CN100390181C - 2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth complex and process for preparing same - Google Patents

2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth complex and process for preparing same Download PDF

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CN100390181C
CN100390181C CNB2005100427489A CN200510042748A CN100390181C CN 100390181 C CN100390181 C CN 100390181C CN B2005100427489 A CNB2005100427489 A CN B2005100427489A CN 200510042748 A CN200510042748 A CN 200510042748A CN 100390181 C CN100390181 C CN 100390181C
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benzimidazolyl
acetyl
rare earth
glycine
schiff base
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CN1699374A (en
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杨一心
王党辉
赵天成
李青翠
陈冬梅
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Northwest University
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Abstract

The present invention discloses a rare earth complex and a preparation method thereof. A 2-acetyl benzimidazolyl glycine-condensate Schiff base rare earth complexes has the following chemical components of M2L3 (NO3)3.2CH3OH, wherein M is equal to La<3+>, Ce<3+>, Pr<3+>, Nd<3+>, Sm<3+>, Eu<3>, Gd<3+>, Tb<3+>, Dy<3+>, Er<3+> and Y<3+>; L is 2-acetyl benzimidazolyl glycine-condensate Schiff base. The preparation method comprises the steps of placing rare earth nitrate and 2-acetyl benzimidazolyl glycine-condensate Schiff base with the molar ratio of 2: 3 in a methanol solvent for reaction for 3 to 10 hours at 45 to 70 DEG C and obtaining a product after filtration. The rare earth complex has favorable upconversion photoluminescent behavior, reach high optical conversion rate and high luminescence property under a high-alkalinity condition, and can serve as new optical material in optical devices.

Description

2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth complex and preparation method thereof
Technical field
The present invention relates to rare earth title complex and preparation method thereof, be specifically related to 2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth complex and preparation method thereof, this rare earth compounding can be used as the optical functional material.
Background technology
Rare earth amino acids title complex is because widely-used at aspects such as agricultural, medicine, is one of focus of studying of people always.Rare earth ion and life metallic element calcium have close ionic radius, add rare earth ion because the existence of 4f electronics and distinctive photoluminescent property can be used as probe and discloses Na in the organism +, K +, Ca 2+Deng the physiological function of metal ion, therefore the research degree of depth and the range of this respect are strengthened day by day.But because Na in the life system +, K +, Ca 2+The residing coordination environment of plasma is very complicated, be not only by embodying its function with amino acid whose effect, therefore in recent years rare earth and simple amino acid binary complex architectural study are reduced just year by year, then the ternary more approaching, the polynary and amino acid whose rare earth compounding modified have been invested with the life entity internal milieu, since the eighties in last century, the physiology biological activity of amino acid Schiff alkali (schiff bases) and metal complexes thereof has become the problem that people pay close attention to, and has carried out a large amount of research.
In the research in this respect, mainly concentrate on active high aldehydes aspect, and do not appear in the newspapers for research with physiologically active and optically active benzoglyoxaline amino acid Schiff alkali.
Document (Cheeseman G.W.H., J Chem.Soc, 1964,4645-4646) reported a kind of method of synthetic precursor 2-ethanoyl benzo imidazoles, there is following defective in it:
1. reaction time consumption is longer, and productive rate is not high, by reappearing the synthesis step of document report, and prolongs reaction times etc. and does not all reach the productive rate of being reported 63%, can only reach about 30%.
2. this synthetic method reaction process is seriously polluted, is difficult to a large amount of synthetic.A large amount of Cr as the hydrolysis generation 3+In fact the chloroform amount that will use in extraction is very big; just in order to guarantee next can synthesize the Schiff aar ligand smoothly. product must carry out twice recrystallization can obtain pure product 2-ethanoyl benzo imidazoles, and this just will make recrystallization solvent with the very big benzene of a large amount of toxicity especially.
Document (P K Dubey, C Ravi Kumar, Balaji Babu.Indian Journal of Chemistry; 2003,42 (B): 3128-3120) reported method also has following deficiency:
Solubleness in used recrystallization solvent normal hexane is very poor, and the product of recrystallization is less than 1g in the normal hexane of 300ml heat, and reagent waste is very big, and recrystallization efficient is very low, does not reach 90% productive rate of its report far away, only has about 60%.
Summary of the invention
The purpose of this invention is to provide class 2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth complex and preparation method thereof; Simultaneously the synthetic method of reacting precursor 2-ethanoyl benzo imidazoles is improved, the title complex that finally obtains can be used as potential optical functional material.
2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth complex with following chemical constitution:
M 2L 3(NO 3) 3·2CH 3OH
Wherein, M=La 3+, Ce 3+, Pr 3+, Nd 3+, Sm 3+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, Er 3+Or Y 3+
L is the 2-acetyl benzimidazolyl-glycin schiff base.
The preparation method of 2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth complex, with mol ratio be 2: 3 rare earth nitrate and 2-acetyl benzimidazolyl-glycin schiff base in methanol solvate in 45-70 ℃ of reaction 3-10 hour down, filter product.Described rare earth nitrate is La 3+, Ce 3+, Pr 3+, Nd 3+, Sm 3+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, Er 3+Or Y 3+Nitrate.
Can the separation and purification part, react in methanol solvate with rare earth nitrate then, also can directly will synthesize the part and the rare earth nitrate that obtain and in methanol solvate, react without separation.
2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth complex part preparation method in turn includes the following steps:
(1) 2-(1 '-hydroxyethyl) benzoglyoxaline is synthetic
The mol ratio of O-Phenylene Diamine and HCl 1: 1 is dissolved in O-Phenylene Diamine among the HCl, is stirred to moltenly entirely, and transferring pH with HCl is 1-3, adds the FeCl of lactic acid and catalytic amount again 3, reflux 2-8 hour, cooling added solid Na 2CO 3Powder neutralization and vigorous stirring, to pH near 7 o'clock, use 20%Na again 2CO 3Transfer to solution and become yellow-green colour by dark red, have a large amount of precipitations to generate, suction filtration gets crude product, and the water recrystallization can be further purified.
(2) precursor 2-ethanoyl benzo imidazoles is synthetic
With KMnO 4Grind in mortar with the solid active aluminum oxide; then 2-(1 '-hydroxyethyl) benzoglyoxaline is added and continue to grind evenly; in mixture, add acetone; acetone extract is separated, evaporates acetone; the residue that obtains is dissolved in the chloroform; wash the inorganics that removes attachment removal with water, the evaporate to dryness chloroform gets 2-ethanoyl benzo imidazoles, recrystallization in normal hexane-acetone mixed solvent.
(3) preparation of part
The 40-70 ℃ of stirring that refluxes adds the methanol solution of 2-ethanoyl benzo imidazoles down in the methanol solution of glycine sylvite, sodium salt or lithium salts, being back to solution colour is dark brown red by xanthochromia, steams methyl alcohol and gets part.
Rare earth compounding of the present invention can replace the organic dye of organic dyeing laser apparatus as the optical functional material under the same terms of organic dyeing laser apparatus (element or electronic installation etc.).Rare earth compounding of the present invention all can dissolve under the condition of prescribed concentration (about 0.00001～0.01 mol) and pH (7-12), be dispersed or suspended in the solvent and use.And under bigger alkaline condition, the rare earth luminescence characteristic of this series title complex is more excellent, and luminous efficiency is than big in the medium of low alkalinity.And rare earth compounding of the present invention has good last converting photoluminescent behavior, and promptly the excitation of growing with wavelength can produce the fluorescence than excitation wave length.Title complex of the present invention reaches high light turnover ratio and the luminosity under the high alkalinity condition, can be used as new optical material and is used for Optical devices.
Improved synthetic method, made reaction process simple, productive rate is greatly improved.In 2-(1 '-hydroxyethyl) benzoglyoxaline synthetic, consider and use 20%Na 2CO 3During neutralization reaction liquid, introduced a large amount of water, made portioned product be dissolved in the waste liquid, caused productive rate to descend, so use Na instead 2CO 3The powder neutralization when the speed of foam generation slows down, promptly near terminal point, adds 20%Na again 2CO 3Neutralization, productive rate is greatly improved.The synthetic title complex has good optical property, as above converting photoluminescent character, and special dissolving properties, be slightly acidic after this series title complex is water-soluble, add dissociation of ligand behind the strong acid and be dissolved in the water, add highly basic then in pH=8～13 scopes, all solubleness heightens, and along with pH value increases and the solubleness increase.
Description of drawings
Fig. 1 is the laser Raman spectroscopy figure of precursor 2-ethanoyl benzo imidazoles.
Fig. 2 is Eu title complex [Eu 2L 3(NO 3) 32CH 3OH] uv-absorbing spectrogram during water-soluble and aqueous solution pH=13.
Fig. 3 is [Eu 2L 3(NO 3) 32CH 3OH] three-dimensional fluorescence of the aqueous solution excites and emmission spectrum figure
Fig. 4 is [Eu 2L 3(NO 3) 32CH 3OH] the solid three-dimensional fluorescence excites and emmission spectrum figure
Fig. 5 is Eu 2L 3(NO 3) 32CH 3The fluorescence spectrum figure of OH in the different pH aqueous solution.
Fig. 6 is Eu 2L 3(NO 3) 32CH 3The fluorescence intensity that the OH aqueous solution records in the time of 75 minutes to 105 minutes in Continuous irradiation.
Fig. 7 is Eu 2L 3(NO 3) 32CH 3The fluorescence intensity that the OH aqueous solution records in the time of 135 minutes to 185 minutes in Continuous irradiation.
Fig. 8 is Eu 2L 3(NO 3) 32CH 3The excimer laser fluorescence excitation spectrum of OH title complex.
Embodiment
The synthetic method of embodiment 1 precursor 2-ethanoyl benzo imidazoles
Synthesizing of step 1:2-(1 '-hydroxyethyl) benzoglyoxaline:
Figure C20051004274800051
In the 100ml three-necked bottle, the 10g O-Phenylene Diamine is dissolved among the 25ml 4mol/LHCl, be stirred to moltenly entirely, transfer pH=2 with HCl, add 0.1g catalyst Fe Cl again 36H 2O and 13ml lactic acid, reflux 4 hours, cooling slowly adds solid Na 2CO 3Powder neutralization and vigorous stirring, to pH near 7 o'clock, use 20%Na again 2CO 3Transfer to solution and become yellow-green colour by dark red, have a large amount of precipitations to generate, place, suction filtration gets crude product.Directly the water recrystallization adds activated carbon decolorizing, and filtered while hot is separated out white crystal 13.5g after the cooling, productive rate 80%, fusing point 180.4-181.0 ℃ (literature value 177-179 ℃).
Step 2: the synthetic method of precursor 2-ethanoyl benzo imidazoles
With KMnO 4(2g, 12.65m mol) and solid active aluminum oxide (2.5g) mix in mortar, grind purple powder most very uniformly into powder, then with 2-(1 '-hydroxyethyl) benzoglyoxaline (1.2g, 7.5m mol) add wherein, at room temperature grind about 10 minutes, add 100ml left and right sides acetone then in mixture, 15 minutes after-filtration of vigorous stirring, evaporate to dryness acetone is dissolved in the residue that obtains in the chloroform of 30mL, uses the 30mL water washing, to remove the inorganics that is adsorbing, use anhydrous Na then 2SO 4Drying obtains yellow crystals 2-ethanoyl benzo imidazoles with the crude product recrystallization in hot normal hexane-acetone mixed solvent that obtains behind the evaporate to dryness chloroform.Prove conclusively by Measurement of melting point and Sadtler standard infared spectrum.Fusing point is 188.1～188.4 ℃ (186～188 ℃ of literature values), productive rate about 70%.Laser Raman spectroscopy figure sees Fig. 1 (cm -1): 1669.5v (C=O), 3273.7,3063.7,3014.7,2913.1 (v-OH and v-NH).
The preparation of embodiment 2 parts
With glycine (0.7507g; 0.01mol) and KOH (0.56g; 0.01mol) be dissolved in the 25mL methyl alcohol; stir about 15 minutes to dissolving; filter; 50 ℃ of stirrings that reflux drip 2-ethanoyl benzo imidazoles down in this solution (solution colour is a dark brown red by xanthochromia after backflow 5-14 hour for 1.602g, 0.01mol) 20mL methanol solution; steam part methyl alcohol; cooling has precipitation to generate suction filtration; respectively with methyl alcohol, chloroform washing; infrared lamp is oven dry down, places vitriol oil moisture eliminator constant weight, gets the khaki color powder.
1H NMR hydrogen spectrum (400MHz, CD 3OD): δ 7.6 (q, 2H, aCoupling peak on the H-Ar), δ 7.3 (q, 2H, bCoupling peak on the H-Ar), and δ 5.311 (d, 1H, H-N), δ 2.582 (s, 2H ,-CH 2-), δ 1.652 (s, 3H, CH 3).
Infrared (cm -1) (KBr) 1643 (C=N), 1570 (v AsCOO -), 1428 (v sCOO -)
Raman (cm -1): 1644.76 (C=N), 1566.93 v AsCOO -), 1436.76 (v sCOO -),
Its empirical formula is KC 11H 10N 3O 21/4CH 3OH, ultimate analysis data (being calculated value in the bracket) are: C:51.51 (51.31) H:4.550 (4.210), N:16.15 (15.96).
Embodiment 3 rare earth Pr title complex [Pr 2L 3(NO 3) 32CH 3OH] preparation
Rare earth nitrate Pr (the NO that under heated and stirred, incites somebody to action 3) 36H 2O (0.87g, 2mmol) the 25mL methanol solution slowly is added drop-wise to and has dissolved metering than being 2: 3 (rare earth ions: Schiff alkali (KL) part (the 0.79g Schiff aar ligand), in 30mL hot methanol solution 3mmol), it is muddy that reaction solution becomes immediately, is khaki color, behind reaction 3h under 50 ℃, cooling, suction filtration, precipitation with the hot methanol solution washing repeatedly after, slowly dry in 50 ℃ the baking oven, put in the vitriol oil moisture eliminator and reach constant weight.
Infrared (cm -1) (KBr): 1655 (C=N), 1591 (v AsCOO -), 1437 (v sCOO -), 1384 (NO - 3), 1508 (NO - 3), 822 (NO - 3), 1316 (NO - 3)
Raman (cm -1): 1639.40 (C=N), 1586.82 (v AsCOO -), 1442.92 (v sCOO -), 1485.49 (NO - 3), 817.80 (NO - 3), 1275.59 (NO - 3)
Pr 3+Ion content and ultimate analysis (Pr 2C 35H 38N 12O 8) result is (bracket in for calculated value %): Pr 3+23.56 (23.87), C:35.77 (35.60), H:2.976 (3.221), N:14.00 (14.24).Molecular composition is Pr 2L 3(NO 3) 32CH 3OH.
Mass spectrum:
In the aqueous solution, 1223.27[Pr 2L ' 3NO 3+ matrix+K] +934.13[Pr 2L ' 3NO 3] +972.02[Pr 2L ' 3+ K] +In the mixed solvent of water and methyl alcohol (1: 1), 1344.96 (theoretical value 1344.85) [Pr 2L ' 3L (NO 3) 2(CH 3OH)+K] +, (L '=C 11H 11N 3O 2).
Embodiment 4 rare earth Eu title complex [Eu 2L 3(NO 3) 32CH 3OH] preparation
With glycine (2.252g; 0.03mol) and KOH (1.68g; 0.03mol) be dissolved in the 40mL methyl alcohol; 50 ℃ were refluxed 15 minutes; stir the 2-ethanoyl benzo imidazoles (4.805g that in this solution, drips 40mL down; 0.03mol) methanol solution, reflux that solution colour is dark brown yellow by xanthochromia after 5 hours, drip Eu (NO then 3) 36H 2O (8.92g, 0.02mol) the 40mL methanol solution is in this reaction solution, and it is muddy that reaction solution becomes immediately, be khaki color, behind reaction 3h under 50 ℃, cooling, suction filtration, precipitation with the hot methanol solution washing repeatedly after, slowly dry in 50 ℃ the baking oven, put in the vitriol oil moisture eliminator and reach constant weight.
Infrared (cm -1) (KBr): 1651 (C=N), 1595 (v AsCOO -), 1444 (v sCOO -), 1384 (NO - 3), 1489 (NO - 3), 823 (NO - 3), 1312 (NO - 3)
Raman (cm -1): 1648.50 (C=N), 1580.24 (v AsCOO -), 1435.12 (v sCOO -), 1481.42 (NO - 3), 820.99 (NO - 3), 1270.42 (NO - 3)
Eu 3+Ion content and ultimate analysis (Eu 2C 35H 38N 12O 8) result is (bracket in for calculated value %): Eu 3+24.96 (25.29), C:34.68 (34.94), H:3.285 (3.161), N:14.52 (13.98).
Mass spectrum (in the aqueous solution): 1057.09 (theoretical value 1056.68) [Eu 2L ' 3NO 3+ K] +,
(L’＝C 11H 11N 3O 2)。
Embodiment 5 rare earth Tb title complex [Tb 2L 3(NO 3) 32CH 3OH] preparation
With glycine (2.252g; 0.03mol) and KOH (1.68g; 0.03mol) be dissolved in the 40mL methyl alcohol; 50 ℃ were refluxed 15 minutes; stir and in this solution, drip 2-ethanoyl benzo imidazoles (4.805g down; 0.03mol) the 30mL methanol solution, reflux that solution colour is dark brown yellow by xanthochromia after 4 hours, drip Tb (NO then 3) 36H 2O (9.06g, 0.02mol) in the reaction solution, it is muddy that reaction solution becomes immediately therewith for methanol solution, be khaki color, behind reaction 3h under 50 ℃, cooling, suction filtration, precipitation with the hot methanol solution washing repeatedly after, slowly dry in 50 ℃ the baking oven, put in the vitriol oil moisture eliminator and reach constant weight.
Infrared (cm -1) (KBr): 1652 (C=N), 1610 (v AsCOO -), 1448 (v sCOO -), 1384 (NO - 3), 1490 (NO - 3), 835 (NO - 3), 1311 (NO - 3)
Raman (cm -1): 1651.05 (C=N), 1581.80 (v AsCOO -), 1435.12 (v sCOO -), 1482.74 (NO - 3), 819.21 (NO - 3), 1265.18 (NO - 3)
Tb 3+Ion content and ultimate analysis (Tb 2C 35H 38N 12O 8) result is (bracket in for calculated value %): Tb 3+25.93 (26.14), C:35.54 (34.55), H:2.822 (3.126), N:14.20 (13.82).
Embodiment 6 rare earth La title complex [La 2L 3(NO 3) 32CH 3OH] (L=C 11H 10N 3O 2) preparation
Rare earth nitrate La (the NO that under heated and stirred, incites somebody to action 3) 36H 2O (0.866g, 2mmol) the 25mL methanol solution slowly is added drop-wise to and has dissolved metering than being 2: 3 (rare earth ions: Schiff alkali (KL) part (the 0.79g Schiff aar ligand), in 30mL hot methanol solution 3mmol), it is muddy that reaction solution becomes immediately, is khaki color, behind reaction 3h under 50 ℃, cooling, suction filtration, precipitation with the hot methanol solution washing repeatedly after, slowly dry in 50 ℃ the baking oven, put in the vitriol oil moisture eliminator and reach constant weight.
Infrared (cm -1) (KBr): 1652 (C=N), 1584 (v AsCOO -), 1432 (v sCOO -), 1384 (NO - 3), 1499 (NO - 3), 817 (NO - 3), 1311 (NO - 3)
Raman (cm -1): 1645.2 (C=N), 1585.16 (v AsCOO -), 1439.62 (v sCOO -), 1487.18 (NO - 3), 816.82 (NO - 3), 1281.18 (NO - 3)
La 3+Ion content and ultimate analysis (La 2C 35H 38N 12O 8) result is (bracket in for calculated value %): La 3+23.39 (23.62), 36.01 (35.72), 3.361 (3.232), 13.88 (14.29).Molecular composition is La 2L 3(NO 3) 32CH 3OH.
Embodiment 7 Rare Earth Y title complex [Y 2L 3(NO 3) 32CH 3OH] (L=C 11H 10N 3O 2) preparation
Rare earth nitrate Y (the NO that under heated and stirred, incites somebody to action 3) 36H 2O (0.766g, 2mmol) the 25mL methanol solution slowly is added drop-wise to and has dissolved metering than being 2: 3 (rare earth ions: Schiff alkali (KL) part (the 0.79g Schiff aar ligand), in 30mL hot methanol solution 3mmol), it is muddy that reaction solution becomes immediately, is khaki color, behind reaction 3h under 50 ℃, cooling, suction filtration, precipitation with the hot methanol solution washing repeatedly after, slowly dry in 50 ℃ the baking oven, put in the vitriol oil moisture eliminator and reach constant weight.
Infrared (cm -1) (KBr): 1655 (C=N), 1629 (v AsCOO -), 1448 (v sCOO -), 1384 (NO - 3), 1506 (NO - 3), 838 (NO - 3), 1309 (NO - 3)
Y 3+Ion content and ultimate analysis (Y 2C 35H 38N 12O 8) result is (bracket in for calculated value %): Y 3+16.25 (16.53), 39.14 (39.09), 3.265 (3.468), 16.02 (15.63).Molecular composition is Y 2L 3(NO 3) 32CH 3OH.
Embodiment 8: rare earth Eu title complex [Eu 2L 3(NO 3) 32CH 3OH] property representation
Fig. 2 has tested the Eu title complex aqueous solution at the ultra-violet absorption spectrum that does not add about alkali and pH=13, and under alkaline condition, tangible red shift has all taken place the maximum absorption wavelength of the transition of electron of title complex, and red shift reaches about 2nm.
Fig. 3 is the three-dimensional fluorescence excitation-emission spectrogram of Eu (III) the title complex aqueous solution.Fluorescence also has tangible center Eu except the part of emission acceptor center ion perturbation is luminous as seen from the figure 3+The ion narrowband emission, promptly at 290.0～340.0nm (the best excites and is 310.0nm) when exciting, launching centre Eu 3+The arrowband fluorescence of ion characteristic is respectively 590.0nm and 615.0nm, belongs to Eu 3+Ionic 5D 0→ 7F 1With 5D 0→ 7F 2Transition.The solid three-dimensional fluorescence that we have also made Eu (III) title complex simultaneously excites and launches, and can see from collection of illustrative plates when solid phase, and fluorescent emission causes the interaction between the molecule to strengthen because state of aggregation is different, makes the transition energy level and the Eu of its part 3+Ionic f-f transition group-overlap, (fluorescent band is 390.0～525.0nm), makes the fluorescent band of Eu title complex broaden, and intensity has obtained strengthening greatly and become broadband emission.
Rare earth compounding not only has very strong normal fluorescence output, thereby also has the performance of good two-photon and multiphoton absorption generation up-conversion fluorescence, and promptly the excitation with the long wavelength can obtain the fluorescence shorter than its wavelength.Schiff aar ligand and all title complex all can send the fluorescence (seeing Fig. 3,4) of the short 455.0nm of wavelength ratio exciting light under the exciting of the exciting light that is in 580.0nm～800.0nm.
Compare with normal fluorescence excitation mode, two-photon and Excited Fluorescence Combined mainly contain two outstanding advantages: (1). and available infrared or near-infrared laser is done light source, improves the penetration power of material, and the deep layer that is implemented in material is observed; (2). two-photon and multiphoton excitation(MPE) process tightly are confined near the focus the very zonule, and the fluorescence of Fa Shenging all is limited in this little zone like this, and so little useful effect volume makes it have superior spatial resolution.Therefore have broad application prospects at aspects such as two-photon fluorescence excitation microscope, frequency upconversion laser, light amplitude limit and light fixed ampllitude, the medical treatment of light power.
Fig. 5 is that (concentration was 1.0 * 10 during the fluorometric investigation of Eu title complex under different alkaline conditions was composed -5Mol), also as can be seen, along with the increase of solution alkalescence, title complex weakens at the hyperfluorescence emission band about 290.0nm: and the hyperfluorescence emission band about 440.0nm significantly strengthens.Red shift has also taken place in corresponding emission wavelength.The Eu of this explanation title complex in alkaline medium 3+Variation has taken place in the ionic coordination environment, thereby causes the conjugated degree of part to strengthen, and the quantum yield of fluorescence strengthens.The fluorometric investigation spectrum of this series title complex under different alkaline conditions be similar to the Eu title complex all.
Fig. 6 and Fig. 7 are about Eu title complex photoluminescence Study on Stability.
In order to study the stability of title complex photoluminescent property, (concentration is 1.0 * 10 to choose europium complex -5Mol/L) as research object, excitation wavelength is 330.0nm, detecting its fluorescent emission wavelength is 458.0nm, it has been carried out the time scan of fluorescence, adopt xenon lamp to excite down for a long time in continuous 4 hours, detect its luminous intensity, find that the photoluminescence stability of this material is very good, the fluorescence relative intensity is stabilized in about 1330.
Fig. 8 is the excimer laser fluorescence excitation spectrum of Eu title complex.At constant voltage 19kV, monopulse 21mJ, 5Hz, operation material are KrF excimer laser λ EXTest this Eu title complex LASER Excited Fluorescence spectrum under the=248nm condition, produced 617.5nm and 592.5nmEu 3+The feature emission peak that ion is stronger.

Claims (2)

1. the 2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth complex that has following chemical constitution:
M 2L 3(NO 3) 3·2CH 3OH
Wherein, M=La 3+, Ce 3+, Pr 3+, Nd 3+, Sm 3+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, Er 3+Or Y 3+
L is the 2-acetyl benzimidazolyl-glycin schiff base.
2. the preparation method of the described 2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth complex of claim 1; it is characterized in that: with mol ratio be 2: 3 rare earth nitrate and 2-acetyl benzimidazolyl-glycin schiff base in methanol solvate in 45-70 ℃ of reaction 3-10 hour down; filter product, described rare earth nitrate is La 3+, Ce 3+, Pr 3+, Nd 3+, Sm 3+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, Er 3+Or Y 3+Nitrate.
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