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

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

Fluorene spirotriphenylamine compound, organic electronic device and display device or lighting device

technical field

The invention relates to a fluorene spirotriphenylamine compound, an organic electronic device, a display device or a photo device, and belongs to the technical field of organic photoelectric materials.

Background technique

An organic light emitting diode (OLED) is a self-luminous device. By applying a voltage, electrons injected from the cathode and holes injected from the anode recombine at the luminescent center to form molecular excitons, and the molecular excitons release energy when returning to the ground state. glow. Organic electroluminescent devices have the characteristics of low turn-on voltage, high brightness, wide color gamut, high color purity, wide viewing angle, fast response, and good temperature adaptability, and can be widely used in mobile phones, computers, MP3, TVs and other electronic product displays.

Currently commercialized organic electroluminescent materials are divided into traditional fluorescent materials and phosphorescent materials, in which fluorescent materials can only utilize 25% of singlet excitons, and the remaining 75% of triplet excitons are lost through heat or other non-radiative means, while Phosphorescent materials can utilize 100% of excitons due to the heavy atom effect. Although the luminous efficiency is much higher than that of traditional fluorescent materials, most phosphorescent devices have a serious efficiency roll-off, that is, at lower brightness or lower current density. With the increase of brightness or current density, the external quantum efficiency of the device generally decreases severely 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 lighting and full-color display.

It is a simple and practical approach to improve the device efficiency and reduce the cost of organic electrophosphorescent devices by designing novel thermally activated delayed fluorescence guest materials. The reported fluorene spirotriphenylamine compounds and oxafluorene spirotriphenylamine compounds as guest materials can improve the device efficiency of organic electrophosphorescent devices and improve the efficiency roll-off of devices, but there is still room for further improvement.

Contents of the invention

The purpose of the present invention is to provide a fluorene spirotriphenylamine compound, an organic electronic device and a display device or a photographic device, which can effectively increase the energy level of the triplet state, reduce the energy gap difference between the singlet state and the triplet state, and increase the fluorescence quantum yield and heat dissipation. Stability, thereby improving the luminous efficiency, efficiency roll-off and operating voltage of organic electroluminescent devices.

In order to achieve the above object, the present invention provides the following technical solutions: a fluorene spirotriphenylamine compound, characterized in that it is represented by the following general formula (1):

wherein, each of R ₁ to R ₃ independently represents a cyano group, or an aromatic hydrocarbon group optionally substituted by one or more R ¹ , having 6 to 30 carbon atoms, or optionally substituted by one or more R ¹ , One or more of aromatic heterocyclic groups having 5 to 30 carbon atoms;

Z means CR ¹ or N;

R ¹ represents hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, NO ₂ , N(R ² ) ₂ , OR ² , SR ² , C(=O)R ² , P( =O)R ² , Si(R ² ) ₃ , substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted One of an 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 or more;

R ² represents 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 One or more of unsubstituted aromatic heterocyclic groups having 5 to 30 carbon atoms.

Further, the R ₁ , R ₂ and R ₃ are each independently selected from a cyano group or any of the following general formulas Ar-1 to Ar-39:

Among them, the wavy line represents the bond bonded to the fluorene spirotriphenylamine core,

R ¹ has the meaning defined according to claim 1.

Further, R ¹ and R ² represent phenyl, biphenyl, terphenyl, quaternyl, pentaphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenylcarbazole , benzoanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuryl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl , benzimidazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenylboryl, triphenylphosphoryloxy, diphenylphosphoryloxy, triphenylsilyl or One or more of tetraphenylsilyl groups.

Further, the fluorene spirotriphenylamine compound is selected from any one of the following general formulas 1-1 to 1-40:

The present invention also provides a preparation method according to the described fluorene spirotriphenylamine compound, comprising the following steps:

The R ₁ , R 2 and R ₃ groups are introduced through a metal-catalyzed coupling reaction _of 2, 4 and 7-functionalized fluorene spirotriphenylamine or a lithium reagent nucleophilic reaction.

The present invention also provides the application of the fluorene spirotriphenylamine compound in the preparation of electronic devices, the electronic devices are selected from organic electroluminescent devices, organic field effect transistors or organic solar cells, especially for the preparation of Application of luminescent guest materials, luminescent host materials, exciton blocking materials or electron transport materials in organic electroluminescent devices.

The present invention also provides an electronic device, which has the fluorene spirotriphenylamine compound.

Further, the electronic device is an organic electroluminescent device, the organic electroluminescent device includes an organic light emitting layer, an exciton blocking layer and an electron transport layer, and the organic electroluminescent device has the fluorene spirotriphenylamine compound.

Compared with the prior art, the beneficial effect of the present invention is that: the fluorene spirotriphenylamine compound of the present invention is introduced into the rigid structure of fluorene spirotriphenylamine, which has excellent film-forming properties and thermal stability, and can be used to prepare organic electroluminescent devices , organic field effect transistors and organic solar cells. In addition, the fluorene spirotriphenylamine compound of the present invention can be used as a constituent material of the hole injection layer, the hole transport layer, the light-emitting layer, the electron blocking layer, the hole blocking layer or the electron transport layer, which can reduce the driving voltage and improve the efficiency and brightness. and lifespan etc. More importantly, the fluorene spirotriphenylamine compound of the present invention can effectively isolate donor and acceptor groups, so it is an ideal framework for constructing thermally activated delayed fluorescent materials. The preparation method of the fluorene spirotriphenylamine compound of the invention is simple, and the raw materials are easy to obtain, which can meet the development demand of industrialization.

The above description is only an overview of the technical solutions of the present invention. In order to understand the technical means of the present invention more clearly and implement them according to the contents of the description, the preferred embodiments of the present invention and accompanying drawings are described in detail below.

Description of drawings

Figure 1 is the ultraviolet absorption spectrum (UV-Vis), room temperature fluorescence spectrum (PL) and low temperature phosphorescence spectrum (Phos) of compound 1-25 in Example 5 of the present invention;

Fig. 2 is an organic electroluminescence spectrum diagram of the OLED device in Example 7 of the present invention.

Detailed ways

The specific implementation manners of the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

The invention provides a fluorene spirotriphenylamine compound, which is a compound represented by the following general formula (1):

Wherein, R ₁ to R ₃ each independently represent a hydrogen atom, a cyano group, or an aromatic hydrocarbon group with 6 to 30 carbon atoms optionally substituted by one or more R ¹ or optionally substituted by one or more R ¹ One or more of substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;

Z means CR ¹ or N;

R ¹ represents hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, NO ₂ , N(R ² ) ₂ , OR ² , SR ² , C(=O)R ² , P( =O)R ² , Si(R ² ) ₃ , substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted One of an 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 or more;

R ² represents 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 One or more of unsubstituted aromatic heterocyclic groups having 5 to 30 carbon atoms.

< _R1 and _R3 >

R ₁ to R ₃ each independently represent a hydrogen atom, a cyano group, or an aromatic hydrocarbon group optionally substituted by one or more R ¹ , having 6 to 30 carbon atoms, or optionally substituted by one or more R ¹ , one or more of aromatic heterocyclic groups having 5 to 30 carbon atoms.

Examples of aromatic hydrocarbon groups having 6 to 30 carbon atoms or aromatic heterocyclic groups having 5 to 30 carbon atoms represented by R ₁ to R ₃ include: phenyl, naphthyl, anthracenyl, benzanthracenyl , phenanthrene, triphenylene, pyrenyl, perylene, fluoranthenyl, benzofluoranthene, tetraphenyl, pentaphenyl, benzopyrenyl, biphenyl, biphenyl, terphenyl Base, quaterphenyl, pentaphenyl, tripolyphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, cis or trans indenofluorenyl, Cis or trans monobenzindenofluorenyl, cis or trans dibenzoindenofluorenyl, triindenyl, isotriindenyl, spirotriindenyl, spiroisotriindenyl, Furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzothienocarbazolyl, pyrrolyl , indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, bipyridyl, terpyridyl, quinolinyl, isoquinolyl, acridinyl , phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, phenothiazinyl, phenoxazinyl, pyrazole base, indazolyl, imidazolyl, benzimidazolyl, naphthimidazolyl, phenanthroimidazolyl, pyridimidazolyl, pyrazinoimidazolyl, quinoxalineimidazolyl, oxazolyl, benzoxazole Base, benzoxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl , pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazaanthracenyl, diazapyrenyl, tetraazaperylene Base, diazanaphthyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorocyclyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthroline Base, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazole Base, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazolyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, Diphenyl-oxadiazolyl, diphenylboryl, triphenylphosphoxy, diphenylphosphoxy, triphenylsilyl, tetraphenylsilyl, and the like.

In the present invention, preferably, R ₁ to R ₃ are each independently selected from a hydrogen atom, a cyano group or the following groups:

Wherein, the wavy line represents the bond bonded to the parent nucleus, and ^R has the meaning defined above.

The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by R ₁ to R ₃ may be unsubstituted, but may have a substituent. Preferably, an aromatic hydrocarbon group having 6 to 30 carbon atoms or an aromatic heterocyclic group having 5 to 30 carbon atoms represented by Ar ₁ to Ar ₆ is substituted by one or more R ¹ and has 5 to 30 carbon atoms. An aromatic hydrocarbon group of 30 carbon atoms or an aromatic heterocyclic group having 5 to 30 carbon atoms substituted by one or more R ¹ .

<R ¹ >

R ¹ represents hydrogen atom, deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, NO ₂ , N(R ² ), OR ² , SR ² , C(=O)R ² , P(= O) R ² , Si(R ² ) ₃ , substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted having One of an alkynyl group with 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group with 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group with 5 to 40 carbon atoms or Multiple.

The alkyl group having 1 to 20 carbon atoms represented by ^R can be exemplified: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso Pentyl, 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, cyclopentyl Hexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl Base etc. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.

The alkyl group having 1 to 20 carbon atoms represented by R ¹ may be unsubstituted, but may also have a substituent. Preferably, the alkyl group having 1 to 20 carbon atoms represented by R ¹ is substituted with one or more of the following R ² . In addition, one or more non-adjacent CH ₂ groups in the alkyl group may 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 are replaced, and one or more hydrogen atoms can be replaced by deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group , Nitro instead.

The alkenyl group having 2 to 20 carbon atoms represented by ^R can be exemplified: ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl Alkenyl, Undecenyl, Dodecenyl, Tridecenyl, Tetradecenyl, Pentadecenyl, Hexadecenyl, Heptadecenyl, Octadecenyl, Nonadecenyl, Etoxy Alkenyl, 2-ethylhexenyl, allyl or cyclohexenyl, etc. The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.

The alkenyl group having 2 to 20 carbon atoms represented by R ¹ may be unsubstituted, or may have a substituent. The substituents can be exemplified by the same substituents shown as the substituents that the alkyl group having 1 to 20 carbon atoms represented by R ¹ optionally has. The patterns that the substituents can take are the same as those of the exemplary substituents.

The alkynyl group having 2 to 20 carbon atoms represented by ^R can be exemplified: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl , Decynyl, etc.

The alkynyl group having 2 to 20 carbon atoms represented by R ¹ may be unsubstituted, or may have a substituent. The substituents can be exemplified by the same substituents shown as the substituents that the alkyl group having 1 to 20 carbon atoms represented by R ¹ optionally has. The patterns that the substituents can take are the same as those of the exemplary substituents.

The aromatic hydrocarbon group having 6 to 40 carbon atoms represented by R ¹ or the aromatic heterocyclic group having 5 to 40 carbon atoms can be enumerated from the aforementioned groups represented by Ar ₁ to Ar ₆ having 6 to 30 carbon atoms The same groups as those shown for the aromatic hydrocarbon group or the aromatic heterocyclic group having 5 to 30 carbon atoms.

The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by R ¹ may be unsubstituted, or may have a substituent. The substituents can be exemplified by the same substituents shown as the substituents that the alkyl group having 1 to 20 carbon atoms represented by R ¹ optionally has. The patterns that the substituents can take are the same as those of the exemplary substituents. In addition, ^two adjacent ^R substituents or two adjacent R substituents optionally can form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which can be One or more ^R2 substitutions; here two or more substituents ^R1 may be connected to each other and may form a ring.

As preferred aromatic hydrocarbon groups having 6 to 40 carbon atoms or aromatic heterocyclic groups having 5 to 40 carbon atoms represented by ^R , phenyl, biphenyl, terphenyl, tetraphenyl Phenyl, pentaphenyl, benzothienocarbazolyl, benzofuranocarbazolyl, benzofluorenylcarbazolyl, benzanthracenyl, triphenanthryl, fluorenyl, spirobifluorenyl, Triazinyl, dibenzofuryl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-benzimidazolyl, diphenyl -Oxadiazolyl, diphenylboryl, triphenylphosphinyl, diphenylphosphinyl, triphenylsilyl, tetraphenylsilyl, etc. The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms may be substituted by one or more R ² .

^<R2>

R ² represents 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 One or more of unsubstituted aromatic heterocyclic groups having 5 to 30 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ² include the same groups as those described above for the alkyl group having 1 to 20 carbon atoms represented by R ¹ .

The aromatic hydrocarbon group having 6 to 30 carbon atoms represented by R or ^the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms can be exemplified from the ^{aforementioned} group represented by R having 6 to 30 A carbon atom aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms is the same group as shown.

An ^alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented by R may be unsubstituted or may have a substituent. Examples of substituents include a deuterium atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a cyano group, and the like.

<Z>

Z represents CR ¹ or N, such as N, CH, CF, C-Cl, C-Br, CI, C-CN, C-NO ₂ , carbon-phenyl, carbon-biphenyl and the like.

R ¹ has the meaning defined above.

In a particularly preferred embodiment of the invention:

Wherein, R ₁ , R ₂ and R ₃ are each independently selected from cyano or the following aromatic or heteroaromatic ring systems: pyridyl, dianilinyl, dimethylboryl, diphenyltriazinyl; Said aromatic or heteroaromatic ring system may be substituted by one or more R ¹ ;

The ^R1 groups at each site are independently selected from: hydrogen, straight chain alkyl having 1 to 5 C atoms.

Preferably, the fluorene spirotriphenylamine compound is selected from any one of the following general formulas 1-1 to 1-40:

The present invention also provides a preparation method according to the described fluorene spirotriphenylamine compound, comprising the following steps:

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, Hartwig-Buchwald coupling, and the like.

The synthesis of compounds of the present invention usually starts from 2,4 and 7-functionalized fluorene spirotriphenylamine compounds, followed by lithium reagent nucleophilic reactions or metal-catalyzed coupling reactions such as Suzuki coupling or Buchwald-Hart Hartwig-Buchwald coupling introduces R ₁ , R ₂ and R ₃ groups.

In a preferred embodiment of the present invention, the fluorene spirotriphenylamine compound is a compound functionalized with a boronic acid compound, and the R ₁ , R ₂ and R ₃ groups are derived from a halogen-functional compound. In another preferred embodiment of the present invention, the fluorene spirotriphenylamine compound is a halogen-functional compound, and the RR ₁ , R ₂ and R ₃ groups are derived from a boronic acid compound-functional compound.

In the third preferred embodiment of the present invention, the fluorene spirotriphenylamine compound is a halogen-functionalized compound, which is reacted with an amine compound under the action of a palladium catalyst to introduce R ₁ , R ₂ and R ₃ group. Among these, the halogen functionalization is preferably brominated, chlorinated, iodized, especially brominated.

In the fourth preferred embodiment of the present invention, the fluorene spirotriphenylamine compound is a halogen-functionalized compound, which reacts with a phosphorylated or silylated or borylated compound under the action of a lithium reagent to introduce R ₁ , R ₂ and R ₃ groups. Among these, the halogen functionalization is preferably brominated, chlorinated, iodized, especially brominated.

Specifically, in the first preferred embodiment described above, it is necessary to prepare the boronic acid-functionalized fluorene spirotriphenylamine compound (intermediate M3) first, and the preferred preparation steps are exemplified as follows:

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 the intermediate M3, add a halogen functional compound such as 2,4-dichloro-6-phenyl-1,3,5-triazine or melamine that can introduce R ₁ , R ₂ and R ₃ groups into the system , and a certain amount of palladium catalysts such as tetrakis(triphenylphosphopalladium), anhydrous potassium carbonate, tetrahydrofuran and water, and react under nitrogen protection at 50-80° C. for 30-35 hours, and the reaction is completed. Evaporate the solvent, dissolve the residue with dichloromethane and water, wash with water, separate the organic layer, extract the aqueous layer with dichloromethane, combine the organic layers, wash twice with water until neutral, evaporate the solvent, and separate by column chromatography , and dried to obtain the product. The molar ratio of intermediate M3 to tetrakis(triphenylphosphopalladium) is 15-20:1, preferably 18:1; by adjusting the reaction conditions, the yield is 65-85%.

The second preferred embodiment as described above, preferably utilizing M2 and the reaction of the compound pyridine-3-boronic acid functionalized with the boronic acid compound, adding tetrakis (triphenylphosphine) palladium, anhydrous potassium carbonate, tetrahydrofuran and water in the system, Under the protection of argon, react at 50-80°C for 30-35 hours, and the reaction is complete. Aftertreatment is the same as the first preferred embodiment. The final product yield can reach 79%.

In the third preferred embodiment as described above, it is preferred to use M2 to react with diphenylamine, a compound functionalized with amine compounds, and add tris(dibenzylideneacetone) dipalladium, sodium tert-butoxide, and trifluoroborate to the system Tert-butylphosphine and toluene were reacted at 90-120°C for 10-30 hours under the protection of argon, and the reaction was completed. After suction filtration, the solvent was evaporated under reduced pressure, separated by column chromatography, and dried to obtain the product. The molar ratio of the intermediate M2 to tris(dibenzylideneacetone)dipalladium is 15-20:1, preferably 18:1; the yield can reach 78% by adjusting the reaction conditions.

In the fourth preferred embodiment described above, M2 is preferably dissolved in tetrahydrofuran, n-butyl lithium is added dropwise at low temperature, stirred at -78°C for 1 hour, and then the boron-functionalized compound dissolved in tetrahydrofuran For example, bis(trimethylphenyl)boron fluoride is slowly added dropwise into the reaction flask, the temperature will be automatically raised after 1 hour, and the reaction will be carried out overnight. A small amount of water was added into the reaction bottle to quench the reaction, the solvent was evaporated under reduced pressure, separated by column chromatography, and dried to obtain the product with a yield of up to 78%.

The present invention also provides the application of the fluorene spirotriphenylamine compound in the preparation of electronic devices, the electronic devices are selected from organic electroluminescent devices, organic field effect transistors or organic solar cells, especially for the preparation of The application of light-emitting host materials, exciton blocking materials or electron transport materials in organic electroluminescent devices.

The present invention additionally relates to electronic devices comprising at least one compound according to the invention. The electronic device is preferably selected from 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 Transistor (O-LET), Organic Integrated Circuit (O-IC), Organic Dye-Sensitized Solar Cell (ODSSC), Organic Optical Detector, Organic Photoreceptor, Organic Field Quenched Device (O-FQD), Luminescence Electrochemistry Battery (LEC), organic laser diode (O-laser) and organic plasma emitting device, etc., preferably organic electroluminescent device (OLED).

An OLED generally includes: a substrate, 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); (EBL); organic light emitting layer (EML); exciton blocking layer (EBL); electron transport layer (ETL); electron injection layer (EIL), such as Liq, Cs ₂ CO ₃ ; cathode, such as Al. It should be noted, however, that there may be one or more layers of each intervening layer and that each layer does not have to be present.

The compound of the present invention can be used in any layer or layers of the device, but is preferably used in the light-emitting layer (EML), more preferably the host material of the light-emitting layer, because it has a high triplet energy level and good stability. The compounds of the 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 capability.

The organic light-emitting layer dopant of the present invention is not particularly limited, preferably a light-emitting metal complex and a light-emitting organic molecule, the light-emitting metal complex is preferably a complex of iridium and platinum, and the light-emitting organic molecule is preferably a fluorescent compound and a thermally excited delayed fluorescence compound . In order to improve device performance, the mass ratio of the dopant is 6%-30%, preferably 6%-20%, more preferably 6%-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. Among them, the substrate uses a glass substrate, and ITO is used as the anode material. The hole injection material uses 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN) commonly used in the prior art , the hole transport material uses 4,4'-(cyclohexane-1,1-diyl)bis(N,N-di-p-tolylaniline) (TAPC) commonly used in the prior art; the electron blocking layer uses the existing Tris(4-(9H-carbazol-9-yl)phenyl)amine (TCTA) commonly used in the prior art; the organic light-emitting layer is doped with the host material commonly used in the prior art using the compound described in the present invention9,9 '-(1,3-phenyl)bis-9H-carbazole (mCP) and 4,4'-bis(9-carbazole)biphenyl (CBP). In addition, the compounds of the present invention doped with 8-hydroxyquinoline-lithium or metal lithium can also be used as electron transport layers, and some devices also use bis(10-hydroxybenzo[H]quinoline) commonly used in the prior art Beryllium (Be(bq) ₂ ) and tris(8-quinolinolato)aluminum (Alq ₃ ). The cathode adopts metal and its mixture structure, such as Mg:Ag, Ca:Ag, etc., and can also be an electron injection layer/metal layer structure, such as LiF/Al, Liq/Al and Li ₂ O/Al. In the present invention, the electron injection material is preferably Liq, and the cathode material is Al.

The following examples are given to illustrate the present invention, and those skilled in the art can understand that the examples are only exemplary descriptions, not exhaustive descriptions. The preparation example is a compound synthesis example, the chemical raw materials and reagents involved are all commercially available or synthesized according to the published literature, and the embodiment is the preparation of a light-emitting device OLED.

Preparation Example

Synthesis of Intermediate M3

The structural formula and synthetic route of intermediate M3 are shown in the following formula:

The preparation method of the compound of formula M1 is as follows: in a 100 mL two-necked flask, 1.6 g (6.2 mmol) of 4-bromo-fluorenone was dissolved in 50 mL of dichloromethane, and stirred in an ice bath. Add 0.67mL (12.8mmol) of liquid bromine dropwise with a constant pressure dropping funnel. After the addition was complete, the system was gradually warmed up to room temperature and reacted for 6 hours. After the reaction was complete, the reaction solution was poured into a saturated sodium bisulfite solution, extracted three times with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by spinning to obtain a crude product. The crude product was separated and purified on a silica gel column with an eluent of dichloromethane:petroleum ether=1:5 (volume ratio) to obtain 2.3 g of M1 with a yield of 90%. MS (EI): m/z 417.05 [M ⁺ ]. Elemental Analysis Calculated value for C ₁₃ H ₅ Br ₃ O (%): C 37.45, H 1.21; found value: C 37.411.20

The preparation method of the compound of formula M2 is: under the protection of nitrogen, 1.6 (4.9 mmol) 2-bromo-triphenylamine was dissolved in 30 mL of anhydrous tetrahydrofuran in a 100 mL two-necked flask, stirred, and cooled to -78 ° C. 2.3mL (5.5mmol) of 2.4M n-butyllithium was added dropwise to the solution through a constant pressure dropping funnel. After the addition was complete, stirring was continued at -78°C for 1 hour. Then 2.0 g (4.9 mmol) of M1 was dispersed into 30 mL of anhydrous tetrahydrofuran under nitrogen protection and added dropwise to the reaction solution. After the addition was completed, the temperature was gradually raised to room temperature, and the reaction was carried out for 12 hours. After the reaction was complete, 5 mL of water was added to quench the reaction, and the THF was spin-dried to remove THF. The crude product was dissolved in 150 mL of dichloromethane and washed 3 times with 60 mL of water. The organic phase was dried with anhydrous sodium sulfate and then spin-dried to remove the solvent to obtain a crude product. The crude product was separated and purified on a silica gel column with an eluent of dichloromethane:petroleum ether=3:1 (volume ratio) to obtain 3.0 g of an intermediate product. In a 50 mL two-necked flask, the obtained intermediate product was dissolved in 25 mL of acetic acid and 2.5 mL of hydrochloric acid was added, stirred and heated to reflux, and reacted for 6 hours. After the reaction was complete, the reaction system was cooled to room temperature, poured into 300 mL of ice water, filtered under reduced pressure, and the filter residue was washed with water three times. The filter residue was separated and purified on a silica gel column with an eluent of dichloromethane:petroleum ether=1:4 (volume ratio) to obtain 2.2 g of M2 with a yield of 70%. MS (EI): m/z 644.54 [M ⁺ ]. Elemental Analysis Calculated for C ₃₁ H ₁₈ Br ₃ N (%): C 57.80, H 2.82, N 2.17; Found: C 57.60, H 2.80, N 2.15.

The preparation method of the intermediate M3 is as follows: in a 100mL Schrank reaction flask, under the protection of argon, put 2.0gM2 (3.05mmol) and 50mL tetrahydrofuran, dissolve and cool, and drop 2.4 M n Butyllithium 1.3mL (3.2mmol), stirring for 1 hour after the dropwise addition, triisopropyl borate 0.8g (4.5mmol) was added dropwise, and after stirring for 1 hour, the temperature was automatically raised and the reaction was carried out overnight. The reaction was quenched by adding 10 mL of aqueous ammonium chloride. Transfer the reaction material to a one-necked bottle, evaporate the solvent under reduced pressure, add 80 mL of dichloromethane and 80 mL of water to the bottle, dissolve, wash with water, separate layers, extract the water layer twice with 15 mL of dichloromethane, and combine the organic phases , and then washed twice with 80mL water until neutral. The water layer was separated, and 15 g of anhydrous sodium sulfate was added to the organic layer, and dried for 3 hours. The solvent was distilled off under reduced pressure to obtain 1.3 g of white solid with a yield of 80%. MS (EI): m/z 539.19 [M ⁺ ]. Elemental Analysis Calcd. for C ₃₁ H ₂₄ B ₃ NO ₆ (%): C 69.08, H 4.49, N 2.60; Found: C 68.95, H 4.40, N 2.58.

Example 1

The structural formula and synthetic route of compound 1-27 are shown in the following formula:

Under nitrogen protection, 1.6g (2.5mmol) M2, 1.11g (9mmol) pyridine-3-boronic acid, toluene 50mL, ethanol 10mL, 2M sodium carbonate aqueous solution 10mL, tetrakistriphenylphosphine palladium 0.15 g (1.25mmol), stirred and heated to 106°C for 24 hours. After the reaction was complete, the reaction system was cooled to room temperature. Extracted three times with dichloromethane, the organic phase was dried by anhydrous sodium carbonate and then spin-dried to remove the solvent to obtain the crude product, which was washed with triethyl ether with dichloromethane:petroleum ether=7:3 (volume ratio) eluent Separation and purification on an amine-basified silica gel column yielded 1.3 g of 1-27 with a yield of 79%. MS (EI): m/z 638.52 [M ⁺ ]. Elemental analysis Calcd. for C ₄₆ H ₃₀ N ₄ (%): C 86.49, H 4.73, N 8.77; Found: C 86.39, H 4.70, N 8.72.

Example 2

The structural formula and synthetic route of compound 1-28 are shown in the following formula:

Under nitrogen protection, 1.6g (2.5mmol) M2, 1.11g (3mmol) pyridine-4-boronic acid, toluene 50mL, ethanol 10mL, 2M sodium carbonate aqueous solution 10mL, tetrakistriphenylphosphine palladium 0.15 g (1.25mmol), stirred and heated to 106°C for 24 hours. After the reaction was complete, the reaction system was cooled to room temperature. Extracted three times with dichloromethane, the organic phase was dried by anhydrous sodium carbonate and then spin-dried to remove the solvent to obtain the crude product, which was washed with triethyl ether with dichloromethane:petroleum ether=7:3 (volume ratio) eluent Separation and purification on an amine-basified silica gel column yielded 1.3 g of 1-28 with a yield of 79%. MS (EI): m/z 638.52 [M ⁺ ]. Elemental analysis Calcd. for C ₄₆ H ₃₀ N ₄ (%): C 86.49, H 4.73, N 8.77; Found: C 86.38, H 4.68, N 8.70.

Example 3

The structural formula and synthetic route of compound 1-6 are shown in the following formula:

Under nitrogen protection, 1.4g (2.5mmol) M3, 2.4g (7.8mmol) 2-chloro-4,6-diphenyl-1,3,5-triazine, toluene 50mL, 10 mL of ethanol, 10 mL of 2M aqueous sodium carbonate solution, and 0.15 g (1.25 mmol) of tetrakistriphenylphosphine palladium were stirred and heated to 106°C for 24 hours to react. After the reaction was complete, the reaction system was cooled to room temperature. Extracted three times with dichloromethane, the organic phase was dried by anhydrous sodium carbonate and then spin-dried to remove the solvent to obtain a crude product, which was put on a silica gel column with an eluent of dichloromethane:petroleum ether=7:3 (volume ratio) Separation and purification were carried out to obtain 2.2 g of 1-6 with a yield of 79%. MS (EI): m/z 1100.25 [M ⁺ ]. Elemental analysis Calcd. for _C76H48N10 ( _% ): C 82.89, H 4.39, N 12.72 _; Found: C 82.80, H 4.37, N 12.74.

Example 4

The structural formula and synthetic route of compound 1-10 are shown in the following formula:

Under nitrogen protection, 3.1 g (4.9 mmol) of M2 was dissolved in 30 mL of anhydrous tetrahydrofuran in a 100 mL two-necked flask, stirred, and cooled to -78°C. 2.3mL (5.5mmol) of 2.4M n-butyllithium was added dropwise to the solution through a constant pressure dropping funnel. After the addition was complete, stirring was continued at -78°C for 1 hour. Then 3.9 g (14.7 mmol) of bis(trimethylphenyl) boron fluoride was dispersed into 30 mL of anhydrous tetrahydrofuran under nitrogen protection and added dropwise to the reaction solution. After the addition was completed, it was gradually raised to room temperature and reacted for 12 hours. After the reaction was complete, 5 mL of water was added to quench the reaction, and the THF was spin-dried to remove THF. The crude product was dissolved in 150 mL of dichloromethane and washed 3 times with 60 mL of water. The organic phase was dried with anhydrous sodium sulfate and then spin-dried to remove the solvent to obtain a crude product. The crude product was separated and purified on a silica gel column with an eluent of dichloromethane:petroleum ether=3:1 (volume ratio) to obtain 4.2 g of 1-10 with a yield of 75%. MS (EI): m/z 1151.69 [M ⁺ ]. Elemental analysis calculated value for C ₈₅ H ₈₄ B ₃ N (%): C 88.62, H 7.35, N 1.22; found value: C 88.50, H 7.30, N 1.20.

Example 5

The structural formula and synthetic route of compound 1-25 are shown in the following formula:

Under nitrogen protection, dissolve 3.1g (4.9mmol) M2, 1.5g (15.3 mmol) cuprous cyanide in 40mL N,N-dimethylformamide in a 100mL two-necked flask, stir, and heat to 150°C for reaction 24 hours. After the reaction was complete, the reaction solution was poured into 50 mL of saturated sodium hydroxide solution, and suction filtered to obtain a crude product. The crude product was dissolved in 150 mL of dichloromethane and washed 3 times with 60 mL of water. The organic phase was dried with anhydrous sodium sulfate and then spin-dried to remove the solvent to obtain a crude product. The crude product was separated and purified on a silica gel column with an eluent of dichloromethane:petroleum ether=3:2 (volume ratio) to obtain 1.8 g of 1-25 with a yield of 77%. MS (EI): m/z 482.36 [M ⁺ ]. Elemental analysis Calcd. for C ₃₄ H ₁₈ N ₄ (%): C 84.63, H 3.76, N 11.61; Found: C 84.47, H 3.71, N 11.50.

Please refer to Fig. 1, Fig. 1 is the ultraviolet absorption spectrum, ultraviolet absorption spectrum (UV-Vis), room temperature fluorescence spectrum (PL) and low temperature phosphorescence spectrum (Phos) of the product 1-25. UV absorption spectrum and room temperature fluorescence spectrum were measured in dichloromethane and toluene dilute solution (1×10 ^-5 mol/L); low temperature phosphorescence spectrum was measured in toluene solution (1×10 ^-3 mol/L) .

Example 6

The structural formula and synthetic route of compound 1-32 are shown in the following formula:

In a 250mL two-necked flask, 1.5g (2.3mmol) M2, 1.5g (8.9mmol) diphenylamine, 0.3g (2.9mmol) sodium tert-butoxide, 0.1g (0.3mmol) tri-tert-butylphosphine tetrafluoroborate, 0.27 g (0.3 mmol) of tris(dibenzylideneacetone) dipalladium, after degassing the reaction system, under the protection of nitrogen, add 150 mL of toluene, stir and heat to 106°C for 12 hours. After the reaction was complete, the system was cooled to room temperature, filtered under reduced pressure, and the filter residue was washed with a large amount of dichloromethane, and the filtrate was concentrated to obtain a crude product, which was eluted with petroleum ether:dichloromethane=2:3 (volume ratio) The reagent was separated and purified on a silica gel column to obtain 1.9 g of the target product 1-32 with a yield of 92%. MS (EI): m/z 908.30 [M ⁺ ]. Elemental analysis Calcd. for C ₆₇ H ₄₈ N ₄ (%): C 88.52, H 5.32, N 6.16; Found: C 88.45, H 5.30, N 6.13.

Device embodiment

Example 7-15

Device preparation: The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, washed three times in acetone and ethanol, baked in a clean environment until the water was completely removed, and then cleaned with ultraviolet light. and ozone cleaning, and bombard the surface with a beam of low-energy cations. Put the ITO conductive glass into the vacuum chamber, and evacuate to 2×10 ^-5 -2×10 ^-5 Pa. Hole injection material (HIL), hole transport material (HIL), electron blocking layer (EBL), organic light-emitting layer (EML), electron transport layer (ETL) and cathode are sequentially evaporated on the above-mentioned ITO conductive glass; , the evaporation rate of the organic material is 0.2nm/s, the evaporation rate of the metal electrode is above 0.5nm/s, the light-emitting layer is co-evaporated with two sources, the evaporation rate of the host material is 0.2nm/s, and the dopant material The evaporation rate is 0.03nm/s.

Device performance test: The current-brightness-voltage characteristics of the device are completed by the Keithley source measurement system (Keithley 2400Sourcemeter, Keithley 2000Currentmeter) with a calibrated silicon photodiode, and the electroluminescence spectrum is measured by the PR655 spectrometer of Photo research company , the external quantum efficiency of the device can be calculated by the method of the literature Adv. Mater., 2003, 15, 1043-1048. All devices were packaged in a nitrogen atmosphere.

The compound structure that embodiment relates to is as follows:

The structure of embodiment 7-12 (respectively device OLED1-6) and the film thickness of each layer are as follows:

OLED1:

ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt% 1-25:CBP(15nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm).

OLED2:

ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt% 1-10:CBP(15nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm).

OLED3:

ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt% 1-27:CBP(15nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm).

OLED4:

ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt% 1-28:CBP(15nm)/TmPyPB(15nm)/Liq(2nm)/Al(120nm).

OLED5:

ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt% 1-32:CBP(15nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm).

OLED6:

ITO/HAT-CN(10nm)/TAPC(40nm)/TCTA(10nm)/2wt% 1-6:CBP(15nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm).

comparative example

The preparation method of Comparative Example 1 is the same as that of Example, except that 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(15nm)/TmPyPB(50nm)/Liq(2nm)/Al(120nm).

The performance data of the device is shown in Table 1:

Table 1: Device Performance Data

As can be seen from Table 1, very good performance data are obtained for the compounds of the invention. Comparative Example 1 and Example 7 use CBP as the host material. The only difference is that the guest material of Example 7 is the compound 1-25 of the present invention. It can be seen from the comparison of device performance data that Example 7 has a lower operating voltage and a higher High external quantum efficiency, device attenuation has been significantly improved. Please refer to FIG. 2 , which shows the organic electroluminescence spectrum of Example 7. It can be seen from the figure that it has a strong luminous intensity, and the energy is fully transferred from the host material to the guest material. It can be seen that, compared with the materials commonly used in the prior art, the compound of the present invention can effectively reduce the operating voltage, increase the external quantum efficiency and improve the problem of device efficiency attenuation.

In summary: the fluorene spirotriphenylamine compound of the present invention has excellent film-forming properties and thermal stability by introducing a rigid structure of fluorene spirotriphenylamine, and can be used to prepare organic electroluminescent devices, organic field effect transistors and organic solar cells . In addition, the fluorene spirotriphenylamine compound of the present invention can be used as a constituent material of the hole injection layer, the hole transport layer, the light-emitting layer, the electron blocking layer, the hole blocking layer or the electron transport layer, which can reduce the driving voltage and improve the efficiency and brightness. and lifespan etc. More importantly, the fluorene spirotriphenylamine compound of the present invention can effectively isolate donor and acceptor groups, so it is an ideal framework for constructing thermally activated delayed fluorescent materials. The preparation method of the fluorene spirotriphenylamine compound of the invention is simple, and the raw materials are easy to obtain, which can meet the development demand of industrialization.

The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on 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:

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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