Cyano-modified free radical, polymer, mixture and application of cyano-modified free radical, polymer and mixture

Abstract

The invention provides a cyano-modified free radical, a polymer, a mixture and application of the cyano-modified free radical, and belongs to the technical field of organic light-emitting materials. The cyano-modified free radical, the cyano-modified free radical polymer and the cyano-modified free radical mixture can be used for preparing organic electroluminescent devices, and high device efficiency and narrow-band gap electroluminescence are achieved. The preparation method of the cyano-modified free radical, the polymer and the mixture is simple, the raw materials are easy to obtain, and the industrial development requirement can be met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic light-emitting materials, in particular to a cyano-modified radical, a polymer, a mixture and application thereof. BACKGROUND

[0002] Organic light-emitting diodes (OLEDs) have been commercialized in the field of lighting and display. However, it is generally difficult to realize high-performance near-infrared light emission in the existing closed-shell molecular system. Light-emitting radicals have the unique advantage of realizing a theoretical internal quantum efficiency of 100% because both the ground state and the excited state thereof are doublet states. Therefore, light-emitting radicals become an important research platform for developing high-efficiency deep red to near-infrared (NIR) light-emitting diodes. The existing technology usually simply constructs light-emitting radicals by donor modification, and the molecular modification method is relatively single. Therefore, how to develop high-performance narrow-bandgap light-emitting radical materials is still a key difficulty in the technical development of the field. SUMMARY

[0003] Therefore, the purpose of the present application is to provide a cyano-modified radical, a cyano-modified radical polymer, a cyano-modified radical mixture, an organic electronic device and a display screen. The cyano-modified radical provided by the present application can realize the improvement of device efficiency while red-shifting the emission wavelength.

[0004] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions: The present application provides a cyano-modified radical having the structure shown in Formula I: Formula I, In Formula I, Ar1-Ar3 are independently C6-C30 aryl or C4-C30 heteroaryl; The number of R1-R3 is independently 1-14; R1-R3 are independently hydrogen, deuterium, fluorine, chlorine, bromine, iodine, cyano, -NO2, -N(R 1 )2, -OR 1 , -SR 1 , -C(=O)R 1 , -P(=O)R 1 , Si(R 1 )3, C1-C20 alkyl, C1-C20 alkyl substituted by one or more R 1 , C1-C20 alkoxy, C1-C20 alkoxy substituted by one or more R 1 , C3-C10 cycloalkyl, C3-C10 cycloalkyl substituted by one or more R 1 , C2-C20 alkenyl, C2-C20 alkenyl substituted by one or more R 1substituted C2-C20alkenyl, C2-C20alkynyl, C6-C30aryl, C4-C30heteroaryl, or any of the following groups substituted with one or more R 1 substituted C2-C20alkenyl, C2-C20alkynyl, C6-C30aryl, C4-C30heteroaryl, or any of the following groups substituted with one or more R 1 substituted C6-C30aryl, C4-C30heteroaryl, or any of the following groups substituted with one or more R 1 substituted C4-C30heteroaryl; the R 1 including hydrogen, deuterium, fluorine, chlorine, bromine, iodine, cyano, -NO2, C1-C20alkyl, C1-C20alkoxy, C3-C10cycloalkyl, C2-C20alkenyl, C2-C20alkynyl, C6-C30aryl, or C4-C30heteroaryl.

[0005] Preferably, R1-R3are independently selected from hydrogen, deuterium, fluorine, cyano, isopropyl, tert-butyl, trifluoromethyl, or any of the following groups of Formula II: Formula II, Formula II denotes the site of attachment.

[0006] Preferably, Ar1-Ar3are independently a phenyl ring or a pyridyl ring.

[0007] Preferably, Ar1-Ar3are independently phenyl, carbazolyl, pyridyl, pyrimidyl, biphenyl, terphenyl, benzothienocarbazolyl, benzofuranocarbazolyl, benzofluorene carbazolyl, benzanthracene, benzophenanthrene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenylboron, triphenylphosphine oxide, diphenylphosphine oxide, triphenylsilicon, or tetraphenylsilicon.

[0008] Preferably, the cyano-modified radical is selected from any of the following: ; ; ; ; ; ; ; ; ; ; .

[0009] The application further provides a cyan-modified free radical polymer, wherein a repeating unit of the cyan-modified free radical polymer comprises the cyan-modified free radical according to the technical solution.

[0010] The application further provides a cyan-modified free radical mixture comprising a free radical and an organic functional material, wherein the free radical comprises the cyan-modified free radical according to the technical solution or the cyan-modified free radical polymer according to the technical solution, and the organic functional material comprises one or more of a hole injection material, a hole transport material, a hole blocking material, an electron injection material, an electron transport material, an electron blocking material, a light-emitting material and a host material.

[0011] The application further provides an organic electronic device comprising one or more of the cyan-modified free radical according to the technical solution, the cyan-modified free radical polymer according to the technical solution or the cyan-modified free radical mixture according to the technical solution.

[0012] Preferably, the organic electronic device comprises a light-emitting layer, and the light-emitting layer comprises one or more of the cyan-modified free radical, the cyan-modified free radical polymer and the cyan-modified free radical mixture.

[0013] The application further provides a display screen, comprising a cover plate, a back plate and the organic electronic device according to the technical solution, wherein the organic electronic device is located between the back plate and the cover plate.

[0014] The application provides a cyan-modified free radical, which emits a red-shifted light-emitting free radical while maintaining high luminous efficiency through synergistic regulation of the acceptor, and a light-emitting device prepared therefrom has high external quantum efficiency, realizes high device efficiency and narrow-bandgap electroluminescence.

[0015] The cyan-modified free radical, the polymer and the mixture according to the application have simple preparation methods and readily available raw materials, and can meet the development needs of industrialization. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 FIG. 2 is an electroluminescence spectrum of an organic electronic device using Z2 and Z3 as light-emitting materials; Figure 2 FIG. 3 is a structural schematic diagram of an organic electronic device in an embodiment of the application; In the figure: 1, transparent ITO glass; 2, hole injection layer; 3, hole transport layer; 4, light-emitting layer; 5, hole blocking layer; 6, electron transport layer; 7, electron injection layer; 8, metal electrode. DETAILED DESCRIPTION

[0017] The present application provides a cyano-modified radical having a structure shown in Formula I: Formula I, In Formula I, Ar1~Ar3independently are C6~C30 aryl or C4~C30 heteroaryl; The number of R1~R3independently is 1~14; R1~R3independently are any one of hydrogen, deuterium, fluorine, chlorine, bromine, iodine, cyano, -NO2, -N(R 1 )2, -OR 1 , -SR 1 , -C(=O)R 1 , -P(=O)R 1 , Si(R 1 )3, C1~C20 alkyl, C1~C20 alkyl substituted with one or more R 1 , C1~C20 alkoxy, C1~C20 alkoxy substituted with one or more R 1 , C3~C10 cycloalkyl, C3~C10 cycloalkyl substituted with one or more R 1 , C2~C20 alkenyl, C2~C20 alkenyl substituted with one or more R 1 , C2~C20 alkynyl, C2~C20 alkynyl substituted with one or more R 1 , C6~C30 aryl, C6~C30 aryl substituted with one or more R 1 , or C4~C30 heteroaryl substituted with one or more R 1 ; R 1 includes hydrogen, deuterium, fluorine, chlorine, bromine, iodine, cyano, -NO2, C1~C20 alkyl, C1~C20 alkoxy, C3~C10 cycloalkyl, C2~C20 alkenyl, C2~C20 alkynyl, C6~C30 aryl, or C4~C30 heteroaryl.

[0018] In the present application, the number of substituents R1connected to Ar1may be specifically 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14; the number of substituents R2connected to Ar2may be specifically 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14; the number of substituents R3connected to Ar3may be specifically 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14; when the number of R1~R3independently is 2~14, the plurality of R1~R3independently includes hydrogen, deuterium, fluorine, chlorine, bromine, iodine, cyano, -NO2, -N(R 1 )2, -OR 1, -SR 1 , -C(=O)R 1 , -P(=O)R 1 , Si(R 1 )3, C1-C20alkyl, C1-C20alkyl substituted by one or more R 1 , C1-C20alkoxy, C1-C20alkoxy substituted by one or more R 1 , C3-C10cycloalkyl, C3-C10cycloalkyl substituted by one or more R 1 , C2-C20alkenyl, C2-C20alkenyl substituted by one or more R 1 , C2-C20alkynyl, C2-C20alkynyl substituted by one or more R 1 , C6-C30aryl, C6-C30aryl substituted by one or more R 1 , C4-C30heteroaryl, or C4-C30heteroaryl substituted by one or more R 1 .

[0019] In the present application, the C1-C20alkyl, C1-C20alkoxy and C3-C10cycloalkyl represented by R1to R3may be unsubstituted or can have a substituent, i.e. the C1-C20alkyl, C1-C20alkoxy and C3-C10cycloalkyl represented by R1to R3are substituted by one or more R 1 , more preferably, one or more non-adjacent CH2groups in the alkyl group are replaced by R 1 C=CR 1 , C≡C, Si(R 1 )3, C=O, C=NR 1 , P(=O)R 1 , SO, SO2, NR 1 , O, S or CONR 1 , and in which one or more hydrogen atoms are preferably replaced by a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group.

[0020] In the present application, the C1-C20 alkyl, C1-C20 alkoxy and C3-C10 cycloalkyl represented by R1to R3independently more preferably include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, 2-methylbutoxy, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl, the C1-C20 alkyl is preferably linear, branched or cyclic; The C2-C20 alkenyl more preferably includes vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl or cyclohexenyl, the C2-C20 alkenyl is preferably linear, branched or cyclic; The C2-C20 alkynyl more preferably includes ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl or decynyl; The C6-C30 aryl or C4-C30 heteroaryl has a substituent, two adjacent R 1 The substituent can form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, which can be substituted by one or more R 1 The two or more substituents R 1 may be linked to each other and can form a ring.

[0021] In the present application, Ar1~Ar3independently are phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, naphthacene, pentacene, benzopyrenyl, biphenyl, biphenyl, terphenyl, quaterphenyl, quinquephenyl, triphenyl, fluorenyl, spirobifluorenyl, dihydophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis or trans indenofluorenyl, cis or trans monobenzoindenofluorenyl, cis or trans dibenzoindenofluorenyl, triindenyl, isotriindenyl, spirotrindenyl, spiroisotriindenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzothienocarbazolyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, bipyridyl, terpyridyl, quinolyl, isoquinolyl, acridyl, phenanthridyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthimidazolyl, phenanthroimidazolyl, pyridimidazolyl, pyrazimidazolyl, quinoximidazolyl, oxazolyl, benzoxazolyl, benzoxadiazolyl, naphthoxazolyl, anthroxazolyl, phenanthroxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafuorenyl, diazanthracenyl, diazopyrenyl, tetrazaperiyl, diazanaphthyl, pyrazinyl, phenoxazinyl, phenothiazinyl, fluorubinyl, naphthidinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofluoro-carbazolyl, benzofluorene-carbazolyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenylboron, triphenylphosphine oxide, diphenylphosphine oxide, triphenylsilicon, or tetraphenylsilicon.

[0022] In the present application, the cyano-modified radical does not contain a structure represented by the following formula: .

[0023] The present application also provides a preparation method of the cyano-modified radical as described in the above technical solution, comprising the following steps: mixing the cyano-modified reaction precursor and the first compound to perform Suzuki coupling reaction to obtain a radical precursor; the first compound includes a borate compound or an amine compound; performing dehydrogenation oxidation reaction on the radical precursor to obtain the cyano-modified radical.

[0024] In the present application, the raw materials used are all commercially available products in the art or prepared by conventional technical means in the art, such as the cyano-modified reaction precursor prepared by nucleophilic attack reaction, unless otherwise specified.

[0025] Preferably, in the present application, the cyano-modified reaction precursor is prepared by selecting αHTTM, potassium hexacyanoferrate, dichlorobis[bis-(4-dimethylaminophenyl)phosphine]palladium(II) and anhydrous sodium carbonate as the raw materials, reacting under anhydrous and oxygen-free conditions at 133℃ for 10h, and then purifying by rotary evaporation and column chromatography.

[0026] In the present application, the preparation principle of the borate compound is shown in the following formula: .

[0027] In the present application, the cyano-modified reaction precursor has the structure shown in formula 1, the borate compound has the structure shown in formula 2, and the free radical precursor has the structure shown in formula 3, and the substituents in formula 1-3 are consistent with those in formula I.

[0028] The present application does not have special limitations on the specific structure of the amine compound, and the cyano-modified free radical can be obtained, which is shown in the following formula: 、 or .

[0029] In the present application, the cyano-modified reaction precursor, the first compound are mixed to perform Suzuki coupling reaction to obtain the free radical precursor; the first compound includes a borate compound or an amine compound.

[0030] In the present application, the molar ratio of the cyano-modified reaction precursor to the first compound is preferably 1-1.5:1.

[0031] In the present application, the Suzuki coupling reaction is preferably performed in the presence of anhydrous sodium carbonate, tetrakis(triphenylphosphine)palladium and a solvent.

[0032] In the present application, the molar ratio of the cyano-modified reaction precursor to anhydrous sodium carbonate is preferably 1-1.5:4.

[0033] In the present application, the molar ratio of the cyano-modified reaction precursor to tetrakis(triphenylphosphine)palladium is preferably 1-1.5:0.05.

[0034] In the present application, the solvent preferably includes methanol, ethanol and water.

[0035] In the present application, the temperature of the Suzuki coupling reaction is preferably 90-100℃, and can be 90, 95 or 100℃ in particular, and the time is preferably 24-48h, and the Suzuki coupling reaction is preferably carried out in a nitrogen atmosphere.

[0036] In the present application, after the Suzuki coupling reaction is completed, the obtained product is preferably sequentially subjected to extraction, rotary evaporation and column chromatography purification to obtain the radical precursor.

[0037] After obtaining the radical precursor, the radical precursor is subjected to a dehydrogenation oxidation reaction in the present application to obtain the cyano-modified radical.

[0038] In the present application, the temperature of the dehydrogenation oxidation reaction is preferably room temperature, and the time is preferably 5-12h, and the dehydrogenation oxidation reaction is preferably carried out in a nitrogen atmosphere.

[0039] In the present application, the dehydrogenation oxidation reaction is preferably carried out in sodium hydride, chloranil and a mixed solvent, and the mixed solvent preferably comprises tetrahydrofuran and N,N-dimethylformamide.

[0040] In the present application, the molar ratio of the radical precursor to sodium hydride is preferably 1:30.

[0041] In the present application, the molar ratio of the radical precursor to chloranil is preferably 1:20.

[0042] In the present application, the radical precursor is preferably added to sodium hydride under light-shielded conditions in a mixed solvent for 4.0h, and then chloranil is added to continue the reaction for 1.5h, and after the reaction is completed, the mixed solvent is introduced into a beaker containing anhydrous ethanol to quench the residual sodium hydride, and then rotary evaporation and column chromatography purification are sequentially performed to obtain the cyano-modified radical.

[0043] The present application also provides an application of the cyano-modified radical, and the cyano-modified radical is applied to an organic electronic device, and the organic electronic device preferably comprises an organic light-emitting diode (OLED, organic electroluminescent device), an organic photovoltaic cell (OPV), an organic light-emitting cell (OLEEC), an organic field-effect transistor (OFET), an organic light-emitting field-effect transistor, an organic laser, an organic spintronic device, an organic sensor or an organic plasmonic nanoparticle light-emitting diode.

[0044] In the present application, the cyano-modified radical is preferably applied to an organic electronic device as a functional material, and the cyano-modified radical is used as a light-emitting guest material.

[0045] The present application also provides a cyano-modified radical polymer, and the repeating unit of the cyano-modified radical polymer comprises the cyano-modified radical according to the above technical solution.

[0046] In the present application, the cyano-modified radical is preferably a non-conjugated high polymer, and the cyano-modified radical is on the side chain.

[0047] In the present application, the cyano-modified radical is preferably a conjugated high polymer.

[0048] In the present application, the molecular weight distribution (PDI) of the cyano-modified radical polymer is preferably 1-5, more preferably 1-3, further preferably 1-2, and most preferably 1-1.5.

[0049] In the present application, the weight average molecular weight of the cyano-modified radical polymer is preferably 10,000-10,000,000, more preferably 50,000-500,000, further preferably 100,000-400,000, and most preferably 200,000-250,000.

[0050] The present application also provides an application of the cyano-modified radical polymer in an organic functional material or an organic electronic device.

[0051] The present application also provides a cyano-modified radical mixture comprising a radical and an organic functional material, wherein the radical comprises the cyano-modified radical or the cyano-modified radical polymer according to the above technical solutions, and the organic functional material comprises one or more of a hole injection material, a hole transport material, a hole blocking material, an electron injection material, an electron transport material, an electron blocking material, a light emitting material, and a host material, and the present application does not have special limitations on the type of the organic functional material, and the type known to those skilled in the art can be used.

[0052] In the present application, the content of the radical in the cyano-modified radical mixture is preferably 1-20 wt%, and specifically can be 1 wt%, 5 wt%, 10 wt%, 15 wt%, or 20 wt%.

[0053] The present application also provides an organic electronic device comprising one or more of the cyano-modified radical, the cyano-modified radical polymer, or the cyano-modified radical mixture according to the above technical solutions.

[0054] In the present application, the organic electronic device preferably comprises a light emitting layer, and the light emitting layer preferably comprises one or more of the cyano-modified radical, the cyano-modified radical polymer, and the cyano-modified radical mixture.

[0055] In the present application, the organic electronic device preferably comprises an anode, a cathode, and an organic thin film layer disposed between the anode and the cathode, the organic thin film layer comprising a light-emitting layer, the light-emitting layer comprising a dopant material and a host material, the dopant material preferably comprising one or more of the cyano-modified radicals, the weight percentage of the dopant material in the light-emitting layer preferably being 0.3-30.0%, and the weight percentage of the host material preferably being 70.0-99.7%.

[0056] In the present application, the light-emitting layer preferably further comprises a sensitizer, in which case the weight percentage of the dopant material in the light-emitting layer preferably is 0.3-10.0%, the weight percentage of the host material preferably is 65-94.7%, and the weight percentage of the sensitizer preferably is 5-25%.

[0057] In the present application, the organic electronic device preferably comprises a substrate, the substrate preferably being transparent, non-transparent, or partially transparent, and a transparent substrate preferably is used to manufacture a transparent light-emitting component.

[0058] In the present application, the substrate preferably is rigid or flexible, the substrate preferably is made of plastic, metal, semiconductor wafer, glass, and composite materials thereof, and the substrate preferably has a smooth surface. In an embodiment of the present application, the substrate is flexible, and the substrate is optionally made of a polymer film (preferably poly(ethylene terephthalate) (PET) or poly(ethylene 2,6-naphthalate) (PEN)) or plastic, and the glass transition temperature (Tg) of the substrate preferably is 150°C or higher, more preferably 200°C or higher, even more preferably 300°C or higher, and most preferably 350°C or higher.

[0059] In the present application, the anode preferably comprises one or more of conductive metal, conductive metal oxide, and conductive polymer, and the anode is capable of injecting holes into a hole-injection layer or a hole-transport layer or a light-emitting layer. In an embodiment of the present application, the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the light-emitter in the light-emitting layer or the p-type semiconductor material used as a hole-injection layer or a hole-transport layer or an electron-blocking layer (hole-blocking layer) preferably is less than 0.5 eV, more preferably less than 0.3 eV, and most preferably less than 0.2 eV, and the material of the anode preferably comprises one or more of Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide, and alloys of the above examples. In the present application, the anode is preferably prepared by a physical vapor deposition method, and the physical vapor deposition method more preferably comprises radio frequency magnetron sputtering, vacuum thermal evaporation, or electron beam deposition.

[0060] In the present application, the anode preferably is a patterned anode, and the patterned anode preferably is a commercially available product.

[0061] In the present application, the cathode preferably comprises an electrically conductive metal and / or an electrically conductive metal oxide, the cathode injects electrons easily into the electron injection layer or the electron transport layer or the light-emitting layer, and the absolute value of the difference between the work function of the cathode and the LUMO level or the conduction band level of the n-type semiconductor of the light-emitter in the light-emitting layer or the electron injection layer or the electron transport layer or the hole-blocking layer is preferably less than 0.5 eV, more preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all cathode materials that can be used in OLED devices are possible as cathode materials in the present application, including Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO. The cathode in the present application is preferably produced by a physical vapor deposition method, more preferably including radio frequency magnetron sputtering, vacuum thermal evaporation or electron beam deposition.

[0062] In an embodiment of the present application, the organic electronic device comprises a light-emitting layer, which comprises one of the cyano-modified radicals described, or comprises one of the cyano-modified radicals described and one phosphorescent emitter, or comprises one of the cyano-modified radicals described and one TADF emitter, or comprises one of the cyano-modified radicals described and one fluorescent emitter, or comprises one of the cyano-modified radicals described and one host material, or comprises one of the cyano-modified radicals described, one bisemissive emitter and one host material, or comprises one of the cyano-modified radicals described, one radical emitter and one host material.

[0063] The present application provides the use of the organic electronic device in various electronic devices, including display devices, lighting devices, light sources or sensors.

[0064] The present application also provides a display screen, comprising a cover plate, a back plate and the organic electronic device described in the above technical solution, wherein the organic electronic device is located between the back plate and the cover plate.

[0065] The present application does not have special limitations on the preparation method of the cyano-modified radical polymer, the cyano-modified radical mixture, the organic electronic device and the display screen, and any method known to those skilled in the art can be used.

[0066] The technical solutions in the present application will be described clearly and completely below in combination with the embodiments in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0067] Compound Example 1 Compound 3-2 was prepared according to the following scheme:

[0068] Compound 1-1 (4.08 g, 1.5 equiv), 2-1 (2.78 g, 1.0 equiv), anhydrous sodium carbonate (3.18 g, 4.0 equiv), and tetrakis triphenylphosphine palladium (0.43 g, 0.05 equiv) were added to a 250 mL two-necked flask with a stir bar under nitrogen protection. 30 mL of toluene, 10 mL of anhydrous ethanol, and 20 mL of deionized water were added in turn. The reaction device was placed in a 95 °C oil bath for 48 h. After the reaction was completed, the reaction solution was separated by a separatory funnel to obtain the organic phase. After removing the solvent by reduced pressure distillation, the crude product was obtained. The crude product was purified by silica gel column, and the eluent was dichloromethane and petroleum ether in a volume ratio of 4:1. Finally, 1.98 g of compound 3-1 was obtained. The yield was 35%. MALDI-TOF-MS (m / z): calculated for C 38 H 21 Cl7N2, 753.9; found, 753.8. Elem. Anal. Calculated for C 38 H 21 Cl7N2: C60.55, H 2.81, N 3.72; found, C 60.36, H 2.63, N 3.79. Calcd for C 38 H 21 Cl7N2:752. 1 H NMR (500 MHz, Methylene Chloride-d2) δ 7.67 (dd, J = 6.9, 1.8 Hz, 2H),7.60 (d, J = 2.0 Hz, 1H), 7.54 (dd, J = 6.2, 1.8 Hz, 2H), 7.46 (d, J = 8.3Hz, 3H), 7.33 – 7.26 (m, 4H), 7.14 – 7.04 (m, 8H), 6.88 (s, 1H). Compound 3-1 (0.75 g, 1.0 equiv) was added to a 250 mL two-necked flask with a stir bar under nitrogen protection, 20 mL and 40 mL of oxygen-free super dry tetrahydrofuran and oxygen-free super dry dimethylformamide were added in sequence, then sodium hydride (1.20 g, 30.0 equiv) was slowly added under nitrogen protection, the mixed solution was reacted at room temperature for 4 h, and tetrachloroquinone (4.91 g, 20.0 equiv) was added under nitrogen atmosphere and the reaction was continued for 1.5 h. After the reaction was completed, the mixed solution was slowly poured into a beaker containing 200 mL of anhydrous ethanol to quench the remaining sodium hydride. Then, 100 mL of dichloromethane and 100 mL of deionized water were added in sequence to the mixed solution. The mixture was separated by a separatory funnel to obtain an organic phase, and the solvent was removed by reduced pressure distillation to obtain a crude product. The crude product was purified by silica gel column, and the eluent was dichloromethane and petroleum ether in a volume ratio of 4:1. Finally, 0.50 g of compound 3-2 was obtained, denoted as Z1. The yield was 67%. MS (EI) m / z: calculated for C 38 H 20 Cl7N2, 752.9; found, 752.5.Elem. Anal. Calculated for C 38 H 20 Cl7N2: C 60.63, H 2.68, N 3.72; found, C60.56, H 2.43, N 3.79. Fluorescence quantum yield was 23%.

[0069] Compound Examples 2~26 The synthesis steps similar to those of compound example 1 were performed, except that the reactants were replaced by corresponding reactants. The reactants, target products, yields, mass spectrometry detection values, and fluorescence quantum yields (PLQY) are shown in Table 1, and the prepared compounds were Z2~Z26, respectively.

[0070] Table 1 Summary of compound examples 2~26

[0071]

[0072]

[0073]

[0074]

[0075] Preparation of an organic light emitting device A glass plate coated with an ITO transparent conductive layer was subjected to ultrasonic treatment in a commercial cleaning agent, rinsing in deionized water, cleaning in acetone and ethanol each three times, baking in a clean environment until complete removal of moisture, cleaning with ultraviolet light and ozone, and surface bombardment with a low-energy cation beam. The ITO conductive glass was placed in a vacuum chamber, vacuumed to below 5 x 10 -4 Pa. The ITO conductive glass was used as an anode, and a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode were sequentially deposited thereon.

[0076] Electroluminescence spectra were collected using a photon multichannel analyzer QEPro (QEPRO-XR300-slitsize) for detection in the spectral region of 350-1050 nm. The external quantum efficiency of the device was obtained by measuring the forward light intensity using an integrating sphere (Hamamatsu A10094). All measurements were performed at room temperature in an atmospheric environment.

[0077] The structures and nomenclature of the functional layer compounds involved in the device are shown below: .

[0078] Device Example A1 A glass substrate coated with indium tin oxide (ITO) having a thickness of 1000 A was placed in distilled water with a cleaning agent dissolved therein and subjected to ultrasonic washing. After washing the ITO for 30 min, ultrasonic washing was repeated twice for 10 min using distilled water, and then using isopropyl alcohol, acetone, and methanol solvents, and drying was performed. The substrate was then transferred to a plasma cleaner. The substrate was cleaned using oxygen plasma for 6 min, and then transferred to a vacuum evaporator.

[0079] Molybdenum trioxide was vacuum-deposited on the transparent ITO electrode to a thickness of 30 A as a hole injection layer.

[0080] A compound 4,4'-cyclohexyl di[N,N-di(4-methylphenyl)aniline] (TAPC) (350 A) as a material for transporting holes was vacuum-deposited on the hole injection layer, thereby forming a hole transport layer.

[0081] Subsequently, a compound Z1 and 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN) were vacuum-deposited on the hole transport layer in a weight ratio of 5:95 to a thickness of 250 A, thereby forming a light-emitting layer.

[0082] Further, 4,6-bis(3,5-di(3-pyridyl)phenyl)-2-methylpyrimidine (B3PYMPM) (100 A) as an electron blocking material was vacuum-deposited on the light-emitting layer, thereby forming a hole blocking layer.

[0083] Then, 2,4,6-tris[3-(diphenylphosphino)phenyl]-1,3,5-triazine (POT2T) is vacuum-deposited on the hole-blocking layer to a thickness of 700 Å, thereby forming an electron transport layer.

[0084] Compound lithium fluoride (8 Å) and metal aluminum (1000 Å) are sequentially deposited on the electron transport layer as an electron injection layer and a metal electrode.

[0085] In the above process, the deposition rate of the hole injection layer material MoO3 and the electron injection layer material LiF is maintained at 0.3 Å / s, the deposition rate of the organic functional layer material, including the hole transport layer material, the electron blocking layer material, the light-emitting layer material, and the electron transport layer material, is maintained at 0.1 Å / s, the deposition rate of the electrode material metal aluminum is maintained at 0.3 Å / s, and the vacuum degree during deposition is maintained at 1×10 -7 ~5×10 -6 ~5×10

[0086] Figure 2 The structure of the organic electronic device in the embodiment of the present application is shown in the schematic diagram, in which: 1, transparent ITO glass; 2, hole injection layer; 3, hole transport layer; 4, light-emitting layer; 5, hole blocking layer; 6, electron transport layer; 7, electron injection layer; 8, metal electrode.

[0087] Device embodiments A2~A16 The same preparation conditions and processes as in device embodiment A1 are adopted, and only the compound Z1 in the light-emitting layer is replaced by the corresponding compound.

[0088] Figure 1 The electroluminescence spectrum of the organic electronic device using Z2 and Z3 as the light-emitting material is shown in the diagram, and it can be seen that the cyano-modified radical of the present application can improve the device efficiency and red-shift the emission wavelength.

[0089] Comparative examples B1~B2 The same preparation conditions and processes as in device embodiment A1 are adopted in comparative examples B1~B2, and only the compound Z1 in the light-emitting layer is replaced by the corresponding compounds R1 and R2, and the structures of R1 and R2 are shown as follows: .

[0090] The corresponding compounds and device parameters are listed in Table 2. It can be seen that, compared with the devices B1 and B2 of R1 and R2 which have been reported (only deep red electroluminescence is achieved), the devices A1~A16 of the compounds Z1~Z16 of the present application achieve near-infrared electroluminescence peak positions with significant red-shift. Moreover, on the basis of achieving significant red-shift of light emission, some of the devices A1~A16 also achieve significant improvement in device performance, and the maximum external quantum efficiency of some of them exceeds 6%.

[0091] Table 2: Performance test results of each device

[0092] In summary, the cyan-modified radical of the present application realizes red shift of emission while maintaining high luminous efficiency through synergistic regulation of the acceptor, and the device performance is excellent. Importantly, the cyan-modified radical of the present application has a simple preparation method and readily available raw materials, and can meet the development needs of industrialization.

[0093] The above only describes the preferred embodiments of the present application, and does not limit the present application in any form. It should be noted that for ordinary skilled persons in the art, some improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A cyano-modified free radical, characterized in that, It has the structure shown in Equation I: Formula I, In Formula I, Ar1 to Ar3 are independently C6 to C30 aryl or C4 to C30 heteroaryl; The number of R1 to R3 is independently 1 to 14; R1 to R3 are independently hydrogen, deuterium, fluorine, chlorine, bromine, iodine, cyano, -NO2, -N(R 1 )2、-OR 1 -SR 1 -C(=O)R 1 -P(=O)R 1 Si(R) 1 3. C1~C20 alkyl group, with one or more R 1 Substituted C1-C20 alkyl, C1-C20 alkoxy, or with one or more R 1 Substituted C1~C20 alkoxy, C3~C10 cycloalkyl, or with one or more R 1 Substituted C3~C10 cycloalkyl, C2~C20 alkenyl, or with one or more R 1 Substituted C2~C20 alkenyl, C2~C20 alkynyl, or with one or more R 1 Substituted C2~C20 alkynyl, C6~C30 aryl, or with one or more R 1 Substituted C6~C30 aryl, C4~C30 heteroaryl, or substituted with one or more R 1 Any of the substituted C4-C30 heteroaryl groups; The R 1 Including hydrogen, deuterium, fluorine, chlorine, bromine, iodine, cyano, -NO2, C1~C20 alkyl, C1~C20 alkoxy, C3~C10 cycloalkyl, C2~C20 alkenyl, C2~C20 alkynyl, C6~C30 aryl or C4~C30 heteroaryl.

2. The cyano-modified free radical according to claim 1, characterized in that, R1 to R3 are independently selected from hydrogen, deuterium, fluorine, cyano, isopropyl, tert-butyl, trifluoromethyl, or any one of formula II: Formula II, In Formula II Indicates the connection site.

3. The cyano-modified free radical according to claim 2, characterized in that, Ar1 to Ar3 are independently benzene rings or pyridine rings.

4. The cyano-modified free radical according to claim 1, characterized in that, The Ar1 to Ar3 are independently phenyl, carbazole, pyridine, pyrimidine, biphenyl, terphenyl, benzothiophenecarbazole, benzofuranocarbazole, benzofluorenocarbazole, benzoanthracene, benzophenanthrene, fluorenyl, spirobisfluorenyl, triazine, dibenzofuranyl, dibenzothiopheneyl, carbazoleyl, N-phenylcarbazoleyl, indocarbazoleyl, benzimidazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenylboryl, triphenylphosphoxy, diphenylphosphoxy, triphenylsilyl, or tetraphenylsilyl.

5. The cyano-modified free radical according to claim 1, characterized in that, The cyano-modified free radical is selected from any of the following: ； ； ； ； ； ； ； ； ； ； 。 6. A cyano-modified free radical polymer, characterized in that, The repeating unit of the cyano-modified free radical polymer comprises any one of the cyano-modified free radicals according to claims 1 to 5.

7. A cyano-modified free radical mixture, characterized in that, It includes free radicals and organic functional materials, wherein the free radicals include cyano-modified free radicals according to any one of claims 1 to 5 or cyano-modified free radical polymers according to claim 6, and the organic functional materials include one or more of hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, luminescent materials, and host materials.

8. An organic electronic device, characterized in that, It includes one or more of the cyano-modified free radicals according to any one of claims 1 to 5, the cyano-modified free radical polymer according to claim 6, or the cyano-modified free radical mixture according to claim 7.

9. The organic electronic device according to claim 8, characterized in that, The organic electronic device includes a light-emitting layer, which comprises one or more of the following: cyano-modified free radicals, cyano-modified free radical polymers, and cyano-modified free radical mixtures.

10. A display screen, characterized in that, It includes a cover plate, a back plate, and the organic electronic device as described in claim 8 or 9, wherein the organic electronic device is located between the back plate and the cover plate.

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