CN109206359A - Thermal activation delayed fluorescence compound, its purposes and organic electroluminescence device - Google Patents
Thermal activation delayed fluorescence compound, its purposes and organic electroluminescence device Download PDFInfo
- Publication number
- CN109206359A CN109206359A CN201710531550.XA CN201710531550A CN109206359A CN 109206359 A CN109206359 A CN 109206359A CN 201710531550 A CN201710531550 A CN 201710531550A CN 109206359 A CN109206359 A CN 109206359A
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- ring
- alkyl
- cyano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/38—[b, e]-condensed with two six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
-
- 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
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
Abstract
The invention discloses a kind of thermal activation delayed fluorescence compound, its purposes and using its organic electroluminescence device.Shown in the compound structure such as formula (I), wherein R1~R6In at least one be CN or cyano-phenyl, at least one be the heteroaryl containing at least two fused rings.Aromatic compound of the invention has smaller Δ E (S1-T1), it is easy to accomplish thermal activation delayed fluorescence, and due to the influence of ortho position substitution group, the luminescent spectrum peak of compound narrows, and shows and applies more suitable for AMOLED.
Description
Technical field
The present invention relates to technical field of organic electroluminescence, more particularly, to a kind of thermal activation delayed fluorescence compound,
Its purposes and the organic electroluminescence device for using it.
Background technique
The dyestuff utilized earliest in OLED is pure small organic molecule luminescent material.Based on the device of such material, the service life is long
And efficiency roll-off is small.But material can only be shone using 25% S1, and 75% T1 is accounted for because the reason of spin forbidden only
It can be lost by the approach of nonradiative transition.1998, the Forrest etc. of Princeton university is reported for the first time to be based on
T1 luminous PHOLEDs.Making T1 at room temperature using spin-orbit cou-pling effect caused by heavy metal Pt atom can effectively send out
Light, so as to theoretically realize 100% internal quantum efficiency.Currently, most phosphorescent coloring is the complex based on Ir.
The hexahedron configuration of Ir complex is conducive to the high luminous efficiency of material, while reducing caused by material stacks and being quenched.Efficiently
RGB light Ir complex has been reported that, and external quantum efficiency is all more than 30%, is using OLED dyestuff the most successful.
But phosphor material is not perfect yet.Firstly, the service life of phosphor material T1 generally more than 1 μ s, it is much high
In the service life of tens nanosecond of fluorescent material, therefore, efficiency roll-off is serious at higher current densities by PHOLEDs.Secondly, phosphor material
Heavy metal atom is needed to promote T1 to shine, still, also because of the presence of heavy metal, so that the price of phosphorescent coloring is high
It is expensive, especially rare metal Ir complex.Again, the wide band gap of blue phosphor materials causes the service life of blue light PHOLEDs very short,
This is also one of the reason of restricting the further industrialization of PHOLED always.
To solve the above-mentioned problems, other than being improved to device architecture, to thermal excitation delayed fluorescence (TADF) material
It is the important channel for promoting pure organic small molecule material exciton utilization rate in device that material, which carries out exploitation,.On the one hand, this kind of material kind
Class is abundant, cheap；On the other hand, this kind of material can pass through lesser Δ ESTIt is passed through between the gap of realization energy, improves T1's
Utilization rate；In another aspect, this kind of material is the current effective way for solving blue light material bottleneck, prepared currently based on TADF material
Blue-light device EQE already exceed 20%, therefore, be of great significance to the exploitation of this kind of material.
Up to now, the device performance based on TADF material still has biggish gap compared with conventional phosphor material, very heavy
The reason of wanting is exactly that TADF material usually has wider luminescent spectrum, is unfavorable for the application that AMOLED is shown.In order to solve this
Problem, we have a series of new material by introducing ortho position blocking group and having designed and developed, can be reduced intramolecular chemical key
Vibration and rotation when material being made to be applied to AMOLED display, avoid viewing angle problem so that the luminescent spectrum of material be made to narrow
It generates, is more advantageous to propulsion commercial applications.
Chinese patent application CN106316924A discloses a kind of thermal activation delayed fluorescence material, the cyanogen indicated for following formula
The structure for the phenyl ring that base and electron donating group replace,
However, to still have fluorescence spectrum wide for compound disclosed in the prior art, exist not when being applied to AMOLED
The problem of sharp place, such as the defects such as that there are driving voltages is high, current efficiency is low, however it remains room for improvement.
Summary of the invention
The main purpose of the present invention is to provide a kind of thermal activation delayed fluorescence compounds or the compound to be prepared with
Purposes in organic electroluminescence devices, or using its organic electroluminescence device, to solve to reduce driving voltage and/or mention
At least one technical problem in high current efficiency.
The main purpose of the present invention is to provide a kind of thermal activation delayed fluorescence compounds, pass through drawing for neighboring group
Enter, the vibration of intramolecular chemical key is prevented by steric effect, to make the fluorescence emission spectrum of compound narrow, with more advantageous
It shows and applies in AMOLED.
To achieve the goals above, as one aspect of the present invention, the present invention provides a kind of thermal activation delayed fluorescences
Compound, shown in the compound structure such as formula (1):
Wherein, R1~R6At least one is cyano or cyano-phenyl, at least one is to contain the miscellaneous of at least two fused rings
Aryl, remaining R1~R6It is independent to be selected from hydrogen, C1~C4Alkyl, halogen, amino, hydroxyl, cyano, nitro；
Shown in the heteroaryl containing at least two fused rings such as formula (2), wherein A ring and/or B ring is independent is selected from
Benzene, furans, thiophene, thiazole, pyridine or pyrimidine；The A ring and/or B ring can further independently with benzene, furans, thiophene, thiophene
Azoles, pyridine or pyrimidine are condensed；Optionally, the benzene, furans, thiophene, thiazole, pyridine or pyrimidine are independently selected from by 1~4
C1~C4Alkyl, halogen, amino, hydroxyl, cyano, nitro replace；
Wherein, atom adjacent with * on A ring in formula (2) is connected with the phenyl ring in formula (1), the atom adjacent with * on B ring
By C1~C4Alkyl replace.
In a preferred embodiment of the present invention, work as R1~R6When at least one is cyano-phenyl, cyano is located at phenyl
On ortho position, meta or para position.
In a preferred embodiment of the present invention, B ring is condensed in the formula (2) on A ring again；It is condensed with A ring
Two B ring structures are same or different；When the two B ring structures condensed with A ring are identical, the substituent group on two B rings is identical
Or it is different.
In a preferred embodiment of the present invention, the formula (2) is as shown in formula (3),
Wherein the * in formula (3) indicates the connection site connecting with the phenyl ring in formula (1)；
A is selected from N or CH；
RaAnd RbIn one be C1~C4Alkyl, another is H；Or RaAnd RbIt is all C1~C4Alkyl, RaWith
RbIt is same or different；
R8And R7Quantity be respectively 0,1,2 or 3；And when there are multiple R8When, R8It is same or different；And works as and deposit
In multiple R7When, R7It is same or different；R8And R7It is independent to be selected from C1~C4Alkyl, halogen, amino, hydroxyl, cyano, nitre
Base；
N is 0 or 1；
When n is 1, L is-NH- ,-O- ,-S- ,-C (RcRd)-；Wherein RcAnd RdIt is independent to be selected from C1~C4Alkyl, halogen
Element, amino, hydroxyl, cyano, nitro.
R in another preferred embodiment of the present invention, in formula (1)1~R6In 2,3,4 or 5 be
The heteroaryl containing at least two fused rings as shown in formula (2)；Preferably, for synthesis cost the considerations of, multiple such as formula (2)
Shown in the heteroaryl containing at least two fused rings structure and with phenyl ring in formula (1) be connected connection site it is identical；It is excellent
Choosing, the substituent group of multiple heteroaryls containing at least two fused rings as shown in formula (2) and substitution site are also identical.
Preferably, the formula (2) is arylamino, dibenzofuran group, dibenzothiophene, carbazyl, phenoxazine
Base, phenothiazinyl, acridinyl and its derivative.
Further preferably, the formula (3) is carbazyl, dibenzofuran group, dibenzothiophene, phenoxazine base, pheno thiophene
Piperazine base, 9,9-dimethylacridan base.
In the present invention, C1~C4Alkyl be methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl；
Halogen refers to fluorine, chlorine, bromine or iodine.
As another aspect of the present invention, the present invention also provides a kind of thermal activation delayed fluorescence chemical combination as described above
Object is preparing the purposes in organic electroluminescence device.
As still another aspect of the invention, the present invention also provides a kind of organic electroluminescence device, which includes
If first electrode, second electrode and the dried organic layer being inserted between the first electrode and second electrode, wherein described several
Contain spiro fluorene cycle compound as described above in organic layer at least one layer.
According to the above-mentioned technical solution, thermal activation delayed fluorescence compound of the invention has smaller Δ EST, thus easily
It is the luminescent material with TADF property in realizing thermal excitation delayed fluorescence, relative to current TADF luminescent material, the present invention
Compound by introduce ortho position blocking group designed and developed a series of new material, the vibration of intramolecular chemical key can be inhibited
And rotation, so that the luminescent spectrum peak shape of material be made to narrow, it is more advantageous to and is shown applied to AMOLED, is conducive to promote commercialization
Using.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment to this hair
It is bright to be described in further detail.
The invention discloses a kind of thermal activation fluorescence decay compounds, shown in the compound structure such as formula (I):
Wherein, R1~R6At least one is cyano or cyano-phenyl, at least one is to contain the miscellaneous of at least two fused rings
Aryl, remaining R1~R6It is independent to be selected from hydrogen, C1~C4Alkyl, halogen, amino, hydroxyl, cyano, nitro；
Shown in the heteroaryl containing at least two fused rings such as formula (2), wherein A ring and/or B ring is independent is selected from
Benzene, furans, thiophene, thiazole, pyridine or pyrimidine；The A ring and/or B ring can further independently with benzene, furans, thiophene, thiophene
Azoles, pyridine or pyrimidine are condensed；Optionally, the benzene, furans, thiophene, thiazole, pyridine or pyrimidine are independently selected from by 1~4
C1~C4Alkyl, halogen, amino, hydroxyl, cyano, nitro replace；
Wherein, atom adjacent with * on A ring in formula (2) is connected with the phenyl ring in formula (1), the atom adjacent with * on B ring
By C1~C4Alkyl replace.
Preferably, the thermal activation delayed fluorescence compound is one of compound A1~compound A-13 1:
The specific preparation method of above-mentioned noval chemical compound of the invention will be described in detail by taking multiple synthetic examples as an example below, but
Preparation method of the invention is not limited to this multiple synthetic example, and those skilled in the art can not depart from its basis
Any modification, equivalent substitution, improvement and etc. are carried out under the premise of principle of the present invention, and this method is expanded into right of the invention and is wanted
Within the scope of seeking the claimed technical solution of book.
Various chemicals used in the present invention such as petroleum ether, ethyl acetate, n-hexane, toluene, tetrahydrofuran, dichloro
The basic chemical industries such as methane, acetic acid, potassium phosphate, sodium tert-butoxide, butyl lithium raw material chemical products can be commercially available at home, be replaced
Carbazole is made by oneself by company.
Synthetic example 1
The synthesis of compound A1:
The synthesis of intermediate (1): 2,4- bis- is added in a 1000mL three-necked flask equipped with magnetic agitation at room temperature
The bromo- 4- methyl iodobenzene 50g (216mmol, 1.16eq) of methylaniline 37g (186mmol, 1eq), 2-, 3 1.7g of pd2 (dba)
(18.6mmol, 1%eq), dppf 2.06g (3.7mmol, 2%eq), sodium tert-butoxide 27g (279mmol, 1.5eq), toluene
500mL is finished, and is replaced nitrogen 3 times, and stirring is opened, and oil bath heating is warming up to reflux (120 DEG C of oil bath temperature) and reacts 5 hours.
The TLC tracking reaction display fully reacting of 2,4- dimethylaniline (PE/EA=20:1) stops reaction.
Reaction solution is down to room temperature, 500mL dilution with toluene is added, short silicagel column filters, and decompression is spin-dried for, be down to room temperature obtain it is brown
Yellow solid 50g further obtains off-white powder 45g with petroleum ether recrystallization (dissolved clarification freezing).HPLC99.66%, yield
It is 80%.
The synthesis of intermediate (2): intermediate is added in a 1000mL three-necked flask equipped with magnetic agitation at room temperature
(1) 30.3g (100mmol, 1eq), Pd (OAc)22.25g (10mmol, 10%eq), P (Cy)3HBF47.36g (20mmol,
20%eq), potassium carbonate 27.8g (200mmol, 2eq), DMAC 300mL, finish, and replace nitrogen 3 times, open stirring, electric jacket
It is heated to back flow reaction 4 hours.TLC tracking reaction display intermediate (1) fully reacting (PE/EA=20:1), stops anti-
It answers.
Reaction solution to be down to room temperature, pure water 900mL, toluene 300mL liquid separation is added, water phase is extracted with toluene (300mL*2),
Merging organic phase, saturated common salt water washing, anhydrous sodium sulfate is dry, and short silicagel column suction filtration is spin-dried for obtaining yellow-brown solid crude product 15g,
100mL petroleum ether recrystallization (freezing) obtains 13.5g white powder solid.HPLC99.84%, yield 60%.
The synthesis of compound A1: it is added in a 100mL three-necked flask equipped with magnetic agitation under the weak nitrogen stream of room temperature
NaH 240mg (6mmol, 6eq) DMF16mL stirs the lower DMF solution 15mL that intermediate (2) 835mg (5mmol, 5eq) is added dropwise,
Drop finishes, and continues that reaction 1 hour is stirred at room temperature.The lower DMF solution that 2,3,4,5- tetrafluoro cyanophenyl 2mg (1mmol, 1eq) is added dropwise of stirring
15mL, drop, which finishes, to be warming up to 80 DEG C and continues to be stirred to react 4 hours.TLC tracking reaction display 2,3,4,5- tetrafluoro cyanophenyl fully reacting
(PE/EA=8:1), stop reaction.
Reaction solution is down to room temperature, 50ml pure water is added, white solid, filtering, ethanol rinse is precipitated.DCM dissolution, it is anhydrous
Sodium sulphate is dry, and short silicagel column filters, depressurize be spin-dried for off-white powder.(1g:20ml) is recrystallized with 1,4- dioxane
Obtain 0.7g white solid.HPLC99.03%, yield 74%.
Product MS (m/e): 931.5, elemental analysis (C67H57N5): theoretical value C, 86.32%；H, 6.16%；N,
7.51%；Measured value C, 86.57%；H, 6.11%；N, 7.36%.1H NMR (400MHz, CDCl3) δ 8.81 (d, J=
5.7Hz, 5H), 7.93 (s, 4H), 7.47 (s, 4H), 7.13 (d, J=0.7Hz, 4H), 7.00 (d, J=8.5Hz, 4H), 2.50
(s,24H),2.31(s,12H).。
Synthetic example 2:
The synthesis of compound A4:
The synthesis of intermediate (3) compound: 2,4- dimethylaniline is only changed to 2- first with intermediate 1 by synthesis step
The bromo- 4- methyl iodobenzene of 2- is changed to the bromo- 6- methyl iodobenzene of 2- by base aniline, and other reagents are constant, obtain compound intermediate (3).
The synthesis of intermediate (4) compound: intermediate (1) is only changed to intermediate (3) with intermediate 2 by synthesis step,
Other reagents are constant, obtain compound intermediate (4).
The synthesis of compound A4: intermediate (2) is only changed to intermediate (4), Qi Tashi with compound A1 by synthesis step
Agent is constant, obtains compound A4.
Product MS (m/e): 875.4, elemental analysis (C63H49N5): theoretical value C, 86.37%；H, 5.64%；N,
7.99%；Measured value C, 86.45%；H, 5.77%；N, 7.45%.1H NMR(400MHz,CDCl3)δ8.75(s,1H),8.45
(s,4H),8.09(s,4H),7.21–6.80(m,16H),2.50(s,24H).。
Synthetic example 3:
The synthesis of compound A6:
The synthesis of intermediate (5) compound: 2,4- dimethylaniline is only changed to 2,4- with intermediate 1 by synthesis step
The bromo- 4- methyl iodobenzene of 2- is changed to bromo- 4, the 6- dimethyl iodobenzene of 2- by dimethylaniline, and other reagents are constant, obtain in compound
Mesosome (5).
The synthesis of intermediate (6) compound: intermediate (1) is only changed to intermediate (5) with intermediate 2 by synthesis step,
Other reagents are constant, obtain compound intermediate (6).
The synthesis of compound A6: intermediate (2) is only changed to intermediate (6), Qi Tashi with compound A1 by synthesis step
Agent is constant, obtains compound A6.
Product MS (m/e): 987.52, elemental analysis (C71H65N5): theoretical value C, 86.28%；H, 6.63%；N,
7.09%；Measured value C, 86.35%；H, 6.43%；N, 7.10%.1H NMR(400MHz,CDCl3)δ8.75(s,1H),8.45
(s,4H),8.09(s,4H),7.21–6.80(m,16H),2.50(s,24H).。
Synthetic example 4:
The synthesis of compound A-28:
The synthesis of intermediate (7) compound: it is added in a 1000mL three-necked flask equipped with magnetic agitation at room temperature
Bromo- 2,3,5,6- phenyl tetrafluoride 10g (32.7mmol, 1eq) of 1-；4- cyanophenylboronic acid 10.6g (71.9mmol, 2.2eq), four triphens
Base phosphorus palladium 0.814g (0.65mmol, 2%eq), potassium carbonate 27g (196.2mmol, 6eq), Isosorbide-5-Nitrae-dioxane/water (400mL/
100mL), it finishes, replaces nitrogen 3 times, open stirring, oil bath heating is warming up to reflux (120 DEG C of oil bath temperature) and reacts 6 hours.
TLC tracking reaction display bromo- 2,3,5,6- phenyl tetrafluoride fully reacting (PE/EA=8:1) of 1-, stops reaction.
Reaction solution is down to room temperature, liquid separation, water phase is extracted with EtOAc (100mL), merges organic phase, saturated common salt washing
It washs, anhydrous sodium sulfate dries, filters, and decompression is spin-dried for obtaining gray solid.Upper silicagel column (200~300 mesh) is taken out after being dissolved with DCM
Filter, black pigment stay on pillar.The off-white powder being spin-dried for is depressurized, is obtained with re crystallization from toluene (1g 20mL toluene)
10.2g white solid intermediate (7).HPLC99.56%, yield 88%.
The synthesis of compound A-28: intermediate (2) is only changed to intermediate (6) with compound A1 by synthesis step, by 2,3,
5,6- tetrafluoro cyanophenyls are changed to intermediate (7), and other reagents are constant, obtain compound A-28.
Product MS (m/e): 1063.56, elemental analysis (C77H69N5): theoretical value C, 86.89%；H, 6.53%；N,
6.58%；Measured value C, 86.83%；H, 6.57%；N, 6.43%.1H NMR (400MHz, Chloroform) δ 8.70 (d, J=
1.4Hz, 4H), 8.61 (s, 1H), 7.98-7.89 (m, 6H), 7.84 (d, J=7.5Hz, 2H), 6.99 (d, J=1.4Hz, 4H),
6.93 (d, J=1.4Hz, 4H), 2.50 (s, 24H), 2.31 (s, 24H)
Synthetic example 5:
The synthesis of compound A12:
The synthesis of intermediate (8): 2,4- dimethylaniline is only changed to 2- isopropyl -4- with intermediate 1 by synthesis step
Methylaniline, other reagents are constant, obtain compound intermediate (8).
The synthesis of intermediate (9): intermediate (1) is only changed to intermediate (8), Qi Tashi with intermediate 2 by synthesis step
Agent is constant, obtains compound intermediate (9).
The synthesis of compound A12: intermediate (2) is only changed to intermediate (9) with compound A1 by synthesis step, by 2,
3,5,6- tetrafluoro cyanophenyls are changed to intermediate (7), and other reagents are constant, obtain compound A12.
Product MS (m/e): 1119.62, elemental analysis (C81H77N5): theoretical value C, 86.82%；H, 6.93%；N,
6.25%；Measured value C, 86.83%；H, 6.57%；N, 6.43%.1H NMR (400MHz, Chloroform) δ 8.80 (d, J=
1.4Hz, 4H), 8.64 (s, 1H), 8.03-7.91 (m, 6H), 7.84 (d, J=7.5Hz, 2H), 7.47 (d, J=7.5Hz, 4H),
7.27 (dd, J=7.5,1.5Hz, 2H), 7.17 (d, J=1.4Hz, 2H), 7.04-6.98 (m, 4H), 2.89-2.84 (m, 3H),
2.50 (s, 12H), 2.31 (s, 12H), 1.17 (d, J=6.4Hz, 25H)
Synthetic example 6:
The synthesis of compound A17:
The synthesis of intermediate (10): by the iodo- 3- methylphenol 1.0mmol and 3- fluorine-2-nitro methylbenzene 1.0mmol of 2- and
2mmol potassium carbonate is dissolved in 10mLDMSO, heating 15 hours under 100 degree.After being cooled to room temperature, a large amount of water are added, use acetic acid
Second vinegar extracts three times.Organic phase washing is concentrated and dried to obtain intermediate 10 afterwards three times.
The synthesis of intermediate (11): the aqueous solution of potassium carbonate will be added in intermediate 10, is stirred overnight, is extracted with ethyl acetate
It takes, organic phase is dry with anhydrous sodium sulfate, and concentration rear pillar chromatographs to obtain intermediate 11.
The synthesis of compound A17: intermediate (2) is only changed to intermediate (11) with compound A1 by synthesis step, by 2,
3,5,6- tetrafluoro cyanophenyls are changed to 3,5- difluorobenzonilyile, and other reagents are constant, obtain compound A17.
Product MS (m/e): 521.21, elemental analysis (C35H27N3O2): theoretical value C, 80.59%；H, 5.22%；N,
8.06；%；Measured value C, 80.51%；H, 5.27%；N, 8.01%.1H NMR(400MHz,Chloroform)δ7.18(s,
2H), 7.11 (s, 1H), 6.83 (t, J=16.0Hz, 12H), 2.13 (s, 12H)
Synthetic example 7:
The synthesis of compound A19:
The synthesis of intermediate (12): 2,4- dimethylaniline is only changed to 2- isopropyl-with intermediate 1 by synthesis step
The bromo- 4- methyl iodobenzene of 2- is changed to the bromo- 4- methyl -6- isopropyl iodobenzene of 2- by 4- methylaniline, and other reagents are constant, changed
It closes object intermediate (12).
The synthesis of intermediate (13): intermediate (1) is only changed to intermediate (12) by synthesis step with intermediate 2, other
Reagent is constant, obtains compound intermediate (13).
The synthesis of compound A19: intermediate (2) is only changed to intermediate (13) with compound A1 by synthesis step, by 2,
3,5,6- tetrafluoro cyanophenyls are changed to 2,4- difluorobenzonilyile, and other reagents are constant, obtain compound A19.
Product MS (m/e): 657.41, elemental analysis (C47H51N3): theoretical value C, 85.80%；H, 7.81%；N,
6.39%；Measured value C, 85.82%；H, 7.75%；N, 6.34%.1H NMR(400MHz,Chloroform)δ8.70(s,
2H), 8.19 (s, 1H), 7.90 (d, J=24.0Hz, 4H), 7.17 (s, 2H), 7.09 (s, 2H), 2.87 (s, 2H), 2.31 (s,
12H),1.17(s,26H).
Synthetic example 8:
The synthesis of compound A22:
The synthesis of compound A22: intermediate (2) is only changed to intermediate (4) with compound A1 by synthesis step, by 2,
3,5,6- tetrafluoro cyanophenyls are changed to 2,4,6- trifluorobenzonitriles, and other reagents are constant, obtain compound A22.
Product MS (m/e): 682.31, elemental analysis (C49H38N4): theoretical value C, 86.19%；H, 5.61%；N,
8.20%；Measured value C, 86.25%；H, 5.63%；N, 8.16%.1H NMR (400MHz, Chloroform) δ 8.38 (d, J=
55.5Hz, 5H), 8.09 (s, 3H), 7.16 (d, J=20.6Hz, 2H), 7.01 (d, J=16.0Hz, 7H), 6.92 (s, 2H),
2.50(s,18H).
Synthetic example 9:
The synthesis of compound A27:
The synthesis of compound A26: intermediate (2) is only changed to intermediate (4) with compound A1 by synthesis step, by 2,
3,5,6- tetrafluoro cyanophenyls are changed to 4- (2,4,6- trifluorophenyl) cyanophenyl, and other reagents are constant, obtain compound A27.
Product MS (m/e): 758.34, elemental analysis (C55H42N4): theoretical value C, 87.04%；H, 5.58%；N,
7.38%；Measured value C, 87.01%；H, 5.62%；N, 7.41%.1H NMR (400MHz, Chloroform) δ 8.45 (s,
3H), 8.35 (s, 2H), 8.12 (t, J=8.9Hz, 2H), 8.01 (d, J=64.0Hz, 4H), 7.84 (s, 2H), 7.16 (d, J=
11.7Hz, 2H), 7.01 (d, J=16.0Hz, 7H), 6.92 (s, 2H), 2.50 (s, 19H)
The quantum chemical method of the compound of synthesis
The energy-structure for the heat lag fluorescent chemicals 1~31 that the above-mentioned preparation method of the present invention obtains can pass through quantum chemistry
It is calculated, uses 09 software of Gauss for platform, using Density-Functional Theory (DFT) as calculation method, with 6-31g (d)
For base group, quantification theory calculating has been carried out to design compound.It is calculated, is obtained by the optimization to design compound geometric configuration
The steric configuration of compound, corresponding molecular orbital energy level (HOMO energy level, lumo energy and Eg energy level) distribution and data；In turn
Calculating with TD-DFT to the excited level of compound obtains the excited level (T1, S1) of compound；And it is screened out from it
Delayed fluorescence material with smaller Δ E (S1-T1).Quantum chemical method the results are shown in Table 1.
The quantum chemical method result of 1 part of compounds of table
The invention also discloses a kind of heat lag fluorescent chemicals as described above in preparing organic electroluminescence device
Purposes.
A kind of main component the invention also discloses hot activation delayed fluorescence material, the hot activation delayed fluorescence material is
Benzene cyanides as described above.
The invention also discloses a kind of organic electroluminescence device, which includes first electrode, second electrode and insertion
If the dried organic layer between the first electrode and second electrode, wherein if containing in at least one layer being somebody's turn to do in dried organic layer
Thermal activation delayed fluorescence compound as described above.
It is shown below by being specifically applied to the compound to test actual use performance in organic electroluminescence device
Technical effect and advantage of the invention with verifying.
Comparing the device application performance of these luminescent materials for convenience, the present invention devises a simple electroluminescence device,
Used as CzTrz light emitting host material, the present invention, as guest emitting material, uses (the synthesis side 4CzBN using A1~A31
Method bibliography Mater.Horiz., 2016,3,145-151 and CN106316924A) it is used as and compares material.It is illustrated below
The structural formula of each used material of functional layer in OLED device:
The substrate in conventional organic luminescence device, such as glass or plastics can be used in substrate.In Organic Electricity of the invention
Glass substrate is selected in electroluminescence device production, ITO makees anode material.
Hole transmission layer can use various tri-arylamine group materials.The institute in organic electroluminescence device production of the invention
The hole mobile material of selection is NPB.
Electron transfer layer can use various electron transport materials.The institute in organic electroluminescence device production of the invention
The electron transport material of selection is Bphen.
Cathode can use metal and its mixture structure, such as Mg:Ag, Ca:Ag, be also possible to electron injecting layer/gold
Belong to layer structure, such as LiF/Al, Li2The common cathodes structure such as O/Al.It is selected in organic electroluminescence device production of the invention
Cathode material is LiF/Al.
Compound in the present invention is as the material of main part in organic electroluminescence device luminescent layer, and 4CzBN is as luminous
Material is prepared for multiple organic electroluminescence devices altogether, and OLEDs vacuum evaporation forms, and structure is as follows: ITO (50nm)/2-
TNATA (60nm) NPB (20nm)/CzTrz:emitter (5wt%) (30nm)/Bphen (20nm)/LiF (0.5nm)/Al
(150nm).Wherein, emitter is guest emitting material.
The material that source is not specified in above-mentioned each layer of organic electroluminescence device is by commercially available or well known in the art
What preparation method was voluntarily prepared.
Device comparative example 1
Organic electroluminescence device preparation process is as follows in the present embodiment:
The glass plate for being coated with ITO (50nm) transparency conducting layer is ultrasonically treated in commercial detergent, in deionized water
Middle flushing, in acetone: ultrasonic oil removing in alcohol mixed solvent (volume ratio 1: 1) is baked under clean environment and completely removes water
Part, with ultraviolet light and ozone clean, and with low energy cation beam bombarded surface.
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5~9 × 10-3Pa, above-mentioned
Vacuum evaporation 2-TNATA on anode tunic (4,4', 4 "-three [N, N- (2- naphthalene)-phenyl amino] triphenylamines), formed with a thickness of
The hole injection layer of 60nm；The vacuum evaporation compound N PB on hole injection layer forms the hole transport with a thickness of 20nm
Layer, evaporation rate 0.1nm/s.
Electroluminescence layer, concrete operations are formed on above-mentioned hole transmission layer are as follows: by the compound as luminous layer main body
CzTrz is placed in the cell of vacuum phase deposition equipment, and the compound 4CzBN as dopant is placed on vacuum gas-phase and is sunk
In another room of product equipment, two kinds of materials are evaporated simultaneously with different rates, the concentration of compound 4CzBN is 20wt%, vapor deposition
Total film thickness is 30nm.
Vacuum evaporation Bphen forms the electron transfer layer that thick film is 20nm on luminescent layer, and evaporation rate is
0.1nm/s。
The LiF of vacuum evaporation 0.5nm is as electron injecting layer and with a thickness of the Al layer conduct of 150nm on the electron transport layer
The cathode of device.
Device embodiments 1~15
Using with the identical production method of device comparative example 1, difference is only that, by guest emitting material 4CzBN points
It is not replaced into A1, A2, A6, A7, A9, A11, A14, A15, A17, A19, A20, A23, A26, A28, A29 of equivalent.
In same brightness 1000cd/m2Under, it is prepared in measurement organic electroluminescence device embodiment 1~15 organic
Driving voltage, current efficiency and the chromaticity coordinates of electroluminescent device, the results are shown in Table 2.
2 organic electroluminescence device performance of table
The above result shows that new organic materials of the invention are used for organic electroluminescence device, the indigo plant that shines can be made
It moves, is display luminous organic material of good performance.Using bipolarity CzTrz as material of main part, since it is with smaller
△ EST, improve fluorescent device exciton utilization rate.The fluorescent device of preparation (1000cd/m in the case where requiring brightness2), current efficiency
Maximum can reach 12.6cd/A, and CIE~y prepares device up to 0.12, compared to the compound for not carrying out ortho position protection, may be implemented
More blue shines.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (9)
1. a kind of compound, which is characterized in that shown in the compound structure such as formula (1):
Wherein, R1~R6At least one is cyano or cyano-phenyl, at least one is the heteroaryl containing at least two fused rings
Base, remaining R1~R6It is independent to be selected from hydrogen, C1~C4Alkyl, halogen, amino, hydroxyl, cyano, nitro；
Shown in the heteroaryl containing at least two fused rings such as formula (2), wherein A ring and/or B ring are independent selected from benzene, furan
It mutters, thiophene, thiazole, pyridine or pyrimidine；The A ring and/or B ring can further independently with benzene, furans, thiophene, thiazole, pyrrole
Pyridine or pyrimidine are condensed；Optionally, the benzene, furans, thiophene, thiazole, pyridine or pyrimidine are independently selected from C by 1~41~C4
Alkyl, halogen, amino, hydroxyl, cyano, nitro replace；
Wherein, atom adjacent with * on A ring in formula (2) is connected with the phenyl ring in formula (1), and the atom adjacent with * is by C on B ring1~
C4Alkyl replace.
2. compound as described in claim 1, it is characterised in that condense B ring in the formula (2) on A ring again.
3. compound as claimed in claim 2, the formula (2) as shown in formula (3),
Wherein the * in formula (3) indicates the connection site connecting with the phenyl ring in formula (1)；
A is selected from N or CH；
RaAnd RbIn one be C1~C4Alkyl, another is H；Or RaAnd RbIt is all C1~C4Alkyl, RaWith RbPhase
It is same or different；
R8And R7Quantity be respectively 0,1,2 or 3；And when there are multiple R8When, R8It is same or different；And when there are multiple
R7When, R7It is same or different；R8And R7It is independent to be selected from C1~C4Alkyl, halogen, amino, hydroxyl, cyano, nitro；
N is 0 or 1；
When n is 1, L is-NH- ,-O- ,-S- ,-C (RcRd)-；Wherein RcAnd RdIt is independent to be selected from C1~C4Alkyl, halogen, ammonia
Base, hydroxyl, cyano, nitro.
4. compound according to any one of claims 1 to 3, it is characterised in that R1~R6In 2,3,4 or 5
For the heteroaryl containing at least two fused rings as shown in formula (2)；Preferably, multiple to contain at least two as shown in formula (2)
The structure of the heteroaryl of a fused rings and with phenyl ring in formula (1) be connected connection site it is identical.
5. compound according to any one of claims 1 to 3, it is characterised in that the C1~C4Alkyl be methyl,
Ethyl, propyl, isopropyl, normal-butyl, isobutyl group and tert-butyl.
6. compound, which is characterized in that the compound is the compound with one of following structural formula:
7. the compound as described in claim 1 to 6 any one is preparing the purposes in organic electroluminescence device.
8. a kind of organic electroluminescence device, it is characterised in that containing compound described in claim 1 to 6 any one and
Bipolar host material；Preferably, the △ E of the bipolar host materialST<0.3eV.
9. a kind of organic electroluminescence device, the device include first electrode, second electrode and be inserted in the first electrode and
If the dried organic layer between second electrode, which is characterized in that if being wanted at least one layer containing such as right in the dried organic layer
Seek compound described in 1 to 6 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710531550.XA CN109206359A (en) | 2017-07-03 | 2017-07-03 | Thermal activation delayed fluorescence compound, its purposes and organic electroluminescence device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710531550.XA CN109206359A (en) | 2017-07-03 | 2017-07-03 | Thermal activation delayed fluorescence compound, its purposes and organic electroluminescence device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109206359A true CN109206359A (en) | 2019-01-15 |
Family
ID=64992297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710531550.XA Withdrawn CN109206359A (en) | 2017-07-03 | 2017-07-03 | Thermal activation delayed fluorescence compound, its purposes and organic electroluminescence device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109206359A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112110873A (en) * | 2020-09-29 | 2020-12-22 | 信阳师范学院 | Synthesis and application of cyano arene aggregation luminescent material |
| CN112614952A (en) * | 2020-12-15 | 2021-04-06 | 昆山国显光电有限公司 | Organic electroluminescent device and display device |
| CN113045483A (en) * | 2019-12-26 | 2021-06-29 | 北京鼎材科技有限公司 | Compound and application thereof |
| CN114685352A (en) * | 2020-12-28 | 2022-07-01 | 北京鼎材科技有限公司 | Organic electronic light emitting device for thermally activating delayed fluorescent material, organic electronic light emitting device comprising the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160126474A1 (en) * | 2014-10-31 | 2016-05-05 | Samsung Electronics Co., Ltd. | Carbazole-based compound and organic light-emitting device including the same |
| US20160268516A1 (en) * | 2013-08-16 | 2016-09-15 | Konica Minolta, Inc. | Organic electroluminescent element, electronic device, light emitting device, and light emitting material |
| CN106316924A (en) * | 2015-06-16 | 2017-01-11 | 清华大学 | Thermally activated delayed fluorescence material |
| CN108473425A (en) * | 2015-12-28 | 2018-08-31 | 九州有机光材股份有限公司 | Compound, luminescent material and organic illuminating element |
-
2017
- 2017-07-03 CN CN201710531550.XA patent/CN109206359A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160268516A1 (en) * | 2013-08-16 | 2016-09-15 | Konica Minolta, Inc. | Organic electroluminescent element, electronic device, light emitting device, and light emitting material |
| US20160126474A1 (en) * | 2014-10-31 | 2016-05-05 | Samsung Electronics Co., Ltd. | Carbazole-based compound and organic light-emitting device including the same |
| CN106316924A (en) * | 2015-06-16 | 2017-01-11 | 清华大学 | Thermally activated delayed fluorescence material |
| CN108473425A (en) * | 2015-12-28 | 2018-08-31 | 九州有机光材股份有限公司 | Compound, luminescent material and organic illuminating element |
Non-Patent Citations (3)
| Title |
|---|
| COLIN W. ANSON ET AL.: "Influence of Substituents on the Through-Space Shielding of Aromatic Rings", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| 美国化学会: "RN：1367780-54-8", 《STN ON THE WEB》 * |
| 美国化学会: "RN：1500889-74-6", 《STN ON THE WEB》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113045483A (en) * | 2019-12-26 | 2021-06-29 | 北京鼎材科技有限公司 | Compound and application thereof |
| CN112110873A (en) * | 2020-09-29 | 2020-12-22 | 信阳师范学院 | Synthesis and application of cyano arene aggregation luminescent material |
| CN112110873B (en) * | 2020-09-29 | 2022-08-26 | 信阳师范学院 | Synthesis and application of cyanoarene aggregate luminescent material |
| CN112614952A (en) * | 2020-12-15 | 2021-04-06 | 昆山国显光电有限公司 | Organic electroluminescent device and display device |
| CN112614952B (en) * | 2020-12-15 | 2022-09-16 | 昆山国显光电有限公司 | Organic light-emitting device and display device |
| CN114685352A (en) * | 2020-12-28 | 2022-07-01 | 北京鼎材科技有限公司 | Organic electronic light emitting device for thermally activating delayed fluorescent material, organic electronic light emitting device comprising the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105884623B (en) | Amine derivative and Organnic electroluminescent device comprising the amine derivative | |
| WO2018033086A1 (en) | Dibenzo six-membered ring substituted compound having xanthone as core and applications thereof | |
| CN106946850B (en) | A kind of hot activation delayed fluorescence luminescent material and its application | |
| CN109206359A (en) | Thermal activation delayed fluorescence compound, its purposes and organic electroluminescence device | |
| CN115785063A (en) | Organic compound and organic electroluminescent device | |
| CN110396081A (en) | Heterocyclic compound and its application and organic electroluminescence device based on carbazole and fluorenes | |
| CN110386923A (en) | Carbazole compound and its application and organic electroluminescence device | |
| CN108276336A (en) | A kind of organic photoelectric functional material and luminescent device and its preparation method and application | |
| CN111303134A (en) | Organic light-emitting material and organic electroluminescent device | |
| CN111269219A (en) | Organic light-emitting material and organic electroluminescent device | |
| CN110452239B (en) | Nitrogen-containing heterocyclic compound, application thereof and organic electroluminescent device | |
| CN109824672A (en) | A kind of quinazo triazole derivatives and its application in field of organic electroluminescence | |
| CN115894491A (en) | Electron transport material, preparation method thereof, light-emitting device and light-emitting device | |
| CN110407838A (en) | Electroluminescent organic material and device | |
| CN109994636A (en) | A kind of organic electroluminescence device | |
| CN108117495A (en) | Spiro fluorene cycle compound, its purposes and use its organic electroluminescence device | |
| CN112125892B (en) | Compound, electron transport material and organic electroluminescent device | |
| CN106467452B (en) | Organic material and the organic electroluminescent element for using it | |
| CN108191853A (en) | A kind of electroluminescent organic material and device | |
| CN109206413A (en) | One kind is containing heavy-atom compounds, its application and organic electroluminescence device | |
| TW201827570A (en) | Iridium complex compound, composition containing said compound, organic electroluminescent element, display device and lighting device | |
| CN109309166A (en) | Organic electroluminescence device and contain 2,6,9,10- quaternary anthracene compounds | |
| CN113321649B (en) | Compound, electron transport material and organic electroluminescent device | |
| CN112028879B (en) | Electron transport material, organic electroluminescent device and display device | |
| CN111732596B (en) | Hole transport materials for functional layers in organic electroluminescent compounds and light-emitting devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190115 |
|
| WW01 | Invention patent application withdrawn after publication |