CN111393424B - Fluoresenotrianiline compound, organic electronic device, and display device or lighting device - Google Patents

Fluoresenotrianiline compound, organic electronic device, and display device or lighting device Download PDF

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CN111393424B
CN111393424B CN202010366067.2A CN202010366067A CN111393424B CN 111393424 B CN111393424 B CN 111393424B CN 202010366067 A CN202010366067 A CN 202010366067A CN 111393424 B CN111393424 B CN 111393424B
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fluorene spiro
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CN111393424A (en
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廖良生
蒋佐权
朱向东
屈扬坤
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Suzhou University
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Abstract

The invention provides a fluorene spiro triphenylamine compound, an organic electronic device, a display device or an electronic device, wherein the fluorene spiro triphenylamine compound has excellent film forming property and thermal stability by introducing a rigid structure of fluorene spiro triphenylamine, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. The fluorene spiro triphenylamine compound of the present invention can be used as a constituent material of a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer, and can reduce a driving voltage, improve efficiency, luminance, and lifetime. More importantly, the fluorene spiro triphenylamine compound can effectively isolate donor groups and acceptor groups, so that the fluorene spiro triphenylamine compound is an ideal framework for constructing a thermal activation delayed fluorescent material. The preparation method of the fluorene spiro triphenylamine compound is simple, the raw materials are easy to obtain, and the industrialized development requirements can be met.

Description

Fluoresenotrianiline compound, organic electronic device, and display device or lighting device
Technical Field
The invention relates to a fluorene spiro triphenylamine compound, an organic electronic device, a display device or a photo device, and belongs to the technical field of organic photoelectric materials.
Background
An Organic Light Emitting Diode (OLED) is a self-light emitting device in which electrons injected from a cathode and holes injected from an anode are recombined at a light emitting center by applying a voltage to form a molecular exciton, and the molecular exciton releases energy when returning to a ground state to emit light. The organic electroluminescent device has the characteristics of low starting voltage, high brightness, wide color gamut, high color purity, wide viewing angle, quick response, good temperature adaptability and the like, and can be widely applied to displays of electronic products such as mobile phones, computers, MP3 s, televisions and the like.
Currently commercialized organic electroluminescent materials are classified into conventional fluorescent materials and phosphorescent materials, wherein the fluorescent materials can only utilize 25% of singlet excitons, the remaining 75% of triplet excitons are lost by heat or other non-radiative means, and the phosphorescent materials can utilize 100% of excitons due to the heavy atom effect, although the luminous efficiency of the phosphorescent materials is far higher than that of the conventional fluorescent materials, most phosphorescent devices have a severe efficiency roll-off, that is, maximum efficiency at a lower luminance or a lower current density, and as the luminance or the current density increases, the external quantum efficiency of the devices generally suffers from severe reduction and is restricted by the price of precious metals. This undoubtedly increases the cost of the device, and affects the application of the organic electrophosphorescent device in illumination and full-color display.
It is a simple and practical approach to improve device efficiency and reduce cost of organic electrophosphorescent devices by designing new thermally activated delayed fluorescent guest materials. The fluorene spiro triphenylamine compounds and the oxafluorene spiro triphenylamine compounds reported at present as guest materials can improve the device efficiency of the organic electrophosphorescent device and improve the efficiency roll-off of the device, but still have a space for further improvement.
Disclosure of Invention
The invention aims to provide a fluorene spiro triphenylamine compound, an organic electronic device, a display device or a photo device, which can effectively improve triplet state energy level, reduce the gap difference between singlet state and triplet state, and improve fluorescence quantum yield and thermal stability, thereby improving the performances of organic electroluminescent devices, such as luminous efficiency, efficiency roll-off, working voltage and the like.
In order to achieve the purpose, the invention provides the following technical scheme: a fluorene spiro triphenylamine compound, which is represented by the following general formula (1):
Figure BDA0002476783740000021
wherein R is 1 ～R 3 Each independently represents cyano or optionally substituted by one or more R 1 Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R 1 One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;
z represents CR 1 Or N;
R 1 represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or NO 2 、N(R 2 ) 2 、OR 2 、SR 2 、C(＝O)R 2 、P(＝O)R 2 、Si(R 2 ) 3 One or more of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;
R 2 represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.
Further, said R 1 、R 2 And R 3 Each independently selected from cyano or any one of the following general formulae Ar-1 to Ar-39:
Figure BDA0002476783740000031
wherein, the wavy line represents a bond bonded with the mother nucleus of the fluorenylspirotriphenylamine,
R 1 have the meaning as defined in claim 1.
Further, R 1 And R 2 Represents one or more of phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenylboryl, triphenylphosphinyl, diphenylphosphinyloxy, triphenylsilyl or tetraphenylsilyl.
Further, the fluorene spiro triphenylamine compound is selected from any one of the following general formulas 1-1 to 1-40:
Figure BDA0002476783740000051
Figure BDA0002476783740000061
the invention also provides a preparation method of the fluorene spiro triphenylamine compound, which comprises the following steps:
the R is introduced by metal catalytic coupling reaction of 2,4 and 7-position functionalized fluorene spiro triphenylamine or nucleophilic reaction of lithium reagent 1 、R 2 And R 3 A group.
The invention also provides application of the fluorene spiro triphenylamine compound in preparing electronic devices, wherein the electronic devices are selected from organic electroluminescent devices, organic field effect transistors or organic solar cells, and especially application of luminescent guest materials, luminescent host materials, exciton blocking materials or electron transport materials in preparing organic electroluminescent devices.
The invention also provides an electronic device which is provided with the fluorene spiro triphenylamine compound.
Further, the electronic device is an organic electroluminescent device, the organic electroluminescent device comprises an organic light emitting layer, an exciton blocking layer and an electron transmission layer, and the organic electroluminescent device is provided with the fluorene spiro triphenylamine compound.
Compared with the prior art, the invention has the beneficial effects that: the fluorene spiro triphenylamine compound has excellent film forming property and thermal stability by introducing the rigid structure of the fluorene spiro triphenylamine, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. The fluorene spirotriphenylamine compound of the present invention can be used as a material constituting a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer, and can reduce a driving voltage, improve efficiency, luminance, and lifetime. More importantly, the fluorene spiro triphenylamine compound can effectively isolate donor groups and acceptor groups, so that the fluorene spiro triphenylamine compound is an ideal framework for constructing a thermal activation delayed fluorescent material. The preparation method of the fluorene spiro-triphenylamine compound is simple, raw materials are easy to obtain, and the industrialized development requirements can be met.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 shows the ultraviolet absorption spectrum (UV-Vis), the room temperature fluorescence spectrum (PL) and the low temperature phosphorescence spectrum (Phos) of compounds 1 to 25 in example 5 of the present invention;
FIG. 2 is a graph showing an organic electroluminescence spectrum of an OLED device in example 7 of the present invention.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The invention provides a fluorene spiro triphenylamine compound, which is a compound containing a general formula (1) as follows:
Figure BDA0002476783740000081
wherein R is 1 ～R 3 Each independently represents a hydrogen atom, a cyano group or optionally substituted by one or more R 1 Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R 1 One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;
z represents CR 1 Or N;
R 1 represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO 2 、N(R 2 ) 2 、OR 2 、SR 2 、C(＝O)R 2 、P(＝O)R 2 、Si(R 2 ) 3 One or more of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;
R 2 represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.
<R 1 And R 3 >
R 1 ～R 3 Each independently represents a hydrogen atom, a cyano group or optionally substituted by one or more R 1 Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R 1 One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms.
From R 1 ～R 3 The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be exemplified by: <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , -3236 zxft 3236- , -5262 zxft 5262- , -3763 zxft 3763- , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> Phenoxazinyl, phenothiazinyl, fluoresceinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazolyl, N-phenylcarbazolylOxazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenylboryl, triphenylphosphoxy, diphenylphosphatoxy, triphenylsilyl, tetraphenylsilyl, and the like.
In the present invention, preferably, R 1 ～R 3 Each independently selected from a hydrogen atom, a cyano group or the following group:
Figure BDA0002476783740000101
wherein the wavy line represents a bond to the parent nucleus, R 1 Have the meaning defined above.
From R 1 ～R 3 The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from Ar 1 ～Ar 6 The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by 1 Substituted, aromatic hydrocarbon radicals having 5 to 30 carbon atoms or substituted by one or more R 1 Substituted aromatic heterocyclic group having 5 to 30 carbon atoms.
<R 1 >
R 1 Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO 2 、 N(R 2 )、OR 2 、SR 2 、C(＝O)R 2 、P(＝O)R 2 、Si(R 2 ) 3 One or more of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms.
From R 1 The alkyl group having 1 to 20 carbon atoms represented may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-butylPentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.
From R 1 The alkyl group having 1 to 20 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from R 1 Alkyl having 1 to 20 carbon atoms represented by one or more of the following R 2 And (4) substitution. In addition, one or more non-adjacent CH in the alkyl group 2 The group can be represented by R 2 C＝CR 2 、C≡C、Si(R 2 ) 3 、C＝O、 C＝NR 2 、P(＝O)R 2 、SO、SO 2 、NR 2 O, S or CONR 2 And wherein one or more hydrogen atoms may be replaced by deuterium atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups.
From R 1 The alkenyl group having 2 to 20 carbon atoms represented may be exemplified by: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, or cyclohexenyl and the like. The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.
From R 1 The alkenyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R 1 The alkyl group having 1 to 20 carbon atoms represented may have the same substituent as that shown for the substituent. The substituents may take the same pattern as that of the exemplary substituents.
From R 1 The alkynyl group having 2 to 20 carbon atoms represented may be exemplified by: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl and the like.
From R 1 The alkynyl group having 2 to 20 carbon atoms represented may be unsubstituted, or may have a substituent. The substituents can be exemplified by the group consisting of R 1 The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.
From R 1 The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the above formula may be exemplified by the group consisting of Ar 1 ～Ar 6 The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by the above formula represent the same groups.
From R 1 The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R 1 The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents. In addition, two adjacent R 1 Substituents or two adjacent R 2 The substituents optionally may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more R 2 Substitution; where two or more substituents R 1 May be connected to each other and may form a ring.
Preferably represented by R 1 The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by (a) may be exemplified by: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazolyl, benzofurocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, triazinyl, dibenzoylFuryl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenylboranyl, triphenylphosphonyloxy, diphenylphosphinyloxy, triphenylsilyl, tetraphenylsilyl, and the like. The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms may be substituted with one or more R 2 And (4) substitution.
<R 2 >
R 2 Represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.
From R 2 The alkyl group having 1 to 20 carbon atoms represented by R 1 The alkyl groups represented by the formulae having 1 to 20 carbon atoms represent the same groups.
From R 2 The aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented by the formula 1 The same groups as those shown for the aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.
From R 2 The alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, or may also have a substituent. The substituents may be exemplified by: a deuterium atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; cyano, and the like.
<Z>
Z represents CR 1 Or N, e.g. N, C-H, C-F, C-Cl, C-Br, C-I, C-CN, C-NO 2 Carbon-phenyl, carbon-biphenyl, and the like.
R 1 Have the meaning as defined above.
In a particularly preferred embodiment of the invention:
wherein R is 1 、R 2 And R 3 Each independently selected from cyano or the following aromatic or heteroaromatic ring systems: pyridyl, diphenylamino, dimethylbutyranyl, diphenyltriazinyl; the aromatic or heteroaromatic ring system may be substituted by one or more R 1 Substitution;
r at each position 1 The groups are independently selected from: hydrogen, straight chain alkyl having 1 to 5C atoms.
Preferably, the fluorene spiro triphenylamine compound is selected from any one of the following general formulas 1-1 to 1-40:
Figure BDA0002476783740000141
Figure BDA0002476783740000151
the invention also provides a preparation method of the fluorene spiro triphenylamine compound, which comprises the following steps:
the compounds according to the present invention can be prepared by synthetic procedures known to those of ordinary skill in the art, such as bromination, suzuki coupling, buhward-Hartwig coupling, etc.
The compound synthesis of the present invention typically begins with 2,4 and a 7-position functionalized fluorene spirotriphenylamine compound, followed by introduction of R by lithium reagent nucleophilic reactions or metal catalyzed coupling reactions such as Suzuki coupling or Buhward-Hardwig-Hartwald coupling 1 、R 2 And R 3 A group.
In a preferred embodiment of the present invention, the fluorene spirotriphenylamine compound is a compound functionalized with a boric acid compound, and R 1 、R 2 And R 3 The groups are derived from halogen functionalized compounds. In another preferred embodiment of the present invention, the fluorene spiro triphenylamine compound is halogen-functionalizedCompound (b), and R R 1 、R 2 And R 3 The group is derived from a compound functionalized with a boronic acid compound.
In a third preferred embodiment of the present invention, the fluorene spiro triphenylamine compound is a halogen-functionalized compound, and is reacted with an amine compound under the action of a palladium catalyst to introduce R 1 、R 2 And R 3 A group. Among these, halogen functionalization is preferably bromination, chlorination, iodination, and particularly bromination.
In a fourth preferred embodiment of the present invention, the fluorene spiro triphenylamine compound is a halogen-functionalized compound, and is reacted with a phosphorus-based or silicon-based or boron-based compound under the action of a lithium reagent to introduce R 1 、R 2 And R 3 A group. Among these, halogen functionalization is preferably bromination, chlorination, iodination, and particularly bromination.
Specifically, as described above for the first preferred embodiment, a boronic acid-functionalized fluorene spiro triphenylamine compound (intermediate M3) is prepared, and preferred preparation steps are exemplified as follows:
Figure BDA0002476783740000161
by controlling the reaction conditions, the yield of M1 can reach 80-92%, the yield of M2 can reach 60-80%, and the yield of M3 can reach 70-85%. After obtaining an intermediate M3, adding an introducible R into the system 1 、R 2 And R 3 Halogen functional compounds of the group such as 2,4-dichloro-6-phenyl-1,3,5-triazine or melamine, and a certain amount of palladium catalyst such as tetrakis (triphenylphosphine palladium), anhydrous potassium carbonate, tetrahydrofuran and water are reacted under nitrogen protection at 50-80 ℃ for 30-35 hours, and the reaction is completed. Evaporating the solvent, dissolving the residue with dichloromethane and water, washing with water, separating organic layer, extracting water layer with dichloromethane, mixing organic layers, washing with water twice to neutrality, evaporating to remove solvent, separating by column chromatography, and drying to obtain the product. The molar ratio of intermediate M3 to tetrakis (triphenylphosphine palladium) is in the range of 15 to 20, preferably 18; by adjusting the reaction conditions, the yield is 65-85％。
In the second preferred embodiment, as mentioned above, preferably using M2 and boric acid compound functionalized compound pyridine-3-boric acid reaction, adding tetrakis (triphenylphosphine) palladium, anhydrous potassium carbonate, tetrahydrofuran and water into the system, and reacting for 30-35 hours at 50-80 ℃ under the protection of argon, and the reaction is completed. The post-treatment is the same as in the first preferred embodiment. The final product yield can reach 79 percent.
In the third preferred embodiment, M2 is preferably reacted with diphenylamine functionalized by amine compounds, and tris (dibenzylideneacetone) dipalladium, sodium tert-butoxide, tri-tert-butylphosphine tetrafluoroborate and toluene are added into the system, and the reaction is completed at 90-120 ℃ for 10-30 hours under the protection of argon. And (4) carrying out suction filtration, decompressing, steaming to remove the solvent, carrying out column chromatography separation, and drying to obtain the product. The molar ratio of intermediate M2 to tris (dibenzylideneacetone) dipalladium is in the range of 15 to 20, preferably 18; by adjusting the reaction conditions, the yield can reach 78%.
As described above in the fourth preferred embodiment, it is preferable that M2 is dissolved in tetrahydrofuran, n-butyllithium is dropped at a low temperature, and stirring is carried out at-78 ℃ for 1 hour, then, a boron-functionalized compound such as bis (trimethylphenyl) boron fluoride dissolved in tetrahydrofuran is slowly dropped into a reaction flask, and after 1 hour, the temperature is automatically raised, and the reaction is carried out overnight. Adding a small amount of water into a reaction bottle to quench the reaction, evaporating the solvent under reduced pressure, carrying out column chromatography separation, and drying to obtain the product, wherein the yield can reach 78%.
The invention also provides application of the fluorene spiro triphenylamine compound in preparing electronic devices, wherein the electronic devices are selected from organic electroluminescent devices, organic field effect transistors or organic solar cells, and especially application of luminescent host materials, exciton blocking materials or electron transport materials in preparing organic electroluminescent devices.
The invention furthermore relates to electronic devices comprising at least one compound according to the invention. The electronic device is preferably selected from the group consisting of organic electroluminescent devices (organic light emitting diodes, OLEDs), organic field effect transistors (O-FETs), organic solar cells (O-SCs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic integrated circuits (O-ICs), organic Dye Sensitized Solar Cells (ODSSCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs), organic laser diodes (O-lasers), organic plasma emitting devices and the like, preferably organic electroluminescent devices (OLEDs).
An OLED generally comprising: substrates such as, but not limited to, glass, plastic, metal; an anode, such as an Indium Tin Oxide (ITO) anode; a Hole Injection Layer (HIL); a Hole Transport Layer (HTL); an Electron Blocking Layer (EBL); an organic light emitting layer (EML); an Exciton Blocking Layer (EBL); an Electron Transport Layer (ETL); electron Injection Layers (EIL), e.g. Liq, cs 2 CO 3 (ii) a A cathode, such as Al. However, it should be noted that there may be one or more layers per layer in between and that each layer need not be present.
The compound of the present invention may be used for any layer or layers of the device, but is preferably used for an emission layer (EML), more preferably a host material of the emission layer, because it has a high triplet level and is stable. The compounds of the present invention can also be used as exciton blocking materials or electron transport materials in Exciton Blocking Layers (EBL) and Electron Transport Layers (ETL) due to their good carrier transport ability.
The organic light-emitting layer dopant of the present invention is not particularly limited, and is preferably a light-emitting metal complex, preferably a complex of iridium and platinum, and a light-emitting organic molecule, preferably a fluorescent compound and a thermally-excited delayed fluorescence compound. In order to improve the device performance, the mass ratio of the dopant is 6% to 30%, preferably 6% to 20%, and more preferably 6% to 15%.
In a preferred embodiment of the present invention, the OLED comprises: substrate/anode/hole injection material (HIL)/hole transport material (HIL)/Electron Blocking Layer (EBL)/organic light emitting layer (EML)/Electron Transport Layer (ETL)/cathode. Wherein, the substrate uses a glass substrate, and ITO is used as an anode material. The hole injection material used was 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN) commonly used in the art, and the hole transport material used was 4,4' - (cyclohexane-1,1-diyl) bis (N, N-CN) commonly used in the art-di-p-Tolylaniline) (TAPC); the electron blocking layer uses tri (4- (9H-carbazole-9-yl) phenyl) amine (TCTA) commonly used in the prior art; the organic light-emitting layer is doped with the compound of the invention in host materials 9,9'- (1,3-phenyl) di-9H-carbazole (mCP) and 4,4' -di (9-Carbazole) Biphenyl (CBP) which are commonly used in the prior art. In addition, the compound doped with 8-hydroxyquinoline-lithium or metallic lithium can be used as an electron transport layer, and part of devices also use bis (10-hydroxybenzo [ H ] common in the prior art]Quinoline) beryllium (Be (bq) 2 ) And tris (8-hydroxyquinoline) aluminum (Alq) 3 ). The cathode adopts metal and mixture structure thereof, such as Mg: ag, ca: ag and the like, and can also be electron injection layer/metal layer structure, such as LiF/Al, liq/Al and Li 2 O/Al. In the invention, liq is preferably used as the electron injection material, and Al is preferably used as the cathode material.
The present invention is described below by way of examples, which are not exhaustive, as those skilled in the art will appreciate that the examples are illustrative only. The preparation examples are compound synthesis examples, the related chemical raw materials and reagents are all commercially available or synthesized according to published documents, and the examples are preparation of light-emitting devices, namely OLEDs.
Preparation examples
Synthesis of intermediate M3
The structural formula and the synthetic route of the intermediate M3 are shown as the following formula:
Figure BDA0002476783740000191
the preparation method of the compound of the formula M1 comprises the following steps: in a 100mL two-necked flask, 1.6g (6.2 mmol) of 4-bromo-fluorenone was dissolved in 50mL of dichloromethane, and the mixture was stirred in an ice bath. 0.67mL (12.8 mmol) of liquid bromine was added dropwise from a dropping funnel with a constant pressure. After the addition, the system was gradually warmed to room temperature and reacted for 6 hours. After the reaction is completed, the reaction solution is poured into saturated sodium bisulfite solution, dichloromethane is used for extraction for 3 times, and after an organic phase is dried by anhydrous sodium sulfate, the solvent is removed by rotary drying to obtain a crude product. The crude product was purified with dichloromethane: petroleum ether =1: the column was purified by separation on silica gel with an eluent of 5 (vol/vol) to give 2.3g of M1 in 90% yield. MS (EI)): m/z 417.05[M + ]. Calculated value of elemental analysis C 13 H 5 Br 3 O (%): c37.45, H1.21; measured value: c37.41 1.20
The preparation method of the compound of the formula M2 comprises the following steps: 1.6 (4.9 mmol) of 2-bromo-triphenylamine was dissolved in 30mL of anhydrous tetrahydrofuran in a 100mL two-necked flask under nitrogen, stirred, and cooled to-78 ℃. 2.3mL (5.5 mmol) of 2.4M n-butyllithium were added dropwise to the solution via a constant pressure dropping funnel, and stirring was continued at-78 ℃ for 1 hour. Then 2.0g (4.9 mmol) of M1 was dispersed in 30mL of anhydrous tetrahydrofuran under nitrogen and added dropwise to the reaction solution. After the addition, the temperature was gradually raised to room temperature, and the reaction was carried out for 12 hours. After the reaction was complete, 5mL of water was added to quench the reaction and the tetrahydrofuran was removed by rotary drying. The crude product was dissolved in 150mL of dichloromethane and washed 3 times with 60mL of water. The organic phase was dried over anhydrous sodium sulfate and the solvent was removed by rotary drying to give the crude product. The crude product was purified with dichloromethane: petroleum ether =3:1 (volume ratio) of eluent was separated and purified on a silica gel column to obtain 3.0g of an intermediate product. The resulting intermediate was dissolved in 25mL of acetic acid in a 50mL two-necked flask and 2.5mL of hydrochloric acid was added, and the mixture was heated to reflux with stirring and reacted for 6 hours. After the reaction is completed, cooling the reaction system to room temperature, pouring the reaction system into 300mL of ice water, carrying out vacuum filtration, and washing filter residues for three times. And (3) using dichloromethane for filter residue: petroleum ether =1:4 (volume ratio) eluent is separated and purified on a silica gel column to obtain 2.2g M2, and the yield is 70%. MS (EI) m/z 644.54[ M ] + ]. Calculated value of elemental analysis C 31 H 18 Br 3 N (%): c57.80, H2.82, N2.17; measured value: c57.60, H2.80, N2.15.
The preparation method of the intermediate M3 comprises the following steps: in a 100mL Schlenk reaction flask, under the protection of argon, 2.0g M2 (3.05 mmol) and 50mL tetrahydrofuran were charged, dissolved and cooled, 2.4M n-butyllithium (1.3 mL (3.2 mmol) was added dropwise at-78 deg.C, stirring was completed for 1 hour, triisopropyl borate (0.8 g) (4.5 mmol) was added dropwise, stirring was performed for 1 hour, the temperature was automatically raised, and the reaction was allowed to stand overnight. The reaction was quenched by the addition of 10mL of aqueous ammonium chloride. Transferring the reaction mass into a single-mouth bottle, evaporating the solvent under reduced pressure, adding 80mL dichloromethane and 80mL water into the bottle, dissolving, washing with water, and layeringThe aqueous layer was extracted twice with 15mL of dichloromethane, the organic phases were combined and washed twice with 80mL of water to neutrality. The aqueous layer was separated, and 15g of anhydrous sodium sulfate was added to the organic layer, followed by drying for 3 hours. The solvent was evaporated under reduced pressure to give 1.3g of a white solid in 80% yield. MS (EI): m/z 539.19[ m ], [ m/z ] + ]. Calculated value of elemental analysis C 31 H 24 B 3 NO 6 (%): c69.08, H4.49, N2.60; measured value: c68.95, H4.40 and N2.58.
Example 1
The structural formulas and synthetic routes of the compounds 1-27 are shown as follows:
Figure BDA0002476783740000201
under nitrogen protection, 1.6g (2.5 mmol) of M2, 1.11 g (9 mmol) of pyridine-3-boronic acid, 50mL of toluene, 10mL of ethanol, 10mL of 2M aqueous sodium carbonate solution, and 0.15g (1.25 mmol) of palladium tetrakistriphenylphosphine were sequentially added to a 100mL two-necked flask, and the mixture was stirred and heated to 106 ℃ for reaction for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature. Extracting with dichloromethane three times, drying the organic phase with anhydrous sodium carbonate, and spin-drying to remove the solvent to obtain a crude product, which is extracted with dichloromethane: petroleum ether =7:3 (volume ratio) of eluent on silica gel column basified by triethylamine to obtain 1.3g of 1-27, the yield is 79%. MS (EI) m/z 638.52[ M ] + ]. Calculated value of elemental analysis C 46 H 30 N 4 (%): c86.49, H4.73, N8.77; measured value: c86.39, H4.70 and N8.72.
Example 2
The structural formulas and synthetic routes of the compounds 1-28 are shown as follows:
Figure BDA0002476783740000211
under the protection of nitrogen, 1.6g (2.5 mmol) of M2, 1.11 g (3 mmol) pyridine-4-boric acid, 50mL toluene, 10mL ethanol, 10mL 2M aqueous sodium carbonate solution, 0.15g (tetrakistriphenylphosphine palladium) and1.25 mmol) was added and heated to 106 ℃ with stirring for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature. Extraction with dichloromethane three times, drying of the organic phase over anhydrous sodium carbonate and spin-drying to remove the solvent to give the crude product, which is purified with dichloromethane: petroleum ether =7:3 (volume ratio) of eluent is separated and purified on a silica gel column alkalized by triethylamine to obtain 1.3g of 1-28, and the yield is 79%. MS (EI) m/z 638.52[ M ] + ]. Calculated value of elemental analysis C 46 H 30 N 4 (%): c86.49, H4.73, N8.77; measured value: c86.38, H4.68 and N8.70.
Example 3
The structural formulas and the synthetic routes of the compounds 1-6 are shown as follows:
Figure BDA0002476783740000212
under the protection of nitrogen, 1.4g (2.5 mmol) of M3, 2.4g (7.8 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 50mL of toluene, 10mL of ethanol, 10mL of 2M aqueous sodium carbonate solution and 0.15g (1.25 mmol) of palladium tetratriphenylphosphine are sequentially added into a 100mL two-neck flask, and the mixture is stirred and heated to 106 ℃ for reaction for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature. Extraction with dichloromethane three times, drying of the organic phase over anhydrous sodium carbonate and spin-drying to remove the solvent to give the crude product, which is purified with dichloromethane: petroleum ether =7:3 (volume ratio) eluent is separated and purified on a silica gel column to obtain 2.2g 1-6, and the yield is 79%. MS (EI) m/z 1100.25[ M ] + ]. Calculated value of elemental analysis C 76 H 48 N 10 (%): c82.89, H4.39, N12.72; measured value: c82.80, H4.37, N12.74.
Example 4
The structural formulas and the synthetic routes of the compounds 1 to 10 are shown as follows:
Figure BDA0002476783740000221
under nitrogen, 3.1g (4.9 mmol) of M2 were dissolved in a 100mL two-necked flaskIn 30mL of anhydrous tetrahydrofuran, stirred and cooled to-78 ℃. 2.3mL (5.5 mmol) of 2.4M n-butyllithium were added dropwise to the solution via a constant pressure dropping funnel, and stirring was continued at-78 ℃ for 1 hour. Then, 3.9g (14.7 mmol) of bis (trimethylphenyl) boron fluoride was dispersed in 30mL of anhydrous tetrahydrofuran under a nitrogen blanket and added dropwise to the reaction solution. After the addition, the temperature was gradually raised to room temperature, and the reaction was carried out for 12 hours. After the reaction was complete, 5mL of water was added to quench the reaction and the tetrahydrofuran was removed by rotary drying. The crude product was dissolved in 150mL of dichloromethane and washed 3 times with 60mL of water. The organic phase is dried by anhydrous sodium sulfate and then the solvent is removed by rotary drying to obtain a crude product. The crude product was purified with dichloromethane: petroleum ether =3:1 (volume ratio) of eluent is separated and purified on a silica gel column to obtain 4.2g of 1-10, and the yield is 75%. MS (EI) m/z 1151.69[ M ], [ M ] + ]. Calculated value of elemental analysis C 85 H 84 B 3 N (%): c88.62, H7.35, N1.22; measured value: c88.50, H7.30, N1.20.
Example 5
The structural formulas and the synthetic routes of the compounds 1 to 25 are shown as follows:
Figure BDA0002476783740000231
in a 100mL two-necked flask, 3.1g (4.9 mmol) of M2,1.5g (15.3 mmol) of cuprous cyanide was dissolved in 40mL of N, N-dimethylformamide under nitrogen, stirred, and heated to 150 ℃ for reaction for 24 hours. After the reaction was completed, the reaction solution was poured into 50mL of saturated sodium hydroxide solution, and filtered under suction to obtain a crude product. The crude product was dissolved in 150mL of dichloromethane and washed 3 times with 60mL of water. The organic phase is dried by anhydrous sodium sulfate and then the solvent is removed by rotary drying to obtain a crude product. The crude product was purified with dichloromethane: petroleum ether =3:2 (volume ratio) on silica gel column to obtain 1.8g 1-25, the yield is 77%. MS (EI) m/z 482.36[ M ] + ]. Calculated value of elemental analysis C 34 H 18 N 4 (%): c84.63, H3.76, N11.61; measured value: c84.47, H3.71, N11.50.
Referring to FIG. 1, FIG. 1 shows the UV absorption of products 1-25Absorption spectra, ultraviolet absorption spectra (UV-Vis), room temperature fluorescence spectra (PL), and low temperature phosphorescence spectra (Phos). Ultraviolet absorption spectrum and room temperature fluorescence spectrum in dilute solution (1X 10) of dichloromethane and toluene respectively -5 mol/L) is measured; low temperature phosphorescence Spectroscopy in toluene solution (1X 10) -3 mol/L) in the reaction mixture.
Example 6
The structural formulas and synthetic routes of the compounds 1-32 are shown as follows:
Figure BDA0002476783740000232
a250 mL two-neck flask was charged with 1.5g (2.3 mmol) of M2,1.5g (8.9 mmol) of diphenylamine, 0.3g (2.9 mmol) of sodium tert-butoxide, 0.1g (0.3 mmol) of tri-tert-butylphosphine tetrafluoroborate, and 0.27 g (0.3 mmol) of tris (dibenzylideneacetone) dipalladium in this order, the reaction system was degassed, 150mL toluene was added under nitrogen protection, and the mixture was stirred and heated to 106 ℃ for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out vacuum filtration, washing filter residue with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and adding petroleum ether: dichloromethane =2:3 (volume ratio) eluent is separated and purified on a silica gel column to obtain 1.9g 1-32 of target products, and the yield is 92%. MS (EI) m/z 908.30[ M ] + ]. Calculated value of elemental analysis C 67 H 48 N 4 (%): c88.52, H5.32, N6.16; measured value: c88.45, H5.30 and N6.13.
Device embodiments
Examples 7 to 15
Preparing a device: the glass plate coated with the ITO transparent conductive layer is subjected to ultrasonic treatment in a commercial cleaning agent, washed in deionized water, washed in acetone and ethanol for three times respectively, baked in a clean environment to completely remove moisture, washed by ultraviolet light and ozone, and bombarded on the surface by low-energy cation beams. Placing ITO conductive glass into a vacuum chamber, and vacuumizing to 2 × 10 -5 -2×10 -5 Pa. Then, a hole injection material (HIL), a hole transport material (HIL), an Electron Blocking Layer (EBL) and an organic light emitting layer (EML) are sequentially evaporated on the ITO conductive glassAn Electron Transport Layer (ETL) and a cathode; wherein, the evaporation rate of the organic material is 0.2nm/s, the evaporation rate of the metal electrode is more than 0.5nm/s, the evaporation rate of the luminescent layer is 0.2nm/s by a double-source co-evaporation method, the evaporation rate of the main material is 0.2nm/s, and the evaporation rate of the doping material is 0.03nm/s.
Testing the performance of the device: the current-luminance-voltage characteristics of the device were obtained from a Keithley source measuring system (Keithley 2400Sourcemeter, keithley 2000 Currentmeter) with calibrated silicon photodiodes, the electroluminescence spectra were measured by a Photo research PR655 spectrometer, and the external quantum efficiencies of the devices were calculated by the method of the documents adv.mater, 2003,15,1043-1048. All devices were encapsulated in a nitrogen atmosphere.
The examples relate to compounds having the following structure:
Figure BDA0002476783740000251
the structures of examples 7 to 12 (devices OLED1 to 6, respectively) and the film thicknesses of the respective layers are as follows:
OLED1：
ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt％1-25:CBP(15 nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm)。
OLED2：
ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt％1-10:CBP(15 nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm)。
OLED3：
ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt％1-27:CBP(15 nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm)。
OLED4：
ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt％1-28:CBP(15 nm)/TmPyPB(15nm)/Liq(2nm)/Al(120nm)。
OLED5：
ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt％1-32:CBP(15 nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm)。
OLED6：
ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt％1-6:CBP(15 nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm)。
comparative example
The preparation method of comparative example 1 is the same as that of the example, only the guest material is changed, and the device structure of comparative example 1 is as follows:
ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt％ACRFLCN:CBP(15 nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm)。
the device performance data is shown in table 1:
table 1: device performance data
Figure BDA0002476783740000261
As can be seen from table 1, the compounds of the invention gave very good performance data. Comparative example 1 and example 7 use CBP as the host material, except that the guest material of example 7 is the compounds 1 to 25 of the present invention, and it can be seen from the comparison of the device performance data that example 7 has a lower operating voltage and a higher external quantum efficiency, and the device attenuation is significantly improved. Referring to fig. 2, the organic electroluminescence spectrum of example 7 is shown, which shows a strong luminescence intensity and sufficient energy transfer from the host material to the guest material. Therefore, compared with the materials commonly used in the prior art, the compound provided by the invention can effectively reduce the working voltage, improve the external quantum efficiency and improve the efficiency attenuation problem of the device.
In summary, the following steps: the fluorene spiro triphenylamine compound has excellent film forming property and thermal stability by introducing the rigid structure of the fluorene spiro triphenylamine, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. The fluorene spirotriphenylamine compound of the present invention can be used as a material constituting a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer, and can reduce a driving voltage, improve efficiency, luminance, and lifetime. More importantly, the fluorene spiro triphenylamine compound can effectively isolate donor groups and acceptor groups, so that the fluorene spiro triphenylamine compound is an ideal framework for constructing a thermal activation delayed fluorescent material. The preparation method of the fluorene spiro triphenylamine compound is simple, the raw materials are easy to obtain, and the industrialized development requirements can be met.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (5)

1. A fluorene spiro triphenylamine compound, characterized by being selected from any one of the following chemical formulae 1-1 to 1-40:
Figure FDA0003890683700000011
Figure FDA0003890683700000021
2. an organic electronic device, comprising: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains the compound according to claim 1.
3. The organic electronic device according to claim 2, wherein the organic layer is composed of one or more of a light emitting material, a sensitizing material, and a host material, and the compound is any one or more of the light emitting material, the sensitizing material, or the host material.
4. The organic electronic device according to claim 2, wherein the organic layer comprises one or more layers of a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, and an electron injection layer, and the compound is contained in a structure of the one or more layers of the hole injection layer, the hole transport layer, the electron blocking layer, the electron transport layer, and the electron injection layer.
5. A display device or a lighting device comprising the organic electronic device according to any one of claims 2 to 4.
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