A nitrogen-containing borapyrylium organic compound and uses thereof

Abstract

The present application relates to a kind of nitrogen-containing boron-containing pyrene organic compounds and its use, wherein organic compound is selected from the structure as shown in general formula (I), according to the organic compound described in the present application, by the aromatic ring on pyrene is replaced by nitrogen-containing boron, it is convenient to improve the stability of material molecule, improve the conductivity of material, to its preparation light emitting device, prolong the life of device. According to the organic compound of the present application, as blue or green fluorescent guest material, by cooperating with suitable host material, it can improve its luminous efficiency and life as electroluminescent device, provide a kind of low manufacturing cost, high efficiency, long life, low roll-down solution of light emitting device.

Description

Technical Field

[0001] This invention relates to the field of electroluminescent materials, and more particularly to an organic compound containing nitrogen-boron-pyrene, mixtures and compositions thereof, and their application in organic electronic devices, especially in organic electroluminescent devices. Background Technology

[0002] Organic semiconductor materials are diverse in synthesis, have relatively low manufacturing costs, and possess excellent optical and electrical properties. Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting.

[0003] To date, fluorescent and phosphorescent luminescent material systems have been developed. Organic light-emitting diodes (OLEDs) using fluorescent materials are characterized by high reliability, but their internal electroluminescence quantum efficiency under electrical excitation is limited to 25% because the branching ratio of singlet and triplet excited states of excitons is 1:3. However, due to the high operating voltage of blue light-emitting materials, the lifetime of devices using blue phosphorescent materials as the luminescent layer still cannot meet practical requirements. Therefore, blue fluorescent luminescent materials remain a hot topic in both production lines and academic research.

[0004] For blue fluorescent light-emitting devices, the performance of the light-emitting material determines the efficiency and lifespan of the blue light-emitting device. Currently, the commonly used blue light host material is a type of organic compound containing anthracene groups; the light-emitting material usually uses pyrene-containing light-emitting materials, but due to the limited charge transport performance and wide emission spectrum of these materials, the device performance is limited.

[0005] Therefore, existing technologies, especially materials solutions, still need to be improved and developed. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the present invention aims to provide an organic compound, a mixture comprising the thereof, a composition, an organic electronic device and an application thereof, in order to solve the problem of insufficient performance of existing blue light emitting materials.

[0007] The technical solution of the present invention is as follows:

[0008] An organic compound having a structure as shown in general formula (I):

[0009]

[0010] in:

[0011] Ar 1 and Ar 2Independently selected from substituted or unsubstituted aromatic groups containing 6-60 C atoms, heteroaromatic groups containing 5-60 ring atoms, or nonaromatic ring systems containing 3-30 ring atoms;

[0012] R0 is independently selected from H, D, or a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, or a silyl group, or a ketone group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, or isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I crosslinkable groups, or combinations of these groups.

[0013] The present invention further relates to a mixture comprising an organic compound as described above, and at least one organic functional material, wherein the organic functional material may be selected from hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, light emitters, or host materials.

[0014] The present invention also relates to a polymer comprising at least one repeating unit, said repeating unit comprising a structure corresponding to an organic compound as described above.

[0015] The present invention also relates to a composition comprising an organic compound or polymer as described above, and at least one organic solvent.

[0016] The present invention further relates to an organic electronic device comprising at least one organic compound or polymer as described above.

[0017] Beneficial Effects: The organic compounds of the present invention replace two carbon atoms in the pyrene unit with nitrogen and boron atoms, thereby improving the charge transport balance of the material molecules and enhancing the stability of the material without altering the main structure of the pyrene unit. This allows for the fabrication of light-emitting devices and extends device lifespan. The organic compounds of the present invention can also be used as blue light-emitting guest materials. By combining them with suitable host materials, their luminous efficiency and lifespan as light-emitting devices can be improved, providing a solution for manufacturing high-performance light-emitting devices. Detailed Implementation

[0018] This invention provides an organic compound comprising a nitrogen-boron-pyrene unit and its application in organic electronic devices. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0019] In this invention, "substitution" means that the hydrogen atom in the substituent is replaced by the substituent.

[0020] In this invention, "ring atom number" refers to the number of atoms in the ring itself of a structural compound (e.g., monocyclic compound, fused-ring compound, cross-linked compound, carbocyclic compound, heterocyclic compound) obtained by atomic bonding to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below unless otherwise specified. For example, the benzene ring has 6 ring atoms, the naphthalene ring has 10 ring atoms, and the thiophene group has 5 ring atoms.

[0021] Aromatic groups refer to hydrocarbon groups containing at least one aromatic ring. Heteroaromatic groups refer to aromatic hydrocarbon groups containing at least one heteroatom. Heteroatoms are preferably selected from Si, N, P, O, S, and / or Ge, and particularly preferably from Si, N, P, O, and / or S. Fused-ring aromatic groups refer to aromatic groups whose rings may have two or more rings, wherein two carbon atoms are shared by two adjacent rings, i.e., fused rings. Fused-heterocyclic aromatic groups refer to fused-ring aromatic hydrocarbon groups containing at least one heteroatom. For the purposes of this invention, aromatic groups or heteroaromatic groups include not only systems with aromatic rings but also non-aromatic ring systems. Therefore, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetraazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, etc., are also considered aromatic groups or heterocyclic aromatic groups for this purpose of the invention. For the purposes of this invention, fused-ring aromatic or fused-heterocyclic aromatic ring systems not only include systems containing aromatic or heterocyclic aromatic groups, but also systems in which multiple aromatic or heterocyclic aromatic groups can be interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% non-H atoms, such as C, N, or O atoms). Therefore, systems such as 9,9'-spirodifluorene, 9,9-diarylfluorene, triarylamines, and diaryl ethers are also considered fused-ring aromatic ring systems for this purpose.

[0022] In this embodiment of the invention, the energy level structure of the organic material, the triplet energy level E T HOMO and LUMO play a crucial role. The determination of these energy levels will be introduced below.

[0023] HOMO and LUMO energy levels can be measured using the photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy), or cyclic voltammetry (CV). Recently, quantum chemical methods, such as density functional theory (DFT), have also become effective methods for calculating molecular orbital energy levels.

[0024] triplet energy level E of organic materials T1It can be measured by low-temperature time-resolved emission spectra or obtained by quantum simulation calculations (such as by Time-dependent DFT), such as by commercial software Gaussian 09W (Gaussian Inc.). For specific simulation methods, please refer to WO2011141110 or as described below in the embodiments.

[0025] It should be noted that HOMO, LUMO, and E T1 The absolute value depends on the measurement or calculation method used. Even for the same method, different evaluation methods, such as those at the starting point and peak point on the CV curve, can give different HOMO / LUMO values. Therefore, a reasonable and meaningful comparison should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, and E... T1 The value is based on a simulation of the Time-dependent DFT, but does not affect the application of other measurement or calculation methods.

[0026] In this invention, (HOMO-1) is defined as the second highest occupied orbital energy level, (HOMO-2) as the third highest occupied orbital energy level, and so on. (LUMO+1) is defined as the second lowest unoccupied orbital energy level, (LUMO+2) as the third lowest occupied orbital energy level, and so on.

[0027] This invention relates to an organic compound having a structure as shown in general formula (I):

[0028]

[0029] in:

[0030] Ar 1 -Ar 2 Independently selected from substituted or unsubstituted aromatic groups containing 6-60 C atoms, heteroaromatic groups containing 5-60 ring atoms, or nonaromatic ring systems containing 3-30 ring atoms;

[0031] R0 is independently selected from H, D, or a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, or a silyl group, or a ketone group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, or isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I crosslinkable groups, or combinations of these systems.

[0032] In a preferred embodiment, Ar 1 -Ar2 Ar is independently selected from substituted or unsubstituted aromatic groups containing 6-50 C atoms or heteroaromatic groups containing 5-50 ring atoms; in a preferred embodiment, Ar 1 -Ar 2 Ar is independently selected from substituted or unsubstituted aromatic groups containing 6-40 C atoms or heteroaromatic groups containing 5-40 cyclic atoms; in a preferred embodiment, Ar 1 -Ar 2 Ar is independently selected from substituted or unsubstituted aromatic groups containing 6-30 C atoms or heteroaromatic groups containing 5-30 cyclic atoms; in a preferred embodiment, Ar 1 -Ar 2 It is independently selected from substituted or unsubstituted aromatic groups containing 6-20 C atoms or heteroaromatic groups containing 5-20 cyclic atoms.

[0033] In one embodiment, Ar 1 -Ar 2 Selected from the following groups:

[0034]

[0035] in:

[0036] Each time Y appears, it independently represents CR1R2, NR1, O, S, SiR1R2, PR1, P(=O)R1, S=O, S(=O)2 or C=O;

[0037] Each time X appears, it independently represents CR1 or N;

[0038] When R1 and R2 each appear, they are independently selected from H, D, or straight-chain alkyl, alkoxy, or thioalkoxy groups having 1 to 20 carbon atoms, or branched or cyclic alkyl, alkoxy, or thioalkoxy groups having 3 to 20 carbon atoms, or silyl groups, or ketone groups having 1 to 20 carbon atoms, or alkoxycarbonyl groups having 2 to 20 carbon atoms, or aryloxycarbonyl groups having 7 to 20 carbon atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, or isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I crosslinkable groups, or substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms, or aryloxy or heteroaromatic groups having 5 to 60 ring atoms, or combinations of these groups.

[0039] Furthermore, Ar 1 -Ar 2 Independently selected from the following groups:

[0040]

[0041]

[0042] Among them, the H atoms on the ring can be further replaced.

[0043] In a preferred embodiment, Ar 1 -Ar 2 Selected from the following groups:

[0044]

[0045] In a preferred embodiment, Ar 1 -Ar 2 At least one of them is selected from substituted or unsubstituted fused-ring aromatic groups containing 6-50 C atoms or fused-ring heteroaromatic groups containing 5-50 ring atoms. In a preferred embodiment, Ar 1 -Ar 2 Selected from substituted or unsubstituted fused-ring aromatic groups containing 10-40 C atoms or fused-ring heteroaromatic groups containing 8-40 ring atoms. In a preferred embodiment, Ar 1 -Ar 2 At least one of them is selected from substituted or unsubstituted fused-ring aromatic groups containing 10-30 C atoms or fused-ring heteroaromatic groups containing 8-30 ring atoms.

[0046] In a preferred embodiment, Ar 1 and Ar 2 Selected from substituted or unsubstituted fused-ring aromatic groups containing 10-30 C atoms or fused-ring heteroaromatic groups containing 8-30 ring atoms. In a more preferred embodiment, Ar 1 and Ar 2 Selected from substituted or unsubstituted fused-ring aromatic groups containing 10-30 C atoms or fused-ring heteroaromatic groups containing 8-30 ring atoms. In a particularly preferred embodiment, Ar 1 and Ar 2 Selected from substituted or unsubstituted fused-ring aromatic groups containing 10-30 C atoms or fused-ring heteroaromatic groups containing 8-30 ring atoms. In a very preferred embodiment, Ar 1 and Ar 2 Selected from substituted or unsubstituted fused-ring aromatic groups containing 10-30 C atoms or fused-ring heteroaromatic groups containing 8-30 ring atoms. In a most preferred embodiment, Ar 1 and Ar 2 Selected from substituted or unsubstituted fused-ring aromatic groups containing 10-30 C atoms or fused-ring heteroaromatic groups containing 8-30 ring atoms.

[0047] In a preferred embodiment, the fused-ring aromatic group or fused-ring heteroaromatic group is selected from the following groups:

[0048]

[0049] More preferably, the fused-ring aromatic group or fused-ring heteroaromatic group is selected from:

[0050]

[0051] In a preferred embodiment, the fused-ring aromatic or heteroaromatic group is selected from: naphthalene, anthracene, fluoranthene, phenanthrene, benzo[a]phenanthrene, dinaphthalene, tetraphenyl, pyrene, benzo[a]pyrene, acenaphthene, fluorene, and their derivatives; the fused-ring heteroaromatic group is selected from benzo[a]furan, benzo[a]thiophene, indole, carbazole, pyrrolo[a]pyrrolo, thiophen[a]pyrrolo, thiophen[a]thiophene, furan[a]pyrrolo, furan[a]furan, thiophen[a]furan, benzo[a]isoxazole, benzo[a]isothiazazole, benzo[a]imidazazole, quinoline, isoquinoline, o-diaznaphthalene, quinoxaline, phenanthridine, primidine, quinazoline, quinazolineone, and their derivatives.

[0052] In a preferred embodiment, Ar 1 -Ar 2 At least one of them is selected from substituted or unsubstituted naphthalene or phenanthrene. In a preferred embodiment, Ar 1 -Ar 2 At least two of them are selected from substituted or unsubstituted naphthalene or phenanthrene. In a preferred embodiment, Ar 1 Selected from substituted or unsubstituted naphthalene or phenanthrene. In a preferred embodiment, Ar 2 Selected from substituted or unsubstituted naphthalene or phenanthrene. In a preferred embodiment, Ar 1 and Ar 2 Selected from substituted or unsubstituted naphthalene or phenanthrene. In a preferred embodiment, Ar 1 and Ar 2 Selected from substituted or unsubstituted naphthalene or phenanthrene; in a preferred embodiment, Ar 1 and Ar 2 Selected from substituted or unsubstituted naphthalene or phenanthrene. In a preferred embodiment, Ar 1 -Ar 2 At least three of them are selected from substituted or unsubstituted naphthalene or phenanthrene.

[0053] In a preferred embodiment, Ar 1 -Ar 2 Both of them are selected from benzene.

[0054] In a preferred embodiment, Ar 1 -Ar 2 At least one of them is selected from heteroaromatic groups.

[0055] In a preferred embodiment, at least one of R1 to R2 in each occurrence is selected from a structural unit containing the following groups;

[0056]

[0057] Wherein: each occurrence of X1 independently represents CR3 or N; preferably, at least one X1 is selected from N; each occurrence of Y1-Y5 independently represents CR4R5, NR4, O, S, SiR4R5, PR4, P(=O)R4, S=O, S(=O)2 or C=O; Ar 5 -Ar 6 R3-R5 are independently selected from substituted or unsubstituted aromatic groups containing 6-60 carbon atoms, heteroaromatic groups containing 5-60 ring atoms, or non-aromatic ring systems containing 3-30 ring atoms; each time R3-R5 appears, they are independently selected from H, D, or straight-chain alkyl, alkoxy, or thioalkoxy groups having 1 to 20 carbon atoms, or branched or cyclic alkyl, alkoxy, or thioalkoxy groups having 3 to 20 carbon atoms, or silyl groups, or ketone groups having 1 to 20 carbon atoms, or groups having 2 carbon atoms. An alkoxycarbonyl group having 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaromatic group having 5 to 60 ring atoms, or a combination of these groups.

[0058] Furthermore, in each occurrence of R1 to R2, at least one is selected from a structural unit containing the following groups;

[0059]

[0060] Specifically, at least one R1-R2 is selected from the following groups:

[0061]

[0062]

[0063] Furthermore, R0 is independently selected from structural units containing the following groups each time it appears.

[0064]

[0065] Where n2, n3, n4, and n5 are all integers greater than or equal to 1.

[0066] The following lists specific structures of organic compounds according to the present invention, but are not limited thereto:

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] The compounds according to the present invention can be used as functional materials in electronic devices, particularly OLED devices. Organic functional materials can be classified into hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injection materials (EIM), electron blocking materials (EBM), hole blocking materials (HBM), emitters (including thermally excited delayed fluorescence materials (TADF)), host materials, and organic dyes. In a preferred embodiment, the compound according to the invention can be used as a guest material, a host material, an electron transport material, or a hole transport material.

[0079] In a preferred embodiment, the compound according to the invention may be used as the guest material.

[0080] As a blue light guest material, it must have an appropriate singlet energy level, i.e., S1. In some embodiments, according to the compound of the invention, its S1 is ≥2.6 eV, preferably ≥2.65 eV, more preferably ≥2.70 eV, and most preferably ≥2.75 eV.

[0081] Good thermal stability is desirable for blue light-emitting guest materials. Generally, the compounds according to the present invention have a glass transition temperature (Tg) ≥ 100℃, preferably ≥ 140℃, and even better ≥ 180℃.

[0082] In some preferred embodiments, the compound according to the invention has ((HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.3 eV, more preferably ≥ 0.4 eV, and most preferably ≥ 0.5 eV.

[0083] In other preferred embodiments, the compound according to the invention has ((LUMO+1)-LUMO) ≥ 0.15 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.30 eV, and most preferably ≥ 0.35 eV.

[0084] In some preferred embodiments, the compounds according to the invention have a T1 ≤ 1.8 eV, preferably ≤ 1.75 eV, more preferably ≤ 1.7 eV, and most preferably ≤ 1.65 eV.

[0085] In some embodiments, the organic compound according to the invention has luminescent properties, with an emission wavelength between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm. Here, luminescence refers to photoluminescence or electroluminescence.

[0086] In another preferred embodiment, the compound according to the invention can be used as a blue or green light-emitting material.

[0087] The present invention also relates to a polymer wherein at least one repeating unit comprises a structure as shown in general formula (I).

[0088] In some embodiments, the polymer is a non-conjugated polymer, wherein the structural units as shown in general formula (I) are on the side chains. In another preferred embodiment, the polymer is a conjugated polymer.

[0089] In a preferred embodiment, the polymer synthesis method is selected from SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-, and ULLMAN.

[0090] In a preferred embodiment, the polymer according to the invention has a glass transition temperature (Tg) ≥100°C, preferably ≥120°C, more preferably ≥140°C, even more preferably ≥160°C, and most preferably ≥180°C.

[0091] In a preferred embodiment, the polymer according to the invention has a molecular weight distribution (PDI) value ranging from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3; even more preferably from 1 to 2; and most preferably from 1 to 1.5.

[0092] In a preferred embodiment, the polymer according to the invention has a weight-average molecular weight (Mw) ranging from 10,000 to 1,000,000; more preferably from 50,000 to 500,000; more preferably from 100,000 to 400,000; even more preferably from 150,000 to 300,000; and most preferably from 200,000 to 250,000.

[0093] This invention also relates to a mixture comprising one of the above-described organic compounds or polymers, and at least one organic functional material. The organic functional material includes hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent materials, or host materials. The luminescent material is selected from singlet luminescent materials (fluorescent materials), triplet luminescent materials (phosphorescent materials), and organic thermally excited delayed fluorescence materials (TADF materials). Various organic functional materials are described in detail, for example, in WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire contents of which are hereby incorporated herein by reference. The organic functional material can be a small molecule or a polymer material.

[0094] In some preferred embodiments, the mixture comprises at least one organic compound according to the invention and a fluorescent host material. The compound according to the invention can be used as a fluorescent guest material, wherein the fluorescent guest weight percentage is ≤10 wt%, preferably ≤9 wt%, more preferably ≤8 wt%, particularly preferably ≤7 wt%, and most preferably ≤5 wt%.

[0095] In another preferred embodiment, the mixture comprises at least one organic compound according to the invention, a TADF material, and a fluorescent host material. In a preferred embodiment, the emission spectrum of the TADF material has a wavelength peak smaller than that of the organic compound.

[0096] For detailed descriptions of the main material and the fluorescent material, please refer to WO2018095395. A detailed introduction to TADF material is as follows.

[0097] 1. Thermally Excited Delayed Fluorescence (TADF) Materials

[0098] Traditional organic fluorescent materials can only utilize 25% of singlet excitons formed by electrical excitation to emit light, resulting in low internal quantum efficiency (maximum 25%). While phosphorescent materials, due to the strong spin-orbit coupling at the heavy atom centers enhancing intersystem crossing, can effectively utilize singlet and triplet excitons formed by electrical excitation to emit light, achieving an internal quantum efficiency of 100%, their high cost, poor material stability, and severe efficiency roll-off limit their application in OLEDs. Thermally activated delayed fluorescence (TERF) materials are the third generation of organic light-emitting materials developed after organic fluorescent and organic phosphorescent materials. These materials generally possess a small singlet-triplet energy level difference (ΔEst), allowing triplet excitons to transform into singlet excitons through anti-intersystem crossing. This fully utilizes singlet and triplet excitons formed under electrical excitation, achieving an internal quantum efficiency of 100%. Furthermore, the material structure is controllable, its properties are stable, and it is inexpensive, requiring no precious metals, making it a promising candidate for OLED applications.

[0099] TADF materials need to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, second best ΔEst < 0.2 eV, and most preferably ΔEst < 0.1 eV. In one preferred embodiment, the TADF material has a relatively small ΔEst, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064(A1), Adachi, et.al.Adv.Mater.,21,2009,4802, Adachi, et.al.Appl.Phys.Lett.,98,2011,083302, Adachi, et.al.Appl. Phys. Lett., 101, 2012, 093306, Adachi, et.al. Chem. Commun., 48, 2012, 11392, Adachi, et.al. Nature Photonics,6,2012,253, Adachi,et.al.Nature,492,2012,234, Adachi,et.al.J.Am.Chem.Soc,134, 2012,14706,Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311,Adachi,et.al.Chem.Commun.,48 ,2012,9580,Adachi,et.al.Chem.Commun.,48,2013,10385,Adachi,et.al.Adv.Mater.,25,2013,33 19, Adachi, et.al.Adv.Mater., 25, 2013, 3707, Adachi, et.al. Chem. Mater., 25, 2013, 3038, Adachi, et.al.Chem.Mater.,25,2013,3766, Adachi,et.al.J.Mater.Chem.C.,1,2013,4599,Adachi,et.al. J.Phys.Chem.A., 117, 2013, 5607. The entire contents of the patents or articles listed above are hereby incorporated herein by reference.

[0100] Below are some examples of suitable TADF luminescent materials:

[0101]

[0102] One object of the present invention is to provide a material solution for vapor-deposited OLEDs.

[0103] In some embodiments, the compounds according to the invention have a molecular weight ≤1100 g / mol, preferably ≤1000 g / mol, very preferably ≤950 g / mol, more preferably ≤900 g / mol, and most preferably ≤800 g / mol.

[0104] Another objective of this invention is to provide a material solution for printed OLEDs.

[0105] In some embodiments, the compounds according to the invention have a molecular weight ≥700 g / mol, preferably ≥900 g / mol, more preferably ≥1000 g / mol, and most preferably ≥1100 g / mol.

[0106] In other embodiments, the compounds according to the invention have a solubility in toluene of ≥10 mg / ml, preferably ≥15 mg / ml, and most preferably ≥20 mg / ml at 25°C.

[0107] The present invention further relates to a composition or ink comprising an organic compound or polymer according to the present invention and at least one organic solvent.

[0108] When used in printing processes, ink viscosity and surface tension are important parameters. Appropriate ink surface tension parameters are suitable for specific substrates and printing methods.

[0109] In a preferred embodiment, the ink according to the invention has a surface tension of about 19 dyne / cm to 50 dyne / cm at the operating temperature or at 25°C; more preferably, it is in the range of 22 dyne / cm to 35 dyne / cm; and most preferably, it is in the range of 25 dyne / cm to 33 dyne / cm.

[0110] In another preferred embodiment, the ink according to the invention has a viscosity of about 1 cps to 100 cps at the operating temperature or 25°C; preferably in the range of 1 cps to 50 cps; more preferably in the range of 1.5 cps to 20 cps; and most preferably in the range of 4.0 cps to 20 cps. The composition thus formulated will facilitate inkjet printing.

[0111] Viscosity can be adjusted by various methods, such as by selecting a suitable solvent and adjusting the concentration of the functional material in the ink. The inks according to the present invention, containing the aforementioned organometallic complexes or polymers, allow for convenient adjustment of the printing ink within an appropriate range according to the printing method used. Generally, the composition according to the present invention contains functional materials in a weight ratio ranging from 0.3% to 30 wt%, preferably from 0.5% to 20 wt%, more preferably from 0.5% to 15 wt%, even more preferably from 0.5% to 10 wt%, and most preferably from 1% to 5 wt%.

[0112] In some embodiments, the ink according to the invention, the at least one organic solvent is selected from aromatic or heteroaromatic solvents, particularly aliphatic chain / ring substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

[0113] Examples of solvents suitable for this invention include, but are not limited to: aromatic or heteroaromatic solvents: p-diisopropylbenzene, pentobenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-di... Methoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvents: 1-tetrahydronaphthone, 2-tetrahydronaphthone, 2-(phenylepoxy)tetrahydronaphthone, 6-(methoxy)tetrahydronaphthone, acetophenone, phenylacetone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylphenylacetone, 3-methylphenylacetone, 2-methylphenylacetone, isophorone, 2,6,8-trimethyl-4-nonanone, fentanyl, 2-nonanone, 3-Nonanone, 5-Nonanone, 2-Decanone, 2,5-Hexanedione, Phlorone, Di-n-Pentylone; Aromatic ether solvents: 3-Phenoxytoluene, Butoxybenzene, Benzylbutylbenzene, p-Anisaldehyde Dimethylacetal, Tetrahydro-2-phenoxy-2H-pyran, 1,2-Dimethoxy-4-(1-Propylene)benzene, 1,4-Benzodioxane, 1,3-Dipropylbenzene, 2,5-Dimethoxytoluene, 4-Ethylethyl ether, 1,2,4- Trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, pentylenetetrazol, dioctyl ether, ethylene glycol Dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; ester solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc.

[0114] Furthermore, in the ink according to the present invention, the solvent of at least one of the solvents may be selected from: aliphatic ketones, such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, phorone, di-n-pentyl ketone, etc.; or aliphatic ethers, such as pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.

[0115] In other embodiments, the printing ink further comprises another organic solvent. Examples of the other organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, naphthane, indene, and / or mixtures thereof.

[0116] In a preferred embodiment, the composition according to the invention is a solution.

[0117] In another preferred embodiment, the composition according to the invention is a suspension.

[0118] The compositions in the embodiments of the present invention may include 0.01 to 20 wt% of the organic compound or mixture thereof according to the present invention, preferably 0.1 to 15 wt%, more preferably 0.2 to 10 wt%, and most preferably 0.25 to 5 wt% of the organic compound or mixture thereof.

[0119] The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, particularly preferably by a preparation method of printing or coating.

[0120] Suitable printing or coating technologies include (but are not limited to) inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, torsional roller printing, offset printing, flexographic printing, rotary printing, spraying, brushing or pad printing, slot extrusion coating, etc. Inkjet printing, nozzle printing, and gravure printing are preferred. The solution or suspension may additionally include one or more components such as surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, binders, etc., to adjust viscosity, film-forming properties, improve adhesion, etc. For detailed information on printing technologies and their related requirements for solutions, such as solvent and concentration, viscosity, etc., please refer to *Handbook of Print Media: Technologies and Production Methods*, edited by Helmut Kipphan, ISBN 3-540-67326-1.

[0121] Based on the aforementioned organic compounds, this invention also provides an application of the organic compounds or polymers described above, namely, applying the organic compounds or polymers to organic electronic devices. These organic electronic devices can be selected from, but are not limited to, organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light-emitting cells (OLEECs), organic field-effect transistors (OFETs), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes (OPDs), with organic electroluminescent devices such as OLEDs, OLEECs, and organic light-emitting field-effect transistors being particularly preferred. In embodiments of this invention, it is preferable to use the organic compound in the light-emitting layer of the electroluminescent device.

[0122] This invention further relates to an organic electronic device comprising at least one organic compound or polymer as described above. Generally, such an organic electronic device comprises at least a cathode, an anode, and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one organic compound or polymer as described above. The organic electronic device may be selected from, but is not limited to, organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light-emitting cells (OLEECs), organic field-effect transistors (OFETs), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes, with organic electroluminescent devices such as OLEDs, OLEECs, and organic light-emitting field-effect transistors being particularly preferred.

[0123] In some particularly preferred embodiments, the electroluminescent device includes a light-emitting layer comprising one of the aforementioned organic compounds, or comprising one of the aforementioned organic compounds and a phosphorescent material, or comprising one of the aforementioned organic compounds, a phosphorescent material, and a host material.

[0124] The electroluminescent devices described above, especially OLEDs, include a substrate, an anode, at least one light-emitting layer, and a cathode.

[0125] The substrate can be opaque or transparent. A transparent substrate can be used to fabricate a transparent light-emitting device. See, for example, Bulovic et al., Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or flexible. The substrate can be plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a smooth surface. A substrate without surface defects is particularly desirable. In a preferred embodiment, the substrate is flexible and can be a polymer film or plastic with a glass transition temperature (Tg) of 150°C or higher, preferably 200°C or higher, more preferably 250°C or higher, and most preferably 300°C or higher. Examples of suitable flexible substrates include polyethylene terephthalate (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

[0126] The anode may comprise a conductive metal or metal oxide, or a conductive polymer. Holes can be readily injected into the hole injection layer (HIL), hole transport layer (HTL), or light-emitting layer. In a preferred embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the light emitter in the light-emitting layer or the p-type semiconductor material serving as the HIL, HTL, or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), etc. Other suitable anode materials are known and can be readily selected by those skilled in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc. In some embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to fabricate devices according to the present invention.

[0127] The cathode may comprise a conductive metal or metal oxide. Electrons can be readily injected into the EIL or ETL or directly into the light-emitting layer. In a preferred embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the luminescent material in the light-emitting layer or the n-type semiconductor material serving as the electron injection layer (EIL), electron transport layer (ETL), or hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials suitable for use as cathodes in OLEDs can be used as cathode materials for the devices of this invention. Examples of cathode materials include, but are not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.

[0128] OLEDs may also include other functional layers, such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of which are hereby incorporated herein by reference.

[0129] In a preferred embodiment, the light-emitting layer of the electroluminescent device according to the present invention is prepared by means of a composition according to the present invention.

[0130] The light-emitting device according to the present invention has an emission wavelength between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm.

[0131] The present invention also relates to the application of the organic electronic devices according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

[0132] The present invention also relates to electronic devices comprising organic electronic devices according to the present invention, including, but not limited to, display devices, lighting devices, light sources, sensors, etc. Specific Implementation

[0134] The present invention will now be described in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should realize that any changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0135] Example 1

[0136]

[0137] The synthetic route of compound (1) is as follows:

[0138]

[0139] Synthesis of Intermediate 1-1: Following the method reported in the literature (Angew. Chem. Int. Ed. 2007, 46, 4940-4943), borazazapyrene without the two bromine groups was synthesized. In a mixed solvent of THF and acetic acid, the mixture was heated to 80°C, liquid bromine was added dropwise, and the reaction was carried out at high temperature for 4 hours to obtain Intermediate 1-1. Intermediate 1-2 was purchased directly from the market with a purity of 99.0%.

[0140] Synthesis of compound (1): The classic Hartwig reaction was used. In a 500 mL three-necked flask, 50 mmol of intermediate 1-1, 105 mmol of intermediate compound 1-2, 50 mmol of sodium tert-butoxide, 1 mmol of Pd(OAc)2, and 300 mL of dry toluene were added. Simultaneously, 1 mmol of tri-tert-butylphosphine was added under a N2 atmosphere. The reaction was carried out at 110 °C, and the reaction progress was monitored by TLC. After the reaction was completed, the temperature was lowered to room temperature. The reaction solution was poured into water and washed to remove the organic base. The organic phases were combined, and the solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by rapid silica gel column chromatography to obtain a solid product. Recrystallization was performed using a mixed solvent of dichloromethane, methanol, and ethanol to obtain 35.5 mmol of the intermediate product, yield: 71.0%. MS (ASAP) = 801.3.

[0141] Example 2

[0142]

[0143] The synthetic route of compound (2) is as follows:

[0144]

[0145] Synthesis of Intermediate 2-1: Following the method reported in the literature (Angew. Chem. Int. Ed. 2007, 46, 4940-4943), borazazapyrene without the two bromine groups was synthesized. In a mixed solvent of THF and acetic acid, the mixture was heated to 80°C, liquid bromine was added dropwise, and the reaction was carried out at high temperature for 4 hours to obtain Intermediate 2-1. Intermediate 2-2 was purchased directly from the market with a purity of 99.0%.

[0146] Synthesis of compound (2): The classic Hartwig reaction was used, similar to the synthetic route of compound (1). The specific synthetic steps are as follows: 50 mmol of intermediate 2-1, 103 mmol of intermediate compound 2-2, 50 mmol of sodium tert-butoxide, 1 mmol of Pd(OAc)2, and 300 ml of dry toluene were added to a 500 ml three-necked flask. At the same time, 1 mmol of tri-tert-butylphosphine was added under a N2 atmosphere. The reaction was carried out at 110 °C, and the reaction progress was monitored by TLC. After the reaction was completed, the temperature was lowered to room temperature. The reaction solution was poured into water and washed to remove the organic base. The organic phases were combined, and the solvent was evaporated under reduced pressure to obtain the crude product. The crude product was purified by rapid silica gel column chromatography to obtain the solid product. The product intermediate was then recrystallized with a mixed solvent of ethyl acetate and methanol to obtain 38.2 mmol of the product intermediate, with a yield of 76.4%. MS (ASAP) = 869.3.

[0147] Example 3

[0148]

[0149] The synthetic route of compound (3) is as follows:

[0150]

[0151] Synthesis of Intermediate 3-1: Following the method reported in the literature (Angew. Chem. Int. Ed. 2007, 46, 4940-4943), borazazapyrene without the two bromine groups was synthesized. In a mixed solvent of THF and acetic acid, the mixture was heated to 80°C, liquid bromine was added dropwise, and the reaction was carried out at high temperature for 4 hours to obtain Intermediate 3-1. Intermediate 3-2 was purchased directly from the market with a purity of 99.0%.

[0152] Synthesis of compound (3): The classic Hartwig reaction was used, similar to the synthetic route of compound (1). The specific synthetic steps are as follows: 50 mmol of intermediate 3-1, 103 mmol of intermediate compound 3-2, 50 mmol of sodium tert-butoxide, 1 mmol of Pd(OAc)2, and 300 ml of dry toluene were added to a 500 ml three-necked flask. At the same time, 1 mmol of tri-tert-butylphosphine was added under a N2 atmosphere. The reaction was carried out at 110 °C, and the reaction progress was monitored by TLC. After the reaction was completed, the temperature was lowered to room temperature. The reaction solution was poured into water and washed to remove the organic base. The organic phases were combined, and the solvent was evaporated under reduced pressure to obtain the crude product. The crude product was purified by rapid silica gel column chromatography to obtain the solid product. The product intermediate was then recrystallized with a mixed solvent of ethyl acetate and ethanol to obtain 35.6 mmol of the product intermediate, with a yield of 71.2%. MS (ASAP) = 857.4.

[0153] Example 4

[0154]

[0155] The synthetic route of compound (4) is as follows:

[0156]

[0157] Synthesis of Intermediate 4-1: Following the method reported in the literature (Angew. Chem. Int. Ed. 2007, 46, 4940-4943), a borazazapyrene containing two isopropyl groups was synthesized. In a mixed solvent of THF and acetic acid, the mixture was heated to 80°C, liquid bromine was added dropwise, and the reaction was carried out at high temperature for 4 hours to obtain Intermediate 4-1. Intermediate 4-2 was purchased directly from the market with a purity of 99.0%.

[0158] Synthesis of compound (4): The classic Hartwig reaction was used, similar to the synthetic route of compound (1). The specific synthetic steps are as follows: 50 mmol of intermediate 4-1, 103 mmol of intermediate compound 4-2, 50 mmol of sodium tert-butoxide, 1 mmol of Pd(OAc)2, and 300 ml of dry toluene were added to a 500 ml three-necked flask. At the same time, 1 mmol of tri-tert-butylphosphine was added under a N2 atmosphere. The reaction was carried out at 110 °C, and the reaction progress was monitored by TLC. After the reaction was completed, the temperature was lowered to room temperature. The reaction solution was poured into water and washed to remove the organic base. The organic phases were combined, and the solvent was evaporated under reduced pressure to obtain the crude product. The crude product was purified by rapid silica gel column chromatography to obtain the solid product. The product intermediate was then recrystallized with a mixed solvent of ethyl acetate and ethanol to obtain 37.3 mmol of the product intermediate, with a yield of 74.6%. MS (ASAP) = 913.4.

[0159] Example 5

[0160]

[0161] The synthetic route of compound (5) is as follows:

[0162]

[0163] Synthesis of Intermediate 5-1: Following the method reported in the literature (Angew. Chem. Int. Ed. 2007, 46, 4940-4943), a borazazapyrene containing two isopropyl groups was synthesized. In a mixed solvent of THF and acetic acid, the mixture was heated to 80°C, liquid bromine was added dropwise, and the reaction was carried out at high temperature for 4 hours to obtain Intermediate 5-1. Intermediate 5-2 was purchased directly from the market with a purity of 99.0%.

[0164] Synthesis of compound (5):

[0165] The classic Hartwig reaction was used, similar to the synthetic route of compound (1). The specific synthetic steps are as follows: 50 mmol of intermediate 5-1, 103 mmol of intermediate compound 5-2, 50 mmol of sodium tert-butoxide, 1 mmol of Pd(OAc)2, and 300 ml of dry toluene were added to a 500 ml three-necked flask. Simultaneously, 1 mmol of tri-tert-butylphosphine was added under a N2 atmosphere. The reaction was carried out at 110 °C, and the reaction progress was monitored by TLC. After the reaction was completed, the temperature was lowered to room temperature. The reaction solution was poured into water and washed to remove the organic base. The organic phases were combined, and the solvent was evaporated under reduced pressure to obtain the crude product. The crude product was purified by rapid silica gel column chromatography to obtain a solid product. Recrystallization was then performed using a mixed solvent of dichloromethane and ethanol to obtain 38.8 mmol of the intermediate product, yield: 77.6%. MS (ASAP) = 897.4.

[0166] Example 6

[0167]

[0168] The synthetic route of compound (6) is as follows:

[0169]

[0170] Synthesis of Intermediate 6-1: Following the method reported in the literature (Angew. Chem. Int. Ed. 2007, 46, 4940-4943), a borazazapyrene containing two isopropyl groups was synthesized. In a mixed solvent of THF and acetic acid, the mixture was heated to 80°C, liquid bromine was added dropwise, and the reaction was carried out at high temperature for 4 hours to obtain Intermediate 6-1. Intermediate 6-2 was purchased directly from the market with a purity of 99.0%.

[0171] Synthesis of compound (6): The classic Hartwig reaction was used, similar to the synthetic route of compound (1). The specific synthetic steps are as follows: 50 mmol of intermediate 6-1, 103 mmol of intermediate compound 6-2, 50 mmol of sodium tert-butoxide, 1 mmol of Pd(OAc)2, and 300 ml of dry toluene were added to a 500 ml three-necked flask. At the same time, 1 mmol of tri-tert-butylphosphine was added under a N2 atmosphere. The reaction was carried out at 110 °C, and the reaction progress was monitored by TLC. After the reaction was completed, the temperature was lowered to room temperature. The reaction solution was poured into water and washed to remove the organic base. The organic phases were combined, and the solvent was evaporated under reduced pressure to obtain the crude product. The crude product was purified by rapid silica gel column chromatography to obtain the solid product. The product intermediate was then recrystallized with a mixed solvent of dichloromethane and ethanol to obtain 41.2 mmol of the product intermediate, with a yield of 82.4%. MS (ASAP) = 897.2.

[0172] Example 7

[0173]

[0174] The synthetic route of compound (7) is as follows:

[0175]

[0176] Synthesis of Intermediate 7-1: Following the method reported in the literature (Angew. Chem. Int. Ed. 2007, 46, 4940-4943), a borazazapyrene containing two isopropyl groups was synthesized. In a mixed solvent of THF and acetic acid, the mixture was heated to 80°C, liquid bromine was added dropwise, and the reaction was carried out at high temperature for 4 hours to obtain Intermediate 7-1. Intermediate 7-2 was purchased directly from the market with a purity of 99.0%.

[0177] Synthesis of compound (7):

[0178] The classic Hartwig reaction was used, similar to the synthetic route of compound (1). The specific synthetic steps are as follows: 50 mmol of intermediate 7-1, 103 mmol of intermediate compound 7-2, 50 mmol of sodium tert-butoxide, 1 mmol of Pd(OAc)2, and 300 ml of dry toluene were added to a 500 ml three-necked flask. Simultaneously, 1 mmol of tri-tert-butylphosphine was added under a N2 atmosphere. The reaction was carried out at 110 °C, and the reaction progress was monitored by TLC. After the reaction was completed, the temperature was lowered to room temperature. The reaction solution was poured into water and washed to remove the organic base. The organic phases were combined, and the solvent was evaporated under reduced pressure to obtain the crude product. The crude product was purified by rapid silica gel column chromatography to obtain a solid product. Recrystallization was then performed using a mixed solvent of dichloromethane and ethanol to obtain 39.8 mmol of the intermediate product, yield: 79.6%. MS (ASAP) = 981.5.

[0179] Example 8

[0180]

[0181] The synthetic route of compound (8) is as follows:

[0182]

[0183] Synthesis of Intermediate 8-1: Following the method reported in the literature (Angew. Chem. Int. Ed. 2007, 46, 4940-4943), a borazazapyrene containing two isopropyl groups was synthesized. In a mixed solvent of THF and acetic acid, the mixture was heated to 80°C, liquid bromine was added dropwise, and the reaction was carried out at high temperature for 4 hours to obtain Intermediate 8-1. Intermediate 8-2 was purchased directly from the market with a purity of 99.0%.

[0184] Synthesis of compound (8): The classic Hartwig reaction was used, similar to the synthetic route of compound (1). The specific synthetic steps are as follows: 50 mmol of intermediate 8-1, 103 mmol of intermediate compound 8-2, 50 mmol of sodium tert-butoxide, 1 mmol of Pd(OAc)2, and 300 ml of dry toluene were added to a 500 ml three-necked flask. At the same time, 1 mmol of tri-tert-butylphosphine was added under a N2 atmosphere. The reaction was carried out at 110 °C, and the reaction progress was monitored by TLC. After the reaction was completed, the temperature was lowered to room temperature. The reaction solution was poured into water and washed to remove the organic base. The organic phases were combined, and the solvent was evaporated under reduced pressure to obtain the crude product. The crude product was purified by rapid silica gel column chromatography to obtain the solid product. The product intermediate was then recrystallized from a mixed solvent of dichloromethane and ethanol to obtain 37.4 mmol of the product intermediate, with a yield of 74.8%. MS (ASAP) = 981.8.

[0185] Comparative Example

[0186]

[0187] The synthesis steps for REF materials are described in the following reference: WO2018159964A1.

[0188] The energy levels of organic compound materials can be obtained through quantum computing, such as using TD-DFT (time-dependent density functional theory) with Gaussian09W (Gaussian Inc.). For specific simulation methods, please refer to WO2011141110. First, the molecular geometry is optimized using the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet). Then, the energy structure of the organic molecule is calculated using TD-DFT (time-dependent density functional theory) to obtain "TD-SCF / DFT / Default Spin / B3PW91" and the basis set "6-31G(d)" (Charge 0 / Spin Singlet). HOMO and LUMO energy levels are calculated according to the calibration formula below.

[0189] HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206

[0190] LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385

[0191] HOMO(G) and LUMO(G) are direct calculations using Gaussian 09W, expressed in Hartree units. The results are shown in Table 1.

[0192] Table 1

[0193] cáiliào HOMO[eV] ΔHOMO[eV] LUMO[eV] ΔLUMO[eV] (1) -5.07 0.50 -2.76 0.32 (2) -5.07 0.57 -2.76 0.30 (3) -5.10 0.57 -2.75 0.31 (4) -5.01 0.56 -2.69 0.33 (5) -5.02 0.66 -2.70 0.25 (6) -5.11 0.51 -2.70 0.28 (7) -4.95 0.64 -2.65 0.27 (8) -5.04 0.50 -2.64 0.27 REF -5.22 0.31 -2.69 0.51

[0194] Among them, ΔHOMO is greater than 0.50 eV, which can greatly improve the electrical stability of the material. Due to the presence of boron-nitropyrene units, the transport balance of electrons and holes in the material is well balanced, thereby improving the rigidity and stability of the material.

[0195] Fabrication of OLED devices:

[0196] The fabrication steps for an OLED device with ITO / NPB (35nm) / MADN: 8%-10% compound material (35nm) / TPBi (65nm) / LiF (1nm) / Al (150nm) / cathode are as follows:

[0197] a. Cleaning of conductive glass substrate: When using it for the first time, it can be cleaned with various solvents, such as chloroform, ketone, and isopropanol, and then treated with ultraviolet ozone plasma.

[0198] b. HTL (35nm), EML (40nm), ETL (35nm): in high vacuum (1×10⁻⁶)-6 It is formed by thermal evaporation in millibar (mbar).

[0199] c. Cathode: LiF / Al (1nm / 150nm) in high vacuum (1×10⁻⁶) -6 It is produced by thermal evaporation in millibars;

[0200] d. Encapsulation: The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0201] The current-voltage (JV) characteristics of each OLED device were characterized using a characterization device, and important parameters such as efficiency, lifetime, and external quantum efficiency were recorded. The results showed that the luminous efficiency and lifetime of OLED1 (corresponding to compound (1)) were 1.2 times that of OLEDRef (corresponding to raw material (Ref)); the luminous efficiency and lifetime of OLED4 (corresponding to compound (4)) were 1.3 times that of OLEDRef (corresponding to raw material (Ref)), with efficiency comparable to that of Ref material as a guest compound; the luminous efficiency of OLED8 (corresponding to compound (8)) was 1.3 times that of OLEDRef, while its lifetime was 1.5 times, and in particular, the maximum external quantum efficiency of OLED8 reached over 6%. All devices were blue-green light-emitting devices. It is evident that the red OLED devices prepared using the main material of this invention exhibit significantly improved luminous efficiency and lifetime, and also a markedly improved external quantum efficiency.

[0202] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. An organic compound having a structure as shown in general formula (I): in: Ar 1 -Ar 2 Selected from the following groups: in: Each time Y appears, it independently represents O or S; Each time X appears, it independently represents CR1; Each time R1 appears, it is independently selected from H, D, or a straight-chain alkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or an aromatic or heteroaromatic group having 5 to 60 cyclic atoms, or a combination of these systems; R0 is independently selected from H, D, or a straight-chain alkyl group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms.

2. The organic compound according to claim 1, characterized in that, Ar 1 and Ar 2 Selected from benzene, dibenzofuran, or dibenzothiophene.

3. The organic compound according to claim 1, characterized in that, Each time R0 appears, it is independently selected from structural units containing the following groups: 。 4. The organic compound according to claim 1, characterized in that, The organic compound is selected from the following structural formulas: 。 5. A mixture comprising an organic compound as described in any one of claims 1 to 4, and at least one organic functional material, wherein the organic functional material may be selected from hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent materials, or host materials.

6. A composition comprising an organic compound as described in any one of claims 1 to 4, and at least one organic solvent.

7. An organic electronic device comprising at least one organic compound as described in any one of claims 1 to 4.

8. The organic electronic device according to claim 7 is an electroluminescent device, comprising a light-emitting layer, characterized in that, The light-emitting layer comprises an organic compound as described in any one of claims 1 to 4.

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