CN108586318A - A kind of hot activation delayed fluorescence material of solution processable and preparation method thereof - Google Patents
A kind of hot activation delayed fluorescence material of solution processable and preparation method thereof Download PDFInfo
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- CN108586318A CN108586318A CN201810037763.1A CN201810037763A CN108586318A CN 108586318 A CN108586318 A CN 108586318A CN 201810037763 A CN201810037763 A CN 201810037763A CN 108586318 A CN108586318 A CN 108586318A
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- delayed fluorescence
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- 239000000463 material Substances 0.000 title claims abstract description 47
- 230000004913 activation Effects 0.000 title claims abstract description 46
- 230000003111 delayed effect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 230000002093 peripheral effect Effects 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 16
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 210000001787 dendrite Anatomy 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 230000000269 nucleophilic effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 17
- 230000003335 steric effect Effects 0.000 abstract description 5
- 238000010791 quenching Methods 0.000 abstract description 4
- 230000000171 quenching effect Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005401 electroluminescence Methods 0.000 abstract description 2
- 239000012779 reinforcing material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000000921 elemental analysis Methods 0.000 description 12
- 238000001819 mass spectrum Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000010189 synthetic method Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- ZIKXHZSORLSPCO-UHFFFAOYSA-N 9h-carbazol-3-ol Chemical class C1=CC=C2C3=CC(O)=CC=C3NC2=C1 ZIKXHZSORLSPCO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000003384 small molecules Chemical class 0.000 description 6
- 150000008359 benzonitriles Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 239000002027 dichloromethane extract Substances 0.000 description 3
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical class BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ACXNSKYDNPWWAG-UHFFFAOYSA-N 1,2-ditert-butyl-9h-carbazole Chemical compound C1=CC=C2C3=CC=C(C(C)(C)C)C(C(C)(C)C)=C3NC2=C1 ACXNSKYDNPWWAG-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical group C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- IOQMWOBRUDNEOA-UHFFFAOYSA-N N#Cc(c(F)c(cc1F)F)c1F Chemical compound N#Cc(c(F)c(cc1F)F)c1F IOQMWOBRUDNEOA-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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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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- Electroluminescent Light Sources (AREA)
- Indole Compounds (AREA)
Abstract
The invention discloses hot activation delayed fluorescence materials of a kind of solution processable and preparation method thereof.Such molecular structure consists of two parts, and a part is the core with hot activation delayed fluorescence property, and another part is the group for having high triplet energy level by alkyl chain link, has structure shown in formula I,Formulas I, wherein R1,R2In at most there are one being hydrogen, remaining is the group with high triplet energy level by alkyl chain link.The advantage of the new material：The space steric effect of peripheral branch can effectively reduce the concentration quenching of triplet excitons, improve the performance of luminescent device；The introducing of alkyl chain being capable of effective reinforcing material dissolubility and film forming.The result shows that：There is the hot activation delayed fluorescence material of this kind of solution processable larger molecular weight, good filming performance to prepare organic electroluminescence device suitable for wet method.And increasing with peripheral branch, device performance is greatly improved.
Description
Technical field
The invention belongs to field of organic electroluminescent materials, and in particular to a kind of novel luminous organic material, i.e., it is a kind of
The hot activation delayed fluorescence material of solution processable.
Background technology
Organic Light Emitting Diode (OLED) is since its driving voltage is low, fast response time, and luminous efficiency is high, manufacture craft letter
List and the advantages that be easily achieved total colouring, is known as the display of new generation of most Research Prospects.And hot activation delay is glimmering
Luminescent material (TADF) realizes 100% internal quantum efficiency since it can make full use of single triplet excitons.Therefore TADF material quilts
It is widely used in Organic Light Emitting Diode.Up to the present, how the researcher of TADF materials improves organic hair if being primarily upon
Optical diode device performance and its excitation purity.
In the TADF materials of small molecule, researchers achieve great achievement in these two aspects.But still have
Challenge restricts this elite clone realization and commercially produces on a large scale.Such as the small molecule hot activation delay of better performances
For fluorescent material since its molecular weight is relatively small, steric hindrance is smaller, easily reunites, and is not suitable for application and is prepared in device with wet method.
So most of small molecule hot activation delayed fluorescence material is all by vacuum vapour deposition making devices.But this preparation process phase
Compared with wet method preparation process, flow is complicated, higher to equipment requirement, so spending higher.It is unfavorable for realizing large-scale commercial
Production.
And the hot activation delayed fluorescence material of polymer is since its molecular weight is larger, steric hindrance is big, is not easy to reunite, film forming
Performance is good, can prepare device by wet methods such as inkjet printing or spin-coating methods, has in terms of large-area flat-plate is shown huge
Research potential.But polymer hot activation delayed fluorescence material, since synthetic route is longer, side reaction is more, purification difficulty compared with
Greatly, and light emission luminance and efficiency are much lower compared with small molecule, so progress is slow at present.
And the hot activation delayed fluorescence material of this novel solution processable consists of two parts, a part is that have heat
It is the group for having high triplet energy level by alkyl chain link to activate the core of delayed fluorescence property, another part.It neither belongs to
It is also not belonging to polymer material in small molecule, but since the space steric effect of the peripheral branch of its alkyl chain link makes it simultaneously
The good film forming of excellent properties and polymer molecule with small molecule.And it is prepared and method of purification relative polymer can letter
It is single very much.Therefore during wet method prepares device, this material has unique advantage.It is so far, to be most suitable for wet
Method prepares the hot activation delayed fluorescence material of device.
Invention content
Technical problem：The purpose of the present invention is improving existing organic material the problem of wet method prepares device,
And a kind of hot activation delayed fluorescence material of novel solution processable is provided on this basis and preparation method thereof.Preparation method
It is to utilize the nucleophilic substitution of alkyl chain to connect the group of peripheral high triplet energy level and inside to have hot activation delay glimmering
The core of light property, obtains product.Again by comparing the different substitution numbers of peripheral branch, studying peripheral branch number has inside
The packaging effect of the core of hot activation delayed fluorescence property.
Technical solution：The present invention has probed into hot activation delayed fluorescence material and its preparation side of novel solution processable
Method.12 class novel dendritic hot activation delayed fluorescence materials of nucleosynthesis with hot activation delayed fluorescence property based on two kinds.
And influence of the peripheral chain branches to the packaging effect of the internal core with hot activation delayed fluorescence property has been probed into for the first time.
The hot activation delayed fluorescence material molecule structure of the solution processable of the present invention consists of two parts, and a part is tool
There is the core of hot activation delayed fluorescence property, another part is the group for having high triplet energy level by alkyl chain link, described
Material have the following structure：
Wherein, R1,R2In at most there are one being hydrogen, remaining is to have high triplet energy level by alkyl chain link
Group.
Wherein, the core of the hot activation delayed fluorescence property is the group such as lower structure：
The group with high triplet energy level by alkyl chain link is the group such as lower structure：
The hot activation delayed fluorescence material has one of following chemical structural formula：
Wherein n is 3,6 or 9.
The preparation method of the hot activation delayed fluorescence material of solution processable of the present invention is：Peripheral dendrite is prepared first,
Then by nucleophilic displacement of fluorine and alkyl chain link, finally prolonged again with hot activation with inside by the necleophilic reaction of an alkylidene chain
The connection of the core of slow photoluminescent property, finally obtains dendritic hot activation delayed fluorescence material.
Advantageous effect：The result shows that：The hot activation delayed fluorescence material of this novel solution processable, peripheral branch
Space steric effect can effectively reduce the concentration quenching of triplet excitons, improve the performance of luminescent device；The introducing energy of alkyl chain
Enough effective reinforcing material dissolubilities and film forming, therefore relatively organic electroluminescence device is prepared suitable for wet method.Specific manifestation
Compared with its inner core, this new material shows excellent device performance during non-impurity-doped, power efficiency with
External quantum efficiency is inner core device more than 2 times.And increasing with peripheral branch, device performance is greatly improved.
Specific implementation mode
The hot activation delayed fluorescence material molecule structure of solution processable of the present invention consists of two parts, and a part is that have
The core of hot activation delayed fluorescence property, another part is the group for having high triplet energy level by alkyl chain link, described
Material has the following structure：
Wherein, R1,R2In at most there are one being hydrogen, remaining is to have high triplet energy level by alkyl chain link
Group.
The core of the hot activation delayed fluorescence property is the group such as lower structure：
The group with high triplet energy level by alkyl chain link is the group such as lower structure：
The hot activation delayed fluorescence material has one of following chemical structural formula：
Wherein n is 3,6 or 9.
The preparation method of the hot activation delayed fluorescence material of solution processable of the present invention is：Peripheral dendrite is prepared first,
Then by nucleophilic displacement of fluorine and alkyl chain link, finally prolonged again with hot activation with inside by the necleophilic reaction of an alkylidene chain
The connection of the core of slow photoluminescent property, finally obtains dendritic hot activation delayed fluorescence material.
For a further understanding of the present invention, the present invention is specifically described with reference to specific embodiment, but following embodiment
It is only used for that the present invention is further explained, without limiting the present invention.
Embodiment 1：The synthesis of compound C1
Step 1, S1CH3The synthesis of O
Be added in 500mL reaction bulbs bromo- two fluorenes of 9,9- spiral shells (10g, 25.12mmol) of 3-, sodium methoxide (50mL,
25.12mmol), CuI (15g, 78.94mmol), n,N-Dimethylformamide (200mL), under nitrogen protection, 120 DEG C of reactions
24h.After reaction, it is cooled to room temperature, adds a large amount of water stirring, filters, obtain crude product.Then, pass through the side of column chromatography
Method purifies to obtain S1CH3The yield of O white solids, S1CH3O is 70%.
Step 2, the synthesis of S1OH
S1CH is added in reaction bulb3Simultaneously the dissolving of 30mL dichloromethane solutions is added in O (6g, 17.19mmol), in ice bath item
Under part, the dichloromethane solution (30mL) dissolved with 3- boron bromides (15mL) is added dropwise with separatory funnel.It is stirred to react at 0 DEG C
4h is quenched with methanol (20mL), and it is neutral to be washed with sodium bicarbonate and adjust the PH of mixed solution.Column chromatography obtains product S1OH,
Yield is 90%.
Step 3, the synthesis of peripheral branch S1O-Br
S1OH (5.18g, 15.47mmol), 1,6- dibromo-hexanes (15mL, 92.3mmol), carbonic acid are added in reaction bulb
Caesium (10.02g, 30.94mmol), DMF (40mL).Stirred under nitrogen atmosphere reacts 1h at 90 DEG C.After, add elutriation to go out,
Dichloromethane extracts.Column chromatography purifies, and obtains product S1O-Br, yield 68%.
Step 4, the synthesis of CZ-2S1O
In reaction bulb be added S1O-Br (5.24g, 10.51mmol), 3,6- dihydroxy -9- hydrogen-carbazole (1.04g,
5.25mmol), cesium carbonate (4.5g, 13.84mmol), DMF (30mL).Stirred under nitrogen atmosphere reacts 6h at 140 DEG C.Reaction
Terminate postcooling, elutriation is added to go out, dichloromethane extraction.Column chromatography purifies, and obtains product CZ-2S1O, yield 60%.
Step 5, the synthesis of C1
Be added in the dry tetrahydrofuran (THF, 20mL) CZ-2S1O (3.26g, 3.15mmol), sodium hydride (0.5g,
20.3mmol), it is stirred to react 0.5h at room temperature, adds 2,3,5,6- tetrafluoro benzonitriles (0.068g, 0.39mmol), at room temperature
It is stirred to react 12h.After reaction plus elutriation quenching, dichloromethane extract.Column chromatography purifies, and obtains final product C1, yield
It is 65%.
Mass spectrum：4208.
Elemental analysis, it is as a result as follows：C:86.34 H:5.87 N：1.76 O:6.10.
The building-up process of C1 is as follows：
Embodiment 2：Synthesize C2
Change 3, the 6- dihydroxy -9- hydrogen-carbazole reacted with S1O-Br in above-described embodiment into 3- hydroxycarbazoles, by with
1 identical synthetic method of embodiment, obtains product C2.Yield 70%.
Mass spectrum：2484.05.
Elemental analysis, it is as a result as follows：C:86.47 H:5.56 N：2.82 O:5.15.
Embodiment 3：Synthesize C3
Step 1, the synthesis of branch CZ-Br
Di-t-butyl carbazole (6.7g, 23.92mmol), 1,6- dibromo-hexanes is added in (80mL) in toluene solution
(33mL, 143.5mmol), KOH (15g, 267.85mmol/ first dissolve in 10mL water), tetrabutylammonium bromide (1g,
1.8mmol).Under nitrogen protection, it is stirred to react 3h for 80 DEG C, is directly spin-dried for after reaction.Column chromatography purifies, and obtains CZ-
Br products, yield 71%.
Step 2, the synthesis of CZ-CZO
Under nitrogen protection environment, CZ-Br (7.23g, 16.26mmol), 3,6- dihydroxy -9- are added in reaction bulb
Hydrogen-carbazole (1.61g, 8.13mmol), cesium carbonate (6.7g, 21.12mmol), DMF (30mL).After reaction condition and its reaction
Processing it is identical as the synthesis of the CZ-2S1O in embodiment 1.Obtain product CZ-CZO, yield 60%.
Step 3, the synthesis of C3
Be added in the dry tetrahydrofuran (THF, 20mL) CZ-CZO (3.90g, 4.08mmol), sodium hydride (0.6g,
24.3mmol), it is stirred to react 0.5h at room temperature, adds 2,3,5,6- tetrafluoro benzonitriles (0.089g, 0.51mmol), at room temperature
It is stirred to react 12h.After reaction plus water quenching, dichloromethane extract.Column chromatography purifies, and obtains final product C5, yield is
75%.
Mass spectrum：3780.45.
Elemental analysis, it is as a result as follows：C:82.78 H：6.46 N：6.33 O：4.43.
The building-up process of C3 is as follows
Embodiment 4：Synthesize C4
Change 3, the 6- dihydroxy -9- hydrogen-carbazole reacted with CZ-Br in above-described embodiment into 3- hydroxycarbazoles, by with
3 identical synthetic method of embodiment, obtains product C4.Yield 82%.
Mass spectrum：2271.86.
Elemental analysis, it is as a result as follows：C:83.59 H:6.02 N：6.91 O:3.49.
Embodiment 5：Synthesize C5
Change the carbazole in embodiment 3 into 9,10- acridans, by with pass through synthetic method same as Example 3,
Obtain product C5.Yield 63%.
Mass spectrum：3220.82.
Elemental analysis, it is as a result as follows：C:83.11 H：7.29 N：5.65 O：3.95.
The building-up process of C5 is as follows
Embodiment 6：Synthesize C6
Change 3, the 6- dihydroxy -9- hydrogen-carbazole reacted with AC-Br in above-described embodiment 5 into 3- hydroxycarbazoles, by with
5 identical synthetic method of embodiment, obtains product C6.Yield 69%.
C mass spectrums：1992.05.
Elemental analysis, it is as a result as follows：C:83.72 H:6.72 N：6.32 O:3.19.
Embodiment 7：Synthesize C7
Change 2,3,5,6- tetrafluoro benzonitriles in above-described embodiment 1 into 2,3,4,5,6- phenyl-pentafluoride formonitrile HCNs, by with implementation
1 identical synthetic method of example, obtains product C7.Yield 60%.
Mass spectrum：5230.26.
Elemental analysis, it is as a result as follows：C:86.50 H:5.78 N：1.61 O:6.13.
Embodiment 8：Synthesize C8
Change 3,6- dihydroxy -9- hydrogen-carbazole in above-described embodiment 7 into 3- hydroxycarbazoles, process is same as Example 7
Synthetic method, obtain product C8.Yield 68%.
Mass spectrum：3079.30.
Elemental analysis, it is as a result as follows：C:86.50 H:5.56 N：2.71 O:5.19.
Embodiment 9：Synthesize C9
By 2 in above-described embodiment 3,3,5,6- tetrafluoro benzonitriles change 2,3,4,5,6- phenyl-pentafluoride formonitrile HCNs into, by with reality
3 identical synthetic method of example is applied, product C9 is obtained.Yield 70%.
Mass spectrum：4699.80.
Elemental analysis, it is as a result as follows：C:86.80 H:6.47 N：6.26 O:4.45.
Embodiment 10：Synthesize C10
Change 3,6- dihydroxy -9- hydrogen-carbazole in above-described embodiment 9 into 3- hydroxycarbazoles, process is same as Example 9
Synthetic method, obtain product C10.Yield 76%.
Mass spectrum：2814.06.
Elemental analysis, it is as a result as follows：C:83.59 H:6.05 N：6.85 O:3.55.
Embodiment 11：Synthesize C11
By 2 in above-described embodiment 5,3,5,6- tetrafluoro benzonitriles change 2,3,4,5,6- phenyl-pentafluoride formonitrile HCNs into, by with reality
5 identical synthetic method of example is applied, product C11 is obtained.Yield 60%.
Mass spectrum：4000.27.
Elemental analysis, it is as a result as follows：C:83.10 H:7.30 N：5.62 O:4.02.
Embodiment 12：Synthesize C12
Change 3,6- dihydroxy -9- hydrogen-carbazole in above-described embodiment 11 into 3- hydroxycarbazoles, by with 11 phase of embodiment
Same synthetic method, obtains product C12.Yield 67%.
Mass spectrum：2464.30.
Elemental analysis, it is as a result as follows：C:83.77 H:6.74 N：6.25 O:3.26.
In following embodiments of the present invention, OLED includes the anode/hole transmission layer/hole injection layer/hair stacked gradually
Photosphere/electron transfer layer/electron injecting layer/cathode.Wherein, anode is ITO, and hole transmission layer is NPB, hole injection layer
PEDOT:PSS, luminescent layer are self luminous C1-C12, and electron transfer layer is TPBI, and electron injecting layer is Cs2CO3, cathode Al.
Above-mentioned material is as follows as the OLED performance datas of luminescent layer:
The hot activation delayed fluorescence material based on this novel solution processable is can be seen that by upper table embodiment
Device can realize the external quantum efficiency much larger than conventional fluorescent material (5%).It has also further demonstrated that this novel solvable
The space steric effect of the peripheral branch of the hot activation delayed fluorescence material of liquid processing can effectively reduce the concentration of triplet excitons
It is quenched, realizes that autonomous agent shines, simplify device architecture.And odd even group embodiment comparison (such as embodiment 1 and embodiment 2 it is right
Than) can obtain：With increasing for peripheral branch, the space steric effect of peripheral branch enhances, to further increase device effect
Rate.
It further illustrates, above example is intended merely to absolutely prove the preferred embodiment of the present invention and act, of the invention
It protects without being limited thereto.Thus the obvious variation extended, still returns the range of the invention.
Claims (5)
1. a kind of hot activation delayed fluorescence material of solution processable, which is characterized in that the fluorescent material molecular structure is by two
It is grouped as, a part is the core with hot activation delayed fluorescence property, and another part is that have high three line by alkyl chain link
The group of state energy level, the material have the following structure：
Wherein, R1,R2In at most there are one being hydrogen, remaining is the group with high triplet energy level by alkyl chain link.
2. a kind of hot activation delayed fluorescence material of solution processable according to claim 1, which is characterized in that described
The core of hot activation delayed fluorescence property is the group such as lower structure：
3. a kind of hot activation delayed fluorescence material of solution processable according to claim 1, which is characterized in that described logical
The group with high triplet energy level for crossing alkyl chain link is the group such as lower structure：
4. according to the hot activation delayed fluorescence material of solution processable described in Claims 2 or 3, which is characterized in that the heat
Activate delayed fluorescence material that there is one of following chemical structural formula：
Wherein n is 3,6 or 9.
5. a kind of preparation method of the hot activation delayed fluorescence material of solution processable as described in claim 1, feature is in this
The preparation method of fluorescent material is：Peripheral dendrite is prepared first, then by nucleophilic displacement of fluorine and alkyl chain link, is finally led to again
The connection for crossing the necleophilic reaction and the internal core with hot activation delayed fluorescence property of an alkylidene chain, finally obtains dendritic
Hot activation delayed fluorescence material.
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| CN113336694A (en) * | 2021-05-13 | 2021-09-03 | 东南大学 | Thermally activated sensitized fluorescent dendritic material capable of being processed in solution and preparation method thereof |
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| CN114957654B (en) * | 2022-05-07 | 2023-04-25 | 江苏海洋大学 | Block-packaged heat-activated delayed fluorescent polymer |
| CN115960033A (en) * | 2023-02-08 | 2023-04-14 | 东南大学 | Carbazole-benzonitrile-based thermally-activated delayed fluorescence dendritic isomer material and preparation method thereof |
| CN115960033B (en) * | 2023-02-08 | 2024-05-07 | 东南大学 | Carbazole-benzonitrile-based thermal activation delayed fluorescence dendritic isomer material and preparation method thereof |
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