CN117343723A - Ultralong organic high Wen Linguang doped luminescent material and preparation method thereof - Google Patents
Ultralong organic high Wen Linguang doped luminescent material and preparation method thereof Download PDFInfo
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- CN117343723A CN117343723A CN202311130907.5A CN202311130907A CN117343723A CN 117343723 A CN117343723 A CN 117343723A CN 202311130907 A CN202311130907 A CN 202311130907A CN 117343723 A CN117343723 A CN 117343723A
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims description 52
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 21
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- HCUARRIEZVDMPT-UHFFFAOYSA-N Indole-2-carboxylic acid Chemical compound C1=CC=C2NC(C(=O)O)=CC2=C1 HCUARRIEZVDMPT-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- BGEVROQFKHXUQA-UHFFFAOYSA-N 71012-25-4 Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=C1C1=CC=CC=C1N2 BGEVROQFKHXUQA-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- UGFOTZLGPPWNPY-UHFFFAOYSA-N 7h-benzo[c]carbazole Chemical compound C1=CC=CC2=C3C4=CC=CC=C4NC3=CC=C21 UGFOTZLGPPWNPY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 5
- STJXCDGCXVZHDU-UHFFFAOYSA-N 7H-Dibenzo[c,g]carbazole Chemical compound N1C2=CC=C3C=CC=CC3=C2C2=C1C=CC1=CC=CC=C12 STJXCDGCXVZHDU-UHFFFAOYSA-N 0.000 claims description 4
- YLRBJYMANQKEAW-UHFFFAOYSA-N 1-bromo-4-(bromomethyl)benzene Chemical compound BrCC1=CC=C(Br)C=C1 YLRBJYMANQKEAW-UHFFFAOYSA-N 0.000 claims description 3
- UWXPDFDHSHDGNZ-UHFFFAOYSA-N 7-methylbenzo[c]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1N(C)C1=CC=CC=C12 UWXPDFDHSHDGNZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- SBOZXXIZLLMJJG-UHFFFAOYSA-N n-methyl-7h-dibenzo(c,g)carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1N(C)C1=CC=C(C=CC=C3)C3=C12 SBOZXXIZLLMJJG-UHFFFAOYSA-N 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 230000009977 dual effect Effects 0.000 abstract description 2
- 239000002019 doping agent Substances 0.000 abstract 1
- 229920006254 polymer film Polymers 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 238000005286 illumination Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229940126214 compound 3 Drugs 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000005283 ground state Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 241000235648 Pichia Species 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004297 night vision Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
The invention discloses an ultralong organic high Wen Linguang doped luminescent material and a preparation method thereof, wherein the luminescent material takes planar rigid molecules as objects and rigid polymers as main bodies to realize ultralong high-temperature phosphorescence emission; the planar rigid structure resists thermal vibration of the object at high temperature, while the rigidity of the host further solidifies the high temperature resistance of the object, ultimately, this dual rigidity activates the very long high Wen Linguang performance of the doping system. The dopant material has an ultralong afterglow of 40s at a maximum of 20 ℃, a lifetime of 4.18s, an ultralong afterglow of 20s at a maximum of 4.18s at a maximum of 100 ℃, an ultralong afterglow of about 6s at a maximum of 140 ℃, an afterglow of 0.77s, and an afterglow visible to the naked eye of 1s even at a high temperature of 160 ℃.
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an ultralong organic high Wen Linguang doped luminescent material and a preparation method thereof.
Background
Phosphorescent material (phosphor materials) refers to a material that can phosphoresce under excitation by electromagnetic radiation and ion radiation. Light that remains emitted after excitation is generally considered to be phosphorescence. When the excited body returns to an equilibrium state, a process of light radiation with little heat is generated therewith, which is called fluorescence. The luminescence of long persistence luminescent materials is typically phosphorescent. The crystal comprises single crystal, film, microcrystalline powder, microcrystalline glass, etc. Common are sulfides, oxides, II-IV and IV-V group compounds, rare earth luminescent materials, and the like. Can be used for display screens, fluorescent lamps, ionizing radiation detection, aircraft instrument panels, laser and infrared night vision devices and the like, and has wide application prospect as a display material.
Compared with inorganic noble metal phosphorescent materials, organic phosphorescent materials have the advantages of low cost, strong plasticity, low toxicity and the like, so that the organic phosphorescent materials have attracted a great deal of attention of many scientists in recent years. The host-guest polymer doping strategy is widely considered as one of effective methods for constructing room temperature phosphorescent materials, and the organic Room Temperature Phosphorescent (RTP) materials with long afterglow phenomenon are concerned by research and development personnel at present, and have unique advantages in the fields of anti-counterfeiting, biological diagnosis and treatment, optoelectronic devices and the like.
After the organic material absorbs the excitation energy, electrons transit from the ground state to the excited state, but the excited state energy is unstable, and the electrons easily return to the ground state in a thermal/non-radiative form due to the movement of molecules. More seriously, the high temperature undoubtedly accelerates the movement of the molecules. Thus, triplet excitons formed by intersystem crossing of singlet excitons are extremely sensitive to temperature, are more susceptible to thermal deactivation, and cause afterglow to disappear rapidly at high temperatures. The defect that phosphorescence emission is not resistant to high temperature greatly influences the application range of organic materials, so that the strategy for researching and constructing the ultralong organic high Wen Linguang material is important.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a doped luminescent material with an ultralong organic height Wen Linguang and a preparation method thereof, wherein the luminescent material is high-temperature resistant and has long afterglow.
In order to achieve the above purpose, the present invention provides the following technical solutions:
an ultralong organic high Wen Linguang doped luminescent material comprises the following substances in parts by weight:
1-3 parts of a guest compound;
500-1500 parts of a host polymer;
the guest compound is a planar rigid organic molecule containing not less than 3 benzene ring structures;
the host polymer is polyvinylpyrrolidone.
The polyvinylpyrrolidone is convenient to purchase, low in price and convenient to prepare, has a strong rigid structure, has a glass transition temperature of 180 ℃, and is more beneficial to high temperature resistance.
As a further improvement of the present invention,
the guest compound is benzocarbazole and derivatives thereof;
the number average molecular weight of the polyvinylpyrrolidone is 5 ten thousand to 40 ten thousand.
As a further improvement of the present invention, the guest compound is at least one of 1, 9H-dibenzo [ a, c ] carbazole, 9-methyl-dibenzo [ a, c ] carbazole, 9-n-butyl-dibenzo [ a, c ] carbazole, 9-benzyl-dibenzo [ a, c ] carbazole, 7H-benzo [ c ] carbazole, 7-methyl-benzo [ c ] carbazole, 7H-dibenzo [ c, g ] carbazole, and 7-methyl-dibenzo [ c, g ] carbazole;
the corresponding structural formula is as follows:
wherein 7H-benzo [ c ] carbazole (purchased from Pichia medicine); 7H-dibenzo [ c, g ] carbazole (purchased from Pichia medicine);
as a further improvement of the present invention,
the preparation method of the 1, 9H-dibenzo [ a, c ] carbazole comprises the following steps:
the indole-2-carboxylic acid, dibenzo [ b, d ] iodocyclopentane-5-onium trifluoro methanesulfonate (purchased from medicine after being obtained), palladium acetate, potassium carbonate and acetic acid are uniformly mixed, then reacted for 10-15 hours at the temperature of 130-160 ℃, and separated and purified after the reaction is finished, thus obtaining the product.
As a further improvement of the present invention, the molar ratio between indole-2-carboxylic acid and dibenzo [ b, d ] iodocyclopentane-5-ium triflate is 1:1.1-1.6.
The divalent palladium activates C-H of indole-2-carboxylic acid to obtain intermediate of palladium insertion, and reacts with dibenzo [ b, d ] iodocyclopentane-5-onium triflate to open loop to form intermediate of tetravalent palladium, and the corresponding product is obtained through continuous decarboxylation, oxidative addition and reduction elimination.
As a further improvement of the invention, the preparation method of the 9-benzyl-dibenzo [ a, c ] carbazole comprises the following steps:
stirring a mixture of a compound NaH,1, 9H-dibenzo [ a, c ] carbazole and N, N-dimethylformamide in an ice bath for 5-20 minutes, and stirring at room temperature for 20-40 minutes; and (3) dropwise adding a mixed solution of 4-bromobenzyl bromide and N, N-dimethylformamide after stirring, reacting at room temperature for 10-20 hours, and separating and purifying after the reaction is finished to obtain a product.
As a further development of the invention, the molar ratio between the compound NaH and the 1, 9H-dibenzo [ a, c ] carbazole is 2-5:1.
As a further improvement of the present invention, the preparation method of the luminescent material comprises: according to the set weight parts, preparing raw materials, dissolving a guest compound and a host polymer in dichloromethane (solvent), stirring and mixing, treating for 1-3 hours at 30-50 ℃ and then treating for 12 hours at 80-120 ℃ after uniformly mixing, and thus obtaining the luminescent material.
The invention has the beneficial effects that: according to the invention, a series of rigid molecules with almost complete molecular configurations are selected as objects, and the planar structure of the planar rigid molecules is not changed along with the influence of external force or internal force, so that the planar structure is always maintained. The planar configuration can reduce vibration and rotation of molecules to the maximum extent, so as to reduce triplet excitons consumed by non-radiative transition, enable more triplet excitons to return to a ground state through radiative transition, and enhance phosphorescence performance, so that the rigid configuration is beneficial to prolonging phosphorescence service life and intensity and prolonging afterglow time and brightness. Secondly, polyvinylpyrrolidone with structural rigidity and glass transition temperature of 180 ℃ is selected as a main body, and the polyvinylpyrrolidone has the advantages of convenient purchase, low price, simple preparation and the like. The good rigidity structure can further inhibit the molecular movement of the object, and the ultra-high glass transition temperature can enable the solid to solidify the molecule according to the old good at high temperature, inhibit the vibration and rotation capacity of the object molecule doped in the solid molecule, reduce the non-radiative transition of the doped material and further improve the phosphorescence performance. This dual rigidity allows the doped material to exhibit excellent ultralong organic high Wen Linguang properties so that afterglow can still be observed at 160 ℃.
Drawings
FIG. 1 is a nuclear magnetic resonance diagram of a guest compound 9H-dibenzo [ a, c ] carbazole according to an embodiment of the present invention;
FIG. 2 is a nuclear magnetic resonance diagram of a guest compound 9-methyl-dibenzo [ a, c ] carbazole according to a second embodiment of the present invention;
FIG. 3 is a nuclear magnetic resonance diagram of a guest compound 9-n-butyl-dibenzo [ a, c ] carbazole according to a second embodiment of the present invention;
FIG. 4 is a nuclear magnetic resonance diagram of a guest compound 9-benzyl-dibenzo [ a, c ] carbazole according to a third embodiment of the present invention;
FIG. 5 is a nuclear magnetic resonance diagram of a guest compound 7H-benzo [ c ] carbazole according to a second embodiment of the present invention;
FIG. 6 is a nuclear magnetic resonance diagram of a guest compound 7-methyl-benzo [ c ] carbazole according to a second embodiment of the present invention;
FIG. 7 is a nuclear magnetic resonance diagram of a guest compound 7H-dibenzo [ c, g ] carbazole according to a second embodiment of the present invention;
FIG. 8 is a nuclear magnetic resonance diagram of a guest compound 7-methyl-dibenzo [ c, g ] carbazole according to a second embodiment of the present invention;
FIG. 9 is a graph showing afterglow comparison at different temperatures after illumination of a 380nm ultraviolet lamp according to the fourth embodiment of the invention;
FIG. 10 is a graph showing afterglow comparison at different temperatures after illumination of a 380nm ultraviolet lamp according to the fifth embodiment of the invention;
FIG. 11 is a graph showing afterglow comparison at different temperatures after illumination by a 380nm ultraviolet lamp according to the sixth embodiment of the invention;
FIG. 12 is a graph showing afterglow comparison at different temperatures after illumination of a 380nm ultraviolet lamp according to the seventh embodiment of the invention;
FIG. 13 is a graph showing afterglow comparison at different temperatures after illumination by a 380nm ultraviolet lamp according to the embodiment of the invention;
FIG. 14 is a graph showing afterglow comparison at different temperatures after illumination by a 380nm ultraviolet lamp according to the embodiment of the invention;
FIG. 15 is a graph showing afterglow at different temperatures after illumination by a 380nm ultraviolet lamp according to an embodiment of the present invention;
FIG. 16 is a graph showing the afterglow at different temperatures after irradiation of a 380nm ultraviolet lamp according to the invention.
Detailed Description
The invention will be further described in detail with reference to examples of embodiments shown in the drawings.
Embodiment one: preparation of Compound 1
A mixture of the compound indole-2-carboxylic acid (322.2 mg,2 mmol), cyclodiethyl iodonium salt (1027.2 mg,2.4 mmol), palladium acetate (44.8 mg,0.2 mmol), potassium carbonate (607.3 mg,4.4 mmol) and acetic acid (12 mL) was stirred at 145℃for 12h, after cooling to room temperature, the reaction mixture was poured into dichloromethane (100 mL), washed three times with water (50 mL) and then dried over anhydrous sodium sulfate. After removal of the solvent under reduced pressure, the residue was purified by flash chromatography on silica gel to give compound 1.
The reaction equation is as follows:
embodiment two:
preparation of guest compound 2, compound 3, compound 6, compound 8:
a mixture of the corresponding carbazole (1 mmol) and potassium tert-butoxide (168 mg,1.5 mmol) was dissolved in THF and heated to 50℃before the corresponding iodide (1.4 mmol) was added. After cooling to room temperature, the reaction mixture was poured into dichloromethane (100 mL), washed three times with water (50 mL) and then dried over anhydrous sodium sulfate. After the solvent was removed under reduced pressure, the residue was purified by flash chromatography on silica gel to give the objective guest compounds 2, 3, 6 and 8.
The reaction equation is as follows:
embodiment III: preparation of guest Compound 3
Sodium hydride (120 mg,60% dispersion in mineral oil, 3 mmol) and compound 1 (268 mg,1 mmol) were placed in a round bottom flask and 4mL of N, N-dimethylformamide solution was added and stirred well. Then stirred in an ice bath for 10 minutes and at room temperature for 30 minutes. After half an hour, a mixture of 4-bromobenzyl bromide (205 mg,1.2 mmol) and 4mLN, N-dimethylformamide was added dropwise to the round bottom flask. The reaction mixture was stirred at room temperature overnight. After water quenching, the reaction mixture was poured into dichloromethane (100 mL), washed three times with water (50 mL) and then dried over anhydrous sodium sulfate. After the solvent was removed under reduced pressure, the residue was purified by flash chromatography on silica gel to give the objective compound 3.
The reaction equation is as follows:
and subjecting the guest compounds 1 to 8 to nuclear magnetic resonance detection respectively, as shown in fig. 1 to 8, wherein a is a hydrogen spectrum of the guest compound 1 in fig. 1, and b is a carbon spectrum of the guest compound 1 in fig. 1; FIG. 2 a shows the hydrogen spectrum of the guest compound 2, and FIG. 2 b shows the carbon spectrum of the guest compound 2; FIG. 3 a shows the hydrogen spectrum of the guest compound 3, and FIG. 3 b shows the carbon spectrum of the guest compound 3; FIG. 4 a shows the hydrogen spectrum of the guest compound 4, and FIG. 4 b shows the carbon spectrum of the guest compound 4; FIG. 5 a shows the hydrogen spectrum of the guest compound 5, and FIG. 5 b shows the carbon spectrum of the guest compound 5; FIG. 6 a shows the hydrogen spectrum of the guest compound 6, and FIG. 6 b shows the carbon spectrum of the guest compound 6; FIG. 7 a shows the hydrogen spectrum of the guest compound 7, and FIG. 7 b shows the carbon spectrum of the guest compound 7; in fig. 8, a is a hydrogen spectrum of the guest compound 8, and in fig. 8, b is a carbon spectrum of the guest compound 8.
According to the figures 1 to 8, the compound which has been synthesized is expected to synthesize the target compound
Embodiment four:
mixing the guest compound 1 obtained in the first embodiment with host polymer polyvinylpyrrolidone, wherein the ratio of the guest compound to the host polymer polyvinylpyrrolidone is 1:500, dissolving the mixture with dichloromethane, carrying out ultrasonic treatment for 20 minutes to completely dissolve and uniformly mix the guest compound and the host polymer, pouring the mixture into a mold, drying the mixture in an oven at 40 ℃ for 2 hours, heating the mixture to 100 ℃ for 12 hours, and obtaining the polymer doped luminescent film material, wherein the luminescent color of the polymer doped luminescent film material changes at different temperatures before and after 380nm ultraviolet irradiation for 60 seconds. Refer to fig. 9.
After the polymer film is activated by 380nm ultraviolet lamp light for 60 seconds, blue fluorescence is displayed under the 380nm ultraviolet lamp at 20 ℃, after the ultraviolet lamp is removed, the polymer film displays green ultralong 40 seconds afterglow, and the service life is 4.18 seconds; at 40 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, green 35 seconds afterglow is displayed after the ultraviolet lamp is removed, and the service life is 4.09 seconds; at 60 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, green 30 seconds afterglow is displayed after the ultraviolet lamp is removed, and the service life is 3.72 seconds; at 80 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, green 25 seconds afterglow is displayed after the ultraviolet lamp is removed, and the service life is 3.05 seconds; at 100 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, green 20-second afterglow is displayed, and the service life is 2.17 seconds; at 120 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, green 15 seconds afterglow is displayed after the ultraviolet lamp is removed, and the service life is 1.30 seconds; at 140 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, green 6-second afterglow is displayed, and the service life is 0.77 second; at 160 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the blue fluorescent lamp shows green afterglow for 1 second, and the service life is 0.33 second;
| temperature (temperature) | Phosphorescent wavelength (nm) | Phosphorescent afterglow(s) | Phosphorescent lifetime(s) |
| 20℃ | 487/516 | 40 | 4.18 |
| 40℃ | 486/516 | 35 | 4.09 |
| 60℃ | 485/515 | 30 | 3.72 |
| 80℃ | 485/515 | 25 | 3.05 |
| 100℃ | 484/516 | 20 | 2.17 |
| 120℃ | 484/515 | 15 | 1.30 |
| 140℃ | 483/516 | 6 | 0.77 |
| 160℃ | 484/516 | 1 | 0.33 |
Fifth embodiment:
mixing the guest compound 2 obtained in the second embodiment with host polymer polyvinylpyrrolidone in a ratio of 1:500, dissolving with dichloromethane, performing ultrasonic treatment for 20 minutes to completely dissolve and uniformly mix the guest compound and the host polymer, pouring into a mold, drying at 40 ℃ for 2 hours, heating to 100 ℃ for 12 hours, and obtaining the polymer doped luminescent film material, wherein the luminescent color of the polymer doped luminescent film material changes at different temperatures before and after 380nm ultraviolet irradiation for 60 seconds. Referring to fig. 10.
After the polymer film is activated by 380nm ultraviolet lamp light for 60 seconds, blue fluorescence is displayed under the 380nm ultraviolet lamp at 20 ℃, after the ultraviolet lamp is removed, the polymer film displays yellow green and ultra-long 40 seconds afterglow, and the service life is 4.12 seconds; at 40 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, the fluorescent lamp displays yellow-green afterglow for 35 seconds, and the service life is 3.93 seconds; at 60 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the blue-green 30-second afterglow is displayed, and the service life is 3.63 seconds; at 80 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, the fluorescent lamp displays yellow-green afterglow for 25 seconds, and the service life is 3.08 seconds; at 100 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 20 seconds afterglow is displayed, and the service life is 2.13 seconds; at 120 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, the fluorescent lamp displays yellow-green 15 seconds afterglow, and the service life is 1.32 seconds; at 140 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 6 seconds afterglow is displayed, and the service life is 0.75 seconds; at 160 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 1 second afterglow is displayed, and the service life is 0.34 second;
| temperature (temperature) | Phosphorescent wavelength (nm) | Phosphorescent afterglow(s) | Phosphorescent lifetime(s) |
| 20℃ | 494/525 | 40 | 4.12 |
| 40℃ | 495/525 | 35 | 3.93 |
| 60℃ | 495/526 | 30 | 3.63 |
| 80℃ | 495/525 | 25 | 3.08 |
| 100℃ | 494/525 | 20 | 2.13 |
| 120℃ | 496/524 | 15 | 1.32 |
| 140℃ | 495/523 | 6 | 0.75 |
| 160℃ | 496/526 | 1 | 0.34 |
Example six:
mixing the guest compound 3 obtained in the second embodiment with host polymer polyvinylpyrrolidone in a ratio of 1:500, dissolving with dichloromethane, performing ultrasonic treatment for 20 minutes to completely dissolve and uniformly mix the guest compound and the host polymer, pouring into a mold, drying at 40 ℃ for 2 hours, heating to 100 ℃ for 12 hours, and obtaining the polymer doped luminescent film material, wherein the luminescent color of the polymer doped luminescent film material changes at different temperatures before and after 380nm ultraviolet irradiation for 60 seconds. Refer to fig. 11.
After the polymer film is activated by 380nm ultraviolet lamp light for 60 seconds, blue fluorescence is displayed under the 380nm ultraviolet lamp at 20 ℃, after the ultraviolet lamp is removed, the polymer film displays yellow green and ultra-long 40 seconds afterglow, and the service life is 4.14 seconds; at 40 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, the fluorescent lamp displays yellow-green afterglow for 35 seconds, and the service life is 3.96 seconds; at 60 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the blue-green 30-second afterglow is displayed, and the service life is 3.53 seconds; at 80 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, the fluorescent lamp displays yellow-green afterglow for 25 seconds, and the service life is 2.95 seconds; at 100 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 20 seconds afterglow is displayed, and the service life is 2.16 seconds; at 120 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, the fluorescent lamp displays yellow-green 15 seconds afterglow, and the service life is 1.22 seconds; at 140 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 6 seconds afterglow is displayed, and the service life is 0.74 seconds; at 160 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 1 second afterglow is displayed, and the service life is 0.32 second;
| temperature (temperature) | Phosphorescent wavelength (nm) | Phosphorescent afterglow(s) | Phosphorescent lifetime(s) |
| 20℃ | 493/525 | 40 | 4.14 |
| 40℃ | 494/525 | 35 | 3.96 |
| 60℃ | 495/525 | 30 | 3.53 |
| 80℃ | 496/526 | 25 | 2.95 |
| 100℃ | 496/527 | 20 | 2.16 |
| 120℃ | 496/525 | 15 | 1.22 |
| 140℃ | 494/524 | 6 | 0.74 |
| 160℃ | 495/525 | 1 | 0.32 |
Embodiment seven:
mixing the guest compound 4 obtained in the third embodiment with host polymer polyvinylpyrrolidone, wherein the ratio of the guest compound to the host polymer polyvinylpyrrolidone is 1:500, dissolving the mixture with dichloromethane, carrying out ultrasonic treatment for 20 minutes to completely dissolve and uniformly mix the guest compound and the host polymer, pouring the mixture into a mold, drying the mixture in an oven at 40 ℃ for 2 hours, heating the mixture to 100 ℃ for 12 hours, and obtaining the polymer doped luminescent film material, wherein the luminescent color of the polymer doped luminescent film material changes at different temperatures before and after 380nm ultraviolet irradiation for 60 seconds. Refer to fig. 12.
After the polymer film is activated by 380nm ultraviolet lamp light for 60 seconds, blue fluorescence is displayed under the 380nm ultraviolet lamp at 20 ℃, and after the ultraviolet lamp is removed, the polymer film displays yellow green and ultra-long 36 seconds afterglow, and the service life is 3.88 seconds; at 40 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 31 seconds afterglow is displayed, and the service life is 3.45 seconds; at 60 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green afterglow is displayed for 26 seconds, and the service life is 3.09 seconds; at 80deg.C, blue fluorescence is shown under 380nm ultraviolet lamp, after removing ultraviolet lamp, yellow-green 20 second afterglow is shown, and at 100deg.C, 2.51 blue fluorescence is shown under 380nm ultraviolet lamp, after removing ultraviolet lamp, yellow-green 15 second afterglow is shown, and the lifetime is 1.66 second; at 120 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 95 seconds afterglow is displayed, and the service life is 1.00 seconds; at 140 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 6 seconds afterglow is displayed, and the service life is 0.66 seconds; at 150 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 1 second afterglow is displayed, and the service life is 0.38 second;
| temperature (temperature) | Phosphorescent wavelength (nm) | Phosphorescent afterglow(s) | Phosphorescent lifetime(s) |
| 20℃ | 494/525 | 36 | 3.88 |
| 40℃ | 495/525 | 31 | 3.45 |
| 60℃ | 495/526 | 26 | 3.09 |
| 80℃ | 495/525 | 20 | 2.51 |
| 100℃ | 494/525 | 15 | 1.66 |
| 120℃ | 496/524 | 9 | 1.00 |
| 140℃ | 495/523 | 4 | 0.66 |
| 150℃ | 496/526 | 1 | 0.38 |
Example eight:
mixing the guest compound 5 obtained in the second embodiment with host polymer polyvinylpyrrolidone in a ratio of 1:500, dissolving with dichloromethane, performing ultrasonic treatment for 20 minutes to completely dissolve and uniformly mix the guest compound and the host polymer, pouring into a mold, drying at 40 ℃ for 2 hours, heating to 100 ℃ for 12 hours, and obtaining the polymer doped luminescent film material, wherein the luminescent color of the polymer doped luminescent film material changes at different temperatures before and after 380nm ultraviolet irradiation for 60 seconds. Refer to fig. 13.
After the polymer film is activated by 380nm ultraviolet lamp light for 60 seconds, blue fluorescence is displayed under the 380nm ultraviolet lamp at 20 ℃, after the ultraviolet lamp is removed, the polymer film displays yellow green and ultra-long 22 seconds afterglow, and the service life is 2.40 seconds; at 40 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, yellow green 19 seconds afterglow is displayed, and the service life is 2.12 seconds; at 60 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, the fluorescent lamp displays yellow-green 16 seconds afterglow, and the service life is 1.40 seconds; at 80 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 12-second afterglow is displayed, the service life is 1.40 seconds, at 100 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 8-second afterglow is displayed, and the service life is 0.87 seconds; at 120 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 6 seconds afterglow is displayed, and the service life is 0.63 seconds; at 140 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the fluorescent lamp displays yellow-green 3 seconds afterglow, and the service life is 0.48 seconds; at 160 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the fluorescent lamp shows yellow-green afterglow for 0.5 seconds, and the service life is 0.09 seconds;
| temperature (temperature) | Phosphorescent wavelength (nm) | Phosphorescent afterglow(s) | Phosphorescent lifetime(s) |
| 20℃ | 491/527 | 22 | 2.40 |
| 40℃ | 492/527 | 19 | 2.12 |
| 60℃ | 492/527 | 16 | 1.81 |
| 80℃ | 492/527 | 12 | 1.40 |
| 100℃ | 493/528 | 8 | 0.87 |
| 120℃ | 493/529 | 6 | 0.63 |
| 140℃ | 492/528 | 3 | 0.48 |
| 160℃ | 493/528 | 0.6 | 0.09 |
Example nine:
mixing the guest compound 6 obtained in the second embodiment with host polymer polyvinylpyrrolidone in a ratio of 1:500, dissolving with dichloromethane, performing ultrasonic treatment for 20 minutes to completely dissolve and uniformly mix the guest compound and the host polymer, pouring into a mold, drying at 40 ℃ for 2 hours, heating to 100 ℃ for 12 hours, and obtaining the polymer doped luminescent film material, wherein the luminescent color of the polymer doped luminescent film material changes at different temperatures before and after 380nm ultraviolet irradiation for 60 seconds. Refer to fig. 14.
After the polymer film is activated by 380nm ultraviolet lamp light for 60 seconds, blue fluorescence is displayed under the 380nm ultraviolet lamp at 20 ℃, after the ultraviolet lamp is removed, the polymer film displays yellow green and ultra-long 22 seconds afterglow, and the service life is 2.23 seconds; at 40 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, yellow green 19 seconds afterglow is displayed, and the service life is 2.03 seconds; at 60 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, yellow green 16 seconds afterglow is displayed, and the service life is 1.73; at 80 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, yellow-green 11 afterglow is displayed after the ultraviolet lamp is removed, the service life is 1.31, blue fluorescence is displayed under a 380nm ultraviolet lamp, yellow-green 7 afterglow is displayed after the ultraviolet lamp is removed, and the service life is 0.76 seconds; at 120 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow-green 5 seconds afterglow is displayed, and the service life is 0.58 seconds; at 140 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the fluorescent lamp displays yellow-green afterglow for 2 seconds, and the service life is 0.33 seconds; at 160 ℃, blue fluorescence is shown under a 380nm ultraviolet lamp, and after the ultraviolet lamp is removed, the fluorescent lamp shows yellow-green afterglow for 0.5 seconds, and the service life is 0.08 seconds.
| Temperature (temperature) | Phosphorescent wavelength (nm) | Phosphorescent afterglow(s) | Phosphorescent lifetime(s) |
| 20℃ | 493/529 | 22 | 2.23 |
| 40℃ | 494/530 | 19 | 2.03 |
| 60℃ | 494/531 | 16 | 1.73 |
| 80℃ | 495/530 | 11 | 1.31 |
| 100℃ | 494/531 | 7 | 0.76 |
| 120℃ | 495/532 | 5 | 0.58 |
| 140℃ | 493/531 | 2 | 0.33 |
| 160℃ | 493/530 | 0.5 | 0.08 |
Example ten:
mixing the guest compound 7 obtained in the second embodiment with host polymer polyvinylpyrrolidone in a ratio of 1:500, dissolving with dichloromethane, performing ultrasonic treatment for 20 minutes to completely dissolve and uniformly mix the guest compound and the host polymer, pouring into a mold, drying at 40 ℃ for 2 hours, heating to 100 ℃ for 12 hours, and obtaining the polymer doped luminescent film material, wherein the luminescent color of the polymer doped luminescent film material changes at different temperatures before and after 380nm ultraviolet irradiation for 60 seconds. Refer to fig. 15.
After the polymer film is activated by 380nm ultraviolet lamp light for 60 seconds, blue fluorescence is displayed under the 380nm ultraviolet lamp at 20 ℃, after the ultraviolet lamp is removed, the polymer film displays yellow and ultralong 13 seconds afterglow, and the service life is 1.38 seconds; at 40 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, yellow afterglow is displayed for 12 seconds after the ultraviolet lamp is removed, and the service life is 1.36 seconds; at 60 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the fluorescent lamp shows yellow afterglow for 10 seconds, and the service life is 1.26 seconds; at 80 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow 8-second afterglow is displayed, the service life is 1.12 seconds, at 100 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow 7-second afterglow is displayed, and the service life is 0.94 seconds; at 120 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the fluorescent lamp displays yellow 5 seconds afterglow, and the service life is 0.68 seconds; at 140 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the fluorescent lamp displays yellow 3 seconds afterglow, and the service life is 0.48 seconds; at 160℃blue fluorescence was exhibited under a 380nm UV lamp, after removal of the UV lamp, a yellow 1 second afterglow was exhibited, with a lifetime of 0.25 seconds.
| Temperature (temperature) | Phosphorescent wavelength (nm) | Phosphorescent afterglow(s) | Phosphorescent lifetime(s) |
| 20℃ | 516/556 | 13 | 1.38 |
| 40℃ | 516/555 | 12 | 1.36 |
| 60℃ | 517/555 | 10 | 1.26 |
| 80℃ | 518/556 | 8 | 1.12 |
| 100℃ | 518/554 | 7 | 0.94 |
| 120℃ | 518/555 | 5 | 0.68 |
| 140℃ | 518/554 | 3 | 0.48 |
| 160℃ | 517/555 | 1 | 0.25 |
Example eleven:
mixing the guest compound 8 obtained in the second embodiment with host polymer polyvinylpyrrolidone in a ratio of 1:500, dissolving with dichloromethane, performing ultrasonic treatment for 20 minutes to completely dissolve and uniformly mix the guest compound and the host polymer, pouring into a mold, drying at 40 ℃ for 2 hours, heating to 100 ℃ for 12 hours, and obtaining the polymer doped luminescent film material, wherein the luminescent color of the polymer doped luminescent film material changes at different temperatures before and after 380nm ultraviolet irradiation for 60 seconds. Refer to fig. 16.
After the polymer film is activated by 380nm ultraviolet lamp light for 60 seconds, blue fluorescence is displayed under the 380nm ultraviolet lamp at 20 ℃, after the ultraviolet lamp is removed, the polymer film displays yellow and ultralong 13 seconds afterglow, and the service life is 1.32 seconds; at 40 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, yellow afterglow is displayed for 11 seconds after the ultraviolet lamp is removed, and the service life is 1.21 seconds; at 60 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the fluorescent lamp displays yellow afterglow for 9 seconds, and the service life is 1.12 seconds; at 80 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow 8-second afterglow is displayed, the service life is 1.02 seconds, at 100 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, yellow 7-second afterglow is displayed, and the service life is 0.89 seconds; at 120 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the fluorescent lamp displays yellow 5 seconds afterglow, and the service life is 0.62 seconds; at 140 ℃, blue fluorescence is displayed under a 380nm ultraviolet lamp, after the ultraviolet lamp is removed, the fluorescent lamp displays yellow 3 seconds afterglow, and the service life is 0.41 seconds; at 160℃blue fluorescence was exhibited under a 380nm UV lamp, after removal of the UV lamp, a yellow 1 second afterglow was exhibited, with a lifetime of 0.22 seconds.
| Temperature (temperature) | Phosphorescent wavelength (nm) | Phosphorescent afterglow(s) | Phosphorescent lifetime(s) |
| 20℃ | 523/561 | 13 | 1.32 |
| 40℃ | 522/562 | 11 | 1.21 |
| 60℃ | 523/562 | 9 | 1.12 |
| 80℃ | 522/562 | 8 | 1.02 |
| 100℃ | 523/563 | 7 | 0.89 |
| 120℃ | 522/562 | 5 | 0.62 |
| 140℃ | 523/562 | 3 | 0.41 |
| 160℃ | 523/563 | 1 | 0.22 |
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (8)
1. An ultralong organic high Wen Linguang doped luminescent material, characterized in that: comprises the following materials in parts by weight:
1-3 parts of a guest compound;
500-1500 parts of a host polymer;
the guest compound is a planar rigid organic molecule containing not less than 3 benzene ring structures;
the host polymer is polyvinylpyrrolidone.
2. The ultra-long organic high Wen Linguang doped luminescent material of claim 1, wherein:
the guest compound is benzocarbazole and derivatives thereof;
the number average molecular weight of the polyvinylpyrrolidone is 5 ten thousand to 40 ten thousand.
3. The ultra-long organic high Wen Linguang doped luminescent material of claim 1, wherein: the guest compound is at least one of 1, 9H-dibenzo [ a, c ] carbazole, 9-methyl-dibenzo [ a, c ] carbazole, 9-n-butyl-dibenzo [ a, c ] carbazole, 9-benzyl-dibenzo [ a, c ] carbazole, 7H-benzo [ c ] carbazole, 7-methyl-benzo [ c ] carbazole, 7H-dibenzo [ c, g ] carbazole and 7-methyl-dibenzo [ c, g ] carbazole.
4. An ultralong organic high Wen Linguang doped luminescent material according to claim 3, wherein: the preparation method of the 1, 9H-dibenzo [ a, c ] carbazole comprises the following steps:
the indole-2-carboxylic acid, dibenzo [ b, d ] iodocyclopentane-5-onium triflate, palladium acetate, potassium carbonate and acetic acid are mixed uniformly and then reacted for 10 to 15 hours at the temperature of 130 to 160 ℃, and after the reaction is finished, the separation and purification are carried out, thus obtaining the product.
5. The ultra-long organic high Wen Linguang doped luminescent material of claim 4, wherein: the molar ratio between indole-2-carboxylic acid and dibenzo [ b, d ] iodocyclopentane-5-ium triflate was 1:1.1-1.6.
6. An ultralong organic high Wen Linguang doped luminescent material according to claim 3, wherein: the preparation method of the 9-benzyl-dibenzo [ a, c ] carbazole comprises the following steps:
stirring a mixture of a compound NaH,1, 9H-dibenzo [ a, c ] carbazole and N, N-dimethylformamide in an ice bath for 5-20 minutes, and stirring at room temperature for 20-40 minutes; and (3) dropwise adding a mixed solution of 4-bromobenzyl bromide and N, N-dimethylformamide after stirring, reacting at room temperature for 10-20 hours, and separating and purifying after the reaction is finished to obtain a product.
7. The ultra-long organic high Wen Linguang doped luminescent material of claim 6, wherein: the molar ratio between the compound NaH and the 1, 9H-dibenzo [ a, c ] carbazole is 2-5:1.
8. The method for preparing the ultralong organic high Wen Linguang doped luminescent material according to any one of claims 1 to 7, wherein: according to the set weight parts, preparing raw materials, dissolving a guest compound and a host polymer in dichloromethane, stirring and mixing, treating for 1-3 hours at the temperature of 30-50 ℃ after uniformly mixing, and then treating for 12 hours at the temperature of 80-120 ℃ to prepare the luminescent material.
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