CN104151368A - Rare earth europium complex and synthetic method thereof - Google Patents
Rare earth europium complex and synthetic method thereof Download PDFInfo
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- CN104151368A CN104151368A CN201410384528.3A CN201410384528A CN104151368A CN 104151368 A CN104151368 A CN 104151368A CN 201410384528 A CN201410384528 A CN 201410384528A CN 104151368 A CN104151368 A CN 104151368A
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Abstract
The embodiment of the invention discloses a rare earth europium complex and a synthetic method thereof. The method comprises the following steps: dispersing ligands L in ethyl alcohol to form a suspension liquid of the ligands L; adding NaOH into the suspension liquid of the ligands L, and adding water to the suspension liquid of the ligands L with NaOH until the turbid suspension liquid becomes transparent to generate a solution of L, wherein the mole ratio of NaOH to the compound L is 7-9; dissolving Eu(NO3)3.6H2O into ethyl alcohol to form ethyl alcohol solution of the Eu(NO3)3.6H2O, and adding the ethyl alcohol solution of the Eu(NO3)3.6H2O into the solution of the ligands L to generate a mixed solution of the rare earth europium complex, wherein the ratio of the mole number of Eu(NO3)3.6H2O to the volume of ethyl alcohol is 0.010-0.17 mol/L; performing evaporative crystallization on the mixed solution of the rare earth europium complex, then filtering and drying to obtain single crystals of the rare earth europium complex. The synthetic method of the rare earth europium complex provided by the invention is simple and easy, the reaction condition is mild, and the synthetic rare earth europium complex is high in purity.
Description
Technical field
The present invention relates to compou nd synthesis field, particularly a kind of Rare Earth Europium Complex and synthetic method thereof.
Background technology
The research of rare-earth europium ionic complex enjoys people to pay close attention to always.The electronic structure of europium element uniqueness has determined optical, electrical, the magnetic properties of its uniqueness, adds and the interaction of part, further modifies, improved these characteristics, and therefore rare-earth europium compound can be widely used in Rare Earth Separation, luminescent material, medicine and other fields.
In numerous parts of rare-earth europium ionic complex, crown ether compound is a very important class.
Nitrogen props up lasso trick crown ether, also claims arm-type crown ether, is that after introducing side-chain radical by Azacrown ether containing, institute forms.
Hydrogen on the nitrogen-atoms of Azacrown ether containing is more active, is other substituent vegetative point, and a lot of groups can be introduced on Azacrown ether containing thus, form arm-type crown ether.Side-chain radical in arm-type crown ether contains donor atom conventionally, when metal ion is in the time that ring atom is combined, also can with the Atomic coordinate of side arm, strengthened coordination ability.And arm-type crown ether has certain flexibility, the three-dimensional space of adjustable induction in coordination process, the selectivity of raising to metal ion; Therefore, be a kind of good part of tempering toughness with gentleness.
But, in the prior art, for utilizing arm-type carboxylic acid-substituted four azepine 18-hats-6 to have not been reported with rare-earth europium ion synthetic compound.
Summary of the invention
For addressing the above problem, the embodiment of the invention discloses a kind of Rare Earth Europium Complex and synthetic method thereof.Technical scheme is as follows:
A kind of Rare Earth Europium Complex, has following chemical formula composition:
[Na
3Eu(L)Cl·6H
2O]·NO
3；
Wherein, described L is 4,7,13,16 – tetra-carboxymethyl – 1,10 – bis-oxygen – 4,7,13,16 – tetraazacyclododecane octadecanes.
Described Rare Earth Europium Complex is carried out after crystalline structure test, and its test result is as follows:
Described Rare Earth Europium Complex is triclinic(crystalline)system, P-1 spacer, unit cell parameters
α=86.565 (2) °, β=78.722 (3) °, γ=85.563 (3) °; V=1668.3 (5) A
3; Z=2; D
c=1.821Mg/m
3; R
1=0.0350, wR
2=0.0725.
Use infrared spectrometer to test the infrared spectra that obtains described Rare Earth Europium Complex to described Rare Earth Europium Complex; Wherein, the wave number of the charateristic avsorption band in infrared spectra is respectively: 3425 (cm
-1), 1598 (cm
-1), 1392 (cm
-1), 1107 (cm
-1) and 1077 (cm
-1).
The present invention also provides a kind of synthetic method of above-mentioned Rare Earth Europium Complex, comprises the following steps:
Ligand L is scattered in ethanol, forms the suspension liquid of ligand L;
In the suspension liquid of ligand L, add NaOH, make ligand L deprotonation, and in the suspension liquid of ligand L of NaOH, add water until this suspension liquid is become transparently from muddiness to adding, generate the solution of ligand L, the mol ratio of described NaOH and ligand L is 7-9;
By Eu (NO
3)
36H
2o is dissolved in ethanol, forms Eu (NO
3)
36H
2the ethanolic soln of O, and by described Eu (NO
3)
36H
2the ethanolic soln of O joins in the solution of described ligand L, generates the mixing solutions of Rare Earth Europium Complex, described Eu (NO
3)
36H
2the mole number of O and the volume ratio of ethanol are 0.10mol/L-0.17mol/L;
The mixing solutions of described Rare Earth Europium Complex is carried out to evaporative crystallization, then filter, be dried, obtain the single crystal of Rare Earth Europium Complex.
In a kind of preferred implementation of the present invention, described ligand L and Eu (NO
3)
36H
2the mol ratio of O is 0.8-1.2.
In a kind of preferred implementation of the present invention, to adding the mode adding water in the suspension liquid of ligand L of NaOH to be: dropwise drip; By described Eu (NO
3)
36H
2the mode that the ethanolic soln of O joins in the solution of described ligand L is dropwise to drip.
In a kind of preferred implementation of the present invention, in the suspension liquid of described ligand L, the mole number of ligand L and the volume ratio of ethanol are: 0.010mol/L-0.013mol/L.
In a kind of preferred implementation of the present invention, the synthetic method of described ligand L is:
By 1,10-dioxy-4,7,13,16-, tetra-nitrogen-18-hat-6 is dissolved in CH
2cl
2after, adding Anhydrous potassium carbonate, reflux 0.5-2h, reheats backflow 18-24 hour after adding ethyl bromoacetate, filters, evaporation, obtains oily matter, wherein, and described ethyl bromoacetate and described 1,10-dioxy-4,7,13,16-, tetra-nitrogen-18-hat-6 and mol ratio be 5-7;
By described oily matter and combined, obtain mixed solution, this mixed solution reflux was filtered after 18-24 hour, obtain filtrate, and described filtrate is carried out to evaporative crystallization, the crystal that described evaporative crystallization obtains is ligand L.
In a kind of preferred implementation of the present invention, described CH
2cl
2volume and described 1,10-dioxy-4, the ratio of 7,13,16-, tetra-nitrogen-18-hat-6 mole numbers is 5L/mol-10L/mol; Described Anhydrous potassium carbonate and described 1,10-dioxy-4, the mol ratio of 7,13,16-, tetra-nitrogen-18-hat-6 is 4-8.
In a kind of preferred implementation of the present invention, in described aqueous hydrochloric acid, the volume ratio of hydrochloric acid and water is 1.5-3; The volume of described aqueous hydrochloric acid and the mass ratio of described oily matter are 15-20.
The present invention passes through Eu (NO
3)
36H
2o and 4,7,13,16 – tetra-carboxymethyl – 1,10 – bis-oxygen – 4,7,13,16 – tetraazacyclododecane octadecanes react, and generate a kind of Rare Earth Europium Complex, and this title complex have single crystal structure.The character of further research crown ether-europium complex is had to important guiding effect.
The synthetic method of Rare Earth Europium Complex provided by the invention is simple and easy, reaction conditions gentleness, and synthetic Rare Earth Europium Complex purity is high.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the molecular structure of the synthetic Rare Earth Europium Complex of the embodiment of the present invention 1;
Fig. 2 is the accumulation graph of the synthetic Rare Earth Europium Complex of the embodiment of the present invention 1;
Fig. 3 is the infrared spectrogram of the synthetic Rare Earth Europium Complex of the embodiment of the present invention 1;
Fig. 4 is Eu (NO
3)
3and the fluorescence spectrum figure of the synthetic Rare Earth Europium Complex of the embodiment of the present invention 1.
Embodiment
In numerous arm-type crown ethers, because carboxyl coordination is strong, make carboxylic Azacrown ether containing on N-substituting group become a class to have the Azacrown ether containing of good ligancy.In addition, the ring texture unit of the relative flexibility of side chain RCOO-and relative rigidity, improves coordination ability thereby this large ring skeleton and replacement side chain are tempered toughness with gentleness.
Utilize this character of arm-type crown ether, contriver designs Eu (NO
3)
36H
2o and 4,7,13,16 – tetra-carboxymethyl – 1,10 – bis-oxygen – 4,7,13,16 – tetraazacyclododecane octadecanes react, and generate a kind of novel rare-earth europium complex, and this Rare Earth Europium Complex are expected to be applied to Rare Earth Separation, luminescent material, medicine and other fields.
A kind of Rare Earth Europium Complex provided by the invention, has following chemical formula composition:
[Na
3Eu(L)Cl·6H
2O]·NO
3；
Wherein, described L is 4,7,13,16 – tetra-carboxymethyl – 1,10 – bis-oxygen – 4,7,13,16 – tetraazacyclododecane octadecanes.
This Rare Earth Europium Complex is carried out after crystalline structure test, and its test result is as follows:
Described Rare Earth Europium Complex is triclinic(crystalline)system, P-1 spacer, unit cell parameters
α=86.565 (2) °, β=78.722 (3) °, γ=85.563 (3) °; V=1668.3 (5) A
3; Z=2; D
c=1.821Mg/m
3; R
1=0.0350, wR
2=0.0725.
Use infrared spectrometer to test the infrared spectra that obtains described Rare Earth Europium Complex to this Rare Earth Europium Complex; Wherein, the wave number of the charateristic avsorption band in infrared spectra is respectively: 3425 (cm
-1), 1598 (cm
-1), 1392 (cm
-1), 1107 (cm
-1) and 1077 (cm
-1).
The preparation method of above-mentioned Rare Earth Europium Complex, can comprise:
1) synthetic 4,7,13,16 – tetra-carboxymethyl – 1,10 – bis-oxygen – 4,7,13,16 – tetraazacyclododecane octadecanes, are called for short L, its synthetic route as shown in the formula:
Its synthetic method is: by 1,10-dioxy-4,7,13,16-, tetra-nitrogen-18-hat-6 is dissolved in CH
2cl
2after, adding Anhydrous potassium carbonate, reflux 0.5-2h, reheats backflow 18-24 hour after adding ethyl bromoacetate, filters, and evaporation, obtains oily matter; Wherein, ethyl bromoacetate and 1,10-dioxy-4,7,13,16-, tetra-nitrogen-18-hat-6 and mol ratio be preferably 5-7; CH
2cl
2volume and 1,10-dioxy-4, the ratio of 7,13,16-, tetra-nitrogen-18-hat-6 mole numbers is preferably 5L/mol-10L/mol; Anhydrous potassium carbonate and 1,10-dioxy-4, the mol ratio of 7,13,16-, tetra-nitrogen-18-hat-6 is preferably 4-8.
By above-mentioned oily matter and combined, obtain mixed solution, this mixed solution reflux was filtered after 18-24 hour, obtain filtrate, and described filtrate is carried out to evaporative crystallization, this evaporative crystallization is preferably filtrate at air natural evaporating solvent with crystallize out; If the crystal of separating out jaundice (representing impure), carries out recrystallization by the dissolution of crystals of separating out in hydrochloric acid water mixed solution so again; After separating out the clear crystal of regular shape, filter, dry, obtain ligand L, wherein, in aqueous hydrochloric acid, the volume ratio of hydrochloric acid and water is preferably 1.5-3; The volume of aqueous hydrochloric acid and the mass ratio of described oily matter are 15-20.
2) synthesizing rare-earth europium complex
Ligand L is scattered in ethanol, forms the suspension liquid of ligand L, in the suspension liquid of L, the mole number of L and the volume ratio of ethanol are preferably 0.010mol/L-0.013mol/L;
In the suspension liquid of ligand L, add NaOH, and in the suspension liquid of L of NaOH, add water until this suspension liquid is become transparently from muddiness to adding, generate the solution of L, the mol ratio of NaOH and ligand L is preferably 7-9; Drip to adding the mode adding water in the suspension liquid of ligand L of NaOH to be preferably dropwise;
By Eu (NO
3)
36H
2o is dissolved in ethanol, forms Eu (NO
3)
36H
2the ethanolic soln of O, described Eu (NO
3)
36H
2the mole number of O and the volume ratio of ethanol are preferably 0.10mol/L-0.17mol/L; By Eu (NO
3)
36H
2the ethanolic soln of O joins in the solution of ligand L, generates the mixing solutions of Rare Earth Europium Complex, described ligand L and Eu (NO
3)
36H
2the mol ratio of O is 0.8-1.2; By Eu (NO
3)
36H
2the ethanolic soln of O joins mode in the solution of ligand L and is preferably dropwise and drips.
The mixing solutions of described Rare Earth Europium Complex is carried out to evaporative crystallization, then filter, be dried, obtain the single crystal of Rare Earth Europium Complex.This step is preferably the mixing solutions of described Rare Earth Europium Complex is at room temperature allowed to solvent evaporates, then filters, dry in air at room temperature, obtains the single crystal of Rare Earth Europium Complex.
In above-mentioned building-up process, filtration can adopt the filter method that chemical field is conventional, for example, adopt the mode of suction filtration to filter, and this is not restricted for the embodiment embodiment of the present invention of filtration.Evaporation can adopt the method for evaporating that chemical field is conventional, the mode of for example rotary evaporation, and the temperature of rotary evaporation, and vacuum tightness and rotating speed, those skilled in the art can select according to practical situation.Recrystallization can adopt the recrystallization method that chemical field is conventional, and the present invention here adopts by by concentrated reaction solution mode of carrying out crystallization, solution can be concentrated into 1/3 original relief crystal and separate out, and obtains corresponding crystal.
The specification of all raw materials of the present invention, if it is not had to specified otherwise, is the specification that the field of chemical synthesis is conventional, and for example, water is deionized water preferably, and ethanol is dehydrated alcohol preferably, etc.Those skilled in the art can technical scheme according to the present invention select the specification of corresponding raw material; Here said specification refers to purity, the concentration etc. of raw material.
Further it should be noted that, all raw materials that the embodiment of the present invention adopts, do not have special restriction to its source, buy or make by oneself and all can on market.
The experimental installation that the embodiment of the present invention adopts in the process of synthetic L and Rare Earth Europium Complex, is the general equipment in this area, there is no special requirement, all can on market, buy.Contriver believes, those skilled in the art completely can be by the description of technical solution of the present invention is selected to suitable experimental installation, and the present invention does not carry out concrete restriction and explanation to experimental installation at this.
In order to further illustrate the present invention, below in conjunction with specific embodiment, this bright technical scheme is described, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
In following examples, reagent used is commercially available.
First synthetic 1,10-dioxy-4,7,13,16-, tetra-nitrogen-18-hat-6
(1) N, synthetic [reference H.S.Grame, J.G.Rodney, Aust.J.Chem.1984,37,959.] of N '-bis-p-toluenesulfonyl quadrol (A)
Its synthetic route is as follows:
Take 16.0gNaOH and be dissolved in 200mL water, be placed in three mouthfuls of round-bottomed flasks, add 13.5mL quadrol, water-bath at 40～50 DEG C adds 80.0g Tosyl chloride in batches under stirring, continues to stir 4h.Add stopped reaction after 50mL dehydrated alcohol backflow 5min, cooling under room temperature, suction filtration, precipitation is washed three times with distillation, ethanol respectively, recrystallization in ethanol for thick product after drying, suction filtration obtains white needle-like crystals A55g, productive rate 74%, m.p.163～165 DEG C (162～164 DEG C of literature values).
(2) synthetic 4,7,13,16-tetra-p-toluenesulfonyl-1,10-dioxy-4,7,13,16-, tetra-nitrogen-18-is preced with-6 (B).[reference J.F.Biernat, E.Luboch, Tetrahedron, 1984,40,1927-1929.]
Its synthetic route is as follows:
Claim 33.3gA, 18.0g K
2cO
3, in 250mL round-bottomed flask, 40.0mL N, N ， – dimethyl formamide, adds 11.9mL2 under magnetic agitation, 2' – dichloro-diethyl ether, stirring reaction 10h under 170 DEG C of oil bath heating conditions.The cooling refrigerator of putting into after stopped reaction, cooling 20h at 5 DEG C.Suction filtration, precipitation is successively with the each washing of acetone, water and acetone three times.Dry and obtain white crystal B5.5g, productive rate 15%, m.p.245 DEG C (conforming to literature value) with DMF recrystallization afterwards.
(3) prepare crown ether parent 1,10-dioxy-4,7,13,16-, tetra-nitrogen-18-is preced with-6 (4N-18-C-6).[reference J.F.Biernat, E.Luboch, Tetrahedron, 1984,40,1927-1929.]
Its synthetic route is as follows:
The about 20g of product B that takes the step (2) of 4 parts, is placed in 100mL round-bottomed flask, adds the 50.0mL vitriol oil.Three days three nights of stirring reaction under 100 DEG C of oil bath heating conditions.After question response liquid cooling but, add NaOH solution to be neutralized to pH=12 left and right, cold filtration, a small amount of trichloromethane washing solid, with the repeatedly fully extraction of a large amount of trichloromethanes, merges organic phase after washings and filtrate merge, and adds appropriate anhydrous Na
2sO
4dry, placement is spent the night.Filter, remove siccative, revolve and steam filtrate.Use normal heptane recrystallization, suction filtration obtains 2.6g4N-18-C-6 product.Productive rate 45%, m.p.59～61 DEG C (literature value is 58～60 DEG C).Crystal determination of elemental analysis value (%): C54.46, H10.76, N21.12; Theoretical value (%): C54.46, H10.62, N20.922..
It should be noted that, those skilled in the art also can adopt other method to synthesize 1,10-dioxy-4,7,13,16-, tetra-nitrogen-18-hat-6, and its concrete synthetic method, the present invention does not do concrete restriction at this.
Embodiment 1
Take 1 of 0.52g (2mmol), 10-dioxy-4,7,13,16-, tetra-nitrogen-18-is preced with-6 in 50mL round-bottomed flask,
Add 20mL CH
2cl
2as solvent, add the Anhydrous potassium carbonate of 1.2g (8.8mmol), backflow 2h, add the ethyl bromoacetate of 1.09mL (10mmol), backflow 24h, after filtration again, filtrate is rotated to evaporation, obtains the oily matter of 1.0g, productive rate approximately 82%.
Press HCl:H
2the volume ratio preparation aqueous hydrochloric acid of O=1.5:1, the oily matter of gained is mixed with aqueous hydrochloric acid (20mL), obtain mixed solution, by filtering after this mixed-liquor return 24h, obtain filtrate, obtained filtrate is evaporated to about 12ml, the hydrochloride crystal of separating out ligand L, filters and collects crystal, at room temperature dry, obtain 0.90gL, productive rate approximately 85%.M.p.>300℃。
Take 0.128g (0.2mmol) ligand L and be placed in 50mL beaker, add 20ml dehydrated alcohol, stir the suspension liquid that forms ligand L.Take the NaOH of 0.056g (1.4mmol), porphyrize adds in above-mentioned suspension liquid, stirs, and solution is still muddy.Dropwise drip deionized water and make its clarification (approximately 20), generate the solution of ligand L.Take the Eu (NO of 0.056g (0.25mmol)
3)
36H
2o, in another clean small beaker, adds 1.6ml anhydrous alcohol solution, forms Eu (NO
3)
36H
2the ethanolic soln of O, by Eu (NO
3)
36H
2the ethanolic soln of O is dropwise added drop-wise in the solution of above-mentioned ligand L, there is immediately white flocks, dissolve very soon immediately, leave standstill, allow its solvent flashing, when liquor capacity remains general 5ml, separate out pine needle shape clear crystal, filter and collect crystal, at room temperature dry, obtain about 0.16g Rare Earth Europium Complex.
Embodiment 2
Claim 1 of 0.78g (3mmol), 10-dioxy-4,7,13,16-, tetra-nitrogen-18-hat-6, in 50mL round-bottomed flask, adds 21mL CH
2cl
2as solvent, add the Anhydrous potassium carbonate of 2.5g (18mmol), backflow 1h, then add the ethyl bromoacetate of 1.96mL (18mmol), backflow 20h, after filtration, is rotated evaporation by filtrate, obtains the oily matter of 1.5g.
Press HCl:H
2the volume ratio preparation aqueous hydrochloric acid of O=2:1, the oily matter of gained is mixed with aqueous hydrochloric acid (25mL), obtain mixed solution, by filtering after this mixed-liquor return 20h, obtain filtrate, obtained filtrate is evaporated to about 10ml, the hydrochloride crystal of separating out ligand L, filters and collects crystal, at room temperature dry, obtain 1.35gL, its M.p.>300 DEG C.
Take 0.192g (0.3mmol) ligand L and be placed in 50mL beaker, add 28mL dehydrated alcohol, stir the suspension liquid that forms ligand L.Take the NaOH of 0.096g (2.4mmol), porphyrize adds in above-mentioned suspension liquid, stirs, and solution is still muddy.Dropwise drip deionized water and make its clarification (approximately 30), generate the solution of ligand L.Take the Eu (NO of 0.0675g (0.3mmol)
3)
36H
2o, in another clean small beaker, adds 2.0mL anhydrous alcohol solution, forms Eu (NO
3)
36H
2the ethanolic soln of O, by Eu (NO
3)
36H
2the ethanolic soln of O is dropwise added drop-wise in the solution of above-mentioned ligand L, there is immediately white flocks, dissolve very soon immediately, leave standstill, allow its solvent flashing, when liquor capacity remains about 8ml, separate out pine needle shape clear crystal, filter and collect crystal, at room temperature dry, obtain 0.25g Rare Earth Europium Complex.
Embodiment 3
Claim 1 of 1.04g (4mmol), 10-dioxy-4,7,13,16-, tetra-nitrogen-18-is preced with-6 in 50mL round-bottomed flask,
Add 20mL CH
2cl
2as solvent, add the Anhydrous potassium carbonate of 4.1g (30mmol), backflow 0.5h, then add the ethyl bromoacetate of 3.04mL (28mmol), backflow 18h, after filtration, is rotated evaporation by filtrate, obtains the oily matter of 2.0g.
Press HCl:H
2the volume ratio preparation aqueous hydrochloric acid of O=3:1, the oily matter of gained is mixed with aqueous hydrochloric acid (30mL), obtain mixed solution, by filtering after this mixed-liquor return 18h, obtain filtrate, obtained filtrate is evaporated to about 15ml, the hydrochloride crystal of separating out ligand L, filters and collects crystal, at room temperature dry, obtain 1.8g L, its M.p.>300 DEG C.
Take 0.256g (0.4mmol) ligand L and be placed in 50mL beaker, add 30mL dehydrated alcohol, stir the suspension liquid that forms L.Take the NaOH of 0.144g (3.6mmol), porphyrize adds in above-mentioned suspension liquid, stirs, and solution is still muddy.Dropwise drip deionized water and make its clarification (approximately 40), generate the solution of ligand L.Take the Eu (NO of 0.074g (0.33mmol)
3)
36H
2o, in another clean small beaker, adds 3.0mL anhydrous alcohol solution, forms Eu (NO
3)
36H
2the ethanolic soln of O, by Eu (NO
3)
36H
2the ethanolic soln of O is dropwise added drop-wise in the solution of above-mentioned ligand L, there is immediately white flocks, dissolve very soon immediately, leave standstill, allow its solvent flashing, when liquor capacity remains general 10ml, separate out pine needle shape clear crystal, filter and collect crystal, at room temperature dry, obtain 0.30g Rare Earth Europium Complex.
Characterize and analyze
1, ultimate analysis
Adopt the elemental analyser (model: Vario EL) of German Elementar company to carry out ultimate analysis to the compound L in embodiment 1 and Rare Earth Europium Complex, analytical results is:
Measured value for compound L: C, H, N is respectively: C37.41, H6.77, N8.53; Press C
20h
36n
4o
104HCl (M
r=638) calculated value that calculates C, H, N is respectively: C37.63; H6.32; N8.78.From results of elemental analyses, embodiment 1 has synthesized target product L.
Measured value for Rare Earth Europium Complex: C, H, N is respectively: C26.75, H4.59, N7.71%;
Press C
20h
44clEuN
5na
3o
19(M
r=915) calculated value is: C, 26.23; H, 4.81; N, 7.65%.From results of elemental analyses, embodiment 1 has synthesized Rare Earth Europium Complex.
2, crystal structure analysis
Adopt the Bruker Smart Apex II type single crystal diffractometer of German Brooker company to carry out crystalline structure test to the synthetic Rare Earth Europium Complex of embodiment 1, test result is:
This title complex is triclinic(crystalline)system, P-1 spacer, unit cell parameters
α=86.565 (2) °, β=78.722 (3) °, γ=85.563 (3) °; V=1668.3 (5) A
3; Z=2; D
c=1.821Mg/m
3; R
1=0.0350, wR
2=0.0725.
Adopt Diamond3.2 software to draw to measured crystal data file analysis, obtain the accumulation graph of the Rare Earth Europium Complex shown in molecular structure and Fig. 2 of Rare Earth Europium Complex as shown in Figure 1.
As can be known from Fig. 1, this Rare Earth Europium Complex is containing [a Na
3eu (L) Cl6H
2o]
+complex cation and a nitrate anion, consist of [Na
3eu (L) Cl6H
2o] NO
3, molecular formula is C
20h
44clEuN
5na
3o
19.
For meeting coordination demand, crown ether cycle is distorted, and upper four carboxyls of L are all sloughed proton and Eu coordination, add the coordination of upper 4 N of the large ring of crown ether and two O, forms ten coordination configurations, and Eu is tightly surrounded by crown ether cycle and side chain thereof.The ligating atom of Eu1 is four nitrogen of crown ether cycle (N1, N2, N3, N4), two oxygen (O1, O2) and four carboxylic acid oxygen (O4, O6, O8, O9).Eu1-O1, Eu1-O2 bond distance be respectively 2.642 (3),
and the bond distance of Eu1-O4, Eu1-O6, Eu1-O8, Eu1-O9 is respectively 2.382 (3), 2.350 (3), 2.395 (3),
visible Eu
3+with the coordination bond lengths ratio of crown ether epoxy and the length of carboxylic acid oxygen, this is the cause slightly strong due to carboxyl oxygen atom electron donation.Eu1-N1, Eu1-N2, Eu1-N3, Eu1-N4 bond distance be respectively 2.849 (3), 2.914 (3), 2.897 (3),
eu
3+for hard acid ion, O and N are hard base ligating atom, and according to hsab theory, hard-hard combination stability is strong; Because N is the alkali softer than O, with Eu
3+bonding force weaken, therefore Eu-N bond distance is obviously greater than Eu-O bond distance.
As can be known from Fig. 2, this title complex is made up of two-layer crown ether-Eu hydrophobic layer and one deck Na – O hydrophilic layer, the about 0.68nm of hydrophobic bed thickness, the about 0.54nm of hydrophilic bed thickness, the about 1.9nm of total thickness.Attract by Van der Waals force between layers, form supramolecular structure.
3, Infrared spectroscopy
Adopt the Fourier transform infrared spectrometer (model: Nicolet360) that Nicolet company of the U.S. produces to carry out examination of infrared spectrum (employing KBr pressed disc method to the synthetic Rare Earth Europium Complex of embodiment 1, under room temperature, scan, test specification is 4000～400cm
-1).Infrared spectrogram as shown in Figure 3.
In Fig. 3,1598cm
-1and 1392cm
-1corresponding carboxylic acid ion (the COO of absorption at place
-) unsymmetrically and symmetrical stretching vibration, this absorption is very strong; 3425cm
-1the absorption explanation of place-OH has water molecules to exist, 1077cm
-1for crown ether C-O-C absorption of vibrations, 1107cm
-1place is the absorption of vibrations of C-N, illustrates and in title complex, has crown ether molecule.
4, fluorescent spectroscopy
Adopt spectrophotofluorometer (model: RF-5301PC) that Japanese Shimadzu company produces Rare Earth Europium Complex and the Eu (NO to preparation in the embodiment of the present invention 1
3)
3carry out fluorometric investigation, fluorescence emission spectrum as shown in Figure 4; Wherein, in test, exciting slit is 1.5nm, and transmitting slit is 3.0nm.
Fig. 4 a is Eu (NO
3)
3emmission spectrum (PL) under 395nm excites.Be positioned at 579,592,617,650, the emission peak of 697nm belongs to respectively Eu
3+'s
5d
0-
7f
0,
5d
0-
7f
1,
5d
0-
7f
2,
5d
0-
7f
3,
5d
0-
7f
4transition, and Eu corresponding to title complex
3+transition is positioned at 579,590,614/618,650,695nm.The strongest emission peak that is positioned at 617nm is electric dipole transition
5d
0-
7f
2, be Eu
3+characteristic red light emission, difference
5d
0-
7f
jthe common detectable Eu of the intensity of transition reflection peak and the division at peak
3+one-tenth key environment.Eu (NO
3)
3with after L coordination, (b), emmission spectrum peak position is substantially constant for Fig. 4, illustrates and really has Eu in title complex
3+; Relative intensity changes, title complex
5d
0-
7f
2with
5d
0-
7f
1relative intensity ratio be 2.97, and Eu (NO
3)
3relative intensity ratio be 2.49, crown ether carboxyl and Eu in title complex are described
3+coordination reduced Eu
3+luminous intensity; Emission peak shape changes, title complex 614, there are two peaks in 618nm place, Eu in title complex is described
3+coordination environment changes, reduced symmetry.
Be understandable that, because the Rare Earth Europium Complex of synthesized in embodiment 2-3 and composition and the structure of the Rare Earth Europium Complex of embodiment 1 synthesized are consistent.Therefore, the present invention this to embodiment 2-3 in the sign of Rare Earth Europium Complex of synthesized be not described specifically, with reference to embodiment 1.
The ligand polymer Na known by above-mentioned analysis, the embodiment of the present invention is synthetic
3eu (L) Cl6H
2o] NO
3for monoclinic crystal structure, this title complex Eu
3+be ten coordination configurations, three Na
+be hexa-coordinate, between Na and Na, by the bridging of water Sauerstoffatom, formed spination one dimensional infinite chain-like structure, crown ether-Eu list of coordination units forms hydrophobic layer and Na-H
2o chain coordination (hydrophilic layer) is connected by crown ether carboxyl oxygen, and hydrophobic layer is distributed in hydrophilic Na-H
2the both sides of O chain coordination, construct the sandwiched type structure of hydrophobic layer-hydrophilic layer-hydrophobic layer.In title complex there is hydrogen bond in boundary, and extraneous (free nitrate radical) is connected with boundary in title complex by hydrogen bond.Between sandwich style layer, attract each other by Van der Waals force, form supramolecular structure.
The present invention passes through 4,7,13,16 – tetra-carboxymethyl – 1,10 – bis-oxygen – 4,7,13,16 – tetraazacyclododecane octadecanes and rare earth Eu
3+in conjunction with, utilize its special coordination feature to synthesize a kind of novel Rare Earth Europium Complex, this title complex is monoclinic crystal structure, this provides good foundation as Rare Earth Separation and extraction, luminescent properties etc. for function of exploring rare earth organic complex.And this Rare Earth Europium Complex is expected to be applied to Rare Earth Separation, luminescent material, medicine and other fields.
Above a kind of Rare Earth Europium Complex provided by the present invention and synthetic method thereof are described in detail.Applied specific embodiment herein principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand method of the present invention and clou thereof.It should be pointed out that for the person of ordinary skill of the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a Rare Earth Europium Complex, is characterized in that, has following chemical formula composition:
[Na
3Eu(L)Cl·6H
2O]·NO
3；
Wherein, described L is 4,7,13,16 – tetra-carboxymethyl – 1,10 – bis-oxygen – 4,7,13,16 – tetraazacyclododecane octadecanes.
2. Rare Earth Europium Complex as claimed in claim 1, is characterized in that, described Rare Earth Europium Complex is carried out after crystalline structure test, and its test result is as follows:
Described Rare Earth Europium Complex is triclinic(crystalline)system, P-1 spacer, unit cell parameters
α=86.565 (2) °, β=78.722 (3) °, γ=85.563 (3) °; V=1668.3 (5) A
3; Z=2; D
c=1.821Mg/m
3; R
1=0.0350, wR
2=0.0725.
3. Rare Earth Europium Complex as claimed in claim 1, is characterized in that, uses infrared spectrometer to test the infrared spectra that obtains described Rare Earth Europium Complex to described Rare Earth Europium Complex; Wherein, the wave number of the charateristic avsorption band in infrared spectra is respectively: 3425 (cm
-1), 1598 (cm
-1), 1392 (cm
-1), 1107 (cm
-1) and 1077 (cm
-1).
4. the synthetic method of Rare Earth Europium Complex as claimed in claim 1, is characterized in that, comprises the following steps:
Ligand L is scattered in ethanol, forms the suspension liquid of ligand L;
In the suspension liquid of ligand L, add NaOH, make ligand L deprotonation, and in the suspension liquid of ligand L of NaOH, add water until this suspension liquid is become transparently from muddiness to adding, generate the solution of ligand L, the mol ratio of described NaOH and ligand L is 7-9;
By Eu (NO
3)
36H
2o is dissolved in ethanol, forms Eu (NO
3)
36H
2the ethanolic soln of O, and by described Eu (NO
3)
36H
2the ethanolic soln of O joins in the solution of described ligand L, generates the mixing solutions of Rare Earth Europium Complex, described Eu (NO
3)
36H
2the mole number of O and the volume ratio of ethanol are 0.10mol/L-0.17mol/L;
The mixing solutions of described Rare Earth Europium Complex is carried out to evaporative crystallization, then filter, be dried, obtain the single crystal of Rare Earth Europium Complex.
5. the synthetic method of Rare Earth Europium Complex as claimed in claim 4, is characterized in that, described ligand L and Eu (NO
3)
36H
2the mol ratio of O is 0.8-1.2.
6. method as claimed in claim 4, is characterized in that, to adding the mode adding water in the suspension liquid of ligand L of NaOH to be: dropwise drip; By described Eu (NO
3)
36H
2the mode that the ethanolic soln of O joins in the solution of described ligand L is dropwise to drip.
7. the synthetic method of Rare Earth Europium Complex as claimed in claim 4, is characterized in that, in the suspension liquid of described ligand L, the mole number of ligand L and the volume ratio of ethanol are: 0.010mol/L-0.013mol/L.
8. method as claimed in claim 4, is characterized in that, the synthetic method of described ligand L is:
By 1,10-dioxy-4,7,13,16-, tetra-nitrogen-18-hat-6 is dissolved in CH
2cl
2after, adding Anhydrous potassium carbonate, reflux 0.5-2h, reheats backflow 18-24 hour after adding ethyl bromoacetate, filters, evaporation, obtains oily matter, wherein, and described ethyl bromoacetate and described 1,10-dioxy-4,7,13,16-, tetra-nitrogen-18-hat-6 and mol ratio be 5-7;
By described oily matter and combined, obtain mixed solution, this mixed solution reflux was filtered after 18-24 hour, obtain filtrate, and described filtrate is carried out to evaporative crystallization, the crystal that described evaporative crystallization obtains is ligand L.
9. method as claimed in claim 8, is characterized in that, described CH
2cl
2volume and described 1,10-dioxy-4, the ratio of 7,13,16-, tetra-nitrogen-18-hat-6 mole numbers is 5L/mol-10L/mol; Described Anhydrous potassium carbonate and described 1,10-dioxy-4, the mol ratio of 7,13,16-, tetra-nitrogen-18-hat-6 is 4-8.
10. method as claimed in claim 8, is characterized in that, in described aqueous hydrochloric acid, the volume ratio of hydrochloric acid and water is 1.5-3; The volume of described aqueous hydrochloric acid and the mass ratio of described oily matter are 15-20.
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| WO2021168567A1 (en) * | 2020-02-25 | 2021-09-02 | Triumf | Chelator compositions for radiometals and methods of using same |
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| US5645818A (en) * | 1989-03-24 | 1997-07-08 | Guerbet S.A. | Diagnostic compositions comprising a complex formed by a nitrogenous macrocyclic ligand with metal ions |
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| WO2021168567A1 (en) * | 2020-02-25 | 2021-09-02 | Triumf | Chelator compositions for radiometals and methods of using same |
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