Synthesis and luminescence properties of rare earth ternary complexes consisting of Tb(Ⅲ), β-diketones and 1,10-phenanthroline (phen)

In order to study the luminescent properties of ternary rare earth complexes with fl-diketone ligand, three new β-diketone ligands, 1-phenyl-3-（p-phenylethynylphenyl）-1,3-propanedione（HPPP）, 1-（2-thienyl）-3-（p-phenylethynylphenyl）-1,3-propanedione （HTPP） and 1-（2-furyl）-3-（p-phenylethynylphenyl）-1,3-propanedione （HFPP）, were synthesized by Sonogashira coupling reaction and Claisen condensation. Three new ternary rare earth complexes, TbL3phen （L = PPP, TPP, or FPP）, were synthesized by the reaction of rare earth chloride TbCl3,1,10-phenanthroline （phen） with HPPP, HTPP, or HFPP respectively, in alcohol solution. The compositions were characterized by means of elemental analysis, chemical analysis, and IR spectra. Luminescent properties of the three new complexes have been studied. The results show that the ternary Yb（Ⅲ） complexes only emit the weak fluorescence of the Tb（Ⅲ） ion, which reveals the triplet state energy of the ligands does not match well with the excited state vibrating energy of Tb^3＋ ion.

Preparation of Ternary Lanthanide Complexes with Unsaturated Acid and 1,10-Phenanthroline, and Their Anti-Inflammatory Action

Four ternary lanthanide complexes with unsaturated acid and 1,10-phenanthroline are prepared in methanol and characterized by elemental analysis, molar conductance, UV, IR, (()~1H) NMR and XPS. The results from this paper show that the complexes Ln(phen)(SA)_3·2H_2O or Ln(phen)(CA)_3·H_2O (Ln=Ce(Ⅲ), Sm(Ⅲ) and Eu(Ⅲ), (phen=1,10-)phenanthroline, SA=Sorbate and CA=Cinnamate) has better anti-inflammatory effect than cerium nitrate and their gremores are steadier than cerium nitrate gremor. And there is a kind of medicament which can replace the cerium nitrate gremor completely in treating burn.

Synthesis,Crystal Structure and Antibacterial Activity of a New Ternary Copper(Ⅱ) Complex with 2,6-Pyridinedicarboxylic Acid and 1,10-Phenanthroline

A new ternary copper（Ⅱ） complex, [C43H27Cu2N7O5][C14H6CuN2O8]＇6.5H2O, has been synthesized by the reaction of copper sulfate, 2,6-pyridinedicarboxylic acid and 1,10- phenanthroline （phen）, and characterized by elemental analysis, IR, UV and X-ray single-crystal diffraction. It crystallizes in triclinic, space group P1, with a = 14.379（5）, b = 15.510（5）, c = 15.835（6） A, a = 78.567（6）, β = 63.594（6）, y = 81.287（6）°, V= 3092.1（19） A3, C57H46Cn3N9O19.5, Mr = 1359.54, Z = 2, Dc = 1.446 Mg/m3, λ（MoKa） = 0.71073 A,μ = 1.101 mm^-1, F（000） = 1362, S = 1.071, the final R = 0.0718 and wR = 0.11960 for 10705 observer reflections （I 〉 2σ（I））. The structure unit of the title complex consisfs of a mononuclear part and a di-nuclear part, and the three copper ions show three coordination modes. Each 6-coordinated geometry of the Cu atom is a distorted octahedral coordination geometry. The 3D supramolecular system is formed by the hydrogen bond O-H-O and π-π stacking interaction between neighboring single cells. The antibacterial activity of the title complex is also studied.

Synthesis and luminescence properties of rare earth ternary complexes consisting of Eu(III), β-diketones and 1,10-phenanthroline

Three novel β-diketones （HPPP, HTPP, and HFPP） ligands were synthesized by Sonogashira coupling reaction and Claisen condensation. The structure of β-diketones was confirmed with elemental analysis, IR, NMR and MS spectra. Three new ternary complexes consisting of Eu（Ⅲ）, β-diketones, and 1,10-phenanthroline（phen） were synthesized and characterized as TbL3phen （L=PPP, TPP, FPP） with elemental analysis, chemical analysis, and IR spectra, and their luminescence properties were studied.

Synthesis and Properties of Ternary Europium Complexes with Aromatic Carboxylic Acid and Nitrogen-Containing Heterocyclic Ligand

Seven ternary Eu （m） complexes were synthesized with aromatic carboxylic acid （benzoic acid, phenylacetic acid, phenylpropionic acid and cinnamic acid） as the first ligand and 1,10-phenanthro- line or 2,2＇-dipyridyl as the second ligand. The ternary Eu（ Ⅲ ） complexes were characterized by elemental analysis, IR and TG-DTG methods. In these complexes, the Eu （Ⅲ） ions are bonded to the oxygen atoms of carboxylate and the nitrogen atoms of neutral ligands. Four complexes whose second ligand is 1,10- phenanthrolin have fine thermal stability. Excitation and luminescence spectra of the tide complexes reveal that the fluorescence of the complexes in which 1,10- phenanthrolin as the second ligand are more intensive than those complexes in which 2, 2＇-dipyridyl as the second ligand. The order of the strongest emission peak of seven ternary complexes is： Eu（β-PPA）3phen 〉 Eu（BA）3phen 〉 Eu（PLA）3phen 〉 Eu（BA）3bipy 〉 Eu （ PEA）3bipy 〉 Eu （ CA ）3phen · H2O 〉 Eu （ CA ）3bipy （BA ： benzoic ; PEA ： phenylacetic ; β-PPA ：

Studies on Intramolecular Stacking Interaction of Ternary Complexes M（Ⅱ）（ATP）￣（2－） with Heteroaromatic N－Base Ligands

o understand the driving forces leading to mixed-ligand complexes in biologi-cal systenis.ternary complexes of M (ATP(L￣(2-) type, where M = Cu￣(2+), Ni￣(2+) orCo￣(2+) , and L= pyridine(Py) , 4-picoline, 3, 5-lutidine, isoquinoline (lq) or benzimi-dazole(Bi) in aqueous solution were studied by spectropliotometry, some of them(M=Cu￣(2+), L = isoquinoline or benzimidazole) were also separately studied hy po-tentiometric pH titration. The results show that an intramolecular stacking interac-tion exists between the heteroaromatic ring of the ligands and the purine moiety ofATP.

Synthesis,Crystal Structure and Antimicrobial Activity of a New Ternary Copper(Ⅱ) Complex with p-Chlorophenoxyacetic Acid and 2-Amino Benzothiazole

A novel ternary complex of Cu（pcpa）2（aben）2 （pcpa=p-chlorophenoxyacetic acid anion,aben=2-amino benzothiazole） was synthesized by the reaction of copper acetate,2-amino benzothiazole and p-chlorophenoxyacetic acid.Elemental analysis,IR,UV and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure.The crystal crystalli-zes in the monoclinic system,space group C2/c with a=25.795（4）,b=7.384（3）,c =17.741（6）,β=107.47（2）°,C30H24Cl2CuN4O6S2,Mr=735.09,V=3223.2（18） 3,Z=4,Dc=1.515 Mg/m3,λ（MoKα）=0.71073 ,μ=1.022 mm-1,F（000）=1500,the final R=0.0464 and wR=0.1244.A total of 3218 unique reflections were collected,of which 2228 with I 〉 2σ（I） were observed.The Cu（II） atom is four-coordinated with two carboxylate oxygen atoms of the two pcpa ligands and two nitrogen atoms in thiazole rings of two aben ligands.The analysis of crystal structure shows intermolecular and intramolecular hydrogen bonds between amino-nitrogen atoms of the two aben ligands and carboxylate oxygen atoms of the two pcpa ligands.The antimicrobial properties of the title complex and its two free ligands were tested against representative bacterial and fungal strains.Results show that the antibacterial activity of the complex is less than or equal to that of 2-amino benzothiazole,but for yeasts and moulds,it exhibits excellent inhibitory effect better than that of its two free ligands.

A Trinuclear Ni(Ⅱ) Mixed-ligand Complex Containing Pentadentate N-butyl-salicylhydrazide and Monodentate Imidazole:Synthesis, Characterization and Crystal Structure

A novel trinuclear nickel（II） complex [Ni3（bushz）z（Himdz）2（H20）2].2DMF （1, bushz = N-butylsalicylhydrazide, Himdz = imidazole, DMF = N,N-dimethyl-forrnamide） has been synthesized and characterized by X-ray single-crystal diffraction characterization. Complex 1 crystallizes in the monoclinic system, space group P2 1/c with a = 7.706（7）, b = 14.882（6）, c = 18.639（6） A, β = 108.08（2）°, V= 2032（1） A3, Dc = 1.525 g/cm3, Mr = 932.95, Z= 2, F（000） = 972,μ = 1.442 mm-1, the final R = 0.0359 and wR = 0.0771. The three nickel（II） atoms in 1 are arranged in a strictly linear structure and exhibit alternating square-planar and octahedral geometries. The complex is connected to form a supramolecule with an infinite three-dimensional network through intermolecular hydrogen bonds. The electrochemical studies reveal that redox of Ni3＋/Ni2＋ in the complex is a quasi-reversible process. The thermal stability of the title complex was also studied.

Synthesis and luminescent properties of ternary complexes of terbium with thenoyltrifluoroacetone and reactive ligand

Three new reactive ternary terbium complexes were synthesized with the first ligand of thenoyltri-(fluoroacetone) and the reactive secondary ligand such as maleic anhydride, undecenoic acid, oleic acid, and characterized by means of elemental analysis, ethylenediamine tetraacetic acid titrimetric method, Fourier transform infrared and ultraviolet spectroscopies. And the luminescent properties of the ternary terbium complexes were investigated. The results show that the ternary terbium complexes possess much higher luminescent intensity than the binary complex of terbium with thenoyltrifluoroacetone, and the synergy ability sequence of the three reactive ligands is as follows: undecenoic acid>oleic acid>maleic anhydride. Because the ternary terbium complexes contain reactive (ligands) that can be copolymerized with other monomers, a new way for the synthesis of the bonding-type rare earth polymer functional materials with excellent luminescent properties is provided.

THE INTRINSIC ACIDITY CONSTANTS AND SPECIFIC SURFACE AREA OF MARINE SOLID PARTICLES II. THE RELATIONSHIP BETWEEN THE INTRINSIC ACIDITY CONSTANT AND THE TERNARY SURFACE COMPLEX

This paper deals with the infrared spectra of " amino acid- clay , calcium carbonate and y-AlOOH" and " Cu (II )-clay-amino acid" model systems, and shows that the model of the ternary surface complex is M-OHLCu (L = amino acid) for marine solid particle-Cu (II)-amino acid. Study of the formation mechanism of the ternary surface complex shows that the specific surface area , and especially the intrinsic acidity constant, determine whether the ternary surface complex is easily formed, and that factor, FTSC,quantifies the relationship between the promoting effect of organics on Mt-marine solid particle ion exchange and the intrinsic acidity constant and specific surface area.

Synthesis and Fluorescent Property of Europium Ternary Complex-MMA Copolymer

Under the mild condition a new ternary rare earth complex Eu （ DBM ）2MA · 2H2O [ DBM： C6H5COCHCOC6H5; MA： CH2C（CH3）COO^- ] was synthesized by the reaction of EuCl3 with dibenzoylmethane and methacrylate in alcohol. A new bonded copolymer Eu（DBM）2MA-MMA was prepared by copolymerization of the Eu（DBM）2MA·2H2O complex with methyl methacrylate（MMA） monomer using AIBN as an initiator. The composition, structure and fluorescence properties of the complex and copolymer were characterized by means of elemental analysis, complex titration, IR, UV-VIS and fluorescent spectra. The thermal stability, glass temperature and average molecular weight of the copolymer Eu（DBM）2MA-MMA were determined by TG-DTA, DSC and GPC, respectively. The research results show that both of the ternary rare earth complex and the copolymer can emit strong Eu（Ⅲ） fluorescence at 613 nm.

pH-Potentiometric Study on Rare Earths and Calcium Binary and Ternary Complexes with DL-Malic Acid and L-Hydroxyproline

The stability constants of ML binary system and MLL′(M=La^3+～Yb^3+, Y^3+ and Ca^2+; L=DLmalic aicd, L′=Lhydroxyproline) ternary system were determined by pHpotentiometric method under the simulating physiological condition(37 ℃, I=015 mol/L NaCl). The complex species MpLqL′rHs(abbr as pqrs) in the sytems were ascertained by program COMPLEX. The results show that there are three species(1101, 1100 and 1200) in ML binary system and one species(1010) in ML′ binary system. In addition to the above four species, a new species, 1112 was found in the MLL′-ternary system, which is the only species of mixed ligands. Rare earth ions form more stable complexes than calcium ion does and the stability differences between their complexes in the ternary system are less than that in the binary system. The distributions of all the species in LaLL′-ternary system vs pH are discussed.

Photophysical Property of Ternary Complex Eu(DPHA)_3·Phen·2H_2O

One ternary complex of europium with the plant growth regulator HDPHA (2-Hydroxydiphenyl acetic acid) and Phen (1,10-Phenanthroline), Eu(DPHA) 3·Phen·2H 2O, was synthesized and characterized by the elemental analysis and DTA-TG measurement. The photophysical property of the complex was investigated by means of IR spectra, Raman spectrum and laser-exited, high-resolved excitation and emission spectra as well as time-resolved luminescence spectra. The luminescence spectra reveal four Eu 3+ sites with energy difference within 25 cm -1 and local symmetries of C 1 or C 2 or C s in the complex. The energy transfer among the Eu 3+ sites is observed. The 7F J sublevel splitting of the Eu 3+ ion is discussed.

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 as 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.

Ternary Complexes of Rare Earth Nitrate with B-15-C-5 and 4-Picoline N-Oxide

A series of ternary complexes of rare earth(Ⅲ)nitrate with benzo-15-crown-5 and 4-picoline N-oxide have been prepared.They have the general formula of RE(NO_3)_3·2(4-picNO)·3H_2O·(1/2)(B-15-C-5) (RE=La～Tm).Their physico-chemical properties have also been studied with conductance,thermal analysis and IR absorption spectroscopy.

Synthesis and Characterization of Ternary Solid Complex of Europium-8HOQ-TTA

Ternary complex of Eu （Ⅲ） with 8-hydroxyquinoline （8HOQ） and thenoyhrifluoro-acetone （TTA）, Eu （TTA） （8HOQ）2·H2O was synthesized. The properties and structure of the complex were studied using elemental analysis, infrared spectra and ultraviolet absorption spectra. The fluorescence characteristics and emission mechanism of the complex were also discussed based on the fluorescence spectra.

Synthesis and Characterization of Ln(NO_3)_3-Phen-Fu Ternary Complexes

A series of solid ternary complexes[Ln(Phen) 2(Fu)(NO 3)](NO 3) 2(Ln=Y, La, Ce, Nd, Sm, Gd, Ho, Phen=1,10 phenanthroline, Fu=5 fluorouracil) were synthesized and characterized by elemental analysis, molar conductivity, IR and 13 C NMR spectra. The preliminary biological activity studies in vitro indicate that lanthanum complex has a good anti cancer activity. These complexes can be considered as an example of study for the more complicated lanthanide nucleic acid interactions.

Preparation and Catalytic Properties of Polymer-Bound Schiff Base Ternary Complexes

The polymer-bound Schiff base ternary manganese complexes [PS-SalPhe-Mn-L(L=Phen, Bipy and 8HQ)] have been prepared from the polymer-bound Schiff base ligand, a manganese salt and the second ligand, such as 1,10-phenanthroline(phen), 2,2′-bipyridyl(bipy) and 8-quinolinol(8HQ). The polymer-bound Schiff base ternary manganese complexes were characterized by means of infrared spectrometry and ICP-AES. The catalytic activities of the complexes have been studied in the aerobic epoxidation of long-chain linear aliphatic olefins. It is shown that 1-octene or 1-decene can be directly oxidized by molecular oxygen when catalyzed by PS-SalPhe-Mn-L(L=Phen, Bipy and 8HQ), and 1,2-epoxy alkane can be afforded in these reactions.

Triboluminescent Complexes of Rare Earth Ⅱ.Mixed-ligand Complexes of Eu^(3+) with Thenoyltrifluoroacetone and Pyridine-N-Oxide or its Substitutive Derivatives

Five triboluminescent mixed-ligand complexes of Eu^(3+)with thenoyltrifluoroacetone(TTA)and pyridine-N-oxide or its substitutive derivatives have been prepared.They are all pale yellow crystalline com- pounds with the formula of Eu(TTA)_3·L(L=py NO.2-pie NO,3-pie NO,4-pic NO,bipy N_2O_2).Their physico-chemical properties have been studied with conductometry,UV and IR absorption and fluorescence spectroscopy.Once the complexes are touched or rubbed by a glass rod,they emit strong red triboluminescent light which is similar to the characteristic fluorescence of Eu^(3+).

Spectra and DNA-binding Properties of Two Novel Mixed-ligand Complexes Containing Organosulfonate

Two novel mixed-ligand complexes, [M（phen）2（ans）2]·H2O （M = Cd（Ⅱ） 1, Zn（Ⅱ） 2; phen is 1, 10-phenanthroline, and ans is 4-aminonaphthalene-1-sulfonate）, were obtained from the reaction of 1, 10-phenanthroline, sodium 4-aminonaphthalene-1-sulfonate tetrahydrate and acetate in mixed solvents. Interaction of the complexes with calf thymus DNA （ctDNA） were investigated using UV-vis absorption spectra, luminescence titrations, steady-state emission quenching by [Fe（CN）6]4 , DNA competitive binding with ethidium bromide （EB） and viscosity measurements. The experimental results indicate that there exist two interaction modes between the complexes and DNA, namely the electrostatic interaction and intercalation, with the binding constants of 1.82 × 10^5 M-1 for 1 and 4.78 ×10^4 M^- 1 for 2 in buffer of 50 mM NaCl and 5 mM Tris-HCI （pH 7.0）.