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1.
《Journal of Coordination Chemistry》2012,65(3-4):401-413
Abstract Ruthenium (II) complexes of the type RuL(CO)2Cl2, [RuL(CO)2L? 2]2+ and [RuL(CO)2Cl L′]+ [L = bipyridine (bpy), phenanthroline (phen), biquinoline (biq) and L′ = pyridine (py), 4-chloropyridine (Cl-py), 4-methoxypyridine (MeO-py)] were synthesized from [Ru(CO)2Cl2]n and L, to produce the intermediate RuL(CO)2Cl2 followed by hydrolysis and reaction with L′. The catalytic activity of these complexes in epoxidation of olefins with iodosylbenzene under ambient conditions was investigated. A possible mechanism of these reactions, explaining the effects of the ligands on the reaction was explored. At least one carbonyl ligand remained bound to the metal through the reaction. The formation of an oxo intermediate was inferred from spectroscopic detection of bridged oxygen Ru—O—Ru and Ru=O species. 相似文献
2.
Ravi Kumar Vuradi Navaneetha Nambigari Pushpanjali Pendyala Srinivas Gopu Laxma Reddy Kotha Deepika G Vinoda Rani M Satyanarayana Sirasani 《应用有机金属化学》2020,34(3):e5332
A set of novel mononuclear polypyridyl complexes of Ru (II) with N – N donar ligands 1, 10 phenanthroline (phen), 2, 2′ bipyridine (bpy), 4, 4′-dimethyl 2, 2′ bipyridine (dmb) and an intercalating ligand (bnpip = 2-(4-butoxy-3-nitrophenyl)-1H-imidazo [4,5-f] [1,10] phenanthroline) have been synthesized and characterized by various spectral methods. The RT - PCR assays suggest that ruthenium (II) complexes inhibit MCF-7, breast cancer cell line by inducing apoptosis via inhibition of cell cycle check points cyclin D, cyclin E and also upregulation of caspase 8 (protein involved in late Apoptosis). Further the binding potency of Ru (II) complexes were investigated using various spectroscopic techniques like UV–visible, fluorescence and viscosity studies. The complex binds to DNA in an intercalative mode as confirmed by viscosity data with differential binding strength. All complexes show cleavage of the pBR322 DNA through a singlet oxygen production. Theoretical evidence via docking of the complex with DNA reveals the significant residues of binding as guanine. 相似文献
3.
Vuradi Ravi Kumar Penumaka Nagababu G. Srinivas Mallepally Rajender Reddy M. Vinoda Rani Mudavath Ravi 《Journal of Coordination Chemistry》2017,70(22):3790-3809
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 (Kb) 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. 相似文献
4.
Juan-Carlos Rodriguz-Ubis Batrice Alpha Dominique Plancherel Jean-Marie Lehn 《Helvetica chimica acta》1984,67(8):2264-2269
The NaBr cryptates of five macrobicyclic ligands containing bipyridine (bpy) and phenanthroline (phen) groups, i.e, of [bpy.bpy.bpy] 1 [bpy.bpy.phen] 2 [phen.phen.-phen] 3 [2.1.phen] 4 and [2.2.phen] 5 , have been prepared. 1, 2, 4 and 5 have been obtained in high yield by condensation of bis(bromomethyl)bipyridine 6 or -phenanthroline 9 with the corresponding macrocyclic diamines in presence of Na2CO3. Direct access to the NaBr complexes of th symmetrical cryptands 1 and 3 was achieved by a one-step macrobicyclisation procedure. The metal-ion complexes of ligands 1-5 have the attractive feature of combining the cation inclusion, nature of cryptates with the photoactivity of bipyridine and phenanthroline groups; they may thus be expected to posses a variety of interesting physical and chemical properties. 相似文献
5.
《Journal of Coordination Chemistry》2012,65(21):3693-3699
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). 相似文献
6.
比较研究了以C2O42-为共反应物时5个结构相关的Ru(II)配合物[Ru(bpy)2L1]2+, [Ru(bpy)2L2]2+, [Ru(bpy)2L3]2+, [Ru(phen)2L1]2+和[Ru(phen)2L2]2+(其中bpy=2,2′-联吡啶, phen=1,10-邻菲啰啉, L1=4-羧基苯基咪唑[4,5-f][1,10]邻菲啰啉, L2=3-羧基-4-羟基苯基咪唑[4,5-f][1,10]邻菲啰啉, L3=3,4-二羟基苯基咪唑[4,5-f][1,10]邻菲啰啉)的电致化学发光(ECL)性质. 结果表明, 酚羟基的存在能有效地淬灭Ru(II)配合物[Ru(bpy)2L2]2+, [Ru(bpy)2L3]2+和[Ru(phen)2L2]2+的ECL, 其它Ru(II)配合物的ECL量子效率与[Ru(bpy)3]2+相差不大. 相似文献
7.
Edwin C. Constable Prof. Dr. Catherine E. Housecroft Prof. Dr. Markus Neuburger Pirmin J. Rösel Dr. Silvia Schaffner Dr. Jennifer A. Zampese Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(43):11746-11757
The templated synthesis of organic macrocycles containing rings of up to 96 atoms and three 2,2′‐bipyridine (bpy) units is described. Starting with the bpy‐centred ligands 5,5′‐bis[3‐(1,4‐dioxahept‐6‐enylphenyl)]‐2,2′‐bipyridine and 5,5′‐bis[3‐(1,4,7‐trioxadec‐9‐enylphenyl)]‐2,2′‐bipyridine, we have applied Grubbs’ methodology to couple the terminal alkene units of the coordinated ligands in [FeL3]2+ complexes. Hydrogenation and demetallation of the iron(II)‐containing macrocyclic complexes results in the isolation of large organic macrocycles. The latter bind {Ru(bpy)2} units to give macrocyclic complexes with exocyclic ruthenium(II)‐containing domains. The complex [Ru(bpy)2(L)]2+ (isolated as the hexafluorophosphate salt), in which L=5,5′‐bis[3‐(1,4,7,10‐tetraoxatridec‐12‐enylphenyl)]‐2,2′‐bipyridine, undergoes intramolecular ring‐closing metathesis to yield a macrocycle which retains the exocyclic {Ru(bpy)2} unit. The poly(ethyleneoxy) domains in the latter macrocycle readily scavenge sodium ions, as proven by single‐crystal X‐ray diffraction and atomic absorption spectroscopy data for the bulk sample. In addition to the new compounds, a series of model complexes have been fully characterized, and representative single‐crystal X‐ray structural data are presented for iron(II) and ruthenium(II) acyclic and macrocyclic species. 相似文献
8.
《Journal of Coordination Chemistry》2012,65(12):2050-2064
AbstractTwo new ruthenium(II) complexes, [Ru(bpy)2(DClPIP)](ClO4)2 (1) and [Ru(phen)2(DClPIP)](ClO4)2 (2) (bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, and DClPIP = 2-(2,4-dichlorophenyl)-1H-imidazo[4,5-f][1, 10]phenanthroline), have been prepared in high yield by using microwave-assisted synthesis technology. The anticancer activity of the two ruthenium(II) complexes against A549, C6, CNE-1 and MDA-MB-231 cell lines has been evaluated by MTT assay and results showed that 2 exhibited higher antitumor activity than 1 toward all the selected tumor cell lines. Besides, A549 cell line was sensitive to both ruthenium(II) complexes, especially to 2 (IC50 = 8.01?±?0.36?μM). Meanwhile, 2 showed low toxicity against MCF-10A human normal cells. Furthermore, the DNA-binding properties of the two new ruthenium(II) complexes with CT-DNA have been investigated by electronic absorption titration, luminescence spectra, circular dichroism spectra and viscosity measurements. The results suggested that 1 and 2 were able to interact with CT-DNA via intercalative mode with a strong binding affinity in the order 2?>?1. All of these results suggested that anticancer activity of both ruthenium(II) complexes could be closely related to their interaction with DNA. 相似文献
9.
Yu Chen WenChao Xu JunFeng Kou XuHui Wei BoLe Yu Hui Chao LiangNian Ji 《中国科学:化学(英文版)》2010,53(10):2099-2105
Three Ru(II) complexes [Ru(bpy)2(1-IQTNH)](ClO4)2 (1), [Ru(bpy)2(2-QTNH)](ClO4)2 (2) and [Ru(bpy)2(3-IQTNH)](ClO4)2 (3) (bpy = 2,2′-bipyridine, 1-IQTNH = 6-(isoquinolin-1-yl)-1,3,5-triazine- 2,4-diamine, 2-QTNH = 6-(quinolin-2-yl)-1,3,5-triazine- 2,4-diamine, 3-IQTNH = 6-(isoquinolin-3-yl)-1,3,5-triazine-2,4-diamine) have been synthesized and characterized by elemental analysis, 1H NMR spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The electrochemical and spectroscopic properties of the complexes differ from those of [Ru(bpy)3]2+ owing to the structural differences between the ligands and their complexes. 相似文献
10.
Ershov A. Yu. Litke S. V. Litke A. S. Mezentseva T. V. Grigor'ev Ya. M. Lyalin G. N. 《Russian Journal of General Chemistry》2001,71(9):1329-1332
Spectral-kinetic luminescence characteristics of the complexes cis-[Ru(bpy)(dppe)X2], cis- [Ru(bpy)2(PPh3)X](BF4) and cis-[Ru(bpy)2X2] [bpy = 2,2'-bipyridyl, dppe = 1,2-bis(diphenylphosphino)ethane, PPh3 is triphenylphosphine, X = NO2
- and CN-] in the ethanol-methanol 4:1 mixtures and adsorbed on the oxide SiO2 or porous polyacrylonitrile polymer surface were studied. Luminescence and luminescence exitation spectra were registered at 77 and 293 K in 230-750 nm range and the luminescence decay time was measured. Introduction of phosphine ligands to the ruthenium(II) bipyridyl complexes inner sphere leads to rise in singlet and triplet state energy at the charge transfer from Ru(II) to 2,2'-bipyridyl in the series [Ru(bpy)2X2] < Ru(bpy)2(PPh3)X](BF4) < [Ru(bpy)(dppe)X2]. The complex adsorption on SiO2 or polyacrylonitrile surface affects noticeably the luminescence spectro-kinetic characteristics. 相似文献
11.
Goutam Ghosh Huimin Yin Susan M.A. Monro Tariq Sainuddin Lloyd Lapoot Alexander Greer Sherri A. McFarland 《Photochemistry and photobiology》2020,96(2):349-357
Ru(II) complexes were synthesized with π-expanding (phenyl, fluorenyl, phenanthrenyl, naphthalen-1-yl, naphthalene-2-yl, anthryl and pyrenyl groups) attached at a 1H-imidazo[4,5-f][1,10]phenanthroline ligand and 4,4′-dimethyl-2,2′-bipyridine (4,4′-dmb) coligands. These Ru(II) complexes were characterized by 1D and 2D NMR, and mass spectroscopy, and studied for visible light and dark toxicity to human malignant melanoma SK-MEL-28 cells. In the SK-MEL-28 cells, the Ru(II) complexes are highly phototoxic (EC50 = 0.2–0.5 µm ) and have low dark toxicity (EC50 = 58–230 µm ). The highest phototherapeutic index (PI) of the series was found with the Ru(II) complex bearing the 2-(pyren-1-yl)-1H-imidazo[4,5-f][1,10]phenanthroline ligand. This high PI is in part attributed to the π-rich character added by the pyrenyl group, and a possible low-lying and longer-lived 3IL state due to equilibration with the 3MLCT state. While this pyrenyl Ru(II) complex possessed a relatively high quantum yield for singlet oxygen formation (Φ∆ = 0.84), contributions from type-I processes (oxygen radicals and radical ions) are competitive with the type-II (1O2) process based on effects of added sodium azide and solvent deuteration. 相似文献
12.
Feng Gao Hui Chao Feng Zhou Lian‐Cai Xu Kang‐Cheng Zheng Liang‐Nian Ji 《Helvetica chimica acta》2007,90(1):36-51
Two novel chiral ruthenium(II) complexes, Δ‐[Ru(bpy)2(dmppd)]2+ and Λ‐[Ru(bpy)2(dmppd)]2+ (dmppd = 10,12‐dimethylpteridino[6,7‐f] [1,10]phenanthroline‐11,13(10H,12H)‐dione, bpy = 2,2′‐bipyridine), were synthesized and characterized by elemental analysis, 1H‐NMR and ES‐MS. The DNA‐binding behaviors of both complexes were studied by UV/VIS absorption titration, competitive binding experiments, viscosity measurements, thermal DNA denaturation, and circular‐dichroism spectra. The results indicate that both chiral complexes bind to calf‐thymus DNA in an intercalative mode, and the Δ enantiomer shows larger DNA affinity than the Λ enantiomer does. Theoretical‐calculation studies for the DNA‐binding behaviors of these complexes were carried out by the density‐functional‐theory method. The mechanism involved in the regulating and controlling of the DNA‐binding abilities of the complexes was further explored by the comparative studies of [Ru(bpy)2(dmppd)]2+ and of its parent complex [Ru(bpy)2(ppd)]2+ (ppd = pteridino[6,7‐f] [1,10]phenanthroline‐11,13 (10H,12H)‐dione). 相似文献
13.
Muath Atmeh Noel R. Russell Robert J. Forster Tia E. Keyes 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):607-612
At room temperature, [Ru(bpy)2(phen-CD)][PF6]2, (phen-CD is 6
A
-(5-amino-1, 10-phenanthroline)-6
A
-deoxy- β-Cyclodextrin and bpy is 2,2'-bipyridine) exhibits an intense metal ligand charge transfer (MLCT) transition at 452 nm
and a long lived luminescence, centred at 618 nm. We demonstrate, for the first time, that the luminescence quantum yield
and lifetime of the Ru (II) polypyridyl centre depends markedly on the solution pH. The pH sensitive range extends from pH
3.9 to pH 13.2 and the luminescence quantum yield changes by more than 60% over this range. This pH sensitivity is attributed
to protonation/deprotonation of the secondary amine group bridge between the phenanthroline unit and CD. The complex exhibits
strong host-guest binding to anthraquinone and anthraquinone-2-carboxylic acid, with concomitant quenching of the [Ru(bpy)2(phen-CD)]2+ excited state. This quenching arises from efficient intramolecular electron transfer. The sensitivity of this photoinduced
process to the protonation state of the bridge is discussed. 相似文献
14.
Two polypyridyl ligands, 5-(4′-ethynylbenzo-15-crown-5)-2,2′-bipyridine (L1) and 3-bromo-8-(4′-ethynylbenzo-15-crown-5)-1,10-phenanthroline (L2), and their Ru(II) complexes [(bpy)2RuL](PF6)2 have been prepared and characterized. Both complexes exhibit metal-to-ligand charge transfer absorption at around 452 nm
and emission at around 640 nm in MeCN solution. Electrochemical studies of the complexes reveal a Ru(II)-centered oxidation
at around 1.31 V and three ligand-centered reductions. The binding ability of the complexes with Na+ has been investigated by UV/Vis absorption, emission, and electrochemical titrations. Addition of Na+ to MeCN solutions of both complexes results in a progressive enhancement of the emission, a red-shift of the UV/Vis absorption,
and a progressive cathodic shift of the Ru(II)-centered E
1/2 couple. The stability constants for the 1:1 stoichiometry adducts of the complexes with Na+ have been obtained from the UV/Vis absorption titrations. 相似文献
15.
Ershov A. Yu. Kucheryavyi P. V. Nikol'skii A. B. 《Russian Journal of General Chemistry》2004,74(5):651-654
Ruthenium(II) bisbipyridyl complexes cis-[Ru(bpy)2(L)NO2](BF4) (bpy is 2,2'-bipyridyl) with 4-substituted pyridine ligands L = 4-(Y)py (Y = NH2, Me, Ph, and CN) were obtained. The equilibrium constants of the reversible nitro-nitrosyl transition [Ru(bpy)2(L)NO2]+ + 2H+ [Ru(bpy)2(L)NO]3
+ + H2O were measured in solutions with pH 1.5-8.5 (ionic strength 0.4). The constants correlate with the protonation constants of free ligands 4-(Y)py. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(20):3676-3687
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. 相似文献
17.
Yun‐Jun Liu Hui Chao Jun‐Hua Yao Hong Li Yi‐Xian Yuan Liang‐Nian Ji 《Helvetica chimica acta》2004,87(12):3119-3130
A novel ligand 3‐(1H‐imidazo[4,5‐f][1,10]phenanthrolin‐2‐yl)‐4H‐1‐benzopyran‐4‐one (ipbp) and its ruthenium(II) complexes [Ru(bpy)2(ipbp)]2+ ( 1 ) and [Ru(ipbp)(phen)2]2+ ( 2 ) (bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline) were synthesized and characterized by elemental analysis and mass, 1H‐NMR, and electronic‐absorption spectroscopy. The electrochemical behavior of the complexes was studied by cyclic voltammetry. The DNA‐binding behavior of the complexes was investigated by spectroscopic methods and viscosity measurements. The results indicate that complexes 1 and 2 bind with calf‐thymus DNA in an intercalative mode. In addition, 1 and 2 promote cleavage of plasmid pBR 322 DNA from the supercoil form I to the open circular form II upon irradiation. 相似文献
18.
Alvaro Delgadillo Paola Romo AnaMaria Leiva Brbara Loeb 《Helvetica chimica acta》2003,86(6):2110-2120
A series of substituted pyrazino[2,3‐f][1,10]‐phenanthroline (Rppl) ligands (with R=Me, COOH, COOMe) were synthetized (see 1 – 4 in Scheme 1). The ligands can be visualized as formed by a bipyridine and a quinoxaline fragment (see A and B ). Homoleptic [Ru(R1ppl)3](PF6)2 and heteropleptic [Ru(R1ppl){(R2)2bpy}2](PF6)2 (R1=H, Me, COOMe and R2=H, Me) metal complexes 5 – 7 and 8 – 13 , respectively, based on these ligands were also synthesized and characterized by conventional techniques (Schemes 2 and 3, resp.). In the heteroleptic complexes, the R1‐ppl ligand reduces at a less‐negative potential than the bpy ligand, reflecting the acceptor property conferred by the quinoxaline moiety. The potentiality of some of these complexes as solar‐cell dyes is discussed. 相似文献
19.
Gao J Wang ZP Yuan CL Jia HS Wang KZ 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(5):1815-1822
A new Ru(II) complex of [Ru(bpy)2(Hmspip)]Cl2 {in which bpy=2,2'-bipyridine, Hmspip=2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline} have been synthesized and characterized. The ground- and excited-state acid-base properties of [Ru(bpy)2(Hmspip)]Cl2 and its parent complex of [Ru(bpy)2(Hpip)]Cl2 {Hpip=2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline} have been studied by UV-visible (UV-vis) and emission spectrophotometric pH titrations. [Ru(bpy)2(Hmspip)]Cl2 acts as a calf thymus DNA intercalators with a binding constant of 4.0×10(5) M(-1) in buffered 50 mM NaCl, as evidenced by UV-vis and luminescence titrations, steady-state emission quenching by [Fe(CN)6]4-, DNA competitive binding with ethidium bromide, reverse salt titrations and viscosity measurements. 相似文献
20.
The synthesis of tri-heteroleptic complex of Ru(II) with diimine ligands is describe. Ten compounds [Ru(R2bpy) (biq) (L)][PF6]2 (R = H, CH3); L = 2,2′-bipyridine (bpy), 4,4′-dimethyl-2,2′-bipyridine (Me2bpy), 2,2′-bipyrimidine (bpm), 2,2′-biisoquinoline (biiq), 1,10-phenanthroline (phen), dipyrido[3,2-c:2′,3′-e]pyridazine (taphen), 2,2′-biquinoline (biq), 6,7-dihydrodipyrido[2,3-b:3,2-j][1,10]-phenanthroline (dinapy), 2-(2[pyridyl)quinoline (pq), 1-(2-pyrimidyl)pyrazole] (pzpm), 2,2′-biimidazole (H2biim) are characterized by elemental analysis, electronic and 1H-NMR spectroscopy. The relative photosustitution rates of biq in MeCN are given at three temperatures. 相似文献