Organic compound and application thereof in electronic device

Abstract

The invention provides an organic compound and application thereof in an electronic device. The organic compound is high in structural stereoscopicity, capable of effectively resisting molecular stacking crystallization, high in thermal stability and capable of improving the luminous efficiency of the device and prolonging the service life of the device.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electronic materials and devices, and in particular to an organic compound, a polymer, a mixture, a composition, an organic electronic device containing the same, and their applications in organic electronic devices, especially in organic light-emitting diodes. Background Art

[0002] Due to the diversity in synthesis, relatively low manufacturing cost, and excellent optical and electrical properties of organic semiconductor materials, organic light-emitting diodes (OLEDs) have great potential in the applications of optoelectronic devices (such as flat panel displays and lighting).

[0003] Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic substances. An organic electroluminescent element using the organic electroluminescence phenomenon usually has a positive electrode and a negative electrode, and an organic layer is included therebetween. To improve the efficiency and lifespan of the organic electroluminescent element, the organic layer has a multi-layer structure, and each layer contains different organic substances. Specifically, it may include a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected into the organic layer from the positive electrode, and electrons are injected into the organic layer from the negative electrode. When the injected holes and electrons meet, excitons are formed, and light is emitted when the excitons transition back to the ground state. Such an organic electroluminescent element has characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness. However, the electron mobility of organic materials is often lower than the hole mobility, which easily leads to unbalanced carrier transport in OLED devices, directly affecting the efficiency of the devices. Therefore, it is crucial to develop high-performance electron transport materials.

[0004] Although a large number of electron transport materials have been reported in the prior art such as CN104109532A, CN105399749A, CN110551154A, CN113402498A, CN113264871A, CN104529870A, and WO2018230969A1, it is still necessary to design and develop new materials to achieve the effects of reducing the device voltage, improving the device efficiency and lifespan. Summary of the Invention

[0005] In view of the above deficiencies of the prior art, the purpose of the present invention is to provide an organic compound, a polymer, a mixture, a composition, an organic electronic device containing the same, and their applications in organic electronic devices, aiming to solve the problem of low efficiency and lifespan of existing organic electronic devices.

[0006] The technical solution of the present invention is as follows:

[0007] An organic compound having a structure represented by the general formula (I):

[0008]

[0009] Wherein, R 1 -R 4 Are the same or different and are each independently selected from a linear alkyl group, alkoxy group, thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group, alkoxy group, thioalkoxy group, silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, carbamoyl group, halocarbonyl group, formyl group, isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF 3 , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups, wherein one or more of these groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded; one or more H in the above various groups may further be replaced by D;

[0010] Meanwhile, at least one of R 1 -R 4 Contains a structure represented by the following general formula (I-1), and R 1 And R 2 May further form a ring, and R 3 And R 4 May further form a ring;

[0011]

[0012] * represents the bonding position;

[0013] L is the same or different in each case and is independently selected from a single bond, or a substituted or unsubstituted subaromatic group having 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted subheteroaromatic group having 2 to 30 ring-forming carbon atoms; wherein, any adjacent groups may form a ring; one or more H in the above groups may further be replaced by D;

[0014] Ar 1The same or different in each case, independently selected from substituted or unsubstituted aromatic groups or heteroaromatic groups having 5 to 60 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 60 ring atoms, or combinations of these groups, wherein one or more of the groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the group is bonded. One or more H in the various groups described above may further be substituted by D, and Ar 1 contains at least one electron-withdrawing group.

[0015] The present invention also provides a polymer comprising at least one repeating unit, and the repeating unit comprises a structure corresponding to an organic compound as described above.

[0016] The present invention also provides a mixture comprising at least one organic compound or polymer as described above, and at least one other organic functional material, and the at least one other organic functional material may be selected from hole (also called electric hole) injection materials (HIM), hole transport materials (HTM), hole blocking materials (HBM), electron injection materials (EIM), electron transport materials (ETM), electron blocking materials (EBM), organic matrix materials (Host), singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), thermally activated delayed fluorescence materials (TADF materials) or organic dyes.

[0017] The present invention also provides a composition comprising at least one organic compound or polymer or mixture as described above, and at least one organic solvent.

[0018] Another object of the present invention is to provide an organic electronic device comprising at least one organic compound or polymer or mixture as described above. The organic electronic device may be selected from organic light-emitting diodes (OLED), organic photovoltaic cells (OPV), organic light-emitting electrochemical cells (OLEEC), organic field-effect transistors (OFET), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors or organic plasmon emitting diodes (Organic Plasmon Emitting Diode).

[0019] In a more preferred embodiment, the organic electronic device is an organic electroluminescent device, which comprises an electron transport region, and the electron transport region comprises at least one organic compound or polymer or mixture as described above.

[0020] In a more preferred embodiment, the organic electronic device is an organic electroluminescent device, which comprises at least two light-emitting units, and there is at least one charge generation layer between two adjacent light-emitting units. The charge generation layer contains one of the organic compounds or polymers or mixtures or is prepared from the above compositions.

[0021] Beneficial effects: Due to the steric hindrance effect, the organic compounds of the present invention can adjust the stacking between molecules, are less likely to crystallize after film formation, and at the same time reduce the intermolecular interaction, having better thermal stability. At the same time, such materials have good electron transport characteristics, which is beneficial to achieving a balanced transport in the device, thereby improving the efficiency and lifespan of related materials and devices. Detailed implementation manners

[0022] The present invention provides an organic compound and its application in an organic electronic device, and an organic electronic device containing the organic compound and its preparation method. To make the objectives, technical solutions and effects of the present invention clearer and more definite, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0023] In the description of the embodiments of the present invention, the numerical range represented by "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

[0024] In the description of the embodiments of the present invention, a substituent can be further substituted by a substituent. "Substituted group a" can mean that group a is substituted by a substituent, and the substituent can be substituted by at least one further substituent or unsubstituted.

[0025] In the present invention, the term "and / or" describes the association relationship of associated objects and indicates that three relationships can exist. For example, A and / or B can mean: A exists alone, A and B exist simultaneously, and B exists alone. Where A and B can be singular or plural. The character " / " generally indicates that the associated objects before and after are an "or" relationship.

[0026] In the present invention, "at least one" means one or more, and "a plurality" means two or more. "At least one (item)" or its similar expression below means any combination of these items, including any combination of single item (item) or plural items (items). For example, "at least one (item) of a, b, or c", or, "at least one (item) of a, b, and c" can both mean: a, b, c, a-b (that is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple respectively.

[0027] It should be understood that in various embodiments of the present invention, the magnitudes of the serial numbers of the above processes do not imply the order of execution. Some or all of the steps may be executed in parallel or sequentially. The order of execution of each process should be determined by its function and internal logic, and should not constitute any limitation to the implementation process of the embodiments of the present invention.

[0028] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The singular forms of "a", "the", and "said" used in the embodiments of the present invention and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0029] The term "OLED" is an abbreviation for "Organic Light Emitting Diode", which represents an organic electroluminescent diode, also known as organic electroluminescent display, organic light-emitting semiconductor (Organic Electroluminescence Display, OLED). OLED belongs to a current-type organic light-emitting device, and is a phenomenon of luminescence caused by the injection and recombination of carriers. The luminescence intensity is proportional to the injected current. Under the action of an electric field, holes generated at the anode and electrons generated at the cathode will move, and are respectively injected into the hole transport layer and the electron transport layer, and migrate to the light-emitting layer. When the two meet in the light-emitting layer, energy excitons are generated, which excite the luminescent molecules to finally generate visible light.

[0030] The term "TADF" is an abbreviation for "Thermally Activated Delayed Fluorescence", which represents thermally activated delayed fluorescence. Its essence is that when the energy of the triplet excited state is close to that of the singlet excited state, the triplet excited state can return to the singlet excited state through thermally activated reverse intersystem crossing. Traditional luminescence is fluorescence and phosphorescence, in which excitons return to the ground state in the form of radiative luminescence from the singlet state and the triplet state respectively. Moreover, the energy level difference between the lower singlet state and the lower triplet state is generally relatively large, resulting in the fact that once the exciton reaches the triplet state through the intersystem crossing (ISC) process from the singlet state, it cannot return to the singlet state.

[0031] In the present invention, the composition, printing ink, and ink have the same meaning and can be interchanged.

[0032] In the present invention, the aromatic group, aromatic, and aromatic ring system have the same meaning and can be interchanged.

[0033] In the present invention, the heteroaromatic group, heteroaromatic, and heteroaromatic ring system have the same meaning and can be interchanged.

[0034] In the present invention, "substituted" means that a hydrogen atom in a compound is replaced by a substituent.

[0035] In the present invention, "the number of ring atoms" refers to the number of atoms among the atoms constituting the ring itself of a structural compound obtained by bonding atoms into a ring (for example, a monocyclic compound, a fused-ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound). When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the following "the number of ring atoms" unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thiophenyl group is 5.

[0036] In the present invention, an aromatic ring system or an aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system. A heteroaromatic ring system or a heteroaromatic group refers to a hydrocarbon group (containing heteroatoms) containing at least one heteroaromatic ring, including a monocyclic group and a polycyclic ring system. The heteroatoms are preferably selected from Si, N, P, O, S, and / or Ge, and particularly preferably selected from Si, N, P, O, and / or S. These polycyclic rings can have two or more rings, in which two carbon atoms are shared by two adjacent rings, that is, fused rings. Among these polycyclic rings, at least one is aromatic or heteroaromatic. For the purposes of the present invention, an aromatic group or a heteroaromatic group includes not only a system of an aromatic group or a heteroaromatic group, but also, in which a plurality of aromatic groups or heteroaromatic groups can also be interrupted by short non-aromatic units (<10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N, or O atoms). Therefore, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc. are also considered aromatic groups for the purposes of this invention.

[0037] Specific examples of aromatic groups include: benzene, naphthalene, anthracene, phenanthrene, coronene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and their derivatives.

[0038] Specific examples of heteroaromatic groups include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thiophenopyrrole, thiophenothiophene, furanopyrrole, furanofuran, thiophenofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, perimidine, quinazoline, quinazolinone, and their derivatives.

[0039] In the present invention, "alkyl" may represent linear, branched and / or cyclic alkyl. The number of carbon atoms of the alkyl may be 1 to 50, 1 to 30, 1 to 20, 1 to 10 or 1 to 6. Non-limiting examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyl octyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, etc.

[0040] In the embodiments of the present invention, the energy level structure of the organic material, singlet energy level S1, triplet energy level T1, HOMO, and LUMO play a crucial role. The determination of these energy levels is introduced below.

[0041] The HOMO and LUMO energy levels can be measured by the photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter referred to as DFT), have also become effective methods for calculating the energy levels of molecular orbitals.

[0042] The singlet energy level S1 of the organic material can be determined by the emission spectrum, and the triplet energy level T1 can be measured by the low-temperature time-resolved emission spectrum. S1 and T1 can also be obtained by quantum simulation calculations (such as through Time-dependent DFT), such as through the commercial software Gaussian 09W (Gaussian Inc.). The specific simulation method can be referred to WO2011141110 or as described in the following examples. EST Defined as (S1-T1).

[0043] It should be noted that the absolute values of HOMO, LUMO, S1, and T1 depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as the starting point and peak point on the CV curve, can give different HOMO / LUMO values. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, S1, and T1 are based on simulations of Time-dependent DFT, but this does not affect the application of other measurement or calculation methods.

[0044] In the invention, (HOMO-1) is defined as the second highest occupied orbital energy level, (HOMO-2) is the third highest occupied orbital energy level, and so on. (LUMO+1) is defined as the second lowest unoccupied orbital energy level, (LUMO+2) is the third lowest unoccupied orbital energy level, and so on.

[0045] The present invention provides an organic compound having a structure represented by the general formula (I):

[0046]

[0047] Wherein, R 1 -R 4 Are the same or different and are each independently selected from a linear alkyl group, alkoxy group, thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group, alkoxy group, thioalkoxy group, silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, carbamoyl group, halocarbonyl group, formyl group, isocyano group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, nitro group, CF 3 , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups, wherein one or more of these groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the group is bonded; one or more H in the above various groups may further be replaced by D;

[0048] Meanwhile, at least one of R 1 -R 4 Contains a structure represented by the following general formula (I-1), and R 1 And R 2 May further form a ring, R 3 And R4 A ring can be further formed;

[0049]

[0050] * represents the bonding position; L is the same or different in each case and is independently selected from a single bond, or a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 30 ring carbon atoms; wherein any adjacent groups can form a ring; one or more H in the above groups can be further substituted by D; Ar 1 is the same or different in each case and is independently selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy group or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded, one or more H in the various groups described above can be further substituted by D, and Ar 1 contains at least one electron-withdrawing group.

[0051] In some preferred embodiments, L is selected from a substituted or unsubstituted arylene group or heteroarylene group having 6 to 20 ring carbon atoms.

[0052] In some preferred embodiments, each Ar 1 is independently selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 30 ring atoms, or an aryloxy group or heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups. In some preferred embodiments, each Ar 1 is independently selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 20 ring atoms, or an aryloxy group or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these groups.

[0053] In some preferred embodiments, the R of the organic compound 1 -R 4 is fully or partially deuterated each time it appears.

[0054] In certain preferred embodiments, the organic compound has a structure shown in General Formula (II-1) to General Formula (II-5):

[0055]

[0056] wherein, L, Ar 1 , R 2 , R 3 and R 4The definition is the same as described above; two adjacent Ls can further form a ring, and adjacent L and R 2 can further form a ring, and adjacent L and R 4 can further form a ring.

[0057] In certain embodiments, L is selected from a single bond, the following structures, or a combination thereof:

[0058]

[0059] wherein, each occurrence of u is independently selected from CR 1 R 2 , NR 1 , O, S, SiR 1 R 2 , PR 1 , P(=O)R 1 R 2 , S=O, S(=O) 2 or C=O; each occurrence of v is independently selected from CR 3 or N; R 1 -R 3 has the same definition as R 1 above.

[0060] In certain preferred embodiments, the organic compound has a structure represented by the following general formulas (III-1) to (III-4):

[0061]

[0062] wherein, m is an integer and can be independently selected from 1, 2, 3, or 4; preferably, m is selected from 1 or 2; Ar 1 has the same definition as above, p has the same definition as u above, and q has the same definition as v above; each Z is the same or different and is independently selected from none, a single bond, CR 4 R 5 , NR 4 , O, S, SiR 4 R 5 , PR 4 , P(=O)R 4 R 5 , S=O, S(=O) 2 or C=O; wherein R 4 -R 5 has the same definition as R 1 above; the above structure can be further substituted by 0, 1, 2, or 3 substituents, and the substituents are selected from D, F, Cl, Br, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl, or C3-C10 cycloalkyl.

[0063] In some more preferred embodiments, the organic compound has a structure represented by the following general formulas (IV-1) to (IV-4):

[0064]

[0065] Wherein, p, m, Z and Ar 1 are as defined above.

[0066] In certain embodiments, Ar 1 is selected from the following structures or combinations thereof:

[0067]

[0068] Wherein, X is as defined above for v, and Y is as defined above for u.

[0069] In certain preferred embodiments, the organic compound has a structure represented by the following general formulas (V-1) to (V-12):

[0070]

[0071]

[0072] Wherein, X, Z, p and m are as defined above; L1 is as defined above for L; R 6 -R 7 is as defined above for R 1 ; the above structure may be further substituted by 0, 1, 2 or 3 substituents, and the substituents are selected from D, F, Cl, Br, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl or C3-C10 cycloalkyl.

[0073] In certain embodiments, an organic compound according to the present invention is preferably, but not limited to, the following structures:

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] In some embodiments, for the organic compound according to the present invention, its glass transition temperature (Tg) ≥ 100 °C; in some preferred embodiments, its Tg ≥ 120 °C; in some more preferred embodiments, its Tg ≥ 140 °C; in some even more preferred embodiments, its Tg ≥ 160 °C; in one most preferred embodiment, its Tg ≥ 180 °C.

[0080] In some more preferred embodiments, for the organic compound according to the present invention, part of the H is deuterated, preferably 10% or more of the H is deuterated, more preferably 20% or more of the H is deuterated, still more preferably 30% or more of the H is deuterated, most preferably 40% or more of the H is deuterated.

[0081] In some more preferred embodiments, for the organic compound according to the present invention, ((LUMO + 1) - LUMO) ≥ 0.1 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, even more preferably ≥ 0.35 eV, still more preferably ≥ 0.4 eV, most preferably ≥ 0.45 eV.

[0082] In some preferred embodiments, for the organic compound according to the present invention, (HOMO - (HOMO - 1)) ≥ 0.15 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, even more preferably ≥ 0.35 eV, still more preferably ≥ 0.4 eV, most preferably ≥ 0.45 eV.

[0083] In some preferred embodiments, the organic compound according to the present invention is a small molecule material.

[0084] In some preferred embodiments, the organic compound according to the present invention is used in vapor deposition type OLED devices. For this purpose, for the organic compound according to the present invention, its molecular weight ≤ 1200 g / mol, preferably ≤ 1000 g / mol, more preferably ≤ 900 g / mol, most preferably ≤ 800 g / mol.

[0085] The present invention also relates to a method for synthesizing an organic compound according to general formula (I), in which raw materials containing active groups are used for the reaction. These active raw materials contain at least one leaving group, for example, chlorine (-Cl), bromine (-Br), iodine (-I), trifluoromethanesulfonate (-OTf), boric acid or borate ester. Appropriate reactions for forming C-C bonds are well known to those skilled in the art and are described in the literature. Particularly appropriate and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.

[0086] The present invention also relates to a polymer comprising at least one repeating unit, and the repeating unit comprises a structure corresponding to an organic compound as described above. In certain embodiments, the polymer is a non-conjugated polymer, and the structural unit as shown in the general formula (I) is on the side chain. In another preferred embodiment, the polymer is a conjugated polymer. The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there is no repeating structure in a small molecule. The molecular weight of a small molecule is ≤3000 g / mol, preferably ≤2000 g / mol, and most preferably ≤1500 g / mol.

[0087] Polymers, i.e., Polymers, include homopolymers, copolymers, and block copolymers. Additionally, in the present invention, polymers also include dendrimers. For the synthesis and applications of dendrimers, please refer to [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH&Co.KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

[0088] A conjugated polymer is a polymer whose backbone is mainly composed of sp 2 hybrid orbitals of C atoms. Well-known examples include polyacetylene and poly(phenylene vinylene). The C atoms on the backbone can also be replaced by other non-C atoms. Moreover, when the sp 2 hybridization on the backbone is interrupted by some natural defects, it is still considered a conjugated polymer. Additionally, in the present invention, the backbone of the conjugated polymer contains aryl amines, aryl phosphines, other heteroaromatics, organometallic complexes, etc.

[0089] In some preferred embodiments, the synthesis method of the polymer is selected from SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, ULLMANT, and BUCHWALD-HARTWIG.

[0090] In some preferred embodiments, for the polymer according to the present invention, its 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 some preferred embodiments, for the polymer according to the present invention, the value range of its molecular weight distribution (PDI) is preferably from 1 to 5, more preferably from 1 to 4, even more preferably from 1 to 3, even more preferably from 1 to 2, and most preferably from 1 to 1.5.

[0092] In some preferred embodiments, for the polymer according to the present invention, the value range of its weight-average molecular weight (Mw) is preferably from 10,000 to 1,000,000, more preferably from 50,000 to 500,000, even 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] The present invention also relates to a mixture comprising at least one organic compound or polymer as described above, and at least one other organic functional material, where the at least one other organic functional material can be selected from hole injection material (HIM), hole transport material (HTM), hole blocking material (HBM), electron injection material (EIM), electron transport material (ETM), electron blocking material (EBM), emitter, host material, organic matrix material, singlet emitter (fluorescent emitter), triplet emitter (phosphorescent emitter), thermally activated delayed fluorescence material (TADF material), or organic dye. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1, and WO2011110277A1, and the entire content of these 3 patent documents is hereby incorporated herein by reference. The organic functional materials can be small molecule and polymer materials.

[0094] In a preferred embodiment, the mixture comprises an organic compound according to the present invention and a phosphorescent emitter. Here, the organic compound according to the present invention can be used as the host, and the weight percentage of the phosphorescent emitter ≤ 30 wt%, preferably ≤ 25 wt%, more preferably ≤ 20 wt%.

[0095] In another preferred embodiment, the mixture comprises an organic compound according to the present invention, another host material, and a phosphorescent emitter. Here, the organic compound according to the present invention serves as a co-host material, and its weight percentage ≥ 10 wt%, preferably ≥ 20 wt%, more preferably ≥ 30 wt%, and most preferably ≥ 40 wt%.

[0096] In a more preferred embodiment, the mixture comprises an organic compound according to the present invention, a phosphorescent emitter, and a host material. In such an embodiment, the organic compound according to the present invention can serve as an auxiliary luminescent material, and the weight ratio thereof to the phosphorescent emitter is from 1:2 to 2:1. In another preferred embodiment, the T1 of the organic compound according to the present invention is higher than that of the phosphorescent emitter.

[0097] In certain embodiments, the mixture comprises an organic compound according to the present invention, and another TADF material.

[0098] In certain more preferred embodiments, the mixture according to the present invention comprises an organic functional material H1 selected from the organic compounds as described above, and at least another organic functional material H2 selected from hole (also known as electric hole) injection or transport materials (HIM / HTM), organic host materials (Host).

[0099] In certain preferred embodiments, in the mixture according to the present invention, at least one of the organic functional material H1 and the organic functional material H2 has ((LUMO + 1) - LUMO) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, even more preferably ≥ 0.35 eV, very preferably ≥ 0.4 eV, most preferably ≥ 0.45 eV.

[0100] In some more preferred embodiments, in the mixture according to the present invention, the organic functional material H1 has ((LUMO + 1) - LUMO) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, even more preferably ≥ 0.35 eV, very preferably ≥ 0.4 eV, most preferably ≥ 0.45 eV.

[0101] In certain preferred embodiments, in the mixture according to the present invention, at least one of the organic functional material H1 and the organic functional material H2 has (HOMO - (HOMO - 1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, even more preferably ≥ 0.35 eV, very preferably ≥ 0.4 eV, most preferably ≥ 0.45 eV.

[0102] In some more preferred embodiments, in the mixture according to the present invention, the organic functional material H2 has (HOMO - (HOMO - 1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, even more preferably ≥ 0.35 eV, very preferably ≥ 0.4 eV, most preferably ≥ 0.45 eV.

[0103] In some more preferred embodiments, for the mixture described, 1) ΔE(S1-T1) of the organic functional material H1 ≤ 0.30 eV, preferably ≤ 0.25 eV, more preferably ≤ 0.20 eV, and most preferably ≤ 0.10 eV; and / or 2) the LUMO of the organic functional material H2 is higher than the LUMO of the organic functional material H1, and the HOMO of the organic functional material H2 is lower than the HOMO of the organic functional material H1.

[0104] In some preferred embodiments, for the organic mixture described, the organic functional materials H1 and H2 have a type-II semiconductor heterojunction structure, and min(LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ min(ET(H1), ET(H2)) + 0.1 eV, where LUMO(H1), HOMO(H1), and ET(H1) are the lowest unoccupied molecular orbital, the highest occupied molecular orbital, and the energy level of the triplet state of the organic functional material H1 respectively, and LUMO(H2), HOMO(H2), and ET(H2) are the lowest unoccupied molecular orbital, the highest occupied molecular orbital, and the energy level of the triplet state of the organic functional material H2 respectively. More preferably, min(LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ min(ET(H1), ET(H2)); even more preferably, min(LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ≤ min(ET(H1), ET(H2)) - 0.1 eV.

[0105] In some preferred embodiments, the organic functional materials H1 and H2 have a type-I semiconductor heterojunction structure, and the singlet energy level and triplet energy level difference (S1-T1) of the organic functional material H1 or the organic functional material H2 ≤ 0.25 eV, preferably ≤ 0.20 eV, more preferably ≤ 0.15 eV, and most preferably ≤ 0.10 eV.

[0106] In some preferred embodiments, for the mixture described, the molar ratio of the organic functional materials H1 and H2 ranges from 1:9 to 9:1; preferably from 2:8 to 8:2; the preferred molar ratio ranges from 3:7 to 7:3; more preferably from 4:6 to 6:4; and most preferably from 4.5:5.5 to 5.5:4.5.

[0107] In some preferred embodiments, for the mixture described, the difference in molecular weight between the organic functional materials H1 and H2 does not exceed 100 g / mol, preferably does not exceed 80 g / mol, more preferably does not exceed 70 g / mol, even more preferably does not exceed 60 g / mol, very preferably does not exceed 40 g / mol, and most preferably does not exceed 30 g / mol.

[0108] In another preferred embodiment, the mixture wherein the difference in sublimation temperature between the organic functional material H1 and the organic functional material H2 does not exceed 50 K; more preferably the difference in sublimation temperature does not exceed 30 K; even more preferably the difference in sublimation temperature does not exceed 20 K; most preferably the difference in sublimation temperature does not exceed 10 K.

[0109] In some embodiments, for the organic functional material H1 and the organic functional material H2 in the mixture according to the present invention, at least one of them has a glass transition temperature (Tg) ≥ 100 °C; in some preferred embodiments, at least one of them has a Tg ≥ 120 °C; in some more preferred embodiments, at least one of them has a Tg ≥ 140 °C; in some even more preferred embodiments, at least one of them has a Tg ≥ 160 °C; in some most preferred embodiments, at least one of them has a Tg ≥ 180 °C.

[0110] The organic compound according to the present invention can be used as a functional material in the organic functional layer of an electronic device. The organic functional layer includes, but is not limited to, a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), an electron injection layer (EIL), an electron blocking layer (EBL), a hole blocking layer (HBL), a light emitting layer (EML), and a charge generation layer (CGL).

[0111] In some embodiments, the organic compound according to the present invention is used in an electron injection layer.

[0112] In some embodiments, the organic compound according to the present invention is used in an electron transport layer.

[0113] In some embodiments, the organic compound according to the present invention is used in a charge generation layer.

[0114] In some embodiments, the organic compound according to the present invention is used in a light emitting layer.

[0115] Some detailed descriptions (but not limited thereto) of phosphorescent emitters, triplet host materials (phosphorescent host materials), triplet emitters (phosphorescent emitters), TADF materials, and EIM / ETM materials will be given below.

[0116] 1. Triplet Host

[0117] Examples of triplet host materials are not particularly limited, and any metal complex or organic compound can be used as the host as long as its triplet energy level is higher than that of the emitter, especially the triplet emitter or phosphorescent emitter. Examples of metal complexes that can be used as triplet hosts include (but are not limited to) the following general structures:

[0118]

[0119] M1 is a metal; (Y 1 -Y 2 ) is a bidentate ligand, Y 1 and Y 2 are independently selected from C, N, O, P or S; L' is a auxiliary ligand; r is an integer whose value ranges from 1 to the maximum coordination number of this metal.

[0120] In some preferred embodiments, the metal complex that can be used as a triplet host has the following form:

[0121]

[0122] (O-N) is a bidentate ligand, in which the metal coordinates with O and N atoms, and r is an integer whose value ranges from 1 to the maximum coordination number of this metal;

[0123] In some embodiments, M1 can be selected from Ir and Pt.

[0124] Examples of organic compounds that can be used as triplet hosts are selected from compounds containing cycloaromatic hydrocarbon groups, such as benzene, biphenyl, triphenylbenzene, benzofluorene; compounds containing aromatic heterocyclic groups, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, dibenzocarbazole, indolocarbazole, pyridoindole, pyrrolodipyridine, pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, oxazole, dibenzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthalene, phthalocyanine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furanopyridine, benzothiophenpyridine, thiophenpyridine, benzoselenophenpyridine and selenophenbenzodipyridine; groups containing 2 to 10 ring structures, which can be the same or different types of cycloaromatic hydrocarbon groups or aromatic heterocyclic groups and are linked to each other directly or through at least one of the following groups, such as oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and alicyclic group. Among them, each Ar can be further substituted, and the substituents can be selected as hydrogen, deuterium, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

[0125] In some preferred embodiments, the triplet host material can be selected from compounds containing at least one of the following groups:

[0126]

[0127] Wherein: Ar2 -Ar 4 is defined as Ar above 1 ; X 1 -X 8 is the same as or different from and is selected from CR 12 R 13 or NR 14 ; Y 3 is selected from CR 12 R 13 、NR 14 、O or S; R 5 -R 14 is defined as R above 1 ; n 1 is selected from integers from 1 to 20.

[0128] Examples of suitable triplet host materials are listed below but are not limited to:

[0129]

[0130] 2. Triplet Emitter

[0131] The triplet emitter is also called a phosphorescent emitter. In some preferred embodiments, the triplet emitter is a metal complex having the general formula M(L 0 )n, where M is a metal atom, and L 0 each occurrence can be the same as or different from, and is an organic ligand that is bonded or coordinately linked to the metal atom M through one or more positions, and n is an integer greater than or equal to 1, preferably 1, 2, 3, 4, 5 or 6. Optionally, these metal complexes are linked to a polymer through one or more positions, preferably through an organic ligand.

[0132] In some preferred embodiments, the metal atom M is selected from transition metal elements or lanthanide elements or actinide elements, preferably selected from Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, and particularly preferably selected from Os, Ir, Ru, Rh, Re, Pd, Au or Pt.

[0133] Preferably, the triplet emitter contains a chelating ligand, that is, a ligand that coordinates to the metal through at least two binding points. Particularly preferably, the triplet emitter contains two or three identical or different bidentate or polydentate ligands. The chelating ligand is beneficial to improving the stability of the metal complex.

[0134] Examples of the organic ligand may be selected from phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2(2-thienyl)pyridine derivatives, 2(1-naphthyl)pyridine derivatives, or 2-phenylquinoline derivatives. All of these organic ligands may be substituted, for example, by fluorine or trifluoromethyl. The auxiliary ligand may preferably be selected from acetylacetone or picric acid.

[0135] In some preferred embodiments, the metal complex that can be used as a triplet emitter has the following form:

[0136]

[0137] wherein M2 is a metal selected from transition metal elements or lanthanide or actinide elements, particularly preferably Ir, Pt, Au; Ar1 may be the same or different each time it appears and is a cyclic group that contains at least one donor atom, i.e., an atom with a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bonded to the metal; Ar2 may be the same or different each time it appears and is a cyclic group that contains at least one C atom, through which the cyclic group is bonded to the metal; Ar1 and Ar2 are covalently linked together and may each carry one or more substituents, and they may also be linked together through the substituents; L” may be the same or different each time it appears and is a bidentate chelating auxiliary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0, 1, 2, or 3, preferably 2 or 3; q2 may be 0, 1, 2, or 3, preferably 1 or 0.

[0138] Examples of materials and applications of some triplet emitters can be found in the following patent documents and literature: WO200070655, WO200141512, WO200202714, WO200215645, EP1191613, EP1191612, EP1191614, WO2005033244, WO2005019373, US2005 / 0258742, WO2009146770, WO2010015307, WO2010031485, WO2010054731, WO2010054728, WO2010086089, WO2010099852, WO2010102709, US20070087219A1, US20090061681A1, US20010053462A1, Baldo, Thompson et al. Nature 403, (2000), 750 - 753, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622 - 1624, J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US2007 / 0252517A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth. Metals 94, 1998, 245, US6824895, US7029766, US6835469, US6830828, US20010053462A1, WO2007095118A1, US2012004407A1, WO2012007088A1, WO2012007087A1, WO2012007086A1, US2008027220A1, WO2011157339A1, CN102282150A, WO2009118087A1, WO2013107487A1, WO2013094620A1, WO2013174471A1, WO2014031977A1, WO2014112450A1, WO2014007565A1, WO2014038456A1, WO2014024131A1, WO2014008982A1, WO 2014023377A1. The entire contents of the above - listed patent documents and literature are hereby incorporated herein by reference.

[0139] Examples of some suitable triplet emitters are listed below:

[0140]

[0141]

[0142] 3.TADF materials

[0143] Traditional organic fluorescent materials can only utilize 25% of singlet excitons formed by electrical excitation to emit light, and the internal quantum efficiency of the device is low (up to 25%). Although phosphorescent materials can effectively utilize singlet and triplet excitons formed by electrical excitation to emit light due to the strong spin-orbit coupling of the heavy atom center, the internal quantum efficiency of the device can reach 100%. However, the application of phosphorescent materials in OLEDs is limited by the high cost, poor material stability, and serious device efficiency roll-off. Thermally activated delayed fluorescence luminescent materials are the third generation of organic light-emitting materials developed after organic fluorescent materials and organic phosphorescent materials. This type of material generally has a small singlet-triplet energy level difference (ΔE ST ), triplet excitons can be transformed into singlet excitons through antisystem crossing to emit light. This can make full use of singlet excitons and triplet excitons formed under electrical excitation. The quantum efficiency of the device can reach 100%. At the same time, the material structure is controllable, the properties are stable, the price is cheap, and no precious metals are required. It has broad application prospects in the field of OLED.

[0144] TADF materials need to have a small singlet-triplet energy level difference, preferably ΔE ST <0.3eV, the next best is ΔE ST <0.2eV, preferably ΔE ST <0.1eV. In a preferred embodiment, the TADF material has a relatively small ΔE ST, in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF-emitting 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., 49, 2013, 10385, Adachi, et.al. Adv. Mater., 25, 2013, 3319, 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 above-listed patents or article documents are hereby incorporated herein by reference.

[0145] Examples of some suitable TADF-emitting materials are listed below:

[0146]

[0147] 4. EIM / ETM Materials

[0148] Examples of EIM / ETM materials are not particularly limited, and any metal complex or organic compound can be used as EIM / ETM as long as they can transport electrons. Preferred organic EIM / ETM materials can be selected from tris(8-hydroxyquinoline) aluminum (AlQ3), phenazine, phenanthroline, anthracene, phenanthrene, fluorene, bifluorene, spirobifluorene, p-phenyleneethyne, pyridazine, pyrazine, triazine, triazole, imidazole, quinoline, isoquinoline, quinoxaline, oxazole, isoxazole, oxadiazole, thiadiazole, pyridine, pyrazole, pyrrole, pyrimidine, acridine, pyrene, perylene, trans-indeno[1,2-b]fluorene, cis-indeno, dibenzo-indeno[1,2-b]fluorene, indeno[1,2,3-cd]naphthalene, benzo[a]anthracene, azaphosphole, azaborole, aromatic ketones, lactams and their derivatives.

[0149] The hole blocking layer (HBL) is usually used to block holes from adjacent functional layers, especially the light emitting layer. Compared with a light emitting device without a blocking layer, the presence of HBL usually leads to an improvement in light emitting efficiency. The hole blocking material (HBM) of the hole blocking layer (HBL) needs to have a lower HOMO than adjacent functional layers such as the light emitting layer. In a preferred embodiment, the HBM has a larger excited state energy level, such as a singlet or triplet state, than the adjacent light emitting layer, depending on the emitter. In another preferred embodiment, the HBM has an electron transport function. EIM / ETM materials with deep HOMO energy levels can usually be used as HBM.

[0150] On the one hand, the compounds that can be used as EIM / ETM / HBM are molecules containing at least one of the following groups:

[0151]

[0152] Y 4 Each occurrence is independently selected from C(R 15 ) 2 or NR 15 or O or S, X 9 Each occurrence is independently selected from CR 15 or N, Ar 1 to Ar 3 Each occurrence is independently selected from an aryl group or a heteroaryl group, R 15 Each occurrence is independently selected from the following groups: hydrogen, deuterium, halogen atoms (F, Cl, Br, I), cyano group, alkyl group, alkoxy group, amino group, alkenyl group, alkynyl group, aralkyl group, heteroalkyl group, aryl group and heteroaryl group, n 2 is an integer selected from 1 to 20.

[0153] On the other hand, examples of metal complexes that can be used as EIM / ETM include (but are not limited to) the following general structures:

[0154]

[0155] (O-N) or (N-N) is a bidentate ligand, in which the metal coordinates with O, N or N,N; L''' is a auxiliary ligand; m1 is an integer with a value ranging from 1 to the maximum coordination number of this metal.

[0156] Examples of suitable EIM / ETM / HBM compounds are listed below:

[0157]

[0158] In another preferred embodiment, an organoalkali metal compound can be used as the EIM. In the present invention, an organoalkali metal compound can be understood as a compound in which there is at least one alkali metal, namely lithium, sodium, potassium, rubidium, cesium, and further contains at least one organic ligand.

[0159] Suitable organoalkali metal compounds include those described in US7767317B2, EP1941562B1 and EP1144543B1.

[0160] Preferred organoalkali metal compounds are as shown below:

[0161]

[0162] Where the arc represents two or three atoms and bonds, so as to form a 5-membered or 6-membered ring with the metal M3 when necessary, and the atoms can also be substituted by one or more R 16 substituted, M3 is an alkali metal, selected from lithium, sodium, potassium, rubidium or cesium, R 15 Each occurrence of R15 is independently selected from the following groups: hydrogen, deuterium, halogen atoms (F, Cl, Br, I), cyano group, alkyl group, alkoxy group, amino group, alkenyl group, alkynyl group, aralkyl group, heteroalkyl group, aryl group and heteroaryl group.

[0163] The organoalkali metal compound can be in the form of a monomer, as described above, or in the form of an aggregate, for example, two alkali metal ions and two ligands, 4 alkali metal ions and 4 ligands, 6 alkali metal ions and 6 ligands or in other forms.

[0164] Preferred organoalkali metal compounds are compounds of the following chemical formulas:

[0165]

[0166] Where: M3, R 16 are defined as above; o1, o2, can be the same or different each time they appear, and are 0, 1, 2, 3 or 4; p1, p2, p3, can be the same or different each time they appear, and are 0, 1, 2 or 3.

[0167] In a preferred embodiment, the alkali metal M3 is selected from lithium, sodium or potassium, more preferably lithium or sodium, and most preferably lithium.

[0168] In a preferred embodiment, the electron injection layer contains an organic alkali metal compound. More preferably, the electron injection layer consists of an organic alkali metal compound.

[0169] In another preferred embodiment, the organic alkali metal compound is doped into other ETMs to form an electron transport layer or an electron injection layer, more preferably, an electron transport layer.

[0170] Examples of suitable organic alkali metal compounds are listed below:

[0171]

[0172] The present invention also relates to a composition comprising at least one of the above-mentioned organic compounds, or polymers, or mixtures, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, cycloaliphatic or olefinic compounds, or borate or phosphate compounds, or a mixture of two or more solvents.

[0173] In a preferred embodiment, for a composition according to the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic-based solvents.

[0174] Examples of aromatic or heteroaromatic-based solvents suitable for the present invention include, but are not limited to: p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene, tripentylbenzene, amyltoluene, 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, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-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, quinoline, isoquinoline, methyl 2-furoate, ethyl 2-furoate, etc.

[0175] Examples of aromatic ketone solvents suitable for the present invention include, but are not limited to: 1-tetralone, 2-tetralone, 2-(phenyloxiranyl)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, etc.

[0176] Examples of aromatic ether solvents suitable for the present invention include, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylbenzyl ethyl ether, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl 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.

[0177] In some preferred embodiments, in the composition according to the present invention, the at least one organic solvent 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, fenchone, phorone, isophorone, 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.

[0178] In some other preferred embodiments, in the composition according to the present invention, the at least one organic solvent may be selected from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkanolactones, alkyl oleates, etc. Octyl octanoate, diethyl sebacate, diallyl phthalate, and isononyl isononanoate are particularly preferred.

[0179] The organic solvent may be used alone or as a mixture of two or more organic solvents.

[0180] In certain preferred embodiments, a composition according to the present invention comprises at least one of the above-described organic compounds or polymers or mixtures and at least one organic solvent, and may further comprise another organic solvent. Examples of the another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, 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, tetralin, decalin, indene and / or mixtures thereof.

[0181] In some preferred embodiments, solvents particularly suitable for the present invention are solvents having Hansen solubility parameters in the following ranges:

[0182] δd (dispersion force) is in the range of 17.0 MPa 1 / 2 to 23.2 MPa 1 / 2 and particularly in the range of 18.5 MPa 1 / 2 to 21.0 MPa 1 / 2 ;

[0183] δp (polar force) is in the range of 0.2 MPa 1 / 2 to 12.5 MPa 1 / 2 and particularly in the range of 2.0 MPa 1 / 2 to 6.0 MPa 1 / 2 ;

[0184] δh (hydrogen bonding force) is in the range of 0.9 MPa 1 / 2 to 14.2 MPa 1 / 2 and particularly in the range of 2.0 MPa 1 / 2 to 6.0 MPa 1 / 2 ;

[0185] For the composition according to the present invention, the boiling point parameter of the organic solvent is considered when selecting. In the present invention, the boiling point of the organic solvent ≥ 150 °C; preferably ≥ 180 °C; more preferably ≥ 200 °C; even more preferably ≥ 250 °C; most preferably ≥ 275 °C or ≥ 300 °C. Boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet print head. The organic solvent can evaporate from the solvent system to form a thin film containing the functional material.

[0186] In a preferred embodiment, the composition according to the present invention is a solution.

[0187] In another preferred embodiment, the composition according to the present invention is a suspension.

[0188] The composition in the embodiments of the present invention may include 0.01 wt% to 10 wt% of the organic compound, polymer or mixture according to the present invention, preferably 0.1 wt% to 10 wt%, more preferably 0.2 wt% to 5 wt%, and most preferably 0.25 wt% to 3 wt%.

[0189] The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, and the preparation method by printing or coating is particularly preferred.

[0190] Among them, suitable printing or coating techniques include (but are not limited to) gravure printing, inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, knife coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brush coating or pad printing, slot die coating, etc. Gravure printing, nozzle printing and inkjet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, water repellents, adhesives, etc. for adjusting viscosity, film-forming properties, improving adhesion, etc. Regarding printing techniques and their related requirements for relevant solutions, such as solvents, concentrations and viscosities.

[0191] The present invention also provides an application of the organic compound, mixture or composition as described above in an organic electronic device. 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 electrochemical 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, etc., and OLEDs are particularly preferred. In the embodiments of the present invention, the organic compound is preferably used in the electron transport layer of an OLED device.

[0192] The present invention further relates to an organic electronic device comprising an organic compound, polymer or mixture as described above. Further, the organic electronic device comprises at least one functional layer, and the functional layer comprises an organic compound, polymer or mixture as described above or is prepared from the above composition. Further, the organic electronic device comprises a cathode, an anode and at least one functional layer, and the functional layer comprises an organic compound, polymer or mixture as described above or is prepared from the above composition. The functional layer is selected from a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer (EML), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL) or a hole blocking layer (HBL); preferably, the functional layer is selected from an electron transport layer.

[0193] In a more preferred embodiment, the organic electronic device is an organic electroluminescent device, which includes an electron transport region that at least contains an organic compound, a polymer, or a mixture as described above.

[0194] In a more preferred embodiment, the organic electronic device is an organic electroluminescent device, which includes at least two light-emitting units, and there is at least one charge generation layer between the two adjacent light-emitting units. The charge generation layer contains an organic compound, a polymer, or a mixture as described above or is prepared from the above-described composition.

[0195] The organic electronic device may be, but is not limited to, an organic light-emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light-emitting electrochemical cell (OLEEC), an organic field-effect transistor (OFET), an organic light-emitting field-effect transistor, an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode, etc. Particularly preferred is an organic electroluminescent device, such as an OLED, an OLEEC, and an organic light-emitting field-effect transistor.

[0196] In some embodiments, the organic electronic device is an organic electroluminescent device and includes: a first electrode; a hole transport region disposed on the first electrode; a light-emitting layer disposed on the hole transport region; an electron transport region disposed on the emitting layer; and a second electrode disposed on the electron transport region; the electron transport region at least contains the organic compound, the polymer, or the mixture as described above.

[0197] In the above-described light-emitting device, particularly an OLED, it includes a substrate, an anode, at least one light-emitting layer, and a cathode.

[0198] The substrate can be opaque or transparent. A transparent substrate can be used to fabricate a transparent light-emitting component. For example, see 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, a semiconductor wafer, or glass. Preferably, the substrate has a smooth surface. A substrate without surface defects is a particularly ideal choice. In a preferred embodiment, the substrate is flexible and can be selected from a polymer film or plastic, and its glass transition temperature (Tg) is above 150 °C, preferably above 200 °C, more preferably above 250 °C, and most preferably above 300 °C. Examples of suitable flexible substrates include polyethylene terephthalate (PET) and polyethylene (2,6-naphthalene) (PEN).

[0199] The anode may include a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes 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 those of ordinary skill in the art can easily select and use them. 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 pattern-structured. Patterned ITO conductive substrates are commercially available and can be used to fabricate the devices according to the present invention.

[0200] The cathode may include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL, 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 light emitter 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 that can be used as the cathode of an OLED can potentially be used as the cathode material of the organic electroluminescent device of the present invention. Examples of cathode materials include, but are not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF 2 / 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.

[0201] The OLED may also include other functional layers, such as a hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL), electron injection layer (EIL), electron transport layer (ETL), and 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.

[0202] Another aspect of the present invention relates to an organic electroluminescent device, which includes a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein one of the organic layers contains an organic compound represented by the general formula (I).

[0203] The organic electroluminescent device can be manufactured using suitable materials known in the art by suitable methods known in the art, except that the organic compound of the general formula (I) is used to form the corresponding organic layer.

[0204] The organic layer of the organic electroluminescent device according to the present invention has a single-layer or multi-layer structure. For example, the organic layer can be a hole injection layer, a hole transport layer, a hole auxiliary layer, a light-emitting layer, an electron transport layer, and an electron injection layer. However, the number of organic layers is not limited and can be increased or decreased.

[0205] According to an embodiment of the present invention, the organic electroluminescent device can include a substrate, a first electrode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a second electrode, wherein an electron transport region containing the organic compound represented by the general formula (I) is interposed between the second electrode and the light-emitting layer. Due to the presence of the organic compound represented by the general formula (I), it is beneficial to the electron transport to the light-emitting layer, and the further improvement of the light-emitting efficiency and lifetime characteristics of the device is achieved.

[0206] A more detailed description of the embodiments of the organic electroluminescent device according to the present invention will be given below.

[0207] The organic electroluminescent device of the present invention includes an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode. The organic electroluminescent device of the present invention can also optionally include a hole injection layer between the anode and the hole transport layer and an electron injection layer between the electron transport layer and the cathode. If necessary, the organic electroluminescent device of the present invention can also include one or two intermediate layers. The intermediate layer can be a hole blocking layer or an electron blocking layer. The organic electroluminescent device of the present invention can also include one or more organic layers having various functions according to the desired characteristics of the device.

[0208] The organic electroluminescent device of the present invention can also include a charge generation layer, wherein the charge generation layer can contain the organic compound represented by the general formula (I).

[0209] The organic electroluminescent device according to the present invention has a light-emitting wavelength between 300 nm and 1200 nm, preferably between 350 nm and 1000 nm, and more preferably between 400 nm and 900 nm.

[0210] The present invention also relates to the use of the organic electroluminescent device according to the present invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

[0211] Examples

[0212] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims define the scope of the present invention. Those skilled in the art should realize that certain changes made to the embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0213] 1. Synthesis of Compounds

[0214] Example 1: Synthesis of Compound 1

[0215]

[0216] Synthesis of Compound 1-1: Accurately weigh adamantane-2,6-dione (16.4 g, 100 mmol) and add it to 100 mL of anhydrous tetrahydrofuran. After evacuating and purging three times in a cycle, cool the temperature to -78 °C, and then dropwise add phenylmagnesium chloride tetrahydrofuran solution (1 M, 200 mL) to the above solution under a nitrogen atmosphere. Allow the temperature to rise to room temperature naturally and react overnight. After the reaction is completed, add an appropriate amount of saturated ammonium chloride solution to quench the reaction at low temperature. After liquid separation, the organic phase is concentrated and then subjected to silica gel column chromatography (n-hexane:dichloromethane = 50:1). After concentration, 21.5 g of Compound 1-1 is obtained, with a yield of 67%. MS(ASAP) = 320.4.

[0217] Synthesis of Compound 1-2: Weigh Compound 1-1 (16.5 g, 51.55 mmol) into a reaction flask, add 250 mL of anhydrous dichloromethane to dissolve it, evacuate and cycle with nitrogen three times, cool the temperature to -10 °C, add triethylamine (20.9 g, 206.2 mmol), stir for 30 minutes, add trifluoromethanesulfonic anhydride (58.2 g, 206.2 mmol), and gradually raise the temperature to room temperature and stir the reaction overnight. After the reaction is completed, add 100 mL of water and stir for 30 minutes. Separate the aqueous layer, and directly pass the organic layer through a short silica gel column and concentrate to obtain 25.6 g of Compound 1-2, with a yield of 85%. MS(ASAP) = 584.5.

[0218] Synthesis of Compound 1: In a dry two-necked flask, add Compound 1-2 (22.9 g, 39.16 mmol), (4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid (30.4 g, 86.15 mmol) and tetrakis(triphenylphosphine)palladium(0) (2.26 g, 1.96 mmol). Then add aqueous potassium carbonate solution (2 M, 200 mL) and 1,4-dioxane (500 mL). Evacuate and refill with nitrogen three times, and stir the reaction mixture at 80 °C overnight. After the reaction is completed, let the reaction solution cool to room temperature, add 300 mL of water, and then extract with dichloromethane. Combine the organic phases and dry over anhydrous sodium sulfate. Concentrate and load onto a silica gel column for chromatography (n-hexane:dichloromethane = 4:1). Concentrate to obtain 27.2 g of Compound 1 with a yield of 77%. MS(ASAP)=903.2.

[0219] Example 2: Synthesis of Compound 2

[0220]

[0221] Synthesis of Compound 2: In a dry two-necked flask, add Compound 1-2 (22.9 g, 39.16 mmol), (3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid (30.4 g, 86.15 mmol) and tetrakis(triphenylphosphine)palladium(0) (2.26 g, 1.96 mmol). Then add aqueous potassium carbonate solution (2 M, 200 mL) and 1,4-dioxane (500 mL). Evacuate and refill with nitrogen three times, and stir the reaction mixture at 80 °C overnight. After the reaction is completed, let the reaction solution cool to room temperature, add 300 mL of water, and then extract with dichloromethane. Combine the organic phases and dry over anhydrous sodium sulfate. Concentrate and load onto a silica gel column for chromatography (n-hexane:dichloromethane = 4:1). Concentrate to obtain 26.2 g of Compound 2 with a yield of 74%. MS(ASAP)=903.2.

[0222] Example 3: Synthesis of Compound 3

[0223]

[0224] Synthesis of Compound 3-1: In a dry two-necked flask, add Compound 1-2 (22.9 g, 39.16 mmol), phenylboronic acid (4.77 g, 39.16 mmol) and tetrakis(triphenylphosphine)palladium(0) (1.13 g, 0.98 mmol). Then add aqueous potassium carbonate solution (2 M, 200 mL) and 1,4-dioxane (500 mL). Evacuate and refill with nitrogen three times, and stir the reaction at 80 °C for 2 hours. After the reaction is completed, let the reaction solution cool to room temperature, add 300 mL of water, then extract with dichloromethane. Combine the organic phases and dry over anhydrous sodium sulfate. After concentration, load the sample with silica gel and perform column chromatography (n-hexane:dichloromethane = 50:1). Concentrate to obtain 18.1 g of Compound 3-1 with a yield of 90%. MS (ASAP) = 512.6.

[0225] Synthesis of Compound 3-2: In a dry two-necked flask, add Compound 3-1 (17.9 g, 35 mmol), 3-chlorophenylboronic acid (6.0 g, 38.5 mmol) and tetrakis(triphenylphosphine)palladium(0) (1.61 g, 0.7 mmol). Then add aqueous potassium carbonate solution (2 M, 200 mL) and 1,4-dioxane (500 mL). Evacuate and refill with nitrogen three times, and stir the reaction at 80 °C overnight. After the reaction is completed, let the reaction solution cool to room temperature, add 300 mL of water, then extract with dichloromethane. Combine the organic phases and dry over anhydrous sodium sulfate. After concentration, load the sample with silica gel and perform column chromatography (n-hexane:dichloromethane = 40:1). Concentrate to obtain 14.5 g of Compound 3-2 with a yield of 87%. MS (ASAP) = 475.1.

[0226] Synthesis of Compound 3: Weigh accurately (4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid (11.7 g, 33 mmol), Compound 3-2 (14.3 g, 30 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.92 g, 1 mmol) and 2-(dicyclohexylphosphino)-2',4',6'-triisopropylbiphenyl (0.95 g, 2 mmol) and add them to a 250 mL two-necked flask. Add 1,4-dioxane (100 mL) and aqueous potassium carbonate solution (2 M, 25 mL) to dissolve. After evacuating and refilling with gas three times in a cycle, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, load the sample with silica gel and perform column chromatography (n-hexane:dichloromethane = 10:1). Concentrate to obtain 19.1 g of Compound 3 with a yield of 85%. MS (ASAP) = 748.0.

[0227] Example 4: Synthesis of Compound 4

[0228]

[0229] Synthesis of Compound 4-1: Weigh accurately 4'-bromo-2,2':6',2”-terpyridine (15.6 g, 50 mmol), bis(pinacolato)diboron (12.7 g, 50 mmol), dichloride [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) (1.1 g, 1.5 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (3.6 g, 7.5 mmol) and potassium acetate (9.8 g, 100 mmol) and add them into a 250 mL two-necked flask. Then add 1,4-dioxane (100 mL) to dissolve. After three cycles of evacuation and ventilation, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and perform silica gel column chromatography with sample mixing (n-hexane:dichloromethane = 4:1). Concentrate to obtain 13.9 g of Compound 4-1 with a yield of 77%. MS(ASAP)=359.2.

[0230] Synthesis of Compound 4: Weigh accurately Compound 3-2 (14.3 g, 30 mmol), Compound 4-1 (10.8 g, 30 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.92 g, 1 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.95 g, 2 mmol) and add them into a 250 mL two-necked flask. Then add 1,4-dioxane (100 mL) and aqueous potassium carbonate solution (2M, 25 mL) to dissolve. After three cycles of evacuation and ventilation, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and perform silica gel column chromatography with sample mixing (n-hexane:dichloromethane = 3:1). Concentrate to obtain 16.9 g of Compound 4 with a yield of 84%. MS(ASAP)=671.9.

[0231] Example 5: Synthesis of Compound 5

[0232]

[0233] Synthesis of Compound 5-1: Add Compound 3-1 (17.9 g, 35 mmol), 4-chlorophenylboronic acid (6.0 g, 38.5 mmol) and tetrakis(triphenylphosphine)palladium(0) (1.61 g, 0.7 mmol) into a dry two-necked flask. Then add aqueous potassium carbonate solution (2M, 200 mL) and 1,4-dioxane (500 mL), evacuate and fill with nitrogen for three cycles, and stir at 80 °C overnight. After the reaction is completed, wait for the reaction solution to cool to room temperature, add 300 mL of water, then extract with dichloromethane. Combine the organic phases, dry with anhydrous sodium sulfate, concentrate, and perform silica gel column chromatography with sample mixing (n-hexane:dichloromethane = 40:1). Concentrate to obtain 14.5 g of Compound 5-1 with a yield of 87%. MS(ASAP)=475.1.

[0234] Synthesis of Compound 5: Accurately weigh (3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid (11.7 g, 33 mmol), Compound 5-1 (14.3 g, 30 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.92 g, 1 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.95 g, 2 mmol) and add them to a 250 mL two-necked flask. Then add 1,4-dioxane (100 mL) and aqueous potassium carbonate solution (2 M, 25 mL) to dissolve. After three cycles of evacuation and ventilation, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and then perform silica gel column chromatography (n-hexane:dichloromethane = 10:1) with silica gel mixing, and concentrate to obtain 19.1 g of Compound 5 with a yield of 85%. MS(ASAP) = 748.0.

[0235] Example 6: Synthesis of Compound 6

[0236]

[0237] Synthesis of Compound 6-1: Accurately weigh Compound 5-1 (23.8 g, 50 mmol), bis(pinacolato)diboron (12.7 g, 50 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.1 g, 1.5 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (3.6 g, 7.5 mmol) and potassium acetate (9.8 g, 100 mmol) and add them to a 250 mL two-necked flask. Then add 1,4-dioxane (100 mL) to dissolve. After three cycles of evacuation and ventilation, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and then perform silica gel column chromatography (n-hexane:dichloromethane = 4:1) with silica gel mixing, and concentrate to obtain 21.8 g of Compound 6-1 with a yield of 77%. MS(ASAP) = 566.6.

[0238] Synthesis of Compound 6: Accurately weigh Compound 6-1 (18.7 g, 33 mmol), 4-(4-bromophenyl)-6-phenyl-2-(pyridin-2-yl)pyrimidine (11.6 g, 30 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.92 g, 1 mmol) and add them to a 250 mL two-necked flask. Then add 1,4-dioxane (100 mL) and potassium carbonate solution (2 M, 25 mL) to dissolve. After three cycles of evacuation and ventilation, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and then perform silica gel column chromatography (n-hexane:dichloromethane = 5:1) with silica gel mixing, and concentrate to obtain 18.0 g of Compound 6 with a yield of 80%. MS(ASAP) = 748.0.

[0239] Example 7: Synthesis of Compound 7

[0240]

[0241] Synthesis of Compound 7-1: Accurately weigh 3,5-dibromobenzonitrile (13.0 g, 50 mmol), bis(pinacolato)diboron (25.4 g, 100 mmol), dichlorobis[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) (2.2 g, 3 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (7.2 g, 15 mmol) and potassium acetate (19.6 g, 200 mmol) and add them to a 250 mL two-necked flask. Add 1,4-dioxane (100 mL) to dissolve. After three cycles of evacuation and ventilation, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and perform silica gel column chromatography (n-hexane). Concentrate to obtain 16.7 g of Compound 7-1 with a yield of 95%. MS (ASAP) = 355.1.

[0242] Synthesis of Compound 7-2: Accurately weigh Compound 7-1 (7.1 g, 20 mmol), 2-chloro-4,6-diphenylpyrimidine (10.7 g, 40 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.69 g, mmol) and add them to a 250 mL two-necked flask. Add 1,4-dioxane (100 mL) to dissolve. After three cycles of evacuation and ventilation, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and perform silica gel column chromatography (n-hexane:dichloromethane = 4:1). Concentrate to obtain 8.5 g of Compound 7-2 with a yield of 92%. MS (ASAP) = 459.4.

[0243] Synthesis of Compound 7: Accurately weigh Compound 7-2 (6.9 g, 15 mmol), Compound 5-1 (7.2 g, 15 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.22 g, 0.3 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.29 g, 0.6 mmol) and add them to a 100 mL two-necked flask. Add 1,4-dioxane (30 mL) and potassium carbonate solution (2 M, 10 mL) to dissolve. After three cycles of evacuation and ventilation, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and perform silica gel column chromatography (n-hexane:dichloromethane = 2:1). Concentrate to obtain 8.8 g of Compound 7 with a yield of 84%. MS (ASAP) = 695.9.

[0244] Example 8: Synthesis of Compound 8

[0245]

[0246] Synthesis of Compound 8-1: In a dry reaction flask, 1-bromo-3-chloronaphthalene (12.1 g, 50 mmol), bis(pinacolato)diboron (15.24 g, 60 mmol), potassium acetate (24.54 g, 250 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.83 g, 2.5 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (1.2 g, 2.5 mmol) were added. Then 1,4-dioxane (250 mL) was added to dissolve the mixture. After evacuating and purging with nitrogen three times, the temperature was raised to 85 °C and the reaction was carried out overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered by suction, and the mother liquor was concentrated. The residue was dissolved in 400 mL of dichloromethane and decolorized by passing through a short silica gel column. After concentration, the residue was triturated with silica gel and purified by column chromatography (n-hexane:dichloromethane = 40:1) to obtain 12.4 g of Compound 8-1 with a yield of 86%. MS (ASAP) = 288.6.

[0247] Synthesis of Compound 8-2: In a dry two-necked flask, Compound 8-1 (11.3 g, 39.16 mmol), Compound 3-1 (20.1 g, 39.16 mmol) and tetrakis(triphenylphosphine)palladium(0) (2.26 g, 1.96 mmol) were added. Then an aqueous solution of potassium carbonate (2 M, 200 mL) and 1,4-dioxane (500 mL) were added. After evacuating and filling with nitrogen three times, the mixture was stirred at 80 °C overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, 300 mL of water was added, and then the mixture was extracted with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate, concentrated, triturated with silica gel and purified by column chromatography (n-hexane:dichloromethane = 40:1). After concentration, 17.9 g of Compound 8-2 was obtained with a yield of 87%. MS (ASAP) = 525.1.

[0248] Synthesis of Compound 8-3: Accurately weigh Compound 8-2 (7.88 g, 15 mmol), bis(pinacolato)diboron (7.62 g, 30 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.33 g, 0.45 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (1.08 g, 2.25 mmol) and potassium acetate (5.89 g, 60 mmol) and add them to a 250 mL two-necked flask. Then 100 mL of 1,4-dioxane was added to dissolve the mixture. After evacuating and filling with nitrogen three times, the mixture was heated to reflux overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, concentrated, triturated with silica gel and purified by column chromatography (n-hexane:dichloromethane = 4:1). After concentration, 7.8 g of Compound 8-3 was obtained with a yield of 84%. MS (ASAP) = 616.7.

[0249] Synthesis of Compound 8: Accurately weigh 2-chloro-4,6-diphenyl-1,3,5-triazine (5.62 g, 21 mmol), Compound 8-3 (6.17 g, 10 mmol), tetrakis(triphenylphosphine)palladium(0) (0.35 g, 0.3 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.29 g, 0.6 mmol), add them to a 250 mL two-necked flask, and dissolve with 1,4-dioxane (60 mL) and potassium carbonate solution (2 M, 20 mL). After three cycles of evacuation and ventilation, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and perform silica gel column chromatography (n-hexane:dichloromethane = 2:1) with silica gel mixing, and concentrate to obtain 5.9 g of Compound 8 with a yield of 82%. MS(ASAP) = 722.0.

[0250] Example 9: Synthesis of Compound 9

[0251]

[0252] Synthesis of Compound 9-1: Add 3,5-dichloro-1-bromobenzene (11.3 g, 50 mmol), bis(pinacolato)diboron (12.7 g, 50 mmol), potassium acetate (24.54 g, 250 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.83 g, 2.5 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (1.2 g, 2.5 mmol) to a dry reaction flask, dissolve with 1,4-dioxane (250 mL), evacuate and replace with nitrogen three times, then heat to 85 °C and react overnight. After the reaction is completed, cool to room temperature, filter by suction, concentrate the mother liquor, dissolve it with 400 mL of dichloromethane and clarify it by passing through a short silica gel column for decolorization, concentrate, and perform silica gel column chromatography (n-hexane), and concentrate to obtain 11.9 g of Compound 9-1 with a yield of 87%. MS(ASAP) = 273.0.

[0253] Synthesis of Compound 9-2: Add Compound 3-1 (20.1 g, 39.16 mmol), Compound 9-1 (10.7 g, 39.16 mmol) and tetrakis(triphenylphosphine)palladium(0) (2.26 g, 1.96 mmol) to a dry two-necked flask, then add aqueous potassium carbonate solution (2 M, 200 mL) and 1,4-dioxane (500 mL), evacuate and fill with nitrogen three times, and stir and react at 80 °C overnight. After the reaction is completed, wait for the reaction solution to cool to room temperature, add 300 mL of water, then extract with dichloromethane, combine the organic phases, dry with anhydrous sodium sulfate, concentrate, and perform silica gel column chromatography (n-hexane:dichloromethane = 10:1) with silica gel mixing, and concentrate to obtain 16.4 g of Compound 9-2 with a yield of 82%. MS(ASAP) = 509.5.

[0254] Synthesis of Compound 9: Weigh accurately (3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid (23.3 g, 66 mmol), Compound 9-2 (10.7 g, 30 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.92 g, 1 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.95 g, 2 mmol) and add them to a 250 mL two-necked flask. Then add 1,4-dioxane (100 mL) and potassium carbonate solution (2 M, 20 mL) to dissolve. After evacuating and purging with nitrogen three times in a cycle, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and then perform silica gel column chromatography (n-hexane:dichloromethane = 3:1) after mixing with silica gel. Concentrate to obtain 26.9 g of Compound 9 with a yield of 85%. MS(ASAP)=1055.3.

[0255] Example 10: Synthesis of Compound 10

[0256]

[0257]

[0258] Synthesis of Compound 10-1: Add 7-bromo-1,3-dichlorodibenz[b,d]furan (15.8 g, 50 mmol), bis(pinacolato)diboron (12.7 g, 50 mmol), potassium acetate (24.54 g, 250 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1.83 g, 2.5 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (1.2 g, 2.5 mmol) to a dry reaction flask. Add 1,4-dioxane (250 mL) to dissolve. After evacuating and replacing with nitrogen three times, heat to 85 °C and react overnight. After the reaction is completed, cool to room temperature, filter by suction, concentrate the mother liquor, dissolve it with 400 mL of dichloromethane and decolorize it through a short silica gel column, and then perform silica gel column chromatography (n-hexane:dichloromethane = 5:1) after mixing with silica gel. Concentrate to obtain 16.5 g of Compound 10-1 with a yield of 91%. MS(ASAP)=363.0.

[0259] Synthesis of Compound 10-2: Add Compound 3-1 (20.1 g, 39.16 mmol), Compound 10-1 (14.2 g, 39.16 mmol) and palladium tetrakis(triphenylphosphine) (2.26 g, 1.96 mmol) into a dry two-necked flask. Then add aqueous potassium carbonate solution (2 M, 200 mL) and 1,4-dioxane (500 mL). Evacuate and refill with nitrogen for three cycles, and stir the reaction at 80 °C overnight. After the reaction is completed, let the reaction solution cool to room temperature, add 300 mL of water, then extract with dichloromethane. Combine the organic phases and dry over anhydrous sodium sulfate. Concentrate and load the sample on silica gel for column chromatography (n-hexane:dichloromethane = 10:1). Concentrate to obtain 18.3 g of Compound 10-2 with a yield of 78%. MS (ASAP) = 599.6.

[0260] Synthesis of Compound 10-3: Add Compound 10-2 (15.8 g, 30 mmol), bis(pinacolato)diboron (7.62 g, 30 mmol), potassium acetate (14.7 g, 150 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (1.22 g, 1.5 mmol) and 2-(dicyclohexylphosphino)-2',4',6'-triisopropylbiphenyl (0.72 g, 1.5 mmol) into a dry reaction flask. Add 1,4-dioxane (250 mL) to dissolve. Evacuate and replace with nitrogen for three times, then heat to 85 °C and react overnight. After the reaction is completed, cool to room temperature, filter by suction, concentrate the mother liquor, dissolve with 400 mL of dichloromethane and clarify by passing through a short silica gel column for decolorization. Concentrate and load the sample on silica gel for column chromatography (n-hexane:dichloromethane = 5:1). Concentrate to obtain 21.4 g of Compound 10-3 with a yield of 91%. MS (ASAP) = 782.6.

[0261] Synthesis of Compound 10: Accurately weigh 2-chloro-4,6-diphenyl-1,3,5-triazine (5.62 g, 21 mmol), Compound 10-3 (7.83 g, 10 mmol), palladium tetrakis(triphenylphosphine) (0.35 g, 0.3 mmol) and 2-(dicyclohexylphosphino)-2',4',6'-triisopropylbiphenyl (0.29 g, 0.6 mmol) and add them into a 250 mL two-necked flask. Add 1,4-dioxane (60 mL) and potassium carbonate solution (2 M, 20 mL) to dissolve. After evacuating and ventilating for three cycles, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate and load the sample on silica gel for column chromatography (n-hexane:dichloromethane = 2:1). Concentrate to obtain 7.3 g of Compound 10 with a yield of 73%. MS (ASAP) = 993.2.

[0262] Example 11: Synthesis of Compound 11

[0263]

[0264] Synthesis of Compound 11-1: Accurately weigh 2-bromo-4'-chloro-biphenyl (26.7 g, 100 mmol), dissolve it in 50 mL of anhydrous tetrahydrofuran, evacuate and fill with nitrogen three times, cool down to -78 °C, slowly add n-butyllithium (75 mL, 1.6 M), control the temperature below -78 °C, keep the temperature for 2 h, then slowly add a solution of adamantane-2,6-dione (8.2 g, 50 mmol) dissolved in anhydrous tetrahydrofuran, control the temperature below -78 °C. After the addition is completed, keep the temperature for 1 h, then naturally rise to room temperature and stir overnight. Add methanol to quench the reaction, concentrate, add ethanol for pulping, white solid precipitates, filter by suction to obtain 16.2 g of crude compound 11-1 in total, with a yield of 60%. MS (ASAP) = 541.5.

[0265] Synthesis of Compound 11-2: Accurately weigh compound 11-1 (16.2, 30 mmol) and add it to a dry three-necked flask, add 120 mL of glacial acetic acid and 120 mL of concentrated hydrochloric acid, heat to 100 °C and reflux for 2 h. Then cool to room temperature, neutralize with saturated sodium carbonate aqueous solution, extract with dichloromethane, combine the organic phases, concentrate, add ethanol for pulping, white solid precipitates, filter by suction to obtain 13.5 g of crude compound 11-2 in total, with a yield of about 89%. MS (ASAP) = 505.5.

[0266] Synthesis of Compound 11-3: Accurately weigh compound 11-2 (7.58 g, 15 mmol), bis(pinacolato)diboron (7.62 g, 30 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (0.33 g, 0.45 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (1.08 g, 2.25 mmol) and potassium acetate (5.89 g, 60 mmol) and add them to a 250 mL two-necked flask, add 1,4-dioxane (100 mL) to dissolve. After evacuating and filling with gas three times in a cycle, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate and then carry out silica gel sample mixing column chromatography (n-hexane:dichloromethane = 4:1), concentrate to obtain 8.7 g of compound 11-3, with a yield of 84%. MS (ASAP) = 688.5.

[0267] Synthesis of Compound 11: Accurately weigh 2-chloro-4,6-diphenyl-1,3,5-triazine (5.62 g, 21 mmol), Compound 11-3 (6.89 g, 10 mmol), tetrakis(triphenylphosphine)palladium(0) (0.35 g, 0.3 mmol) and 2-(dicyclohexylphosphino)-2',4',6'-triisopropylbiphenyl (0.29 g, 0.6 mmol), add them to a 250 mL two-necked flask, and dissolve with 1,4-dioxane (60 mL) and potassium carbonate solution (2 M, 20 mL). After three cycles of evacuation and ventilation, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and then carry out silica gel mixing column chromatography (n-hexane:dichloromethane = 2:1). Concentrate to obtain 7.4 g of Compound 11 with a yield of 82%. MS(ASAP) = 899.1.

[0268] Example 12: Synthesis of Compound 12

[0269]

[0270] Synthesis of Compound 12-1: Accurately weigh adamantane-2,6-dione (16.4 g, 100 mmol), add it to 100 mL of anhydrous tetrahydrofuran. After three cycles of evacuation and ventilation, cool to -78 °C, and then dropwise add phenylmagnesium chloride tetrahydrofuran solution (1 M, 100 mL) to the above solution under a nitrogen atmosphere. Naturally warm to room temperature and react overnight. After the reaction is completed, add an appropriate amount of saturated ammonium chloride solution to quench the reaction at low temperature. After liquid separation, the organic phase is concentrated and then subjected to silica gel mixing column chromatography (n-hexane:dichloromethane = 50:1). Concentrate to obtain 20.4 g of Compound 12-1 with a yield of 84%. MS(ASAP) = 242.3.

[0271] Synthesis of Compound 12-2: Weigh Compound 12-1 (12.5 g, 51.55 mmol) into a reaction flask, add 250 mL of anhydrous dichloromethane solution, evacuate and circulate nitrogen three times, cool to -10 °C, add triethylamine (10.4 g, 103.1 mmol), stir for 30 minutes, add trifluoromethanesulfonic anhydride (29.1 g, 103.1 mmol), and gradually warm to room temperature and stir to react overnight. After the reaction is completed, add 100 mL of water and stir for 30 minutes. Separate the aqueous layer, and directly pass the organic layer through a short silica gel column. Concentrate the mother liquor to obtain 17.4 g of Compound 12-2 with a yield of 90%. MS(ASAP) = 374.4.

[0272] Synthesis of Compound 12-3: Add Compound 12-2 (13.1 g, 35 mmol), phenylboronic acid (4.7 g, 38.5 mmol) and tetrakis(triphenylphosphine)palladium(0) (1.61 g, 0.7 mmol) into a dry two-necked flask. Then add aqueous potassium carbonate solution (2 M, 25 mL) and 1,4-dioxane (100 mL). Evacuate and refill with nitrogen three times, and stir the reaction at 80 °C overnight. After the reaction is completed, let the reaction solution cool to room temperature, add 20 mL of water, then extract with dichloromethane. Combine the organic phases and dry over anhydrous sodium sulfate. Concentrate and load the residue on a silica gel column for chromatography (n-hexane:dichloromethane = 40:1). Concentrate to obtain 9.9 g of Compound 12-3 with a yield of 94%. MS (ASAP) = 302.4.

[0273] Synthesis of Compound 12-4: Weigh accurately 2-bromo-4,4'-dichlorobiphenyl (9.67 g, 32 mmol), dissolve it in 20 mL of anhydrous tetrahydrofuran. Evacuate and refill with nitrogen three times, cool to -78 °C, slowly add n-butyllithium (20 mL, 1.6 M), control the temperature below -78 °C, keep the temperature for 2 h, then slowly add a solution of Compound 12-3 (9.07 g, 30 mmol) dissolved in anhydrous tetrahydrofuran, control the temperature below -78 °C. After the addition is complete, keep the temperature for 1 h, then let it warm to room temperature naturally and stir overnight. Add methanol to quench the reaction, concentrate, add ethanol for pulping, white solid precipitates, filter by suction to obtain 11.0 g of crude Compound 12-4 with a yield of 70%. MS (ASAP) = 525.5.

[0274] Synthesis of Compound 12-5: Weigh accurately Compound 12-4 (10.5 g, 20 mmol) and add it into a dry three-necked flask. Add 80 mL of glacial acetic acid and 80 mL of concentrated hydrochloric acid, heat to 100 °C and reflux for 2 h. Then cool to room temperature, neutralize with saturated aqueous sodium carbonate solution, extract with dichloromethane, combine the organic phases, concentrate, add ethanol for pulping, white solid precipitates, filter by suction to obtain 9.1 g of crude Compound 12-5 with a yield of about 90%. MS (ASAP) = 507.5.

[0275] Synthesis of Compound 12-6: Accurately weigh Compound 12-5 (7.61 g, 15 mmol), bis(pinacolato)diboron (7.62 g, 30 mmol), dichlorobis[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) (0.33 g, 0.45 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (1.08 g, 2.25 mmol) and potassium acetate (5.89 g, 60 mmol), add them to a 250 mL two-necked flask, and dissolve with 1,4-dioxane (100 mL). After evacuating and purging three times in a cycle, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and perform silica gel mixing column chromatography (n-hexane:dichloromethane = 4:1). Concentrate to obtain 8.0 g of Compound 12-6 with a yield of 77%. MS(ASAP)=690.5.

[0276] Synthesis of Compound 12: Accurately weigh 2-chloro-4,6-diphenyl-1,3,5-triazine (5.62 g, 21 mmol), Compound 12-6 (7.61 g, 10 mmol), tetrakis(triphenylphosphine)palladium(0) (0.35 g, 0.3 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.29 g, 0.6 mmol), add them to a 250 mL two-necked flask, and dissolve with 60 mL of 1,4-dioxane (0.35 g, 0.3 mmol) and potassium carbonate solution (2 M, 20 mL). After evacuating and purging three times in a cycle, heat to reflux and react overnight. After the reaction is completed, cool to room temperature, concentrate, and perform silica gel mixing column chromatography (n-hexane:dichloromethane = 2:1). Concentrate to obtain 7.0 g with a yield of 78%. MS(ASAP)=901.1.

[0277] 2. Energy Structure of Organic Compounds

[0278] The energy levels of organic materials can be obtained by quantum calculation. For example, using TD-DFT (Time-Dependent Density Functional Theory) through Gaussian 09W (Gaussian Inc.). The specific simulation method can be referred to WO2011141110. First, optimize the molecular geometry structure with the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet), and then the energy structure of the organic molecule is calculated by the TD-DFT (Time-Dependent Density Functional Theory) method "TD-SCF / DFT / Default Spin / B3PW91" and the basis set "6-31G(d)" (Charge 0 / Spin Singlet). The HOMO and LUMO energy levels are calculated according to the following calibration formula, and S1 and T1 are used directly.

[0279] HOMO (eV) = ((HOMO(G) × 27.212) - 0.9899) / 1.1206

[0280] LUMO (eV) = ((LUMO(G) × 27.212) - 2.0041) / 1.385

[0281] Where HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, with the unit of Hartree. The results are shown in Table 1 as follows:

[0282] Table 1

[0283]

[0284]

[0285] 3. Preparation and Characterization of OLED Devices

[0286] The following specific examples are used to illustrate in detail the preparation process of the above OLED devices. The structure of the green light device is

[0287] PD:HT-1 = 3:100 (30) / HT-1 (50) / HT-2 (10) / BH:BD = 100:3 (25) / ET:LiQ = 50:50 (30) / LiQ (1) / Al (100)

[0288]

[0289] a. Cleaning of ITO (indium tin oxide) conductive glass substrate: Clean it with various solvents (such as one or several of chloroform, acetone or isopropanol), and then perform ultraviolet ozone treatment.

[0290] b. Evaporation: Transfer the substrate into a vacuum vapor deposition device. Under high vacuum (1 × 10 -6 mbar), control the ratio of PD and HT-1 to be 3:100 to form a 30 nm hole injection layer (HIL). Subsequently, deposit compound HT-1 on the hole injection layer to form a 50 nm first hole transport layer (HTL-1). Immediately deposit compound HT-2 on the first hole transport layer to form a 10 nm second hole transport layer (HTL-2). Subsequently, use two evaporation sources, and the materials are vaporized at different rates. The weight ratio of BH:BD is 100:3 to form a 25 nm light-emitting layer. Then evaporate ET and LiQ and place them in different evaporation units, and co-deposit them at a ratio of 50 wt% respectively to obtain a 30 nm electron transport layer. Subsequently, deposit 1 nm of LiQ as the electron injection layer, and finally deposit an Al cathode with a thickness of 100 nm on the electron injection layer.

[0291] c. Encapsulation: The device is encapsulated with ultraviolet-curable resin in a nitrogen glove box.

[0292] The device performances of the above-mentioned examples and comparative examples were tested, as shown in Table 2 specifically; among them, the driving voltage and current efficiency were tested at a current density of 10 mA / cm 2 The device lifetime of T95 refers to the time when the brightness decays to 95% at a constant current density of 50 mA / cm 2 of the current density.

[0293] Table 2

[0294]

[0295]

[0296] Compared with Comparative Example 1 and Comparative Example 2, in Examples 1-12 of the device, due to the presence of the organic compound of the present invention as an electron transport material, the driving voltage can be effectively reduced, the emission efficiency can be improved, and the device lifetime can be extended, indicating the beneficial effects of the compound of the present invention applied to OLED devices.

[0297] The core structure of the present invention is that an electron-withdrawing group and an aryl group are connected by an adamantyl group in a 2,2-substituted and 6,6-substituted manner. Through the spatial conjugation effect, the compound molecule has a suitable LUMO energy level and electron mobility, which is suitable for the electron transport region of organic electroluminescent devices, especially suitable for the electron transport layer; at the same time, this molecular structure has good amorphous stacking performance, which can reduce the crystallinity of the material and extend the device lifetime.

[0298] The above-mentioned embodiments only represent several implementation manners of the present invention, and the description is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. An organic compound having a structure as shown in general formula (I): in, R 1 -R 4 are the same or different and are independently selected from a linear alkyl, alkoxy, thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy, silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, Isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, a cross-linkable group, or a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups, wherein one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring bonded to the group; one or more H in the various groups mentioned above can be further substituted by D; At the same time, R 1 -R 4 At least one of them contains the structure shown in the following general formula (I-1), and R 1 With R 2 Can further form a ring, R 3 With R 4 Can further form rings; *-L-Ar1 (II) * indicates the location of bonding; L is the same or different in each case and is independently selected from a single bond, or a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 30 ring carbon atoms; wherein any adjacent groups may form a ring; and one or more H in the above groups may be further substituted by D; Ar 1 are identical or different in each case and are independently selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 60 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 60 ring atoms, or combinations of these groups, wherein one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded, and one or more of the H in the various groups described above can be further substituted by D, and Ar 1 Contains at least one electron withdrawing group.

2. The organic compound according to claim 1, having a structure as shown in general formula (II-1) to general formula (II-5): in, Two adjacent L can further form a ring, and adjacent L and R 2 Can further form a ring, adjacent L and R 4 Can be further looped.

3. The organic compound according to claim 1 or 2, wherein L is selected from a single bond, the following structure or a combination thereof: in, u, at each occurrence, is independently selected from CR1R2, NR1, O, S, SiR1R2, PR1, P(=O)R1R2, S=O, S(=O)2 or C=O; v each occurrence is independently selected from CR3 or N; R1-R3 are as defined in claim 1 1 .

4. The organic compound according to any one of claims 1 to 3, having the following structures represented by general formula (III-1) to (III-4): in, m is an integer independently selected from 1, 2, 3 or 4; p is defined as u in claim 3, and q is defined as v in claim 3; Each Z is the same or different and is independently selected from none, a single bond, CR4R5, NR4, O, S, SiR4R5, PR4, P(=O)R4R5, S=O, S(=O)2 or C=O; wherein R4-R5 are defined as R in claim 1 1 ; The above structure may be further substituted by 0, 1, 2 or 3 substituents selected from D, F, Cl, Br, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl or C3-C10 cycloalkyl.

5. The organic compound according to any one of claims 1 to 4, having the following structures represented by general formula (IV-1) to (IV-4):

6. An organic compound according to any one of claims 1 to 5, wherein Ar 1 Selected from the following structures or combinations thereof: in, The definition of X is the same as that of v in claim 3, and the definition of Y is the same as that of u in claim 3.

7. The organic compound according to any one of claims 1 to 6, having the following structures represented by general formulas (V-1) to (V-12): in, L1 is defined as L in claim 1; R6-R7 are defined as R in claim 1 1 ; The above structure may be further substituted by 0, 1, 2 or 3 substituents selected from D, F, Cl, Br, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl or C3-C10 cycloalkyl.

8. A polymer comprising at least one repeating unit, wherein the repeating unit comprises a structure corresponding to the organic compound according to any one of claims 1 to 7.

9. A mixture, characterized in that The method comprises at least one organic compound as described in any one of claims 1 to 7 or a high polymer as described in claim 8, and at least one other organic functional material, wherein the at least one other organic functional material can be selected from hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, organic matrix materials, singlet light emitters, triplet light emitters, thermally excited delayed fluorescence materials or organic dyes.

10. A composition, characterized in that The method comprises at least one organic compound according to any one of claims 1 to 7, or the high polymer according to claim 8, or the mixture according to claim 9, and at least one organic solvent.

11. An organic electronic device, characterized in that: Contains at least one organic compound according to any one of claims 1 to 7, or the polymer according to claim 8, or the mixture according to claim 9.

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