CN101921285A - Method of solvothermal synthesis of D-tartaric acid rare earth complex - Google Patents

Method of solvothermal synthesis of D-tartaric acid rare earth complex Download PDF

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CN101921285A
CN101921285A CN2009100996632A CN200910099663A CN101921285A CN 101921285 A CN101921285 A CN 101921285A CN 2009100996632 A CN2009100996632 A CN 2009100996632A CN 200910099663 A CN200910099663 A CN 200910099663A CN 101921285 A CN101921285 A CN 101921285A
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rare earth
tartaric acid
earth complex
tartrate
solvothermal synthesis
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吕耀康
王晓娟
陈静
苏虹
冯云龙
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Zhejiang Normal University CJNU
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Zhejiang Normal University CJNU
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Abstract

The invention provides a method of solvothermal synthesis of D-tartaric acid rare earth complex, belonging to the field of synthesis of chiral compounds. The invention can control the size and the feature of the grain of the product by changing raw material proportioning, crystallization temperature and cooling rate, and has simple technical process and convenient operation; and the synthesized D-tartaric acid rare earth complex has favourable thermostability, keeps stable under the alkaling condition and can be used for a photoactivation material or chiral resolving agent.

Description

The method of solvothermal synthesis of D-tartaric acid rare earth complex
Technical field
The present invention relates to chiral material D-tartaric acid rare earth complex synthetic method.The synthetic field that belongs to chipal compounds.
Background technology
Organometallic complex has and enriches regulatable crystalline structure, and synthetic and research organometallic complex is an active field.Tartrate (tartaric acid) claims 2,3 dihydroxybutanedioic acid again, is a kind of simple, common Alpha-hydroxy diacid, is widely used in chemical industry and the foodstuffs industry; It has two symmetrical chiral carbon, has three kinds of optically active isomers, is respectively: Ltartaric acid (D-tartaric acid), levotartaric acid (L-tartaric acid), mesotartaric acid (meso-tartaric acid).Tartrate and derivative thereof are not only chirality synthesis material commonly used and chiral separation agent, and are added in the food as antioxidant.Some tartrates have important physical propertiess such as piezoelectricity, ferroelectricity and can be used for electronic industry.
Rare earth element has unique 4f electronic structure and big magnetic moment of atom, very strong physico-chemical properties such as spin coupling, makes rare earth compound show the light of many excellences, electricity, magnetic function, becomes the treasure-house of novel material.The atom of rare earth element has the 4f-5d electronic configuration that is subjected to extraneous shielding of underfilling, when their 4f electronics within the f-f configuration or between the f-d configuration during transition, nearly surplus in the of 20 ten thousand in its energy level transition passage, can produce diversified radiation absorption and emission, constitute luminescent material widely.And rare earth element has the characteristics of the orbital momentum of not eliminating that is produced by the f orbitals of internal layer, except Gd (III), Eu (II) has f7 electronic configuration and the non-degenerate ground state of track, and all other rare earth elements all have the ground state by spin orbit coupling and crystal field effects institute splitted orbital degeneracy.For the rare earth element that contains the f electronics and the transition metal of d electronics, the influence of crystal field effects than the influence of spin orbit coupling come little.The magnetic moment of rare earth element middle orbit is important more than the magnetic moment of the track in the transition metal.Therefore to depend mainly in the rare earth element anisotropy of f electronic spin and track coupling, especially magnetic bigger usually for the magnetic of rare earth element, so rare earth element is widely used for magneticsubstance.
The synthetic method of some tartaric acid rare earth complexes that at present bibliographical information arranged, but do not see bibliographical information as yet by solvent thermal synthetic tartaric acid rare earth complex.
Summary of the invention
The method that the objective of the invention is solvothermal synthesis of D-tartaric acid rare earth complex, the granular size and the pattern of the temperature by changing proportion of raw materials, crystallization and the rate-controlling product of cooling.This method technical process is terse, easy to operate, is fit to suitability for industrialized production.
Technical scheme provided by the invention is:
(1) rare earth oxide and D-tartrate are packed in the solvent thermal reaction still by certain mass ratio.
(2) in reactor, add an amount of solution.
(3) heating crystallization.
(4) cooling is cooled to room temperature.
(5) filter washing, drying.
In the method for solvothermal synthesis of D-tartaric acid rare earth complex of the present invention, in the described step (1), the tartaric mass ratio of described rare earth oxide and D-is 1: 1～1: 2, can control the pattern and the granular size of product by regulating raw material rare earth oxide and the tartaric mass ratio of D-in this scope.
In the method for solvothermal synthesis of D-tartaric acid rare earth complex of the present invention, in the described step (1), described rare earth oxide also can substitute with rare earth nitrate or lanthanon acetate, but obviously adopts rare earth oxide more economical and convenient.
In the method for solvothermal synthesis of D-tartaric acid rare earth complex of the present invention, in the described step (2), described solvent is ethanol, water, N, one or more mixing solutionss in dinethylformamide, the dimethyl sulfoxide (DMSO).Can control the pattern and the granular size of product by the component that changes solvent.
In the method for solvothermal synthesis of D-tartaric acid rare earth complex of the present invention, in the described step (3), described crystallization time was generally 1～3 day.
In the method for solvothermal synthesis of D-tartaric acid rare earth complex of the present invention, in the described step (3), described crystallization temperature is 135～185 ℃, can control the pattern and the granular size of product in this scope by the temperature of regulating crystallization.
In the method for solvothermal synthesis of D-tartaric acid rare earth complex of the present invention, in the described step (4), described cooling rate can be controlled the pattern and the granular size of product for per hour lowering the temperature 1 ℃～15 ℃ by the temperature of regulating crystallization in this scope.
Advantage of the present invention is:
1. D-tartaric acid rare earth complex method of the present invention, technical process is terse, and is easy to operate;
2. the selection of raw material derives from general chemical;
3. chiral material D-tartaric acid rare earth complex of the present invention has showed good thermostability, and in highly basic (7mol/L KOH) stable existence, can be used to photoactivation material or chiral separation agent.
Be examples more of the present invention below,, and should do not regard as any aspect is limited to some extent only as illustration.Obviously, for a person skilled in the art, under the prerequisite of spirit and scope that do not depart from disclosure and rights and interests claimed range, can and discuss the present invention is improved and deepens according to aforementioned disclosure.
Description of drawings:
The molecular structure of Fig. 1 D-cerous tarate.
The accumulation graph of Fig. 2 D-cerous tarate.
The molecular structure of Fig. 3 D-tartrate dysprosium.
The accumulation graph of Fig. 4 D-tartrate dysprosium.
The molecular structure of Fig. 5 D-tartrate europium.
The accumulation graph of Fig. 6 D-tartrate europium.
The molecular structure of Fig. 7 D-tartrate neodymium.
The accumulation graph of Fig. 8 D-tartrate neodymium.
The molecular structure of Fig. 9 D-tartrate samarium.
The accumulation graph of Figure 10 D-tartrate samarium.
The molecular structure of Figure 11 D-tartrate terbium.
The accumulation graph of Figure 12 D-tartrate terbium.
The microscopic appearance of Figure 13 D-tartrate yttrium.
The microscopic appearance of Figure 14 D-lanthanum tartrate.
Embodiment:
Embodiment 1:
0.3g cerium oxide and 0.3g D-tartrate are packed in the 20ml reactor, add 2ml ethanol, 16ml water uniform mixing.140 ℃ of crystallization of constant temperature were cooled to room temperature with 5 ℃ the speed of per hour lowering the temperature after 3 days, can obtain a millimeter level D-cerous tarate complex crystal.The molecular formula of institute's synthetic product D-cerous tarate is: [Ce 2(D-TAR) 3(H 2O) 3] 3H 2O, spacer is P1, unit cell parameters is a=6.1155 (5)
Figure B2009100996632D0000031
B=7.4514 (6)
Figure B2009100996632D0000032
C=13.0570 (10)
Figure B2009100996632D0000033
α=88.381 (4) °, β=81.242 (4) °, γ=89.335 (4) °, V=587.81 (8)
Figure B2009100996632D0000034
Z=1, Dc=2.352g/cm 3, its structure is under the excitation of 250nm at wavelength as shown in Figure 1 and Figure 2, sends the fluorescence that wavelength is 355nm.
Embodiment 2:
0.3g dysprosium oxide and 0.3g D-tartrate are packed in the 20ml reactor, add 2ml ethanol, 16ml water uniform mixing.140 ℃ of crystallization of constant temperature were cooled to room temperature with 5 ℃ the speed of per hour lowering the temperature after 3 days, can obtain a millimeter level D-tartrate dysprosium complex crystal.The molecular formula of institute's synthetic product D-tartrate dysprosium is: [Dy 2(D-TAR) 3(H 2O) 2] 3H 2O, spacer is P1, unit cell parameters is a=5.9811
Figure B2009100996632D0000035
B=7.4016 (7)
Figure B2009100996632D0000036
C=13.2110 (13) α=102.852 (5) °, β=101.447 (5) °, γ=90.888 (5) °, V=557.76 (9)
Figure B2009100996632D0000038
Z=1, Dc=2.558g/cm 3, its structure is under the excitation of 265nm at wavelength as shown in Figure 3, Figure 4, can both send the fluorescence that wavelength is 480nm.
Embodiment 3:
0.3g europium sesquioxide and 0.3g D-tartrate are packed in the 20ml reactor, add 2ml ethanol, 16ml water uniform mixing.140 ℃ of crystallization of constant temperature were cooled to room temperature with 5 ℃ the speed of per hour lowering the temperature after 3 days, can obtain a millimeter level D-tartrate europium complex crystal.At solvent thermal synthesis of chiral porous fluorescent material D-tartrate europium of the present invention, in the method for L-tartrate europium, it is characterized in that the molecular formula of institute's synthetic product D-tartrate europium is: [Eu 2(D-TAR) 3(H 2O) 2] 3H 2O, spacer is P1, unit cell parameters is a=6.0216 (2)
Figure B2009100996632D0000039
B=7.4518 (2) C=13.2293 (3)
Figure B2009100996632D00000311
α=102.6560 (10) °, β=101.3860 (10) °, γ=90.8310 (10) °, V=566.76 (3)
Figure B2009100996632D00000312
Z=1, Dc=2.409g/cm 3, its structure such as Fig. 5, shown in Figure 6 are under the excitation of 260nm at wavelength, can both send the fluorescence that wavelength is 560nm.
Embodiment 4:
0.3g Neodymium trioxide and 0.3g D-tartrate are packed in the 20ml reactor, add 2ml ethanol, 16ml water uniform mixing.140 ℃ of crystallization of constant temperature were cooled to room temperature with 5 ℃ the speed of per hour lowering the temperature after 3 days, can obtain a millimeter level D-tartrate neodymium complex crystal.At solvent thermal synthesis of chiral porous fluorescent material D-tartrate neodymium of the present invention, in the method for L-tartrate neodymium, it is characterized in that the molecular formula of institute's synthetic product D-tartrate neodymium is: [Nd 2(D-TAR) 3(H 2O) 3] 3H 2O, spacer is P1, unit cell parameters is a=6.0913 (7)
Figure B2009100996632D0000041
B=7.4121 (10) C=13.0058 (18)
Figure B2009100996632D0000043
α=88.398 (10) °, β=81.063 (8) °, γ=89.220 (9) °, V=579.82 (13)
Figure B2009100996632D0000044
Z=1, Dc=2.408g/cm 3, its structure such as Fig. 7, shown in Figure 8 are under the excitation of 600nm at wavelength, send the fluorescence that wavelength is 825nm.
Embodiment 5:
0.3g Samarium trioxide and 0.3g D-tartrate are packed in the 20ml reactor, add 2ml ethanol, 16ml water uniform mixing.140 ℃ of crystallization of constant temperature were cooled to room temperature with 5 ℃ the speed of per hour lowering the temperature after 3 days, can obtain a millimeter level D-tartrate samarium complex crystal.The molecular formula of institute's synthetic product D-tartrate samarium is: [Sm 2(D-TAR) 3(H 2O) 2] 3H 2O, spacer is P1, unit cell parameters is a=6.0107 (8)
Figure B2009100996632D0000045
B=7.4039 (10)
Figure B2009100996632D0000046
C=13.2262 (17)
Figure B2009100996632D0000047
α=102.639 (7) °, β=101.118 (6) °, γ=91.019 (7) °, V=562.45 (13)
Figure B2009100996632D0000048
Z=1, Dc=2.465g/cm 3, its structure such as Fig. 9, shown in Figure 10 are under the excitation of 260nm at wavelength, send the fluorescence that wavelength is 560nm.
Embodiment 6:
0.3g terbium sesquioxide and 0.3g D-tartrate are packed in the 20ml reactor, add 3ml ethanol, 15ml water uniform mixing.140 ℃ of crystallization of constant temperature were cooled to room temperature with 5 ℃ the speed of per hour lowering the temperature after 3 days, can obtain a millimeter level D-tartrate terbium coordination compound crystal.The molecular formula of institute's synthetic product D-tartrate terbium is: [Tb 2(D-TAR) 3(H 2O) 2] 3H 2O, spacer is P1, unit cell parameters is a=5.9989 (6)
Figure B2009100996632D0000049
B=7.4191 (8)
Figure B2009100996632D00000410
C=13.2602 (16)
Figure B2009100996632D00000411
α=103.085 (8) °, β=101.593 (7) °, γ=90.678 (7) °, V=562.10 (11)
Figure B2009100996632D00000412
Z=1, Dc=2.517g/cm 3, its structure such as Figure 11, shown in Figure 12 are under the excitation of 240nm at wavelength, can both send the fluorescence that wavelength is 545nm.
Embodiment 7:
1g yttrium oxide and 1g D-tartrate are packed in the 20ml reactor, add 8ml ethanol, 10ml water uniform mixing.160 ℃ of crystallization of constant temperature were cooled to room temperature with 5 ℃ the speed of per hour lowering the temperature after 3 days, mainly obtained the D-tartrate yttrium complex powder of yardstick between 1～10um.
Embodiment 8:
1g yttrium oxide and 1g D-tartrate are packed in the 20ml reactor, add 6ml ethanol, 6ml N, dinethylformamide, 6ml water uniform mixing.175 ℃ of crystallization of constant temperature were cooled to room temperature with 10 ℃ the speed of per hour lowering the temperature after 3 days, mainly obtained the D-tartrate yttrium complex powder of yardstick between 100～500nm, and its microscopic appearance as shown in figure 13.
Embodiment 9:
0.8g lanthanum trioxide and 0.8g D-tartrate are packed in the 20ml reactor, add 6ml ethanol, 2ml N, dinethylformamide, 2ml methyl-sulphoxide, 8ml water uniform mixing.175 ℃ of crystallization of constant temperature were cooled to room temperature with 8 ℃ the speed of per hour lowering the temperature after 3 days, mainly obtained the D-lanthanum tartrate title complex powder of yardstick between 1～5um, and its microscopic appearance as shown in figure 14.

Claims (6)

1. the method for a solvothermal synthesis of D-tartaric acid rare earth complex is characterized in that following these steps to carrying out:
(1) rare earth oxide and D-tartrate are packed in the solvent thermal reaction still by certain mass ratio.
(2) in reactor, add an amount of solution.
(3) heating crystallization.
(4) cooling is cooled to room temperature.
(5) filter washing, drying.
2. the method for solvothermal synthesis of D-tartaric acid rare earth complex according to claim 1, it is characterized in that, in the described step (1), the tartaric mass ratio of described rare earth oxide and D-is 1: 1～1: 2, can control the pattern and the granular size of product by regulating raw material rare earth oxide and the tartaric mass ratio of D-in this scope.
3. the method for solvothermal synthesis of D-tartaric acid rare earth complex according to claim 1 is characterized in that, in the described step (1), described rare earth oxide also can substitute with rare earth nitrate or lanthanon acetate.
4. the method for solvothermal synthesis of D-tartaric acid rare earth complex according to claim 1 is characterized in that, in the described step (2), described solvent is ethanol, water, N, one or more mixing solutionss in dinethylformamide, the dimethyl sulfoxide (DMSO).Can control the pattern and the granular size of product by the component that changes solvent.
5. the method for solvothermal synthesis of D-tartaric acid rare earth complex according to claim 1, it is characterized in that, in the described step (3), described crystallization temperature is 135～185 ℃, can control the pattern and the granular size of product in this scope by the temperature of regulating crystallization.
6. the method for solvothermal synthesis of D-tartaric acid rare earth complex according to claim 1, it is characterized in that, in the described step (4), described cooling rate can be controlled the pattern and the granular size of product for per hour lowering the temperature 1 ℃～15 ℃ by the temperature of regulating crystallization in this scope.
CN2009100996632A 2009-06-15 2009-06-15 Method of solvothermal synthesis of D-tartaric acid rare earth complex Pending CN101921285A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516276A (en) * 2011-11-08 2012-06-27 宁波大学 Tartaric acid terbium ferroelectric functional material and preparation method thereof
CN103073565A (en) * 2012-12-21 2013-05-01 湖州师范学院 Hydrous L-(+)-tartaric acid cerium and ferro electric function material and preparation method thereof
CN103254063A (en) * 2013-04-24 2013-08-21 宁波大学 Hydrate D-cerous tartrate ferroelectric functional material and preparation method thereof
CN105924459A (en) * 2016-04-29 2016-09-07 山西大学 Neodymium complex, and preparation method and application thereof
CN113788499A (en) * 2021-09-22 2021-12-14 江南大学 Chiral manganese oxide nano particle and preparation method and application thereof
CN114957802A (en) * 2022-04-14 2022-08-30 陕西科技大学 Preparation method of rare earth fluorescent film based on cellulose photonic crystal forbidden band modulation

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516276A (en) * 2011-11-08 2012-06-27 宁波大学 Tartaric acid terbium ferroelectric functional material and preparation method thereof
CN102516276B (en) * 2011-11-08 2014-11-05 宁波大学 Tartaric acid terbium ferroelectric functional material and preparation method thereof
CN103073565A (en) * 2012-12-21 2013-05-01 湖州师范学院 Hydrous L-(+)-tartaric acid cerium and ferro electric function material and preparation method thereof
CN103254063A (en) * 2013-04-24 2013-08-21 宁波大学 Hydrate D-cerous tartrate ferroelectric functional material and preparation method thereof
CN105924459A (en) * 2016-04-29 2016-09-07 山西大学 Neodymium complex, and preparation method and application thereof
CN105924459B (en) * 2016-04-29 2018-04-03 山西大学 A kind of Nd complex and its preparation method and application
CN113788499A (en) * 2021-09-22 2021-12-14 江南大学 Chiral manganese oxide nano particle and preparation method and application thereof
CN114957802A (en) * 2022-04-14 2022-08-30 陕西科技大学 Preparation method of rare earth fluorescent film based on cellulose photonic crystal forbidden band modulation

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