과를 통해 이 리간드는 $[H_4LMX_2(H_2O)]{\cdot}nH_2O$ (M = Cu(II), Ni(II), Co(II), X = Cl 또는 $NO_3$)의 일반식을 갖는 착물2-5에서는 중성의 삼배위 리간드로 행동한다. 또는 $[H_4L(ZrO)_2Cl_2]{\cdot}8H_2O$ 의 일반식을 갖는 착물 6-9 에서는 이염기성 육배위 리간드로 행동한다. DMF 용액에서의 몰전기전도도 실험결과 이들 착물은 비이온성을 나타낸다. 고체 구리착물 2, 5 및 6 의 ESR 스펙트럼에서 $g_{\parallel}$ >g> $g_e$을 보이는데, 이는 일그러진 팔면체구조와 큰 공유결합성을 갖는 $d{_x}^2{_{-y}}^2$ 오비탈에 비공유 전자쌍이 존재함을 의미한다. 이합체 구리(II) 착물 $[H_2LCu_2Cl_2(H_2O)_4]{\cdot}3H_2O$ (6)에 대해 두 구리원자 사이의 거리를 ESR 스펙트럼으로부터 추정한 parallel component 의 field zero splitting 파라메타를 이용하여 계산하였다. 이들 화합물의 항박테리아 및 항균 활성도를 측정한 결과, 몇가지 금속 착물의 경우 표준시약인 tetracycline (박테리아) 및 Amphotricene B (균류)보다 더 큰 저해효과를 보였다.