CN117069741A - Polymorphic luminescent type thermal activation delayed fluorescent molecule and preparation method and application thereof - Google Patents
Polymorphic luminescent type thermal activation delayed fluorescent molecule and preparation method and application thereof Download PDFInfo
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- CN117069741A CN117069741A CN202311110752.9A CN202311110752A CN117069741A CN 117069741 A CN117069741 A CN 117069741A CN 202311110752 A CN202311110752 A CN 202311110752A CN 117069741 A CN117069741 A CN 117069741A
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- 230000003111 delayed effect Effects 0.000 title claims abstract description 59
- 238000007725 thermal activation Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 238000010791 quenching Methods 0.000 claims abstract description 15
- 238000004020 luminiscence type Methods 0.000 claims abstract description 11
- 230000000171 quenching effect Effects 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000012074 organic phase Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 16
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 229940126062 Compound A Drugs 0.000 claims description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- JPJGNZQDELRZGE-UHFFFAOYSA-N (phenyl-$l^{2}-phosphanyl)benzene Chemical compound C=1C=CC=CC=1[P]C1=CC=CC=C1 JPJGNZQDELRZGE-UHFFFAOYSA-N 0.000 claims description 4
- YEYRWRVHDLPUGQ-UHFFFAOYSA-N 1,2-dibromo-4,5-dioctoxybenzene Chemical compound CCCCCCCCOC1=CC(Br)=C(Br)C=C1OCCCCCCCC YEYRWRVHDLPUGQ-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical compound C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 claims description 3
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 3
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000004305 biphenyl Chemical group 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 15
- 230000002441 reversible effect Effects 0.000 abstract description 7
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 abstract description 5
- 125000006617 triphenylamine group Chemical group 0.000 abstract description 5
- 239000000370 acceptor Substances 0.000 abstract description 3
- 238000012984 biological imaging Methods 0.000 abstract description 3
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 abstract 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 36
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 32
- 239000000843 powder Substances 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 10
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- FVIZARNDLVOMSU-UHFFFAOYSA-N ginsenoside K Natural products C1CC(C2(CCC3C(C)(C)C(O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O FVIZARNDLVOMSU-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- -1 triphenylene dithiadiazole Chemical compound 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
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- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- 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
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- 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
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
- C09K2211/1081—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms with sulfur
Abstract
The invention relates to the technical field of organic light-emitting diodes and biological imaging, in particular to a polymorphic luminescent type thermal activation delay fluorescent molecule, a preparation method and application thereof; the molecule is of a V-type molecular structure with D-pi-A-pi-D, and the molecule provided by the invention takes groups such as triphenylamine and the like as electron donors and groups such as triphenylamine diazosulfide and the like as electron acceptors; triphenylamine is a classical luminophore, has a relatively distorted conformation in solution, and a molecular system fusing the structure of triphenylamine is easy to obtain delayed fluorescence emission in the solution state; in the solid state, it also has a relatively distorted conformation, not only avoids quenching luminescence by too tight pi-pi stacks, but also can vibrate effectively, thereby facilitating reversible intersystem crossing, and thus can emit delayed fluorescence. The polymorphic luminescent type thermally activated delayed fluorescence molecule provided by the invention can realize delayed fluorescence emission in solid state and solution simultaneously.
Description
Technical Field
The invention relates to the technical field of organic light-emitting diodes and biological imaging, in particular to a polymorphic luminescent type thermal activation delay fluorescent molecule, a preparation method and application thereof.
Background
In recent years, organic materials having long-life heat-activated delayed fluorescence (TADF) are widely used in the fields of organic light emitting diodes, bioimaging, forgery prevention, sensors, and the like. In TADF materials, the energy level difference between the singlet state and the triplet state is [ ]△ E ST ) Very little time, spin-orbit coupling can occur between singlet and triplet excited states, and under thermal activation, triplet excitons cross to singlet through reverse intersystem crossing and then decay back to ground state through radiation, giving off delayed fluorescence. Recent studies have shown that there are large△E ST May be emitted by vibrational coupling of the two triplet states. This mechanism assumes that the first phase is 3 CT (charge transfer) 3 The vibrational coupling process between LE (local emission) states is then followed by a second phase 1 CT sum 3 Reverse inter-system cross-over (RISC) procedure between LE states. However, such TADF promoted by vibrational coupling can only be observed in solution. One reason for this is that most molecules in the solid state undergo aggregation-induced emission quenching (ACQ); another reason is that the solid state limits the vibration of the molecule, thereby quenching TADF. Thus, achieving vibratory coupling of TADF in the solid state remains very challenging due to the lack of a suitable molecular system.
Disclosure of Invention
The technical problems solved by the invention are as follows: the prior art lacks suitable molecular systems while achieving thermally activated delayed fluorescence emission in both solid state and solution.
In order to solve the technical problems, the invention adopts the following technical scheme:
a polymorphic luminescent type thermally activated delayed fluorescence molecule having the structural formula:
；
wherein R is 1 And R is 2 Are identical or different and are each independently selected from alkoxy groups; ar (Ar) 1 Selected from benzene rings; ar (Ar) 2 Selected from 1,2, 5-thiadiazole; m is 0 or 1, ar when m is 1 3 Is a bridging group and is selected from one of benzene ring and biphenyl ring; l (L) 1 And L 2 Are identical or different electron donating groups and are each independently selected from one of the following groups:
。
optionally, the R 1 And said R 2 Are identical or different and are each independently selected from the group consisting of C1-C20 alkoxy groups.
Alternatively, the polymorphic luminescent type thermally activated delayed fluorescence molecule comprises a molecule having the structural formula, wherein n is an integer greater than 0:
。
the invention also provides a preparation method of the polymorphic luminescent type heat-activated delayed fluorescence molecule, which comprises the following steps:
step S1, mixing a compound A, a potassium carbonate solution, a compound B, tetrakis (triphenylphosphine) palladium and tetrahydrofuran to obtain a first mixed solution;
s2, carrying out a first stirring reaction on the first mixed solution, cooling to room temperature, and separating and purifying a reaction product to obtain polymorphic luminescent type heat-activated delayed fluorescent molecules;
wherein, the structural formula of the compound A is as follows:
；
the compound B is selected from one of the following compounds:
。
optionally, in the step S1, the temperature of the first stirring reaction is 70-80 ℃ and the time is 18-22h.
Optionally, in the step S2, the separating and purifying a reaction product includes: and extracting the reaction product by using dichloromethane, washing the organic phases by using saturated saline after combining the organic phases, drying the organic phases by using anhydrous sodium sulfate, concentrating the organic phases under reduced pressure, and performing silica gel column chromatography and recrystallization purification to obtain the polymorphic luminescent type heat-activated delayed fluorescence molecule.
Optionally, in the step S1, the preparation method of the compound a includes:
step S11, mixing a compound C, a potassium phosphate solution 4, 7-dibromobenzo [ C ] [1,2,5] thiadiazole, tetrakis (triphenylphosphine) palladium and tetrahydrofuran to obtain a second mixed solution;
step S12, performing a second stirring reaction on the second mixed solution, adding a saturated ammonium chloride aqueous solution for quenching reaction, and separating and purifying a reaction product to obtain a compound D;
step S13, mixing the compound D, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone and dichloromethane, cooling to 0-4 ℃, adding trifluoromethanesulfonic acid, stirring for reaction, adding saturated sodium bicarbonate aqueous solution for quenching reaction, and separating and purifying a reaction product to obtain a compound A;
wherein, the structural formula of the compound C is as follows:
。
optionally, in step S12, the temperature of the second stirring reaction is 70-80 ℃ and the time is 46-50h.
Optionally, in the step S11, the preparation method of the compound C includes:
step S111, mixing 1, 2-dibromo-4, 5-dioctyl oxybenzene, bisboric acid pinacol ester, [1, 1-bis (diphenylphosphorus) ferrocene ] palladium dichloride, potassium acetate and 1, 4-dioxane to obtain a third mixed solution;
and step S112, performing a third stirring reaction on the third mixed solution, adding a saturated ammonium chloride aqueous solution to quench the reaction, extracting the reaction product with ethyl acetate, merging organic phases, washing the organic phases with saturated saline water, and separating and purifying the reaction product to obtain the compound C.
The invention also provides application of the polymorphic luminescent type thermal activation delay fluorescent molecule as an organic light emitting diode and a biological imaging material.
Compared with the prior art, the polymorphic luminescent type thermal activation delayed fluorescent molecule provided by the invention has a V-shaped molecular structure of D-pi-A-pi-D, and takes groups such as triphenylamine and the like as electron donors and groups such as triphenylamine and the like as electron acceptors; triphenylamine is a classical luminophor, has a three-dimensional conformation, has a relatively distorted conformation in solution, and can generate effective vibration, so that reversible intersystem crossing is promoted, and delayed fluorescence emission in the solution state can be obtained; the molecules provided by the invention also have relatively distorted conformations in a solid state, so that luminescence quenching caused by too tight pi-pi stacking is avoided, and effective vibration can be generated, thereby promoting reversible intersystem crossing, and further, delayed fluorescence can be emitted; therefore, the polymorphic luminescent type heat-activated delayed fluorescent molecules provided by the invention can realize delayed fluorescent emission in solid state and solution simultaneously; the molecules can be used in the fields of organic light emitting diodes and bioimaging.
Drawings
FIG. 1 is a structural general formula of a polymorphic luminescent type heat-activated delayed fluorescence molecule in an embodiment of the present invention;
FIG. 2 is a thermogravimetric analysis of compound E;
FIG. 3 is a graph showing the ultraviolet-visible absorption spectrum in chloroform solution (10. Mu.M) of Compound E;
FIG. 4 is a graph showing fluorescence spectra of chloroform solutions (10. Mu.M) of Compound E at room temperature tested in an air atmosphere and a nitrogen atmosphere, respectively;
FIG. 5 is a delayed spectrum of compound E powder;
FIG. 6 is a graph of fluorescence lifetime of chloroform solution (10. Mu.M) of Compound E;
FIG. 7 is a graph of phosphorescence lifetime of chloroform solution (10. Mu.M) of Compound E;
FIG. 8 is a graph of fluorescence lifetime of compound E powder;
FIG. 9 is a graph of phosphorescence lifetime of compound E powder;
FIG. 10 is a thermogravimetric analysis of compound J;
FIG. 11 is a graph showing the ultraviolet absorption spectrum in a chloroform solution (10. Mu.M) of Compound J;
FIG. 12 is a graph of fluorescence spectrum at room temperature of Compound J;
FIG. 13 is a graph showing a room temperature retardation spectrum of Compound J;
FIG. 14 is a graph of fluorescence lifetime of chloroform solution (10. Mu.M) of Compound J;
FIG. 15 is a graph of phosphorescence lifetime of chloroform solution (10. Mu.M) of Compound J;
FIG. 16 is a graph of fluorescence lifetime of compound J powder;
FIG. 17 is a graph of phosphorescence lifetime of compound J powder.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It should be noted that, without conflict, features in the embodiments of the present invention may be combined with each other. The terms "comprising," "including," "containing," and "having" are intended to be non-limiting, as other steps and other ingredients not affecting the result may be added.
As shown in fig. 1, the embodiment of the invention provides a polymorphic luminescence type thermal activation delay fluorescent molecule, and the structural general formula of the polymorphic luminescence type thermal activation delay fluorescent molecule is as follows:
；
wherein R is 1 And R is 2 Are identical or different and are each independently selected from alkoxy groups; ar (Ar) 1 Selected from benzene rings; ar (Ar) 2 Selected from 1,2, 5-thiadiazole; m is 0 or 1, ar when m is 1 3 One selected from benzene rings and biphenyl rings; l (L) 1 And L 2 Are identical or different and are each independentlyIs selected from one of the following groups:
。
compared with the prior art, the polymorphic luminescent type thermal activation delayed fluorescent molecule provided by the embodiment of the invention has a V-shaped molecular structure with D-pi-A-pi-D, specifically, a series of groups are connected to two sides of the isocenter of the triphenylene dithiadiazole, so that a V-shaped structure is formed, and the molecule takes the groups such as triphenylamine and the like as electron donor and the groups such as the triphenylene dithiadiazole and the like as electron acceptor; triphenylamine is a classical luminophor, has a three-dimensional conformation, has a relatively distorted conformation in solution, and can generate effective vibration, so that reversible intersystem crossing is promoted, and delayed fluorescence emission in the solution state can be obtained; the molecules provided by the invention also have relatively distorted conformations in a solid state, so that not only too tight pi-pi stacking quenching luminescence is avoided, but also effective vibration can be generated, thereby promoting reversible intersystem crossing, and further, delayed fluorescence can be emitted; therefore, the polymorphic luminescent type heat-activated delayed fluorescent molecules provided by the invention can realize delayed fluorescent emission in solid state and solution simultaneously; the molecules can be used in the fields of organic light emitting diodes and bioimaging.
Illustratively, the polymorphic luminescent thermally activated delayed fluorescence molecule comprises a molecule having the structural formula:
in some embodiments of the invention, the R 1 And said R 2 Are identical or different and are each independently selected from the group consisting of C1-C20 alkoxy groups. The polymorphic luminescent type heat-activated delayed fluorescent molecules provided by the invention are more than most classical fluorescent molecules due to the modification of long alkyl chainsThe delayed fluorescent molecule of (2) has better solubility and can be processed by solution; meanwhile, the molecule is easy to form a relatively twisted structure, so that the molecule can vibrate effectively in different states to perform polymorphic emission. In addition, the molecule can reach microsecond luminescence life, and compared with fluorescent molecules with the life in nanosecond, the molecule can be better applied to time resolution imaging.
The invention also provides a preparation method of the polymorphic luminescent type heat-activated delayed fluorescence molecule, which comprises the following steps:
step S1, mixing a compound A, a potassium carbonate solution, a compound B, tetrakis (triphenylphosphine) palladium and tetrahydrofuran to obtain a first mixed solution;
s2, carrying out a first stirring reaction on the first mixed solution, cooling to room temperature, and separating and purifying a reaction product to obtain polymorphic luminescent type heat-activated delayed fluorescent molecules;
wherein, the structural formula of the compound A is as follows:
；
the compound B is selected from one of the following compounds:
。
in some embodiments of the present invention, in the step S1, the temperature of the first stirring reaction is 70-80 ℃ for 18-22 hours.
Optionally, in the step S2, the separating and purifying a reaction product includes: and extracting the reaction product by using dichloromethane, washing an organic phase by using saturated saline after combining, drying by using anhydrous sodium sulfate, concentrating the organic phase under reduced pressure, purifying by using silica gel column chromatography, and recrystallizing to obtain the polymorphic luminescent type heat-activated delayed fluorescent molecule.
In some embodiments of the invention, the recrystallization purifies the solvent used that is formulated from chloroform and ethanol.
In some embodiments of the present invention, in the step S1, the preparation method of the compound a includes:
step S11, mixing a compound C, a potassium phosphate solution, 4, 7-dibromobenzo [ C ] [1,2,5] thiadiazole, tetrakis (triphenylphosphine) palladium and tetrahydrofuran to obtain a second mixed solution;
step S12, performing a second stirring reaction on the second mixed solution, adding a saturated ammonium chloride aqueous solution for quenching reaction, and separating and purifying a reaction product to obtain a compound D;
step S13, mixing the compound D, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone and dichloromethane, cooling to 0-4 ℃, adding trifluoromethanesulfonic acid, stirring for reaction, adding saturated sodium bicarbonate aqueous solution for quenching reaction, and separating and purifying a reaction product to obtain a compound A;
wherein, the structural formula of the compound C is as follows:
。
in some embodiments of the invention, in the step S12, the temperature of the second stirring reaction is 70-80 ℃ for 46-50 hours.
In some embodiments of the present invention, in the step S11, the preparation method of the compound C includes:
step S111, mixing 1, 2-dibromo-4, 5-dioctyl oxybenzene, bisboric acid pinacol ester, [1, 1-bis (diphenylphosphorus) ferrocene ] palladium dichloride, potassium acetate and 1, 4-dioxane to obtain a third mixed solution;
and step S112, performing a third stirring reaction on the third mixed solution, adding a saturated ammonium chloride aqueous solution to quench the reaction, extracting the reaction with ethyl acetate, merging organic phases, washing the organic phases with saturated saline solution, drying the organic phases with anhydrous sodium sulfate, concentrating the organic phases under reduced pressure, and purifying the organic phases by silica gel column chromatography to obtain the compound C.
In some embodiments of the invention, in step S112, the temperature of the third stirring reaction is 80-90 ℃ for 22-26 hours.
The invention also provides application of the polymorphic luminescent type heat-activated delayed fluorescence molecule as a luminescent material. The polymorphic luminescent type thermally activated delayed fluorescent molecules are used as luminescent materials for manufacturing organic light-emitting diodes.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1 preparation of Compound C
1, 2-dibromo-4, 5-bis-octyloxybenzene (2.00 g,6.76 mmol), pinacolato-diboronate (1.80 g,7.10 mmol), [1, 1-bis (diphenylphosphorus) ferrocene ] palladium dichloride (0.50 g,0.67 mmol), potassium acetate (3.32 g,33.80 mmol) and 1, 4-dioxane (40 mL) were added to a 250 mL round bottom flask equipped with a magnetic stirrer and the mixture stirred at 85℃for 24 hours; the reaction system was quenched by adding saturated aqueous ammonium chloride solution, extracted with ethyl acetate, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and the organic phase was concentrated under reduced pressure, followed by purification by silica gel column chromatography to give compound C in 45% yield. The synthesis of compound C is shown below:
example 2 preparation of Compound A
Potassium phosphate (12.74 g,0.06 mol) was added to 20mL of water to prepare a potassium phosphate solution; this solution was mixed with compound C (5.86 g,10.0 mmol), 4, 7-dibromobenzo [ C ] [1,2,5] thiadiazole (6.00 g,25.0 mmol) and tetrakis (triphenylphosphine) palladium (1.16 g,1.0 mmol) and tetrahydrofuran (200 mL), the mixture was stirred under reflux for 48 hours, a saturated aqueous ammonium chloride solution was added to the reaction system to quench the reaction, and extracted with methylene chloride, the organic phases were combined and washed with saturated brine, the organic phases were dried over anhydrous sodium sulfate for half an hour, the organic phases were concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography using a solvent composed of methylene chloride and n-hexane to give compound D; compound D (0.56 g,0.74 mmol), 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (0.50 g,2.20 mmol) and 100mL dichloromethane were added to a 250 mL three-necked flask, cooled to 0 ℃, and trifluoromethanesulfonic acid (0.5 mL,0.0074 mmol) was added, followed by stirring for 4 hours; the synthesis of compound a is shown below:
characterization data for compound a were: 1 H NMR (600MHz，Chloroform-d) δ 10.1 (s, 2H), 8.9 (s, 2H), 4.5 (t,J= 9.6 Hz, 4H), 2.1 (m, 4H), 1.70 (m, 4H), 1.47-1.25 (m, 16H), 0.91 (t,J=8.8 Hz, 6H)。
example 3 preparation of Compound E
Potassium carbonate (12.4 mg,0.09 mmol) was added to 2mL of water to prepare a potassium carbonate solution; the solution was mixed with compound a (15 mg,0.02 mmol), compound B (0.05 mmol), tetrakis (triphenylphosphine) palladium (2.3 mg,0.002 mmol) and tetrahydrofuran (12 mL), the mixture was stirred under reflux for 20h, the temperature was lowered to room temperature, extraction was performed with methylene chloride, the organic phases were combined and then washed with saturated brine, the organic phases were dried over anhydrous sodium sulfate for half an hour, the organic phases were concentrated under reduced pressure, the crude product obtained was purified by silica gel column chromatography using a solvent composed of methylene chloride and petroleum ether, and recrystallization purification was performed using a solvent composed of chloroform and ethanol to give an orange-red solid compound E in a yield of 47%; wherein the structural formula of the compound B is as follows:
。
the synthesis of compound E is shown below:
the structural formula of the subscript E in the above reaction formula represents a compound E.
The nuclear magnetic characterization data of compound E are: 1 H NMR (400 MHz，Chloroform-d) δ = 9.61 (s，2H)，8.39 (s，2H)，7.76 (d，J=8.6Hz，4H)，7.23 (d，J=7.6Hz，6H)，7.14 (d，J=8.0 Hz，14H)，7.02(t，J=7.3Hz，4H)，4.06 (t，J=6.7Hz，4H)，1.87 (p，J=6.8 Hz，4H)，1.52(p，J=8.3，7.4Hz，4H)，1.39-1.25(m，16H)，0.88-0.81(m，6H)。
mass spectrum characterization data for compound E were: m/z=1086.7 [ m+h ]] + 。
Example 4 preparation of Compound F
The structural formula of the compound F is as follows:
。
the preparation method of the compound F is different from that of the compound E in that the structural formula of the compound B is as follows:
。
characterization data for compound F were: 1 H NMR(400 MHz，Chloroform-d) δ10.08 (s, 2H), 8.83 (s, 2H), 8.08 (d,J= 8.2 Hz, 4H),7.80 (d,J=8.2 Hz, 4H), 7.64-7.55 (m, 4H), 7.33-7.27 (m, 8H), 7.18 (dd,J= 8.3, 6.7 Hz, 14H), 7.09 -7.02 (m, 4H), 4.34 (t,J=6.8 Hz, 4H), 2.04 (m, 4H), 1.55 (m, 4H), 1.42-1.28 (m, 16H), 0.91-0.84 (m, 6H). The mass spectrum characterization data of compound F are: m/z=1240.6 [ m+h ]] + 。
Example 5 preparation of Compound G
The structural formula of the compound G is
。
The preparation method of the compound G is different from that of the compound E in that the structural formula of the compound B is as follows:
。
mass spectrum characterization data for compound G were: m/z=1360.7 [ m+h ]] + 。
Example 6 preparation of Compound H
The structural formula of the compound H is as follows:
。
the preparation method of the compound H is different from that of the compound E in that the structural formula of the compound B is as follows:
。
mass spectrum characterization data for compound H were: m/z=996.4 [ m+h ]] + 。
EXAMPLE 7 preparation of Compound I
The structural formula of the compound I is as follows:
。
the preparation method of the compound I is different from that of the compound E in that the structural formula of the compound B is as follows:
。
mass spectral characterization data for compound I were: m/z=932.2 [ m+h] + 。
Example 8 preparation of Compound J
The structural formula of the compound J is as follows:
。
the preparation method of the compound J is different from that of the compound E in that the structural formula of the compound B is as follows:
。
mass spectrum characterization data for compound E, compound J, were: m/z=1084.4 [ m+h ]] + 。
Example 9 preparation of Compound K
The structural formula of the compound K is as follows:
。
the preparation method of the compound K is different from the compound E in that the structural formula of the compound B is as follows:
。
mass spectral characterization data for compound K were: m/z=968.3 [ m+h ]] + 。
Experimental example
The polymorphic luminescent type thermally activated delayed fluorescence molecular compound E prepared in example 3 was subjected to thermogravimetry, ultraviolet absorption spectrum, fluorescence spectrum, delayed spectrum, solution state and solid state life analysis, and the test results are shown in fig. 2-9, and fig. 2 is a thermogravimetric analysis chart of the compound E, and as can be seen in fig. 2, the decomposition temperature of the compound E is 404.2 ℃, which indicates that the compound E has good thermal stability. FIG. 3 is a graph showing the ultraviolet-visible absorption spectrum of a chloroform solution (10. Mu.M) of Compound E, and it can be seen from FIG. 3 that the absorption of Compound E at wavelengths of 270nm and 310nm is pi-pi absorption, and the absorption at wavelengths of 400nm is absorption in the intramolecular charge transfer state (CT). FIG. 4 is a graph of fluorescence spectra of chloroform solution (10. Mu.M) of Compound E at room temperature tested in an air atmosphere and a nitrogen atmosphere, respectively, because TADF molecular luminescence is relatively sensitive to oxygen, and thus it is verified whether oxygen has an effect on it by comparing its luminescence intensities in a nitrogen atmosphere and in an air atmosphere. As can be seen from the figure, the luminescence intensity of compound E after oxygen removal is significantly enhanced. FIG. 5 is a delayed spectrum of the powder of the compound E, and it can be seen from FIG. 5 that the instant fluorescence and the delayed fluorescence spectrum of the compound E are approximately at the same position, and that the instant fluorescence and the delayed fluorescence have the same spectrum, which indicates that part of the delayed fluorescence is from the S1 energy level. FIG. 6 is a graph showing fluorescence lifetime of a chloroform solution (10. Mu.M) of Compound E, FIG. 7 is a graph showing phosphorescence lifetime of a chloroform solution (10. Mu.M) of Compound E, FIG. 8 is a graph showing fluorescence lifetime of a powder of Compound E, and FIG. 9 is a graph showing phosphorescence lifetime of a powder of Compound E. As can be seen from fig. 6-9, the short lifetime of compound E is in the nanosecond range, long lifetime can reach the microsecond range, and is a typical TADF molecule, and delayed fluorescence emission in both solid and solution can be achieved.
The polymorphic luminescence type thermally activated delayed fluorescence molecular compound J prepared in example 8 was subjected to thermogravimetry, ultraviolet absorption spectrum, fluorescence spectrum, delayed spectrum, solution state and solid state life analysis, and the test results are shown in FIGS. 10-17, and FIG. 10 is a thermogravimetric analysis chart of the compound J, and as can be seen in FIG. 10, the decomposition temperature of the compound J is 208.9 ℃, which indicates that the compound J has good thermal stability. FIG. 11 is a graph showing the ultraviolet absorption spectrum of a chloroform solution (10. Mu.M) of Compound J. As can be seen from FIG. 11, the absorption of Compound J at wavelengths of 240nm and 270nm is pi-. Pi.absorption, and the absorption at wavelengths of 390nm is absorption in the intramolecular charge transfer state (CT). FIG. 12 is a graph of the fluorescence spectrum at room temperature for compound J. As can be seen from FIG. 12, the emission band is narrower due to the relatively flat carbazole donor molecules, and the fluorescence emission spectrum is blue shifted compared to the triphenylamine donor. FIG. 13 is a graph of the delayed spectrum of compound J at room temperature, and it can be seen from FIG. 13 that the instant fluorescence and the delayed fluorescence spectrum of the compound J powder are substantially at the same position, indicating that the portion of the delayed fluorescence is derived from the S1 energy level. FIG. 14 is a fluorescent lifetime graph of a chloroform solution (10. Mu.M) of Compound J, FIG. 15 is a phosphorescent lifetime graph of a chloroform solution (10. Mu.M) of Compound J, FIG. 16 is a fluorescent lifetime graph of Compound J powder, and FIG. 17 is a phosphorescent lifetime graph of Compound J powder. From fig. 14-17, respectively, the short lifetime of compound J is nanosecond, long lifetime can reach microsecond, and is a typical TADF molecule that can achieve delayed fluorescence emission in both solid and solution. It should be noted that IRF in the drawings represents a reference.
In addition, although the present invention is disclosed above, the scope of the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications will fall within the scope of the invention.
Claims (10)
1. A polymorphic luminescent type thermally activated delayed fluorescence molecule, characterized in that the polymorphic luminescent type thermally activated delayed fluorescence molecule has a structural general formula:
；
wherein R is 1 And R is 2 Are identical or different and are each independently selected from alkoxy groups; ar (Ar) 1 Selected from benzene rings; ar (Ar) 2 Selected from 1,2, 5-thiadiazole; m is 0 or 1, ar when m is 1 3 One selected from benzene rings and biphenyl rings; l (L) 1 And L 2 Are identical or different groups and are each independently selected from one of the following groups:
。
2. the polymorphic luminescent type thermally activated delayed fluorescence molecule of claim 1 wherein R 1 And said R 2 Are identical or different and are each independently selected from the group consisting of C1-C20 alkoxy groups.
3. The polymorphic luminescent type thermally activated delayed fluorescent molecule of claim 1 which comprises a molecule having the structural formula wherein n is an integer greater than 0:
。
4. a method of preparing a polymorphic luminescent type thermally activated delayed fluorescence molecule in accordance with claim 1 or 2, comprising:
step S1, mixing a compound A, a potassium carbonate solution, a compound B, tetrakis (triphenylphosphine) palladium and tetrahydrofuran to obtain a first mixed solution;
s2, carrying out a first stirring reaction on the first mixed solution, cooling to room temperature, and separating and purifying a reaction product to obtain polymorphic luminescent type heat-activated delayed fluorescent molecules;
wherein, the structural formula of the compound A is as follows:
；
the compound B is selected from one of the following compounds:
。
5. the method of claim 4, wherein in the step S1, the temperature of the first stirring reaction is 70-80℃and the time is 18-22 hours.
6. The method for preparing a polymorphic luminescent type heat-activated delayed fluorescence molecule according to claim 4, wherein in the step S2, the separation and purification of the reaction product comprises: and extracting the reaction product by using dichloromethane, merging organic phases, washing by using saturated saline, drying by using anhydrous sodium sulfate, concentrating under reduced pressure, and purifying by using silica gel column chromatography, and recrystallizing to obtain the polymorphic luminescent type heat-activated delayed fluorescent molecule.
7. The method for preparing a polymorphic luminescent type heat-activated delayed fluorescence molecule according to claim 4, wherein in the step S1, the method for preparing the compound a comprises:
step S11, mixing a compound C, a potassium phosphate solution, 4, 7-dibromobenzo [ C ] [1,2,5] thiadiazole, tetrakis (triphenylphosphine) palladium and tetrahydrofuran to obtain a second mixed solution;
step S12, performing a second stirring reaction on the second mixed solution, adding a saturated ammonium chloride aqueous solution for quenching reaction, and separating and purifying a reaction product to obtain a compound D;
step S13, mixing the compound D, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone and dichloromethane, cooling to 0-4 ℃, adding trifluoromethanesulfonic acid, stirring for reaction, adding saturated sodium bicarbonate aqueous solution for quenching reaction, and separating and purifying a reaction product to obtain a compound A;
wherein the structure of the compound C is as follows:
。
8. the method for preparing a delayed fluorescence molecule for polymorphic luminescence type thermal activation according to claim 7, wherein in said step S12, the temperature of said second stirring reaction is 70-80 ℃ for 46-50 hours.
9. The method for preparing a polymorphic luminescent type heat-activated delayed fluorescence molecule according to claim 7, wherein in the step S11, the method for preparing the compound C comprises:
step S111, mixing 1, 2-dibromo-4, 5-dioctyl oxybenzene, bisboric acid pinacol ester, [1, 1-bis (diphenylphosphorus) ferrocene ] palladium dichloride, potassium acetate and 1, 4-dioxane to obtain a third mixed solution;
and step S112, performing a third stirring reaction on the third mixed solution, adding a saturated ammonium chloride aqueous solution to quench the reaction, extracting the reaction product with ethyl acetate, merging organic phases, washing the organic phases with saturated saline water, and separating and purifying the reaction product to obtain the compound C.
10. Use of a polymorphic luminescent thermally activated delayed fluorescence molecule according to any of claims 1 to 3 as luminescent and bioimaging material.
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