邻羟基苯乙酮类化合物—稀土配合物的合成及发光性质研究
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摘要
以间苯二酚和乙酸酐为原料,合成了4,6-二乙酰基间苯二酚;通过苯酚衍生物和冰醋酸的酯化反应、Fries重排合成了一系列邻羟基苯乙酮的衍生物;以邻羟基苯乙酮和噻吩-2-甲醛、苯甲醛衍生物为原料,合成了一系列邻羟基查尔酮;以乙二胺和冰乙酸为原料,合成了四乙酰乙二胺,采用溶剂法培养出其单晶并对结构进行了解析;以对甲氧基苯胺为原料,合成了5-乙酰氨基-2-羟基苯乙酮;所有目标化合物均经过元素分析、红外光谱、紫外光谱、熔点的证实。合成了一系列的稀土配合物,实验结果的分析表明,化合物可以通过羰基氧和酚羟基氧与稀土配位形成配合物。对所合成的配合物进行了元素分析、红外光谱、荧光光谱,差热-热重分析,对其结构和性质进行了表征,还分别测试了4,6-二乙酰基间苯二酚和邻羟基苯乙酮与钆所形成的配合物的低温磷光,并通过计算得出其最低三重态,对其荧光强度的差异进行了合理的解释。
以1,10-邻菲咯啉和2,2-联吡啶为原料,经氧化合成1,10-邻菲咯啉氮氧化合物,1,10-邻菲咯啉-5,6-二酮,吡嗪[2,3-f]并邻菲咯啉,2,2-联吡啶氮氮氧化物;并以其为第二配体,合成了4,6-二乙酰基间苯二酚,邻羟基苯乙酮与铕的三元配合物,并根据实验结果计算得出了配合物的荧光寿命和量子产率,系统研究了第二配体其对配合物发光性能的影响。
实验结果表明,4,6-二乙酰基间苯二酚,邻羟基苯乙酮与Eu~(3+)配位后,在紫外-可见光区均有强的吸收,并能够发射铕(Ⅲ)的特征红光,最强荧光发射峰位在611 nm附近。但是这些配体与Tb(Ⅲ)、Dy(Ⅲ)、Sm(Ⅲ)形成的配合物的发光强度很弱,这是由于这些配体的能级与不同稀土离子能级匹配程度的差别所致。
引入第二配体后,可以极大地减少配合物形成过程中水分子的配位,减少O-H振动带来的能量损耗,增强荧光效率;荧光光谱数据比较发现三元配合物的荧光强度要大于二元配合物的荧光强度,同时第二配体的引入增强了配合物的荧光寿命和量子效率。
在SiO_2溶胶-凝胶体系中,合成了4,6-二乙酰基间苯二酚与Eu~(3+)的系列配合物,研究了基质、不同惰性稀土离子,第二配体,对配合物发光性能的影响。
本文用X-射线衍射方法测定了四乙酰乙二胺的晶体结构,主要晶体数据如下:C_(10)H_(16)N_2O_4,单斜晶系,空间群P2_1/c,a=5.95220(10)(?),b=10.2591(2)(?),c=9.3392(2)(?),β=95.6980(10)°,V=567.473(19)(?)~3,Z=2,F=244,D_(calc)=1.336g/cm~3,μ=0.104 mm~(-1),R_1(＞2σ(I))=0.0390,wR_2(＞2σ(I)=0.1093。
In this paper,β-diketone-like compounds,for example,2'-Hydroxyacetophenone (HOHAP) and its derivatives,4,6-diacetyl-resorcinol,2'-Hydroxychalcone and its derivatives,5-Acetamido-2-hydroxyacetophenone,N,N,N',N'-tetraacetylethylenediamine and so on,were synthesized.All structures were proved via elementary analysis,IR,UV, and by contrasting their melting point with their reference.Based experimental,all the ligands are coordinated to rare earth ion via the carbonyl and phenolic oxygens,and 4,6-diacetyl-resorcinol is concluded to be bis-bidentate donor.The complexes were characterized by elementary analysis,IR,UV and thermo-gravimetric analysis.The results show that in these complexes,only those of Eu(Ⅲ) with 4,6-diacetyl-resorcinol and 2'-Hydroxyacetophenone can emit strong red fluorescence,and the position of fluorescence emission is around 611 nm.Other complexes cannot emit fluorescence.The phenomenon was interpreted by electron-effect and energy-matching mechanism.The "Antenna effect" between the rare earth ions and the ligands was proved again.Energy transfer mechanism of the luminescence in the complexes was discussed.
In order to eliminate O-H oscillators in the short range and reduce the nonradiative decay from the excited state of Ln(Ⅲ),some synergic ligands with aromatic segment, 1,10-phenanthroline-1-oxide,1,10-Phenanthroline-5,6-dioxide and 2,2'-Bipyridine N,N' -Dioxide were synthesized.Because when they were coordinated with Eu(Ⅲ) via N atom, the coordination sphere should be supplemented.Quenching water molecules in the coordination sphere of lanthanide ion can be replaced by the synergic ligand and thus the luminescence intensity of the complex is enhanced.Based on our luminescence observations,the luminescence intensity of the ternary complexes is larger than that of the binary complexes,and the life time and quantum yield were increased.
The Gd~(3+) complexes with 2'-Hydroxyacetophenone and 4,6-diacetyl-resorcinol were prepared and the phosphorescence spectra were measured,the triplet state of HOHAP(L~1) can be calculated to be 23095cm~(-1)(21739cm~(-1)).With that we can explain the differences in luminescence intensity.
Crystal structure for L~7 was measured by X-ray diffractomer.Crystallographic data was shown as follows:L~7:C_(10)H_(16)N_2O_4,crystal system monoclinic,space group P2_1/c,a =5.95220(10)(??,b=10.2591(2)(?),c=9.3392(2)(?),β=95.6980(10)°,V=567.473(19) (?)~3,Z=2,F=244,R_1(＞2σ(I))=0.0390,wg_2(＞2σ(I))=0.1093.
以1,10-邻菲咯啉和2,2-联吡啶为原料,经氧化合成1,10-邻菲咯啉氮氧化合物,1,10-邻菲咯啉-5,6-二酮,吡嗪[2,3-f]并邻菲咯啉,2,2-联吡啶氮氮氧化物;并以其为第二配体,合成了4,6-二乙酰基间苯二酚,邻羟基苯乙酮与铕的三元配合物,并根据实验结果计算得出了配合物的荧光寿命和量子产率,系统研究了第二配体其对配合物发光性能的影响。
实验结果表明,4,6-二乙酰基间苯二酚,邻羟基苯乙酮与Eu~(3+)配位后,在紫外-可见光区均有强的吸收,并能够发射铕(Ⅲ)的特征红光,最强荧光发射峰位在611 nm附近。但是这些配体与Tb(Ⅲ)、Dy(Ⅲ)、Sm(Ⅲ)形成的配合物的发光强度很弱,这是由于这些配体的能级与不同稀土离子能级匹配程度的差别所致。
引入第二配体后,可以极大地减少配合物形成过程中水分子的配位,减少O-H振动带来的能量损耗,增强荧光效率;荧光光谱数据比较发现三元配合物的荧光强度要大于二元配合物的荧光强度,同时第二配体的引入增强了配合物的荧光寿命和量子效率。
在SiO_2溶胶-凝胶体系中,合成了4,6-二乙酰基间苯二酚与Eu~(3+)的系列配合物,研究了基质、不同惰性稀土离子,第二配体,对配合物发光性能的影响。
本文用X-射线衍射方法测定了四乙酰乙二胺的晶体结构,主要晶体数据如下:C_(10)H_(16)N_2O_4,单斜晶系,空间群P2_1/c,a=5.95220(10)(?),b=10.2591(2)(?),c=9.3392(2)(?),β=95.6980(10)°,V=567.473(19)(?)~3,Z=2,F=244,D_(calc)=1.336g/cm~3,μ=0.104 mm~(-1),R_1(＞2σ(I))=0.0390,wR_2(＞2σ(I)=0.1093。
In this paper,β-diketone-like compounds,for example,2'-Hydroxyacetophenone (HOHAP) and its derivatives,4,6-diacetyl-resorcinol,2'-Hydroxychalcone and its derivatives,5-Acetamido-2-hydroxyacetophenone,N,N,N',N'-tetraacetylethylenediamine and so on,were synthesized.All structures were proved via elementary analysis,IR,UV, and by contrasting their melting point with their reference.Based experimental,all the ligands are coordinated to rare earth ion via the carbonyl and phenolic oxygens,and 4,6-diacetyl-resorcinol is concluded to be bis-bidentate donor.The complexes were characterized by elementary analysis,IR,UV and thermo-gravimetric analysis.The results show that in these complexes,only those of Eu(Ⅲ) with 4,6-diacetyl-resorcinol and 2'-Hydroxyacetophenone can emit strong red fluorescence,and the position of fluorescence emission is around 611 nm.Other complexes cannot emit fluorescence.The phenomenon was interpreted by electron-effect and energy-matching mechanism.The "Antenna effect" between the rare earth ions and the ligands was proved again.Energy transfer mechanism of the luminescence in the complexes was discussed.
In order to eliminate O-H oscillators in the short range and reduce the nonradiative decay from the excited state of Ln(Ⅲ),some synergic ligands with aromatic segment, 1,10-phenanthroline-1-oxide,1,10-Phenanthroline-5,6-dioxide and 2,2'-Bipyridine N,N' -Dioxide were synthesized.Because when they were coordinated with Eu(Ⅲ) via N atom, the coordination sphere should be supplemented.Quenching water molecules in the coordination sphere of lanthanide ion can be replaced by the synergic ligand and thus the luminescence intensity of the complex is enhanced.Based on our luminescence observations,the luminescence intensity of the ternary complexes is larger than that of the binary complexes,and the life time and quantum yield were increased.
The Gd~(3+) complexes with 2'-Hydroxyacetophenone and 4,6-diacetyl-resorcinol were prepared and the phosphorescence spectra were measured,the triplet state of HOHAP(L~1) can be calculated to be 23095cm~(-1)(21739cm~(-1)).With that we can explain the differences in luminescence intensity.
Crystal structure for L~7 was measured by X-ray diffractomer.Crystallographic data was shown as follows:L~7:C_(10)H_(16)N_2O_4,crystal system monoclinic,space group P2_1/c,a =5.95220(10)(??,b=10.2591(2)(?),c=9.3392(2)(?),β=95.6980(10)°,V=567.473(19) (?)~3,Z=2,F=244,R_1(＞2σ(I))=0.0390,wg_2(＞2σ(I))=0.1093.
引文
1.Urbrain G.,Bull.Chem.Soc.Jpn.,1896,15(3):347.
2.Weissman S.I.,Intramolecular Energy Transfer The Fluorescence of Complexes of Europium[J],J.Chem.Phys.,1942,10(4):214.
3.Charles R.G.,Riedel E.P.,Properties of some europium laser chelates derived from benzoyltrifluoroacetone[J],J.Inorg.Nucl.Chem.,1966,28(12):3005.
4.Bhaumik M.L.,Fletcher P.C.,Nugent L.J.,et al.,Laser Emission from a Europium Benzoylacetonate Alcohol Solution[J],J.Phys.Chem.,1964,68(6):1490.
5.Crosby G.A.,Whan R.E.,Freeman J.J.,Spectroscopic studies of rare earth chelates [J],J.Phys.Chem.,1962,66(12):2493.
6.Freeman J.J.,Crosby G.A.,Spectra and decay times of the luminescences observed from chelated rare earth ions[J],J.Phys.Chem.,1963,67(12):2717.
7.Dawson W.R.,Kropp J.L.,Windsor M.W.,Internal-Energy-Transfer Efficiencies in Eu~(3+) and Tb~(3+) Chelates Using Excitation to Selected Ion Levels[J],J.Chem.Phys.,1966,45(7):2410.
8.朱卫国,苑同锁,魏孝强等,噻吩甲酰三氟丙酮-酰基吡唑啉酮-邻菲咯啉合铕(Ⅲ)四元配合物的合成和表征[J],高等学校化学学报,2000,21(10):1527.
9.肖尊宏,谭松庭,周洪波等,2-烯丙基-1,3-二苯基-1,3-丙二酮的合成及其稀土配合物光致发光性质研究[J],中国稀土学报,2002,20(6):667.
10.谭松庭,杨娜,赵斌等,4-正辛烷氧基二苯甲酰甲烷-邻菲口罗啉-铕三元配合物的合成与光致发光[J],液晶与显示,2002,17(5):341.
11.刘胜利,祁素素.1-(2-羟基苯基)-3-苯基-1,3-丙二酮及其与铕(Ⅲ)配合物的合成和发光研究[J],中国稀土学报,2005,23(5):561.
12.李建宇,稀土发光材料及其应用[M].2003,北京,化学工业出版社.p 192.
13.Richardson F.S.,Terbium(Ⅲ) and europium(Ⅲ) ions as luminescent probes and stains for biomolecular systems[J],Chem.Rev.,1982,82(5):541.
14.李建宇,稀土发光材料及其应用[M].2003,北京,化学工业出版社.p250.
15.Morita M.,Iwamura M.,Rau D.,et al.,Luminescence of metal ion-activated nanophosphor supported by nanoporous sol-gel SiO_2 matrices[J],J.Lumin.,In Press,Corrected Proof.
16.Lenaerts P.,Gorier W.C.,Binnemans K..Luminescent europium(Ⅲ) and terbium(Ⅲ) nicotinate complexes covalently linked to a 1,10-phenanthroline functionalised sol-gel glass[J],J.Lumin.,2006,117(2):163.
17.Luo Y.,Han Y.H,Lin J..Synthesis and luminescent properties of europium(Ⅲ)schiff base complexes covalently bonded to silica xerogels[J],J.Lumin.,In Press,Corrected Proof.
18.Konkowski A.M.,Szakowska I.,Lis S.,et al.,Luminescent materials consisting of Eu(Ⅲ) ions complexed with cryptand ligand and coligands entrapped in xerogel matrices[J],J.Lumin.,2005,115(3-4):122.
19.Wang F.,Fan X.P.,Wang M.Q.,et al.,Luminescence behavior of the dibenzoyl methane europium(Ⅲ) complexes in sol-gel derived host materials[J],J.Lumin.,2005,114(3-4):281.
20.Lenaerts P.,Ryckebosch E.,Driesen K.,et al.,Study of the luminescence of tds(2-thenoyltrifluoroacetonato)lanthanide(Ⅲ) complexes covalently linked to 1,10-phenanthroline-functionalized hybrid sol-gel glasses[J],J.Lumin.,2005,114(1):77.
21.Wang H.S.,Qian G.D.,Wang Z.Y.,et al.,1.53 um photoluminescence from ORMOSIL films doped with erbium complexes[J],J.Lumin.,2005,113(3-4):214.
22.Reisfeld R.,Saraidarov T.,Ziganski E.,et al.,Intensification of rare earths luminescence in glasses[J],J.Lumin.,2003,102-103:243.
23.Modta M.,Rau D.,Kai T.,Luminescence and circularly polarized luminescence of macrocyclic Eu(Ⅲ) and Tb(Ⅲ) complexes embedded in xerogel and sol-gel SiO_2glasses[J],J.Lumin.,2002,100(1-4):97.
24.Morita M.,Kajiyama S.,Kai T.,et al.,Physicochemical control of valence in luminescence of Cr(Ⅲ) and V(Ⅲ,Ⅳ) complexes embedded in xero-gel and sol-gel SiO_2glasses[J],J.Lumin.,2001,94-95:91.
25.Li H.,Inoue S.,Machida K.,et al.,Preparation and luminescence properties of inorganic-organic hybrid materials doped with lanthanide(Ⅲ) complexes[J],J.Lumin.,2000,87-89:1069.
26.Yan B.,Zhang H.J.,Wang S.B.,et al.,Luminescence properties of the ternary rare earth complexes with β-diketones and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method[J],Materials Chemistry and Physics,1997,51(1):92.
27.Yan B.,Zhang H.,Wang S.,et al.,Luminescence properties of rare-earth(Eu~(3+) and Tb~(3+)) complexes with paraaminobenzoic acid and 1,10-phenanthroline incorporated into a silica matrix by sol-gel method[J],Mater.Res.Bull.,1998,33(10):1517.
28.Yan B.,Zhang H.J.,Wang S.B.,et al.,Luminescence properties of rare earth(Eu~(3+)and Tb~(3+) complexes with conjugated carboxylic acids and 1,10-phenanthro line incorporated in silica matrix[J],J.Photochem.Photobiol.,A,1998,112(2-3):231.
29.Sabbatini N.,Dellonte S.,Blasse G.,The luminescence of the rare earth cryptates [Tb:2.2.1]~(3+) and[Sm:2.2.1]~(3+)[J],Chem.Phys.Lett.,1986,129(6):541.
30.Okamoto Y.,Ueba Y.,Dzhanibekov N.F.,et al.,Rare earth metal containing polymers.3.Characterization of ion-containing polymer structures using rare earth metal fluorescence probes[J],Macromolecules,1981,14(1):17.
31.Li W.L.,Mishima T.,Adachi G.Y.,et al.,The fluorescence of transparent polymer films of rare earth complexes[J],Inorg.Chim.Acta,1986,121(1):97.
32.Sabbatini N.,Ciano M.,Dellonte S.,et al.,Absorption and emission properties of a europium(Ⅱ) cryptate in aqueous solution[J],Chem.Phys.Lett.,1982,90(4):265.
33.闫冰,张洪杰,王淑彬等,稀土3,4-呋喃二甲酸,1,10-二氮杂菲配合物的光物理性质[J],中国稀土学报,1998,16(4):375.
34.张颂培,李建宇,姜晓琳等,Eu~(3+)-β-二酮、三正辛胺三元配合物的合成与光谱特性[J],化学试剂,2003,25(3):187.
35.郑向军,万永红,金林培等,一个新颖的光致发光和光致变色铕配合物[J],科学通报,2001,46(22):1861.
36.Sato S.,Wada M..Relations between Intrarnolecular Energy Transfer Efficiencies and Triplet State Energies in Rare Earth β-diketone Chelates[J],Bull.Chem.Soc.Jpn.,1970,43(7):1955.
37.Sato S.,Wada M.,Seki T..Some Properties of Europium β-diketone Chelates (Synthesis and Fluorescent Properties)[J],Jpn.J.Appl.Phys.,1968,7:7.
38.Tang C.W.,VanSlykes S.A..Organic electroluminescent diodes[J],Appl.Phys.Lett.,1987,51:913.
39.Burroughes J.H.,Bradley D.D.C.,Brown A.R.,et al.,Light-emitting diodes based on conjugated polymers[J],Nature,1990,347:539
40.邵炎,邱勇.有机金属配合物电致发光材料[J],现代显示,1998,2:32.
41.Liu X.T.,Zhang Y.L.,Shi C.S.,et al.,Hydrothermal synthesis and luminescent properties of BaBeF_4:RE(RE=Eu,Tb)[J],J.Solid State Chem.,2005,178(6):2167.
42.Yan B.,Zhang H.J.,Ni J.Z.,Luminescence properties of the rare earth(Eu~(3+) and Tb~(3+)) complexes with 1,10-Phenanthroline incorporated in silica matrix by a sol-gel method[J],Materials Science and Engineering B,1998,52(2-3):123.
43.Santos B.S.,de Mello Donega C.,de Sa G.F.,Photophysical properties of Eu~(3+),Gd~(3+) and Tb~(3+) complexes with 2-hydroxy-2,4,6-cycloheptatrien-l-one[J],J.Lumin.,1997,72-74:535.
44.Zhang X.M.,Sun R.G.,Zheng Q.B.,et al.,Temperature-dependent electroluminescence from(Eu,Gd) coordination complexes[J],Appl.Phys.Lett.,1997,71(18):2596.
45.Liu Y.,Ye C.F.,Qian G.D.,et al.,Enhanced luminescence of Eu~(3+) by Gd~(3+) in ternary chelate doped in gel glasses via in situ technique[J],J.Lumin.,2006,118(2):158.
46.Chu B.L.,Guo C.F.,Su Q..Luminescence and energy transfer in Sr_2Gd_xY_(7.9)-xLn_(0.1)(SiO_4)_6O_2(Ln=Sm,Dy,Eu)[J],Materials Chemistry and Physics,2004,84(2-3):279.
47.Armaroli N.,Balzani V.,Barigelletti F.,et al.,Luminescence properties of Eu~(3+),Tb~(3+),and Gd~(3+) complexes of the hexadentate N-donor podand tris-[3-(2-pyridyl)pyrazol-lyl]hydroborate[J],Chem.Phys.Lett.,1997,276(5-6):435.
48.Guo L.Q.,Zhu X.W..Crystal Structure of Complex Tris(4,4,4-trifluoro -1-phenyl-1,3-butanedione)(1,10-phenanthroline) Europium(Ⅲ)[J],Chin.J.Chem,2003,21:211.
49.孙文秀,徐怡庄,李维红等,聚乙二醇基质中纳米乙酰丙酮铽的荧光特性研究[J],中国稀土学报,2001,19(6):540.
50.Kawachi J.J.,Matsubara H.,Nakahara Y.,et al.,Process for producing 4,6-diaminoresorcinols[J],[P]US005892118,1999.
51.Tschaen D.M.,Abramson L.,Cai D.W.,et al.,Asymmetric Synthesis of MK-0499[J],J.Org.Chem.,1995,60(14):4324.
52.Kohler E.P.,Bruce W.F.,The oximes of ortho hydroxydroxy benzophenone[J],J.Am.Chem.Soc.,1931,53(4):1569.
53.Mariella R.P.,Brown K.H..Diacetylation of amines[J],J.Org.Chem.,1971,36(5):735.
54.Matsushima R.,Kishimoto T.,Suzuki Morio Photoreactions of flavanones[J],Bull.Chem.Soc.Jpn.,1980,53(10):2938.
55.Husain A.,Shaharyar M..Synthesis and antibacterial activity of epoxides derived from chalcones[J],Asian J.Chem.,2005,17(1):624.
56.Witczak Z.,Krolikowska M..Chalcone oximes.Part Ⅴ.Reaction of hydroxylamine with 4-substituted 2'-hydroxychalcones[J],Pol.J.Chem.,1981,55(1):89.
57.John K.,Sommerville N J.β-Pyridylacrylophenone and analogs.New class of active coronary dilating agents[J],J.Pharm.Sci.,1964,53(11):1329.
58.Weinheimer C.,Choi Y.,Caldwell T.,et al.,Effect of a steric spacer on chromophoric interactions of ruthenium complexes containing covalently bound anthracene[J],J.Photochem.Photobiol.,A,1994,78(2):119.
59.Calderazzo F.,Marchetti F.,Pampaloni G.,et al.,Co-ordination properties of 1,10-phenanthroline-5,6-dione towards group 4 and 5 metals in low and high oxidation states[J],J.Chem.Soc.,Dalton Trans.,,1999:4389
60.袁继兵,李嘉航,梁万里.三种新的铕(Ⅲ)三元配合物的合成及发光性质研究[J],化学学报,2004,62(22):2282.
61.Simpson P.G.,Vinciguerra A.,Quagliano J.V..The donor properties of 2,2'-bipydine N,N'-Dioxide[J],Inorg.Chem.,1963,2(2):282.
62.Plater M.J.,Kemp S.,Lattmann E..Heterocyclic free radicals.Part 1.4,5-Diazafluorene derivatives of Koelseh's free radical:an EPR and metal-ion complexation study[J],J.Chem.Soc.,Perkin Trans.,2000,1:971.
63.Meng Q.G.,Zhang H.J.,Wang S.B.,et al.,Preparation and characterization of luminescent thin films doped with rare earth(Tb~(3+),Eu~(3+)) complexes derived from a sol-gel process[J],Materials Letters,2000,45(3-4):213.
64.Meng Q.G.,Fu L.S.,Lin J.,et al.,Preparation and characterization of a layered transparent luminescent thin film of silica-CTAB-Tb(acac)_3 composite with mesostructure[J],Journal of Physics and Chemistry of Solids,2003,64(1):63.
65.Guo J.F.,Fu L.S.,Li H.R.,et al.,Preparation and luminescence properties of ormosil hybrid materials doped with Tb(Tfacac)_3phen complex via a sol-gel process[J],Materials Letters,2003,57(24-25):3899.
66.陈国珍,黄贤智,许金钩,荧光分析法(第二版)[M].1990,科学出版社.p 15.
67.朱东霞,王悦,邵奎占等,双水杨醛缩苯二胺锌荧光量子效率的研究[J],东北师大学报自然科学版,2004,36(3):52.
68.Kim K.B.,Kim Y.I.,Chun H.G.,et al.,Structural and Optical Properties of BaMgAl_(10)O_(17):Eu~(2+) Phosphor[J],Chem.Mater.,2002,14(12):5045.
69.Wrighton M.S.,Ginley D.S.,Morse D.L.,Technique for the determination of absolute emission quantum yields of powdered samples[J],J.Phys.Chem.,1974,78(22): 2229.
70.Malta O.L.,Brito H.F.,Menezes J.F.S.,et al.,Experimental and theoretical emission quantum yield in the compound Eu(thenoyltrifluoroacetonate)_3 2(dibenzyl sulfoxide)[J],Chem.Phys.Lett.,1998,282(3-4):233.
71.Bril A.,Absolute Efficiencies of Phosphors with Ultraviolet and Cathode-ray Excitation In Luminescence of Organic and Inorganic Materials[M].1962,Wiley,Eindhove.p 479.
72.Shyamala B.S.,Jayatyagaraju Vuppalapati bis-Bidenticity of 2,4-Dihydroxy-5-acetylacetophenone and Its Derivatives with Divalent Nickel and Copper[J],Synthesis and Reactivity in Inorganic,Metal-Organic,and Nano-Metal Chemistry,2003,33(1):63.
73.Takano A,Ohba M.,Okawa H..Structures and magnetic properties of 4,6-diacetylresorcinate-bridged dinuclear copper(Ⅱ) complexes[J],Molecular crystals and liquid crystals science and technology.Section A,Molecular crystals and liquid crystals,1999,335 941.
74.Pettinari C.,Marchetti F.,Cingolani A.,et al.,Syntheses,structural and spectroscopic investigation(IR,NMR and luminescence) of new terbium and europium acylpyrazolonates[J],Inorg.Chim.Acta,2004,357(14):4181.
75.Zhang Z.F.,Su C.Y.,Liu W.M.,et al.,Study on tribological properties of the complex of rare earth dialkyldithiocarbamate and phenanthroline in lubricating grease[J],Wear,1996,192(1-2):6.
76.Xu C.J,Xie F,Guo X.Z.,et al.,Synthesis and cofluorescence of Eu(Ⅲ) complexes with salicylic acid and o-phenanthroline[J],Spectrochim.Acta,Part A,2005,61(9):2005.
77.Chang C.H.,Yun M.H.,Choi W.J..Synthesis and photoluminescence properties of Eu(pzc)_3(phen) and Eu(mpzc)_3(phen)[J],Synth.Met.,2004,145(1):1.
78.Yan B.,Zhang H.g J.,Wang S.B.,et al.,Luminescence properties of the ternary rare earth complexes with β-diketones and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method[J],Materials Chemistry and Physics,1997,51(1):92.
79.孙丽宁,符连社,刘丰祎.无机/有机稀土配合物杂化发光材料研究进展[J],发光学报,2005,26(1):15.
80.连锡山,盛慧,刘占梅.苯甲酸稀土(Eu,La)配合物的红外和荧光光谱研究[J],光谱学与光学分析,1999,19(4):562.
81.阎冰,张洪杰,王淑彬.铽苯二甲酸同多核和异多核配合物的发光性能[J],应用化学,1997,14(6):84.
2.Weissman S.I.,Intramolecular Energy Transfer The Fluorescence of Complexes of Europium[J],J.Chem.Phys.,1942,10(4):214.
3.Charles R.G.,Riedel E.P.,Properties of some europium laser chelates derived from benzoyltrifluoroacetone[J],J.Inorg.Nucl.Chem.,1966,28(12):3005.
4.Bhaumik M.L.,Fletcher P.C.,Nugent L.J.,et al.,Laser Emission from a Europium Benzoylacetonate Alcohol Solution[J],J.Phys.Chem.,1964,68(6):1490.
5.Crosby G.A.,Whan R.E.,Freeman J.J.,Spectroscopic studies of rare earth chelates [J],J.Phys.Chem.,1962,66(12):2493.
6.Freeman J.J.,Crosby G.A.,Spectra and decay times of the luminescences observed from chelated rare earth ions[J],J.Phys.Chem.,1963,67(12):2717.
7.Dawson W.R.,Kropp J.L.,Windsor M.W.,Internal-Energy-Transfer Efficiencies in Eu~(3+) and Tb~(3+) Chelates Using Excitation to Selected Ion Levels[J],J.Chem.Phys.,1966,45(7):2410.
8.朱卫国,苑同锁,魏孝强等,噻吩甲酰三氟丙酮-酰基吡唑啉酮-邻菲咯啉合铕(Ⅲ)四元配合物的合成和表征[J],高等学校化学学报,2000,21(10):1527.
9.肖尊宏,谭松庭,周洪波等,2-烯丙基-1,3-二苯基-1,3-丙二酮的合成及其稀土配合物光致发光性质研究[J],中国稀土学报,2002,20(6):667.
10.谭松庭,杨娜,赵斌等,4-正辛烷氧基二苯甲酰甲烷-邻菲口罗啉-铕三元配合物的合成与光致发光[J],液晶与显示,2002,17(5):341.
11.刘胜利,祁素素.1-(2-羟基苯基)-3-苯基-1,3-丙二酮及其与铕(Ⅲ)配合物的合成和发光研究[J],中国稀土学报,2005,23(5):561.
12.李建宇,稀土发光材料及其应用[M].2003,北京,化学工业出版社.p 192.
13.Richardson F.S.,Terbium(Ⅲ) and europium(Ⅲ) ions as luminescent probes and stains for biomolecular systems[J],Chem.Rev.,1982,82(5):541.
14.李建宇,稀土发光材料及其应用[M].2003,北京,化学工业出版社.p250.
15.Morita M.,Iwamura M.,Rau D.,et al.,Luminescence of metal ion-activated nanophosphor supported by nanoporous sol-gel SiO_2 matrices[J],J.Lumin.,In Press,Corrected Proof.
16.Lenaerts P.,Gorier W.C.,Binnemans K..Luminescent europium(Ⅲ) and terbium(Ⅲ) nicotinate complexes covalently linked to a 1,10-phenanthroline functionalised sol-gel glass[J],J.Lumin.,2006,117(2):163.
17.Luo Y.,Han Y.H,Lin J..Synthesis and luminescent properties of europium(Ⅲ)schiff base complexes covalently bonded to silica xerogels[J],J.Lumin.,In Press,Corrected Proof.
18.Konkowski A.M.,Szakowska I.,Lis S.,et al.,Luminescent materials consisting of Eu(Ⅲ) ions complexed with cryptand ligand and coligands entrapped in xerogel matrices[J],J.Lumin.,2005,115(3-4):122.
19.Wang F.,Fan X.P.,Wang M.Q.,et al.,Luminescence behavior of the dibenzoyl methane europium(Ⅲ) complexes in sol-gel derived host materials[J],J.Lumin.,2005,114(3-4):281.
20.Lenaerts P.,Ryckebosch E.,Driesen K.,et al.,Study of the luminescence of tds(2-thenoyltrifluoroacetonato)lanthanide(Ⅲ) complexes covalently linked to 1,10-phenanthroline-functionalized hybrid sol-gel glasses[J],J.Lumin.,2005,114(1):77.
21.Wang H.S.,Qian G.D.,Wang Z.Y.,et al.,1.53 um photoluminescence from ORMOSIL films doped with erbium complexes[J],J.Lumin.,2005,113(3-4):214.
22.Reisfeld R.,Saraidarov T.,Ziganski E.,et al.,Intensification of rare earths luminescence in glasses[J],J.Lumin.,2003,102-103:243.
23.Modta M.,Rau D.,Kai T.,Luminescence and circularly polarized luminescence of macrocyclic Eu(Ⅲ) and Tb(Ⅲ) complexes embedded in xerogel and sol-gel SiO_2glasses[J],J.Lumin.,2002,100(1-4):97.
24.Morita M.,Kajiyama S.,Kai T.,et al.,Physicochemical control of valence in luminescence of Cr(Ⅲ) and V(Ⅲ,Ⅳ) complexes embedded in xero-gel and sol-gel SiO_2glasses[J],J.Lumin.,2001,94-95:91.
25.Li H.,Inoue S.,Machida K.,et al.,Preparation and luminescence properties of inorganic-organic hybrid materials doped with lanthanide(Ⅲ) complexes[J],J.Lumin.,2000,87-89:1069.
26.Yan B.,Zhang H.J.,Wang S.B.,et al.,Luminescence properties of the ternary rare earth complexes with β-diketones and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method[J],Materials Chemistry and Physics,1997,51(1):92.
27.Yan B.,Zhang H.,Wang S.,et al.,Luminescence properties of rare-earth(Eu~(3+) and Tb~(3+)) complexes with paraaminobenzoic acid and 1,10-phenanthroline incorporated into a silica matrix by sol-gel method[J],Mater.Res.Bull.,1998,33(10):1517.
28.Yan B.,Zhang H.J.,Wang S.B.,et al.,Luminescence properties of rare earth(Eu~(3+)and Tb~(3+) complexes with conjugated carboxylic acids and 1,10-phenanthro line incorporated in silica matrix[J],J.Photochem.Photobiol.,A,1998,112(2-3):231.
29.Sabbatini N.,Dellonte S.,Blasse G.,The luminescence of the rare earth cryptates [Tb:2.2.1]~(3+) and[Sm:2.2.1]~(3+)[J],Chem.Phys.Lett.,1986,129(6):541.
30.Okamoto Y.,Ueba Y.,Dzhanibekov N.F.,et al.,Rare earth metal containing polymers.3.Characterization of ion-containing polymer structures using rare earth metal fluorescence probes[J],Macromolecules,1981,14(1):17.
31.Li W.L.,Mishima T.,Adachi G.Y.,et al.,The fluorescence of transparent polymer films of rare earth complexes[J],Inorg.Chim.Acta,1986,121(1):97.
32.Sabbatini N.,Ciano M.,Dellonte S.,et al.,Absorption and emission properties of a europium(Ⅱ) cryptate in aqueous solution[J],Chem.Phys.Lett.,1982,90(4):265.
33.闫冰,张洪杰,王淑彬等,稀土3,4-呋喃二甲酸,1,10-二氮杂菲配合物的光物理性质[J],中国稀土学报,1998,16(4):375.
34.张颂培,李建宇,姜晓琳等,Eu~(3+)-β-二酮、三正辛胺三元配合物的合成与光谱特性[J],化学试剂,2003,25(3):187.
35.郑向军,万永红,金林培等,一个新颖的光致发光和光致变色铕配合物[J],科学通报,2001,46(22):1861.
36.Sato S.,Wada M..Relations between Intrarnolecular Energy Transfer Efficiencies and Triplet State Energies in Rare Earth β-diketone Chelates[J],Bull.Chem.Soc.Jpn.,1970,43(7):1955.
37.Sato S.,Wada M.,Seki T..Some Properties of Europium β-diketone Chelates (Synthesis and Fluorescent Properties)[J],Jpn.J.Appl.Phys.,1968,7:7.
38.Tang C.W.,VanSlykes S.A..Organic electroluminescent diodes[J],Appl.Phys.Lett.,1987,51:913.
39.Burroughes J.H.,Bradley D.D.C.,Brown A.R.,et al.,Light-emitting diodes based on conjugated polymers[J],Nature,1990,347:539
40.邵炎,邱勇.有机金属配合物电致发光材料[J],现代显示,1998,2:32.
41.Liu X.T.,Zhang Y.L.,Shi C.S.,et al.,Hydrothermal synthesis and luminescent properties of BaBeF_4:RE(RE=Eu,Tb)[J],J.Solid State Chem.,2005,178(6):2167.
42.Yan B.,Zhang H.J.,Ni J.Z.,Luminescence properties of the rare earth(Eu~(3+) and Tb~(3+)) complexes with 1,10-Phenanthroline incorporated in silica matrix by a sol-gel method[J],Materials Science and Engineering B,1998,52(2-3):123.
43.Santos B.S.,de Mello Donega C.,de Sa G.F.,Photophysical properties of Eu~(3+),Gd~(3+) and Tb~(3+) complexes with 2-hydroxy-2,4,6-cycloheptatrien-l-one[J],J.Lumin.,1997,72-74:535.
44.Zhang X.M.,Sun R.G.,Zheng Q.B.,et al.,Temperature-dependent electroluminescence from(Eu,Gd) coordination complexes[J],Appl.Phys.Lett.,1997,71(18):2596.
45.Liu Y.,Ye C.F.,Qian G.D.,et al.,Enhanced luminescence of Eu~(3+) by Gd~(3+) in ternary chelate doped in gel glasses via in situ technique[J],J.Lumin.,2006,118(2):158.
46.Chu B.L.,Guo C.F.,Su Q..Luminescence and energy transfer in Sr_2Gd_xY_(7.9)-xLn_(0.1)(SiO_4)_6O_2(Ln=Sm,Dy,Eu)[J],Materials Chemistry and Physics,2004,84(2-3):279.
47.Armaroli N.,Balzani V.,Barigelletti F.,et al.,Luminescence properties of Eu~(3+),Tb~(3+),and Gd~(3+) complexes of the hexadentate N-donor podand tris-[3-(2-pyridyl)pyrazol-lyl]hydroborate[J],Chem.Phys.Lett.,1997,276(5-6):435.
48.Guo L.Q.,Zhu X.W..Crystal Structure of Complex Tris(4,4,4-trifluoro -1-phenyl-1,3-butanedione)(1,10-phenanthroline) Europium(Ⅲ)[J],Chin.J.Chem,2003,21:211.
49.孙文秀,徐怡庄,李维红等,聚乙二醇基质中纳米乙酰丙酮铽的荧光特性研究[J],中国稀土学报,2001,19(6):540.
50.Kawachi J.J.,Matsubara H.,Nakahara Y.,et al.,Process for producing 4,6-diaminoresorcinols[J],[P]US005892118,1999.
51.Tschaen D.M.,Abramson L.,Cai D.W.,et al.,Asymmetric Synthesis of MK-0499[J],J.Org.Chem.,1995,60(14):4324.
52.Kohler E.P.,Bruce W.F.,The oximes of ortho hydroxydroxy benzophenone[J],J.Am.Chem.Soc.,1931,53(4):1569.
53.Mariella R.P.,Brown K.H..Diacetylation of amines[J],J.Org.Chem.,1971,36(5):735.
54.Matsushima R.,Kishimoto T.,Suzuki Morio Photoreactions of flavanones[J],Bull.Chem.Soc.Jpn.,1980,53(10):2938.
55.Husain A.,Shaharyar M..Synthesis and antibacterial activity of epoxides derived from chalcones[J],Asian J.Chem.,2005,17(1):624.
56.Witczak Z.,Krolikowska M..Chalcone oximes.Part Ⅴ.Reaction of hydroxylamine with 4-substituted 2'-hydroxychalcones[J],Pol.J.Chem.,1981,55(1):89.
57.John K.,Sommerville N J.β-Pyridylacrylophenone and analogs.New class of active coronary dilating agents[J],J.Pharm.Sci.,1964,53(11):1329.
58.Weinheimer C.,Choi Y.,Caldwell T.,et al.,Effect of a steric spacer on chromophoric interactions of ruthenium complexes containing covalently bound anthracene[J],J.Photochem.Photobiol.,A,1994,78(2):119.
59.Calderazzo F.,Marchetti F.,Pampaloni G.,et al.,Co-ordination properties of 1,10-phenanthroline-5,6-dione towards group 4 and 5 metals in low and high oxidation states[J],J.Chem.Soc.,Dalton Trans.,,1999:4389
60.袁继兵,李嘉航,梁万里.三种新的铕(Ⅲ)三元配合物的合成及发光性质研究[J],化学学报,2004,62(22):2282.
61.Simpson P.G.,Vinciguerra A.,Quagliano J.V..The donor properties of 2,2'-bipydine N,N'-Dioxide[J],Inorg.Chem.,1963,2(2):282.
62.Plater M.J.,Kemp S.,Lattmann E..Heterocyclic free radicals.Part 1.4,5-Diazafluorene derivatives of Koelseh's free radical:an EPR and metal-ion complexation study[J],J.Chem.Soc.,Perkin Trans.,2000,1:971.
63.Meng Q.G.,Zhang H.J.,Wang S.B.,et al.,Preparation and characterization of luminescent thin films doped with rare earth(Tb~(3+),Eu~(3+)) complexes derived from a sol-gel process[J],Materials Letters,2000,45(3-4):213.
64.Meng Q.G.,Fu L.S.,Lin J.,et al.,Preparation and characterization of a layered transparent luminescent thin film of silica-CTAB-Tb(acac)_3 composite with mesostructure[J],Journal of Physics and Chemistry of Solids,2003,64(1):63.
65.Guo J.F.,Fu L.S.,Li H.R.,et al.,Preparation and luminescence properties of ormosil hybrid materials doped with Tb(Tfacac)_3phen complex via a sol-gel process[J],Materials Letters,2003,57(24-25):3899.
66.陈国珍,黄贤智,许金钩,荧光分析法(第二版)[M].1990,科学出版社.p 15.
67.朱东霞,王悦,邵奎占等,双水杨醛缩苯二胺锌荧光量子效率的研究[J],东北师大学报自然科学版,2004,36(3):52.
68.Kim K.B.,Kim Y.I.,Chun H.G.,et al.,Structural and Optical Properties of BaMgAl_(10)O_(17):Eu~(2+) Phosphor[J],Chem.Mater.,2002,14(12):5045.
69.Wrighton M.S.,Ginley D.S.,Morse D.L.,Technique for the determination of absolute emission quantum yields of powdered samples[J],J.Phys.Chem.,1974,78(22): 2229.
70.Malta O.L.,Brito H.F.,Menezes J.F.S.,et al.,Experimental and theoretical emission quantum yield in the compound Eu(thenoyltrifluoroacetonate)_3 2(dibenzyl sulfoxide)[J],Chem.Phys.Lett.,1998,282(3-4):233.
71.Bril A.,Absolute Efficiencies of Phosphors with Ultraviolet and Cathode-ray Excitation In Luminescence of Organic and Inorganic Materials[M].1962,Wiley,Eindhove.p 479.
72.Shyamala B.S.,Jayatyagaraju Vuppalapati bis-Bidenticity of 2,4-Dihydroxy-5-acetylacetophenone and Its Derivatives with Divalent Nickel and Copper[J],Synthesis and Reactivity in Inorganic,Metal-Organic,and Nano-Metal Chemistry,2003,33(1):63.
73.Takano A,Ohba M.,Okawa H..Structures and magnetic properties of 4,6-diacetylresorcinate-bridged dinuclear copper(Ⅱ) complexes[J],Molecular crystals and liquid crystals science and technology.Section A,Molecular crystals and liquid crystals,1999,335 941.
74.Pettinari C.,Marchetti F.,Cingolani A.,et al.,Syntheses,structural and spectroscopic investigation(IR,NMR and luminescence) of new terbium and europium acylpyrazolonates[J],Inorg.Chim.Acta,2004,357(14):4181.
75.Zhang Z.F.,Su C.Y.,Liu W.M.,et al.,Study on tribological properties of the complex of rare earth dialkyldithiocarbamate and phenanthroline in lubricating grease[J],Wear,1996,192(1-2):6.
76.Xu C.J,Xie F,Guo X.Z.,et al.,Synthesis and cofluorescence of Eu(Ⅲ) complexes with salicylic acid and o-phenanthroline[J],Spectrochim.Acta,Part A,2005,61(9):2005.
77.Chang C.H.,Yun M.H.,Choi W.J..Synthesis and photoluminescence properties of Eu(pzc)_3(phen) and Eu(mpzc)_3(phen)[J],Synth.Met.,2004,145(1):1.
78.Yan B.,Zhang H.g J.,Wang S.B.,et al.,Luminescence properties of the ternary rare earth complexes with β-diketones and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method[J],Materials Chemistry and Physics,1997,51(1):92.
79.孙丽宁,符连社,刘丰祎.无机/有机稀土配合物杂化发光材料研究进展[J],发光学报,2005,26(1):15.
80.连锡山,盛慧,刘占梅.苯甲酸稀土(Eu,La)配合物的红外和荧光光谱研究[J],光谱学与光学分析,1999,19(4):562.
81.阎冰,张洪杰,王淑彬.铽苯二甲酸同多核和异多核配合物的发光性能[J],应用化学,1997,14(6):84.