A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]py...A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.展开更多
Light conversion agents Eul-xLx（TTA）3Phen (L denotes (La3+, Gd3+, Y3+)) complexes were prepared, and the influence of doping ions on fluorescence properties was investigated by elementary analysis, FTIR and fluoresc...Light conversion agents Eul-xLx（TTA）3Phen (L denotes (La3+, Gd3+, Y3+)) complexes were prepared, and the influence of doping ions on fluorescence properties was investigated by elementary analysis, FTIR and fluorescent spectra. The results show that FTIR spectra of Eul-xLx（TTA）3Phen complex system are identical with that of EuTTA3Phen, which indicates that the complexes (Eul-xLx（TTA）3Phen) are similar in structure to （Eu （TTA）3Phen.） For the above doping elements, co-fluorescence enhancement has the following order: Gd3+>Y3+>La3+, and the optimum mole fractions of doping elements are 0.4, 0.2 and 0.5 respectively for Gd3+, Y3+, La3+. Among all the complexes, Eu0.6Gd0.4（TTA）3Phen complex has the strongest fluorescent intensity. Applying Eu0.6Gd0.4（TTA）3Phen complex to plastic and printing inks, bright red fluorescence plastic and printing inks are obtained when the content of europium reaches 0.1%（mass fraction）.展开更多
A new homochiral ligand,（R）-2-（4-pyridyl）-4,5-dihydrothiazole-4-carboxylic acid（HL^R）, has been synthesized. Two complexes, [ZnL2^R（H2O）2]·H2O（1） and [MnL2^R（H2O）2]？H2O（2） have been prepared by the...A new homochiral ligand,（R）-2-（4-pyridyl）-4,5-dihydrothiazole-4-carboxylic acid（HL^R）, has been synthesized. Two complexes, [ZnL2^R（H2O）2]·H2O（1） and [MnL2^R（H2O）2]？H2O（2） have been prepared by the reactions of Zn（Ⅱ） and Mn（Ⅱ） ions with the ligand HLR, and characterized by single-crystal X-ray diffraction analysis and fluorescence. Complexes 1 and 2 are isomorphs, and both of the Zn（Ⅱ） and Mn（Ⅱ） centers in 1 and 2 are six-coordinated by the two NO units of two ligands and two water oxygen atoms, showing distorted octahedral coordination geometry. Complexes 1 and 2 show fluorescent properties in the solid state at room temperature.展开更多
The enhancement effects of Y ( Ⅲ) ions on the fluorescence of Ce ( Ⅲ) in Ce ( Ⅲ)-Y ( Ⅲ)-PMMA (polymethylmethacrylate ) or Ce ( Ⅲ)-Y ( Ⅲ)-PVC (polyvinyl chloride ) complex systems were observed. The influence of ...The enhancement effects of Y ( Ⅲ) ions on the fluorescence of Ce ( Ⅲ) in Ce ( Ⅲ)-Y ( Ⅲ)-PMMA (polymethylmethacrylate ) or Ce ( Ⅲ)-Y ( Ⅲ)-PVC (polyvinyl chloride ) complex systems were observed. The influence of Y ( Ⅲ) ions on the emission spectra of PMMA ligands in PMMA-Y ( Ⅲ) and the fluorescent enhance- ment of Y( Ⅲ) on Ce( Ⅲ) emission in PMMA-Ce-Y by Y( Ⅲ) ion were studied. It was also of interest to note that when Y ( Ⅲ) ions were added into PMMA and into bpy(bipyridine ) , respectively , the emission spectrum of PMMA ligands was split into fine structure bands by Y ( Ⅲ) , and the fluorescence intensities of bpy ligands in bpy-Y ( Ⅲ) complexes were considerably increased.展开更多
The binary complexes of europium with benzoic acid and its derivatives(phthalic acid, m-phthalic acid, o-aminobenzoic acid, salicylic acid, and sulfosalicylic acid) weresynthesized and their compositions were identifi...The binary complexes of europium with benzoic acid and its derivatives(phthalic acid, m-phthalic acid, o-aminobenzoic acid, salicylic acid, and sulfosalicylic acid) weresynthesized and their compositions were identified by elemental analyses. UV and IR of the complexeshave been investigated. The UV spectra indicated that the complexes' ultraviolet absorption weremainly the ligands' absorption. The IR spectra showed that the IR spectra of complexes are differentfrom those of free ligands. The fluorescence properties of them were investigated by usingluminescence spectroscopy, the results showed that only three complexes appear as betterluminescence, they were Eu-benzoic acid, Eu-m-phthalic acid and Eu-phthalic acid, while the othersexhibited the ligands' wideband emission.展开更多
A new complex of {[Eu2(2-BrBA)6(2,2’-bpy)2]2·CH3CH2OH·H2O} (2-BrBA=2-bromobenzoate; 2,2’-bpy=2,2’-bipyridine) was prepared by solvent method and characterized with X-ray single-crystal diffraction, IR spe...A new complex of {[Eu2(2-BrBA)6(2,2’-bpy)2]2·CH3CH2OH·H2O} (2-BrBA=2-bromobenzoate; 2,2’-bpy=2,2’-bipyridine) was prepared by solvent method and characterized with X-ray single-crystal diffraction, IR spectroscopy, UV spectroscopy, and fluorescence spectroscopy. The complex crystallized in triclinic crystal system, Pī space group, with a=1.17196(4) nm, b=2.36142(9) nm, c=2.59151(9) nm, α=113.266(2)°, β=101.100(2)°, and γ=94.400(2)°. Two independent dinuclear molecules were contained in the asymmetric unit. The two molecules were similar to each other. Each Eu(Ⅲ) ion was nine-coordinated with seven oxygen atoms from five 2-BrBA ligands and two nitrogen atoms from 2,2’-bpy molecule. The carboxylate groups acted as bidentate-chelating, bidentate-bridging and chelating-bridging coordination modes. The complex adopted a distorted monocapped square-antiprism coordination geometry. Five peaks at 579, 591, 613, 652, and 697 nm appeared in the fluorescence spectrum, corresponding to 5D0→7F0, 5D0→7F1, 5D0→7F2, 5D0→7F3, and 5D0→7F4 transition emissions of the Eu(Ⅲ) ion, respectively.展开更多
A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.95...A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.展开更多
Three new complexes TbL3dipy （H2O）2, TbL3phen （H2O） 2 and TbL2 （TPPO） 2NO3 were synthesized （L = phenylglyoxylate ion, dipy = 2, 2-dipyridine, phen = 1,10-phenanthmline, TPPO = Triphenyl phosphine oxide）. Elem...Three new complexes TbL3dipy （H2O）2, TbL3phen （H2O） 2 and TbL2 （TPPO） 2NO3 were synthesized （L = phenylglyoxylate ion, dipy = 2, 2-dipyridine, phen = 1,10-phenanthmline, TPPO = Triphenyl phosphine oxide）. Elemental analysis, conductivity, IR spectra, and ^1HNMR spectra studies were performed. IR spectra indicate that the carboxylate ion of phenylglyoxylate is coordinated to the Tb（Ⅲ） ion as an unidentate ligand. In ^1HNMR, the signals of different hydrogens in phenylglyoxylate ion shift upfield. The excitation and emission spectra of the three solid complexes were recorded at morn temperature, in which the optimum excitation wavelengths are, 361.0, 359.0 and 367.0 nm for these three complexes, respectively. Four emission bands due to the ^5D4-^7Fj（j = 6, 5, 4, 3） transitions were observed for TbL3dipy（H2O）2（489.0, 545.0, 584.0, 620.0 nm） and TbL3phen（H2O）2（490.0, 544.0, 583.0, 620.0 nm）. Under the same conditions, only one emission band due to the ^5D4-^7F5 transition was observed for the complex TbL2（TPPO）2NO3. The emission intensity of TbL3dipy（H2O）2 is the strongest among the three complexes.展开更多
Two ternary complexes of RE(ClO_4)_3-DPSO-phen and two binary complexes of RE(ClO_4)_3-phen have been synthesized (RE=Eu, Tb; DPSO=diphenyl sulfoxide, phen=1,10-phenanthroline). Elemental analysis and TG-DTA studies s...Two ternary complexes of RE(ClO_4)_3-DPSO-phen and two binary complexes of RE(ClO_4)_3-phen have been synthesized (RE=Eu, Tb; DPSO=diphenyl sulfoxide, phen=1,10-phenanthroline). Elemental analysis and TG-DTA studies suggest that the ternary complexes consist of RE(ClO_4)_3(DPSO)(phen)_3·nH_2O (n=1, 3) and binary complexes consist of RE(phen)_4(ClO_4)_3. IR spectra studies indicate that the DPSO ligand is bonded with RE(Ⅲ) through oxygen atom in sulfinyl group and phen ligand is bonded to RE(Ⅲ) through nitrogen atom. The molar conductivities measured in the acetonitrile solution indicate that two inorganic anions ClO_4^- are coordinated and binary complexes are nonelectrolyte. In the fluorescent spectra it was found that the fluorescence emission intensity of the ternary complexes more intensive than that of the binary complexes.展开更多
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...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.展开更多
A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid（H4bptc） has been synthesized, {[Tb（Hbptc）（H2O）4]×H2O}n（1）. Its structure was determined by single-crystal X-ray diffraction analysi...A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid（H4bptc） has been synthesized, {[Tb（Hbptc）（H2O）4]×H2O}n（1）. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. Title complex crystallizes in monoclinic, space group P21/n with a = 14.090（2）, b = 8.0824（13）, c = 15.5591（17） ?, V = 1775.4（5） ?3, Mr = 576.22, Dc = 2.156 g/cm3, μ（Mo Kα） = 4.059 mm-1, F（000） = 1128, Z = 4, the final R = 0.027 and w R = 0.0726 for 3296 observed reflections（I > 2σ（I））. Complex 1 exhibits a 2 D layer structure, and such layers are further united together into a three-dimensional supramolecular structure through π···π interaction and intricate hydrogen bonding. The fluorescence excitation and emission spectroscopy of 1 showed that H4 bptc is a kind of highly efficient sensitizer for terbium（Ⅲ） ion. The title complex also displays efficient ligand sensitized luminescence in the visible region with long lifetime of 2.02 ms in the solid state.展开更多
A new dinuclear manganese complex [Mn2（L）2（2,2＇-bipy）2（H2O）512·3H2O has been synthesized with MnSO4·H2O, 2,2＇-bibenzoic acid （H2L） and 2,2＇-bipyridine（2,2＇-bipy） in the mixed solvent ethanol an...A new dinuclear manganese complex [Mn2（L）2（2,2＇-bipy）2（H2O）512·3H2O has been synthesized with MnSO4·H2O, 2,2＇-bibenzoic acid （H2L） and 2,2＇-bipyridine（2,2＇-bipy） in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group Pi with a = 9.9944（10）, b = 21.939（2）, c = 25.628（3） A, a = 108.429（3）, β = 100.613（4）, 7 = 102.821（3）°, V = 4997.9（9） A3, Dc= 1.355 g/cm^3, Z = 2, F（000） = 2108, GOOF = 1.074, the R= 0.0626 and wR= 0.1531. The structure of the complex contains two [Mn2（L）2（2,2＇-bipy）2] units, ten coordinated H2O molecules and three uncoordinated H2O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.展开更多
A new dinuclear copper（II） complex [Cu2（L）2（phen）2]·5H2O （1） with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid （H2L） and 1,10-phenanthroline （phen） as ligands has been synthesized in the mixed sol...A new dinuclear copper（II） complex [Cu2（L）2（phen）2]·5H2O （1） with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid （H2L） and 1,10-phenanthroline （phen） as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925（4）, b = 19.908（4）, c = 11.235（2） A, β = 97.65（3）°, V= 3973.4（14） A3, Dc = 1.552 g/cm^3, Z = 8, F（000） = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 ：η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.展开更多
Series of doped rare earth compiexes-EuxGd(1-x) (CA)3·nH2O (CA = citric acid) were synthesized. Some characterizations were taken for these complexes. The experimental results shows that the doped rare earth comp...Series of doped rare earth compiexes-EuxGd(1-x) (CA)3·nH2O (CA = citric acid) were synthesized. Some characterizations were taken for these complexes. The experimental results shows that the doped rare earth complexes have the best fluorescence property when the ratio of Eu and Gd is from 0.7 to 0.3. Silicon rubber-based composites were prepared by mechanical blending the EuxGd(1-x) (CA)3·nH2O and silicon rubber. Then, the fluorescent property of the composites was studied. It is found that the fluorescence intensity of the composites increase linearly with the contents of the rare earth complexes increasing.展开更多
Terbium perchlorate reacted with isonicotinic acid （Hpya） and biphenyl-2,2＇-dicarboxylic acid （H2dpa） under hydrothermal condition, a new ternary terbium complex [ Tb （pya） （dpa） （H2O） n （ 1 ） was synthes...Terbium perchlorate reacted with isonicotinic acid （Hpya） and biphenyl-2,2＇-dicarboxylic acid （H2dpa） under hydrothermal condition, a new ternary terbium complex [ Tb （pya） （dpa） （H2O） n （ 1 ） was synthesized. The structure of the ternary complex was determined by X-ray single crystal diffraction and characterized by elemental analysis, fluorescence measurement. The fluorescence spectrum shows the title complex emits strong green light. The crystal data for the com- plex： monoclinic, P21/n space group, a =0.8908（5）nm, b = 1.0569（6）nm, c =2.0969（11）nm, β = 98.446（8）°, V = 1.9528（18） nm^3, Z = 4, R = 0.0241, wR2 = 0.0534. The center Tb3＋ ion is eight coordinated. The coordination polyhedron around Tb3 ＋ ion can be described as a distorted square antiprism. The complex forms an infinite one-dimenand sional alternating chain polymer by bridging carboxyl groups of pyadpa.展开更多
Ternary europium complex with dibenzoylmethane(DBM)and 1,10phenanthroline(phen)was insitu synthesized in thin SiO2/polyvinyl butyral(PVB)hybrid films by a twostep solgel process and characterized by means of fluoresce...Ternary europium complex with dibenzoylmethane(DBM)and 1,10phenanthroline(phen)was insitu synthesized in thin SiO2/polyvinyl butyral(PVB)hybrid films by a twostep solgel process and characterized by means of fluorescence spectroscopy.The luminescence spectra,fluorescence lifetimes and photostability were all investigated.The results showed that the hybrid films exhibited the characteristic emission bands of the central rare earth Eu3+.In addition,Eu3+presented longer fluorescence lifetime than in an ethanol solution and the complex had a higher photostability in the hybrid film than in the PVB film containing the corresponding pure complex.展开更多
A sensitive method based on the fluorescence quenching effect of the Tb^3＋-Tiron complex is proposed for the determination of alkali-labile phosphoprotein phosphorus （ALP） released from fish plasma. The detection l...A sensitive method based on the fluorescence quenching effect of the Tb^3＋-Tiron complex is proposed for the determination of alkali-labile phosphoprotein phosphorus （ALP） released from fish plasma. The detection limit was 5.4 ng/ml （S/N=2）, and the relative standard deviation of the quenching effect （6 replicates） was 4.6%. The results obtained by the proposed method were in good agreement with those obtained by the colorimetric assay. The advantages of the present method are its relatively simple detection procedure, the lack of toxic organic solvents, and high sensitivity.展开更多
Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synth...Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synthesized by solvent method and determined by X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group Pi. Both are binuclear molecules with an inversion center. In complex 1, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu^3＋ ion is eight-coordinated with six O atoms from five 2-TFMBA ligands and two N atoms from one 2,2′-bipy molecule. In complex 2, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu^3＋ ion is nine-coordinated with seven O atoms from five 2-TFMBA ligands and two N atoms from one 1,10-phen molecule. The two complexes both exhibited strong red fluorescence under ultraviolet light, and the ^5D0→^7Fj （j=0-4） transition emissions of Eu^3＋ ion were observed in their emission spectra.展开更多
Two new 1-naphthoate-based Pb（Ⅱ） complexes, [Pb（phen）（NA）2]n 1 and [Pb（bpp）（NA）2]n 2 （NA = 1-naphthoate, phen = 1,10-phenanthroline, and bpp = 1,3-bi（4-pyri- dyl）propane）, were hydrothermally synthesize...Two new 1-naphthoate-based Pb（Ⅱ） complexes, [Pb（phen）（NA）2]n 1 and [Pb（bpp）（NA）2]n 2 （NA = 1-naphthoate, phen = 1,10-phenanthroline, and bpp = 1,3-bi（4-pyri- dyl）propane）, were hydrothermally synthesized and structurally characterized. 1 is of monoclinic system, space group C2/c with a = 28.114（3）, b = 10.9601（10）, c = 8.6843（8） , β = 93.3760（10）°, V = 2671.3（4） 3, Dc = 1.814 g/cm3, Mr = 729.73, Z = 4, F（000） = 1416, μ = 6.360 mm-1, the final R = 0.0346 and wR = 0.0948 for 2184 observed reflections with I 〉 2σ（I）. Complex 2 crystallizes in monoclinic, space group C2/c with a = 26.491（2）, b = 8.7773（6）, c = 27.893（2） , β = 113.3020（10）°, V = 5956.8（8）3, Dc = 1.668 g/cm3, Mr = 747.78, Z = 8, F（000） = 2928, μ = 5.706 mm-1, the final R = 0.0211 and wR = 0.0493 for 3677 observed reflections with I 〉 2σ（I）. Both complexes present one-dimensional （1-D） zigzag chains extended by anionic NA linkers for 1 and bridged by neutral bpp connectors for 2, which are further aggregated into 2-D supramolecular networks by interchain π···π stacking interactions. In addition, the two solid-state complexes exhibit different strong emissions at room temperature, suggesting their potential applications as fluorescence materials.展开更多
文摘A trinuclear copper complex [Cu_(3)(L2)_(2)(SO_(4))_(2)(H_(2)O)_(7)]·8H_(2)O(1)(HL2=1-hydroxy-3-(pyrazin-2-yl)-N-(pyrazin-2-ylmethyl)imidazo[1,5-a]pyrazine-8-carboxamide) with a multi-substituted imidazo[1,5-a]pyrazine scaffold was serendipitously prepared from the reaction of the pro-ligand of H_(2)L1(N,N'-bis(pyrazin-2-ylmethyl)pyrazine-2,3-dicarboxamide) with CuSO_(4)·5H_(2O) in aqueous solution at room temperature.Complex 1 was characterized by IR,single-crystal X-ray analysis,and magnetic susceptibility measurements.Single-crystal X-ray analysis reveals that the complex consists of three Cu(Ⅱ) ions,two in situ transformed L2~-ligands,two coordinated sulfates,seven coordinated water molecules,and eight uncoordinated water molecules.Magnetic susceptibility measurement indicates that there are obvious ferromagnetic coupling interactions between the adjacent Cu(Ⅱ) ions in 1.CCDC:1852713.
文摘Light conversion agents Eul-xLx（TTA）3Phen (L denotes (La3+, Gd3+, Y3+)) complexes were prepared, and the influence of doping ions on fluorescence properties was investigated by elementary analysis, FTIR and fluorescent spectra. The results show that FTIR spectra of Eul-xLx（TTA）3Phen complex system are identical with that of EuTTA3Phen, which indicates that the complexes (Eul-xLx（TTA）3Phen) are similar in structure to （Eu （TTA）3Phen.） For the above doping elements, co-fluorescence enhancement has the following order: Gd3+>Y3+>La3+, and the optimum mole fractions of doping elements are 0.4, 0.2 and 0.5 respectively for Gd3+, Y3+, La3+. Among all the complexes, Eu0.6Gd0.4（TTA）3Phen complex has the strongest fluorescent intensity. Applying Eu0.6Gd0.4（TTA）3Phen complex to plastic and printing inks, bright red fluorescence plastic and printing inks are obtained when the content of europium reaches 0.1%（mass fraction）.
基金supported by the National Natural Science Foundation of China(No.21271129)
文摘A new homochiral ligand,（R）-2-（4-pyridyl）-4,5-dihydrothiazole-4-carboxylic acid（HL^R）, has been synthesized. Two complexes, [ZnL2^R（H2O）2]·H2O（1） and [MnL2^R（H2O）2]？H2O（2） have been prepared by the reactions of Zn（Ⅱ） and Mn（Ⅱ） ions with the ligand HLR, and characterized by single-crystal X-ray diffraction analysis and fluorescence. Complexes 1 and 2 are isomorphs, and both of the Zn（Ⅱ） and Mn（Ⅱ） centers in 1 and 2 are six-coordinated by the two NO units of two ligands and two water oxygen atoms, showing distorted octahedral coordination geometry. Complexes 1 and 2 show fluorescent properties in the solid state at room temperature.
文摘The enhancement effects of Y ( Ⅲ) ions on the fluorescence of Ce ( Ⅲ) in Ce ( Ⅲ)-Y ( Ⅲ)-PMMA (polymethylmethacrylate ) or Ce ( Ⅲ)-Y ( Ⅲ)-PVC (polyvinyl chloride ) complex systems were observed. The influence of Y ( Ⅲ) ions on the emission spectra of PMMA ligands in PMMA-Y ( Ⅲ) and the fluorescent enhance- ment of Y( Ⅲ) on Ce( Ⅲ) emission in PMMA-Ce-Y by Y( Ⅲ) ion were studied. It was also of interest to note that when Y ( Ⅲ) ions were added into PMMA and into bpy(bipyridine ) , respectively , the emission spectrum of PMMA ligands was split into fine structure bands by Y ( Ⅲ) , and the fluorescence intensities of bpy ligands in bpy-Y ( Ⅲ) complexes were considerably increased.
文摘The binary complexes of europium with benzoic acid and its derivatives(phthalic acid, m-phthalic acid, o-aminobenzoic acid, salicylic acid, and sulfosalicylic acid) weresynthesized and their compositions were identified by elemental analyses. UV and IR of the complexeshave been investigated. The UV spectra indicated that the complexes' ultraviolet absorption weremainly the ligands' absorption. The IR spectra showed that the IR spectra of complexes are differentfrom those of free ligands. The fluorescence properties of them were investigated by usingluminescence spectroscopy, the results showed that only three complexes appear as betterluminescence, they were Eu-benzoic acid, Eu-m-phthalic acid and Eu-phthalic acid, while the othersexhibited the ligands' wideband emission.
基金Project supported by the Natural Science Foundation of Beijing (2073022)
文摘A new complex of {[Eu2(2-BrBA)6(2,2’-bpy)2]2·CH3CH2OH·H2O} (2-BrBA=2-bromobenzoate; 2,2’-bpy=2,2’-bipyridine) was prepared by solvent method and characterized with X-ray single-crystal diffraction, IR spectroscopy, UV spectroscopy, and fluorescence spectroscopy. The complex crystallized in triclinic crystal system, Pī space group, with a=1.17196(4) nm, b=2.36142(9) nm, c=2.59151(9) nm, α=113.266(2)°, β=101.100(2)°, and γ=94.400(2)°. Two independent dinuclear molecules were contained in the asymmetric unit. The two molecules were similar to each other. Each Eu(Ⅲ) ion was nine-coordinated with seven oxygen atoms from five 2-BrBA ligands and two nitrogen atoms from 2,2’-bpy molecule. The carboxylate groups acted as bidentate-chelating, bidentate-bridging and chelating-bridging coordination modes. The complex adopted a distorted monocapped square-antiprism coordination geometry. Five peaks at 579, 591, 613, 652, and 697 nm appeared in the fluorescence spectrum, corresponding to 5D0→7F0, 5D0→7F1, 5D0→7F2, 5D0→7F3, and 5D0→7F4 transition emissions of the Eu(Ⅲ) ion, respectively.
基金supported by the Construct Program of the Key Discipline in Hunan Province
文摘A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.
文摘Three new complexes TbL3dipy （H2O）2, TbL3phen （H2O） 2 and TbL2 （TPPO） 2NO3 were synthesized （L = phenylglyoxylate ion, dipy = 2, 2-dipyridine, phen = 1,10-phenanthmline, TPPO = Triphenyl phosphine oxide）. Elemental analysis, conductivity, IR spectra, and ^1HNMR spectra studies were performed. IR spectra indicate that the carboxylate ion of phenylglyoxylate is coordinated to the Tb（Ⅲ） ion as an unidentate ligand. In ^1HNMR, the signals of different hydrogens in phenylglyoxylate ion shift upfield. The excitation and emission spectra of the three solid complexes were recorded at morn temperature, in which the optimum excitation wavelengths are, 361.0, 359.0 and 367.0 nm for these three complexes, respectively. Four emission bands due to the ^5D4-^7Fj（j = 6, 5, 4, 3） transitions were observed for TbL3dipy（H2O）2（489.0, 545.0, 584.0, 620.0 nm） and TbL3phen（H2O）2（490.0, 544.0, 583.0, 620.0 nm）. Under the same conditions, only one emission band due to the ^5D4-^7F5 transition was observed for the complex TbL2（TPPO）2NO3. The emission intensity of TbL3dipy（H2O）2 is the strongest among the three complexes.
文摘Two ternary complexes of RE(ClO_4)_3-DPSO-phen and two binary complexes of RE(ClO_4)_3-phen have been synthesized (RE=Eu, Tb; DPSO=diphenyl sulfoxide, phen=1,10-phenanthroline). Elemental analysis and TG-DTA studies suggest that the ternary complexes consist of RE(ClO_4)_3(DPSO)(phen)_3·nH_2O (n=1, 3) and binary complexes consist of RE(phen)_4(ClO_4)_3. IR spectra studies indicate that the DPSO ligand is bonded with RE(Ⅲ) through oxygen atom in sulfinyl group and phen ligand is bonded to RE(Ⅲ) through nitrogen atom. The molar conductivities measured in the acetonitrile solution indicate that two inorganic anions ClO_4^- are coordinated and binary complexes are nonelectrolyte. In the fluorescent spectra it was found that the fluorescence emission intensity of the ternary complexes more intensive than that of the binary complexes.
文摘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.
基金supported by the National Natural Science Foundation of China(No.21671114 and U1804131)Natural Science Foundation of Henan Province(No.182300410166,182102310909 and 182102310897)
文摘A new terbium complex based on biphenyl-2,3,3’,5’-tetracarboxylic acid（H4bptc） has been synthesized, {[Tb（Hbptc）（H2O）4]×H2O}n（1）. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analyses. Title complex crystallizes in monoclinic, space group P21/n with a = 14.090（2）, b = 8.0824（13）, c = 15.5591（17） ?, V = 1775.4（5） ?3, Mr = 576.22, Dc = 2.156 g/cm3, μ（Mo Kα） = 4.059 mm-1, F（000） = 1128, Z = 4, the final R = 0.027 and w R = 0.0726 for 3296 observed reflections（I > 2σ（I））. Complex 1 exhibits a 2 D layer structure, and such layers are further united together into a three-dimensional supramolecular structure through π···π interaction and intricate hydrogen bonding. The fluorescence excitation and emission spectroscopy of 1 showed that H4 bptc is a kind of highly efficient sensitizer for terbium（Ⅲ） ion. The title complex also displays efficient ligand sensitized luminescence in the visible region with long lifetime of 2.02 ms in the solid state.
基金Supported by the Key Project of Science and Technology Plan of Hunan Province(2012FJ2002)Science and Technology Committee of Hengyang(2013KG77)the Construct Program of the Key Discipline in Hunan Province
文摘A new dinuclear manganese complex [Mn2（L）2（2,2＇-bipy）2（H2O）512·3H2O has been synthesized with MnSO4·H2O, 2,2＇-bibenzoic acid （H2L） and 2,2＇-bipyridine（2,2＇-bipy） in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group Pi with a = 9.9944（10）, b = 21.939（2）, c = 25.628（3） A, a = 108.429（3）, β = 100.613（4）, 7 = 102.821（3）°, V = 4997.9（9） A3, Dc= 1.355 g/cm^3, Z = 2, F（000） = 2108, GOOF = 1.074, the R= 0.0626 and wR= 0.1531. The structure of the complex contains two [Mn2（L）2（2,2＇-bipy）2] units, ten coordinated H2O molecules and three uncoordinated H2O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.
基金Supported by the Construct Program of the Key Discipline in Hunan Province and Key Project of Production Plan of Hengyang City(2013)
文摘A new dinuclear copper（II） complex [Cu2（L）2（phen）2]·5H2O （1） with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid （H2L） and 1,10-phenanthroline （phen） as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925（4）, b = 19.908（4）, c = 11.235（2） A, β = 97.65（3）°, V= 3973.4（14） A3, Dc = 1.552 g/cm^3, Z = 8, F（000） = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 ：η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.
基金Project supported by the National Natural Science Foundation of China and the China Energy Conservation Investment Corporation (50173004 and 50503002)the Beijing New Star Project (2003A11)+1 种基金the National High-Tech Research Developing Foundation (863. 2003AA324030) Beijing Municipal Commission of Education (JD100100403)
文摘Series of doped rare earth compiexes-EuxGd(1-x) (CA)3·nH2O (CA = citric acid) were synthesized. Some characterizations were taken for these complexes. The experimental results shows that the doped rare earth complexes have the best fluorescence property when the ratio of Eu and Gd is from 0.7 to 0.3. Silicon rubber-based composites were prepared by mechanical blending the EuxGd(1-x) (CA)3·nH2O and silicon rubber. Then, the fluorescent property of the composites was studied. It is found that the fluorescence intensity of the composites increase linearly with the contents of the rare earth complexes increasing.
文摘Terbium perchlorate reacted with isonicotinic acid （Hpya） and biphenyl-2,2＇-dicarboxylic acid （H2dpa） under hydrothermal condition, a new ternary terbium complex [ Tb （pya） （dpa） （H2O） n （ 1 ） was synthesized. The structure of the ternary complex was determined by X-ray single crystal diffraction and characterized by elemental analysis, fluorescence measurement. The fluorescence spectrum shows the title complex emits strong green light. The crystal data for the com- plex： monoclinic, P21/n space group, a =0.8908（5）nm, b = 1.0569（6）nm, c =2.0969（11）nm, β = 98.446（8）°, V = 1.9528（18） nm^3, Z = 4, R = 0.0241, wR2 = 0.0534. The center Tb3＋ ion is eight coordinated. The coordination polyhedron around Tb3 ＋ ion can be described as a distorted square antiprism. The complex forms an infinite one-dimenand sional alternating chain polymer by bridging carboxyl groups of pyadpa.
文摘Ternary europium complex with dibenzoylmethane(DBM)and 1,10phenanthroline(phen)was insitu synthesized in thin SiO2/polyvinyl butyral(PVB)hybrid films by a twostep solgel process and characterized by means of fluorescence spectroscopy.The luminescence spectra,fluorescence lifetimes and photostability were all investigated.The results showed that the hybrid films exhibited the characteristic emission bands of the central rare earth Eu3+.In addition,Eu3+presented longer fluorescence lifetime than in an ethanol solution and the complex had a higher photostability in the hybrid film than in the PVB film containing the corresponding pure complex.
基金Project supported by the Hi-Tech Research and Development Program (863) of China (No. 2006AA06Z424) the National Basic Research Program (973) of China (No. 2003CB415001)the Pilot Project of Knowledge Innovation Program of Chinese Academy of Sciences (No. KJCX2-SW-H06).
文摘A sensitive method based on the fluorescence quenching effect of the Tb^3＋-Tiron complex is proposed for the determination of alkali-labile phosphoprotein phosphorus （ALP） released from fish plasma. The detection limit was 5.4 ng/ml （S/N=2）, and the relative standard deviation of the quenching effect （6 replicates） was 4.6%. The results obtained by the proposed method were in good agreement with those obtained by the colorimetric assay. The advantages of the present method are its relatively simple detection procedure, the lack of toxic organic solvents, and high sensitivity.
基金supported by the Natural Science Foundation of Beijing (2073022)
文摘Two complexes [Eu2（2-TFMBA）6（2,2′-bipy）2]·2H2O （1） and Eu2（2-TFMBA）6（1,10-phen）2 （2） （2-TFMBA=2-（Trifluoromethyl） benzoate; 2,2′-bipy=2,2′-bipyridine; 1,10-phen= 1,10-phenanthroline） were synthesized by solvent method and determined by X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system with space group P21/c, whereas complex 2 crystallizes in triclinic system with space group Pi. Both are binuclear molecules with an inversion center. In complex 1, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in bidentate-bridging mode. Each Eu^3＋ ion is eight-coordinated with six O atoms from five 2-TFMBA ligands and two N atoms from one 2,2′-bipy molecule. In complex 2, two center Eu^3＋ ions are linked together by four 2-TFMBA ligands in two modes, namely, bidentate-bridging and tridentate-bridging. Each Eu^3＋ ion is nine-coordinated with seven O atoms from five 2-TFMBA ligands and two N atoms from one 1,10-phen molecule. The two complexes both exhibited strong red fluorescence under ultraviolet light, and the ^5D0→^7Fj （j=0-4） transition emissions of Eu^3＋ ion were observed in their emission spectra.
基金NNSFC (Grants 21171129 and 21173157)Tianjin Educational Committee (2006ZD07)
文摘Two new 1-naphthoate-based Pb（Ⅱ） complexes, [Pb（phen）（NA）2]n 1 and [Pb（bpp）（NA）2]n 2 （NA = 1-naphthoate, phen = 1,10-phenanthroline, and bpp = 1,3-bi（4-pyri- dyl）propane）, were hydrothermally synthesized and structurally characterized. 1 is of monoclinic system, space group C2/c with a = 28.114（3）, b = 10.9601（10）, c = 8.6843（8） , β = 93.3760（10）°, V = 2671.3（4） 3, Dc = 1.814 g/cm3, Mr = 729.73, Z = 4, F（000） = 1416, μ = 6.360 mm-1, the final R = 0.0346 and wR = 0.0948 for 2184 observed reflections with I 〉 2σ（I）. Complex 2 crystallizes in monoclinic, space group C2/c with a = 26.491（2）, b = 8.7773（6）, c = 27.893（2） , β = 113.3020（10）°, V = 5956.8（8）3, Dc = 1.668 g/cm3, Mr = 747.78, Z = 8, F（000） = 2928, μ = 5.706 mm-1, the final R = 0.0211 and wR = 0.0493 for 3677 observed reflections with I 〉 2σ（I）. Both complexes present one-dimensional （1-D） zigzag chains extended by anionic NA linkers for 1 and bridged by neutral bpp connectors for 2, which are further aggregated into 2-D supramolecular networks by interchain π···π stacking interactions. In addition, the two solid-state complexes exhibit different strong emissions at room temperature, suggesting their potential applications as fluorescence materials.
