Synthesis,spectroscopic characterization,DNA cleavage and antibacterial studies of a novel tridentate Schiff base and some lanthanide（III） complexes

A novel potential tridentate Schiff base was prepared by condensing equimolar quantities of 2-hydroxyacetophenone and 2-aminopyrimidine in methanol. This ligand was versatile in forming a series of complexes with lanthanide ions such as La（III）, Pr（III）, Nd（III）, Sm（III）, Gd（III）, Dy（III） and Yb（III）. The ligand and the metal complexes were characterized through elemental analysis, molar conductance, UV-Visible, IR, 1H NMR, and mass spectral studies. The spectral studies indicated that the ligand was coordinated to the metal ion in neutral tridentate fashion through the azomethine nitrogen, one of the nitrogen atoms in the pyrimidine ring and the phenolic oxygen without deprotonation. Thermal decomposition and luminescence property of lanthanum（III） complex were also examined. The X-ray diffraction patterns showed the crystalline nature of the ligand and its lanthanum（III） complex. The DNA cleavage studies of the ligand and the metal complexes were carried out and it was observed that the lanthanum（III） and neo-dymium（III） complexes cleaved the pUC19 DNA effectively. The ligand and the metal complexes were screened for their antibacte-rial activities. The metal complexes were found to be more potent bactericides than the ligand.     

Complexation of N＇- [1-（3-aminophenyl）ethylidine] isonicotinohydrazide with La3＋, Pr3＋, Nd3＋, Sm3＋, Eu3＋ and Gd3＋ ions and associated thermodynamics

A novel Schiff base N′-[1-(3-aminophenyl)ethylidine]isonicotinohydrazide was prepared and its complexation behavior towards some selected lanthanides had been studied employing pH-metric and calorimetric titration and spectral techniques. pH-metric studies were carried out for the trivalent La, Pr, Nd, Sm, Eu, and Gd complexes in 30% aqueous-dioxane medium at constant ionic strength of 0.05 mol/L NaClO4 and at different temperatures of 293, 303 and 313 K. The proton-ligand formation constants of the ligand indicated the presence of only one dissociable proton while the metal-ligand formation constants were compatible with the formation of 1:1 Ln(Ⅲ) complexes. The sta-bility of the complexes followed the order: La3+Gd3+, showing a break at gadolinium. The thermodynamic parame-ters, ΔG, ΔH and ΔS associated with protonation and complexation reactions were negative which suggested that all reactions were exother-mic and enthalpy-driven. Isothermal calorimetric studies of Gd3+-aeINH systems at 303 K also showed exothermic nature of the complexation reaction and formation of 1:1 complex in agreement with the pH-metric data. Formation of 1:1 complexes was confirmed by the characteriza-tion of Nd(Ⅲ) complex. A seven coordinated geometry was assigned for the complex based on its elemental and spectral data.     

Microwave assisted synthesis, spectroscopic, thermal, and antifungal studies of some lanthanide(Ⅲ) complexes with a heterocyclic bishydrazone

A bishydrazone formed by the condensation of isatinmonohydrazone and salicylaldehyde reacted with lanthanide(Ⅲ) chloride to form complexes of the type [Ln(HISA)2Cl3], where, Ln=La(Ⅲ), ce(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sin(Ⅲ), Eu(Ⅲ), or Gd(Ⅲ) and HISA=[(2-hydroxybenzaldehyde)-3-isatin]bishydrazone. Both reactions were carried out under microwave conditions. The ligand and the metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV visible, infrared, far infrared, and proton NMR spectral data. The ligand acted as neutral tridentate, coordinating through the carbonyl oxygen, azomethine nitrogen, and phenolic oxygen without deprotonation. The ligand and lanthanum(Ⅲ) complex were subjected to X-ray diffraction studies. The X-ray diffraction pattern of ligand exhibited its crystalline nature and that of the lanthanum(Ⅲ) complex indicated its amorphous character. The thermal decomposition behaviour of the complex, [La(HISA)2Cl3], was examined in the temperature range of 40-800 ℃ using TG, DTG, and DTA. The ligand and the metal complexes were screened for their antifungal activities.     

Synthesis, spectroscopic characterization, and thermal decomposition kinetics of some lanthanide(Ⅲ) nitrate complexes of 2-(N-o-hydroxyacetophenone) amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene

Complexes of La(Ⅲ), Ce(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), Dy(Ⅲ), Yb(Ⅲ), and Lu(Ⅲ) with 2-(N-o- hydroxyacetophenone)amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene (HAAT) formed by the condensation of o-hydroxyacetophenone and 2-amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene were synthesized and characterized on the basis of elemental analyses, molar conductance measurements, magnetic susceptibility data, UV-Visible, IR, and NMR spectral studies. The spectral data revealed that the ligand acted as a neutral tridentate coordinating to the metal ion through ONO donor sequence. A coordination number nine was proposed for the complexes. Thermal decomposition studies of the ligand and lanthanum(Ⅲ) complex were carried out and kinetic parameters were calculated using Coats-Redfern equation. The decomposition reactions followed random nucleation mechanism with one nucleus on each particle.     

Cytotoxicity of new Ho(Ⅲ) and Pr(Ⅲ) complexes

New complexes of coumarin-3-carboxylic acid(HCCA) with Ho(Ⅲ) and Pr(Ⅲ) were synthesized and their structures and spectral properties were investigated by elemental analysis,IR,Raman and NMR measurements.According to the experimental data the complexes’ formula and geometries were suggested.Vibrational frequencies,IR intensities and Raman activities as well as 1H NMR chemical shifts of HCCA and its Ho(Ⅲ) and Pr(Ⅲ) complexes were presented.The comparative experimental vibrational and NMR analyses of both the ligand and the Ln(Ⅲ) complexes predicted the bidentate binding to Ho(Ⅲ) and Pr(Ⅲ) through the deprotonated carboxylic oxygen and the carbonylic oxygen of the ligand.The cytotoxic/cytostatic properties of the ligand and the newly synthesized complexes of coumarin-3-carboxylic acid with Ho(Ⅲ) and Pr(Ⅲ) were tested by MTT reduction assay against two mouse tumor cell lines:melanoma B16 and fibrosarcoma L929.They were also tested for cytotoxicity against normal mouse peritoneal macrophages.The proliferation inhibitory effect of the complexes compared to that of the ligand proved their cytotoxic/cytostatic properties against both the tumor cell lines.In addition,the complexes were less cytotoxic against normal mouse macrophages and were able to modulate NO release by activated macrophages.The obtained results were in accordance with our previously published data concerning the activity of lanthanide(Ⅲ) complexes with other coumarin derivatives.     

Microwave assisted synthesis,spectroscopic, thermal,and antifungal studies of some lanthanide（Ⅲ） complexes with a heterocyclic bishydrazone

A bishydrazone formed by the condensation of isatinmonohydrazone and salicylaldehyde reacted with lanthanide（Ⅲ） chloride to form complexes of the type [Ln（HISA）2Cl3], where, Ln=La（Ⅲ）, Ce（Ⅲ）, Pr（Ⅲ）, Nd（Ⅲ）, Sm（Ⅲ）, Eu（Ⅲ）, or Gd（Ⅲ） and HISA= [（2-hydroxybenzaldehyde）-3-isatin]bishydrazone. Both reactions were carried out under microwave conditions. The ligand and the metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV visible, infrared, far infrared, and proton NMR spectral data. The ligand acted as neutral tridentate, coordinating through the carbonyl oxygen, azomethine nitrogen, and phenolic oxygen without deprotonation. The ligand and lanthanum（Ⅲ） complex were subjected to X-ray diffraction studies. The X-ray diffraction pattern of ligand exhibited its crystalline nature and that of the lanthanum（Ⅲ） complex indicated its amorphous character. The thermal decomposition behaviour of the complex, [La（HISA）2Cl3], was examined in the temperature range of 40-800 ℃ using TG, DTG, and DTA. The ligand and the metal complexes were screened for their antifungal activities.     

Synthesis and spectroscopic properties of rare earth picrate complexes with a new dinaphthalenelamide

The new ligand N-benzyl-2-{2’-[(benzyl-ethyl-carbamoyl)-methoxy]-dinaphthalene-2-yloxy}-N-ethyl-acetamide(L) and its complexes of rare earth picrates were synthesized.The complexes were characterized by elemental analysis,IR,UV-vis spectra and conductivity measurements.The fluorescence properties of the europium complex in solid state and CHCl3,ethyl acetone,acetonitrile and DMF were investigated.Under the excitation,the europium complex exhibited characteristic emissions of europium.The lowest triplet state energy level of the ligand indicated that the triplet state energy level of the ligand matched better to the resonance level of Eu(Ⅲ) than Tb(Ⅲ) ion.     

Synthesis and Photoluminescence of Three Europium （ Ⅲ ） Ternary Complexes with New Secondary Ligands of Different Structure

Three new 1,10-phenanthroline derivatives, dipyrido (3,2-f: 2,3-h) quinoxaline (DPQN), imidazo (5,6-f)-( 1,10)-phenanthroline (IP) and 3-phenyl-imidazo (5,6-f)- ( 1,10)-phenanthroline (PIP) were designed and synthesized was a secondary ligand to coordinate with europium (Ⅲ) ion while dibenzoylmethane (DBM) was used as the first ligand. The compositions of the ligands and the europium (Ⅲ) ternary complexes were confirmed by elementary analysis, IR and ^1H-NMR-spectroscopy. The UV-visible absorption spectra, thermal stability, photoluminescence spectra, quantum yield and fluorescence life time of the Eu( Ⅲ) complexes were investigated. The effect of the structure of the secondary ligand on the photoluminescence of the complexes was discussed. The results show that the synthesized Eu(Ⅲ) complexes are good red-emitiing materials for potential application in fabrication of organic electroluminescence devices.     

Synthesis, characterization, fluorescence and DNA-binding studies of europium（Ⅲ） pirates complexes with amide-based 2,3-dihydroxynaphthalene derivatives

Two ligands 2,2′-[2,3-naphthylenebis(oxy)]-bis(N-benzyl(acetamide))(L1) and 2,2′-[2,3-naphthylenebis (oxy)]-bis(N,N-diphenyl (acetamide))(L2) and their europium(Ⅲ) picrate complexes were synthesized. The complexes were characterized by elemental analysis, infra-red (IR), thermogravimetry and differential thermal analysis (TG-DTA) and molar conductivity. Fluorescent experiments showed that the resonance level of the Eu) matched better to the triplet state energy level of the ligand L2 than that of the ligand L1 and the fluorescence in-tensities of the complexes were reduced with the raising coordination ability of solvent. In addition, the interactions between the complexes and DNA were studied by means of spectrometry and cyclic voltammetry. The results suggested that the complexes could bind to DNA through intercalation and the complex 1 binded to DNA more strongly than the complex 2.     

Synthesis and Characterization of Some Lanthanide（Ⅲ） Complexes with 4- [N-（2-methoxy benzylinine）formy1]-2, 3-dimethyl-1-phenyl-3-pyazolin-5-one

A series of seven novel lanthanide（Ⅲ ） nitrato complexes with 4-[ N-（2-methoxybenzylimine）formyl] 1-2, 3- dimethyl-1-phenyl-3-pyazolin-5-one （2mbfa）, were synthesized. These complexes were characterized by elemental analysis, molecular mass determination, conductance and magnetic moment measurements, IR, UV-visible, and ^13CNMR spectral studies, In these complexes, the Schiff base, 2mbfa, acts as neutral bidentate ligand by utilizing the carbonyl oxygen and azomethine nitrogen as donor sites. All the three nitrate ions are also coordinated unidentately with 7 coordination for the lanthanide（Ⅲ） ions with a tentative monocapped octahedral geometry for the complexes. All the seven lanthanide（Ⅲ） complexes have a general formula, [ Ln（2mbfa）：（NO3）3 ].     

Synthesis and Photoluminescence Properties of Rare Earth Complexes with 3-Allyl-2, 4-Pentanedione

In order to combine the merits of rare earth organic complexes with excellent material performances of polymers,a polymerizable chelating agent, 3-allyl-2, 4-pentane dione (APD), was synthesized by phase transfer catalysis and its rare earth complexes were prepared. The compounds were characterized by EA, IR and ^1H NMR. Their UV spectra and fluorescence spectra were investigated. The effects of allyl on the luminescence properties of the complexes were studied.The results show that the sensitization of APD is changed by allyl in comparison with that of acetyl acetone (acac), and it becomes an ideal novel ligand of Eu. In addition, intramolecular energy transfer mechanism in the luminescence process in the complexes was also discussed in detail.     

Synthesis,spectroscopic characterization,and thermal decomposition kinetics of some lanthanide（Ⅲ） nitrate complexes of 2-（N-o-hydroxyacetophenone） amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene

Complexes of La（Ⅲ）, Ce（Ⅲ）, Pr（Ⅲ）, Nd（Ⅲ）, Sm（Ⅲ）, Eu（Ⅲ）, Gd（Ⅲ）, Dy（Ⅲ）, Yb（Ⅲ）, and Lu0ID with 2-（N-o- hydroxyacetophenone）amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene （HAAT） formed by the condensation of o-hydroxyacetophenone and 2-amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene were synthesized and characterized on the basis of elemental analyses, molar conductance measurements, magnetic susceptibility data, UV-Visible, IR, and NMR spectral studies. The spectral data revealed that the ligand acted as a neutral tridentate coordinating to the metal ion through ONO donor sequence. A coordination number nine was proposed for the complexes. Thermal decomposition studies of the ligand and lanthanum（Ⅲ） complex were carried out and kinetic parameters were calculated using Coats-Redfem equation. The decomposition reactions followed random nucleation mechanism with one nucleus on each particle.     

Synthesis and luminescent properties of novel pyrazolone rare earth complexes

A novel pyrazolone pyridine-containing ligand,2,6-bis(1-phenyl-4-ethoxycarbonyl-5-pyrazolone-3-yl)pyridine (H2L) was de-signed and synthesized from pyridine-2,6-dicarboxylic acid (1),and its Eu(III) and Tb(III) complexes were prepared.The ligand and com-plexes were characterized in detail based on FT-IR spectra,1H NMR,elemental analysis and thermal analysis,and the formula of Ln2L3·4H2O (Ln=Eu or Tb) of rare earth complexes was confirmed.The UV-vis absorption spectra and photoluminescence properties of the complexes were investigated,which showed that the Eu(III) and Tb(III) ions could be sensitized efficiently by the ligand (H2L) and emit the photolumi-nescence with high intensity,narrow half-peak width,and monochromic light.The results indicated that the complexes showed potential as excellent luminescent materials.     

Microwave assisted synthesis, spectroscopy and biochemical aspects of lanthanum(Ⅲ) and praseodymium(Ⅲ) complexes with oxadiazole functionalised dithiocarbazinates

The new lanthanum (Ⅲ) and praseodymium (Ⅲ) complexes of the general formula [Ln(L)3] (Ln=La(Ⅲ) or Pr(Ⅲ); LK=potassium salt of dithiocarbazinates) were prepared by both, conventional thermal and by the use of microwave technology. Elemental analyses, elec-trical conductance, magnetic moment and electronic, infrared, far-infrared, 1H and 13C NMR spectral studies were used to characterize the complexes. The molecular weights of few complexes were determined by FAB-mass spectra. Nephelauxetic ratio, covalency parameter and bonding parameter for these complexes were also calculated. The probable structures of the complexes were proposed. The antifungal and antibacterial activities of the complexes were evaluated. The activities were correlated with the structures of the compounds.     

Synthesis and spectral characterization of lanthanide complexes with 1,2-diphenyl-4-butyl-3,5-pyrazolidinedione： Luminescent property of Tb（Ⅲ） complex

The complexes of rare earth elements with 1,2-diphenyl-4-butyl-3,5-Pyrazolidinedione (PBH, phenylbutazone) were synthesized and characterized by elemental analysis, molar conductance, IR, UV-Vis, EPR and magnetic moment measurements. Based on these studies the complexes were formulated as [Ln(PB)3(H2O)2]?nH2O, where Ln=Eu(III), Gd(III), Tb(III), Dy(III) and Er(III). From IR spectra, it was found that PBH acted as a bidentate mono-ionic ligand coordinating through two carbonyl oxygen of the pyrazolidinedione ring. The thermal analysis of all the complexes was carried out at a heating rate of 10 oC/min. The kinetic aspects of the complexes were evaluated. The nega-tive entropy value of the complexes indicated a more ordered state for the activated complexes. The photoluminescence property of Tb(III) complex was investigated. It showed all the characteristic emission peaks of Tb3+ with a life time of 0.98914 ms.     

Solution and Thermodynamic Studies on Binary and Ternary Complexes of Lanthanides

The interactions of La(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), Dy(Ⅲ), and Yb(Ⅲ) with cytosine, 5-bromocytosine, 5-azacytosine and 5-flurocytosine as primary ligands (L) and guanine (A) as secondary ligand for both binary (1:1) as well as ternary (1:1:1) systems were investigated by potentiometric equilibrium measurements at 25, 35 and 45 ℃ in aqueous solution (ionic strength, μ=0.1 mol·dm-3 NaNO3). The stability constants of the binary (1:1) and ternary (1:1:1) metal-ligand complexes follow the following order La＜Pr＜Nd＜Sm＜Eu＞Gd＜Dy＞Yb. Results also indicate that the ternary lanthanide complexes of La(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), Dy(Ⅲ), and Yb(Ⅲ) are more stable than corresponding binary lanthanide complexes. The enthalpy (Δhof) and entropy (Δsof) changes for the formation of binary and ternary complexes were calculated from temperature coefficient data. The ΔΔSof values are positive for all the metal ligand systems. The negative ΔΔHof values indicate the extra stability of the ternary complexes by the exothermic enthalpy changes (ΔΔSof=ΔTSof-ΔBSof and ΔΔHof=ΔTHof-ΔBHof where ΔTSof, ΔTHof and ΔBSof, ΔBHof are the entropy and enthalpy values associated with the ternary and binary complexes, respectively). It was also proposed that the guanine is bonded to metal ions through N1/C6=O and N7 whereas cytosine and its derivatives are bonded through N3 atoms in ternary complexes.     

Synthesis,characterization and fluorescence properties of a novel rare earth complexes with a multi-branched ligand and 1,10-phen

A novel multi-branched ligand with multiple ester groups,multiple benzene rings and multiple carboxyls was synthesized.The composition and structure of the ligand were characterized through the Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance spectrum(1H NMR) and UV spectrometer.The composition and fluorescence properties of rare earth complexes with the ligand and 1,10-phenanthroline(phen) were researched via FT-IR,EA and fluorescent spectrometer.The results presented that the resulting complex had strong characteristic fluorescence spectrum of the rare earth ions,which was attributed to the synergistic effects of the ligand,phen,and rare earth ion.     

Synthesis,spectral characterization,thermal and biological studies of lanthanide(Ⅲ) complexes of oxyphenbutazone

Lanthanide(III) complexes of 4-butyl-1-(4-hydroxyphenyl)-2-phenyl-3,5-pyrazolidinedione(OPB) were prepared by homogeneous precipitation. The solid complexes were characterized by elemental analysis, magnetic susceptibility data, molar conductivity measurements and IR, UV-Vis, mass,1H NMR and13C NMR spectral methods. The thermal decomposition of the complexes under static air atmosphere was investigated by simultaneous TG/DTG at a heating rate of 10 °C/min. The final decomposition products were found to be metal oxides. The spectroscopic data suggested that OPB acted as a bidentate, mono-ionic ligand coordinating through two carbonyl oxygens of the pyrazolidinedione ring. The kinetic and thermodynamic parameters such as activation energy, pre-exponential factor and entropy of activation for each step of the decomposition reactions were evaluated using Coats-Redfern and MacCallum-Tanner equations. The negative entropy values of the complexes indicated that the activated complexes had a more ordered structure than the reactant and that the reactions were slower than normal. Investigations of antimicrobial activity of the compounds were carried out by the disk diffusion technique.     

Synthesis, characterization, and anticancer properties of rare earth complexes with Schiff base and o-phenanthroline

Five novel ternary complexes of the rare earth ions with o-phenanthroline（Phen） and Schiff base salicylaldehyde L-phenyla- lanine（KHL） were synthesized in ethanol. Their compositions were characterized by elemental analysis, molar conductance, ^1H NMR, FT-IR, and Raman spectra. The formulas of the complexes were verified to be RE（L）（Phen）Cl（H2O） （RE=La^3＋, Ce^3＋, Nd^3＋, Er^3＋, and Gd^3＋; L=Schiff base salicylaldehyde L-phenylalanine; phen=o-phenanthroline）. Methyl thiazolyl tetrazolium （MTT） colorimetry and flow cytometry were used to test the anticancer effect of the complexes with K562 tumor cell. The research showed that the complexes could inhibit K562 tumor cell＇s growth, generation, and induce apoptosis. The inhibition ratio was accelerated by increasing the dosage, and it had significant positive correlation with the medication dosage.     

Evaporable luminescent lanthanide complexes based on novel tridentate ligand

A novel tridentate ligand N-(6-(diphenylphosphoryl)pyridin-2-yl)-2,2,2-trifluoroacetamide(DPPOPFA) was designed and synthesized. Crystal structure of the ligand revealed the "keto" form of ligand in solid state other than the "enol" one, and it was also found that two kinds of molecules with different conformations were connected by hydrogen bonding between amide N–H and phosphoryl P=O. This ionic ligand was used to coordinate a variety of lanthanide ions, forming neutral 3:1 complexes. Absolute overall quantum yields of these complexes in solid states were 36% for Eu(Ⅲ), 29% for Tb(Ⅲ) and 3% for Dy(Ⅲ) with lifetimes of 1.1, 1.1 and 0.087 ms, respectively. The complexes had excellent thermal stability and did not decompose till 370 °C. And they could sublimate in vacuum(1×10~(–4) Pa) at 330 °C due to the weak molecular interaction.