Hydrothermal Syntheses and Crystal Structures of Three Lanthanide(Ⅲ)Complexes Based on Carboxyl Derivatives of 1,10-Phenanthroline

Three lanthanide(III) complexes [Ln(4-NCP)(1,4-BDC)]n·xn H2O(Ln = Pr(1), Sm(2), Nd(3). 4-HNCP = 2-(4-carboxyphenyl)imidazo(4,5-f)(1,10)phenanthroline, 1,4-H2 BDC = benzene-1,4-dicarboxylic acid) have been hydrothermally synthesized and characterized via elemental analysis, infrared spectrometry and single-crystal X-ray diffraction. Structural analyses revealed that complexes 1~3 possess similar porous three-dimensional frameworks with the point symbol {4^(12)·6~3}. Meanwhile, complexes 1~3 exhibit excellent thermal stabilities and complex 2 exhibits characteristic luminescent property.

Synthesis and Characterization of Rare Earth Tesnary Complexes with Cinnamic Acid and O-Phenanthroline

Thirteen solid rare earth tesnary complexes with cinnamic acid C 6H 5CH=CHCOOH, HL and o phenanthroline (phen), RE(phen)L 3 were synthesized. Their IR absorption spectra, molar conductance, TG DTA, X ray power diffraction analysis and fluorescence spectra were studied. The results show that all coordination compounds are oxidized and decomposed around 400 ℃ to 540 ℃. They are all crystalline material. The fluorescence spectra indicate that the fluorescence emission intensity of Eu(phen)L 3 is the highest among them.

HYDROXYLATION OF PHENOL BY IRON(Ⅱ)-PHENANTHROLINE(PHEN)/MCM-41 ZEOLITE

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Fluorescence of complexes of EuⅢwith aromatic carboxylic acid-1,10-phenanthroline

The 1,10 phenan throline aromatic carboxylic acid(benzoic acid and o phthalic acid) binary and ternary complexes of europium were synthesized.The fluorescence and FT IR spectroscopy,elemental analysis,UV spectroscopic studies on these complexes were also performed.These complexes can emit strong red fluorescence of Eu? excited by UV light.At the same excited wavelength,the fluorescence spectra of the complexes were also studied.The results indicated that the fluorescence intensities of ternary complexes are stronger than that of binary complexes.The reason is that phenanthroline has higher electron density and higher orbit scope in the conjugated system and consequently an easier energy transfer to the europium ion,which makes the fluorescence intensity of ternary complexes be stronger than that of binary complexes.

Photophysical Properties of Rare Earth Complexes with 3,4-Furandicarboxylic Acid and 1,10-Phenanthroline

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RUTHENIUM COORDINATION COMPOUBNDS WITH POLYPYRIDINES Ⅳ SYNTHESIS AND CHARACTERIZATION OF （2－PHENYL）IMIDAZO［f］ 1， 10－PHENANTHROLINE AND THEIR Ru（Ⅱ） COORDINATION COMPOUNDS

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PREPARATION AND MAGNETIC PROPERTIES OF POLY(SCHIFF BASE) COMPLEXES CONTAINING PHENANTHROLINE UNITS

Two poly(Schiff base)s (PDBT and PDPE) were synthesized by polycondensation of 1,10-phenanthroline-5,6- dione (PD) with 2,2′-diamino-4,4′-bithiazole (DABT) and 4,4′-diaminodiphenyl ether (DAPE),respectively.The structures of the polymers were determined by FTIR and element analysis.The metal (Fe^(2+),Ni^(2+)) complexes were prepared from the polymers with FeSO_4 or NiSO_4,and the metal contents of the complexes were measured by complexometric titration.The magnetic behaviors of the complexes were examine...

Synthesis and Crystal Structure of Quaternary Mixed Anion Complexes of Lanthanide Containing 1,10-Phenanthroline

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Synthesis and Crystal Structure of trans(N)-(1,10-Phenanthroline)-bis (DL-Al aninato)-Cobalt( Ⅲ ) Chloridetrihydrate

The title compound was synthesized by the reaction of cis-[Co(phen)2Cl2]Cl·3H2O with DL-alanine at pH = 8, and isolated using a column chromatographic method. Its crystal structure was determined. The crystal structure belongs to mono-clinic system, space group P21/c, with a = 0. 9549(6) nm, b=2.3746(8) nm, c= 1.0782(4) nm, β=114.13(3)°? Z = 4, Dc= 1. 50 g/cm3. The final refinement converged to R = 0. 047 for 3246 independent observed reflections. In the octahedral coordination sphere formed by the cobalt atom and the coordinate atoms, N, O of DL-alan-inato ligands are in the configuration of trans-N ,N form.

Chemiluminescence Determination of Thiourea Using Tris(1,10-phenanthroline)-ruthenium(Ⅱ) -KMnO_4 System

The light emission produced by thiourea in oxidation process by permanganate in acidic solution in the presence of Ru(phen) 2+ 3 is used to determine 1.0×10 -8 \|1.0×10 -5 mol/L thiourea. The limit of detection is 9.8×10 -9 mol/L and the relative standard deviation is 1.1% for a 1.0×10 -5 mol/L thiourea solution ( n =10). The method was applied satisfactorily to the determination of thiourea.

Synthesis, characterization, and stability of iron (III) complex ions possessing phenanthroline-based ligands

It has previously been demonstrated that phenanthroline-based ligands used to make gold metallotherapuetics have the ability to exhibit cytotoxicity when not coordinated to the metal center. In an effort to help assess the mechanism by which these ligands may cause tumor cell death, iron binding and removal experiments have been considered. The close linkage between cell proliferation and intracellular iron concentrations suggest that iron deprivation strategies may be a mechanism involved in inhibiting tumor cell growth. With the creation of iron (III) phen complexes, the iron binding abilities of three polypyridal ligands [1,10-phenanthroline (phen), 2,9-dimethyl-1, 10-phenanthroline (methylphen), and 2,9-di-sec-butyl-1, 10-phenanthroline (sec-butylphen)] can be tested via a competition reaction with a known iron chelator. Therefore, iron (III) complexes possessing all three ligands were synthesized. Initial mass spectrometric and infrared absorption data indicate that iron (III) tetrachloride complex ions with protonated phen ligands (RphenH+) were formed: [phenH][FeCl4], [methylphenH][FeCl4], [sec-butylphenH][FeCl4]. UV-vis spectroscopy was used to monitor the stability of the complex ions, and it was found that the sec-butylpheniron complex was more stable than the phen and methylphen analogues. This was based on the observation that free ligand was observed immediately upon the addition of EDTA to the [phenH][FeCl4] and [methylphenH] [FeCl4] complex ions.

A model study on the stacking interaction of phenanthroline ligand with nucleic acid base pairs: An ab initio, MP2 and DFT studies

The stacking of phenanthroline(phen) ligand within base pair sequences is one of the important factors for the stabilization of metalphen complex within DNA. The stacking ability of this ligand has been assessed to deduce the base pair selectivity as well as to identify the favored region of intercalation. Different level of theories have been used to predict the favorable regions for stacking interaction of phen ligand with base pair, but the results of MP2/6-31+G(d,p) is found to be reasonably good for monitoring such interactions.

Synthesis and Structure of Dimeric Copper (I) Complex from Bis[(2,2’)-dimethyl 2,2’-(1,10-phenanthroline-2,9-diyl) bis(methan-1-yl-1-ylidene)-bis(hydrazinecarbo dithioate)]

Metal complex, bis[(2,2’)-dimethyl 2,2’-(1,10-phenanthrline-2,9-diyl)bis(methan-1-yl-1-ylidene)-bis(hydrazinecarrbo dithioate)copper(I)], was synthesized from the reaction of Schiff base, (2,2’)-dimethyl 2,2’-(1,10-phenanthroline-2,9-diyl)bis(methan-1-yl-1-ylidene)-bis(hydrazinecarbo dithioate) and CuCl2 at reflux condition in methanol. The copper centers of the complex appear to be reduced. This probably was facilitated by in situ oxidative formation of disulfide bond at the uncomplexed ligand moieties. Single crystal X-ray diffraction analysis reveals the distorted tetrahedral geometry around the copper centers. This compound crystallizes in the triclinic space group, P-1 with crystallographic parameters: a = 10.006(3) ?, b = 13.272(3) ?, c = 22.123(6) ?, α = 85.656(6)°, β = 81.656(6)°, γ = 73.097(5)°, μ = 1.223 mm-1 , V = 2779.5(13) ?3, Z = 2, Dc = 1.437 Mg/m3, T = 293 (2) K.

2-27 A Density Functional Theory Study on Amide-substituted Phenanthroline Ligands for the Separation of Lanthanides and Actinides

As the novel ligands for the separation of trivalent actinides from lanthanides for spent nuclear fuel reprocessing,the amide-substituted 1,10-phenanthroline derivations were found to have high selectivity on Am(III) and Eu(III) in nitric acid media[1;2]. However, the origin of their extraction abilities is still an open question.

Molecular Recognition of Human Telomeric DNA by Phenanthroline-Based G-Quadruplex Ligands

G-quadruplexes (G4) are non-canonical DNA structures assumed by guanine rich sequences. G4 are stabilized by the presence of cations and are characterized by a high degree of structural polymorphism with different patterns of groove, loop arrangement, strand orientations and stoichiometry. G-rich sequences are over-represented in the promoter regions of many oncogenes as well as at human telomeres, d(TTAGGG) repeats, ranging in size from 3 to 15 kb, involved in protecting chromosomal ends. A specialized enzyme, called telomerase, provides a telomere maintenance mechanism by elongating the end of the G-strand and it is activated in the majority of cancer cells. Therefore there are two general strategies of telomerase targeting in cancer treatment. One is a direct targeting of telomerase to cause its inhibition;the other one is the use of G4 stabilizers which block telomerase access to telomere, thus causing an indirect enzyme inhibition. Here, we evaluated the molecular recognition of some phenanthroline-based ligands against four different experimental models of the human telomeric sequence d[AG3(T2AG3)3] by means of docking simulations. Our theoretical analysis was able to reproduce the experimental affinity measurements, with a linear squared correlation factor r2 equal to 0.719 among all the studied models. These findings highlighted the importance to consider the polymorphism of the DNA G4. Interestingly, this correlation resulted always improved with respect to that of the single folds, with the exception of the parallel structure, thus suggesting a key role of this G4 conformation in the interaction network of the tested binders. Moreover, we identified the moieties of the phenanthroline scaffold directly involved in the complex formation. This allowed to rationalize the improved binding affinity always associated with a bis-phenanthroline system and to explain why a phenanthroline substituted with a pyridine ring is favored with respect to the pyrimidine one.

Efficacious selective separation of U(Ⅵ) over Mo(Ⅵ) using novel 2,9-diamide-1,10-phenanthroline ligands: Liquid-liquid extraction and coordination chemistry

Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the four phenanthroline diamide ligands were synthesized, and extraction and stripping experiments were performed under different conditions to evaluate the potential application of these ligands for separation of U(Ⅵ) over Mo(Ⅵ). With the growth of alkyl chain, the solubility of ligands could be greatly improved, and the separation effect of U(Ⅵ) over Mo(Ⅵ) gradually increased. The SF_(U/Mo) were around 10,000 at 4 mol/L HNO3. Three stripping agents were tested with the stripping efficiency of Na_(2)CO_(3)(5%) > H_(2)O > HNO_(3)(0.01 mol/L). The stripping percentages of the three stripping agents were all close to unity, indicating that the ligands had the potential to be recycled. The chemical stoichiometry of U(Ⅵ) complexes with ligands was evaluated as 1:1 using electrospray ionization mass spectrometry,ultraviolet visible spectroscopy and single-crystal X-ray diffraction. The consistency between theoretical calculation and experimental results further explains the coordination mechanism.

Phenanthroline Derivatives as Efficient Organic Photocatalysts for Visible-Light-Mediated PET-RAFT Polymerization

Phenanthroline is an excellent and stableπ-electron acceptor with a large conjugated chromophore.Phenanthroline derivatives are widely used in adsorption,photodegradation,solar cells,biology,and so on.At present,there are still limited organic molecules utilized to efficiently photocatalyze reversible-deactivation radical polymerization(RDRP).Therefore,the design of organic photocatalysts(OPCs)for RDRP remains a challenge.Herein,according to the strategy of combining the donor groups and weak acceptor groups,donor-acceptor(D-A)type OPCs based on phenanthroline were utilized for the first time in photoinduced electron transfer-reversible addition-fragmentation chain transfer(PET-RAFT)polymerization.1,10-Phenanthroline-5-amine(Aphen)with a donor group-amino was screened out for efficacious photo-controlled radical polymerization under blue light for various monomers with conjugated and unconjugated structures with high monomer conversion and well-defined narrow dispersity polymers(Đ<1.20).Controllable homo-polymers and block copolymers were successfully realized by chain extension reaction and block copolymerization of structurally diverse monomers.

Host-guest complexes of cucubit[8]uril with phenanthrolines and some methyl derivatives

The host-guest relationship between cucurbit[8]uril,phenanthrolines and some methyl substituted 1,10-phenanthrolines has been investigated by using 1H NMR spectroscopy and fluorescence spectroscopy.The results showed that phenanthrolines as molecular guests bind in the cavity and portal of cucurbit[8]uril in a ratio of 2:1 (guest to host).The phenanthroline isomers 1,10-,1,7-and 4,7-showed red shifts between 47 and 108 nm and pronounced in-creases in fluorescent intensity.These same isomers produced inclusion complexes with cucur-bit[8]uril which had moderate to fast exchange rates on the 1H NMR time scale.The methyl substituted 1,10-phenanthrolines studied gave stable inclusion complexes in a ratio of 2:1 which showed slow exchange rates.These guests formed p-p stacked pairs which were cavity bound but also partly protruded from only one portal forming unsymmetrical host-guest complexes.In addition,these p-p stacked pairs formed orientation isomers within the confines of the cucur-bit[8]uril cavity.

The structural characterization of some palladium (Ⅱ) complexes of 1,10-phenanthroline and amino acids by NMR spectroscopy

The complexes [Pd(phen)(aa)]Cl.3H2O, where phen is 1,10-phenanthroline and aa is the anion of glycine (gly), .DL-alanine (ala), DL-serine (ser) or DL-asparagine (asn), were synthesized and characterized by spectroscopies. The NMR signals were assigned completely on the basis of the double irradiation, 1H-1H COSY and 1H-13C COSY techniques. In the 1H NMR spectra of phen in the complexes, the signals of 2-H and 9-H show upfield shifts 0.8-1 ppm, while the signals of 4-H and 3-H show downfield shifts or almost no shift, as compared to the free phen ligand, and the signal of 4-H appears in the lowest field. The signals of ring B which is trans to the carboxyl group show significant upfield shifts as compared to those of ring A. The probable structures were described on the basis of a metal-non-bonded hydrogen interaction, trons effect and ligand-ligand interaction. There may exist three conformation isomers in the [Pd(phen)(asn)]Cl.3H2O complex at room temperature. The preferred conformation isomer is

Synthesis, Structures and Room Temperature Phosphorescence of 2-(2-Methoxynaphthyl)-1H-imidazo[4,5-f][1,10]-(1)phenanthroline-Cu(I) Complexes

A new ligand,2-(2-methoxynaphthyl)-1H-imidazo[4,5-f][1,10]phenanthroline(mnipH),was synthesized by the condensation of 2-methoxy-1-naphthaldehyde and 5,6-diamino-1,10-phenanthroline.Then three ionic copper(I)complexes were obtained through the reactions of[Cu(MeCN)4]ClO4,mnipH and the chelating diphosphine ligands with a molar ratio of 1:1:1.The photoluminescence and the corresponding luminescent mechanism of all copper(I)complexes in the solid state were investigated at room temperature.