Condensed ring organic compounds and their applications

Abstract

The present invention relates to a fused ring organic compound and its application. The compound has the general structural formula shown in Chemical Formula (I). The compound has good stability, high luminous efficiency, long life, and simple synthesis. #imgabs0#

Description

[0001] This application claims priority to a Chinese patent application filed with the Patent Office of China on December 10, 2018, with application number 201811500630X and invention name “An organic compound, composition and its application in organic electronic device”, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The present invention relates to the technical field of organic electroluminescence, in particular to a condensed-ring organic compound and application thereof. Background Art

[0003] Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat-panel displays and lighting due to the synthetic diversity, relatively low manufacturing costs, and excellent optical and electrical properties of organic semiconductor materials.

[0004] Organic electroluminescence (OLED) refers to the conversion of electrical energy into light energy using organic substances. OLED elements that utilize this phenomenon typically have a positive electrode and a negative electrode with an organic layer between them. To improve the efficiency and lifespan of OLED elements, the organic layer has a multilayer structure, with each layer containing 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, and the like. In such an OLED element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, and electrons are injected from the negative electrode into the organic layer. When the injected holes and electrons meet, excitons are formed, which then emit light when they transition back to the ground state. Such OLED elements exhibit characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.

[0005] Both theory and experiment have proven that the luminescent material is the most important factor in determining the efficiency of OLED devices. Currently, the luminescent layer of organic electroluminescent elements typically uses a mixed system of host material / dopant as the luminescent material, which can improve color purity, luminous efficiency, and stability. Generally speaking, when using a host material / dopant system, the selection of the host material is crucial because the host material greatly affects the efficiency and stability of the OLED device. Preferably, the host material should have an appropriate molecular weight for deposition under vacuum, and also need to have a high glass transition temperature and thermal decomposition temperature to ensure thermal stability, high electrochemical stability to ensure long service life, easy formation of amorphous thin films, good interface interaction with adjacent functional layer materials, and low molecular motion.

[0006] A large number of host materials have been reported in existing patents and literature. For example, indolocarbazole derivatives have attracted considerable attention from both academia and industry due to their superior carrier transport capacity, photoelectric response properties, and thermal stability, and are widely used in organic light-emitting diodes. However, most currently developed indolocarbazole derivatives still suffer from poor chemical and environmental stability. This is primarily due to the fact that the lone pair of electrons from the nitrogen atom in these materials (patents WO2007063796A1; WO2007063754A1; US2016293856A1) is conjugated to the benzene ring, forming a high electron cloud density and highly reactive C-H bond. This results in poor chemical and environmental stability and a short device lifespan. Researchers have also developed indolofluorene derivatives (patent WO2010136109A1), but device efficiency still needs further improvement.

[0007] Therefore, there is still a need to further improve materials, especially host material systems suitable for forming co-hosts, especially n-type host materials with electron transport properties, and their combination with p-type materials. Summary of the Invention

[0008] In view of the above-mentioned deficiencies in the prior art, the present invention aims to provide a condensed-ring organic compound and its application, aiming to solve the problems of efficiency and life span of the existing OLED.

[0009] The technical solution is as follows:

[0010] A fused ring organic compound, the general structural formula of which is shown in formula (I):

[0011]

[0012] in,

[0013] Ring M represents a heterocyclic ring fused at any position of two adjacent rings, and its general structural formula is shown in (I-1):

[0014]

[0015] X represents a single bond, O, S, NR9, CR 10 R 11 or SiR 12 R 13 ;

[0016] R1-R 13is a substituent, independently selected at each occurrence from H, D, a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a substituted 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, a cyano group (-CN), a carbamoyl group (—C(═O)NH 2 ), a haloformyl group, a formyl group (—C(═O)—H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF 3 group, Cl, Br, F, a crosslinkable group or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems;

[0017] L is a linking group selected from a single bond, a C6-C60 arylene group; a fluorenylene group; a C2-C60 heteroaromatic group; a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring, and the group consisting of the foregoing;

[0018] Ar is selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combinations of these systems.

[0019] A polymer comprises at least one repeating unit, wherein the repeating unit comprises the structural unit represented by the above formula (1).

[0020] A mixture comprising the above-mentioned organic compound or the above-mentioned polymer, and at least one organic functional material, wherein the organic functional material is selected from hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent materials, host materials or organic dyes.

[0021] A composition comprising at least one of the above organic compounds, or the above polymers, or the above mixtures, and at least one organic solvent.

[0022] An organic electronic device comprises a functional layer, wherein the functional layer contains the above-mentioned organic compound, the above-mentioned high polymer or the above-mentioned mixture.

[0023] Beneficial Effects: The organic compounds according to the present invention, when used in OLEDs, particularly as light-emitting layer materials, can provide superior device performance. This is likely due to, but not limited to, the following: the organic compounds of the present invention exhibit relatively balanced carrier transport, improving the efficiency and lifespan of related materials and devices. DETAILED DESCRIPTION

[0024] The present invention provides a fused-ring organic compound, a mixture and composition comprising the same, and uses thereof. To clarify and clarify the objectives, technical solutions, and effects of the present invention, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are intended only to illustrate the present invention and are not intended to limit the present invention.

[0025] In the present invention, composition and printing ink, or ink have the same meaning and can be used interchangeably.

[0026] In the present invention, main material, matrix material, host or matrix material have the same meaning and can be interchanged.

[0027] In the present invention, "substituted" means that a hydrogen atom in a substituted group is replaced by a substituent.

[0028] In the present invention, the "number of ring atoms" refers to the number of atoms in the atoms that constitute the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, or a heterocyclic compound) formed by atoms bonded together to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The "number of ring atoms" described below also applies 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 thienyl group is 5.

[0029] In the embodiments of the present invention, the energy level structure of the organic material, the triplet energy levels ET, HOMO, and LUMO, play a key role. The following is an introduction to the determination of these energy levels.

[0030] HOMO and LUMO energy levels can be measured by photoelectric effects, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy), or by cyclic voltammetry (CV). Recently, quantum chemical methods, such as density functional theory (DFT), have also become effective methods for calculating molecular orbital energy levels.

[0031] The triplet energy level ET1 of the organic material can be measured by low-temperature time-resolved luminescence spectroscopy, or obtained by quantum simulation calculation (such as by Time-dependent DFT), such as by the commercial software Gaussian 03W (Gaussian Inc.). The specific simulation method can be found in WO2011141110 or as described below in the examples.

[0032] It should be noted that the absolute values of HOMO, LUMO, and ET1 depend on the measurement 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 and evaluation methods. The values of HOMO, LUMO, and ET1 described in the embodiments of the present invention are based on time-dependent DFT simulations, but this does not affect the application of other measurement or calculation methods.

[0033] In the present invention, (HOMO-1) is defined as the second-highest occupied molecular orbital energy level, (HOMO-2) is the third-highest occupied molecular orbital energy level, and so on. (LUMO+1) is defined as the second-lowest unoccupied molecular orbital energy level, (LUMO+2) is the third-lowest occupied molecular orbital energy level, and so on.

[0034] The present invention relates to a fused ring organic compound, the general structural formula of which is shown in formula (I):

[0035]

[0036] in,

[0037] Ring M represents a heterocyclic ring fused at any position of two adjacent rings, and its general structural formula is shown in (I-1):

[0038]

[0039] X is selected from single bond, O, S, NR9, CR 10 R 11 or SiR 12 R 13 In a preferred embodiment, X is selected from a single bond; In a preferred embodiment, X is selected from O, S, NR9 or CR 10 R 11 ;

[0040] R1-R 13is a substituent, independently selected at each occurrence from H, D, a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a substituted 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, a cyano group, a carbamoyl group (—C(═O)NH 2 ), a haloformyl group, a formyl group (—C(═O)—H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF 3 group, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems;

[0041] L is a linking group selected from a single bond, a C6-C60 arylene group; a fluorenylene group; a C2-C60 heteroaromatic group; a fused ring group of a C3-C60 aliphatic ring and a C6-C60 aromatic ring, and groups composed of the above;

[0042] Ar is selected from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combinations of these systems, 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.

[0043] Further, in some preferred embodiments, R1-R 13 Each occurrence of R1 to R4 is independently selected from D, cyano, straight-chain alkyl having 1-18 carbon atoms, or branched or cyclic alkyl, alkoxy, thioalkoxy or silyl having 3-18 carbon atoms, or substituted or unsubstituted aromatic, heteroaromatic, aryloxy or heteroaryloxy having 5-30 ring atoms; in a more preferred embodiment, each occurrence of R1 to R4 is independently selected from D, straight-chain alkyl having 1-12 carbon atoms, or substituted or unsubstituted aromatic, heteroaromatic, aryloxy or heteroaryloxy having 5-20 ring atoms; in a most preferred embodiment, each occurrence of R1 to R4 is independently selected from D, straight-chain alkyl having 1-6 carbon atoms, or substituted or unsubstituted aromatic, heteroaromatic, aryloxy or heteroaryloxy having 5-15 ring atoms.

[0044] In some preferred embodiments, the structural formula of the fused ring organic compound is selected from any one of (II-1) to (II-12):

[0045]

[0046]

[0047] in,

[0048] X is selected from O, S, NR9, CR 10 R 11 or SiR 12 R 13 .

[0049] In some preferred embodiments, the R1-R 13 or L are independently selected from one of the following structural groups:

[0050]

[0051] in:

[0052] Each time V appears, it is independently selected from CR 14 or N;

[0053] W is selected from CR 15 R 16 、SiR 15 R 16 NR 15 , C(=O), S or O;

[0054] R 14 -R 16 is a substituent, each occurrence being independently selected from H, D, a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a substituted 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, a cyano group, a carbamoyl group (-C(=O)NH2 ), a haloformyl group, a formyl group (—C(═O)—H), an isocyanate group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF3 group, Cl, Br, F, a crosslinkable group or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems; wherein one or more of the groups can form a ring system with each other and / or the groups to which they are bonded;

[0055] Furthermore, in some preferred embodiments, R 14 -R 16Each occurrence is independently selected from D, cyano, a linear alkyl group having 1 to 18 carbon atoms, or a branched or cyclic alkyl group, alkoxy group, thioalkoxy group or silyl group having 3 to 18 carbon atoms, or a substituted or unsubstituted aromatic group, heteroaromatic group, aryloxy group or heteroaryloxy group having 5 to 30 ring atoms; in a more preferred embodiment, R5 to R7 each occurrence is independently selected from D, a linear alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aromatic group, heteroaromatic group, aryloxy group or heteroaryloxy group having 5 to 20 ring atoms; in the most preferred embodiment, R 14 -R 16 Each occurrence is independently selected from D, a straight-chain alkyl group having 1 to 6 C atoms, or a substituted or unsubstituted aromatic group, heteroaromatic group, aryloxy group or heteroaryloxy group having 5 to 15 ring atoms.

[0056] In a preferred embodiment, R1-R 13 All are selected from H.

[0057] In some preferred embodiments, the R1-R 13 Each occurrence is fully or partially deuterated, respectively.

[0058] In a preferred embodiment, L is selected from a single bond.

[0059] In a preferred embodiment, L is biphenyl, or one or more carbon atoms in these structures are replaced by nitrogen atoms. Preferably, at least one V is selected from N.

[0060] In another preferred embodiment, L is benzene, or one or more carbon atoms in these structures are replaced by nitrogen atoms. Preferably, at least one V is selected from N.

[0061] In another preferred embodiment, L is selected from Preferably, at least one V is selected from N.

[0062] In one embodiment, L is selected from one of the following structural groups, wherein H on the ring can be arbitrarily substituted:

[0063]

[0064] In some of the most preferred embodiments, L is selected from one of the following structural groups, wherein H on the ring can be arbitrarily substituted:

[0065]

[0066] Ar is selected at each occurrence from substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 40 ring atoms, or combinations of these systems, wherein one or more of the groups form a polycyclic aliphatic or aromatic ring system with each other and / or the ring to which they are bonded.

[0067] In some preferred embodiments, Ar can be selected from deuterated or undeuterated substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 20 ring atoms, or deuterated or undeuterated aryloxy or heteroaryloxy groups having 5 to 20 ring atoms, or combinations of these systems, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the rings to which they are bonded.

[0068] In some more preferred embodiments, Ar can be selected from deuterated or undeuterated substituted or unsubstituted aromatic or heteroaromatic groups having 5 to 15 ring atoms, or deuterated or undeuterated aryloxy or heteroaryloxy groups having 5 to 15 ring atoms, or combinations of these systems, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which they are bonded.

[0069] In some most preferred embodiments, Ar is selected from benzene, naphthalene, phenanthrene, triphenylene, biphenyl, terphenyl, or one or more carbon atoms in these structures are replaced by nitrogen atoms.

[0070] In the present invention, an "aromatic group" refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. A "heteroaromatic group" refers to a hydrocarbon group (containing heteroatoms) containing at least one aromatic heterocyclic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings can have two or more rings, wherein two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these polycyclic ring species is aromatic or heteroaromatic. For the purposes of the present invention, an aromatic group or heteroaromatic group includes not only systems of aromatic or heteroaromatic groups, but also systems in which multiple aromatic or heteroaromatic groups are interrupted by short non-aromatic units (such as C, N, O, Si, S or P atoms). Therefore, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc. are also considered aromatic groups for the purposes of this invention.

[0071] Specifically, examples of the aromatic group include benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.

[0072] Specifically, examples of heteroaromatic groups include furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary idine, quinazoline, quinazolinone, and derivatives thereof.

[0073] In a particularly preferred embodiment, the fused-ring organic compound of the present invention has an electron transport function.

[0074] In certain preferred embodiments, Ar in the above-mentioned fused ring organic compound contains an electron-withdrawing group, and the electron-withdrawing group can be selected from F, cyano or one of the following groups:

[0075]

[0076] Wherein, n is 1, 2 or 3;

[0077] X 1 -X 8 Independently selected from CR 18 or N, and at least one of them is N;

[0078] M 1 、M 2 、M 3 Each independently selected from NR 18 , CR 18 R 19 、SiR 18 R 19 、O、C=NR 18 、C=CR 18 R 19 PR 18 、P(=O)R 18 , S, S=O, SO2 or none;

[0079] R 17 -R 19is a substituent, each independently selected at each occurrence from H, D, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a substituted 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, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF3 group, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

[0080] In some more preferred embodiments, the Ar comprises the following groups:

[0081]

[0082] Among them: The H atoms on the ring can be further substituted.

[0083] In certain preferred embodiments, the compounds of the present invention have a small singlet-triplet energy level difference, generally ΔEst≤0.3 eV, preferably ΔEst≤0.2 eV, more preferably ΔEst≤0.15 eV, most preferably ΔEst≤0.10 eV.

[0084] Specific examples of the organic compound represented by the general formula (I) of the present invention are listed below, but are not limited thereto:

[0085]

[0086]

[0087]

[0088]

[0089] In a preferred embodiment, the organic compound of the present invention has a glass transition temperature Tg ≥ 100°C, preferably, T g ≥120℃, more preferably, T g ≥140℃, more preferably, T g ≥160℃, most preferably, T g ≥180℃.

[0090] In a more preferred embodiment, the organic compound of the present invention is partially deuterated, preferably 10% of the H is deuterated, more preferably 20% of the H is deuterated, further preferably 30% of the H is deuterated, and most preferably 40% of the H is deuterated.

[0091] In a preferred embodiment, the organic compound of the present invention is a small molecule material.

[0092] In certain embodiments, the fused ring compounds according to the present invention have a relatively high triplet energy level T1, generally T1≥2.2eV, preferably T1≥2.3eV, more preferably T1≥2.4eV, even more preferably T1≥2.5eV, and most preferably T1≥2.6eV.

[0093] In certain embodiments, the fused ring compounds according to the present invention have a relatively high triplet energy level S1, generally S1≥2.2 eV, preferably S1≥2.4 eV, more preferably S1≥2.6 eV, and even more preferably S1≥2.9 eV.

[0094] In a preferred embodiment, the organic compounds of the present invention are used in vapor-deposited OLED devices. For this purpose, the compounds of the present invention have a molecular weight of ≤1000 mol / kg, preferably ≤900 mol / kg, more preferably ≤850 mol / kg, even more preferably ≤800 mol / kg, and most preferably ≤700 mol / kg.

[0095] The invention further relates to a method for synthesizing an organic compound of formula (I), wherein a raw material containing an active group is used to react. These active raw materials comprise at least one leaving group, for example, bromine, iodine, boric acid or boric ester. Suitable reactions for forming C-C connections are well known to those skilled in the art and are described in the literature, and particularly suitable and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.

[0096] The present invention also relates to a polymer, wherein at least one repeating unit comprises a structure as represented by general formula (I). In certain embodiments, the polymer is a non-conjugated polymer, wherein the structural unit represented by general formula (I) is located on a side chain. In another preferred embodiment, the polymer is a conjugated polymer.

[0097] As defined herein, the term "small molecule" refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, a small molecule lacks a repeating structure. A small molecule has a molecular weight of ≤3000 g / mol, preferably ≤2000 g / mol, and more preferably ≤1500 g / mol.

[0098] Polymers include homopolymers, copolymers, and block copolymers. In the present invention, polymers also include dendrimers. For information on the synthesis and application of dendrimers, please refer to [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].

[0099] A conjugated polymer is a polymer whose main chain backbone is primarily composed of sp2 hybrid orbitals of carbon atoms. Well-known examples include polyacetylene and poly(phenylenevinylene). Carbon atoms in the main chain can be replaced by non-carbon atoms, and even when the sp2 hybridization in the main chain is interrupted by natural defects, it is still considered a conjugated polymer. In the present invention, conjugated polymers also include those containing arylamines, arylphosphine, other heteroaromatics, and organometallic complexes in the main chain.

[0100] In a preferred embodiment, the polymer is synthesized by a method selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

[0101] In a preferred embodiment, the glass transition temperature (Tg) of the polymer of the present invention is ≥100°C, preferably ≥120°C, more preferably ≥140°C, further preferably ≥160°C, and most preferably ≥180°C.

[0102] In a preferred embodiment, the molecular weight distribution (PDI) of the polymer of the present invention is preferably in the range of 1 to 5; more preferably 1 to 4; more preferably 1 to 3, further preferably 1 to 2, and most preferably 1 to 1.5.

[0103] In a preferred embodiment, the weight average molecular weight (Mw) of the polymer according to the present invention is preferably in the range of 10,000 to 1,000,000; more preferably 50,000 to 500,000; more preferably 100,000 to 400,000; even more preferably 150,000 to 300,000; and most preferably 200,000 to 250,000.

[0104] The present invention also provides a mixture comprising an organic compound H1 and an organic functional material H2, wherein H1 is an organic compound of the present invention, and H2 is selected from a hole injection material (HIM), a hole transport material (HTM), a p-dopant, an electron transport material (ETM), an electron injection material (EIM), an electron blocking material (EBM), a hole blocking material (HBM), an emitter, a host material (Host), or an organic dye. For example, various organic functional materials are described in detail in US2017092880A1, US2018006247A1, and EP3301097A2, and the entire contents of these three patent documents are hereby incorporated herein by reference.

[0105] In a preferred embodiment, the mixture comprises at least one organic compound or polymer of the present invention and a hole transport material (HTM).

[0106] In a preferred embodiment, the general structural formula of H2 is shown in formula (III):

[0107]

[0108] Wherein, A represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 100 ring atoms; D is an electron-rich group; and p is an integer of 1 to 6.

[0109] In certain preferred embodiments, the electron-rich (or electron-donating) group D in the general formula (III) comprises any of the following groups, wherein the H on the ring may be arbitrarily substituted:

[0110]

[0111] Wherein, Ar3 represents an aromatic group or heteroaromatic group having 5 to 40 ring atoms;

[0112] Z 1 、Z 2 、Z 3 Each independently represents a single bond, CR 23 R 24 、SiR 23 R 24 NR 23, O, C(=O), S, S=O or SO2, but Z 2 and Z 3 Not all are single bonds;

[0113] R 21 -R 24 Each occurrence is independently selected from H, D, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a silyl group, or a substituted 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, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, a CF3 group, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

[0114] More preferably, the D comprises any of the following groups, wherein the H on the ring can be arbitrarily substituted:

[0115]

[0116] In one embodiment, the electron-rich (or electron-donating) group D in formula (III) comprises any of the following groups, wherein the H on the ring may be arbitrarily substituted:

[0117]

[0118] In certain preferred embodiments, p is an integer of 1-4; in more preferred embodiments, p is an integer of 1-3; and in the most preferred embodiment, p is an integer of 1-2.

[0119] In some preferred embodiments, H2 is selected from one of the following structural formulas:

[0120]

[0121] In a more preferred embodiment, the mixture comprises at least one organic compound or polymer of the present invention and a luminescent material, and the luminescent material is selected from a singlet emitter (fluorescent emitter), a triplet emitter (phosphorescent emitter) or a TADF emitter.

[0122] In certain preferred embodiments, the mixture comprises at least one organic compound or polymer of the present invention and a fluorescent light-emitting body, wherein the weight percentage of the fluorescent light-emitting body is ≤10wt%, preferably ≤9wt%, more preferably ≤8wt%, further preferably ≤7wt%, and most preferably ≤5wt%.

[0123] In a preferred embodiment, the mixture comprises at least one organic compound or polymer of the present invention and a phosphorescent light emitter, wherein the weight percentage of the phosphorescent light emitter is ≤25 wt%, preferably ≤20 wt%, and more preferably ≤15 wt%.

[0124] In another more preferred embodiment, the mixture comprises the organic compound or polymer of the present invention, and a TADF material; wherein the functions of the TADF material are preferably: 1) forming a co-host material with the organic compound of the present invention, and the weight ratio of the two is 1:6 to 6:1; 2) forming an Exciplex with the organic compound of the present invention, which can be directly used as a light-emitting body, wherein the weight percentage of the TADF material is ≤15wt%, preferably ≤10wt%, and more preferably ≤8wt%.

[0125] In a particularly preferred embodiment, the mixture comprises the organic compound or polymer H1 of the present invention and another organic functional material H2. Such a mixture can serve as a phosphorescent mixed host material and can further comprise a phosphorescent emitter, wherein the weight percentage of the phosphorescent emitter is ≤25 wt%, preferably ≤20 wt%, and more preferably ≤15 wt%.

[0126] The following is a detailed description of the mixture containing H1 and H2 as the phosphorescent mixed host material.

[0127] In a preferred embodiment, the another organic functional material H2 has hole transport properties.

[0128] More preferably, the H2 has both hole transport properties and electron transport properties.

[0129] Generally, the molar ratio of the first organic compound (H1) to the second organic compound (H2) is 1:9 to 9:1.

[0130] Preferably, the molar ratio of the first organic compound (H1) to the second organic compound (H2) is 3:7 to 7:3.

[0131] More preferably, the molar ratio of the first organic compound (H1) to the second organic compound (H2) is 4:6 to 6:4.

[0132] Most preferably, the molar ratio of the first organic compound (H1) to the second organic compound (H2) is 5:5.

[0133] In certain embodiments, according to the mixture of the present invention, H1 or H2 has a higher triplet energy level T1, generally T1≥2.2eV, preferably T1≥2.3eV, more preferably T1≥2.4eV, even more preferably T1≥2.5eV, and most preferably T1≥2.6eV.

[0134] In certain preferred embodiments, the organic mixture, wherein H1 and H2 form a type II heterojunction structure, that is, the highest occupied molecular orbital energy level (HOMO) of H1 is lower than the HOMO of H2, and the lowest unoccupied molecular orbital energy level (LUMO) of H1 is lower than the LUMO of H2.

[0135] In a more preferred embodiment, for the mixture, min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1))≤min(ET(H1), ET(H2))+0.1eV, wherein LUMO(H1), HOMO(H1) and ET(H1) are the lowest unoccupied orbital, highest occupied orbital and triplet energy levels of H1, respectively, and LUMO(H2), HOMO(H2) and ET(H2) are the lowest unoccupied orbital, highest occupied orbital and triplet energy levels of H2, respectively.

[0136] In a preferred embodiment, for the mixture, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2)).

[0137] In a more preferred embodiment, for the mixture, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))-0.05 eV.

[0138] In a more preferred embodiment, for the mixture, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))-0.1 eV.

[0139] In a very preferred embodiment, for the mixture, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))-0.15 eV.

[0140] In a most preferred embodiment, the mixture, min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))-0.2 eV;

[0141] The following are specific examples of compounds H2 represented by general formula (II), but are not limited to:

[0142]

[0143]

[0144]

[0145] In a more preferred embodiment, according to the mixture of the present invention, at least one of H1 and H2, preferably H1, has ((LUMO+1)-LUMO) ≥ 0.1eV, preferably ≥ 0.15eV, more preferably ≥ 0.20eV, further preferably ≥ 0.25eV, and most preferably ≥ 0.30eV.

[0146] In another preferred embodiment, according to the mixture of the present invention, at least one of H1 and H2, preferably H2, has (HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.30 eV, further preferably ≥ 0.35 eV, and most preferably ≥ 0.40 eV.

[0147] One object of the present invention is to provide a material solution for vapor deposition type OLEDs.

[0148] In a preferred embodiment, the mixture of the present invention is used in an evaporative OLED device. For this purpose, the molecular weight of H1 and H2 in the fused ring organic compound or mixture according to the present invention is ≤1000 mol / kg, preferably ≤900 mol / kg, more preferably ≤850 mol / kg, even more preferably ≤800 mol / kg, and most preferably ≤700 mol / kg.

[0149] In a preferred embodiment, in the mixture, the difference in molecular weight between H1 and H2 does not exceed 100 Dalton; preferably, the difference in molecular weight does not exceed 60 Dalton; more preferably, the difference in molecular weight does not exceed 30 Dalton.

[0150] In another preferred embodiment, in the mixture, the difference in sublimation temperature between H1 and H2 does not exceed 30K; preferably, the difference in sublimation temperature does not exceed 20K; more preferably, the difference in sublimation temperature does not exceed 10K.

[0151] Another object of the present invention is to provide a material solution for printed OLEDs.

[0152] For this purpose, at least one, and preferably both, of H1 and H2 in the fused ring organic compound or mixture of the present invention satisfies the following conditions: its molecular weight is ≥700 g / mol, preferably ≥800 g / mol, more preferably ≥900 g / mol, further preferably ≥1000 g / mol, and most preferably ≥1100 g / mol.

[0153] In a premixed co-host for vapor-deposited OLEDs, the two host materials must possess similar chemical or physical properties, such as molecular weight and sublimation temperature. The present invention has discovered that in solution-processed OLEDs, two host materials with different properties can enhance film formation, thereby improving device performance. These properties, in addition to molecular weight and sublimation temperature, can also include other properties, such as glass transition temperature and different molecular volumes. Preferred embodiments of the mixture for printed OLEDs according to the present invention include:

[0154] 1) The difference in molecular weight between H1 and H2 is ≥120 g / mol, preferably ≥140 g / mol, more preferably ≥160 g / mol, and most preferably ≥180 g / mol.

[0155] 2) The difference in sublimation temperature between H1 and H2 is ≥60K, preferably ≥70K, more preferably ≥75K, and most preferably ≥80K.

[0156] 3) The difference in glass transition temperature between H1 and H2 is ≥20K, preferably ≥30K, more preferably ≥40K, and most preferably ≥45K.

[0157] 4) The difference in molecular volume between H1 and H2 is ≥20%, preferably ≥30%, more preferably ≥40%, and most preferably ≥45%.

[0158] In other embodiments, at least one, preferably both, of H1 and H2 in the fused ring organic compound or mixture of the present invention has a solubility in toluene of ≥2 mg / ml, preferably ≥3 mg / ml, more preferably ≥4 mg / ml, and most preferably ≥5 mg / ml at 25°C.

[0159] The following is a detailed description of triplet host materials, singlet emitters, triplet emitters, TADF materials and HTM (but not limited to these):

[0160] 1. Triplet Host Material:

[0161] Examples of triplet host materials are not particularly limited. Any metal complex or organic compound may be used as a host, as long as its triplet energy level is higher than that of the light emitter, particularly a triplet light emitter or a phosphorescent light emitter. Examples of metal complexes that can be used as triplet hosts include (but are not limited to) the following general structure:

[0162]

[0163] M is a metal; (Y 3 -Y 4 ) is a bidentate ligand, Y 3 and Y 4 is independently selected from C, N, O, P and S; L is an auxiliary ligand; m is an integer ranging from 1 to the maximum coordination number of the metal; in a preferred embodiment, the metal complex that can be used as a triplet host has the following form:

[0164]

[0165] (ON) is a bidentate ligand in which the metal is coordinated to both O and N atoms, and m is an integer ranging from 1 to the maximum coordination number of the metal;

[0166] In a preferred embodiment, M can be selected from Ir and P.

[0167] Examples of organic compounds that can serve as triplet hosts are selected from compounds containing cyclic aromatic 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, indole, carbazole, pyridine, indole, pyrrole, dipyridine, pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazines, oxathiazines, oxadiazines, indole, benzimidazole, indazole, oxazole, diphenyl The present invention also includes oxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, quinoxaline, naphthalene, phthalide, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophene pyridine, thiophene pyridine, benzoselenophene pyridine and selenophene benzodipyridine; groups containing 2 to 10 ring structures, which can be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, and are directly or through at least one of the following groups connected together, such as oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Each Ar can be further substituted, and the substituents can be selected from hydrogen, deuterium, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl groups.

[0168] In a preferred embodiment, the triplet host material may be selected from compounds comprising at least one of the following groups:

[0169]

[0170]

[0171] X 1 -X 8 Same meaning as above, X 9 Selected from CR 9 R 10 or NR 11 ,Ar 1 ~Ar 3 Selected from aromatic groups or heteroaromatic groups, R 1 -R 11 is selected from H, deuterium, halogen atoms (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl, and n2 is selected from integers of 1 to 20.

[0172] Examples of suitable triplet host materials are listed in the table below, but are not limited to:

[0173]

[0174] 2. Singlet Emitter

[0175] Singlet emitters often have long conjugated π-electron systems. Many examples exist, such as styrylamines and their derivatives disclosed in JP2913116B and WO2001021729A1, indenofluorenes and their derivatives disclosed in WO2008 / 006449 and WO2007 / 140847, and triarylamine derivatives of pyrene disclosed in US7233019 and KR2006-0006760.

[0176] In a preferred embodiment, the singlet emitter can be selected from monostyrylamines, distyrylamines, tertiary styrylamines, tetrastyrylamines, styrylphosphines, styrylethers and aromatic amines.

[0177] A monostyrylamine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tert-styrylamine is a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tetrastyrylamine is a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A preferred styrene is diphenylethylene, which may be further substituted. The corresponding phosphines and ethers are defined similarly to the amines. An arylamine or aromatic amine is a compound comprising three unsubstituted or substituted aromatic or heterocyclic rings directly attached to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Preferred examples include aromatic anthracenamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chryseneamines, and aromatic chrysenediamines. An aromatic anthracenamine is a compound in which one diarylamine group is directly attached to anthracene, preferably at the 9-position. An aromatic anthracenediamine is a compound in which two diarylamine groups are directly attached to anthracene, preferably at the 9- and 10-positions. Aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysamines, and aromatic chrysenediamines are similarly defined, with the diarylamine groups preferably attached to the 1- or 1,6-positions of the pyrene.

[0178] Examples, also preferred examples, of singlet emitters based on vinylamines and aromatic amines can be found in the following patent documents: WO 2006 / 000388, WO 2006 / 058737, WO 2006 / 000389, WO 2007 / 065549, WO 2007 / 115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006 / 210830 A, EP 1957606 A1 and US 2008 / 0113101 A1. The entire contents of the above-mentioned patent documents are hereby incorporated herein by reference.

[0179] Examples of singlet emitters based on stilbene and its derivatives are disclosed in US Pat. No. 5,121,029.

[0180] Further preferred singlet emitters can be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006 / 122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO 2008 / 006449, and dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007 / 140847.

[0181] Further preferred singlet emitters can be selected from fluorene-based fused ring systems, such as those disclosed in US2015333277A1, US2016099411A1, and US2016204355A1.

[0182] More preferred singlet emitters can be selected from pyrene derivatives, such as the structure disclosed in US2013175509A1; triarylamine derivatives of pyrene, such as the triarylamine derivatives of pyrene containing dibenzofuran units disclosed in CN102232068B; other triarylamine derivatives of pyrene with specific structures, such as those disclosed in CN105085334A and CN105037173A. Other materials that can be used as singlet emitters are polycyclic aromatic hydrocarbon compounds, especially derivatives of the following compounds: anthracene such as 9,10-bis(2-naphthoanthracene), naphthalene, tetraphenyl, xanthene, phenanthrene, pyrene (such as 2,5,8,11-tetra-t-butylperylene), indenopyrene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolylvinyl)-1,1'-biphenyl), diindenopyrene, decacyclopentane, hexabenzophenone, fluorene, spirobifluorene, arylpyrene (such as US20060222886), arylenevinyl (such as US51210 29, US5130603), cyclopentadiene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4-(dicyanomethylene)-6-(4-(p-dimethylaminophenyl)-2-methyl)-4H-pyran (DCM), thiopyran, bis(azinyl)imine boron compounds (US2007 / 0092753A1), bis(azinyl)methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles, and dione pyrrolopyrroles. Some materials for singlet emitters can be found in the following patent documents: US20070252517A1, US4769292, US6020078, US2007 / 0252517A1, and US2007 / 0252517A1. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0183] The following table lists some examples of suitable singlet emitters:

[0184]

[0185] 3. Triplet Emitter

[0186] Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex having the general formula M(L)n, where M is a metal atom, L can be the same or different at each occurrence, and is an organic ligand that is bonded or coordinated to the metal atom M at one or more positions, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5, or 6. Alternatively, these metal complexes are linked to a polymer at one or more positions, preferably via the organic ligand.

[0187] In a preferred embodiment, the metal atom M is selected from transition metal elements, lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, and particularly preferably Os, Ir, Ru, Rh, Re, Pd, Au or Pt.

[0188] Preferably, the triplet emitter contains a chelating ligand, i.e., a ligand that coordinates to the metal via at least two binding points. It is particularly preferred that the triplet emitter contains two or three identical or different bidentate or multidentate ligands. Chelating ligands contribute to improving the stability of the metal complex.

[0189] Examples of organic ligands 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, with fluorine-containing or trifluoromethyl groups. Auxiliary ligands may preferably be selected from acetone acetate or picric acid.

[0190] In a preferred embodiment, the metal complexes which can be used as triplet emitters are of the following form:

[0191]

[0192] Wherein M is a metal selected from transition metal elements, lanthanides or actinides, and is particularly preferably Ir, Pt or Au;

[0193] Ar1 can be the same or different each time it appears, and is a cyclic group containing at least one donor atom, that is, an atom with a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinated to the metal; Ar2 can be the same or different each time it appears, and is a cyclic group containing at least one C atom, through which the cyclic group is connected to the metal; Ar1 and Ar2 are linked together by covalent bonds, and each can carry one or more substituents, and they can also be linked together through substituents; L' can be the same or different each time it appears, and is a bidentate chelating auxiliary ligand, preferably a monoanionic bidentate chelating ligand; q1 can be 0, 1, 2 or 3, preferably 2 or 3; q2 can be 0, 1, 2 or 3, preferably 1 or 0.

[0194] Examples of some triplet emitter materials and their applications can be found in the following patent documents and literature: WO200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP1191614, WO 2005033244, WO 2005019373, US 2005 / 0258742, WO 2009146770, WO2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO2010099852, WO 2010102709, US 20070087219 A1,US 20090061681 A1,US 20010053462A1,Baldo,Thompson et al.Nature 403,(2000),750-753,US 20090061681 A1,US20090061681 A1,Adachi et al. al.Appl.Phys.Lett.78(2001),1622-1624,J.Kido etal.Appl.Phys.Lett.65(1994),2124,Kido et al.Chem.Lett.657,1990,US 2007 / 0252517A1,Johnson et al.,JACS 105,1983,1795,Wrighton,JACS 96,1974,998,Ma et al.,Synth.Metals 94,1998,245,US 6824895,US 7029766,US 6835469,US 6830828,US20010053462 A1,WO 2007095118 A1,US 2012004407A1,WO 2012007088A1,WO2012007087A1,WO 2012007086A1,US 2008027220A1,WO 2011157339A1,CN 102282150A,WO 2009118087A1,WO 2013107487A1,WO 2013094620A1,WO 2013174471A1,WO2014031977A1,WO 2014112450A1,WO 2014007565A1,WO 2014038456A1,WO 2014024131A1,WO 2014008982A1,WO2014023377A1.The entire contents of the above-listed patent documents and publications are hereby incorporated herein by reference.

[0195] Some examples of suitable triplet emitters are listed in the table below:

[0196]

[0197]

[0198] 4.TADF materials

[0199] Traditional organic fluorescent materials can only utilize 25% of the singlet excitons formed by electrical excitation for luminescence, resulting in a low internal quantum efficiency (up to 25%). Although phosphorescent materials, due to the strong spin-orbit coupling at the heavy atom center, enhance intersystem crossing, they can effectively utilize singlet and triplet excitons formed by electrical excitation for luminescence, achieving a device internal quantum efficiency of 100%. However, the high cost, poor material stability, and severe device efficiency roll-off of phosphorescent materials limit their application in OLEDs. Thermally activated delayed fluorescence (TADF) materials are the third generation of organic light-emitting materials developed after organic fluorescent and organic phosphorescent materials. These materials generally have a small singlet-triplet energy level difference (ΔEst), allowing triplet excitons to be converted to singlet excitons through anti-TAF crossing. This fully utilizes the singlet and triplet excitons formed by electrical excitation, resulting in a device internal quantum efficiency of 100%. Furthermore, the materials offer controllable structure, stable properties, low cost, and the absence of precious metals, making them promising for application in OLEDs.

[0200] TADF materials need to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, second preferably ΔEst < 0.2 eV, and most preferably ΔEst < 0.1 eV. In one preferred embodiment, the TADF material has a relatively small ΔEst. In another preferred embodiment, the TADF material has a good fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064(A1), Adachi, et al. Adv. Mater.,21,2009,4802,Adachi,et.al.Appl.Phys.Lett.,98,2011,083302,Adachi,et.al.Appl.Phys.Lett.,101,2012,093306,Adachi,et.al.Chem.Commun.,48,2012,11392,Adachi,et.al.Nature Photonics, 6, 2012, 253, Adachi, et.al. Nature, 492, 2012, 234, Adachi, et.al. J. Am. Chem. Soc, 134, 2012, 14706, Adachi, et. al. Angew. Chem. Int.Ed,51,2012,11311,Adachi,et.al.Chem.Commun.,48,2012,9580,Adachi,et.al.Chem.Commun.,48,2013,10385,Adachi,et.al.Adv.Mate r., 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.

[0201] Some examples of suitable TADF emitters are listed in the table below:

[0202]

[0203]

[0204]

[0205] 5. HTM

[0206] Suitable organic HTM materials may include compounds having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl triarylamine, thiophene, thiophene, pyrrole, aniline, carbazole, indolizine and fluorene, and their derivatives.

[0207] Examples of cyclic aromatic amine derivative compounds useful as HTMs include, but are not limited to, the following general structure:

[0208]

[0209] Each Ar 1 ~Ar 9 Can be independently selected from cyclic aromatic hydrocarbon compounds, such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenanthene, phenanthren, fluorene, pyrene, chrysene, perylene, azulene; aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, carbazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoleazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthylene, quinazoline, Quinoxaline, naphthalene, phthalide, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene, benzofuranpyridine, indolecarbazole, pyridineindole, pyrroledipyridine, furandipyridine, benzothiophenepyridine, thiophenepyridine, benzoselenophenepyridine and selenophenedipyridine; containing groups with 2 to 10 ring structures, which can be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, and are directly or through at least one of the following groups linked together, such as oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structure units and aliphatic ring groups. Among them, Ar 1 ~Ar 9 It may be further substituted, and the substituents may be selected from hydrogen, deuterium, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

[0210] In some preferred embodiments, Ar 1 ~Ar 9 Can be independently selected from the group comprising the following structural units:

[0211]

[0212] n is an integer from 1 to 20; X 1 ~X 8 is CH or N; Ar 10 Same definition as Ar1.

[0213] Additional examples of cyclic aromatic amine derivative compounds can be found in US Pat. Nos. 3,567,450, 4,720,432, 5,061,569, 3,615,404 and 5,061,569.

[0214] Examples of metal complexes useful as HTMs include, but are not limited to, the following general structure:

[0215]

[0216] M is a metal having an atomic weight greater than 40. In another embodiment, M is selected from Ir, Pt, Os, and Zn.

[0217] (Y 1 -Y 2 ) is a bidentate ligand, Y 1 and Y 2 is independently selected from C, N, O, P and S; L is an auxiliary ligand. m is an integer ranging from 1 to the maximum coordination number of the metal.

[0218] In one embodiment, (Y 1 -Y 2 ) is a 2-phenylpyridine derivative. In another embodiment, (Y 1 -Y 2 ) is a carbene ligand. In another embodiment, the HOMO of the metal complex is greater than -5.5 eV (relative to vacuum level).

[0219] Examples of suitable HTM compounds are listed in the table below:

[0220]

[0221] The present invention further relates to a composition or ink comprising any one of the above fused-ring organic compounds or mixtures, and at least one organic solvent.

[0222] When used in printing processes, ink viscosity and surface tension are important parameters. The appropriate surface tension parameters of the ink are suitable for a specific substrate and a specific printing method.

[0223] In a preferred embodiment, the surface tension of the ink according to the present invention at operating temperature or 25°C is about 19 dyne / cm to 50 dyne / cm; preferably 22 dyne / cm to 35 dyne / cm; more preferably 25 dyne / cm to 33 dyne / cm.

[0224] In another preferred embodiment, the viscosity of the ink according to the present invention is about 1 cps to 100 cps at working temperature or 25° C., preferably 1 cps to 50 cps, more preferably 1.5 cps to 20 cps, and most preferably 4.0 cps to 20 cps. The composition thus formulated will facilitate inkjet printing.

[0225] Viscosity can be adjusted by various methods, such as by selecting the appropriate solvent and adjusting the concentration of the functional material in the ink. The ink comprising the metal organic complex or polymer according to the present invention facilitates adjustment of the printing ink within an appropriate range according to the printing method used. Generally, the weight ratio of the functional material in the composition of the present invention is preferably 0.3 wt% to 30 wt%, more preferably 0.5 wt% to 20 wt%, further preferably 0.5 wt% to 15 wt%, even more preferably 0.5 wt% to 10 wt%, and most preferably 1 wt% to 5 wt%.

[0226] According to a composition of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic compounds, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, alicyclic or olefinic compounds, or borate or phosphate compounds, or a mixture of two or more solvents.

[0227] In a preferred embodiment, according to a composition of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents.

[0228] Examples of aromatic or heteroaromatic solvents suitable for the present invention include, but are not limited to: p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethyl Naphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 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, 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.

[0229] Examples of aromatic ketone-based solvents suitable for the present invention include, but are not limited to: 1-tetralone, 2-tetralone, 2-(phenylepoxy)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.

[0230] Examples of aromatic ether-based 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-ethylhexyl 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, and ethyl-2-naphthyl ether.

[0231] In some preferred embodiments, according to the composition of the present invention, the at least one organic solvent can be selected from: aliphatic ketones, for example, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, fenchone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers, for example, amyl 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.

[0232] In other preferred embodiments, according to the composition of the present invention, the at least one organic solvent can be selected from ester-based solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc. Octyl octanoate, diethyl sebacate, diallyl phthalate, and isononyl isononanoate are particularly preferred.

[0233] The solvent can be used alone or as a mixture of two or more organic solvents.

[0234] In certain preferred embodiments, a composition according to the present invention comprises the fused-ring organic compound or mixture as described in any one of the above items, and at least one organic solvent, and may further comprise another organic solvent. Examples of the other 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.

[0235] The present invention also relates to the use of the composition as printing ink in the preparation of organic electronic devices, and is particularly preferably a preparation method by printing or coating.

[0236] Suitable printing or coating techniques include, but are not limited to, inkjet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush coating or pad printing, slot extrusion coating, and the like. Preferred are gravure printing, screen printing, and inkjet printing. Gravure printing and inkjet printing are used in embodiments of the present invention. The solution or suspension may further include one or more components, such as a surfactant, lubricant, wetting agent, dispersant, hydrophobic agent, adhesive, and the like, to adjust viscosity, film-forming properties, and improve adhesion. For detailed information on printing techniques and their requirements for the relevant solutions, such as solvent concentration, viscosity, and the like, please refer to "Handbook of Print Media: Technologies and Production Methods," edited by Helmut Kipphan, ISBN 3-540-67326-1.

[0237] The functional layer formed by the preparation method described above has a thickness of 5 nm to 1000 nm.

[0238] The present invention also relates to the use of the fused-ring organic compound or mixture in organic electronic devices.

[0239] The present invention further relates to an organic electronic device comprising the fused-ring organic compound, polymer or mixture as described above.

[0240] The organic electronic device can be selected from, but not limited to, organic light emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light emitting cells (OLEECs), organic field effect transistors (OFETs), organic light emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diodes), etc., and organic electroluminescent devices such as OLEDs, OLEECs and organic light emitting field effect transistors are particularly preferred.

[0241] In some particularly preferred embodiments, the organic electronic device is an organic electroluminescent device, which comprises at least one light-emitting layer, and the light-emitting layer comprises a condensed-ring organic compound or a mixture as described above.

[0242] The organic electroluminescent device described above, in particular the OLED, comprises a substrate, an anode, at least one light-emitting layer, and a cathode.

[0243] The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting element. 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 elastic. The substrate can be plastic, metal, semiconductor wafer or glass. It is best if the substrate has a smooth surface. Substrates without surface defects are particularly ideal. In a preferred embodiment, the substrate is flexible and can be selected from a polymer film or plastic with a glass transition temperature Tg of above 150°C, preferably above 200°C, more preferably above 250°C, and most preferably above 300°C. Examples of suitable flexible substrates are polyethylene terephthalate (PET) and polyethylene (2,6-naphthalene) (PEN).

[0244] The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can readily inject holes into the hole injection layer (HIL) or hole transport layer (HTL) or light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO energy level or valence band energy level of the light-emitting material in the light-emitting layer or the p-type semiconductor material serving as the HIL or 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), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

[0245] The cathode may comprise a conductive metal or metal oxide. The cathode can readily inject electrons into the EIL or ETL or directly into the light-emitting layer. In one embodiment, the absolute difference between the work function of the cathode and the LUMO energy level or conduction band energy level of the luminophore 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 cathodes in OLEDs may be used as cathode materials for the devices of the present invention. Examples of cathode materials include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloys, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material may 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), and the like.

[0246] OLEDs may also include other functional layers, such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of which are hereby incorporated by reference.

[0247] In a preferred embodiment, in the organic electroluminescent device according to the present invention, the light-emitting layer thereof comprises the organic compound or mixture of the present invention.

[0248] In another preferred embodiment, the light-emitting layer of the organic electroluminescent device can be formed by one of the following methods:

[0249] (1) A mixture containing H1 and H2 is deposited as a source by vacuum evaporation.

[0250] (2) H1 and H2 are deposited as two separate sources by vacuum evaporation.

[0251] (3) Depositing the composition by solution processing, particularly printing.

[0252] According to the light emitting device of the present invention, the emission wavelength is between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm.

[0253] The present invention also relates to applications 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.

[0254] 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 summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should realize that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention. Specific embodiments

[0256] 1. Synthesis of compounds

[0257]

[0258] Comp-1 and Comp-2 synthesis:

[0259]

[0260] Synthesis Example 1

[0261] Synthesis of Intermediate 2: Compound 1 (15 g, 61 mmol), o-nitrophenylboronic acid 1 (10.7 g, 64 mmol), potassium carbonate 1 (25 g, 180 mmol), and tetrakis(triphenylphosphine)palladium (2.1 g, 1.8 mmol) were dissolved in a mixture of approximately 200 mL of toluene and 90 mL of water. The atmosphere was replaced with nitrogen and refluxed for 24 h. The reaction mixture was cooled to room temperature, the organic layer was separated, and extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate. After concentration, the residue was separated by chromatography to obtain a yellow solid in a 70% yield.

[0262] Synthesis of Intermediate 3: Compound 2 (10 g, 7.8 mmol) was placed in 70 mL of triethyl phosphite and stirred at 170° C. After the reaction was complete, the solvent was removed under reduced pressure and separated by chromatography to obtain a light yellow solid with a yield of 45%.

[0263] Synthesis of Comp 1: Compound 3 (2 g, 7.8 mmol) was dissolved in approximately 30 mL of anhydrous N,N-dimethylacetamide and placed in an ice-water bath. Sodium hydride was added stepwise to the reaction mixture. After half an hour of reaction, a solution of compound 4 (2.68 g, 7.8 mmol) in N,N-dimethylacetamide (10 mL) was added dropwise to the reaction mixture. After stirring for 2 hours, the mixture was slowly poured into ice water to quench the reaction. The mixture was filtered and washed with the solution to obtain solid Comp-1 in 85% yield.

[0264] Synthesis Example 2

[0265] Synthesis of Comp 2: Compound 3 (2 g, mmol) was dissolved in approximately 30 mL of anhydrous N,N-dimethylacetamide and placed in an ice-water bath. Sodium hydride was added stepwise to the reaction mixture. After half an hour of reaction, a solution of compound 5 (2.46 g, 7.8 mmol) in N,N-dimethylacetamide (10 mL) was added dropwise to the reaction mixture. After stirring for 2 hours, the mixture was slowly poured into ice water to quench the reaction. The mixture was filtered and washed with solvent to obtain solid Comp-2 in an 82% yield.

[0266] Comp-3 and Comp-4 synthesis:

[0267]

[0268] Synthesis of Intermediate 7: Compound 6 (15 g, 61 mmol), o-nitrophenylboronic acid (10.7 g, 64 mmol), potassium carbonate (25 g, 180 mmol), and tetrakis(triphenylphosphine)palladium (2.1 g, 1.8 mmol) were dissolved in a mixture of approximately 200 mL of toluene and 90 mL of water. The atmosphere was replaced with nitrogen and refluxed for one day. The reaction mixture was cooled to room temperature, the organic layer was separated, and extracted with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulfate. After concentration, the residue was separated by chromatography to obtain a yellow solid in a 75% yield.

[0269] Synthesis of Intermediate 8: Compound 7 (10 g, 7.8 mmol) was placed in triethyl phosphite and stirred at 170° C. After the reaction was complete, the solvent was removed under reduced pressure and the product was separated by chromatography to obtain a light yellow solid with a yield of 65%.

[0270] Synthesis of Comp 3: Compound 8 (3 g, 11.7 mmol), compound 9 (4.65 g, 12 mmol), and Pd2(dba)3 (0.32 g, 0.35 mmol) were dissolved in approximately 60 mL of toluene and the atmosphere was purged with nitrogen. Tri-tert-butylphosphine was added and the mixture was refluxed and stirred for one day. After cooling to room temperature, the mixture was quenched with water and extracted with ethyl acetate. The organic solvents were mixed and dried over anhydrous sodium sulfate. The reaction mixture was concentrated and separated by column chromatography to obtain solid Comp-3 in 80% yield.

[0271] Synthesis of Comp 4: Compound 8 (3 g, 11.7 mmol) was dissolved in approximately 40 mL of anhydrous N,N-dimethylacetamide and placed in an ice-water bath. Sodium hydride was added stepwise to the reaction mixture. After half an hour of reaction, a solution of compound 10 (3.7 g, 11.7 mmol) in N,N-dimethylacetamide was added dropwise to the reaction mixture. The mixture was stirred for 2 hours and then slowly poured into ice water to quench the reaction. The mixture was filtered and washed with solvent to obtain Comp-4 in an 87% yield.

[0272] Synthesis Example 3

[0273] Comp-5 Synthesis:

[0274]

[0275] Synthesis of Intermediate 12: Compound 11 (5 g, 25.2 mmol) was dissolved in approximately 70 mL of anhydrous dichloromethane. Boron tribromide (1 M) was added at -78°C and stirred for 1 hour before warming to room temperature. The reaction solution was slowly added to ice water and extracted with ethyl acetate. After drying over sodium sulfate, the solid was evaporated to dryness under reduced pressure to give an 85% yield.

[0276] Synthesis of Intermediate 13: Compound 12 (3.8 g, 20.6 mmol), o-nitrofluorobenzene (3 g, 21 mmol), and potassium carbonate (5.5 g, 40 mmol) were placed in approximately 60 mL of N,N-dimethylacetamide, heated to 80°C, and stirred overnight. After cooling to room temperature, water was added to precipitate a solid, which was filtered and washed with solvent to obtain a yellow solid in 85% yield.

[0277] Synthesis of intermediate 14: Compound 13 (5 g, 16.4 mmol) was placed in triethyl phosphite and stirred at 170°C for 3 h. After the reaction was complete, the solvent was removed under reduced pressure and the solid was separated by chromatography with a yield of 60%.

[0278] Synthesis of Comp 5: Compound 14 (2.5 g, 9.1 mmol), compound 15 (3.16 g, 9.2 mmol), Pd2 ( dba)3 (0.41 g, 0.45 mmol) was dissolved in approximately 80 mL of toluene and the atmosphere was replaced with nitrogen. Tri-tert-butylphosphine was added and the mixture was refluxed with stirring for one day. After the system was cooled to room temperature, water was added to quench the reaction, and the mixture was extracted with ethyl acetate. The organic solvents were mixed and dried over anhydrous sodium sulfate. The reaction solution was concentrated and separated by column chromatography to obtain solid Comp-5 in an 88% yield.

[0279] Synthesis Example 4

[0280] Comp-6 Synthesis:

[0281]

[0282] Synthesis of Intermediate 16: Compound 6 (10 g, 41 mmol), 2-acetylaniline (5.4 g, 40 mmol), and Pd2(dba)3 (1.1 g, 1.2 mmol) were dissolved in approximately 150 mL of toluene and the atmosphere was purged with nitrogen. Tri-tert-butylphosphine was added and the mixture was refluxed and stirred for one day. After cooling to room temperature, the mixture was quenched with water and extracted with ethyl acetate. The organic solvents were mixed and dried over anhydrous sodium sulfate. The reaction mixture was concentrated and separated by column chromatography to obtain Compound 16 in an 80% yield.

[0283] Synthesis of intermediate 17: Compound 16 (8 g, 26.6 mmol) was dissolved in approximately 120 mL of anhydrous tetrahydrofuran. Butyl lithium was added at -78°C and stirred for one hour. The reaction was quenched with aqueous ammonium chloride solution, extracted with ethyl acetate, and dried over anhydrous sodium sulfate. The reaction solution was concentrated and compound 17 was isolated by column chromatography with a yield of 92%.

[0284] Synthesis of Intermediate 18: Compound 17 (6 g, 19 mmol) was dissolved in approximately 80 mL of dichloromethane, and methanesulfonic acid was added and stirred for 4 hours. After the reaction was complete, aqueous sodium bicarbonate was added for neutralization. The mixture was extracted with ethyl acetate and dried over anhydrous sodium sulfate. The reaction mixture was concentrated and compound 18 was isolated by column chromatography in a 68% yield.

[0285] Synthesis of Comp-6: Compound 18 (2 g, 6.7 mmol), compound 19 (2.3 g, 6.7 mmol), and Pd2(dba)3 (0.18 g, 0.2 mmol) were dissolved in approximately 60 mL of toluene and the atmosphere was purged with nitrogen. Tri-tert-butylphosphine was added and the mixture was refluxed and stirred for one day. After cooling to room temperature, the mixture was quenched with water and extracted with ethyl acetate. The organic solvents were mixed and dried over anhydrous sodium sulfate. The reaction mixture was concentrated and separated by column chromatography to obtain solid Comp-6 in a 78% yield.

[0286] Synthesis Example 5

[0287] Comp-7 Synthesis:

[0288]

[0289] Synthesis of intermediate 22: Under nitrogen, (20.2 g, 50 mmol) of compound 20 and (17.2 g, 100 mmol) of compound 21, (3.5 g, 3 mmol) of tetrakis(triphenylphosphine)palladium, (8.1 g, 25 mmol) of tetrabutylammonium bromide, (4 g, 100 mmol) of sodium hydroxide, (20 mL) of water and (150 mL) of toluene were added into a 300 mL three-necked flask. The mixture was stirred at 80°C for 12 hours. After the reaction was terminated, the reaction solution was rotary evaporated to remove most of the solvent, and the mixture was washed three times with dichloromethane and water. The organic solution was collected and mixed with silica gel column for purification with a yield of 75%.

[0290] Synthesis of intermediate 23: Compound 22 (14.9 g, 30 mmol) and 100 mL of N,N-dimethylformamide were added to a 250 mL single-necked flask. A 30 mmol solution of NBS in N,N-dimethylformamide was added dropwise under ice bath. The mixture was stirred in the dark for 12 h. After termination of the reaction, the reaction solution was poured into 300 mL of water and filtered. The residue was recrystallized with a yield of 90%.

[0291] Synthesis of Comp 7: Under nitrogen environment, (11.5 g, 20 mmol) of compound 23 and (34.4 g, 20 mmol) of compound 24, (0.7 g, 0.6 mmol) of tetrakis(triphenylphosphine)palladium, (3.2 g, 10 mmol) of tetrabutylammonium bromide, (1.6 g, 40 mmol) of sodium hydroxide, (10 mL) of water and (80 mL) of toluene were added into a 250 mL three-necked flask, heated to 80 ° C and stirred for 12 hours, and the reaction was terminated. The reaction solution was rotary evaporated to remove most of the solvent, dissolved in dichloromethane and washed three times with water, and the collected organic liquid was mixed with silica gel and purified by column chromatography with a yield of 85%.

[0292] Synthesis Example 6

[0293] Comp-8 Synthesis:

[0294]

[0295] Synthesis of Comp 8: Under nitrogen environment, (11.5 g, 20 mmol) of compound 23 and (44.4 g, 20 mmol) of compound 25, (0.7 g, 0.6 mmol) of tetrakis(triphenylphosphine)palladium, (3.2 g, 10 mmol) of tetrabutylammonium bromide, (1.6 g, 40 mmol) of sodium hydroxide, (10 mL) of water and (80 mL) of toluene were added into a 250 mL three-necked flask, heated to 80 ° C and stirred for 12 hours, and the reaction was terminated. The reaction solution was rotary evaporated to remove most of the solvent, dissolved in dichloromethane and washed three times with water, and the organic liquid was collected and mixed with silica gel column for purification, with a yield of 85%.

[0296] 2. Energy level structure of compounds

[0297] The energy structure of organic repeating units can be determined through quantum calculations, such as using TD-DFT (time-dependent density functional theory) with Gaussian03W (Gaussian Inc.). For detailed simulation methods, see WO2011141110. The molecular geometry is first optimized using the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / SpinSinglet). The energy structure of the organic molecule is then calculated using TD-DFT (time-dependent density functional theory) using the "TD-SCF / DFT / Default Spin / B3PW91" basis set "6-31G(d)" (Charge 0 / SpinSinglet). The HOMO and LUMO energy levels are calculated using the following calibration formulas, with S1 and T1 used directly.

[0298] HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206

[0299] LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385

[0300] HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 03W, with the unit of eV. The results are shown in Table 1, where ΔHOMO = HOMO - (HOMO - 1):

[0301] Table 1

[0302]

[0303]

[0304]

[0305] Among them: Comp-7-Comp-10 are the materials of H2 in the mixture.

[0306] 3. Preparation and measurement of OLED devices

[0307] The following is a detailed description of the preparation process of the above-mentioned OLED device through a specific embodiment. The structure of the red OLED device is: ITO / HI / HI-1 / HT-2 / EML / ET: Liq / Liq / Al.

[0308]

[0309] The preparation steps are as follows:

[0310] a. Cleaning of ITO (Indium Tin Oxide) conductive glass substrates: Use various solvents (such as one or more of chloroform, acetone or isopropyl alcohol) to clean, and then perform UV ozone treatment;

[0311] b. HI (30 nm), HT-1 (60 nm), HT-2 (10 nm), main materials: 3% RD (40 nm), ET:Liq (50:50; 30 nm), Liq (1 nm), Al (100 nm) in high vacuum (1 × 10 -6 The ITO substrate was moved into a vacuum vapor deposition device and heated in a high vacuum (1×10 -6At 100 mbar, a resistive heating evaporation source was used to form a 30nm thick HI layer. A 60nm thick HT-1 and a 10nm thick HT-2 layer were then formed on the HI layer. Comp-1 was then placed in one evaporation unit, and compound RD was placed in another evaporation unit as a dopant. The materials were vaporized at different rates, resulting in a comp-1:RD weight ratio of 100:3. This formed a 40nm thick luminescent layer on the hole transport layer. ET and LiQ were then co-deposited in separate evaporation units at a 50% weight ratio, forming a 30nm thick electron transport layer on the luminescent layer. A 1nm thick LiQ was then deposited on the electron transport layer as an electron injection layer. Finally, a 100nm thick Al cathode was deposited on the electron injection layer.

[0312] c. Packaging: The device is encapsulated with UV-curable resin in a nitrogen glove box.

[0313] The implementation methods of device examples 2-9 are the same as those of device example 1. Different host materials are used to replace comp-1, as detailed in Table 2. Co-host refers to two compounds placed in different evaporation units to control the weight ratio of the materials.

[0314] The current-voltage-luminescence (IVL) characteristics of the red OLED devices were characterized using a characterization setup, recording key parameters such as efficiency, lifetime, and drive voltage. The performance of the red OLED devices is summarized in Table 2. The lifetime values are presented as relative values.

[0315] Table 2

[0316]

[0317]

[0318] After testing, the luminous efficiency and life of the device examples 1-9 are significantly improved compared with the comparative example 1. It can be seen that the luminous efficiency and life of the OLED device prepared by using the organic compound of the present invention are greatly improved.

[0319] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0320] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A fused-ring organic compound, characterized in that: Its general structural formula is selected from any one of formulas (II-3), (II-7) and (II-10): Among them, R1-R8, R 10 、R 11 is a substituent, each occurrence being independently selected from H, D, a linear alkyl group having 1 to 12 C atoms, or a branched or cyclic alkyl group having 3 to 18 C atoms; L is a linking group selected from One of the following; Each time V appears, it is independently selected from CR 14 or N; R 14 Each occurrence is independently selected from H, D, linear alkyl having 1 to 12 C atoms, or branched or cyclic alkyl having 3 to 18 C atoms, or phenyl; Ar is selected from benzene, naphthalene, phenanthrene, triphenylene, biphenyl or terphenyl.

2. The fused-ring organic compound according to claim 1, characterized in that The L is selected from And at least one V is selected from N.

3. The fused-ring organic compound according to claim 1, characterized in that The L is selected from And at least one V is selected from N.

4. The fused-ring organic compound according to claim 1, characterized in that Described L is selected from one of the following structural groups:

5. The fused-ring organic compound according to claim 1, characterized in that Has any of the following structures:

6. A mixture, characterized in that It comprises an organic compound H1 and an organic functional material H2, wherein H1 is selected from the condensed ring organic compound according to any one of claims 1 to 5; and H2 is selected from one or more of hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent materials, host materials, and organic dyes.

7. The mixture according to claim 6, characterized in that The H2 is selected from the compound represented by the following general formula (III): in, A is selected from an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group or an aromatic heterocyclic group having 5 to 100 ring atoms; D is an electron-rich group; and p is an integer of 1 to 6.

8. The mixture according to claim 7, characterized in that The D comprises any of the following groups, wherein the H on the ring can be arbitrarily substituted: Wherein: Ar3 represents an aromatic group or heteroaromatic group having 5 to 40 ring atoms; Z 1 、Z 2 、Z 3 Each independently represents a single bond, CR 23 R 24 、SiR 23 R 24 NR 23 , O, C(=O), S, S=O or SO2, but Z 2 and Z 3 Not all are single bonds; R 21 -R 24 Each occurrence is independently selected from H, D, a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, or a straight-chain thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group having 3 to 20 C atoms, or a branched alkoxy group having 3 to 20 C atoms, or a cyclic alkoxy group having 3 to 20 C atoms, or a branched thioalkoxy group having 3 to 20 C atoms, or a cyclic thioalkoxy group having 3 to 20 C atoms, or a silyl group, a keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, a hydroxyl group, a nitro group, a CF3 group, Cl, Br, F, or an aromatic or heteroaromatic group having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

9. A composition, characterized in that The composition comprises the fused-ring organic compound according to any one of claims 1 to 5, or the mixture according to any one of claims 6 to 8, and at least one organic solvent.

10. An organic electronic device, characterized in that: The organic electronic device comprises a functional layer, wherein the functional layer comprises the fused-ring organic compound according to any one of claims 1 to 5, or the mixture according to any one of claims 6 to 8.

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