Synthesis,characterization, and DNA binding of ruthenium(II) complexes with 2-benzo[b] furan-2-yl-1H-imidazo[4,5f][1,10]phenanthroline as an intercalative ligand

DNA-binding properties of a number of ruthenium complexes with different polypyridine ligands are reported. The new polypyridine ligand BFIP (=2-benzo[b] furan-2-yl-1H-imidazo[4,5-f][1,10]phenanthroline) and its ruthenium complexes [Ru(bpy)₂BFIP]²⁺ (bpy = 2,2′-bipyridine), [Ru(dmb)₂BFIP]²⁺ (dmb = 4,4′-dimethyl-2,2′-bipyridine), and [Ru(phen)₂BFIP]²⁺ (phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, mass spectra, IR, UV-Vis, ¹H- and ¹³C-NMR, and cyclic voltammetry. The DNA binding of these complexes to calf-thymus DNA (CT-DNA) was investigated by spectrophotometric, fluorescence, and viscosity measurements. The results suggest that ruthenium(II) complexes bind to CT-DNA through intercalation. Photocleavage of pBR 322 DNA by these complexes was also studied, and [Ru(phen)₂BFIP]²⁺ was found to be a much better photocleavage agent than the other two complexes.     

Synthesis,characterization, and DNA-binding of [Co(phen)2(CPIA)]3+, [Co(phen)2(BIP)]3+, and [Co(phen)2(CIP)]3+

Three ligands, 2-(3-(carboxymethyl)-1,10-phenanthroline-[5,6-d]imidazole-1-yl)acetate (CPIA), 2-(benzo[d][1,3]dioxol-4-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (BIP), and 2-(9H-carbazol-3-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (CIP), and their complexes, [Co(phen)₂(CPIA)]³⁺ (1) (phen = 1,10-phenanthroline), [Co(phen)₂(BIP)]³⁺ (2), and [Co(phen)₂(CIP)]³⁺ (3), have been synthesized and characterized. Binding of the three complexes with calf thymus DNA (CT-DNA) has been investigated by spectroscopic methods, cyclic voltammetry, and viscosity measurements. The three complexes bind to DNA through an intercalative mode, and the size and shape of the intercalative ligands have significant effects on the binding affinity of complexes to CT-DNA.     

Effect of the ancillary ligands on the binding of ruthenium(II) complexes [Ru(dmp)2(MCMIP)]2+ and [Ru(dmb)2(MCMIP)]2+ with DNA

Two polypyridine ruthenium(II) complexes, [Ru(dmp)₂(MCMIP)]²⁺ (1) (MCMIP = 2-(6-methyl-3-chromonyl)imidazo[4,5-f][1,10]-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline) and [Ru(dmb)₂(MCMIP)]²⁺ (2) (dmb = 4,4′-dimethyl-2,2′-bipyridine), have been synthesized and characterized by elemental analysis, ES-MS and ¹H NMR. The DNA-binding behaviors of these complexes were investigated by electronic absorption titration, fluorescence spectroscopy, viscosity measurements and thermal denaturation. The results show that 1 and 2 effectively bind to CT-DNA; the DNA-binding affinities are closely related to the ancillary ligand.     

Synthesis,characterization and DNA binding and photocleavage studies of [Ru(bpy)2BDPPZ]2+, [Ru(dmb)2BDPPZ]2+ and [Ru(phen)2BDPPZ]2+ complexes and their antimicrobial activity

Polypyridyl ligand 9a,13a‐dihydro‐4,5,9,14‐tetraaza‐benzo[b]triphenylene‐11‐yl)‐phenyl‐methanone (BDPPZ) and its complexes [Ru(bpy)₂BDPPZ]²⁺, [Ru(dmb)₂BDPPZ]²⁺ and [Ru(phen)₂BDPPZ]²⁺ (where bpy = 2,2′‐bipyridine, dmb = 4,4′‐dimethyl‐2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized and characterized by elemental analysis, IR, UV–vis, ¹H‐NMR, ¹³C‐NMR and mass spectra. The DNA‐binding properties of the complexes were investigated by absorption, emission, melting temperature and viscosity measurements. Experimental results indicate that the three complexes can intercalate into DNA base pairs. Photo activated cleavage of pBR‐322 DNA by the three complexes was also studied. Further, all three Ru(II) complexes synthesized were screened for their antimicrobial activity. Copyright © 2009 John Wiley & Sons, Ltd.     

Investigation of DNA/BSA binding of three Ru(II) complexes by various spectroscopic methods,molecular docking and their antimicrobial activity

An intercalative ligand, ppip (ppip = {2-(4-(piperidin-1-yl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline}), and its mononuclear Ru(II) polypyridyl complexes, [Ru(phen)₂(ppip)]²⁺ (1) (phen=1,10-phenanthrolene), [Ru(bpy)₂(ppip)]²⁺ (2) (bpy=2,2′-bipyridine) and [Ru(dmb)₂(ppip)]²⁺ (3) (dmb=4,4′-dimethyl-2,2′-bipyridine), have been synthesized and characterized by elemental analysis and spectroscopic techniques such as UV–vis, IR, ¹H, as well as ¹³C NMR and ESI-MS. The interaction of these complexes with DNA/BSA (bovine serum albumin) was investigated using absorption, emission spectroscopy, viscosity measurements and molecular docking studies. The docking study infers that the binding strength (K_b) of these complexes was in agreement with results from absorption and emission techniques. These studies reveal that these three Ru(II) polypyridyl complexes bind to DNA/BSA. The binding ability of these complexes in the presence of different ions and solvents were also reported. All complexes were effectively cleaving pBR322 DNA in different forms and follows order which is similar to absorption and emission studies. These complexes were effective exhibiting the antimicrobial activity against different microbes Bacillus subtilis, Escherichia coli and Staphylococcus aureus.     

Synthesis, characterization and DNA-binding studies of ruthenium(II) mixed-ligand complexes containing dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline

A novel ligand dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline (dpoq) and its complexes [Ru(bpy)₂(dpoq)]²⁺ and [Ru(phen)₂(dpoq)]²⁺ (bpy = 2,2′-bipyridine; phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, electrospray mass spectra and ¹H NMR. The interaction of Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by absorption spectroscopy, fluorescence spectroscopy, thermal denaturation and viscosity measurements. Results suggest that two Ru(II) complexes bind to DNA via an intercalative mode.     

Study of the interaction between ruthenium(II) complexes and CT-DNA: synthesis,characterisation, photocleavage and antimicrobial activity studies

Two polypyridyl ligands 6-fluro-3-(1H-imidazo [4,5-f] [1,10]-phenanthroline-2-yl)-4H-chromen-4-one (FIPC), 6-chloro-3-(1H-imidazo [4,5-f] [1,10]-phenanthroline-2-yl)-4H-chromen-4-one (ClIPC) polypyridyl ligands and their Ru(II) complexes [Ru(bipy)₂FIPC]²⁺(1), [Ru(dmb)₂FIPC]²⁺(2), [Ru(phen)₂FIPC]²⁺(3), [Ru(bipy)₂ClIPC]²⁺(4), [Ru(dmb)₂ClIPC]²⁺(5) and [Ru(phen)₂ClIPC]²⁺(6) ((bipy = 2,2′-bipyridine, dmb = 4,4′-dimethyl-2,2′-bipyridine and phen = 1,10-phenanthroline) have been synthesised and characterised by elemental analysis, Mass spectra, IR, ¹H and ¹³C-NMR. The DNA-binding of the six complexes to calf-thymus DNA (CT-DNA) has been investigated by different spectrophotometric, fluorescence and viscosity measurements. The results suggest that 1–6 complexes bind to CT-DNA through intercalation. The variation in binding affinities of these complexes is rationalised by a consideration of electrostatic, steric factors and nature of ancillary ligands. Under irradiation at 365 nm, the three complexes have also been found to promote the photocleavage of plasmid pBR 322 DNA. Inhibitor studies suggest that singlet oxygen (¹O₂) plays a significant role in the cleavage mechanism of Ru(II) complexes. Thereby, under comparable experimental conditions [Ru(phen)₂FIPC]²⁺(3), [Ru(phen)₂ClIPC]²⁺(6) cleaves DNA more effectively than 1, 2, 4 and 5 complexes do. The Ru(II) polypyridyl complexes (1–6) have been screened for antimicrobial activities.     

Synthesis,DNA-binding,and photocleavage properties of Ru(II) complexes containing dppz-based ligand

A ligand ipdp (ipdp?=?indeno[1′,2′?:?5,6]pyrazino[2,3-i]dipyrido[3,2-a?:?2′,3′-c]phenazine-8-one) and its ruthenium complexes, [Ru(L)₂(ipdp)]²⁺ (L?=?bpy (2,2′-bipyridine), phen (1,10-phenanthroline)), have been synthesized and characterized by elemental analysis, electrospray mass spectra, and ¹H NMR. The interaction between the complexes and calf thymus DNA (CT-DNA) has been investigated by spectroscopic methods and viscosity measurements. The results indicate that the complexes can bind to CT-DNA in an intercalative mode. In addition, both complexes promote the photocleavage of plasmid pBR322 DNA under irradiation. The mechanistic studies reveal that singlet oxygen ¹O₂ plays a significant role in DNA photocleavage.     

Complexes of (bpy)2Ru(II) and (Ph2bpy)2Ru(II) with a series of thienophenanthroline ligands: synthesis,characterization, and electronic spectra

A series of complexes (bpy)₂LRu(II) and (Ph₂bpy)₂LRu(II), where bpy is 2,2′-bipyridine, Ph₂bpy is 4,4′-diphenyl-2,2′-bipyridine and L is 1,10-phenanthroline (phen), [1]benzothieno[2,3-c][1,10]phenanthroline (btp), naphtho[1′,2′?:?5,4]thieno[2,3-c][1,10]phenanthroline [ntpl, l=linear], and naphtho[1′,2′?:?4,5]thieno[2,3-c][1,10]phenanthroline (ntph, h=helical) were synthesized and characterized using 2D COSY NMR spectra. The UV spectra were assigned to study their metal to ligand charge transfer (MLCT) excited states. Complexes of (bpy)₂LRu(II) showed identical absorption wavelengths (λ _max) for the MLCT of all four members of the series with the only variation being the intensity (log _ε ) for each. The MLCT of (Ph₂bpy)₂LRu(II) showed the similar behavior only with different wavelengths showing that in this heteroleptic series of complexes the MLCT is exclusively to the bpy ligands with none to thienophenanthroline (btp, ntpl, or ntph).     

Synthesis,characterization and interaction of mixed polypyridyl ruthenium(II) complexes with calf thymus DNA

New mixed polypyridyl {HPIP = 2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline, phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, dmb = 4,4-dimethyl-2,2-bipyridine} ruthenium(II) complexes [Ru(phen)₂(HPIP)]²⁺, [Ru(dmp)₂(HPIP)]²⁺ and [Ru(dmb)₂(HPIP)]²⁺ were synthesized and characterized by elemental analyses ¹H-n.m.r., u.v.–vis. spectroscopy and cyclic voltammetry. Their DNA-binding properties were demonstrated by absorption, luminescence titrations, steady-state emission quenching and viscosity measurements. The results suggested that all the examined complexes bind with CT-DNA intercalatively. Methyl groups substituted at the 4,4-positions of bpy has no obvious effect on its DNA binding, whereas substituents at the 2- and 9-positions of phen have an impressive effect on its DNA-binding, as revealed by the decreased binding affinity.     

Synthesis,characterization, DNA-binding and DNA-photocleavage studies of [Ru(bpy)2(BPIP)] and [Ru(phen)2(BPIP)] (BPIP = 2-(4′-biphenyl)imidazo[4,5-f][1,10]phenanthroline)

New ligand 2-(4′-biphenyl)imidazo[4,5-f][1,10]phenanthroline (BPIP) and its complexes [Ru(bpy)₂(BPIP)]²⁺ (1) (bpy = 2,2′-bipyridine) and [Ru(phen)₂(BPIP)]²⁺ (2) (phen = 1,10-phenanthroline) have been synthesized and characterized by mass spectroscopy, ¹H NMR and cyclic voltammetry. The interaction of two Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by spectroscopic and viscosity measurements. Results indicate that both complexes bind to DNA via an intercalative mode and the DNA-binding affinity of complex 2 is much greater than that of complex 1. Furthermore, when irradiated at 365 nm, both complexes have also been found to promote the photocleavage of plasmid pBR 322 DNA.     

Synthesis,DNA interaction and photocleavage studies of ruthenium(II) complexes with 2-(pyrrole) imidazo[4,5-f]-1,10-phenanthroline as an intercalative ligand

Three Ru(II) complexes, namely [Ru(bipy)₂PRIP]²⁺ (1), [Ru(dmb)₂PRIP]²⁺ (2), and [Ru(phen)₂PRIP]²⁺ (3) (dmb = 4,4′-dimethyl-2,2′-bipyridine; PRIP = 2-(pyrrole) imidazo [4,5-f]-1,10-phenanthroline) have been synthesized and characterized by elemental analysis, mass spectra, IR, ¹H NMR and ¹³C NMR. The DNA-binding properties of the three complexes with calf-thymus DNA (CT-DNA) were investigated by spectrophotometry, fluorescence methods and viscosity measurements. The results suggest that all three complexes bind to CT-DNA through intercalation. Also, when irradiated at 365 nm, the three complexes promote the photocleavage of plasmid pBR-322 DNA. Under comparable experimental conditions, complex 3 cleaves DNA more effectively than complexes 1 and 2.     

Synthesis and DNA interaction studies of ruthenium(II) complexes with isatino[1, 2-b]-1,4,8,9-tetraazatriphenylene as an intercalative ligand

The binding of the ruthenium(II) complexes [Ru(bpy)₂(ITAP)](ClO₄)₂ (bpy = 2,2’-bipyridine) and [Ru(phen)₂(ITAP)](ClO₄)₂ (phen = 1,10-phenanthroline, ITAP = isatino[1,2-b]-1,4,8,9-tetraazatriphenylene) to calf thymus DNA (CT-DNA) have been investigated with UV–visible and emission spectroscopy, viscosity measurements, thermal denaturation, and photoactivated cleavage. The experimental results indicate that the two complexes bind to CT-DNA through an intercalative mode. The two Ru(II) complexes in the presence of plasmid pBR322 DNA have been found to give rise to nicking of DNA upon irradiation.     

Five new cobalt(II) complexes based on indazole derivatives: synthesis,DNA binding and molecular docking study

Five cobalt(II) complexes based on 1H-indazole-3-carboxylic acid (H₂L), [Co(phen)(HL)₂]·2H₂O (1), [Co(5,5′-dimethyl-2,2′-bipy)(HL)₂] (2), [Co(2,2′-bipy)₂(HL)₂]·5H₂O (3), [Co₂(2,9-dimethyl-1,10-phen)₂(L)₂] (4) and [Co₂(6,6′-dimethyl-2,2′-bipy)₂(L)₂]·H₂O (5) (2,2'-bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline), have been synthesized and structurally characterized by elemental analyses, IR and UV-vis spectroscopies and single-crystal X-ray crystallography. The results indicate that 1–3 possess mononuclear Co(II) structures, while 4 and 5 exhibit binuclear structure. 1D water tape which is linked by the multiple hydrogen bonds was embedded in the 3D motif of complex 3. Complexes 4 and 5 show two orthogonal planes of motif that was constituted by phen/2,2′-bipy and indazole acid, respectively. The intermolecular interactions including hydrogen bonding and π-π stacking interactions are stabilizing these complexes. The interactions of the synthesized complexes with calf-thymus DNA (CT-DNA) have been investigated by UV-vis absorption titration, ethidium bromide displacement assay and viscosity measurements. The results reveal that the complexes could interact with CT-DNA via a groove binding mode. Their behavior rationalization was further theoretically studied by molecular docking.     

Improved syntheses of Ru(CO)2 (O3SCF3)2 (bidentate) complexes and their conversion into new [Ru(CO)2 (bidentate)2]2+ complexes

Reaction of the complexes Ru(CO)₂Cl₂L [L = 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen)] with trifluoromethanesulphonic acid under carefully controlled conditions yields Ru[cis-(CO)₂] [cis-(O₃SCF₃)₂] (bidentate complexes. From reactions of the trifluoromethanesulphonates with the appropriate bidentate ligands, the new complexes [cis-Ru(CO)₂-L(L′)]²⁺ (L as above; L′ = 4,4′-dimethyl-2,2′-bipyridyl or 4,4′-diisopropyl-2,2′-bipyridyl) as well as the known [_cis-Ru(CO)₂L₂]²⁺ and [cis-Ru(CO)₂bpy(phen)]²⁺ have been prepared.     

Synthesis,DNA-binding and photocleavage studies of cobalt(III) complexes [Co(bpy)<Subscript>2</Subscript>(dpta)]<Superscript>3+</Superscript> and [Co(bpy)<Subscript>2</Subscript>(amtp)]<Superscript>3+</Superscript>

Two novel cobalt(III) mixed-polypyridyl complexes [Co(bpy)₂(dpta)]³⁺ and [Co(bpy)₂(amtp)]³⁺ (bpy = 2,2′-bipyridine, dpta = dipyrido-[3,2-a;2′,3′-c]-thien-[3,4-c]azine, amtp = 3-amino-1,2,4-triazino[5,6-f]-1,10-phenanthroline) have been synthesized and characterized. The interaction of Co^III complexes with calf thymus DNA was investigated by spectroscopic and viscosity measurements. Results suggest that the two complexes bind to DNA via an intercalative mode. Moreover, Co^III complexes have been found to promote the photocleavage of plasmid DNA pBR322 under irradiation at 365 nm. The mechanism studies reveal that hydroxyl radical (OH^•) is likely to be the reactive species responsible for the cleavage of plasmid DNA by [Co(bpy)₂(dpta)]³⁺ and superoxide anion radical (O ₂ ^•− ) acts as the key role in the cleavage reaction of plasmid DNA by [Co(bpy)₂(amtp)]³⁺.     

Two new lead(II) nitrite complexes,crystal structure of [Pb(phen)2(NO2)2] an eight-coordinate lead(II) complex

Two new lead(II) complexes containing nitrite, [Pb(L)₂(NO₂)₂], L?=?1,10-phenanthroline (phen) or 2,2′-bipyridine (bpy), have been synthesized and characterized. The crystal structure of [Pb(phen)₂(NO₂)₂] shows monomeric units. The coordination number is eight (four from “phen” ligands and four nitrite anions), weak interaction of lead(II) with oxygen atoms of adjacent molecules produce dimer units in the solid state. The arrangement of ligands exhibits a coordination hole around the lead(II), occupied possibly by a stereoactive lone pair of electrons on lead(II), and the coordination around lead is hemidirected. There is a π–π stacking interaction between the parallel aromatic rings that may help to increase the “gap” around lead(II).     

Synthesis,characterization, DNA binding studies and in vitro cytotoxicity of platinum(II)-dihalogenido complexes containing bidentate chelating N-donor ligands

Platinum(II) complexes, [Pt(L_x)X₂] (1–6), where X = Br or I and L_x = 2,2′-bipyridine or 1,10-phenanthroline derivatives (5,5′-dimethyl-2,2′-bipyridine (5-Mebpy), 4,4′-dimethyl-2,2′-bipyridine (4-Mebpy), and 5-amino-1,10-phenanthroline (5-NH₂phen)) were prepared. The complexes were characterized by the elemental analysis, mass spectrometry, infrared, and multinuclear (¹H, ¹³C and ¹⁹⁵Pt) 1-D and 2-D NMR spectroscopies, and by single-crystal X-ray analysis of [Pt(4-Mebpy)I₂] (4). All the platinum(II) complexes (1–6) were evaluated for in vitro cytotoxicity against human cancer cell lines A2780 and A2780R, and against non-malignant MRC5 cell line. All the complexes were nontoxic up to the 50 μM concentration, although they were found to readily bind to calf-thymus DNA (CT-DNA), as determined by spectrophotometric titration (K_b ≈ 10⁷ M^?1) and ethidium bromide displacement assay.     

Effect of substituents on DNA-binding behaviors of ruthenium(II) complexes: [Ru(dmb)2(dtmi)]2+ and [Ru(dmb)2(dtni)]2+

Two Ru(II) complexes [Ru(dmb)₂(dtmi)](ClO₄)₂ (1) (dmb = 4, 4′-dimethyl-2, 2′-bipyridine, dtmi = 3-(pyrazin-2-yl)-as-triazino[5, 6-f]-5-methoxylisatin) and [Ru(dmb)₂(dtni)](ClO₄)₂ (2) (dtni = 3-(pyrazin-2-yl)-as-triazino[5, 6-f]-5-nitroisatin) have been synthesized and characterized by elemental analysis, ES-MS, and ¹H NMR. DNA-binding behaviors of these complexes have been investigated by spectroscopic titration, viscosity measurements, and thermal denaturation. The results indicate that the two complexes interact with calf thymus DNA by intercalation.     

Substitution reactions of trans-[PdXPh(SbPh3)2J (X=Cl or Br) with nitrogen,phosphines and arsenic donor ligands. Crystal structures of trans-[PdClPh(PPh3)2], [PdClPh(bipy)], [PdClPh(dppm)]2, and [PdBrPh(dppm)]2

Exchange reactions of trans-[PdXPh(SbPh₃)₂] (1) (X=Cl or Br) with ligands L in refluxing dichloromethane give the palladium phenyl complexes [PdXPhL₂] (X=Cl, L=PPh₃, AsPh₃, L₂=2,2′-bipyridine (bipy), 4,4′-dimethyl-2,2′-bipyridine (dmbipy), 1,10-phenanthroline (phen); X=Br, L=PPh₃, L₂=bipy). Treatment of the complexes with bis(diphenylphosphino)methane (dppm) in refluxing dichloromethane gives [PdXPh(dppm]₂. These complexes have been characterised by microanalysis, IR and ¹H NMR spectroscopic data together with single crystal X-ray determinations of the phenyl palladium complexes, trans-[PdClPh(PPh₃)₂], [PdClPh(bipy)], [PdClPh(dppm)]₂, and [PdBrPh(dppm)]₂.