CN116355130B - Organic long afterglow polymer with blue light or full-color circular polarized luminescence and preparation method thereof - Google Patents
Organic long afterglow polymer with blue light or full-color circular polarized luminescence and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000002796 luminescence method Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 39
- 238000004020 luminiscence type Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 16
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007850 fluorescent dye Substances 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 229920006254 polymer film Polymers 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- TUFFYSFVSYUHPA-UHFFFAOYSA-M rhodamine 123 Chemical compound [Cl-].COC(=O)C1=CC=CC=C1C1=C(C=CC(N)=C2)C2=[O+]C2=C1C=CC(N)=C2 TUFFYSFVSYUHPA-UHFFFAOYSA-M 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims 1
- 229940020947 fluorescein sodium Drugs 0.000 claims 1
- 230000010287 polarization Effects 0.000 abstract description 13
- 238000013461 design Methods 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NJDNXYGOVLYJHP-UHFFFAOYSA-L disodium;2-(3-oxido-6-oxoxanthen-9-yl)benzoate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=CC(=O)C=C2OC2=CC([O-])=CC=C21 NJDNXYGOVLYJHP-UHFFFAOYSA-L 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001296 phosphorescence spectrum Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- -1 9H-carbazolyl-9-yl Chemical group 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002165 resonance energy transfer Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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Abstract
The invention discloses an organic long afterglow polymer with blue light or full-color circular polarization luminescence and a preparation method thereof, which belong to the field of organic luminescent materials, and specifically designs and prepares the organic long afterglow polymer with blue light circular polarization luminescence, compared with the current chiral long afterglow material: the fluorescent lamp does not contain halogen, is simple to prepare, has ultra-long afterglow luminescence in a film state, and has the service life of 3 s; meanwhile, the afterglow has excellent luminous asymmetry factorg lum ) Up to-7.8X10 ‑3 . And a strategy for constructing a full-color circular polarization organic long afterglow material through energy and chiral cooperative transmission is provided, the blue light circular polarization organic long afterglow polymer is used as a host material and some commercial water-soluble organic fluorescent materials are used as guest materials, the blue light circular polarization organic long afterglow polymer and the commercial water-soluble organic fluorescent materials are physically blended according to a certain proportion, and a full-color CPRTP system with blue light, red light and white light is successfully prepared through double transmission of triplet energy and chirality.
Description
Technical Field
The invention belongs to the field of organic luminescent materials, and particularly relates to an organic long afterglow polymer with blue light or full-color circularly polarized luminescence and a preparation method thereof.
Background
The pure organic Room Temperature Phosphorescence (RTP) material has the characteristics of long light emission life, good processing performance, large Stokes shift and the like, and is widely paid attention to in academic circles in recent years. In the design of RTP molecules, functional RTP molecules and materials with Circular Polarized Luminescence (CPL) property are gradually becoming scientific leading-edge research. At present, a circular polarization organic room temperature phosphorescence (CPRTP) material is used as a novel optical functional material, has the advantages of obvious spatial resolution, optical sensitivity, flexibility, biocompatibility and the like, has wide application prospect in the fields of multiple encryption anti-counterfeiting, three-dimensional optical imaging, chiral sensing and the like, and becomes a focus of attention. However, most of the reported organic circularly polarized light emitting materials are mainly focused on organic fluorescent materials with high brightness and high efficiency and thermally activated delayed fluorescent materials, whereas CPRTP materials with an ultra-long lifetime of more than 1s are rarely reported. The preparation of high performance CPRTP materials with very long lifetimes remains a difficult challenge because triplet excitons of organic optoelectronic materials are easily quenched by water and oxygen and non-radiative transitions are easily taken place at room temperature.
Full color luminescence is particularly important in optoelectronic applications such as multicolor displays, multicolor bioimaging, high density encryption storage, and the like. Currently, most scholars consider that the luminescence of chiral organic long afterglow is the aggregated luminescence of molecules, and the luminescence color of the material becomes red shift, so most of chiral organic long afterglow colors reported at present are green and yellow. The regulation and control of the chiral organic long afterglow luminescence color is generally realized by regulating the accumulation state of molecules to form different aggregation states or modifying the luminescence groups with different colors. However, these methods have poor experimental reproducibility and insufficiently accurate adjustment of the emission color, so that preparing chiral organic long afterglow materials with full color emission remains a significant challenge.
Disclosure of Invention
The invention provides a strategy for constructing a full-color circular polarization organic long afterglow material through energy and chiral cooperative transmission, and a proper chiral transmission distance and a stable molecular configuration are important factors for realizing the strategy. By reasonable moleculesThe design is that chiral acrylic acid 2- ((2- (9H-carbazolyl-9-yl) propionyl) oxy) ethyl ester (R/S-VCOOCz) is synthesized for the first time, and then is subjected to free radical copolymerization with acrylamide to obtain blue light organic long afterglow polymers S-PAMCOOCz and R-PAMCOOCz with CPL properties. The polymer is used as a host material and a plurality of commercial water-soluble organic fluorescent materials are used as guest materials, and then the host material and the guest materials are physically blended according to a certain proportion, and a full-color CPRTP system with blue light, red light and white light is successfully prepared by applying a Flank process through double transfer of triplet energy and chirality. The afterglow life of the polymer of the system can reach 3s and chiral asymmetry factorg lum The I can reach 7.8x10 -3 。
The technical scheme is as follows:
the organic long afterglow polymer with blue light circular polarized luminescence related in the full-color chiral organic long afterglow material system has the structure as shown in the formula (I) and the formula (II):
(I)；
(II)；
wherein x=1, y=100;
the structures of the organic fluorescent dye sodium fluorescein, rhodamine 123 and sulforhodamine related by the system are respectively shown as a formula (III), a formula (IV) and a formula (V):
(III)；
(Ⅳ)；
(Ⅴ)。
another object of the present invention is a process for the preparation of an organic long afterglow polymer having the emission of blue light circularly polarized light comprising the steps of:
s1, under the argon atmosphere, carbazole and sodium hydride are dissolved in tetrahydrofuran solution under ice water bath, and then S-2-methyl chloropropionate or R-2-methyl chloropropionate is injected into a reaction bottle to react to obtain a system A;
s2, adding tetrahydrofuran and methanol into the reaction system A, adding a sodium hydroxide solution (0.074 g/mL) by using a syringe, and after the reaction is finished, dropwise adding concentrated hydrochloric acid (12 mol/L) into the reaction solution until white precipitate is completely separated out to obtain a system B;
s3, EDCI and 4-dimethylaminopyridine are added into the reaction system B, and methylene dichloride solution is added under ice water bath. Adding 2-hydroxyethyl acrylate into the mixture by using a syringe to react to obtain a system C;
s4, dissolving the reaction system C, acrylamide and azodiisobutyronitrile in tetrahydrofuran solution under argon atmosphere, dropwise adding the reaction solution into methanol after the reaction is finished, precipitating white precipitate, filtering and collecting white solid to obtain the R/S-PAMCOOCz polymer system.
Based on the method, the preparation method of the organic long afterglow polymer with full-color circular polarized luminescence comprises the following steps:
dissolving R-PAMCOOCz or S-PAMCOOCz in deionized water, and performing ultrasonic dissolution; subsequently, the water-soluble organic fluorescent dye sodium fluorescein (Fluc) was incorporated into the solution in a mass ratio of 0.1wt.% and stirred until the solution was clear; finally, pouring the fully mixed solution into a culture dish, and drying to obtain a green chiral organic long afterglow polymer film material; according to the method, organic fluorescent dyes rhodamine 123 (Rh 123) and sulforhodamine (SR 101) with the mass ratio of 0.1wt.% are respectively added, so that yellow and red chiral organic long afterglow polymer film materials are obtained.
Preferably, in step S1, the tetrahydrofuran solution is added to maintain the system temperature at 0℃and S-2-methyl chloropropionate or R-2-methyl chloropropionate needs to be added at room temperature. The molar ratio of carbazole to sodium hydride to S-2-methyl chloropropionate (or R-2-methyl chloropropionate) is 1:1.2:1.2, and the reaction time is 12-16h; water and methylene chloride are used in the extraction step.
Preferably, in the step S2, the reaction time is 4-6 hours; the reaction temperature is 55 ℃; the volume ratio of tetrahydrofuran to methanol is 2:1.
Preferably, in step S3, the reaction time is 12-16 hours; the reaction temperature is room temperature; water and methylene dichloride are adopted in the extraction step; the molar ratio of the system B, EDCI, 4-dimethylaminopyridine to the 2-hydroxyethyl acrylate is 2:1:1:2.4.
Preferably, in step S4, the reaction time is 12-16 hours; the reaction temperature is 55 ℃; methanol is adopted in the sedimentation step; the mol ratio of the system C to the acrylamide is 1:100; the molar mass of the azodiisobutyronitrile is 1 percent of the total mole of the reaction system.
Preferably, the preparation method of the organic long afterglow polymer with blue light circularly polarized luminescence has the dissolution temperature of 50-60 ℃; the drying temperature was 70 ℃.
The full-color chiral organic long afterglow polymer can be applied to the field of anti-counterfeiting encryption.
The invention has the beneficial effects that:
1. compared with the prior art, the invention carries out chemical modification of chiral alkyl chain on carbazole monomer, then carries out copolymerization on carbazole monomer and acrylamide to obtain blue light polymer long afterglow materials R-PAMCOOCz and S-PAMCOOCz with circular polarization, and induces a molecular rigid environment through a hydrogen bond network with dense polymer matrix so as to stabilize triplet state excitons and chiral configuration, so that afterglow service life of the polymer can reach 3S and chiral asymmetry factorg lum The I can reach 7.8x10 -3 。
2. In view of the excellent afterglow performance and circular polarization property of R/S-PAMCOOCz, the R/S-PAMCOOCz is used as an energy donor material (host) to be physically blended with some commercial water-soluble achiral fluorescent dyes (objects) according to a certain proportion, and a series of full-color organic long afterglow materials with circular polarization properties from blue light to red and white are prepared through the F-channel resonance energy transfer from a host triplet state to an object singlet state. The obtained full-color organic long afterglow material has a luminous life of more than 1s and |g lum The I all reach 10 -3 The above.
3. The invention successfully realizes the dual transfer of intermolecular triplet energy and chirality, provides a universal strategy for expanding colorful circular polarization luminescent organic materials, and provides a feasible and effective design idea for constructing multifunctional organic long afterglow materials with near infrared luminescence, stimulus response and the like.
Drawings
FIG. 1 is a photoluminescence spectrum and steady state phosphorescent lifetime of an organic long afterglow polymer R/S-PAMCOOCz having circularly polarized luminescence of blue light;
FIG. 2 shows CPL spectra and sum of organic long afterglow polymers R/S-PAMCOOCz with blue light circularly polarized luminescenceg lum ；
FIG. 3 shows the phosphorescence spectrum of R-PAMCOOCz film and the absorption spectrum of Fluc, rh123, SR101 in solution, photoluminescence spectra of different Fluc contents and lifetime;
FIG. 4 shows CPL spectrum and g of the Fluc/R-PAMCOOCz system lum ；
FIG. 5 shows photoluminescence spectra, lifetime and CPL spectra of Rh123/R-PAMCOOCz system and SR101/R-PAMCOOCz system;
FIG. 6 is a full color circularly polarized light emitting organic long persistence polymer system g lum 。
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1: synthesis of chiral monomer R/S-COOCz
Carbazole (3 g,0.018 mol) and sodium hydride (0.518 g,0.022 mol) were placed in a 250mL double-necked flask under argon atmosphere, then 25mL tetrahydrofuran was added under ice-water bath, and the reaction was stirred at room temperature for 1h. Subsequently, methyl R/S-2-chloropropionate (2.4 mL,0.022 mol) was rapidly injected into the reaction flask, and stirred at room temperature for 12 hours. After the completion of the reaction, the reaction solution was extracted three times with 50mL of water and 200mL of methylene chloride, and the lower organic phase solution was collected and dried over anhydrous sodium sulfate for 4 hours. Finally, the crude product obtained was purified by silica gel column chromatography with dichloromethane and petroleum ether (V: v=1:1) and yielded 2.8g of a pure white solid (yield 61.1%). 1HNMR (400 MHz, CDCl3, ppm): delta 8.02 (t, J=8.6 Hz, 2H), 7.37 (t, J=7.6 Hz, 2H), 7.29 (d, J=8.2 Hz, 2H), 7.18 (t, J=7.3 Hz, 2H), 5.35 (q, J=7.2 Hz, 1H), 3.61 (s, 3H), 1.76 (d, J=7.2 Hz, 3H). The structure is as follows:
example 2: synthesis of chiral monomer R/S-COOHCz
R/S-COOCz (1 g,0.004 mol) was placed in a 250mL double-necked flask, followed by addition of 20mL of tetrahydrofuran and 10mL of methanol, and stirring at room temperature for 10min. After the solid was completely dissolved, 20mL of sodium hydroxide solution (0.074 g/mL) was added by syringe and reacted at 55℃for 4 hours. After the reaction, the reaction solution was cooled to room temperature, and the organic solvent was dried by spin drying. Subsequently, concentrated hydrochloric acid (12 mol/L) was added dropwise until the white precipitate was completely separated out, and the precipitate was washed with water, filtered and dried to give 0.738g of a gray solid (yield: 77.2%). 1HNMR (400 MHz, DMSO-d6,ppm):δ13.09(s,1H),8.16(d,J=7.7Hz,2H),7.53(d,J=8.2Hz,2H),7.43(t,J=7.6Hz,2H),7.21(t,J=7.4Hz,2H),5.77(q,J=6.9Hz,1H),1.68(d,J=7.1 hz,3 h). The structure is as follows:
example 3: synthesis of chiral monomer R/S-VCOOCz
R/S-COOHCz (0.36 g,0.0015 mol),EDCI (0.144 g,0.00075 mol) and 4-dimethylaminopyridine (0.0915 g,0.00075 mol) were placed in a 250mL double-necked flask, 20mL of methylene chloride was added under an ice-water bath, and stirred for 20min. After the solid was completely dissolved, 2-hydroxyethyl acrylate (0.209 g,0.0018 mol) was added by syringe and stirred at room temperature for 12h. After the reaction was completed, the reaction solution was extracted 3 times with water and methylene chloride, and the organic phase was collected and dried over anhydrous sodium sulfate. Finally, the obtained crude product was purified by silica gel column chromatography with ethyl acetate and petroleum ether (V: v=1:3), and 0.1653g of a yellow oil was obtained (yield: 32.7%). 1HNMR (400 MHz, CDCl3, ppm): delta 8.02 (d,J=7.7Hz,2H),7.36(t,J=7.5Hz,2H),7.30(d,J=8.2Hz,2H),7.18-7.11(m,2H),6.13(d,J=17.3Hz,1H),5.84(dd,J=17.3,10.4Hz,1H),5.68(d,J=10.5Hz,1H),5.37(q,J=7.3Hz,1H),4.35-4.02(m,4H),1.79(t,J=10.9hz, 3 h). The structure is as follows:
example 4: synthesis of blue light chiral polymer R/S-PAMCOOCz
R-VCOOCz (0.1 g,0.0003 mol), acrylamide (2.13 g,0.03 mol) and azobisisobutyronitrile (0.05 g,0.000303 mol) were placed in a 250mL double-necked flask under an argon atmosphere, and 20mL tetrahydrofuran was injected under an ice-water bath, followed by stirring for 20min. After the solid was completely dissolved, the ice water bath was removed, slowly warmed to 55 ℃, and stirred for 16h. After the reaction was completed, the reaction solution was added dropwise to 200mL of methanol, and a white precipitate was precipitated, filtered and a white solid was collected. Subsequently, the white solid was purified by washing with methylene chloride and acetone, and dried to obtain the final product. The resulting product was dissolved in deionized water and subjected to aqueous dialysis treatment, and finally dried to obtain 2.18g of a solid (yield: 95.83%). 1HNMR (400 MHz, D2O, ppm): delta 8.17 (br, arH), 7.73 (br, arH), 7.48 (br, arH), 7.29 (br, arH), 6.95 (br, arH), 5.72 (br, CH), 3.94-3.51 (br, CH 2), 2.23 (br, J=41.3 Hz, CH), 1.66 (br, J=44.5 Hz, CH 2): structure is as follows:
(I)；
(II)。
dissolving R-PAMCOOCz or S-PAMCOOCz in deionized water, and performing ultrasonic dissolution; subsequently, the water-soluble organic fluorescent dye sodium fluorescein (Fluc) was incorporated into the solution in a mass ratio of 0.1wt.% and stirred until the solution was clear; finally, pouring the fully mixed solution into a culture dish, and drying to obtain a green chiral organic long afterglow polymer film material; according to the method, organic fluorescent dyes rhodamine 123 (Rh 123) and sulforhodamine (SR 101) with the mass ratio of 0.1wt.% are respectively added, so that yellow and red chiral organic long afterglow polymer film materials are obtained.
Characterization of full color chiral organic long afterglow polymer performance
The invention judges the molecular structure of the synthetic material through ultraviolet-visible absorption spectrum, powder X-ray diffraction (XRD) and nuclear magnetic resonance test; through steady-state spectrum, phosphorescence spectrum (delay 10 ms), fluorescence/phosphorescence life decay curve, time-resolved luminescence spectrum (TRES) and absolute photoluminescence quantum efficiency (PLQY) test, R/S-VCOOCz is copolymerized with acrylamide to obtain blue light polymer long afterglow materials R-PAMCOOCz and S-PAMCOOCz with circular polarization, and molecular rigid environment is induced through a hydrogen bond network dense by a polymer matrix so as to stabilize triplet state excitons and chiral configuration, so that afterglow life of the polymer can reach 3S, and the life of the sensitized colorful polymer is over 1S; through CPL spectrum test, the chiral asymmetry factor |g of the blue light chiral polymer system lum The I can reach 7.8x10 -3 The chiral asymmetry factor of the sensitized colorful polymer system is 10 -3 The above has excellent chiral characteristics. 1-6, the research work successfully realizes the dual transfer of intermolecular triplet energy and chirality, and provides a method for expanding colorful circular polarization luminescent organic materialsThe universality strategy also provides a feasible and effective design idea for constructing the multifunctional organic long afterglow material with near infrared luminescence, stimulus response and the like.
Claims (9)
1. The blue light circularly polarized light-emitting organic long afterglow polymer is characterized by comprising the following two structural formulas:
(I)；
(II)；
where x=1 and y=100.
2. The method for preparing the organic long afterglow polymer having the blue light circularly polarized light emission of claim 1, comprising the steps of:
s1, under the argon atmosphere, carbazole and sodium hydride are dissolved in tetrahydrofuran solution under ice water bath, and then S-2-methyl chloropropionate or R-2-methyl chloropropionate is injected into a reaction bottle to react to obtain a system A;
s2, adding tetrahydrofuran and methanol into the reaction system A, adding sodium hydroxide solution with the concentration of 0.074g/mL by using a syringe, and after the reaction is finished, dropwise adding concentrated hydrochloric acid into the reaction solution with the concentration of 12mol/L until white precipitate is completely separated out to obtain a system B;
s3, adding EDCI and 4-dimethylaminopyridine into the reaction system B, adding a dichloromethane solution under ice water bath, and adding 2-hydroxyethyl acrylate into the reaction system B by using a syringe to react to obtain a system C;
s4, dissolving the reaction system C, acrylamide and azodiisobutyronitrile in tetrahydrofuran solution under argon atmosphere, dropwise adding the reaction solution into methanol after the reaction is finished, precipitating white precipitate, filtering and collecting white solid to obtain the R/S-PAMCOOCz polymer system.
3. The preparation method of the organic long afterglow polymer with full-color circular polarized luminescence is characterized by comprising the following steps:
dissolving the R-PAMCOOCz or S-PAMCOOCz obtained by the preparation method of claim 2 and an organic fluorescent dye in deionized water, and carrying out ultrasonic dissolution; subsequently, the mixture is stirred until the solution is clear; finally, pouring the fully mixed solution into a culture dish, and drying to obtain various polymer film materials with different colors;
wherein the water-soluble organic fluorescent dye comprises fluorescein sodium, rhodamine 123 and sulforhodamine, and the structural formulas of the water-soluble organic fluorescent dye are as follows:
(III)；
(Ⅳ)；
(Ⅴ)。
4. the method for preparing the organic long afterglow polymer having full color circular polarized luminescence according to claim 3, characterized in that: in the step S1, tetrahydrofuran solution is added to keep the system temperature at 0 ℃, and S-2-methyl chloropropionate or R-2-methyl chloropropionate needs to be added at room temperature; the molar ratio of carbazole, sodium hydride and S-2-methyl chloropropionate or R-2-methyl chloropropionate is 1:1.2:1.2, and the reaction time is 12-16 h.
5. The method for preparing the organic long afterglow polymer having full color circular polarized luminescence according to claim 3, characterized in that: in the step S2, the reaction time is 4-6 hours; the reaction temperature is 55 ℃; the volume ratio of tetrahydrofuran to methanol is 2:1.
6. The method for preparing the organic long afterglow polymer having full color circular polarized luminescence according to claim 3, characterized in that: in the step S3, the reaction time is 12-16h; the reaction temperature is room temperature; the molar ratio of the system B, EDCI, 4-dimethylaminopyridine to the 2-hydroxyethyl acrylate is 2:1:1:2.4.
7. The method for preparing the organic long afterglow polymer having full color circular polarized luminescence according to claim 3, characterized in that: in the step S4, the reaction time is 12-16h; the reaction temperature is 55 ℃; methanol is adopted in the sedimentation step; the mol ratio of the system C to the acrylamide is 1:100; the molar mass of the azodiisobutyronitrile is 1 percent of the total mole of the reaction system.
8. The method for preparing the organic long afterglow polymer having full color circular polarized luminescence according to claim 3, characterized in that: the dissolution temperature is 50-60 ℃; the drying temperature was 70 ℃.
9. The use of the method for preparing an organic long afterglow polymer having full color circular polarized luminescence according to claim 3, characterized in that it can be applied to the field of anti-counterfeit encryption.
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