An anthracene-based fluorescent material, its preparation method and application

Abstract

This invention provides an anthracene-based fluorescent material, its preparation method, and its applications. The anthracene-based fluorescent material is as shown in Compound I. The compounds of this invention utilize the electron-donating effect of aromatic amine units such as carbazole and the electron-withdrawing effect of phosphonyl / sulfonyl groups, effectively improving the electron and hole transport capabilities of the molecules. Furthermore, the steric hindrance effect, resulting in a distorted molecular configuration, can suppress intermolecular interactions, thereby reducing the device efficiency roll-off caused by concentration quenching. The thermal exciton mechanism enables these molecules to achieve an exciton utilization rate exceeding that of traditional fluorescent molecules by 25%.

Description

Technical Field

[0001] This invention relates to the field of luminescent materials technology, and in particular to an anthracene-based fluorescent material, its preparation method, and its applications. Background Technology

[0002] As a next-generation display and lighting technology, Organic Light Emitting Diodes (OLEDs) possess outstanding advantages such as high efficiency, high brightness, and flexibility. Among the various indicators used to evaluate high-performance OLED devices, color purity is a key parameter. Achieving excellent color purity requires simultaneously meeting standard color coordinate requirements and a narrow electroluminescence half-width. Among the red, green, and blue primary colors required for OLED displays, high-purity, high-efficiency deep blue light-emitting materials still require significant breakthroughs.

[0003] Phosphorescent materials utilize the strong spin-orbit coupling effect of heavy metal atoms such as iridium and platinum to achieve direct radiative transitions from the lowest triplet state (T1) to the ground state, theoretically achieving 100% internal quantum efficiency. However, due to the nonradiative quenching effect involving the d orbitals of the metal center, deep blue OLED devices based on phosphorescent emitters often struggle to simultaneously achieve high color purity, high efficiency, and long lifetime.

[0004] As a new generation of highly efficient luminescent materials, thermally activated delayed fluorescence (TADF) materials can also achieve 100% exciton utilization through a reverse intersystem crossing process, which benefits from its singlet state. The triplet energy level difference is extremely small. However, due to their inherent donor-acceptor molecular structure, these materials usually cannot simultaneously achieve deep blue light emission and narrow-band emission, and are often accompanied by significant spectral redshift and broadening, with generally large full width at half maximum (FWHM).

[0005] While traditional fluorescent materials and luminescent systems based on triplet-triplet annihilation mechanisms can easily achieve deep blue light emission, their theoretical upper limits for exciton utilization efficiency are 25% and 62.5%, respectively, which still cannot fully meet the requirements of high-efficiency OLED devices. Summary of the Invention

[0006] The present invention aims to at least solve one of the aforementioned technical problems existing in the prior art. Therefore, the object of the present invention is to provide anthracene-based fluorescent material, its preparation method, and its applications.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] In a first aspect, the present invention provides a compound of formula I: ; Wherein, Ar is selected from any of the aromatic amine units shown in (1)-(7): , , , , , , The aromatic amine unit is optionally unsubstituted, or is converted by one or more C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C6 alkyl groups. 14 Aryl substitution; R is selected from C1-C6 alkylsulfonyl, C3-C6 cycloalkylsulfonyl, C6-C 14 arylsulfonyl, diC1-C6 alkylphosphine oxide, diC3-C6 cycloalkylphosphine oxide, C6-C 14 Aryl C1-C6 alkyl phosphine oxide, C5-C 16 Aryloxyphosphine group.

[0009] In some embodiments, Ar is selected from any of the aromatic amine units shown below: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

[0010] In some embodiments, R is selected from any of the following acyl or phosphoxy units: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

[0011] In some embodiments, the compound of formula I is selected from the following compounds: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

[0012] A second aspect of the present invention provides a method for preparing the compound of formula I, comprising the following steps: Compound of Formula II is prepared by reacting it with compound of Formula III; , ; X is selected from halogens, such as F, Cl, Br, and I; Ar and R are defined as described above.

[0013] In some embodiments, the reaction is carried out under a catalyst; the catalyst includes a palladium catalyst; the palladium catalyst includes at least one of tris(diphenylmethylene ketone)palladium, tetra(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, bis(dibenzylacetone)palladium, palladium acetate, and palladium chloride; the palladium catalyst may also be used in conjunction with a palladium catalyst; the palladium catalyst ligand includes at least one of triphenylphosphine (PPh3), tricyclohexylphosphine (PCy3), 2,2'-bis(diphenylphosphine)-1,1'-binaphthyl (BINAP), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos), 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl (RuPhos), and 2-dicyclohexylphosphino-2'-N,N-dimethylaminobiphenyl (DavePhos).

[0014] In some embodiments, the reaction is carried out under a weak base; the weak base includes at least one of potassium phosphate, potassium carbonate, sodium carbonate, cesium carbonate, triethylamine, and diisopropylethylamine.

[0015] In some implementations, the reaction is carried out in an inert atmosphere.

[0016] In some embodiments, the reaction temperature is 80~120 ℃; such as 90 ℃, 100 ℃, 110 ℃, etc.

[0017] A third aspect of the present invention provides an organic electroluminescent composition comprising a dopant material and a host material; said dopant material comprising the aforementioned compound.

[0018] In some embodiments, the organic electroluminescent composition preferably contains 0.3-30.0 wt% of the compound described above as a dopant material, with the remainder being 99.7-70.0 wt% of the host material.

[0019] A fourth aspect of the present invention provides an electronic device comprising the aforementioned compound.

[0020] In some embodiments, the electronic device includes any one of organic electroluminescent devices, organic light-emitting field-effect transistors, organic field-effect transistors, organic sensors, organic lasers, and organic spintronic devices.

[0021] In some embodiments, the organic electroluminescent device includes a functional layer comprising a light-emitting layer of the compound or the organic electroluminescent composition.

[0022] In some embodiments, the functional layer comprises 0.5-50 wt% of the compound and 10-99.5 wt% of organic functional materials.

[0023] In some embodiments, the organic functional material includes at least one of hole injection material, hole transport material, hole blocking material, electron injection material, electron transport material, electron blocking material, exciton blocking material, thermally activated delayed fluorescence material, phosphorescent material, and host material.

[0024] In some embodiments, the organic electroluminescent device includes an anode layer, a cathode layer, and the functional layer disposed between the anode and the cathode.

[0025] In some embodiments, the organic electroluminescent device includes a substrate, an anode layer, a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an emissive layer (EML), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), and a cathode layer.

[0026] In some embodiments, organic electroluminescence may include one or more protective layers that protect the device from damage caused by exposure to harmful substances in the environment, including, for example, moisture, vapors and / or gases.

[0027] In some embodiments, the organic electroluminescent device includes an OLED having the following inverted layer structure: a substrate, a cathode layer, an electron injection layer (EIL), an electron transport layer (ETL), a hole blocking layer (HBL), an emissive layer, an electron blocking layer (EBL), a hole transport layer (HTL), a hole injection layer (HIL), and an anode layer.

[0028] OLEDs may optionally include each layer selected from the group consisting of HIL, HTL, EBL, HBL, ETL, and EIL. Different layers may be combined, and an OLED may include more than one layer of each of the layer types defined above.

[0029] The substrate can be formed from any material or a combination of materials. Most commonly, a glass slide is used as the substrate. Alternatively, a thin metal layer (e.g., copper, gold, silver, or aluminum film) or a plastic film or glass slide can be used. This allows for a greater degree of flexibility. The anode layer is primarily composed of a material that allows for a (substantially) transparent film. Because at least one of the two electrodes should be (substantially) transparent to allow light emission from the OLED, the anode or cathode layer is transparent. Preferably, the anode layer comprises a large amount of transparent conductive oxide (TCO) or is even composed of transparent conductive oxide (TCO). Such an anode layer can, for example, include indium tin oxide, aluminum zinc oxide, fluorine-doped tin oxide, indium zinc oxide, PbO, SnO, zirconium oxide, molybdenum oxide, vanadium oxide, tungsten oxide, graphite, doped Si, doped Ge, doped GaAs, doped polyaniline, doped polypyrrole, and / or doped polythiophene.

[0030] The anode layer can (basically) be made of indium tin oxide (ITO) (e.g., (InO3)). 0.9 (SnO2) 0.1The anode layer roughness caused by transparent conductive oxides (TCOs) can be compensated by using a hole injection layer (HIL). Furthermore, the HIL can promote the injection of quasi-charge carriers (i.e., holes) by facilitating their transport from the TCO to the hole transport layer (HTL). The hole injection layer (HIL) can comprise poly-3,4-ethylenedioxythiophene (PEDOT), polystyrene sulfonate (PSS), MoO2, V2O5, CuPC, or CuI, particularly mixtures of PEDOT and PSS. The hole injection layer (HIL) also prevents metal diffusion from the anode layer into the hole transport layer (HTL). The HIL may include, for example, PEDOT:PSS (poly-3,4-ethylenedioxythiophene:polystyrene sulfonate), PEDOT (poly-3,4-ethyldioxythiophene), mMTDATA (4,4',4”-tris[phenyl(m-tolyl)amino]triphenylamine), spiro-TAD (2,2',7,7'-tetra(n,n-diphenylamino)-9,9'-spirodifluorene), DNTPD (N1,N1'-(biphenyl-4,4'-diyl)bis(N1-phenyl-N4,N4-di-m-tolylphenyl-1,4-diamine), NPB (N,N'-bis) -(1-naphthyl)-N,N'-bisphenyl-((1,1'-biphenyl)-4,4'-diamine), NPNPB(N,N'-diphenyl-N,N'-di-[4-(N,N-diphenyl-amino)phenyl]p-diaminobiphenyl), MeO-TPD(N,N,N',N'-tetra(4-methoxyphenyl)p-diaminobiphenyl), HAT-CN(1,4,5,8,9,11-hexaazatriphenyl-hexacarboxynitrile) and / or spiro-NPD(N,N'-diphenyl-N,N'-bis-(1-naphthyl)-9,9'-spirobisfluorene-2,7-diamine).

[0031] A hole transport layer (HTL) is typically disposed adjacent to the anode layer or hole injection layer (HIL). Any hole transport compound can be used herein. For example, electron-rich heteroaromatic compounds such as triarylamines and / or carbazole can be used as hole transport compounds. The HTL can reduce the energy barrier between the anode layer and the emissive layer (EML). The hole transport layer (HTL) can also be an electron blocking layer (EBL). Preferably, the hole transport compound has a relatively high triplet energy level T1. For example, the hole transport layer (HTL) may include star-shaped heterocycles such as tris(4-carbazolyl-9-ylphenyl)amine (TCTA), poly-TPD (poly(4-butylphenyl-diphenylamine)), [α]-NPD (poly(4-butylphenyl-diphenylamine)), TAPC (4,4'-cyclohexylene-bis[N,N-bis(4-methylphenyl)aniline]), 2-TNATA (4,4',4”-tris[2-naphthyl(phenyl)amino]triphenylamine), spiro-TAD, DNTPD, NPB, NPNPB, MeO-TPD, HAT-CN, and / or TrisPcz (9,9'-biphenyl-6-(9-phenyl-9H-carbazolyl-3-yl)-9H,9'H-3,3'-bicarbazolyl). Furthermore, the HTL may include... p The doped layer can consist of inorganic or organic dopants in an organic hole transport matrix. Transition metal oxides, such as vanadium oxide, molybdenum oxide, or tungsten oxide, can be used as inorganic dopants. For example, tetrafluorotetracyanoquinoline (F4-TCNQ), copper pentafluorobenzoate (Cu(I)pFBz), or transition metal complexes can be used as organic dopants.

[0032] EBLs may include, for example, mCP (1,3-bis(carbazole-9-yl)benzene), TCTA, 2-TNATA, mCBP (3,3-bis(9H-carbazole-9-yl)biphenyl), tris-Pcz, CzSi (9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole) and / or DCB (N,N'-dicarbazole-1,4-dimethylbenzene).

[0033] Adjacent to the hole transport layer (HTL), an emissive layer (EML) is typically disposed. The EML comprises at least one luminescent molecule. In particular, the EML comprises at least one compound according to the invention. In one embodiment, the emissive layer comprises only the compound according to the invention. Typically, the EML also comprises one or more host materials H. For example, the host material is selected from CBP (4,4'-bis-(N-carbazolyl)-biphenyl), mCP, mCBP, Sif87 (dibenzo[b,d]thiophene-2-yltriphenylsilane), CzSi, Sif88 (dibenzo[b,d]thiophene-2-yl)diphenylsilane), DPEPO (bis[2-(diphenylphosphino)phenyl] ether oxide), 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9- The group consisting of [3-(dibenzothiophene-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzothiophene)phenyl]-9H-carbazole, T2T (2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine), T3T (2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine), and / or TST (2,4,6-tris(9,9'-spirodifluorene-2-yl)-1,3,5-triazine). The host material H should generally be chosen to exhibit first triplet (T1) and first singlet (S1) energy levels that are energized higher than those of the organic molecule.

[0034] In some embodiments, the EML comprises a so-called hybrid host system having at least one hole-dominant host and one electron-dominant host. In a particular embodiment, the EML specifically comprises a luminescent organic molecule according to the invention and a hybrid host system comprising a T2T as the electron-dominant host and a host selected from the group consisting of CBP, mCP, mCBP, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophene-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole and 9-[3,5-bis(2-dibenzothiophene)phenyl]-9H-carbazole as the hole-dominant host. In another embodiment, the EML comprises, by weight, 50-80%, preferably 60-75%, of a body selected from the group consisting of CBP, mCP, mCBP, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole and 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole; 10-45%, preferably 15-30%, of T2T; and 5-40%, preferably 10-30%, of the compound according to the invention.

[0035] Adjacent to the emissive layer (EML), an electron transport layer (ETL) can be formed. Any electron transport agent can be used herein. Exemplarily, electron-depleted compounds such as benzimidazole, pyridine, triazole, oxadiazole (e.g., 1,3,4-oxadiazole), phosphine oxides, and sulfones can be used. The electron transport agent can also be a star-shaped heterocycle such as 1,3,5-tris(1-phenyl-1H-benzi[d]imidazole-2-yl)phenyl (TPBi). ETLs may include NBphen (2,9-bis(naphthyl-2-yl)-4,7-diphenyl-1,10-phenanthroline), Alq3 (aluminum-tris(8-hydroxyquinoline)), TSPO1 (diphenyl-4-triphenylsilylphenyl-phosphine oxide), BPyTP2 (2,7-bis(2,2'-bipyridin-5-yl)triphenyl), Sif87 (dibenzo[b,d]thiophene-2-yltriphenylsilane), Sif88 (dibenzo[b,d]thiophene-2-yl)diphenylsilane), BmPyPhB (1,3-bis[3,5-bis(pyridin-3-yl)phenyl]phenyl) and / or BTB (4,4'-bis-[2-(4,6-diphenyl-1,3,5-triazinyl)]-1,1'-biphenyl). Optionally, the ETL may be doped with materials such as Liq. Electron transport layer (ETL) can also block holes or introduce hole blocking layer (HBL).

[0036] HBLs can include, for example, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), BAlq (bis(8-hydroxy-2-methylquinoline)-(4-phenylphenoxy)aluminum), NBphen (2,9-bis(naphthyl-2-yl)-4,7-diphenyl-1,10-phenanthroline), Alq3 (aluminum-tris(8-hydroxyquinoline)), and TSPO1 (diphenyl-4-triphenylsilane). Phosphorus oxyphenyloxide), T2T (2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine), T3T (2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine), TST (2,4,6-tris(9,9'-spirodifluorene-2-yl)-1,3,5-triazine) and / or TCB / TCP (1,3,5-tris(N-carbazole)benzene / 1,3,5-tris(carbazole)-9-yl)benzene).

[0037] Adjacent to the electron transport layer (ETL), a cathode layer C may be disposed. The cathode layer C may, for example, comprise a metal (e.g., Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, LiF, Ca, Ba, Mg, In, W, or Pd) or a metal alloy, or be composed of a metal (e.g., Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, LiF, Ca, Ba, Mg, In, W, or Pd) or a metal alloy. For practical reasons, the cathode layer may also be composed of (essentially) opaque metals such as Mg, Ca, or Al. Optionally or additionally, the cathode layer C may also comprise graphite and / or carbon nanotubes (CNTs). Optionally, the cathode layer C may also be composed of nanoscale silver wires.

[0038] OLEDs may also optionally include a protective layer (which may be designated as an electron injection layer (EIL)) between the electron transport layer (ETL) and the cathode layer C. This layer may include lithium fluoride, cesium fluoride, silver, Liq (lithium 8-hydroxyquinoline), Li2O, BaF2, MgO, and / or NaF.

[0039] Optionally, the electron transport layer (ETL) and / or hole blocking layer (HBL) may also contain one or more host compounds H.

[0040] To further alter the emission and / or absorption spectra of the emissive layer EML, the emissive layer EML may also include one or more additional emitter molecules F. Such emitter molecules F can be any emitter molecule known in the art. Preferably, such emitter molecules F are molecules having a structure different from that of the molecule E according to the invention. Emitter molecule F can optionally be a TADF emitter. Optionally, emitter molecule F can optionally be a fluorescent and / or phosphorescent emitter molecule capable of shifting the emission and / or absorption spectra of the emissive layer EML. Exemplarily, triplet and / or singlet excitons can transfer from the organic emitter molecule according to the invention to emitter molecule F, and then relax to the ground state S0 by emitting light that is typically redshifted compared to the light emitted by the organic molecule. Optionally, emitter molecule F can also induce a two-photon effect (i.e., absorbing two photons at half the maximum absorption energy).

[0041] The beneficial effects of this invention are: (1) The compounds of the present invention are deep blue light materials based on anthracene bipolar transmission, which are relatively simple to synthesize and have a high yield; (2) The compounds of this invention utilize the electron-donating effect of aromatic amine units such as carbazole and the electron-withdrawing effect of phosphonyl / sulfonyl groups, effectively improving the electron and hole transport capabilities of the molecules. Furthermore, the steric hindrance effect, resulting in a distorted molecular configuration, can suppress intermolecular interactions, thereby reducing the device efficiency roll-off caused by concentration quenching. The thermal exciton mechanism enables these molecules to achieve an exciton utilization rate exceeding that of traditional fluorescent molecules by 25%.

[0042] (3) The compounds of the present invention have good thermal stability, with thermal decomposition temperatures all above 300 °C; and good solubility, which can be used in solution-processed organic electronic devices to simplify device structure and solve the technical defects of large-area flexible organic electroluminescent devices.

[0043] (4) The electroluminescent device of the present invention has deep blue light and narrow bandwidth emission, and has high color purity. Attached Figure Description

[0044] Figure 1 , Figure 2 The images show the hydrogen and carbon NMR spectra of compound 1 of the present invention in deuterated dichloromethane, respectively.

[0045] Figure 3 , Figure 4 The figures are the hydrogen NMR spectrum and carbon NMR spectrum of compound 2 of the present invention in deuterated dichloromethane, respectively.

[0046] Figure 5 The emission spectra of compounds 1 and 2 of the present invention in toluene solution are shown.

[0047] Figure 6 The results are the performance test results of the OLED device based on compound 1 of this invention; (a) is the device structure and energy level; (b) is the electroluminescence spectrum; (c) is the current density-voltage-brightness curve; (d) is the external quantum efficiency-brightness; (e) is the power density-brightness; and (f) is the current density-brightness curve. Detailed Implementation

[0048] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials, reagents, or apparatus used in the embodiments and comparative examples are all available from conventional commercial sources or can be obtained by existing technical methods. Unless otherwise specified, the test or experimental methods are conventional methods in the art.

[0049] definition "Substitution" refers to the replacement of a hydrogen atom by a substituent. It is important to note that the substituent on a specific atom is restricted by its valence state.

[0050] As used herein, the term "alkyl" includes straight-chain or branched alkyl groups. For example, C1-C6 alkyl groups refer to straight-chain or branched alkyl groups having 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc.

[0051] As used herein, the term "alkoxy" refers to a group having an alkyl-oxy group structure. For example, "C1-C6 alkoxy" refers to a straight-chain or branched alkoxy group having 1-6 carbon atoms, including methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, etc.

[0052] The term "cycloalkyl" refers to a substituent in a saturated or partially unsaturated monocyclic or polycyclic nonaromatic hydrocarbon, wherein the cycloalkyl ring atom contains 3 to 6 carbon atoms. Non-limiting examples of monocyclic cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, and cyclohexyl.

[0053] The term "aryl" refers to a 6- to 14-membered all-carbon monocyclic or fused polycyclic (i.e., a ring sharing adjacent carbon atom pairs) group having a conjugated π-electron system. The aryl ring atom is preferably 6- to 10-membered, such as phenyl and naphthyl. Phenyl is more preferred.

[0054] Example 1 In this embodiment, compound 1 was prepared, and the specific process is as follows:

[0055] Step 1: Synthesize compound B:

[0056] Compound A, 3,6-di-tert-butyl-9-(2-(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)phenyl)-9H-carbazole (6.74 g, 14.0 mmol), 1-bromo-4-chlorobenzene (3.22 g, 16.8 mmol), and Pd(PPh3)4 (0.97 g, 0.84 mmol) were added to a flask containing toluene (100 mL), methanol (30 mL), and a 2.0 mol / L aqueous solution of potassium carbonate (15 mL). The reaction mixture was heated and stirred at 110 °C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the solvent was evaporated by column chromatography in a suitable petroleum ether / dichloromethane eluent system to give the target product (white solid, 6.07 g, 93% yield). 1 H NMR (400 MHz, CDCl3) δ 8.07 (d, J =1.4 Hz, 2H, Ar), 7.62 (m, 1H, Ar), 7.59 – 7.49 (m, 2H, Ar), 7.47 – 7.41 (m, 1H, Ar), 7.33 (m,2H, Ar), 7.07 – 6.98 (m, 4H, Ar), 6.95 (d, J = 8.6 Hz, 2H, Ar), 1.44 (s, 18H, t Bu). 13 C NMR (101 MHz, CDCl3) δ 142.44, 139.73, 139.68, 137.32, 135.43,133.19, 131.26, 129.91, 129.20, 129.02, 128.59, 128.39, 123.44, 123.12,116.07, 109.26, 34.68 ( t Bu), 32.00 ( t Bu). Step 2: Synthesize compound C

[0057] Compound B, 3,6-di-tert-butyl-9-(4'-chloro-[1,1'-biphenyl]-2-yl)-9H-carbazole (6.06 g, 13.0 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-di(1,3,2-dioxoborane) (4.95 g, 19.5 mmol), triphenylferrocene palladium (0.36 g, 0.39 mmol), potassium acetate (2.55 g, 26.0 mmol), tricyclohexylphosphine (0.22 g, 0.78 mmol), and anhydrous 1,4-dioxocyclohexane (100 mL), was degassed under nitrogen atmosphere with stirring for 1 h. The reaction mixture was then maintained at 80 °C under nitrogen atmosphere for 24 h. The mixture was diluted with dichloromethane and washed three times with distilled water (100 mL). The organic layer was dried with anhydrous magnesium sulfate and then evaporated under vacuum to give a crude product, which was purified by column chromatography with dichloromethane / n-hexane to obtain the target product (white powder, 10.14 mmol, 5.65 g, 78% yield). 1 H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 1.7 Hz, 2H, Ar), 7.65 (dd, J = 7.6, 1.6 Hz, 1H, Ar), 7.53 (dtd, J =16.7, 7.4, 1.5 Hz, 3H, Ar), 7.45 (d, J = 8.0 Hz, 2H, Ar), 7.29 (dd, J = 8.6, 1.9 Hz, 2H, Ar), 7.10 (d, J = 8.2 Hz, 2H,Ar), 6.95 (d, J = 8.5 Hz, 2H, Ar), 1.41 (s, 18H, t Bu), 1.24 (s, 12H, Bpin). 13 CNMR (101 MHz, CDCl3) δ 142.10, 141.68, 140.92, 139.82, 135.45, 134.53,131.43, 129.85, 128.80, 128.46, 127.21, 123.29, 123.05, 115.99, 109.27, 83.62(Bpin), 34.61 ( t Bu), 31.97 ( t Bu), 24.76 (Bpin). Step 3: Synthesize compound D

[0058] Compound C3,6-di-tert-butyl-9-(4'-(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)-[1,1'-biphenyl]-2-yl)-9H-carbazole (5.58 g, 10.0 mmol), 1-bromo-2-iodobenzene (3.39 g, 12.0 mmol), and Pd(PPh3)4 (0.69 g, 0.6 mmol) were added to a flask containing toluene (80 mL), methanol (20 mL), and a 2.0 mol / L aqueous solution of potassium carbonate (10 mL). The reaction mixture was heated and stirred at 110 °C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the solvent was evaporated by column chromatography in a suitable petroleum ether / dichloromethane eluent system to give the target product (white solid, 5.16 g, 88% yield). 1 H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 1.8 Hz, 2H, Ar), 7.78 – 7.72 (m, 1H, Ar), 7.64 – 7.52 (m, 4H, Ar), 7.38 –7.29 (m, 3H, Ar), 7.22 (td, J =7.5, 1.2 Hz, 1H, Ar), 7.13 – 6.98 (m, 7H, Ar), 1.42 (s, 18H, t Bu). 13 C NMR (101 MHz, CDCl3) δ 142.19, 140.10, 139.82, 139.42,138.06, 135.45, 132.84, 131.28, 130.91, 129.65, 129.07, 128.68, 128.51,128.37, 127.45, 127.06, 123.25, 123.06, 122.57, 115.88, 109.42, 34.63 ( t Bu), 32.01 ( t Bu). Step 4: Synthesize compound E

[0059] Compound D 9-(2''-bromo-[1,1':4',1''-triphenyl]-2-yl)-3,6-di-tert-butyl-9H-carbazole (4.69 g, 8.0 mmol) was dissolved in 40 mL of anhydrous tetrahydrofuran (THF), and the resulting solution was stirred at -78 °C. 7.4 mL of n-butyllithium solution (1.3 M) was added dropwise. After reacting at -78 °C for two hours, an excess of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxoborane was added dropwise. The resulting mixture was reacted overnight at room temperature. After the reaction was complete, the mixture was diluted with dichloromethane and washed three times with distilled water (100 mL). The organic layer was dried over anhydrous magnesium sulfate and evaporated under vacuum to give the crude product, which was purified by column chromatography using dichloromethane / n-hexane to obtain the target product. (White powder, 6.0 mmol, 3.8 g, yield 75%) 1 H NMR (400 MHz, CDCl3) δ 8.09 –8.01 (m, 2H, Ar), 7.69 (dd, J = 7.7, 1.4 Hz, 1H, Ar), 7.63 – 7.53 (m, 3H, Ar), 7.51 – 7.46 (m, 1H, Ar), 7.38 – 7.31 (m, 3H, Ar), 7.25 – 7.21 (m, 2H, Ar), 7.19 (d, J =7.8 Hz, 1H, Ar), 7.17 – 7.11 (m, 2H, Ar), 7.09 – 6.97 (m, 3H, Ar), 1.42 (s, 18H, t Bu), 0.96 (s, 12H, Bpin). 13 C NMR (101 MHz, CDCl3) δ 146.69,142.11, 141.87, 141.40, 140.43, 137.51, 135.62, 134.17, 131.63, 130.08,129.86, 128.96, 128.89, 128.62, 128.57, 127.56, 126.14, 123.36, 123.28,116.04, 109.42, 83.56 (Bpin), 34.63 ( t Bu), 32.02 ( t Bu), 24.37 (Bpin). Step 5: Synthesize compound 1

[0060] Compound E 3,6-di-tert-butyl-9-(2''-(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)-[1,1':4',1''-triphenyl]-2-yl)-9H-carbazole (1.27 g, 2.0 mmol), (4-(10-bromoanthrabenzo-9-yl)phenyl)diphenylphosphonic acid oxide (1.28 g, 2.4 mmol), palladium tris(diphenyldiboronic acid) (0.11 g, 0.12 mmol), potassium phosphate (1.02 g, 4.8 mmol), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.10 g, 0.24 mmol) were added to a flask containing toluene (20 mL) under a nitrogen atmosphere. The reaction mixture was heated at 110 °C and stirred under a nitrogen atmosphere for 24 hours. After cooling to room temperature, the solvent was evaporated under vacuum, and the residue was purified by column chromatography using a suitable petroleum ether / dichloromethane elution system. Recrystallization was then performed to obtain the target product (white solid, 1.31 g, yield 68%). 1 H NMR (400 MHz, CD2Cl2) δ 8.08 (s, 2H, Ar), 7.88 (m, 6H, Ar), 7.67 – 7.44 (m, 14H, Ar), 7.44 – 7.38 (m, 2H, Ar), 7.36 – 7.20 (m, 10H, Ar), 6.83 (d,J = 8.6 Hz, 2H, Ar), 6.71 (q, J = 20.3, 8.3 Hz, 4H, Ar), 1.43 (s, 18H, t Bu). 13 C NMR (151 MHz, CD2Cl2) δ 143.17 (d, J = 2.7 Hz), 142.38, 140.39, 140.01,139.74, 137.03 (d, J = 36.9 Hz), 136.69, 135.64, 135.19, 132.74 (d, J = 104.1Hz), 132.33, 132.28, 132.15, 132.12, 132.08, 132.03 (d, J = 4.0 Hz), 131.77, 131.70 (d, J = 2.8 Hz), 131.63, 131.59, 131.28, 130.53, 129.68 (d, J = 91.8 Hz), 129.49, 128.71 (d, J = 12.1 Hz), 128.63, 128.37, 128.22, 128.14, 127.35,127.20, 127.01, 126.51, 125.27 (d, J = 3.2 Hz), 123.38, 123.09, 116.02, 109.40,34.58 ( t Bu), 31.81 ( t Bu). 31 P NMR (243 MHz, CD2Cl2) δ 28.30 (s). Example 2 In this embodiment, compound 2 was prepared, and the specific process is as follows:

[0061]

[0062] Compound E 3,6-di-tert-butyl-9-(2''-(4,4,5,5-tetramethyl-1,3,2-dioxoborane-2-yl)-[1,1':4',1''-triphenyl]-2-yl)-9H-carbazole (1.27 g, 2.0 mmol), 9-bromo-10-(4-(benzenesulfonyl)phenyl)anthracene (1.14 g, 2.4 mmol), tris(diphenyldiethyl ketone)palladium (0.11 g, 0.12 mmol), potassium phosphate (1.02 g, 4.8 mmol), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.10 g, 0.24 mmol) were added to a flask containing toluene (20 mL) under a nitrogen atmosphere. The reaction mixture was heated and stirred at 110 °C for 24 hours under a nitrogen atmosphere. After cooling to room temperature, the solvent was evaporated under vacuum, and the residue was purified by column chromatography using a suitable petroleum ether / dichloromethane elution system. Recrystallization was then performed to obtain the target product (white solid, 1.17 g, yield 65%). 1 HNMR (400 MHz, CD2Cl2) δ 8.20 – 8.13 (m, 2H, Ar), 8.10 (m, 4H, Ar), 7.70 – 7.59 (m, 3H, Ar), 7.59 – 7.53 (m, 4H, Ar), 7.49 (m, 2H, Ar), 7.45 – 7.39 (m, 4H, Ar), 7.36 – 7.24 (m, 6H, Ar), 7.24 – 7.18 (m, 4H, Ar), 6.83 (d, J = 8.6 Hz, 2H,Ar), 6.69 (q, J = 8.3 Hz, 4H, Ar), 1.42 (s, 18H, t Bu). 13C NMR (101 MHz, CD2Cl2) δ144.73, 142.37, 142.33, 141.71, 140.95, 140.33, 139.97, 139.69, 137.22,137.14, 136.53, 135.18, 134.66, 133.41, 132.47, 132.45, 132.26, 131.24,130.51, 129.89, 129.49, 129.22, 128.63, 128.35, 128.17, 127.85, 127.74,127.68, 127.33, 127.18, 127.03, 126.18, 125.40, 125.25, 123.35, 123.06, 116.00, 109.36, 34.55, 31.76. Experimental Example 1 1H and 1C NMR spectra were obtained at room temperature using a Bruker Avance III 600 (600 MHz) illuminometer, with 0.03% tetramethylsilane (TMS) as the internal standard for deuteration. The highest molecular orbital (HOMO) and lowest molecular orbital (LUMO) energy levels were determined by three-electrode cyclic voltammetry (CV), using a glassy carbon electrode as the working electrode, a silver / silver ion electrode as the reference electrode, and a platinum electrode as the counter electrode. Potentials were measured from 0 V to 1.8 V in a 0.1 M solution of tetrabutylammonium hexafluorophosphate in dichloromethane, with ferrocene used as the internal standard. The thermal stability of the material was determined under a nitrogen atmosphere using a TA Instruments Q500 thermogravimetric analyzer at a heating rate of 10 °C / min. The thermal decomposition temperature (TDI) was [not specified in the original text]. T d The temperature at which the material loses 5% of its total mass is taken. The fluorescence emission spectrum (PL) of the material in toluene solution at room temperature was measured using an Edinburgh FLS1000, and the full width at half maximum (FWHM) value of the emission spectrum was obtained. The excitation wavelength was 375 nm. The lowest triplet excited state energy level (T1) was measured by low-temperature phosphorescence spectroscopy.

[0063] Figure 1 , Figure 2 The images show the 1H and 1C NMR spectra of compound 1 in deuterated dichloromethane, respectively. Figure 3 , Figure 4 The images show the 1H and 1C NMR spectra of compound 2 in deuterated dichloromethane, respectively. Figure 5 The emission spectra of compounds 1 and 2 in toluene solution are shown.

[0064] The photophysical and electrochemical data of compounds 1 and 2 are shown in Table 1: Table 1. Photophysical and electrochemical data of compounds 1 and 2

[0065] Example 3 This embodiment demonstrates the fabrication of an organic electroluminescent device, the specific process of which is as follows: Two sets of devices were fabricated using vacuum evaporation. The device structures include: 1. a conductive glass layer ITO; 2. a hole injection layer HATCN; 3. a hole transport layer TAPC; 4. an electron blocking layer TATC; 5. a light-emitting layer; 6. an electron transport layer TmPyPB; 7. an electron injection layer Liq; and 8. a cathode Al.

[0066] The fabrication method for the electroluminescent device is as follows: Before loading into the deposition chamber, the ITO substrate is cleaned with detergent and deionized water, dried in an oven at 120°C for 4 hours, and then treated with ultraviolet ozone for 20 minutes. (The last sentence appears to be incomplete and possibly refers to a specific process or method.) -6 Under a pressure of mbar, organic layers were sequentially evaporated onto an ITO substrate to fabricate the device. A 2 nm thick Liq layer was deposited on the electron transport layer to improve electron injection. Finally, a 120 nm thick aluminum layer was deposited as the cathode. The light-emitting area of ​​the device was determined to be 0.09 cm² based on the overlap area of ​​the anode and cathode. 2 The current density-voltage and brightness-voltage curves of the device were measured using a Keithley 4200 source meter and a calibrated silicon photodiode. All measurements were performed in a glove box at room temperature.

[0067] The specific structure of the device is ITO / HATCN (6 mm) / TAPC (30 nm) / TCTA (10 nm) / 5% 1 in mCBP (20 mm) / TmPyPB (40 nm) / Liq (2 nm) / Al (120 nm), where the host material is mCBP, which is commonly used in organic electroluminescent devices. High device performance is achieved by optimizing the doping concentration of guest compound 1.

[0068] Figure 6 The results show the performance test results of the OLED device based on compound 1; where (a) is the device structure and energy level; (b) is the electroluminescence spectrum; (c) is the current density-voltage-brightness curve; (d) is the external quantum efficiency-brightness; (e) is the power density-brightness; and (f) is the current density-brightness curve.

[0069] The electroluminescence performance of the above devices was tested, and the results are shown in Table 2 below: Table 2 Device Performance Data

[0070] a The data are in the order of current efficiency, power efficiency, and external quantum efficiency.

[0071] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A compound of formula I: ###0001### I wherein Ar is selected from the group consisting of aromatic amine units according to any one of (1) to (7): ###0002### (1) (2) (3) (4) (5) (6) (7) wherein R is selected from the group consisting of H, F, CI, Br, I, CN, N02, NCS, N3, NH2, NHR, NR2, SH, SR, SiR3, SnR3, B(OR)2, OS02CF3, CF3, CH2F, CHF2, CF2H, CF3, C(CH3)2F, C(CF3)2H, C(CF3)3, C(CF3)2CH3, C(CH3)2CF3, C(CH3)3, OCF3, OCF2H, OCH2F, OCHF2, OCH2CF3, OCH(CF3)2, OCH(CF3)3, OCH2CH2F, OCH2CHF2, OCH2CF2H, OCH2CF2H, OCH2CH(CF3)2, OCH2CH(CF3)3, OCH(CF3)2, OCH(CF3)3, OC(S)NR2, OC(S)SR, OC(S)OR, SC(S)R, SC(S)OR, SC(S)SR, SC(S)NR2, SC(O)R, SC(O)OR, SC(O)NR2, SC(O)SR, SC(NR2)R, SC(NR2)OR, SC(NR2)SR, SC(NR2)NR2, SC(NR2)2, SC(NR2)3, SC(NR2)4, SC(NR2)5, SC(NR2)6, SC(NR2)7, SC(NR2)8, SC(NR2)9, SC(NR2)10, SC(NR2)11, SC(NR2)12, SC(NR2)13, SC(NR2)14, SC(NR2)15, SC(NR2)16, SC(NR2)17, SC(NR2)18, SC(NR2)19, SC(NR2)20, SC(NR2)21, SC(NR2)22, SC(NR2)23, SC(NR2)24, SC(NR2)25, SC(NR2)26, SC(NR2)27, SC(NR2)28, SC(NR2)29, SC(NR2)30, SC(NR2)31, SC(NR2)32, SC(NR2)33, SC(NR2)34, SC(NR2)35, SC(NR2)36, SC(NR2)37, SC(NR2)38, SC(NR2)39, SC(NR2)40, SC(NR2)41, SC(NR2)42, SC(NR2)43, SC(NR2)44, SC(NR2)45, SC(NR2)46, SC(NR2)47, SC(NR2)48, SC(NR2)49, SC(NR2)50, SC(NR2)51, SC(NR2)52, SC(NR2)53, SC(NR2)54, SC(NR2)55, SC(NR2)56, SC(NR2)57, SC(NR2)58, SC(NR2)59, SC(N ； wherein ​ , , , , , , The aromatic amine unit is optionally unsubstituted, or is converted by one or more C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C6 alkyl groups. 14 Aryl substitution; R is selected from C1-C6 alkylsulfonyl, C3-C6 cycloalkylsulfonyl, C6-C 14 arylsulfonyl, diC1-C6 alkylphosphine oxide, diC3-C6 cycloalkylphosphine oxide, C6-C 14 Aryl C1-C6 alkyl phosphine oxide, C5-C 16 Aryloxyphosphine group.

2. The compound of claim 1, wherein: ​ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 3. The compound of claim 1, wherein: ​ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 4. A process for the preparation of a compound of formula I, characterized by: ​ ​ 、 ； ​ 5. An organic electroluminescent composition characterized by comprising: ​ 6. An electronic device, characterized by: ​ 7. Electronic device according to claim 6, characterized in that: ​ 8. Electronic device according to claim 7, characterized in that: ​ 9. Electronic device according to claim 8, characterized in that: ​ 10. The electronic device of claim 8, wherein: ​

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