CN1803804A - Rare earth complex and process for preparing the same - Google Patents
Rare earth complex and process for preparing the same Download PDFInfo
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- CN1803804A CN1803804A CN 200610023560 CN200610023560A CN1803804A CN 1803804 A CN1803804 A CN 1803804A CN 200610023560 CN200610023560 CN 200610023560 CN 200610023560 A CN200610023560 A CN 200610023560A CN 1803804 A CN1803804 A CN 1803804A
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Abstract
The related rare-earth complex has structural formula as Ln2M1(M2)2R with two trivalent Ln as central ions and ligand M contained M1 as 3,5-bi(4-carboxylbenzoate)phenyl benzoate and M2 as 1, 10-orthophenanthroline(phen) and R as solvent. Wherein, the reaction needs 5-20h at 20-80Deg. This invention can be used as luminous complex with high efficiency, intensity and stability.
Description
Technical field
The present invention relates to rare earth title complex and preparation method thereof, be meant a kind of 3 especially, 5-two (4-carboxyl benzoic ether) methyl benzoate rare earth compounding and preparation method thereof, this rare earth compounding can be used as the photoelectric functional material in various fields such as being applied to agricultural, biology, electrotechnical, electronic.
Background technology
Rare earth compounding is the coordination compound that a class is formed round center rare earth ion Ln by part M, because all there is special 4f electron structure in contained rare earth ion in the title complex, behind the optical excitation rare earth organic complex that is subjected to certain wavelength, organic ligand absorbed radiation energy wherein, the electronics that makes rare earth is owing to energy level transition produces fluorescence.Therefore the title complex of rare earth is the luminescent material that a class has advantages of higher stability, be applied at present in the various transform light energy agent materials, and in alkaline earth sulfide, organic fluorescence materials, three kinds of transform light energy agent materials of rare earth organic complex, it is that illumination effect is significantly a kind of, agent makes an addition in the canopy film as transform light energy with it on agricultural, UV-light can be converted to the needed spectral component of photosynthesis of plant---ruddiness and blue light, strengthen photosynthesis, obtain the effect of increasing crop yield, precocity and raising nutrition.In addition, again because rare earth ion and life metallic element calcium have close ionic radius, thereby can be used as probe and disclose the interior Na of organism
+, K
+, Ca
2+Deng the physiological function of metallics, be widely used in fields such as biological probe, UV radiation dose meter, fluorescent plate.
But the f-f transition of its rare earth cation is often by partly shielding effect in the title complex, and therefore, the absorption of rare earth ion itself and the intensity of emmission spectrum are very weak.Yet fluorescence intensity can strengthen by organic ligand.As the ideal organic ligand, not only to have excellent efficiency of light absorption, and deposit the possibility of energy transformation efficiently between part and rare earth ion.For obtaining the excellent fluorescent characteristic and the rare earth compounding of suitable different application field needs, cause people's attention, and carried out a large amount of research, specifically be summarized as follows:
1. inorganic complexes
The glass that contains neodymium with widespread use in the electronics of laser beam is representative, and is because of producing and processing difficulties, expensive and the use of this glass is restricted.
2. organic coordination compound
As title complex [Nd
III(HFA)
3]; organic coordination compounds such as 2-acetyl benzimidazolyl glycine-condensate Schiff base rare-earth; although these organic coordination compounds are better than inorganic optical material on processing characteristics; but they all select the organic compound with the big π key of conjugation for use is part; also introducing second part that has; but; because part is aromatic series and aliphatic blended valence link; because aliphatic existence; make molecule rotation easily on space structure of part; motion; and make molecule be unsure state; and influenced its stability, thus cause part can not effectively carry out high efficiency light conversion, the luminous efficiency of title complex is reduced.Thereby exist luminescent lifetime to lack and the low shortcoming of luminous efficiency.With patent of invention CN1249754A, CN1699374A is representative.
In sum, how to select to have the focus that rare earth compounding that the part of the conversion of intramolecular energy efficiently forms will become people's research.
Summary of the invention
The purpose of this invention is to provide a kind of RE compound material with high-performance photoelectric functional, to solve the problems referred to above that prior art exists, the made photochromics of this rare earth compounding of the present invention should have the characteristic except that having usual production, it also should have high light conversion efficiency and stronger fluorescence radiation character, and the good characteristics such as high stability of title complex.Therefore can be used as new optical material is applied to multiple luminous Application Areas.
Another object of the present invention provides the manufacture method of above-mentioned rare earth compounding.
The structural formula of rare earth compounding provided by the present invention is Ln
2M
1(M
2)
2R, wherein, central ion is two trivalent rare earth ions Ln, by a M
1With two M
2Three parts obtain through complex reaction, specifically composed as follows:
(1) described Ln is a rare earth ion, is specially in europium, lanthanum, cerium, praseodymium, rubidium, samarium, gadolinium, dysprosium, holmium, terbium, erbium, thulium, the lutetium class rare earth ion any one;
(2) described part M is by M
1And M
2Form M
1Be 3,5-two (4-carboxyl benzoic ether) methyl benzoate; M
2Be 1,10-o-phenanthroline (phen);
(3) described R is the part solvent, is methyl-sulphoxide, N, dinethylformamide, acetone, any one in methyl ethyl ketone, ether, tetrahydrofuran (THF), chloroform, methylene dichloride, methyl alcohol, the alcohol solvent.
In the above-mentioned rare earth compounding, the effect of described rare earth ion provides and special can produce the 4f electronics that energy level transition is sent fluorescence; Described part M is by M
1And M
2Form part M
1Be the organic compound of many carboxyls, many phenyl ring, at M
1In carbonyl in Sauerstoffatom on lone-pair electron and the π bond energy on the phenyl ring form hyperconjugation.This will make gained part M
1Have bigger conjugate planes, favorable rigidity structure and structural stability, this is very important for the rare earth compounding that forms the structure excellence.Simultaneously because part M
1Special many phenyl ring connecting structure, part M
1The energy that is absorbed can pass to rare earth ion effectively by " oxo bridge ", and this will make rare earth compounding of the present invention have the luminescent material of excellent photoelectric functional.M
2Be another kind of part, insert 1 respectively by two rare earth ion Ln, the 10-o-phenanthroline constitutes the superpower conjugated structure effect between 5 parts; In addition, the solvent action of part is for promoting part M
1Dissolving, and then impel complex reaction to quicken.
The method for preparing rare earth compounding of the present invention is by 3, synthetic, the part M of 5-methyl dihydroxy benzoate
1Three steps of carrying out successively synthetic, the title complex preparation form, concrete steps are as follows:
Synthesizing of (1) 3,5-methyl dihydroxy benzoate
Get chemical pure 3,5-resorcylic acid and weight percent concentration are that the mol ratio of the methyl alcohol more than 99% is 1: 3～1: 15, are that catalyzer, temperature of reaction are to react under 60～90 ℃ the condition at tosic acid, and the reaction times is 10～20 hours; Prepared liquid is 3 with 80ml～200ml deionized water dissolving unreacted reactant again, and 5-resorcylic acid and methyl alcohol stir standing demix after 20～40 minutes, and the oil reservoir that takes off face promptly gets 3, the 5-methyl dihydroxy benzoate.
(2) part M
1Synthetic
With above-mentioned 3, the routine in molar ratio scope of 5-methyl dihydroxy benzoate and chemical pure p-phthaloyl chloride is 1: 2, putting into 40ml～80ml weight percent concentration is 99% N, in the dinethylformamide solvent, simultaneously dripping chemical pure pyridine liquid 2～10ml again reacts, temperature of reaction is 40 ℃～130 ℃, and the reaction times is 2～10 hours, until there not being HCl to emit; Pour in the deionized water after reaction solution cooling caused room temperature, churning time is 10～20 minutes, obtains white powder; White powder is cleaned 2～5 times repeatedly with deionized water, and filtering drying promptly obtains part M
1
(3) title complex preparation
A. with the oxide dissolution of rare earth metal in hydrochloric acid or nitric acid, be 1: 10～20 with the oxide compound of rare earth metal and the mol ratio of hydrochloric acid or nitric acid, solvent temperature is 20～60 ℃, dissolution time is 20～50 minutes, with the solution oven dry, makes LnCl
3Or Ln (NO
3)
3, get 3～8 mmole LnCl
3Or Ln (NO
3)
3Add weight percent concentration and be among the ethanolic soln 10～35ml more than 99%, obtain solution 1;
B. with the chemical pure 1 of 3～8 mmoles, it is among ethanolic soln 10～35ml more than 99%, to obtain solution 2 that the 10-o-phenanthroline is dissolved in weight percent concentration;
C. with the part M of 2～5 mmoles
1With weight percent concentration be that the solvent R 30～50ml of the part more than 99% mixes, stir 10～20 minutes until part M
1Dissolving fully, and with the P of basic solution
HValue adjusts to 6～12, obtains solution 3.Described basic solution is ammoniacal liquor, sodium hydroxide, diethylamino or triethylamine.The solvent R of described part is methyl-sulphoxide, N, dinethylformamide, acetone, methyl ethyl ketone, ether, tetrahydrofuran (THF), chloroform, methylene dichloride, methyl alcohol, ethanol;
D. 10～35ml solution 1 and 10～35ml solution 2 are mixed, temperature be 40 ℃～80 ℃ stir 10～30 minutes after, 30～50ml solution 3 is added wherein, at room temperature leave standstill after above-mentioned mixed solution is stirred and obtained pressed powder in 5～20 hours.Pressed powder is cleaned 1～3 time repeatedly with ethanol, and filtration and oven dry obtain title complex.
Advantage of the present invention is that selected raw material is streat drug, and preparation technology is simple, the part M that makes
1The part that has bigger efficiently hyperconjugation planar, can change in efficiently for many phenyl ring connecting structure, many carboxyls, thus obtain efficiently, the rare earth luminous title complex of high strength, high stable.In addition, can also control the size of the fluorescence intensity of title complex, obtain having the title complex of different photoelectric functionals by the pH value of adjusting complex reaction and the different sorts that changes the part solvent.
Embodiment
Embodiment 1:3,5-methyl dihydroxy benzoate synthetic
In the three-necked bottle of 250ml, with 50g chemical pure 3, the 5-resorcylic acid is added in the solution of 100ml that weight percent concentration is 99.7% methyl alcohol, promptly 3, the mol ratio of the methyl alcohol of 5-resorcylic acid and weight percent 99.7% is 1: 10, add 0.1g catalyzer tosic acid again, temperature of reaction is 70 ℃, reaction times is under 10 hours the condition, prepared liquid is used its unreacted reactant of 100ml deionized water dissolving (3,5-resorcylic acid and methyl alcohol) again, stirs standing demix after 20 minutes, the oil reservoir that takes off face promptly get productive rate be 95% 3, the 5-methyl dihydroxy benzoate.
Embodiment 2: part M
1Synthetic
With 3 of above-mentioned 14mmol, the chemical pure p-phthaloyl chloride of 5-methyl dihydroxy benzoate and 28mmol, putting into weight percent concentration is 99.7%N, among the dinethylformamide solvent 50ml, simultaneously dripping chemical pure pyridine liquid 2.5ml again reacts, temperature of reaction is 95 ℃, and the reaction times is 8 hours, until there not being HCl to emit; Pour in the deionized water after reaction solution cooling caused room temperature, churning time is 15 minutes, obtains white powder; White powder is cleaned 3 times repeatedly with deionized water, and filtering drying promptly obtains part M
1
Embodiment 3: rare-earth europium title complex [Eu
2M
1(M
2)
2R] preparation
A. with the oxide dissolution of rare earth metal europium in HCl, be 1: 15 with the oxide compound of rare-earth europium and the mol ratio of hydrochloric acid, solvent temperature is 40 ℃, the time is 20 minutes, makes europium chloride solution, with its oven dry; Getting 6 mmole europium chlorides, to add weight percent concentration be in 99.7% the ethanol 30ml solution, wiring solution-forming 1;
B. with the chemical pure 1 of 6 mmoles, it is among 99.7% the ethanolic soln 20ml, to obtain solution 2 that the 10-o-phenanthroline is dissolved in weight percent concentration;
C. with the part M of 3 mmoles
1With weight percent concentration be that the solvent methyl-sulphoxide 40ml of 99.7% part mixes, stir 15 minutes until part M
1Dissolving fully, and use basic solution ammoniacal liquor, with P
HValue adjusts to 7, obtains solution 3.
D.30ml solution 1 and 20ml solution 2 mix, and stirring added 40ml solution 3 wherein after 20 minutes under temperature is 50 ℃, at room temperature leave standstill after above-mentioned mixed solution is stirred and obtain pressed powder in 10 hours.Pressed powder is cleaned 2 times repeatedly with ethanol, and filtration and oven dry obtain title complex.
Embodiment 4: rare earth samarium title complex [Sm
2M
1(M
2)
2R] preparation
A. with the oxide dissolution of rare earth metal in HCl, be 1: 15 with the oxide compound of rare earth samarium and the mol ratio of hydrochloric acid, solvent temperature is 40 ℃, the time is 20 minutes, makes Samarium chloride solution, with its oven dry; Getting 6 mmole Samarium chlorides, to add weight percent concentration be in 99.7% the ethanol 30ml solution, wiring solution-forming 1;
B. with the chemical pure 1 of 6 mmoles, it is among 99.7% the ethanolic soln 20ml, to obtain solution 2 that the 10-o-phenanthroline is dissolved in weight percent concentration;
C. with the part M of 3 mmoles
1With weight percent concentration be the solvent N of 99.7% part, dinethylformamide 40ml mixes, and stirs 15 minutes until part M
1Dissolving fully, and use basic solution ammoniacal liquor, pH value is adjusted to 7, obtain solution 3.
D.30ml solution 1 and 20ml solution 2 mix, and stirring added 40ml solution 3 wherein after 20 minutes under temperature is 50 ℃, at room temperature leave standstill after above-mentioned mixed solution is stirred and obtain pressed powder in 10 hours.Pressed powder is cleaned 2 times repeatedly with ethanol, and filtration and oven dry obtain title complex.
Claims (5)
1. a rare earth compounding is characterized in that with two trivalent rare earth ionses be central ion, by a M
1With two M
2Three parts obtain through complex reaction, the structural formula of described title complex is Ln
2M
1(M
2)
2R, described Ln are rare earth ion; Described M is a part; Described R is the part solvent.
2. rare earth compounding according to claim 1 is characterized in that described rare earth ion Ln is any one in europium, lanthanum, cerium, praseodymium, rubidium, samarium, gadolinium, dysprosium, holmium, terbium, erbium, thulium, the lutetium class rare earth ion.
3. rare earth compounding according to claim 1 is characterized in that described part M is by M
1And M
2Form M
1Be 3,5-two (4-carboxyl benzoic ether) methyl benzoate; M
2Be 1, the 10-o-phenanthroline.
4. rare earth compounding according to claim 1, it is characterized in that described part solvent R is methyl-sulphoxide, N, any one in dinethylformamide, acetone, methyl ethyl ketone, ether, tetrahydrofuran (THF), chloroform, methylene dichloride, ethanol, the methanol solvate.
5. make the method for the described rare earth compounding of claim 1, it is characterized in that this method is by 3, synthetic, the part M of 5-methyl dihydroxy benzoate
1Three steps of carrying out successively synthetic, the title complex preparation form, concrete steps are as follows:
Synthesizing of (1) 3,5-methyl dihydroxy benzoate
Get chemical pure 3,5-resorcylic acid and weight percent concentration are that the mol ratio of the methyl alcohol more than 99% is 1: 3～1: 15, are that catalyzer, temperature of reaction are to react under 60～90 ℃ the condition at tosic acid, and the reaction times is 10～20 hours; Prepared liquid is 3 with 80ml～its unreacted reactant of 200ml deionized water dissolving again, and 5-resorcylic acid and methyl alcohol stir standing demix after 20～40 minutes, and the oil reservoir that takes off face promptly gets 3, the 5-methyl dihydroxy benzoate;
(2) part M
1Synthetic
With above-mentioned 3,5-methyl dihydroxy benzoate and chemical pure p-phthaloyl chloride are 1: 2 in molar ratio, putting into 40ml～80ml weight percent concentration is 99% N, in the dinethylformamide solvent, simultaneously dripping chemical pure pyridine liquid 2～10ml again reacts, temperature of reaction is 40 ℃～130 ℃, and the reaction times is 2～10 hours, until there not being HCl to emit; Pour in the deionized water after reaction solution cooling caused room temperature, churning time is 10～20 minutes, obtains white powder; White powder is cleaned 2～5 times repeatedly with deionized water, and filtering drying promptly obtains part M
1
(3) title complex preparation
A. with the oxide dissolution of rare earth metal in hydrochloric acid or nitric acid, be 1: 10～20 with the oxide compound of rare earth metal and the mol ratio of hydrochloric acid or nitric acid, solvent temperature is 20～60 ℃, dissolution time is 20～50 minutes, with the solution oven dry, makes LnCl
3Or Ln (NO
3)
3, get 3～8 mmole LnCl
3Or Ln (NO
3)
3Add weight percent concentration and be among the ethanolic soln 10～35ml more than 99%, obtain solution 1;
B. with the chemical pure 1 of 3～8 mmoles, it is among ethanolic soln 10～35ml more than 99%, to obtain solution 2 that the 10-o-phenanthroline is dissolved in weight percent concentration;
C. with the part M of 2～5 mmoles
1With weight percent concentration be that the solvent R 30～50ml of the part more than 99% mixes, stir 10～20 minutes until part M
1Dissolving fully, and with the P of basic solution
HValue adjusts to 6～12, obtains solution 3, and described basic solution is ammoniacal liquor, sodium hydroxide, diethylamino or triethylamine; The solvent R of described part is methyl-sulphoxide, N, dinethylformamide, acetone, methyl ethyl ketone, ether, tetrahydrofuran (THF), chloroform, methylene dichloride, methyl alcohol, ethanol;
D. 10～35ml solution 1 and 10～35ml solution 2 are mixed, temperature be 40 ℃～80 ℃ stir 10～30 minutes after, 30～50ml solution 3 is added wherein, at room temperature leave standstill after above-mentioned mixed solution is stirred and obtained pressed powder in 5～20 hours; Pressed powder is cleaned 1～3 time repeatedly with ethanol, and filtration and oven dry obtain title complex.
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| CN101838860A (en) * | 2010-05-24 | 2010-09-22 | 天津工业大学 | Method for preparing rare earth fluorescent fiber |
| CN102321106A (en) * | 2011-07-18 | 2012-01-18 | 中国工程物理研究院化工材料研究所 | Preparation method of heterotetranuclear f-f' isomerism and/or configurational isomerism compounds |
| CN103745981A (en) * | 2013-12-04 | 2014-04-23 | 广东普加福光电科技有限公司 | Ultraviolet response type rare earth light conversion film and application thereof |
| CN104098492A (en) * | 2014-07-29 | 2014-10-15 | 景德镇陶瓷学院 | Method for preparing thiourea dioxide with strong reductibility by using homogeneous phase terrae rare complex under conditions of constant temperature and weak base |
| CN105482811A (en) * | 2015-11-28 | 2016-04-13 | 天津工业大学 | Dual-arm benzoic-acid organic rare-earth efficient luminescent material and preparation method thereof |
| CN105777787A (en) * | 2016-03-08 | 2016-07-20 | 伊犁师范学院 | Method for synthesizing dicaryon ternary complex |
| CN106916317A (en) * | 2017-02-27 | 2017-07-04 | 三峡大学 | A kind of Rare Earth Europium base organic crystalline material, prepares and the application on fluorescence identifying antibiotic |
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| CN101838860A (en) * | 2010-05-24 | 2010-09-22 | 天津工业大学 | Method for preparing rare earth fluorescent fiber |
| CN102321106A (en) * | 2011-07-18 | 2012-01-18 | 中国工程物理研究院化工材料研究所 | Preparation method of heterotetranuclear f-f' isomerism and/or configurational isomerism compounds |
| CN103745981A (en) * | 2013-12-04 | 2014-04-23 | 广东普加福光电科技有限公司 | Ultraviolet response type rare earth light conversion film and application thereof |
| CN104098492A (en) * | 2014-07-29 | 2014-10-15 | 景德镇陶瓷学院 | Method for preparing thiourea dioxide with strong reductibility by using homogeneous phase terrae rare complex under conditions of constant temperature and weak base |
| CN104098492B (en) * | 2014-07-29 | 2016-06-29 | 景德镇陶瓷大学 | A kind of method utilizing homogeneous rare earth compounding to prepare strong reducing property thiourea dioxide when room temperature weak base |
| CN105482811B (en) * | 2015-11-28 | 2019-11-22 | 天津工业大学 | A kind of both arms benzoic acids organic RE high efficient luminous material and preparation method thereof |
| CN105482811A (en) * | 2015-11-28 | 2016-04-13 | 天津工业大学 | Dual-arm benzoic-acid organic rare-earth efficient luminescent material and preparation method thereof |
| CN105777787A (en) * | 2016-03-08 | 2016-07-20 | 伊犁师范学院 | Method for synthesizing dicaryon ternary complex |
| CN106916317B (en) * | 2017-02-27 | 2019-10-08 | 三峡大学 | A kind of Rare Earth Europium base organic crystalline material, preparation and the application on fluorescence identifying antibiotic |
| CN106916317A (en) * | 2017-02-27 | 2017-07-04 | 三峡大学 | A kind of Rare Earth Europium base organic crystalline material, prepares and the application on fluorescence identifying antibiotic |
| CN107603072A (en) * | 2017-10-16 | 2018-01-19 | 天津城建大学 | A kind of nanometer heat stabilizer |
| CN108547009A (en) * | 2018-04-28 | 2018-09-18 | 大连工业大学 | A kind of nano fluorescence fiber material and preparation method thereof |
| CN108547009B (en) * | 2018-04-28 | 2020-08-11 | 大连工业大学 | Nano fluorescent fiber material and preparation method thereof |
| CN113150295A (en) * | 2021-03-12 | 2021-07-23 | 北京科技大学 | Preparation method of bimetal doped rare earth MOFs material |
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Granted publication date: 20090527 Termination date: 20120124 |