Phenanthroline Derivatives Research Articles

Regioselective synthesis of pyrano[3,2-f]quinoline and phenanthroline derivatives using molecular iodine

A series of polysubstituted pyrano[3,2-f]quinoline and phenanthroline derivatives have been synthesized by molecular iodine-catalyzed tandem reaction of various propargylic alcohols with or without substituted amines in excellent yields. Moreover, the cyclized side products are also pyrano[3,2-f]quinoline and phenanthroline derivatives.

D–π–A Dye Sensitizers Made of Polymeric Metal Complexes Containing 1,10‐Phenanthroline and Alkylfluorene or Alkoxybenzene: Synthesis, Characterization and Photovoltaic Performance for Dye‐Sensitized Solar Cells

AbstractFour polymeric metal complexes (P1–P4) based on 1,10‐phenanthroline metal complexes and alkylfluorene or alkoxybenzene were synthesized by the Heck coupling reaction and were developed for dye‐sensitized solar cell applications. The target dyes use alkoxybenzene or alkylfluorene as the electron donor, a C=C moiety as the π linker, and the phenanthroline derivative complex was used as the electron acceptor. Bipyridine derivatives were ancillary ligands as well as providing anchoring groups. The thermal, photophysical, electrochemical and photovoltaic properties of these copolymers were investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), C–V curves and I–V curves. Dye‐sensitized solar cells with these polymeric metal complexes as dye sensitizers exhibited considerable power conversion efficiencies (PCE). The dyes containing alkoxybenzenes (P3, P4) exhibited higher PCE values than the corresponding target polymers containing alkylfluorenes (P1, P2), The dye P3 showed the maximal power conversion efficiency of 2.12 % (Jsc = 4.91 mA/cm2, Voc = 0.69 V, FF = 62.5). In addition, the four polymers possessed excellent stabilities, and their thermal decomposition temperatures all exceeded 300 °C, indicating that these polymeric metal complexes are suitable for the fabrication processes of optoelectronic devices.

ChemInform Abstract: Direct Arylation of Phenanthroline Derivatives via Oxidative C—H/C—H Cross‐Coupling: Synthesis and Discovery of Excellent Ligands.

AbstractA protocol for the synthesis of aryl functionalized phenanthrolines (I) is developed.

Asymmetric Ruthenium‐Catalyzed Hydrogenation of 2‐ and 2,9‐Substituted 1,10‐Phenanthrolines

A ‘Phen'atic: The title reaction proceeds in the presence of the chiral cationic ruthenium diamine catalyst (R,R)-1 (Tf=trifluoromethanesulfonyl, Ts=4-toluenesulfonyl). Both chiral 1,2,3,4-tetrahydro- and 1,2,3,4,7,8,9,10-octahydro-1,10- phenanthroline derivatives could be obtained in high yields with excellent enantio- and diastereoselectivity.

Synthesis, characterization, and crystal structure of new four-coordinated cobalt(II) complexes containing phenanthroline derivatives

Two new tetrahedral Co(II) complexes, [Co(dmphen)Cl2)] (1) and [Co(ph2dmphen)Cl2]2·CHCl3 (2), (where dmphen = 2,9-dimethyl-1,10-phenanthroline, or neocuproine and ph2dmphen = 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, or bathoneocuproine) were synthesized and characterized by elemental analysis, and by IR, UV–visible and 1H NMR spectroscopy. Single-crystal X-ray diffraction study of the two compounds revealed analogous tetrahedral arrangements of the ligands around the cobalt(II) ion. Measurement of magnetic susceptibility (χ = 2.31 × 10−5 and 6.96 × 10−6) of 1 and 2 by 1H NMR spectroscopy (Evans method) revealed their magnetic moments were 4.32 and 4.29 BM, respectively, which also suggests tetrahedral coordination in the two complexes, with S = 3/2.

The coupling of carbon dioxide and epoxides by phenanthroline derivatives containing different Cu(II) complexes as catalyst

A series of the mononuclear Cu(II) metal complexes containing the ligand Bdppz [(9a,13a-dihydro-4,5,9,14-tetraaza-benzo[b]triphenylene-11-yl)-phenyl-methanone] (L1) and Aqphen [(12,17-dihydronaphthol[2,3-h]dipyrido[3,2-a:2′,3′-c]-phenazine-12,17-dione)] (L2) were synthesized and used as catalyst for the coupling of carbon dioxide (CO2) and liquid epoxide which served as both reactant and solvent. Dimethylamino pyridine (DMAP) was used as co-catalyst. The yields of epoxides to corresponding cyclic carbonates were determined by comparing the ratio of product to substrate in the 1H NMR spectrum of an aliquot of the reaction mixture. The mononuclear Cu(II) complexes of these ligands were synthesized by treating an ethanol solvent of the appropriate ligand with a different molar amount of CuCl2·2H2O. The Cu(II) complexes were characterized by FT-IR, UV–Vis, elemental analysis, melting point analysis, mass spectra, molar conductivity measurements and magnetic susceptibility techniques. The reaction of the Bdppz and Aqphen ligands in a 1:1, 1:2 or 1:3 mole ratio with CuCl2·2H2O afforded ionic Cu(II) complexes in the presence of Et3N.

Catalysis of Alkene Epoxidation by a Series of Gallium(III) Complexes with Neutral N-Donor Ligands

Six gallium(III) complexes with N-donor ligands were synthesized to study the mechanism of Ga(III)-catalyzed olefin epoxidation. These include 2:1 ligand/metal complexes with the bidentate ligands ethylenediamine, 5-nitro-1,10-phenanthroline, and 5-amino-1,10-phenanthroline, as well as 1:1 ligand/metal complexes with the tetradentate N,N'-bis(2-pyridylmethyl)-1,2-ethanediamine, the potentially pentadentate N,N,N'-tris(2-pyridylmethyl)-1,2-ethanediamine, and the potentially hexadentate N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethanediamine. In solution, each of the three pyridylamine ligands appears to coordinate to the Ga(III) through four donor atoms. The six complexes were tested for their ability to catalyze the epoxidation of alkenes by peracetic acid. Although the complexes with relatively electron-poor phenanthroline derivatives display faster initial reactivity, the gallium(III) complexes with the polydentate pyridylamine ligands appear to be more robust, with less noticeable decreases in their catalytic activity over time. The more highly chelating trispicen and tpen are associated with markedly decreased activity.

Lanthanide pentafluorophenolates. Synthesis, structure and luminescent properties

The pentafluorophenolates of lanthanides Ln(OC6F5)3 (Ln = Nd (1), Tb (2), Er (3)) were prepared by the reactions of pentafluorophenol with appropriate silylamides Ln[N(SiMe3)2]3 in benzene or toluene solution. The same reactions in ether or methanol medium afforded the solvated complexes Ln(OC6F5)3(Et2O)3 (Ln = Nd (4), Eu (5), Tb (6), Er (7), Gd (8)) or Nd(OC6F5)3(MeOH)3 (9), respectively. The phenanthroline complexes Ln(C6F5O)3(phen) (Ln = Pr (10), Nd (11), Er (12)), Ln(OC6F5)3(phen)2 (Ln = Sm (13), Tb (14), Ho (15), Ln(OC6F5)3(phen)2(Et2O) (Ln = Eu (16), Yb (17)), and Ln(OC6F5)3(phen)(Et2O)3 (Ln = Eu (18), Nd (19), Ce (20), Dy (21)), Ln(OC6F5)3(phen)2(H2O) (Ln = Sm (22), Ho (23)), and Gd(OC6F5)3(phen)2(MeOH) (24) were obtained when the reactions were carried out in the presence of 1,10-phenanthroline. The complexes with pyridine Tb(OC6F5)3(py)5 (25) and 2,2′-bipyridyl Ln(OC6F5)3(bpy)2 (Ln = Tb (26), Yb (27)) were synthesized similarly. Compounds 7, 22, 23, and 24 were characterized by X-ray analysis. The complexes Ln(OC6F5)3 decompose above 150 °C in vacuum to give lanthanide fluorides and octofluorodibenzo-p-dioxine. Phenanthroline derivatives are stable up to 310 °C. Luminescence spectra of all the obtained complexes in visible region contain a broad band of ligand-centered emission peaked at 405–415 nm. Spectra of samarium 13, europium 5, 16, 18 and terbium 14, 25, 26 derivatives display also the characteristic narrow bands of Sm3+, Eu3+ and Tb3+ ions.

N,N-Diphenyl-4-(1H-pyrrolo[1,2-f][1,10]phenanthrolin-2-yl)aniline ethanol monosolvate

The title compound, C32H21N4·C2H5OH, crystallized as an ethanol monosolvate. In the mol­ecule of this phenanthroline derivative, the pyridine rings are almost coplanar, making a dihedral angle of 1.54 (13)°. The tri­phenyl­amine group, introduced as an electron donor, shows a propeller-type structure, and the dihedral angles between the benzene rings are 68.71 11), 63.92 (16) and 70.81 (15)°. In the crystal, the phenanthroline mol­ecules are linked via the solvent mol­ecule by N—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds, leading to the formation of zigzag chains propagating along [010]. These chains are linked via C—H⋯N hydrogen bonds, forming undulating two-dimensional networks extending in the a- and b-axis directions.

Searching for Vanadium‐Based Prospective Agents against Trypanosoma cruzi: Oxidovanadium(IV) Compounds with Phenanthroline Derivatives as Ligands

AbstractSearching for new promising metal‐based drugs for the treatment of parasitic diseases against Trypanosoma cruzi, three related oxidovanadium(IV) complexes, [VIVO(SO4)(H2O)2(NN)], with the phenanthroline derivatives (NN) 1,2,5thiadiazolo[3,4‐f]1,10phenanthroline (tdzp), 1,10‐phenanthroline‐5, 6‐dione (phendione), and 5,6‐epoxy‐5,6‐dihydro‐1,10‐phenanthroline (epoxyphen) are synthesized, characterized, and evaluated in vitro as anti‐T. cruzi agents. The compounds are characterized in the solid state and in solution by elemental analysis, electrospray ionization mass spectrometry (ESI‐MS), conductimetric measurements, and infrared (FTIR), UV/Vis, and electronic paramagnetic resonance (EPR) spectroscopy. EPR spectroscopy suggests that the ligands act as bidentate, binding through both nitrogen donor atoms in an axial‐equatorial mode. DFT calculations corroborate the structural assignments. The stability of the complexes in solution is evaluated by EPR and 51V‐ NMR spectroscopy and all complexes show reasonable stability. The anti‐T. cruzi activity of the complexes was tested by measuring the growth inhibitory effect on the epimastigote life cycle form of the parasite (Dm28c strain). All complexes show IC50 values in the micromolar range against T. cruzi and display activities of the same order of that of Nifurtimox, but lower than that of the previously reported analogue [VIVO(SO4)(H2O)2(dppz)] (dppz = dipyrido[3, 2‐a:2′,3′‐c]phenazine). Furthermore, DNA was evaluated as a potential target by using atomic force microscopy (AFM), showing that the complexes display ability to interact with this biomolecule.

Iridium-Catalyzed C–H Borylation of Cyclopropanes

The borylation of cyclopropanes catalyzed by the combination of (η(6)-mes)IrBpin3 or [Ir(COD)OMe]2 and a phenanthroline derivative is reported. The borylation occurs selectively at the methylene C-H bonds of the cyclopropane ring over methine or methyl C-H bonds. High diasteroselectivities were observed from reactions catalyzed by the combination of iridium and 2,9-Me2phenanthroline. The cyclopropylboronate esters that are generated are versatile synthetic intermediates that can be converted to trifluoroborate salts, boronic acids, cyclopropylarenes, cyclopropylamines, and cyclopropanols.

Are Cu(I)-mesoionic NHC carbenes associated with nitrogen additives the best Cu-carbene catalysts for the azide–alkyne click reaction in solution? A case study

Copper(I)-catalyzed azide alkyne cycloaddition is now a widely used tool for the synthesis of elaborated compounds. Until now, few stable and efficient copper(I) catalysts are available despite the limitations inherent to approaches employing the in situ reduction of a CuII species to deliver the catalytic system. We report that the combination of a copper(I)-mesoionic N-heterocyclic carbene (MIC) with a phenanthroline derivative generates a highly active catalyst, functioning in aqueous alcoholic solvent, without the intervention of a reducing agent. This catalytic system surpasses related ‘normal’ N-heterocyclic carbene-based systems in their efficiency.

White light emission from a mixed organogel of lanthanide(iii)-containing organogelators

We prepared Eu(III) and Tb(III) complexes (Eu2 and Tb2) with phenanthroline derivatives which formed organogels in n-decane. The organogels of Eu2 and Tb2 showed red and green emissions, respectively, when excited at 330 nm. TEM images of dry gels of Eu2 and Tb2 showed entangled fiber network structures with fiber diameters ranging from 20 to 60 nm. Eu2 and Tb2 formed stable mixed gels of different compositions in n-decane. The emission spectrum of a mixed gel showed emission peaks from Eu(III) at 595 and 618 nm and from Tb(III) at 496 and 551 nm when excited at 330 nm. A broad emission was observed around 470 nm that was attributed primarily to the ligands of Tb2. At a ratio of Eu2/Tb2 of 1 : 19 by weight, the mixed gel exhibited white luminescence. The CIE color coordinates of the mixed gel were x = 0.36 and y = 0.30 in the white region. The TEM image of the dry gel revealed entangled fibers with diameters ranged from 20 nm to 80 nm without evidence of self-sorting. Trimetallic organogelators, Eu4 and Tb4, were prepared by coordination of Eu2 and Tb2 with two 1,3-diketone groups. Eu4 showed three transitions of Eu(III) ion in the red region and a ligand-centered emission but Tb4 showed only a broad emission in the greenish blue region from the ligands. Eu4 and Tb4 also formed a homogeneous mixed gel in n-decane, showing a whitish luminescence at the ratio of 3 : 1 by weight.

Synthesis and binding studies of novel di-substituted phenanthroline compounds with genomic promoter and human telomeric DNA G-quadruplexes

Six novel di-substituted phenanthroline derivatives 5a-7a and 3b-5b have been prepared, and their binding interactions with human telomeric (h-telo) and promoter (c-kit2 and c-myc) G-quadruplex DNAs were investigated. All the compounds are potent stabilisers of the G-quadruplex structures and compounds 3b, 4b, and 5b exhibit high G-quadruplex DNA selectivity over duplex DNA. The binding affinities of these compounds to G-quadruplex DNA are higher than to duplex DNA. CD spectra show that the compound can induce the formation of an anti-parallel structure of the h-telo G-quadruplex. Each h-telo quadruplex binds two compound molecules by the end-stacking mode. Six new compounds are able to inhibit significantly the telomerase activity at low μM concentration.

A Novel 3D Mn(II) Supramolecular Coordination Polymer Constructed by 1,10-Phenanthroline Derivative and Flexible Dicarboxylate

A new Mn(II) coordination polymers based on the 1,10- phenanthroline derivative and flexible dicarboxylate, namely [Mn2(L)2(trans-1,4-chdc)] (1), where L = 11-fluoro-dipyrido[3,2-a: 2′,3′-c]phenazine and trans-1,4-chdc = 1,4-cyclohexanedicar- boxylate, has been successfully synthesized under hydrothermal condition. Compound 1 shows a one-dimensional chain structure. The neighboring chains are extended into a 3D supramolecular architecture by π-π interactions. Its thermal property was also investigated.

Direct arylation of phenanthroline derivatives via oxidative C–H/C–H cross-coupling: synthesis and discovery of excellent ligands

A concise synthetic protocol for aryl functionalized phenanthrolines has been developed. It was demonstrated that 3,8-diphenyl-1,10-phenanthroline (7a) is competent in promoting transition-metal-free direct arylation and 2,3,8,9-tetraphenyl-1,10-phenanthroline (8a) is a highly efficient ligand in the in situ Pd-catalysed Heck reaction.

A phenanthroline derivative as exciton blocking material for organic solar cells

Abstract Functionalization of phenanthroline in the 4,7-positions with pyridine groups is reported. The new material, 2,9-dimethyl-4,7-di(pyridin-4-yl)-1,10-phenanthroline (DMPP), shows lower HOMO and LUMO levels than those of bathophenanthroline (BPhen). DMPP-based zinc phthalocyanine (ZnPc):C 60 flat-heterojunction solar cells exhibit a 3.5% power efficiency which is higher than that of those devices with BPhen as the exciton blocking material.

Microwave-assisted Synthesis of Imidazole[4,5f][1,10]phenanthroline Derivatives and Microwave Nonthermal Effect

A series of imidazole[4,5f][1,10]phenanthroline and its derivatives were synthesized using 1,10-phenanthroline and various benzaldehydes and substitute benzaldehydes as raw materials in Pyrex reactor through application of microwave-assisted heating technology with the yield of 52% —89%,and the target compounds were characterized and in agreement with that of literature.The orthogonal test methods were used to optimize the synthesis conditions of PIP and the results indicated that the yield of PIP will reach to 89% under the irradiation of microwave for 20 min at 100 ℃ with a reactant ratio of n(phenanthroline) ∶ n(benzaldehydes) = 1.0∶ 1.5.Compared with the conventional synthesis method,microwave-assisted synthesis offers a simple feasible method to synthesize imidazole[4,5f][1,10]phenanthroline and its derivatives with high yield in a short time.Further studies on the synthesis of p-BrPIP in SiC vial,which adsorb the microwave and transfer it to heat instantly,showed a reducing yield but improving stability of the reaction compare to that in prexy vial attributed to the nonthermal effect of microwave.

A high performance liquid chromatography method to determine phenanthroline derivatives used in OLEDs and OSCs

A high performance liquid chromatography (HPLC) method to detect commonly used electron transport layer (ETL) and hole blocking layer (HBL) materials in organic light emitting diodes (OLED) and organic solar cells (OSC) was established and optimized. The novel method enables the investigation of degradation processes of a range of ETL and HBL materials that were previously difficult to discriminate using the HPLC technique. For instance, 4,7-diphenyl-1,10-phenanthroline (Bphen) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), which are commonly used in OLEDs and OSCs, as well as the new phenanthroline derivatives 2,4,7,9-tetraphenyl-1,10-phenanthroline (TPphen), (2–naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline (HNBphen) and 2,9-di(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline (NBphen) were distinguished. The detection of these molecules was achieved on a phenyl column using an acetonitrile/water mixture (78:22, v/v%) as mobile phase and a photodiode array detector (PDA) for absorbance detection. The factors affecting peak tailing were studied and optimized. The addition of triethylamine (TEA) to the mobile phase after flushing the HPLC system with ethylenediaminetetraacetic acid disodium salt (Na2EDTA) showed the best reduction of the tailing effect. Furthermore, the influence of the tailing on the calculation of the peak area from HPLC chromatograms was investigated.

The interactions of phenanthroline compounds with DNAs: Preferential binding to telomeric quadruplex over duplex

Compounds that bind and stabilize selectively human telomeric quadruplex DNA structures are of significant interest due to their potential to inhibit telomerase and to halt tumor cell proliferation. In our previous study, we found that three novel phenanthroline derivatives could induce and stabilize significantly the formation of an antiparallel structure of human telomeric G-quadruplex DNA (G3(T2AG3)3), moreover, these compounds could bind selectively to G-quadruplex over duplex. In order to understand their binding nature, in this work we investigated the interactions of compounds 1–3 with human telomeric G-quadruplex and i-motif (C3(A2TC3)3) DNAs together with calf thymus DNAs (ct DNA) by means of absorption, fluorescence and CD spectroscopies and competition dialysis assay. Results showed that all three compounds showed the highest affinity for G-quadruplex structure although with least affinity for ct DNA. Compounds 1–3 could also stabilize the structure of i-motif with an increase in melting temperature (ΔTm) of 7.6, 7.2 and 10.1°C, respectively, in the presence of 10 times excess of compounds. Their binding stoichiometric ratios were 2:1 and 1:1 for G-quadruplex and i-motif DNAs, respectively. The thermodynamic parameters results indicated that the binding of compound to either quadruplex or duplex DNAs was entropically driven and hydrophobic force played a major role in the reaction.