CN105037423A - Effective rare earth complex luminescent material excited by shortwave ultraviolet - Google Patents
Effective rare earth complex luminescent material excited by shortwave ultraviolet Download PDFInfo
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Abstract
The invention discloses a rare earth complex luminescent material based on aromatic heterocyclic carboxylic class three-tooth anionic ligands and preparing method and application thereof. The general formula of rare earth complex is Ln (L)3. The L is 2-carboxyl-pyridines, 2-carboxyl-Furan, 2-carboxyl-thiophenes three-tooth anionic ligands replaced by phosphine oxygen radicals, sulfoxide group or sulphone. The Ln represents rare earth europium, terbium and dysprosium ions. The rare earth complex presents electric neutrality and is saturate in coordination structure, quenching, caused by solvent molecules, of rare earth luminescence is eliminated, and dissociation of the ligands is not likely to happen. The rare earth complex luminescent material is an effective and stable luminescent material. Particularly the luminescent quantum yield of the complex of europium and terbium reaches over 90%. The rare earth complex can be used as a conversion luminescence material excited by shortwave ultraviolet.
Description
Technical field
The present invention relates to a kind of efficient rare-earth complexes luminous material and and application thereof of short wave ultraviolet excitation.
Background technology
Rare earth ion is subject to people's extensive concern and research because of the characteristics of luminescence (narrowband emission, stokes displacement are large, luminescent lifetime long) of its uniqueness, is applied to the aspects such as illumination, display, false proof, bio-imaging.Because rare earth ion f-f transition is prohibited, himself extinction is very weak.And rare earth ion is prepared into rare earth compounding, the strong absorption of part (sensitizing agent) to light can be utilized greatly to improve the emissive porwer (" antenna " effect) of rare earth ion.So rare earth compounding is a kind of luminescent material of superior performance, obtain attention and the extensively research of people.
Rare earth compounding is formed by the rare earth ion of positive trivalent and electronegative anion ligand and other neutral ligand usually.With Eu (TTA) 3phen, (TTA is 2-thenoyltrifluoroacetone, phen is 1,10-phenanthroline) be example, title complex contains three beta-diketon class bidentate anion ligands and a bidentate neutral ligand (Inorg.Chem.1994,33,3229), such structure had both met electroneutral requirement, made rare earth ion reach coordination saturation (ligancy is 8) simultaneously.Wherein, neutral ligand eliminates the rare earth luminous water molecules of strong cancellation or solvent molecule, plays an important role for the photoluminescence quantum yield (PhotoluminescenceQuantumYield, PLQY) improving rare earth compounding.But the coordination of neutral ligand and rare earth ion is general more weak, easily there is dissociating of part and rare earth ion in (such as high temperature, pole dilute concentration product, acid-base condition) under some extreme conditions, which limits the Application Areas of title complex.
The thinking of improvement does not use a neutral ligand, but adopt three tooth anion ligands to prepare rare earth compounding.Tridentate ligand and rare earth ion, by 3: 1 coordinations, not only can be got rid of solvent molecule, make rare earth ion reach coordination saturation, improve luminous efficiency, and neutral ligand can also be avoided to dissociate the trouble brought simultaneously.
Pyridine carboxylic acid is a kind of common ligand constructing rare earth compounding, can form rare earth compounding (J.Coord.Chem.2008,61,3981 that having from zero dimension to three-dimensional enriches structure; Inorg.Chim.Acta, 2012,392,46).This part energy level is higher, the rare earth compounding obtained can under the exciting of short wavelength UV (254nm) characteristic luminescence of generation rare earth.But according to the literature, such title complex Rare Earth Ion is general, and all coordination is unsaturated, have solvent molecule and participate in coordination, fluorescent quenching is serious, and the title complex luminous efficiency obtained is not high.
Therefore, pyridine (and heteroaromatic analogs) carboxylic acid compound is expanded for tridentate chelating ligand and and rare-earth ion coordination, be a kind of important method reducing solvent cancellation, improve photoluminescence quantum yield.Although the pyridine carboxylic acid class tridentate ligand (Inorg.Chem.2009 having bibliographical information amide group to replace,, but still the saturated coordination of desired rare earth ion cannot be obtained 48,6178), the complicated structure of title complex, the luminous efficiency of material is not largely increased yet.Contriver finds in recent research, and phosphine oxygen base, sulfoxide group and sulfuryl can be incorporated in part as chelation group, and increasing the ligancy of part, is a kind of outstanding group with powerful Chelating Properties.Phosphine oxygen base, sulfoxide group and sulfuryl are incorporated in pyridine (and heteroaromatic analogs) carboxylic acid compound by the present invention, being expanded is three tooth anion ligands, can form the rare-earth complexes luminous material with high quantum yield (PLQY > 90%) with rare-earth ion coordination.Simultaneously, phosphine atom in these groups and sulphur atom adopt sp3 hydridization, not strong with the conjugative effect of pyridine ring (and other aromatic heterocycles), the energy level of part does not decline to a great extent, thus makes title complex maintain outstanding short wave ultraviolet excitation character.
Summary of the invention
The aromatic heterocycle carboxylic-acid three tooth anion ligand that object of the present invention provides a kind of phosphine oxygen base, sulfoxide group or sulfuryl to replace, and the luminous efficiency of constructing short wave ultraviolet excitation is high, the rare-earth complexes luminous material of Heat stability is good.
Concrete, technical scheme of the present invention is as follows:
Based on a rare earth compounding for aromatic heterocycle carboxylic-acid three tooth anion ligand, general structure is Ln (L)
3, wherein L be the 2-carboxy-pyrid class shown in formula I to III, 2-carboxy-furan class, 2-carboxy-thiophen anionoid part, Ln represents rare earth ion.The structure of corresponding rare earth compounding is such as formula shown in IV to VI:
In formula I-VI, R is phosphine oxygen base, sulfoxide group or sulfuryl.Wherein, phosphine oxygen base form is P (=O) (R
1)
2, sulfoxide form is S (=O) R
1, sulfone form is S (=O) (=O) R
1; Above-mentioned R
1for alkyl or aryl, the straight or branched alkyl of the preferred C1-C18 of described alkyl, more preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-octyl, dodecyl, n-hexadecyl, Octadecane base; Described aryl is phenyl, naphthyl, p-methylphenyl.
In formula IV-VI, a Sauerstoffatom in phosphine oxygen base, sulfoxide group or sulfuryl participates in the coordination with rare earth ion.
In formula IV-VI, Ln represents rare earth ion, preferred europium, terbium, dysprosium ion.
The preparation method of middle-weight rare earths title complex of the present invention, adopts formula I to react in a solvent to three tooth anion ligands, alkali and the rare earth salts in formula III, obtained rare earth compounding shown in formula III to formula VI.Described alkali is oxyhydroxide, carbonate or amine, pyridines organic bases, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, ammoniacal liquor, triethylamine, Tetramethylammonium hydroxide.Described rare earth salts comprises the hydrochloride, nitrate, acetate, trifluoro sulfonate etc. of rare earth.In described method, described formula I is 3: 3: 1 to the mol ratio of three tooth anion ligands, alkali and the rare earth salts reaction in formula III.In described method, the temperature of reaction is 60 ~ 120 DEG C, and the time is 10 minutes ~ 10 hours.Described solvent is selected from water, ethanol, methyl alcohol, Virahol, acetone, tetrahydrofuran (THF), acetonitrile, toluene, methylene dichloride, trichloromethane, ether, DMF etc., can be wherein any one or two kinds and above mixture.
Rare earth compounding of the present invention can be used as the organic fluorescence materials of ultraviolet excitation, and its application mode comprises: a) use in solid form, such as pressed powder, or forms film etc. after using solution spraying to remove solvent; B) be entrained in certain matrix and use, such as in ink, colloid, high molecule plastic or other solid material.
2-carboxyl described in the present invention-heterocyclic arene class part triplet energy level higher (about can reaching 28000 wave numbers), so be very applicable to sensitization Tb
3+ion (20400 wave number) obtains the green emission become clear, Eu
3+ion (17500 wave number) obtains the red emission become clear, can also sensitization Dy
3+ion (21000 wave number) obtains the yellowish-white light become clear.
Rare earth compounding described in the present invention, presents electric neutrality and coordination structure is saturated, not only eliminates solvent molecule to rare earth luminous cancellation, and is not easy to occur dissociating of part, is a kind of efficient, stable luminescent material.
Such as, the terbium coordination compound that embodiment 1 obtains, its pressed powder quantum yield up to 96%, the europium complex that embodiment 2 obtains, its pressed powder quantum yield up to 93%, far beyond the luminous efficiency of the rare earth compounding based on pyridine carboxylic acid class part reported in document.
And the rare earth compounding described in the present invention has good thermostability, the terbium coordination compound that embodiment 1 obtains, its heat decomposition temperature is up to 400 degrees Celsius.
In addition, rare earth compounding of the present invention, because the energy level of part is higher, excitation wavelength is shorter, can realize sending bright fluorescence under shortwave 254nm excites, and substantially not luminous under long wave 365nm irradiates, in fluorescence falsification preventing, there is very large potential using value.
Accompanying drawing explanation
Fig. 1 is the excitation spectrum (determined wavelength is 545nm) of the rare-earth terbium complex pressed powder shown in formula IV-1 that the embodiment of the present invention 1 records.
Fig. 2 is the emmission spectrum (excitation wavelength is 280nm) of the rare-earth terbium complex pressed powder shown in formula IV-1 that the embodiment of the present invention 1 records.
Fig. 3 is the emmission spectrum (excitation wavelength is 280nm) of the Rare Earth Europium Complex pressed powder shown in formula IV-2 that the embodiment of the present invention 2 records.
Fig. 4 is the emmission spectrum (excitation wavelength is 280nm) of the rare earth dysprosium title complex pressed powder shown in formula IV-3 that the embodiment of the present invention 3 records.
Embodiment
Below by specific embodiment, product of the present invention, preparation method and application thereof are further described, but the protection domain that these specific embodiments do not limit the present invention in any way.
It is adopt integrating sphere to record in the FLS920 type stable state transient state fluorescence spectrophotometer of EdinburghInstrumentsLtd. company production that the present invention tests photoluminescence quantum yield.Heat decomposition temperature is N on the Q600SDT spectrometer of TA company of U.S. production
2record under atmosphere.
The synthetic route related in embodiment 1. the present embodiment is as follows:
(1) synthesis of DPPOPyC (2-carboxyl-6-diphenylphosphine oxygen yl pyridines, 6-diphenylphosphorylpicolinicacid)
The diphenyl phosphine chloride of 10mmol is joined in the tetrahydrofuran solution of sodium Metal 99.5 (20mmol), reflux 12h, the sodium salt of 10mmol2-carboxylic acid-6-bromopyridine is joined the diphenylphosphine sodium ((Ph) of fresh preparation
2pNa) in solution, reflux 12h.Add the m-chloro-benzoic acid peroxide (mCPBA) of equivalent after reaction terminates, stir 1h, rear 2MHCl regulator solution pH to 2-3.Be separated through post, recrystallizing methanol, vacuum-drying can obtain white powder 1.8g, productive rate 56%.
1HNMR(400MHz，CDCl
3)：δ8.49(ddd，J＝7.5，5.4，0.9Hz，1H)，8.33(d，J＝7.9Hz，1H)，8.14(td，J＝7.8，3.2Hz，1H)，7.90-7.73(m，4H)，7.59(td，J＝7.3，1.2Hz，2H)，7.50(td，J＝7.6，3.1Hz，4H)。Mass spectroscopy (m/z, ESI): calculated value 323.1, experimental value 324.1 (M+H).Ultimate analysis (mass percentage %): C, 66.18 (66.87); H, 4.38 (4.37); N, 4.13 (4.33), be theoretical value in bracket.
(2) rare earth compounding (i.e. R=DPPO in formula IV, i.e. diphenylphosphine oxygen base, Ln=Tb) shown in synthesis type IV-1
0.12gNaOH and part 0.97gDPPOPyC is mixed, adds 15mL dissolve with methanol, instilled (373mg (1mmol) is dissolved in 20mL methyl alcohol) in the methanol solution of six trichloride hydrate terbiums, reflux half an hour.By solvent evaporate to dryness, add methylene chloride to product and dissolve, filter desalination.And then by dichloromethane solution evaporate to dryness, obtain white powder 1.0g, productive rate 86%.Mass spectroscopy (m/z, ESI): calculated value 1125.1, experimental value 1126.1 (M+H).Ultimate analysis (mass percentage %): C, 55.75 (55.71); H, 3.72 (3.94); N, 3.54 (3.54), be Tb (DPPOPyC) 31.5CH in bracket
3oH1.1H
2o theoretical value.
Obtained terbium coordination compound Tb (DPPOPyC) 3 can obtain bright-coloured green emission under the exciting of ultraviolet lamp.As shown in Figure 1, emmission spectrum (excitation wavelength is 280nm) as shown in Figure 2 for the excitation spectrum (determined wavelength is 545nm) of its pressed powder.Pressed powder quantum yield is up to 96%. in addition, and thermogravimetric analysis records its heat decomposition temperature up to 400 degrees Celsius.
Rare earth compounding (i.e. R=DPPO in formula IV, i.e. diphenylphosphine oxygen base, Ln=Eu) shown in embodiment 2. synthesis type IV-2
Synthesis step, with embodiment 1, just changes rare-earth salts into six trichloride hydrate europiums.Obtain target europium complex white powder 0.95g.Mass spectroscopy (m/z, ESI): calculated value 1119.1, experimental value 1120.1 (M+H).Ultimate analysis (mass percentage %): C, 57.20 (57.19); H, 3.70 (3.62); N, 3.76 (3.71), be Eu (DPPOPyC) 30.9H in bracket
2o theoretical value.
Obtained europium complex Eu (DPPOPyC) 3 can obtain bright-coloured red emission under the exciting of ultraviolet lamp.The emmission spectrum (excitation wavelength is 280nm) of its pressed powder as shown in Figure 3.Pressed powder quantum yield is up to 93%.
Rare earth compounding (i.e. R=DPPO in formula IV, i.e. diphenylphosphine oxygen base, Ln=Dy) shown in embodiment 3. synthesis type IV-3
Synthesis step, with embodiment 1, just changes rare-earth salts into six trichloride hydrate dysprosiums.Obtain target dysprosium title complex white powder 1.0g.Mass spectroscopy (m/z, ESI): calculated value 1130.1, experimental value 1131.1 (M+H).Ultimate analysis (mass percentage %): C, 53.30 (53.22); H, 4.17 (4.19); N, 3.40 (3.39), be Dy (DPPOPyC) 30.9CH in bracket
3oH4.5H
2o theoretical value.
Obtained dysprosium title complex Dy (DPPOPyC)
3yellowish-white light emission can be obtained under the exciting of ultraviolet lamp.Emmission spectrum (excitation wavelength is 28lnm) as shown in Figure 4.Pressed powder quantum yield can reach 10%.
Rare earth compounding (i.e. R=DEPO in formula IV, i.e. diethyl phosphine oxygen base, Ln=Tb) shown in embodiment 4. synthesis type IV-4
Synthesis step, with embodiment 1, just changes diphenyl phosphine chloride into diethyl phosphonium chloride.Obtain white object terbium coordination compound 0.75g.Mass spectroscopy (m/z, ESI): calculated value 837.1, experimental value 838.1 (M+H).Ultimate analysis (mass percentage %): C, 42.49 (42.51); H, 4.90 (4.85); N, 4.89 (4.91), be Tb (DEPOPyC) in bracket
30.3CH
3oH0.5H
2o theoretical value.Obtained terbium coordination compound Tb (DEPOPyC)
3bright-coloured green emission can be obtained under the exciting of ultraviolet lamp.
Rare earth compounding (i.e. R=OSO in formula V, i.e. pungent sulfoxide group, Ln=Tb) shown in embodiment 5. synthesis type IV-5
Synthetic route is as follows:
(1) synthesis of OSOPyC (the pungent sulfoxide group pyridine of 2-carboxyl-6-, 6-octylsulfinylpicolinicacid)
The spicy thioalcohol of 10mmol is entered in the tetrahydrofuran solution of sodium Metal 99.5 (10mmol), reflux 1h, the sodium salt of 10mmol2-carboxylic acid-6-bromopyridine is joined in spicy thioalcohol sodium (OSNa) solution of fresh preparation, reflux 12h.Add the m-chloro-benzoic acid peroxide (mCPBA) of equivalent after reaction terminates, stir 1h, rear 2MHCl regulator solution pH to 2-3.Be separated through post, recrystallizing methanol, vacuum-drying can obtain white powder 2.2g, productive rate 79%.
1HNMR(400MHz，DMSO)：δ8.49(d，J＝7.2Hz，1H)，8.30(dd，J＝7.2，7.1Hz，1H)，8.16(d，J＝7.1Hz，1H)，δ3.11(d，J＝4.5Hz，1H)，2.90(s，1H)，1.71(d，J＝5.5Hz，1H)，1.34(dd，J＝12.6，5.0Hz，3H)，1.26-1.10(m，8H)，0.83(s，3H)。Mass spectroscopy (m/z, ESI): calculated value 283.1, experimental value 284.1 (M+H).Ultimate analysis (mass percentage %): C, 59.32 (59.34); H, 7.50 (7.47); N, 4.93 (4.94), be theoretical value in bracket.
(2) rare earth compounding (i.e. R=OSO in formula IV, i.e. pungent sulfoxide group, Ln=Tb) shown in synthesis type IV-5
Synthesis step, with embodiment 1, just changes part DPPOPyC into OSOPyC.Obtain white powder 0.9g, productive rate 90%.Mass spectroscopy (m/z, ESI): calculated value 1005.3, experimental value 1006.3 (M+H).Ultimate analysis (mass percentage %): C, 49.65 (49.68); H, 6.16 (6.14); N, 4.08 (4.09), be Tb (OSOPyC) in bracket
30.5CH
3oH0.3H
2o theoretical value.Obtained title complex Tb (OSOPyC)
3bright-coloured green emission can be obtained under the exciting of ultraviolet lamp.
Rare earth compounding (i.e. R=OSOO in formula IV, i.e. pungent sulfuryl, Ln=Tb) shown in embodiment 6. synthesis type IV-6
(1) synthesis of OSOOPyC (the pungent sulfuryl pyridine of 2-carboxyl-6-, 6-octylsulfonylpicolinicacid)
Synthesize OSOPyC2g by synthesis step 5, then add the m-chloro-benzoic acid peroxide (mCPBA) of equivalent, stir 1h, be separated through post, recrystallizing methanol, vacuum-drying can obtain white powder 1.9g, productive rate 90%.
1HNMR(400MHz，DMSO)：δ8.65(d，J＝7.5Hz，1H)，8.50(dd，J＝7.5，7.2Hz，1H)，8.44(d，J＝7.2Hz，1H)，δ3.58-3.42(m，2H)，1.68-1.52(m，2H)，1.40-1.27(m，2H)，1.20(d，J＝11.7Hz，8H)，0.83(t，J＝6.9Hz，3H)。Mass spectroscopy (m/z, ESI): calculated value 298.1, experimental value 299.1 (M+H).Ultimate analysis (mass percentage %): C, 56.32 (56.36); H, 6.80 (6.76); N, 4.67 (4.69), be theoretical value in bracket.
(2) rare earth compounding (i.e. R=OSOO in formula IV, i.e. pungent sulfuryl, Ln=Tb) shown in synthesis type IV-6
Synthesis step, with embodiment 5, just changes OSOPyC into OSOOpyC.Obtain white object terbium coordination compound 1.0g.Mass spectroscopy (m/z, ESI): calculated value 1053.3, experimental value 1054.3 (M+H).Ultimate analysis (mass percentage %): C, 47.36 (47.37); H, 5.80 (5.79); N, 3.96 (3.95), be Tb (OSOOPyC) in bracket
30.6H
2o theoretical value.Obtained title complex Tb (OSOPyC)
3bright-coloured green emission can be obtained under the exciting of ultraviolet lamp.
Rare earth compounding (i.e. R=DEPO in formula V, i.e. diethyl phosphine oxygen base, Ln=Tb) shown in embodiment 7. synthesis type V-1
Synthesis step, with embodiment 1, just changes diphenyl phosphine chloride into diethyl phosphonium chloride, and 6-bromo-2-pyridinecarboxylic acid changes 6-bromo-2-carboxylic acid furans into.Obtain white object terbium coordination compound 0.75g.Mass spectroscopy (m/z, ESI): calculated value 804.1, experimental value 805.1 (M+H).Ultimate analysis (mass percentage %): C, 39.50 (39.52); H, 4.94 (4.93), be Tb (DEPOFnC) in bracket
31.0CH
3oH0.8H
2o theoretical value.Obtained title complex Tb (DEPOFnC)
3bright-coloured green emission can be obtained under the exciting of ultraviolet lamp.
Rare earth compounding (i.e. R=PSO in formula VI, base benzene sulfoxide group, Ln=Tb) shown in embodiment 8. synthesis type VI-1
Synthesis step, with embodiment 5, just changes spicy thioalcohol into thiophenol, and 6-bromo-2-pyridinecarboxylic acid changes 6-bromo-2-carboxylic acid thiophene into.Obtain target terbium coordination compound white powder 0.67g.Mass spectroscopy (m/z, ESI): calculated value 911.9, experimental value 912.9 (M+H).Ultimate analysis (mass percentage %): C, 42.92 (42.91); H, 2.43 (2.42), be Tb (PSOTpC) in bracket
30.6H
2o theoretical value.Obtained title complex Tb (PSOTpC)
3bright-coloured green emission can be obtained under the exciting of ultraviolet lamp.
Claims (7)
1., based on a rare earth compounding for aromatic heterocycle carboxylic-acid three tooth anion ligand, general structure is Ln (L)
3, wherein L be the 2-carboxy-pyrid class shown in formula I to III, 2-carboxy-furan class, 2-carboxy-thiophen anionoid part, Ln represents rare earth ion.The structure of corresponding rare earth compounding is such as formula shown in IV to VI:
In formula I-VI, R is phosphine oxygen base, sulfoxide group or sulfuryl.Wherein, phosphine oxygen base form is P (=O) (R
1)
2, sulfoxide form is S (=O) R
1, sulfone form is S (=O) (=O) R
1; A Sauerstoffatom in above-mentioned phosphine oxygen base, sulfoxide group or sulfuryl participates in the coordination with rare earth ion; Above-mentioned R
1for alkyl or aryl, described alkyl is the straight or branched alkyl of C1-C18; Described aryl is phenyl, naphthyl, p-methylphenyl.
2. rare earth compounding as claimed in claim 1, it is characterized in that, described rare earth ion is selected from europium, terbium, dysprosium ion.
3. rare earth compounding as claimed in claim 1, is characterized in that, described phosphine oxygen base P (=O) (R
1)
2, sulfoxide group S (=O) R
1or sulfuryl S (=O) (=O) R
1in R
1for methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-octyl, dodecyl, n-hexadecyl, Octadecane base, phenyl, naphthyl, p-methylphenyl.
4. rare earth compounding as claimed in claim 1, is characterized in that, described phosphine oxygen base P (=O) (R
1)
2, sulfoxide group S (=O) R
1or sulfuryl S (=O) (=O) R
1in R
1for ethyl, normal-butyl, phenyl.
5. the preparation method of the rare earth compounding in Claims 1 to 4 described in any one, adopts three tooth anion ligands, alkali and the rare earth salts shown in formula I-III to react in a solvent, obtained rare earth compounding shown in IV-VI.Wherein, described alkali is selected from oxyhydroxide, carbonate, ammoniacal liquor, organic amine compound, pyridine compounds and their; Described rare earth salts is selected from the hydrochloride of rare earth, nitrate, acetate or trifluoro sulfonate.
6. preparation method as claimed in claim 5, is characterized in that, the mol ratio of three tooth anion ligands, alkali and the rare earth salts reaction shown in described formula I-III is 3: 3: 1; Described solvent is selected from one or more the mixture in following solvent: water, ethanol, methyl alcohol, Virahol, acetone, tetrahydrofuran (THF), acetonitrile, toluene, methylene dichloride, trichloromethane, ether, DMF; The temperature of reaction is-10 ~ 120 DEG C, and the time is 10 minutes ~ 24 hours.
7. the rare earth compounding in Claims 1 to 4 described in any one is as the application of luminescent material.
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| CN105694858B (en) * | 2016-03-18 | 2018-02-23 | 北京石油化工学院 | A kind of green fluorescent material and preparation method thereof |
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| CN109385267A (en) * | 2018-10-12 | 2019-02-26 | 复旦大学 | A kind of rare earth-phosphonic acids ultra-thin two-dimension material and its preparation method and application |
| CN112812049A (en) * | 2020-12-31 | 2021-05-18 | 广东省科学院化工研究所 | Dimethylcholines rare earth complex and preparation method and application thereof |
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