171565-44-9Relevant articles and documents
Computational and spectroscopic studies of the imidazole-fused phenanthroline derivatives containing phenyl, naphthyl, and anthryl groups
Wang, Jinglan,Xu, Shengxian,Zhao, Feng,Xia, Hongying,Wang, Yibo
, p. 46 - 53 (2016)
Three N,N-bidentate ligands, 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline (1), 2-(2-naphyl)-1H-imidazo[4,5-f]phenanthroline (2), and 2-(2-anthryl)-1H-imidazo[4,5-f]phenanthroline (3) have been synthesized and characterized. Effects of aryl subsistiuents (phenyl, naphthyl, and anthryl) on the photophysical properties of these ligands in solution have been studied. Ligand 1 exhibit the main absorption band at 283 nm with the shoulder bands at 300-350 nm and these bands are assigned as the typical π→π(imPhen) state (imPhen = 1H-imidazo[4,5-f][1,10]phenanthroline). A similar absorption spectrum was also observed in the case of 2, in which the charge transfer (CT) state should be considered. 3 shows the slightly different absorption properties compared to that of 1 and 2. The highest-lying absorption band at 257 nm is assigned as a mixed π→π(imPhen)/π→π(Anth) (Anth = anthracene) state. Additionally, the characteristic absorption band of anthryl group with three vibronic bands at 352, 367, and 386 nm also observed in the visible region range from 340 to 400 nm. 1 shows the typical ligand-centered 1π→πemission, while 2 and 3 emit from the mixed 1π→π/CT states. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) were employed to rationalize the photophysical properties of these ligands studied. The theoretical data confirm the assignment of the experimental absorption spectra and the nature of the emitting states.
Synthesis and Characterization of Ru(II) Complexes with π-Expansive Imidazophen Ligands for the Photokilling of Human Melanoma Cells
Ghosh, Goutam,Yin, Huimin,Monro, Susan M.A.,Sainuddin, Tariq,Lapoot, Lloyd,Greer, Alexander,McFarland, Sherri A.
, p. 349 - 357 (2020)
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.
Platinum phenanthroimidazole complexes as G-quadruplex DNA selective binders
Kieltyka, Roxanne,Fakhoury, Johans,Moitessier, Nicolas,Sleiman, Hanadi F.
, p. 1145 - 1154 (2008)
Complexes that bind and stabilize G-quadruplex DNA structures are of significant interest due to their potential to inhibit telomerase and halt tumor cell proliferation. We here report the synthesis of the first PtII G-quadruplex selective molecules, containing π-extended phenanthroimidazole ligands. Binding studies of these complexes with duplex and quadruplex d(T 4G4T4)4 DNA were performed. Intercalation to duplex DNA was established through UV/Vis titration, CD spectroscopy, and thermal denaturation studies. Significantly stronger binding affinity of these phenanthroimidazole PtII complexes to G-quadruplex DNA was observed by UV/Vis spectroscopy and competitive equilibrium dialysis studies. Observed binding constants to quadruplex DNA were nearly two orders of magnitude greater than for duplex DNA. Circular dichroism studies show that an increase in π-surface leads to a significant increase in the thermal stability of the PtII/quadruplex DNA complex. The match in the π-surface of these phenanthroimidazole PtII complexes with quadruplex DNA was further substantiated by molecular modeling studies. Numerous favorable π-stacking interactions with the large aromatic surface of the intermolecular G-quadruplex, and unforeseen hydrogen bonds between the ancillary ethylenediamine ligands and the quadruplex phosphate backbone are predicted. Thus, both biological and computational studies suggest that coupling the square-planar geometry of PtII with π-extended ligands results in a simple and modular method to create effective G-quadruplex selective binders, which can be readily optimized for use in telomerase-based antitumor therapy.
A Rhodium(III) Complex as an Inhibitor of Neural Precursor Cell Expressed, Developmentally Down-Regulated 8-Activating Enzyme with in Vivo Activity against Inflammatory Bowel Disease
Zhong, Hai-Jing,Wang, Wanhe,Kang, Tian-Shu,Yan, Hui,Yang, Yali,Xu, Lipeng,Wang, Yuqiang,Ma, Dik-Lung,Leung, Chung-Hang
, p. 497 - 503 (2017)
We report herein the identification of the rhodium(III) complex [Rh(phq)2(MOPIP)]+ (1) as a potent and selective ATP-competitive neural precursor cell expressed, developmentally down-regulated 8 (NEDD8)-activating enzyme (NAE) inhibitor. Structure-activity relationship analysis indicated that the overall organometallic design of complex 1 was important for anti-inflammatory activity. Complex 1 showed promising anti-inflammatory activity in vivo for the potential treatment of inflammatory bowel disease.
Synthesis of polypyridyl ruthenium complexes with 2-(1-aryl)-1H-imidazo[4,5-f]-1,10-phenanthroline ligand and its application for luminescent oxygen sensing
Ji, Shaomin,Wu, Wanhua,Wu, Wenting,Guo, Huimin,Yang, Qi,Wang, Quan,Zhang, Xin,Wu, Yubo,Zhao, Jianzhang
, p. 193 - 199 (2010)
Polypyridyl ruthenium (Ru) complexes 1-3 were prepared. Their photophysical properties were investigated by UV-Vis absorption and luminescence emission spectra. The luminescent lifetimes of these Ruthenium complex were prolonged by more than 5 folds (τ = 2. 50 μs for complex 3) when compared with the parent Ru complex 1 (τ = 0. 45 μs). We propose that the extended luminescent lifetime of complex 3 is due to the equilibrium between 3MLCT state and the pyrene localized 3π-π* triplet state (3IL). The luminescent O2-sensing property of the complexes in solution and the IMPEK-C polymer film were studied, and the O2 sensing was quantified with the two-site model. The oxygen-sensing property of the Ru complexes can be improved by 104-fold with extension of the luminescent lifetimes. For example, the quenching constant KSV was improved from 0. 0023 Torr-1 of 1 to 0. 2393 Torr-1 for 3. Our results demonstrated a versatile approach for the preparation of Ru (II) polypyridine complexes with extended luminescent lifetimes as functional materials, for example, for luminescent oxygen-sensing applications.
Intramolecular electron transfer in Cu(ii) complexes with aryl-imidazo-1,10-phenanthroline derivatives: experimental and quantum chemical calculation studies
Fedorova, Olga A.,Shepel, Nikolay E.,Tokarev, Sergey D.,Lukovskaya, Elena V.,Sotnikova, Yulia A.,Moiseeva, Anna A.,D'Aléo, Anthony,Fages, Frédéric,Maurel, Fran?ois,Fedorov, Yury V.
, p. 2817 - 2827 (2019)
1H-Imidazo[4,5-f][1,10]phenanthrolines containing phenyl (1), 4-(N,N-dimethylamino)phenyl (2), 4-(azadithiacrown-ether)phenyl (3), 3,4-dimethoxyphenyl (4) and 2,2′-bithiophen-5-yl (5) were synthesized and their Cu(ii) complexes were studied to determine the effect of substituents, geometry of complexes and solvent nature on the spectral and redox properties of the copper complexes. It was found that in the case of 4-(N,N-dimethylamino)phenyl- and 4-(azadithiacrown-ether)phenyl substituents, the formation of a L2·Cu2+ complex of pseudo-tetrahedral geometry causes the appearance of an intense metal-to-ligand charge transfer (MLCT) band in the visible region and induces a positive shift in the reduction potential causing the occurrence of autoreduction of Cu(ii). Density functional theory (DFT) and its extension to time dependent density functional theory (TD-DFT) were employed to study the molecular structure and electronic and spectroscopic properties of copper with the 4-(N,N-dimethylamino)phenyl-1H-imidazo[4,5-f][1,10]phenanthroline ligand (2). The calculation results are in agreement with those obtained from optical measurements. Electrochemical studies showed that the autoreduction is observed when Cu2+/Cu+ transfer and oxidation of the ligand occur under the closed electrochemical condition.
Red-emitting cyclometalated platinum(II) complexes with imidazolyl phenanthrolines: Synthesis and photophysical properties
Sarkar, Ankita,Adusumalli, Venkata N.K.B.,Gupta, Parna
, p. 86 - 92 (2018)
Three cyclometalated platinum(II) complexes with substituted imidazolyl phenanthrolines L1–L3 have been synthesized and characterized using spectral and electrochemical techniques. The effect of substituent (in the appended aromatic ring to the imidazolyl moiety) on the electronic feature and redox potential of the cyclometalated platinum(II) complexes of general formula [Pt(ppy)(L1-L3)]Cl (1–3) are discussed. Complexes 1–3 are luminescent in the solution and solid state. Complex 1, with two trifluoromethyl moieties present in the ligand shows a higher degree of PtII?PtII interaction than the ligand incorporated with N,N-dimethyl moiety. The excimer formation through π ? π and d ? π (Pt?Pt) interactions is evident and the degree of excimer formation is in the order 1 >2 > 3. Excited-state properties are corroborated by static and time-dependent density-functional theory.
Cation-dependent structural diversity of zinc(II), calcium(II) mono- and binuclear complexes of aryl-imidazo-1,10-phenanthroline derivatives
Sotnikova, Yulia,Lukovskaya, Elena,Bobylyova, Alla,Fedorov, Yury,Novikov, Valentin,Peregudov, Alexander,Anisimov, Aleksander,D'Aléo, Anthony,Fages, Frédéric,Fedorova, Olga
, p. 103 - 109 (2016)
The syntheses of azacrown-containing aryl-imidazophenanthroline by reaction of 1,10-phenanthroline-5,6-dion with 4-(1.4.7.10-tetraoxa-13-azacyclopentadecan-13-yl)benzaldehyde producing the ligand 2 in high yield is described. Examination of their Zn(II), Ca(II) and mixed complexes by UV/Vis and NMR spectroscopy suggests electronic communication between the two metal centers of ligand 2. Stability constants, determined by spectrophotometric titration, indicate that the Zn(II) possesses higher affinity toward phenanthroline residue than Ca(II) and does not bind with azacrown-ether residue. This selectivity allows to prepare a mixed Zn(II)/Ca(II) complex.
Luminescent ruthenium(II)-para-cymene complexes of aryl substituted imidazo-1,10-phenanthroline as anticancer agents and the effect of remote substituents on cytotoxic activities
Ashok Kumar, S. K.,Banerjee, Subhasis,De, Sourav,Gauthaman, Ashna,Moorthy, Anbalagan,Paira, Priyankar,Selva Kumar, R.
, (2020/10/18)
Ruthenium complexes are currently significant attention in medicinal chemistry as they offer various properties which make them an appropriate choice for drug development. Herein, a series of ruthenium(II)-p-cymene-2-aryl-imidazo-1,10-phenanthroline derivatives have been prepared and characterised by elemental analysis, infrared, LC-mass and NMR techniques. The structural and chemical properties shows that Ru(II) complexes have got rigidity, planarity, aromaticity, hydrogen donating and accepting capability which aids both solubility and interaction with biomolecules. The binding strength of these complexes with DNA and BSA were found to be 104–106 M?1. The competitive displacement of ethidium bromide (EtBr) from DNA in the presence of complex reveals an intercalation or groove binding further this was supported by viscosity and in-silico studies. The cytotoxicity study of these Ru(II) complexes were conducted with two cancer cell lines (MDA-MB-231 and HeLa) and one human embryonic kidney cells (HEK-293). The study revealed that [(η6-p-cymene)RuCl (κ2-N,N-2-(4-fluorophenyl)-1H-imidazo[4,5-f][1,10]Phenanthroline].PF6 (4e), [(η6-p-cymene)RuCl(κ2-N,N-2-(4-bromophenyl)-1H-imidazo[4,5-f][1,10]Phenanthroline].PF6 (4f) and [(η6-p-cymene)RuCl(κ2-N,N-2-(4-nitrophenyl)-1H-imidazo[4,5-f][1,10]Phenanthro line].PF6 (4g) were found exhibit least inhibitory concentration (IC50) and high selectivity with respect to HeLa and MDA-MB-231. The activity of the Ru(II) complexes were position and substituents dependent.
Imidazole fused phenanthroline (PIP) ligands for the preparation of multimodal Re(i) and 99mTc(i) probes
Banevicius, Laura,Edem, Patricia E.,Mercanti, Natalie,Pitchumony, Tamil Selvi,Slikboer, Samantha R.,Valliant, John F.
, p. 14826 - 14836 (2020/11/11)
A small library of [2 + 1] 99mTc(i) complexes based on phenyl-imidazole-fused phenanthroline (PIP) ligands were synthesized and evaluated as multimodal molecular imaging probes. Using either a two-step or a one-pot synthesis method, 99mTc-PIP complexes containing N-methylimidazole as the monodentate ligand were prepared and isolated in good (54 to 89%) radiochemical yield, with the exception of one derivative bearing a strongly electron-withdrawing substituent. The stability of the [2 + 1] complexes was assessed in saline and in cysteine and histidine challenge studies, showing 6 hours stability, making them suitable for in vivo studies. In parallel, the Re(i) analogues were prepared as reference standards to verify the structure of the 99mTc complexes. The optical properties were consistent with other previously reported [2 + 1] type Re(i) complexes that have been used as cellular dyes and sensors. To facilitate the development of targeted derivatives, a tetrazine-PIP ligand was also synthesized. The 99mTc complex of the tetrazine PIP ligand effectively coupled to compounds containing a trans-cyclooctene (TCO) group including a TCO-albumin derivative, which was prepared as a model targeting molecule. An added benefit of the Re-PIP-Tz construct is that the emission from the metal complex was quenched by the presence of the tetrazine. Following the addition of TCO, there was a 70-fold increase in fluorescence emission, which can in future be leveraged during in vitro studies to reduce background signal. This journal is
