CN114891032B - Monoboro derivative based on fluorene-based aniline fusion donor, preparation and application thereof - Google Patents

Monoboro derivative based on fluorene-based aniline fusion donor, preparation and application thereof Download PDF

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CN114891032B
CN114891032B CN202210431760.2A CN202210431760A CN114891032B CN 114891032 B CN114891032 B CN 114891032B CN 202210431760 A CN202210431760 A CN 202210431760A CN 114891032 B CN114891032 B CN 114891032B
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CN114891032A (en
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王磊
段亚磊
郭闰达
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Huazhong University of Science and Technology
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Abstract

The invention belongs to the field of preparation and application of organic photoelectric materials, and discloses a mono-boron derivative based on fluorene aniline fusion donor, and preparation and application thereof, wherein the mono-boron derivative has a general structure shown as at least one of general formulas A-1 to A-3; wherein the R group is selected from: fluorene or fluorene derivative group having 13 to 38 carbon atoms; and, for the general formulas A-2 and A-3, the R groups are bonded to the boron atom in the general formulas, the bonding atom is its carbon atom in position 3, and the nitrogen atom is bonded to its carbon atom in position 4. According to the mono-boron derivative based on the fluorene-based aniline fusion donor, FWHM below 30nm can be realized based on the B-N resonance effect, and the color purity of an OLED device can be effectively improved.

Description

Monoboro derivative based on fluorene-based aniline fusion donor, preparation and application thereof
Technical Field
The invention belongs to the field of preparation and application of organic photoelectric materials, and in particular relates to a mono-boron derivative based on fluorene benzidine fusion donor, and preparation and application thereof.
Background
Organic electroluminescence (OLED) technology has been widely used in the display field due to its outstanding advantages of self-luminescence, fast response speed, flexibility, foldability, etc. Meanwhile, with the continuous development of OLED related technologies and the continuous improvement of consumer demand on product performance, the current organic light-emitting materials generally face the problem that the half-width (FWHM) of the emission spectrum is too wide (70-100 nm), so that the OLED cannot directly realize high color purity and wide color gamut display, and a corresponding solution is needed.
The third generation heat activation delay fluorescent material (TADF) realizes 100% internal quantum efficiency in small organic molecules, is expected to replace the traditional fluorescent material and phosphorescent luminescent material, and has the advantages of cost and efficiency. However, due to the molecular design, the TADF material generally has a strong structural relaxation characteristic, so that the half-width (FWHM) of an emission spectrum of the TADF material is usually more than 70nm, and the color purity of an OLED device is greatly affected. To solve this problem, professor t.hatakeyama, university of about western university, et al, developed a thermally-induced delayed fluorescent material (MR-TADF) with multiple induced resonance characteristics by achieving separation of HOMO/LUMO molecules at the atomic scale through the opposite resonance effects of electron-deficient atoms (B) and electron-rich atoms (N), thereby obtaining extremely narrow FWHM while maintaining the characteristics of TADF materials. However, most of the MR-TADF molecules reported at present adopt a simple donor to construct a resonance framework, and the types of materials are limited. The sensitization strategy for improving the performance of the device effectively at the present stage also faces the problems of large physical and chemical property difference between the sensitizer material and the luminescent object, less combination of high matching degree and the like. Therefore, the MR-TADF isomer with similar molecular structure and similar physical and chemical properties is developed to build a self-sensitized luminescent material system to improve the comprehensive performance of the OLED, and the MR-TADF isomer has great technological value and industrial application prospect.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention aims to provide a mono-boron derivative based on a fluorene-based aniline fusion donor, and preparation and application thereof, wherein the mono-boron derivative based on the fluorene-based aniline fusion donor can be obtained by modifying and reforming a simple group donor, introducing a rigid group fluorene derivative on the basis of retaining electron-rich N atoms, combining to form a novel fusion donor, the fusion donor based on the fluorene-based aniline has the characteristic of rigidity and large volume, and meanwhile, the electron-donating ability of the fusion donor is slightly stronger than that of a parent group diphenylamine of the fusion donor, and the group is introduced into an MR-TADF molecular system as a novel electron-rich group, so that the mono-boron derivative based on the fluorene-based aniline fusion donor can be obtained, FWHM below 30nm can be realized on the basis of B-N resonance effect, and the color purity of an OLED device can be effectively improved; meanwhile, a fluorene skeleton extending from a fluorene fusion donor can realize conjugate regulation and control at different closed-loop positions, so that gradient red shift of light color is obtained, energy transfer between isomers can be realized when the fluorene fusion donor is applied to an organic electroluminescent device as a luminescent material, and higher device efficiency is obtained. In addition, the thermal stability of the material is obviously improved due to the enhancement of the rigidity of the monoboro derivative of the fluorene-based aniline fusion donor.
In order to achieve the above object, according to one aspect of the present invention, there is provided a mono-boron derivative based on a fluorene-based benzidine fusion donor, characterized in that the mono-boron derivative has a general structure as shown in at least one of the general formulas a-1 to a-3:
Wherein the R group is selected from: a fluorene group or fluorene derivative group having 13 to 38 carbon atoms;
And, for the general formulas A-2 and A-3, the R group is bonded to the boron atom in the general formula, the bonding atom is the carbon atom in position 3 of the R group, and the nitrogen atom is bonded to the carbon atom in position 4 of the R group.
As a further preferred aspect of the present invention, the mono-boron derivative is prepared from an intermediate having a general structure represented by formula a, and the target product is three stereoisomeric mono-boron derivatives having general structures represented by formulas a-1 to a-3;
as a further preferred aspect of the present invention, the R group is fluorenyl;
or the R group is 9, 9-dimethylfluorenyl;
or the R group is 9, 9-diphenylfluorenyl;
Or the R group is a 9-fluorenone group;
Or the R group is 9,9' -spirobifluorenyl;
Or the R group is dibenzofuranyl;
or the R group is dibenzothienyl;
or R is spiro [ fluorene-9, 9' -xanthene ] group;
or R group is spiro [ fluorene-9, 9' -thioxanthene ] group;
Or the R group is 10-phenyl-10H-spiro [ acridine-9, 9' -fluorene ] group;
or the R group is 10, 10-dimethyl-10H-spiro [ anthracene-9, 9' -fluorene ] group;
or the R group is 10, 10-diphenyl-10H-spiro [ anthracene-9, 9' -fluorene ] group.
According to another aspect of the present invention, there is provided a method for preparing the above mono-boron derivative based on a fluorene-based aniline fusion donor, which is characterized by comprising the steps of:
(1) Taking 1,3, 5-trihalogen substituted benzene as a raw material, and matching with raw material diphenylamine to perform Buchwald-Hartwig reaction to obtain a3, 5-dihalogen triphenylamine compound;
(2) Taking a halide R-X corresponding to an R group as a raw material, and simultaneously matching with raw material aniline, and carrying out a C-N coupling reaction on the halide R-X and the raw material aniline through palladium catalysis to obtain a fluorene-containing aniline fusion donor containing the R group; wherein, for the halide corresponding to the R group, halogen X is positioned at the No. 4 site of the R group; the halogen X is fluorine, chlorine, bromine or iodine;
(3) Taking the 3, 5-dihalogenotriphenyl compound obtained in the step (1) and the fluorene-containing benzidine fusion donor containing the R group obtained in the step (2) as raw materials, and carrying out a C-N coupling reaction on the 3, 5-dihalogenotriphenyl compound and the fluorene-containing benzidine fusion donor through palladium catalysis to obtain an intermediate shown in a general formula A;
(4) Using a halogen substituent BX 3 of boron to the intermediate obtained in the step (3) to generate a boron heterofriedel-Crafts Reaction (Tandem Bora-Friedel-Crafts Reaction), thereby obtaining a mono-boron derivative based on a fluorene-based benzidine fusion donor; wherein the halogen substituent BX 3 of the boron is specifically boron trichloride BCl 3, boron tribromide BBr 3 or boron triiodide BI 3.
As a further preferred aspect of the present invention, in the step (1), the C-N coupling reaction is carried out in a solvent system in the presence of a ligand and a base, specifically, 1,3, 5-trihalogen substituted benzene raw material, diphenylamine raw material, palladium catalyst, ligand, base and solvent are added into a reaction apparatus in a volume ratio of 1mmol to 0.01-0.03mmol to 3-5mmol to 5-10ml, and then air is blown off by nitrogen, and then the reaction is heated to reflux state under nitrogen protection condition for 8-48 hours, and after the reaction is completed, the reaction is cooled to room temperature and subjected to purification post-treatment, thereby obtaining the 3, 5-dihalo-triphenylamine compound;
Wherein, the halogen at the 1 st position, the 3 rd position and the 5th position in the 1,3, 5-trihalogen substituted benzene is selected from fluorine, chlorine, bromine and iodine, and the reactivity of the halogen at the 1 st position is higher than that of the 3 rd position and the 5th position; the ligand is a phosphine-containing ligand, preferably tri-tert-butylphosphine tetrafluoroborate (t-Bu 3PHBF4); the base is an organic base, preferably sodium t-butoxide (t-BuONa); the solvent is dry toluene; the palladium catalyst is preferably dibenzylidene acetone dipalladium.
As a further preferred aspect of the present invention, in the step (2), the C-N coupling reaction is performed in a solvent system in the presence of a ligand and a base, specifically, a halide raw material corresponding to an R group, an aniline raw material, a palladium catalyst, a ligand, a base and a solvent are added into a reaction device according to the volume ratio of the halide raw material, the aniline raw material, the palladium catalyst, the ligand and the base to the solvent of 1mmol:1-2mmol:0.01-0.03 mmol:0.03-0.03 mmol:3-5mmol:5-10ml, then nitrogen is used for blowing air, then heating is performed to a reflux state under the protection of nitrogen for 8-48 hours, and after the reaction is completed, the mixture is cooled to room temperature for purification, and then the fluorene-aniline fusion donor containing the R group is obtained;
Wherein the ligand is a phosphine-containing ligand, preferably tri-tert-butylphosphine tetrafluoroborate (t-Bu 3PHBF4); the base is an organic base, preferably sodium t-butoxide (t-BuONa); the solvent is dry toluene; the palladium catalyst is preferably dibenzylidene acetone dipalladium.
In the step (3), the C-N coupling reaction is carried out in a solvent system in the presence of a ligand and a base, specifically, 3, 5-dihalotriazole compound raw material, fluorene-containing benzidine fusion donor raw material containing R group, palladium catalyst, ligand, base and solvent are added into a reaction device according to the volume ratio of 1mmol:2-2.5mmol:0.02-0.05 mmol:0.05-3-6 mmol:6-15ml of 3, 5-dihalotriazole compound raw material, fluorene-containing benzidine fusion donor raw material containing R group, palladium catalyst, ligand and base to the solvent, and then nitrogen is used to blow off air, and then heated to reflux state under the condition of nitrogen protection to react for 12-60 hours, and after the reaction is completed, the mixture is cooled to room temperature to purify the mixture, thus obtaining the intermediate shown in the general formula a;
wherein the ligand is a phosphine-containing ligand, preferably 2-dicyclohexylphosphine-2 ',6' -dimethoxy biphenyl (SPhos); the base is an organic base, preferably sodium t-butoxide (t-BuONa); the solvent is dry toluene; the palladium catalyst is palladium acetate (Pd (OAc) 2).
As a further preferred aspect of the present invention, the step (4) specifically includes: vacuum drying the intermediate for 8-24 hours at 80-120 ℃ before reaction, dissolving the intermediate into o-dichlorobenzene (o-DCB) solvent, completely dissolving the intermediate by ultrasound, blowing out nitrogen, stirring at room temperature under the protection of nitrogen, slowly dropwise adding BX 3 under the condition of being lower than room temperature, heating the reaction system to 150-250 ℃ after dropwise adding, and stirring for reacting for 20-48 hours; then cooling to room temperature, placing the system into ice bath, keeping the temperature below 0 ℃, adding N.N-Diisopropylethylamine (DIPEA), reacting for 1-5 hours, removing the solvent by reduced pressure distillation, and separating and purifying by column chromatography to obtain the monoboro derivative with the general structure shown in the general formulas A-1 to A-3;
Wherein the ratio of the amount of the intermediate, the volume of o-dichlorobenzene, the amount of BX 3 and the amount of N.N-Diisopropylethylamine (DIPEA) satisfies 1mmol:10-30ml:1.5-24mmol:12-18mmol.
According to a further aspect of the invention, the application of the monoboro derivative based on fluorene-based aniline fusion donor in the light-emitting layer of an organic electroluminescent device is provided;
Preferably, the organic electroluminescent device sequentially includes: an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode;
More preferably, an exciton blocking layer is further provided between the hole transport layer and the light emitting layer; an exciton blocking layer is further disposed between the light emitting layer and the electron transport layer.
As a further preferred aspect of the present invention, the mono-boron derivative based on a fluorene-based benzidine fusion donor is specifically applied as a guest light emitting material in a light emitting layer of an organic electroluminescent device.
As a further preferred aspect of the present invention, the monoboron derivative has a general structure represented by two or three of the general formulae a-1 to a-3.
Compared with the prior art (especially compared with the reported MR-TADF compound), the single boron derivative of the fluorene-type benzidine fusion donor has multiple induced resonance effect and thermally-induced delayed fluorescence characteristics, can realize half-width narrowing of a luminescence spectrum and high-efficiency fluorescence emission, is applied to an organic electroluminescent device (OLED) luminescent layer structure as an organic fluorescence luminescent material, and is beneficial to improving the OLED luminescent color purity. In the invention, the mono-boron derivative based on the same R group has three isomeride configurations, which are three stereoisomers with different degrees of conjugate extension, can realize that light color has the characteristic of red shift of luminous peak wavelength gradient, especially can mix three or two isomeride materials together, realizes gradient energy transfer through self-sensitization effect, is beneficial to improving exciton utilization efficiency and improves the integral performance of an electroluminescent device.
According to the invention, resonance core skeletons of fluorene fusion donor type MR-TADF molecules are regulated and controlled through different ring closing positions of B atoms, when B atoms are closed between an amino benzene ring of a fluorene benzidine fusion donor and a benzene ring of diphenylamine (namely a compound represented by a general formula A-1), the resonance skeletons of the mono-boron derivatives are similar to the conventional MR-TADF, conjugated extension is not obtained, and the light color is within the range of 440-460 nm; when B atoms are closed between the amino benzene ring of the fluorene-type benzidine fusion donor and the 3 rd position of the amino fluorene ring of the other fluorene-type benzidine fusion donor (namely, a compound represented by a general formula A-2), the resonance skeleton of the mono-boron derivative is conjugated and extended, and the light color of the mono-boron derivative is red shifted and is in the range of 460-480 nm; when B atoms are closed between the 3 # positions of the amino fluorene rings of the two fluorene-type aniline fusion donors (namely the compound represented by the general formula A-3), the conjugation of the resonance skeleton of the mono-boron derivative is further extended, and the light color of the mono-boron derivative is continuously red shifted and is in the range of 480-500 nm. The invention realizes the gradient red shift regulation of MR-TADF molecular light color of three stereoisomers of the same R group, and can be obtained by the following examples: the fluorene fusion donor type MR-TADF compounds 1-1, 2-1 to 12-1 contained in the general formula A-1 have the luminescence wavelength in a deep blue light region, and the luminescence peak value is 440 to 460nm; the fluorene fusion donor type MR-TADF compounds 1-2, 2-2 to 12-2 contained in the general formula A-2 have luminescence wavelengths in a pure blue light region, and the luminescence peak value is 460 to 480nm; the fluorene fusion donor type MR-TADF compounds 1-3, 2-3 to 12-3 contained in the general formula A-3 have light emission wavelengths in the sky blue region, and have light emission peaks of 480 to 500nm.
In particular, the invention can achieve the following beneficial effects:
(1) The resonance core of the mono-boron derivative based on fluorene-based benzidine fusion donor can extend outwards, and the electron cloud distribution is more delocalized. The fluorene fusion donor is adopted to expand a new MR-TADF luminescent molecular system, and meanwhile, the introduction of the rigid group is beneficial to further inhibiting vibration relaxation in the excited state of the molecule so as to narrow the luminescence spectrum, reduce the non-radiative energy loss path and improve the exciton utilization efficiency.
(2) The fluorene-based benzidine fusion donor has slightly higher electron donating ability than diphenylamine (original parent group of fluorene-based benzidine fusion donor), so that the closed loop position can be ensured to be carried out according to the target requirement during the boronation reaction, and three needed mono-boron derivatives with different skeleton extension and photochromic echelon red shift and stereoisomers are generated. In addition, the synthesis process is simple and feasible, and is favorable for large-scale industrialized production.
(3) The single boron derivative based on the fluorene-based benzidine fusion donor has three isomerides on the same R group, and the three isomerides have similar structures and similar properties, are easier to realize high-performance mixed component matching in industrial application to prepare devices, and are beneficial to simplifying the preparation process and reducing the cost. Besides selecting one of the mono-boron derivatives as a luminescent guest, the blend of two or three stereoisomerism mono-boron derivatives can be selected as a luminescent material to be applied to an OLED device according to the requirements of light color, and the stability and the reliability of the electroluminescent device are improved by utilizing the self-sensitization characteristic realized by energy transfer among materials.
(4) In addition, for three mono-boron derivatives based on fluorene-based aniline fusion donors of the same R group, due to the gradient increase of the self-conjugation degree (wherein, the conjugation degree of the general formula A-1 is minimum, the conjugation degree of the general formula A-3 is maximum, and the general formula A-2 is positioned between the two), the energy transfer from low conjugation to high conjugation exists between the mono-boron derivatives in the doped film or the electroluminescent device prepared based on blending of the two or three mono-boron derivatives; therefore, when the kind of R group is fixed, in addition to applying the mono-boron derivative satisfying one of the general formulae A-1, A-2, A-3 to the light emitting layer in the organic electroluminescent device, the present invention can further improve the device performance by applying the mono-boron derivative satisfying two or even three of the general formulae A-1, A-2, A-3 (i.e., a mixture of two or three mono-boron derivatives having isomers) to the light emitting layer in the organic electroluminescent device.
Drawings
Fig. 1 is a schematic diagram of an electroluminescent device.
FIG. 2 is a diagram showing the energy transfer process of a three-component mixed system constructed by taking a monoboro derivative of a fluorene-based benzidine fusion donor as a light-emitting guest material.
FIG. 3 is a single crystal analysis of compounds 1-1 to 5-3.
FIG. 4 is a graph comparing the thermal decomposition temperatures of compounds 1-1, 2-1, 3-3, 5-3 with the conventional MR-TADF compound PAB.
Fig. 5 is an external quantum efficiency-current density characteristic curve of the three-component self-sensitized device in device examples 1 to 5.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In general, the fluorene-based benzidine fusion donor-based monoboro derivative of the present invention, an intermediate thereof having a general structure as shown in formula a, has a general structure as shown in at least one of the general formulae a-1 to a-3 (two R groups in either general formula are the same group):
wherein the R group is selected from: a fluorene group or fluorene derivative group having 13 to 38 carbon atoms; for the R group position: when it is bonded to a boron atom in the formula (particularly, the formulas A-2 and A-3), the bonding atom is the carbon atom in the 3-position of the R group, and the nitrogen atom is bonded to the carbon atom in the 4-position of the R group.
The R group may be a fluorene group or a fluorene derivative group such as fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-fluorenonyl, 9 '-spirobifluorenyl, dibenzofuranyl, dibenzothienyl, spiro [ fluorene-9, 9' -xanthene ] yl, spiro [ fluorene-9, 9 '-thioxanthene ] yl, 10-phenyl-10H-spiro [ acridine-9, 9' -fluorenyl ] yl, 10-dimethyl-10H-spiro [ anthracene-9, 9 '-fluorenyl ] yl, 10-diphenyl-10H-spiro [ anthracene-9, 9' -fluorenyl ] yl, and the like.
Taking the intermediate structural formulas as shown in the formulas 1 to 12 as an example, the intermediates can correspond to 12 classes of 36 mono-boron derivative compounds. Wherein, formula 1-1 to formula 12-3 correspond to mono-boron derivatives of 36 fluorene-based aniline fusion donors, specifically:
in the formula 1 and the formulas 1-1 to 1-3, R is fluorenyl;
In the formula 2 and the formulas 2-1 to 2-3, R is 9, 9-dimethylfluorenyl;
in the formula 3 and the formulas 3-1 to 3-3, R is 9, 9-diphenyl fluorenyl;
in the formula 4 and the formulas 4-1 to 4-3, R is 9-fluorenonyl;
in the formula 5 and the formulas 5-1 to 5-3, R is 9,9' -spirobifluorenyl.
In the formula 6 and the formulas 6-1 to 6-3, R is dibenzofuranyl.
In the formula 7 and the formulas 7-1 to 7-3, R is dibenzothienyl.
In the formula 8 and the formulas 8-1 to 8-3, R is a spiro [ fluorene-9, 9' -xanthene ] group.
In the formula 9 and the formulas 9-1 to 9-3, R is a spiro [ fluorene-9, 9' -thioxanthene ] group.
In the formula 10 and the formulas 10-1 to 10-3, R is 10-phenyl-10H-spiro [ acridine-9, 9' -fluorene ] group.
In the formula 11, the formulas 11-1 to 11-3, R is 10, 10-dimethyl-10H-spiro [ anthracene-9, 9' -fluorene ] group.
In the formula 12, the formulas 12-1 to 12-3, R is 10, 10-diphenyl-10H-spiro [ anthracene-9, 9' -fluorene ] group.
The structural formulas of the specific intermediate and the mono-boron derivative compound are as follows:
Correspondingly, the preparation method of the mono-boron derivative of the fluorene-based aniline fusion donor can comprise the following steps:
(1) Taking 1,3, 5-trihalogen substituted benzene (halogen on 1,3 and 5 positions is selected from fluorine, chlorine, bromine and iodine, and the reactivity of the halogen on 1 position is higher than that of the halogen on 3 and 5 positions) as a raw material, and matching with raw material diphenylamine to generate Buchwald-Hartwig reaction to obtain a 3, 5-dihalogen triphenylamine compound (the Buchwald-Hartwig reaction can be controlled only aiming at the halogen on 1 position in the 1,3, 5-trihalogen substituted benzene by strictly controlling the proportion of the raw materials of the reaction, and the reaction activity is known in the prior art to strictly follow the activity sequence of the halogen such as iodine, bromine, chlorine and fluorine);
(2) Taking a halide R-X corresponding to an R group as a raw material, and simultaneously matching with raw material aniline, and carrying out a C-N coupling reaction on the halide R-X and the raw material aniline through palladium catalysis to obtain a fluorene-containing aniline fusion donor containing the R group; wherein, for the halide corresponding to the R group, halogen X is positioned at the No. 4 site of the R group; the halogen X is fluorine, chlorine, bromine or iodine;
(3) Taking the 3, 5-dihalogenotriphenyl compound obtained in the step (1) and the fluorene-containing benzidine fusion donor containing the R group obtained in the step (2) as raw materials, and carrying out a C-N coupling reaction on the 3, 5-dihalogenotriphenyl compound and the fluorene-containing benzidine fusion donor through palladium catalysis to obtain an intermediate shown in a general formula A;
(4) The intermediate obtained in the step (3) is subjected to a boron heterofriedel-Crafts Reaction (Tandem Bora-Friedel-Crafts Reaction) using a halogen substituent BX 3 (X represents halogen, BX 3 is boron trichloride, boron tribromide, boron triiodide) of boron, thereby obtaining a monoboro derivative based on a fluorene-based aniline fusion donor.
In some synthesis examples, the specific processes involved in the steps (1), (2) and (3) may be that the bromine-containing or iodine-containing raw material and aniline raw material, palladium catalyst is chosen to be tribenzylideneacetone dipalladium (Pd 2(dba)3), ligand is chosen to be tri-tert-butylphosphine tetrafluoroborate, alkali is chosen to be tert-sodium butoxide, solvent is chosen to be dry toluene, the bromine-containing or iodine-containing raw material, aniline raw material, tri-dibenzylideneacetone dipalladium, tri-tert-butylphosphine tetrafluoroborate, tert-sodium butoxide and toluene are added into the reaction device according to the amount or volume ratio (toluene) of 1 mol:1-2mmol, 0.01-0.03mmol, 0.03-0.05mmol, 3-5mmol, 5-10ml (e.g. 1mmol, 0.01mmol, 0.03mmol, 3mmol, 6 ml) of air is blown off by nitrogen (e.g. 15 min), then the mixture is heated to reflux state under the condition for 8-48 hours (e.g. 12 hours), the chromatographic detection reaction is cooled to be completely cooled to room temperature, and the compound is purified in the step (1), (2) after the step (2).
Or: the specific process involved can be to fuse the chloro-or fluoro-substituted raw material with the fluorene-containing benzidine as the donor raw material, the reactivity of chlorine and fluorine is reduced, palladium catalyst is changed to palladium acetate, ligand is changed to 2-dicyclohexylphosphine-2 ',6' -dimethoxy biphenyl, the rest is kept unchanged, the chloro-or fluoro-substituted raw material, the fluorene-containing benzidine as the donor raw material, palladium acetate, 2-dicyclohexylphosphine-2 ',6' -dimethoxy biphenyl, sodium tert-butoxide and toluene are added into a reaction device according to the amount or volume ratio (toluene) of 1mmol:2-2.5mmol:0.02-0.05mmol:0.05 mmol:3-6.10 mmol:6-15ml (for example, 1mmol:2mmol:0.02mmol:0.05mmol:3mmol:6 ml), air is blown by nitrogen (for example, 15 minutes), then the mixture is heated to reflux state under the condition for reaction for 12-60 hours (for example, 18-24 hours), the 3-room temperature is detected by chromatography, and the three-dimensional structure of the 3-dimensional boron-containing fluorene derivative is obtained after the 3-dimensional structure is completely purified by cooling the 3-dimensional donor.
In some synthesis embodiments, the step (4) may specifically be: the method comprises the specific processes that an intermediate of a mono-boron derivative of a fluorene-containing aniline fusion donor is dried in vacuum for 8-24 hours (such as 10 hours) at 80-120 ℃ (such as 120 ℃), then the intermediate is dissolved in o-dichlorobenzene solvent, the solvent is completely dissolved by ultrasonic, nitrogen is blown off (such as 30 minutes), then BX 3 is slowly dripped under the condition of being under the condition of 25 ℃ under the condition of stirring at room temperature for 30 minutes, the system is programmed to be heated to 150 ℃ -250 ℃ (such as 180 ℃ -200 ℃) after the dripping is finished, stirring is carried out for 20-48 hours (such as 20-24 hours), the system is placed in an ice bath to keep 0 ℃ after being cooled to room temperature, N.N-Diisopropylethylamine (DIPEA) is added, the solvent is removed by reduced pressure distillation after 1-5 hours (such as 2 hours), and then three mono-boron derivatives based on the fluorene-containing aniline fusion donor are obtained by column chromatography separation and purification; wherein the feed ratio of the amount of the substance of the intermediate of the mono-boron derivative of the fluorene-containing aniline fusion donor, the volume of the o-dichlorobenzene, the amount of the substance of the BX 3 and the amount of the substance of the N.N-Diisopropylethylamine (DIPEA) is 1 mmol/10-30 ml/1.5-24 mmol/12-18 mmol (e.g. 1 mmol/20 ml/2-4 mmol/15-18 mmol).
In addition, similar to the conventional treatment in the prior art, in the synthetic example, the eluent of the column chromatography is cyclohexane or a mixed solution of cyclohexane and dichloromethane with different volume ratios. The benign solvents of the system selected in the recrystallization operation are methylene dichloride and toluene, and the poor solvents are methanol and cyclohexane.
The following are synthetic examples:
Synthesis example 1: the compounds 1-1 to 1-3 of the present invention can be synthesized by the following methods:
(1) 1-bromo-3, 5-dichlorobenzene (20 g,88.5 mmol), diphenylamine (15.0 g,88.5 mmol), dibenzylideneacetone dipalladium (0.82 g,0.89 mmol), tri-tert-butylphosphine tetrafluoroborate (0.77 g,2.66 mmol), sodium tert-butoxide (25.5 g,265.5 mmol), dry toluene (200 mL) were added to a 500mL three-neck flask, purged with nitrogen for 15 minutes, then heated to 120℃under nitrogen atmosphere with reflux and stirred for 12 hours, after the reaction was completed, cooled to room temperature, the organic layer was collected by extraction with dichloromethane and water, dried and concentrated, column chromatography was performed for preliminary purification, and the crude product was further recrystallized with dichloromethane and methanol to give 3, 5-dichloro-triphenylamine as a white solid powder, 27.3g, yield 98.5%.
(2) 4-Bromofluorene (15 g,61.5 mmol), aniline (5.8 g,61.5 mmol), dibenzylideneacetone dipalladium (0.57 g,0.62 mmol), tri-tert-butylphosphine tetrafluoroborate (0.54 g,1.85 mmol), sodium tert-butoxide (17.7 g,184.5 mmol), dry toluene (200 mL) were added to a 500mL three-neck flask, nitrogen was purged for 15 minutes, then heated to 120℃under nitrogen atmosphere, reflux stirred for reaction for 12 hours, after the reaction was completed, cooled to room temperature, the organic layer was collected by extraction with dichloromethane and water, concentrated after drying, column chromatography was performed for preliminary purification, and the crude product was further recrystallized with dichloromethane and methanol to give N-phenyl-9H-fluoren-4-amine as a white solid powder, 14.6g, yield 92.1%.
(3) N-phenyl-9H-fluoren-4-amine (14.6 g,56.8 mmol), 3, 5-dichloro-triphenylamine (8.8 g,28.4 mmol), palladium acetate (0.13 g,0.57 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (0.70 g,1.71 mmol), sodium tert-butoxide (16.4 g,170.4 mmol), and dry toluene (200 mL) were then added to a 500mL three-necked flask, purged with nitrogen for 15 minutes, then heated to 120℃under nitrogen atmosphere under reflux with stirring, after the reaction was completed, cooled to room temperature, the organic layer was collected by extraction with dichloromethane and water, dried and concentrated, column chromatography was performed for preliminary purification, and the crude product was further recrystallized with dichloromethane and methanol to give compound 1 as a white solid powder, 18.2g, yield 84.7%.
(4) Compound 1 (10.0 g,13.2 mmol) is dried in vacuum in advance and then is dissolved into 200ml of o-dichlorobenzene, ultrasound is adopted to completely dissolve the compound, an oil pump is used to repeatedly pump air, then 3.82ml of boron tribromide is slowly dripped in the nitrogen environment below 25 ℃, reflux stirring reaction is carried out for 24 hours at 180 ℃, after the reaction is completed, the temperature is cooled to 0 ℃, 32.7ml of N.N-Diisopropylethylamine (DIPEA) is added, then the stirring reaction is carried out for 2 hours at 0 ℃, the o-dichlorobenzene is removed after the reaction is completed by reduced pressure distillation, concentrated mother liquor is collected, column chromatography is carried out for preliminary purification (cyclohexane as eluent), the crude product is further recrystallized by toluene and methanol to obtain light yellow solid powder, the mixture of three stereoisomers of 1-1, 1-2 and 1-3 is obtained, the yield is 66.8%, then the ratio of the three stereoisomers is 3:4:3 (mass ratio, the same) through supercritical fluid chromatographic analysis (reverse phase column, the volume ratio of methanol and water is 95:5, the same) is further carried out, and the positions of three stereoisomers in the space of the three isomers shown in the figure can be confirmed through analysis of the position of the three atom shown in the figure, and the ring closure structure shown in the figure can be judged.
Compound 1-1: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 763.3159, test value: 764.5170. elemental analysis results: theoretical value: 88.07% of C; h is 5.02%; 1.42 percent of B; n is 5.50%. Experimental values: 88.10 percent of C; h4.96%; b1.41%; n is 5.54%. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is between two benzene rings, and the product has a correct structure and is the target compound 1-1. The material has good thermal stability, and the decomposition temperature reaches above 460 ℃.
Compound 1-2: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 763.3159, test value: 764.3192. elemental analysis results: theoretical value: 88.07% of C; h is 5.02%; 1.42 percent of B; n is 5.50%. Experimental values: 88.04% of C; h is 4.99 percent; b1.45%; n is 5.53%. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is between the fluorene group of the fusion donor and the benzene ring of the other fusion donor, and the product has a correct structure and is the target compound 1-2. The material has good thermal stability, and the decomposition temperature reaches above 460 ℃.
Compounds 1-3: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 763.3159, test value: 764.2597. elemental analysis results: theoretical value: 88.07% of C; h is 5.02%; 1.42 percent of B; n is 5.50%. Experimental values: 88.09% of C; h is 4.99 percent; b1.41%; n is 5.52%. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is on fluorene groups of two fused donors, and the product has a correct structure and is the target compound 1-3. The material has good thermal stability, and the decomposition temperature reaches more than 470 ℃.
Synthesis example 2: the compounds 2-1 to 2-3 of the present invention can be synthesized by the following methods:
This example is substantially identical to synthetic example 1, except that: in this example, it was necessary to replace 4-bromofluorene with an equivalent amount of the number 4 site bromo of 9, 9-dimethylfluorene, and the remaining conditions were kept unchanged. Finally, a bright yellow solid powder is obtained, which is a mixture of three stereoisomers of 2-1, 2-2 and 2-3, 8.1g, and the yield is 74.9%, then, the three stereoisomers are further analyzed by supercritical fluid chromatography, the ratio of the three stereoisomers is 3:5:2, the spatial structures of the three stereoisomers can be confirmed by single crystal analysis, as shown in fig. 3, the different positions of B atoms and N atoms are indicated in the figure, and the structures of the three isomers can be judged by the closed loop positions of the B atoms.
Compound 2-1: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 819.3785, test value: 820.3818. elemental analysis results: theoretical value: 87.90 percent of C; h is 5.66%; 1.32% of B; n is 5.13%. Experimental values: 87.96% of C; h is 5.63%; 1.33% of B; n is 5.09%. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is between two benzene rings, and the product has a correct structure and is the target compound 2-1. The material has good thermal stability, and the decomposition temperature reaches above 510 ℃.
Compound 2-2: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 819.3785, test value: 820.5098. elemental analysis results: theoretical value: 87.90 percent of C; h is 5.66%; 1.32% of B; n is 5.13%. Experimental values: 87.92% of C; h is 5.62%; 1.34% of B; n is 5.14%. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is between the fluorene group of the fusion donor and the benzene ring of the other fusion donor, and the product has a correct structure and is the target compound 2-2. The material has good thermal stability, and the decomposition temperature reaches above 510 ℃.
Compound 2-3: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 819.3785, test value: 820.5205. elemental analysis results: theoretical value: 87.90 percent of C; h is 5.66%; 1.32% of B; n is 5.13%. Experimental values: 87.91% of C; h is 5.63%; 1.34% of B; n is 5.13%. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed loop position of the B atom is on fluorene groups of two fused donors, and the product has a correct structure and is the target compound 2-3. The material has good thermal stability, and the decomposition temperature reaches above 510 ℃.
Synthesis example 3: the compounds 3-1 to 3-3 of the present invention can be synthesized by the following methods:
This example is substantially identical to synthetic example 1, except that: in this example, it was necessary to replace 4-bromofluorene with an equivalent amount of the number 4 site bromo of 9, 9-diphenylfluorene, and the remaining conditions were kept unchanged. Finally, a bright yellow solid powder is obtained, which is a mixture of 3-1, 3-2 and 3-3 stereoisomers, 8.3g, and the yield is 58.6%, then, the three stereoisomers are further analyzed by supercritical fluid chromatography, the ratio of the three stereoisomers is 3:6:1, the spatial structures of the three stereoisomers can be confirmed by single crystal analysis, as shown in fig. 3, the different positions of B atoms and N atoms are indicated in the figure, and the structures of the three isomers can be judged by the closed loop positions of the B atoms.
Compound 3-1: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 1067.4411, test value: 1068.1430. elemental analysis results: theoretical value: 89.96 percent of C; h is 5.10%; 1.01 percent of B; n is 3.93 percent. Experimental values: 89.99 percent of C; h5.07%; 1.02 percent of B; n is 3.92%. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is between two benzene rings, and the product has a correct structure and is the target compound 3-1. The material has good thermal stability, and the decomposition temperature reaches more than 440 ℃.
Compound 3-2: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 1067.4411, test value: 1068.3526. elemental analysis results: theoretical value: 89.96 percent of C; h is 5.10%; 1.01 percent of B; n is 3.93 percent. Experimental values: 89.98% of C; h is 5.08%; 1.03 percent of B; n is 3.92%. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is between the fluorene group of the fusion donor and the benzene ring of the other fusion donor, and the product has a correct structure and is the target compound 3-2. The material has good thermal stability, and the decomposition temperature reaches above 460 ℃.
Compound 3-3: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 1067.4411, test value: 1068.5410. elemental analysis results: theoretical value: 89.96 percent of C; h is 5.10%; 1.01 percent of B; n is 3.93 percent. Experimental values: 89.99 percent of C; h is 5.05%; 1.04 percent of B; n is 3.91 percent. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed loop position of the B atom is on fluorene groups of two fused donors, and the product has a correct structure and is the target compound 3-3. The material has good thermal stability, and the decomposition temperature reaches more than 530 ℃.
Synthesis example 4: the compounds 4-1 to 4-3 of the present invention can be synthesized by the following methods:
This example is substantially identical to synthetic example 1, except that: in this example, it was necessary to replace 4-bromofluorene with the equivalent amount of the No. 4 site bromo of 9-fluorenone, and the remaining conditions were kept unchanged. Finally, a bright yellow solid powder is obtained, which is a mixture of three stereoisomers of 4-1, 4-2 and 4-3, 5.8g and 55.3% yield, then the three stereoisomers are further analyzed by supercritical fluid chromatography with the ratio of 2:7:1, the spatial structures of the three stereoisomers can be confirmed by single crystal analysis, as shown in fig. 3, the different positions of B atoms, O atoms and N atoms are indicated in the figure, and the structures of the three isomers can be judged by the closed loop positions of the B atoms.
Compound 4-1: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 791.2744, test value: 792.2778. elemental analysis results: theoretical value: 84.96% of C; h4.33%; b1.37%; n is 5.31%; 4.04 percent of O. Experimental values: 84.99% of C; h4.30%; 1.33% of B; n is 5.34%; 4.05% of O. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is between two benzene rings, and the product has a correct structure and is the target compound 4-1. The material has good thermal stability, and the decomposition temperature reaches more than 400 ℃.
Compound 4-2: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 791.2744, test value: 792.4827. elemental analysis results: theoretical value: 84.96% of C; h4.33%; b1.37%; n is 5.31%; 4.04 percent of O. Experimental values: 84.97% of C; h4.31%; 1.36% of B; n is 5.32%; 4.06% of O. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is between the fluorene group of the fusion donor and the benzene ring of the other fusion donor, and the product has a correct structure and is the target compound 4-2. The material has good thermal stability, and the decomposition temperature reaches more than 430 ℃.
Compound 4-3: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 791.2744, test value: 792.4882. elemental analysis results: theoretical value: 84.96% of C; h4.33%; b1.37%; n is 5.31%; 4.04 percent of O. Experimental values: 84.98% of C; h4.32%; 1.36% of B; n is 5.33%; 4.02% of O. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed loop position of the B atom is on fluorene groups of two fused donors, and the product has a correct structure and is the target compound 4-3. The material has good thermal stability, and the decomposition temperature reaches above 460 ℃.
Synthesis example 5: the compounds 5-1 to 5-3 of the present invention can be synthesized by the following methods:
This example is substantially identical to synthetic example 1, except that: in this example, it was necessary to replace 4-bromofluorene with an equivalent amount of the number 4 site bromo of 9,9' -spirobifluorene, and the remaining conditions were kept unchanged. Finally, a bright yellow solid powder is obtained, which is a mixture of three stereoisomers of 5-1, 5-2 and 5-3, 6.6g, and the yield is 46.8%, then the space structures of the three stereoisomers can be confirmed through single crystal analysis by analyzing the ratio of the three stereoisomers to 2:7:1 through supercritical fluid chromatography, as shown in figure 3, wherein different positions of B atoms and N atoms are indicated, and the structures of the three isomers can be judged through the closed loop positions of the B atoms.
Compound 5-1: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 1063.4098, test value: 1064.4131. elemental analysis results: theoretical value: 90.30% of C; h4.74%; 1.02 percent of B; n is 3.95%. Experimental values: 90.31% of C; h4.77%; 1.02 percent of B; n is 3.92%. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is between two benzene rings, and the product has a correct structure and is the target compound 5-1. The material has good thermal stability, and the decomposition temperature reaches more than 470 ℃.
Compound 5-2: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 1063.4098, test value: 1064.4336. elemental analysis results: theoretical value: 90.30% of C; h4.74%; 1.02 percent of B; n is 3.95%. Experimental values: 90.34% of C; h4.73%; 1.01 percent of B; n is 3.93 percent. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed ring position of the B atom is between the fluorene group of the fusion donor and the benzene ring of the other fusion donor, and the product has a correct structure and is the target compound 5-2. The material has good thermal stability, and the decomposition temperature reaches above 490 ℃.
Compound 5-3: high resolution mass spectrometer APCI-MS (m/z): theoretical molecular weight 1063.4098, test value: 1064.4872. elemental analysis results: theoretical value: 90.30% of C; h4.74%; 1.02 percent of B; n is 3.95%. Experimental values: 90.32% of C; h4.72%; 1.01 percent of B; n is 3.96%. As can be seen from mass spectrum and elemental analysis results and single crystal structure analysis (figure 3), the closed loop position of the B atom is on fluorene groups of two fused donors, and the product has a correct structure and is the target compound 5-3. The material has good thermal stability, and the decomposition temperature reaches above 490 ℃.
Similarly, the mono-boron derivatives of compounds 6-1, 6-2, 6-3 to 12-1, 12-2, 12-3 can be synthesized similarly.
The decomposition temperature of the monoboro derivative based on fluorene-based aniline fusion donor is higher than that of conventional materials, such as MR-TADF compound PAB (decomposition temperature-375 ℃ C., organic electronics.2021, 97:106275) reported earlier in the subject group, as shown in FIG. 4. Good thermal stability of the material is beneficial to improving the stability of the device.
The monoboro derivative of the fluorene-based aniline fusion donor can be applied to an organic electroluminescent device, for example, one of the monoboro derivatives of the fluorene-based aniline fusion donor or a mixture of two or three monoboro derivatives with isomers can be used as a light-emitting guest material of a light-emitting layer in the organic electroluminescent device. Fig. 1 is a schematic diagram of an exemplary electroluminescent device. FIG. 2 is a schematic diagram of the energy transfer process of a three-component mixed system constructed by taking a monoboro derivative of a fluorene-based benzidine fusion donor as a light-emitting guest material, wherein the compound represented by the general formula A-1 has the smallest conjugation degree, the compound represented by the general formula A-3 has the largest conjugation degree, and the compound represented by the general formula A-2 has the conjugation degree between the two, so that the energy transfer from a low-conjugation, short-wavelength compound to a high-conjugation, long-wavelength compound can be realized. The organic electroluminescent device comprises a counter electrode, a transmission layer, a luminescent layer and an injection layer between the counter electrode, wherein the luminescent layer is the monoboro derivative containing the fluorene benzidine fusion donor.
One of the mono-boron derivatives of the fluorene-type benzidine fusion donor or a mixture of two or three mono-boron derivatives with isomers can be used as a guest luminescent material to be applied to OLED electroluminescent devices. Specific device fabrication processes may include, for example: (1) And (3) preprocessing a substrate, namely sequentially ultrasonically cleaning an ITO (indium tin oxide) glass substrate in an ITO cleaning agent, isopropanol, acetone, ethanol and deionized water for 30 minutes, drying by dry nitrogen, and drying for 2 hours at 120 ℃. Before preparing the device, the ITO glass substrate is subjected to surface treatment by oxygen plasma for 5 minutes, then is conveyed into an organic vacuum chamber to evaporate the organic functional layer material, and after the preparation, the ITO glass substrate is subjected to vacuum transfer to a metal vacuum chamber to evaporate a metal electrode. In a specific preparation process, the optimal host material, exciton blocking layer material or injection transport layer material may be selected according to the self-properties of one of the mono-boron derivatives of the fluorene-based acene fusion donor or a mixture of two or three mono-boron derivatives having isomers, such as luminescence peak position, lowest singlet and triplet energy level values; in addition, the film thickness of each functional layer and the concentration of host-guest doping are also systematically optimized.
The following are device embodiments (each organic functional layer optimized):
Device example 1:
ITO/PEDOT：PSS(40nm)/TAPC(15nm)/mCP(5nm)/mCP:Dopant(8wt％,25nm)/TSPO1(5nm)/TmPyPb(20nm)/LiF(1nm)/Al(140nm).
The light-emitting layer guest light-emitting material (Dopant) is one or two or three of mono-boron derivatives 1-1, 1-2 and 1-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 1-1, the electroluminescent peak wavelength is 442nm, the full width at half maximum (FWHM) is 22nm, the maximum external quantum efficiency (EQE max) is 15.6%, and the device lifetime LT 95 is 80 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 1-1 and 1-3 (1-1 and 1-3 are in a ratio of 9:1; mass ratio, the same applies hereinafter). The peak wavelength of electroluminescence was 490nm, FWHM was 28nm, EQE max was 18.3%, and device lifetime LT 95 was 95 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 1-1, 1-2, and 1-3 (1-1 and 1-2 and 1-3 in a ratio of 6:3:1), the peak wavelength of electroluminescence is 460 nm, FWHM is 28nm, EQE max is 25.5%, and device lifetime LT 95 is 110 hours @ initial luminance 2000cd/m 2.
Device example 2:
ITO/TAPC(50nm)/TCTA(30nm)/mCP(5nm)/mCP:Dopant(10wt％,30nm)/TmPyPb(30nm)/LiF(1nm)/Al(100nm).
The light-emitting layer guest light-emitting material (Dopant) is one or two or three of mono-boron derivatives 2-1, 2-2 and 2-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 2-1, the electroluminescent peak wavelength is 449nm, the full width at half maximum (FWHM) is 21nm, the maximum external quantum efficiency (EQE max) is 15.4%, and the device lifetime LT 95 is 74 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 2-1 and 2-2 (the ratio of 2-1 to 2-2 is 20:1). The peak wavelength of electroluminescence was 469nm, FWHM was 25nm, EQE max was 23.1%, and device lifetime LT 95 was 88 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 2-1, 2-2, and 2-3 (the ratio of 2-1 to 2-2 to 2-3 is 10:2:1), the peak wavelength of electroluminescence is 4815 nm, FWHM is 27nm, EQE max is 27.1%, and device lifetime LT 95 is 105 hours @ initial luminance 2000cd/m 2.
Device example 3:
ITO/NPD(60nm)/TCTA(20nm)/mCP(5nm)/mCBP:Dopant(5wt％,20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
The light-emitting layer guest light-emitting material (Dopant) is one or two or three of monoboro derivatives 3-1, 3-2 and 3-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 3-1, the electroluminescent peak wavelength is 455nm, the full width at half maximum (FWHM) is 23nm, the maximum external quantum efficiency (EQE max) is 17.8%, and the device lifetime LT 95 is 92 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 3-2 and 3-3 (the ratio of 3-2 to 3-3 is 10:1). The peak wavelength of electroluminescence was 492nm, FWHM was 26nm, EQE max was 29.3%, and device lifetime LT 95 was 98 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 3-1, 3-2 and 3-3 (the ratio of 3-1 to 3-2 to 3-3 is 6:3:1), the peak wavelength of electroluminescence is 492nm, FWHM is 27nm, EQE max is 34.8%, and device lifetime LT 95 is 118 hours @ initial luminance 2000cd/m 2.
Device example 4:
ITO/HATCN(50nm)/TCTA(30nm)/mCP(5nm)/mCBP:Dopant(3wt％,20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
the light-emitting layer guest light-emitting material (Dopant) is one or two or three of mono-boron derivatives 4-1, 4-2 and 4-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 4-1, the electroluminescent peak wavelength is 442nm, the full width at half maximum (FWHM) is 23nm, the maximum external quantum efficiency (EQE max) is 13.5%, and the device lifetime LT 95 is 61 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 4-1 and 4-2 (the ratio of 4-1 to 4-2 is 9:1). The peak wavelength of electroluminescence was 460nm, FWHM was 27nm, EQE max was 18.1%, and device lifetime LT 95 was 82 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 4-1, 4-2, and 4-3 (the ratio of 4-1 to 4-2 to 4-3 is 20:5:1), the peak wavelength of electroluminescence is 481nm, FWHM is 29nm, EQE max is 26.5%, and device lifetime LT 95 is 92 hours @ initial luminance 2000cd/m 2.
Device example 5:
ITO/NPD(60nm)/TCTA(20nm)/mCP(5nm)/mCBP:Dopant(6wt％,20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
The light-emitting layer guest light-emitting material (Dopant) is one or two or three of mono-boron derivatives 5-1, 5-2 and 5-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 5-1, the electroluminescent peak wavelength is 458nm, the full width at half maximum (FWHM) is 20nm, the maximum external quantum efficiency (EQE max) is 19.1%, and the device lifetime LT 95 is 94 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 5-1 and 5-2 (the ratio of 5-1 to 5-2 is 10:1). The peak wavelength of electroluminescence was 478nm, FWHM was 23nm, EQE max was 23.9%, and device lifetime LT 95 was 104 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 5-1, 5-2, and 5-3 (5-1 and 5-2 and 5-3 in a ratio of 20:5:1), the peak wavelength of electroluminescence is 4954 nm, FWHM is 26nm, EQE max is 28.5%, and device lifetime LT 95 is 125 hours @ initial luminance 2000cd/m 2.
Device example 6:
ITO/HAT-CN(15nm)/TAPC(15nm)/mCP(5nm)/mCP:Dopant(1wt％,20nm)/PPF(6nm)/TmPyPb(20nm)/LiF(1nm)/Al(60nm).
The light-emitting layer guest light-emitting material (Dopant) is one or two or three of mono-boron derivatives 6-1, 6-2 and 6-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 6-1, the electroluminescent peak wavelength is 440nm, the full width at half maximum (FWHM) is 24nm, the maximum external quantum efficiency (EQE max) is 16.9%, and the device lifetime LT 95 is 65 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 6-1 and 6-3 (the ratio of 6-1 to 6-3 is 9:1). The peak wavelength of electroluminescence was 284 nm, FWHM was 26nm, EQE max was 25.8%, and device lifetime LT 95 was 96 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 6-1, 6-2 and 6-3 (6-1 and 6-2 and 6-3 in a ratio of 6:3:1), the peak wavelength of electroluminescence is 4815 nm, FWHM is 27nm, EQE max is 30.1%, and device lifetime LT 95 is 102 hours @ initial luminance 2000cd/m 2.
Device example 7:
ITO/HAT-CN(15nm)/TAPC(15nm)/mCP(5nm)/mCP:Dopant(1wt％,20nm)/PPF(6nm)/TmPyPb(20nm)/LiF(1nm)/Al(60nm).
The light-emitting layer guest light-emitting material (Dopant) is one or two or three of monoboro derivatives 7-1, 7-2 and 7-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 7-1, the electroluminescent peak wavelength is 441nm, the full width at half maximum (FWHM) is 23nm, the maximum external quantum efficiency (EQE max) is 17.0%, and the device lifetime LT 95 is 71 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 7-1 and 7-2 (the ratio of 7-1 to 7-2 is 20:1). The peak wavelength of electroluminescence was 460 nm, FWHM was 25nm, EQE max was 25.6%, and device lifetime LT 95 was 89 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 7-1, 7-2, and 7-3 (the ratio of 7-1 to 7-2 to 7-3 is 20:2:1), the peak wavelength of electroluminescence is 4815 nm, FWHM is 25nm, EQE max is 28.2%, and device lifetime LT 95 is 106 hours @ initial luminance 2000cd/m 2.
Device example 8:
ITO/NPD(30nm)/TCTA(20nm)/mCP(5nm)/mCBP:Dopant(3wt％,20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
the light-emitting layer guest light-emitting material (Dopant) is one or two or three of mono-boron derivatives 8-1, 8-2 and 8-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 8-1, the electroluminescent peak wavelength is 455nm, the full width at half maximum (FWHM) is 23nm, the maximum external quantum efficiency (EQE max) is 17.6%, and the device lifetime LT 95 is 82 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 8-2 and 8-3 (the ratio of 8-2 to 8-3 is 10:1). The peak wavelength of electroluminescence is 496nm, FWHM is 26nm, EQE max is 27.9%, and device lifetime LT 95 is 99 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 8-1, 8-2 and 8-3 (the ratio of 8-1 to 8-2 to 8-3 is 6:3:1), the peak wavelength of electroluminescence is 497nm, FWHM is 27nm, EQE max is 29.5%, and device lifetime LT 95 is 121 hours @ initial luminance 2000cd/m 2.
Device example 9:
ITO/NPB(30nm)/TCTA(15nm)/mCP(5nm)/mCBP:Dopant(5wt％,25nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
The light-emitting layer guest light-emitting material (Dopant) is one or two or three of mono-boron derivatives 9-1, 9-2 and 9-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 9-1, the electroluminescent peak wavelength is 456nm, the full width at half maximum (FWHM) is 23nm, the maximum external quantum efficiency (EQE max) is 18.1%, and the device lifetime LT 95 is 83 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 9-1 and 9-2 (the ratio of 9-1 to 9-2 is 10:1). The peak wavelength of electroluminescence was 476nm, FWHM was 25nm, EQE max was 27.6%, and device lifetime LT 95 was 88 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 9-1, 9-2, and 9-3 (the ratio of 9-1 to 9-2 to 9-3 is 20:3:1), the peak wavelength of electroluminescence is 498nm, FWHM is 26nm, EQE max is 32.7%, and device lifetime LT 95 is 122 hours @ initial luminance 2000cd/m 2.
Device example 10:
ITO/TAPC(60nm)/TCTA(5nm)/mCP(5nm)/mCBP:Dopant(5wt％,20nm)/TmPyPB(40nm)/LiF(1nm)/Al(100nm).
The light-emitting layer guest light-emitting material (Dopant) is one or two or three of mono-boron derivatives 10-1, 10-2 and 10-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 10-1, the electroluminescent peak wavelength is 458nm, the full width at half maximum (FWHM) is 20nm, the maximum external quantum efficiency (EQE max) is 16.2%, and the device lifetime LT 95 is 91 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 10-1 and 10-2 (10-1 and 10-2 ratio 20:1). The peak wavelength of electroluminescence was 480nm, FWHM was 23nm, EQE max was 24.8%, and device lifetime LT 95 was 102 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 10-1, 10-2 and 10-3 (10-1 and 10-2 and 10-3 in a ratio of 20:3:1), the peak wavelength of electroluminescence is 499nm, FWHM is 26nm, EQE max is 34.7%, and device lifetime LT 95 is 123 hours @ initial luminance 2000cd/m 2.
Device example 11:
ITO/HAT-CN(10nm)/TAPC(30nm)/TCTA(15nm)/mCP(5nm)/mCP:Dopant(1wt％,20nm)/PPF(6nm)/TPBi(20nm)/LiF(1nm)/Al(100nm).
The light-emitting layer guest light-emitting material (Dopant) is one or two or three of monoboro derivatives 11-1, 11-2 and 11-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 11-1, the electroluminescent peak wavelength is 452nm, the full width at half maximum (FWHM) is 23nm, the maximum external quantum efficiency (EQE max) is 16.6%, and the device lifetime LT 95 is 66 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 11-1 and 11-3 (the ratio of 11-1 to 11-3 is 10:1). The peak wavelength of electroluminescence is 493nm, FWHM is 26nm, EQE max is 24.9%, and device lifetime LT 95 is 93 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 11-1, 11-2 and 11-3 (the ratio of 11-1 to 11-2 to 11-3 is 20:5:1), the peak wavelength of electroluminescence is 493nm, FWHM is 26nm, EQE max is 29.5%, and device lifetime LT 95 is 104 hours @ initial luminance 2000cd/m 2.
Device example 12:
ITO/HAT-CN(15nm)/TAPC(15nm)/mCP(5nm)/mCP:Dopant(3wt％,20nm)/DPEPO(5nm)/TmPyPb(20nm)/LiF(1nm)/Al(60nm).
the light-emitting layer guest light-emitting material (Dopant) is one or two or three of mono-boron derivatives 12-1, 12-2 and 12-3 of the fluorene-based benzidine fusion donor.
When Dopant is only 12-1, the electroluminescent peak wavelength is 450nm, the full width at half maximum (FWHM) is 21nm, the maximum external quantum efficiency (EQE max) is 17.5%, and the device lifetime LT 95 is 73 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 12-1 and 12-2 (12-1 and 12-2 ratio 20:1). The peak wavelength of electroluminescence was 471nm, FWHM was 23nm, EQE max was 26.0%, and device lifetime LT 95 was 89 hours @ initial luminance 2000cd/m 2.
When Dopant is a mixture of 12-1, 12-2 and 12-3 (the ratio of 12-1 to 12-2 to 12-3 is 20:5:1), the peak wavelength of electroluminescence is 460 nm, FWHM is 25nm, EQE max is 33.6%, and device lifetime LT 95 is 107 hours @ initial luminance 2000cd/m 2.
The above examples demonstrate that the monoboro derivatives based on fluorene-based benzidine fusion donors of the present invention have extremely narrow half-peak widths, which can effectively improve the color purity of the device. Through optimizing the device preparation process, the OLED device of the single boron derivative of the single fluorene-type benzidine fusion donor or the two or three-component self-sensitized OLED device with the isomer can obtain higher device efficiency, and the external quantum efficiency (EQE (equivalent to energy) of the self-sensitized device with the two or three components with the isomer can be improved by more than 50% compared with that of the device with the single component.
FIG. 5 is an external quantum efficiency versus current density characteristic of the three-component self-sensitized devices of device examples 1 to 5. The external quantum efficiency curve of the three-component self-sensitized device can be used for obtaining a clear conclusion, the luminous efficiency of the material is at a higher level, and the requirement of the industrial application of the organic electroluminescent material is met.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (6)

1. A mono-boron derivative with narrowed half-width of emission spectrum based on fluorene-based aniline fusion donor, characterized in that the mono-boron derivative has a structure as shown in at least one of formulas 1-1、1-2、1-3、2-1、2-2、2-3、3-1、3-2、3-3、4-1、4-2、4-3、5-1、5-2、5-3、6-1、6-2、6-3、7-1、7-2、7-3、8-1、8-2、8-3、9-1、9-2、9-3、10-1、10-2、10-3、11-1、11-2、11-3、12-1、12-2、12-3:
2. Use of the monoboro derivative with narrowed half-width of emission spectrum based on fluorene-based benzidine fusion donor as claimed in claim 1 in the light-emitting layer of organic electroluminescent device.
3. The use according to claim 2, wherein the organic electroluminescent device comprises, in order: an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode.
4. The use of claim 3, wherein an exciton blocking layer is further disposed between the hole transport layer and the light emitting layer; an exciton blocking layer is further disposed between the light emitting layer and the electron transport layer.
5. The use according to claim 2, wherein the mono-boron derivative with a narrowed half-width of the emission spectrum based on the fluorene-based aniline fusion donor is used as a guest light-emitting material in the light-emitting layer of an organic electroluminescent device.
6. The use according to claim 2, wherein the mono-boron derivative is a mixture of two or three of formulae 1-1, 1-2, 1-3, or a mixture of two or three of formulae 2-1, 2-2, 2-3, or a mixture of two or three of formulae 3-1, 3-2, 3-3, or a mixture of two or three of formulae 4-1, 4-2, 4-3, or a mixture of two or three of formulae 5-1, 5-2, 5-3, or a mixture of two or three of formulae 6-1, 6-2, 6-3, or a mixture of two or three of formulae 7-1, 7-2, 7-3, or a mixture of two or three of formulae 8-1, 8-2, 8-3, or a mixture of two or three of formulae 9-1, 9-2, 9-3, or a mixture of two or three of formulae 10-1, 10-2, 10-3, or a mixture of two or three of formulae 11-1, 7-3, 11-12, or a mixture of two or three of formulae 11-3, 11-12.
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