CN102503965B - Rare earth complex with light conversion function and preparation method thereof - Google Patents
Rare earth complex with light conversion function and preparation method thereof Download PDFInfo
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- CN102503965B CN102503965B CN201110315824.4A CN201110315824A CN102503965B CN 102503965 B CN102503965 B CN 102503965B CN 201110315824 A CN201110315824 A CN 201110315824A CN 102503965 B CN102503965 B CN 102503965B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 39
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229910052693 Europium Inorganic materials 0.000 claims description 32
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000013329 compounding Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 18
- 230000007704 transition Effects 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 claims description 7
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000935 solvent evaporation Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 abstract description 10
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 abstract description 7
- -1 life sciences Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract 2
- 239000003814 drug Substances 0.000 abstract 1
- 239000007850 fluorescent dye Substances 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 16
- 150000001793 charged compounds Chemical class 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 230000005284 excitation Effects 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a rare earth complex with the light conversion characteristic and a synthesis method thereof. The synthesis method of the rare earth complex is characterized in that bipyridyl ligand with a pinene functional group reacts with rear earth beta-diketone complex to generate the mixed rare earth complex comprising Beta-diketone and 2,2'- bipyridyl derivatives. The rare earth complex provided by the invention has good light absorption properties in the ultraviolet region and can emit visible light, thereby having the light conversion characteristic. The rare earth complex can be used as the critical material of the light conversion film for improving the spectral response characteristics of the solar cell and can be used as the agricultural light conversion film to increase the light energy utilization rate of the crop. The rare earth complex has important application value and wide application prospect in the aspects of analytical chemistry, medicine, life sciences, fluorescent probes and light-emitting devices, etc.
Description
Technical field
The present invention relates to have rare earth compounding and the synthetic method thereof of light conversion characteristic.
Background technology
Sun power is the inexhaustible sustainable energies of the mankind, fully and to effectively utilize sun power be an important channel that solves current energy dilemma.The spectral range of sun power is very wide, the solar radiation spectral distribution graph recording according to experiment can be found, whole sunlight can be divided into UV-light, and (wavelength is less than 400nm, account for 8.3%), (wavelength is about 400-760nm to visible ray, account for 40.3%) and infrared light (wavelength is greater than 760nm, accounts for 51.4%).But often only have in actual applications the wherein luminous energy of a part to be used effectively.For example, in solar cell, the photon that only has those energy to be greater than its energy gap could produce electron-hole pair in the time being absorbed in material, even and those photons that are less than its energy gap be absorbed and can not produce electron-hole pair (they just make material heating).On the other hand, the growth needs sunlight of plant provides energy, but in sunlight, the light of different wave length can produce different impacts to the growth of plant.Blue light is conducive to the growth of plant leaf, and ruddiness can stimulate chlorophyll to promote photosynthesis, is conducive to the formation of fruit, and purple light and UV-light suppress plant-growth.Therefore, need to develop efficiency light transition material the energy of light is carried out to lower conversion (UV-light is converted into visible ray) or upper conversion (infrared light is converted into can be by light), to improve solar cell and the photosynthesis of plant utilising efficiency to light.
Rare earth compounding is one of the most frequently used light-converting material.The outer electronic structure of rare earth ion uniqueness, makes it forming after organic or mineral compound, easily absorbs near-ultraviolet light and is excited, thereby launch the visible fluorescence transmitting corresponding to central ion.Because f → f transition of electron of rare earth ion itself is Laporte forbidden transition jing, absorption intensity is very low.If make these rare earth ions and there is the organic ligand complexing that uptake factor is higher, shift by intramolecular energy, can obtain the light-converting material of higher photoluminescence efficiency.In recent years, contain mishmetal title complex (for example Eu (TTA) of beta-diketon and pyridine derivate
3and Eu (TTA) (bpy)
3(phen), wherein TTA is 2-thenoyltrifluoroacetone, and bpy is 2,2-dipyridyl, and phen is o-phenanthroline) because its good luminescent properties receives much concern.But, dipyridyl and o-phenanthroline are indifferent at ultraviolet region extinction, simultaneously because the excited energy producing after dipyridyl and o-phenanthroline absorb light is higher, do not mate with rare earth ion excited level, can not carry out effective energy transfer, thereby cause power loss.
Summary of the invention
In order to overcome above-mentioned defect, the technical problem to be solved in the present invention is: in the problem being greater than more than 400nm, provide the rare earth compounding of the light of the following wavelength of a kind of 400nm of absorption for the light absorbing scope of existing smooth transition function title complex.
In order to overcome the defect existing in background technology, the technical solution adopted for the present invention to solve the technical problems is: a kind of rare earth compounding, and its chemical structure is:
In its Chinese style I, II, III, rare earth Ln is europium or terbium, R
1for methyl, phenyl, 2-thienyl or 2-furyl, R
2for methyl, phenyl, trifluoromethyl or the tertiary butyl.
The preparation method of middle-weight rare earths title complex of the present invention, adopts formula IV to react in organic solvent with formula V, formula VI or formula VII, obtains the light transition function title complex of described structural formula I, II or III,
Wherein, rare earth Ln=europium or terbium, R
1for methyl, phenyl, 2-thienyl or 2-furyl, R
2for methyl, phenyl, trifluoromethyl or the tertiary butyl.
Described organic solvent is one or more the mixture in methyl alcohol, ethanol, own nitrile, acetone, tetrahydrofuran (THF), methylene dichloride, chloroform, normal hexane in the present invention.
The described compound of structural formula IV and the mol ratio of the compound of structural formula V, formula VI or formula VII are 1:1 in the present invention.
The described compound of structural formula IV and the temperature of reaction of the compound of structural formula V, formula VI or formula VII are 0～80 DEG C in the present invention, and the reaction times is 1～12 hour.
Also comprising the solid filtering in the solution after reaction is finished or organic solvent evaporation is removed in the present invention, obtains the rare earth compounding of described structural formula I, formula II or formula III.
Beneficial effect: synthesized a class in the present invention with 2 of firpene functional group, 2-bipyridine ligand, due to the strong electron supplying capacity of firpene functional group, gained part maximum absorption band has obvious red shift and photon absorbing intensity obviously to increase, utilize these parts to react with rare earth beta-diketone complex, obtain a class containing beta-diketon and 2, the mixed rare-earth title complex of 2 '-dipyridyl derivatives.The rare earth compounding that obtains has better extinction characteristic in ultraviolet region, have higher fluorescence quantum yield, thereby have good light conversion characteristic under the exciting of UV-light simultaneously.Simultaneously can absorbing wavelength in the UV-light of 200nm～400nm, being converted into wavelength is the visible ray of 620nm left and right.
Brief description of the drawings
Fig. 1 is the europium complex shown in formula IV of the present invention
1h NMR figure;
Fig. 2 is the fluorescence excitation spectrogram (λ of the europium complex shown in formula IV of the present invention
em=614nm)
Fig. 3 is the fluorescent emission spectrogram (λ of the europium complex shown in formula IV of the present invention
ex=316nm)
Embodiment
A class of the present invention has the synthetic method of light transition function rare earth compounding, and its reaction process is as described below:
Rare earth Ln=Eu in its Chinese style I (II, III), Tb, R
1for 2-thienyl, 2-furyl, phenyl, R
2for methyl, trifluoromethyl, the tertiary butyl.
The synthetic method of rare earth compounding of the present invention, its concrete steps are as described below:
Structure is reacted in organic solvent suc as formula the compound of IV with structure suc as formula the compound of V (VI, VII), obtain structure suc as formula light conversion rare earth compounding I (II, III) Suo Shu.
Above-mentioned reaction can be carried out in many organic solvents, for example methyl alcohol, ethanol, own nitrile, acetone, tetrahydrofuran (THF), methylene dichloride, chloroform, a kind of or its mixture in normal hexane.
Taking following embodiment as example, illustrate synthetic method and the effect thereof of the rare earth compounding shown in above-mentioned formula
Embodiment 1, composite structure formula VIII suc as formula shown in europium complex (be Ln=Eu in formula III, R
1for 2-thienyl, R
2trifluoromethyl)
Get compounds Ⅳ (Ln=Eu, R
1for 2-thienyl, R
2trifluoromethyl) 0.05mmol is dissolved in acetone and makes solution A, gets structure and is dissolved in hot ethanol and makes solution B suc as formula the 0.05mmol of ligand compound shown in VII, the solution of B is slowly added drop-wise in solution A.50 DEG C are stirred 1h, and evaporated under reduced pressure solvent, obtains the light yellow solid 58mg of structure suc as formula VIII.
Light yellow solid obtained above is carried out to mass spectrum (ESI) analysis, record molecular ion peak M/Z=1159.99; Ultimate analysis (quality percentage composition): C, 49.63%(49.70%); H, 3.45%(3.48%); N, 2.44%(2.42%), in bracket, be theoretical value.Nuclear magnetic resonance spectrum show above-mentioned light yellow solid product be formula VIII suc as formula shown in europium complex, its
1h NMR composes as shown in Figure 1.
Fluorescence excitation spectrum (the λ of the europium complex that formula institute VIII is shown
ex=316nm) as shown in Figure 2; Fluorescence emission spectrum (the λ of this title complex
em=614nm) as shown in Figure 3.The result of Fig. 2-3 shows, europium complex provided by the present invention has excellent light conversion properties energy.
Embodiment 2, composite structure formula IX suc as formula shown in europium complex (be Ln=Eu in formula III, R
1and R
2be trifluoromethyl)
Get structure suc as formula IV (Ln=Eu, R
1and R
2be trifluoromethyl) shown in compound 0.05mmol be dissolved in acetone and make solution A, get structure and be dissolved in hot ethanol and make solution B suc as formula the 0.05mmol of ligand compound shown in VII, the solution of B is slowly added drop-wise in solution A.50 DEG C are stirred 1h, and evaporated under reduced pressure solvent, obtains structure suc as formula the light yellow solid 55mg shown in IX.
Light yellow solid obtained above is carried out to mass spectrum (ESI) analysis, record molecular ion peak M/Z=1117.61; Ultimate analysis (quality percentage composition): C, 41.88%(41.91%); H, 2.78%(2.80%); N, 2.49%(2.51%), in bracket, be theoretical value.Nuclear magnetic resonance spectrum show above-mentioned light yellow solid product be formula IX suc as formula shown in europium complex,
According to the method for embodiment 1, record and under ultraviolet excitation, present very strong fluorescent emission (λ suc as formula the europium complex shown in IX
em=614nm), show that this title complex has excellent light conversion properties energy.
Embodiment 3, composite structure formula X suc as formula shown in europium complex (be Ln=Eu in formula III, R
1and R
2be methyl)
Get structure suc as formula IV (Ln=Eu, R
1and R
2be methyl) shown in compound 0.05mmol be dissolved in acetone and make solution A, get structure and be dissolved in hot ethanol and make solution B suc as formula the 0.05mmol of ligand compound shown in VII, the solution of B is slowly added drop-wise in solution A.50 DEG C are stirred 1h, and evaporated under reduced pressure solvent, obtains the light yellow solid 39mg of structure suc as formula X.
Light yellow solid obtained above is carried out to mass spectrum (ESI) analysis, record molecular ion peak M/Z=793.78; Ultimate analysis (quality percentage composition): C, 58.95%(59.01%); H, 6.20%(6.22%); N, 3.51%(3.53%), in bracket, be theoretical value.Nuclear magnetic resonance spectrum show above-mentioned light yellow solid product be formula X suc as formula shown in europium complex,
According to the method for embodiment 1, record and under ultraviolet excitation, present very strong fluorescent emission (λ suc as formula the europium complex shown in X
em=614nm), show that this title complex has excellent light conversion properties energy.
Embodiment 4, composite structure formula XI suc as formula shown in europium complex (be Ln=Eu in formula III, R
1for methyl, R
2for trifluoromethyl)
Get structure suc as formula IV (Ln=Eu, R
1for methyl, R
2for trifluoromethyl) shown in compound 0.05mmol be dissolved in acetone and make solution A, get structure and be dissolved in hot ethanol and make solution B suc as formula the 0.05mmol of ligand compound shown in VII, the solution of B is slowly added drop-wise in solution A.50 DEG C are stirred 1h, and evaporated under reduced pressure solvent, obtains the light yellow solid 47mg of structure suc as formula XI.
Light yellow solid obtained above is carried out to mass spectrum (ESI) analysis, record molecular ion peak M/Z=1159.99; Ultimate analysis (quality percentage composition): C, 48.96%(49.01%); H, 4.20%(4.22%); N, 2.90%(2.93%), in bracket, be theoretical value.Nuclear magnetic resonance spectrum show above-mentioned light yellow solid product be formula XI suc as formula shown in europium complex,
According to the method for embodiment 1, record and under ultraviolet excitation, present very strong fluorescent emission (λ suc as formula the europium complex shown in XI
em=614nm), show that this title complex has excellent light conversion properties energy.
Embodiment 5, composite structure formula XII suc as formula shown in europium complex (be Ln=Eu in formula III, R
1for phenyl, R
2for trifluoromethyl)
Get structure suc as formula IV (Ln=Eu, R
1for phenyl, R
2for trifluoromethyl) shown in compound 0.05mmol be dissolved in acetone and make solution A, get structure and be dissolved in hot ethanol and make solution B suc as formula the 0.05mmol of ligand compound shown in VII, the solution of B is slowly added drop-wise in solution A.50 DEG C are stirred 1h, and evaporated under reduced pressure solvent, obtains the light yellow solid 57mg of structure suc as formula XII.
Light yellow solid obtained above is carried out to mass spectrum (ESI) analysis, record molecular ion peak M/Z=1141.90; Ultimate analysis (quality percentage composition): C, 56.75%(56.80%); H, 4.02%(4.06%); N, 2.44%(2.45%), in bracket, be theoretical value.Nuclear magnetic resonance spectrum show above-mentioned light yellow solid product be formula XII suc as formula shown in europium complex,
According to the method for embodiment 1, record and under ultraviolet excitation, present very strong fluorescent emission (λ suc as formula the europium complex shown in XII
em=614nm), show that this title complex has excellent light conversion properties energy.
Embodiment 6, composite structure formula X III suc as formula shown in europium complex (be Ln=Eu in formula III, R
1and R
2be phenyl)
Get structure suc as formula IV (Ln=Eu, R
1and R
2be phenyl) shown in compound 0.05mmol be dissolved in acetone and make solution A, get structure and be dissolved in hot ethanol and make solution B suc as formula the 0.05mmol of ligand compound shown in VII, the solution of B is slowly added drop-wise in solution A.50 DEG C are stirred 1h, and evaporated under reduced pressure solvent, obtains the light yellow solid 58mg of structure suc as formula X III.
Light yellow solid obtained above is carried out to mass spectrum (ESI) analysis, record molecular ion peak M/Z=1166.20; Ultimate analysis (quality percentage composition): C, 71.01%(71.06%); H, 5.23%(5.27%); N, 2.35%(2.40%), in bracket, be theoretical value.Nuclear magnetic resonance spectrum show above-mentioned light yellow solid product be formula X III suc as formula shown in europium complex,
According to the method for embodiment 1, record suc as formula the europium complex shown in X III and under ultraviolet excitation, present very strong fluorescent emission (λ
em=614nm), show that this title complex has excellent light conversion properties energy.
Embodiment 7, composite structure formula X IV suc as formula shown in europium complex (be Ln=Eu in formula III, R
1for 2-furyl, R
2for trifluoromethyl)
Get structure suc as formula IV (Ln=Eu, R
1for 2-furyl, R
2for trifluoromethyl) shown in compound 0.05mmol be dissolved in acetone and make solution A, get structure and be dissolved in hot ethanol and make solution B suc as formula the 0.05mmol of ligand compound shown in VII, the solution of B is slowly added drop-wise in solution A.50 DEG C are stirred 1h, and evaporated under reduced pressure solvent, obtains the light yellow solid 55mg of structure suc as formula X IV.
Light yellow solid obtained above is carried out to mass spectrum (ESI) analysis, record molecular ion peak M/Z=1111.79; Ultimate analysis (quality percentage composition): C, 51.81%(51.85%); H, 3.60%(3.63%); N, 2.49%(2.52%), in bracket, be theoretical value.Nuclear magnetic resonance spectrum show above-mentioned light yellow solid product be formula X IV suc as formula shown in europium complex,
According to the method for embodiment 1, record suc as formula the europium complex shown in X IV and under ultraviolet excitation, present very strong fluorescent emission (λ
em=614nm), show that this title complex has excellent light conversion properties energy.
Embodiment 8, composite structure formula X V suc as formula shown in europium complex (be Ln=Eu in formula III, R
1for methyl, R
2for the tertiary butyl)
Get structure suc as formula IV (Ln=Eu, R
1for methyl, R
2for the tertiary butyl) shown in compound 0.05mmol be dissolved in acetone and make solution A, get structure and be dissolved in hot ethanol and make solution B suc as formula the 0.05mmol of ligand compound shown in VII, the solution of B is slowly added drop-wise in solution A.50 DEG C are stirred 1h, and evaporated under reduced pressure solvent, obtains the light yellow solid 48mg of structure suc as formula X V.
Light yellow solid obtained above is carried out to mass spectrum (ESI) analysis, record molecular ion peak M/Z=968.02; Ultimate analysis (quality percentage composition): C, 59.52%(59.56%); H, 6.92%(6.98%); N, 2.87%(2.89%), in bracket, be theoretical value.Nuclear magnetic resonance spectrum show above-mentioned light yellow solid product be formula X V suc as formula shown in europium complex,
According to the method for embodiment 1, record suc as formula the europium complex shown in X V and under ultraviolet excitation, present very strong fluorescent emission (λ
em=614nm), show that this title complex has excellent light conversion properties energy
Claims (8)
1. a light transition function rare earth compounding, its chemical structure is:
In its Chinese style I, rare earth Ln is europium or terbium, R
1for methyl, phenyl, 2-thienyl or 2-furyl, R
2for methyl, phenyl, trifluoromethyl or the tertiary butyl.
2. smooth transition function rare earth compounding as claimed in claim 1, is characterized in that: described formula I is formula II or formula III, and the chemical structure of formula II and formula III is:
3. the preparation method of smooth transition function rare earth compounding as claimed in claim 1, is characterized in that: adopts formula IV to react in organic solvent with formula V, obtains the light transition function rare earth compounding of described structural formula I,
Wherein, rare earth Ln=europium or terbium, R
1for methyl, phenyl, 2-thienyl or 2-furyl, R
2for methyl, phenyl, trifluoromethyl or the tertiary butyl.
4. the preparation method of smooth transition function rare earth compounding as claimed in claim 3, is characterized in that: described formula V is formula VI or formula VII, and the chemical structure of formula VI and formula VII is:
5. the preparation method of smooth transition function rare earth compounding as claimed in claim 3, is characterized in that: described organic solvent is one or more the mixture in methyl alcohol, ethanol, own nitrile, acetone, tetrahydrofuran (THF), methylene dichloride, chloroform, normal hexane.
6. the preparation method of smooth transition function rare earth compounding as claimed in claim 3, is characterized in that: the mol ratio of the compound of described structural formula IV and the compound of structural formula V is 1:1.
7. the preparation method of smooth transition function rare earth compounding as claimed in claim 3, is characterized in that: the temperature of reaction of the compound of the compound of structural formula IV and structural formula V is 0～80 DEG C, and the reaction times is 1～12 hour.
8. the preparation method of smooth transition function rare earth compounding as claimed in claim 3, is characterized in that: also comprise the solid filtering in the solution after reaction is finished or organic solvent evaporation is removed, obtaining the light transition function rare earth compounding of described structural formula I.
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| CN102964367B (en) * | 2012-12-07 | 2015-02-18 | 中国计量学院 | Rare earth complex luminescent material and preparation method thereof |
| 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 |
| CN103694265B (en) * | 2013-12-31 | 2015-04-15 | 中国计量学院 | Novel light-emitting beta-diketone rare earth complex crystal form material |
| CN103694993B (en) * | 2013-12-31 | 2015-04-15 | 中国计量学院 | Beta-diketone rare earth complex red fluorescent material |
| CN106967101B (en) * | 2017-04-07 | 2019-04-09 | 盐城工学院 | A kind of rare earth organic light conversion agents and anti-aging light conversion film |
| CN106967100B (en) * | 2017-04-07 | 2019-04-09 | 盐城工学院 | A kind of preparation method of rare earth organic light conversion agents Eu (BMPD) nL and anti-aging light conversion film |
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| CN1557907A (en) * | 2004-02-03 | 2004-12-29 | 复旦大学 | Rare earth complexes containing dipyridyl derivatives and their use as electroluminescent materials |
| CN101522787A (en) * | 2006-10-18 | 2009-09-02 | 桑维克股份有限公司 | Fluorescent resin composition and solar battery module using the same |
| CN101671457A (en) * | 2009-09-29 | 2010-03-17 | 苏州福斯特光伏材料有限公司 | Ethene-vinyl acetate composition and application thereof |
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