Organic compound, organic mixture and composition containing organic compound, and application of organic compound in organic electronic device

Abstract

The invention discloses an organic compound based on aza-dibenzofuran and an application of the organic compound in an organic electronic device. The invention further discloses an organic mixture which comprises a first compound H1 and a second compound H2, the first compound H1 is a p-type material with dicarbazole as a core structure, and the second compound H2 is the organic compound according to the invention as an n-type material. Through the matching of the two main body materials, the energy of excitons can be utilized to the maximum extent, the organic electroluminescent material has a relatively balanced transmission property, the concentration of the excitons and the working voltage of the device are reduced, the efficiency and the service life of related electronic devices, especially phosphorescent OLEDs, can be effectively improved, and an effective scheme is provided for improving the overall performance of the organic electronic devices. The invention also relates to printing inks comprising said organic compounds or organic mixtures.

Description

Technical Field

[0001] The present invention relates to the technical field of organic luminescent materials, in particular to an organic compound, an organic mixture and a composition containing the same, and applications thereof in organic electronic devices, in particular to applications of the organic compound or organic mixture in electroluminescent devices. Background Art

[0002] Organic light-emitting diodes (OLEDs) are considered by the industry to be the most promising next-generation display and lighting technology due to their lightweight, active luminescence, high color purity, wide viewing angle, high contrast, high luminous efficiency, low energy consumption, and ease of fabrication for flexible and large-scale panels. To promote the large-scale industrialization of OLEDs, further improving their luminous performance and lifespan is a key challenge that needs to be addressed. The development of high-performance organic optoelectronic materials is crucial to addressing this issue.

[0003] Organic light-emitting diodes (OLEDs) are electroluminescent devices that convert electrical energy into light. To further improve the luminous efficiency of OLEDs, it is necessary to maximize energy conversion efficiency and minimize energy loss. For electroluminescent devices, according to the statistical laws of electron spin in quantum mechanics, singlet and triplet excitons are generated in a ratio of 1:3. This results in a maximum energy utilization rate (internal quantum efficiency) of only 25% for conventional fluorescent materials. However, phosphorescent materials, due to the heavy atom effect, enhance spin-orbit coupling in the triplet state, enabling the previously spin-forbidden transition from the triplet state to the ground state. Both singlet and triplet excitons can radiate light, and the energy utilization rate can theoretically reach 100%. Currently, significant progress has been made in red and green phosphorescent materials, both in terms of host and guest properties, leading to industrialization. However, the performance of phosphorescent blue OLEDs, particularly their lifetime, remains far below commercial standards, forcing the use of fluorescent blue OLEDs in current commercial displays. Due to their low efficiency, fluorescent blue OLEDs are the primary limiting factor in OLED display energy consumption. Blue phosphorescent materials have become the last holy grail of OLED materials.

[0004] Blue phosphorescent OLEDs depend on the host and guest materials. The host material can achieve a balance between energy level matching and charge transfer, preventing exciton aggregation quenching, and is an indispensable component for improving the device lifespan and stability of organic light-emitting diodes. Using exciplexes as phosphorescent host materials is a relatively common method. This method can use two organic compounds of different polarities to form an intermediate state, namely an exciplex, to improve the device lifespan (see, for example, Kim et al., Adv. Mater., Vol 26, 5864, (2014)). To date, many companies have reported technologies using exciplexes as co-hosts. For example, Rohm and Haas Electronic Materials Korea Ltd. disclosed a co-host in which the first host and the second host are a bicarbazole derivative and a carbazole derivative, respectively (US2017 / 0062730). Samsung disclosed a co-host in which the two host materials are selected from an electron transport host and a hole transport host, respectively (KR20160026744). Recently, Sun et al. reported a blue phosphorescent device (DOI: 10.1038 / s41566-022-00958-4) that achieved a significant breakthrough in lifetime. The device utilizes SiCzCz as a p-type host and SiTrzCz2 as an n-type host, effectively forming exciplexes. However, the lifetime remains far from meeting commercial requirements, likely due to the poor stability of the n-type host (SiTrzCz2).

[0005]

[0006] Therefore, more stable n-type host materials still need to be developed. Summary of the Invention

[0007] In view of the above-mentioned deficiencies in the prior art, one object of the present invention is to provide an organic compound based on azadibenzofuran; another object of the present invention is to provide a class of organic mixtures, namely, co-host materials, comprising two compounds (a first compound H1 and a second compound H2), wherein the first compound H1 is a p-type material with bicarbazole as the core structure, and the second compound H2 is an organic compound according to the present invention (as an n-type material), aiming to solve the problems of low stability and device life of existing organic electronic devices.

[0008] The technical solutions of the present invention are as follows:

[0009] An organic compound having the structure of the following chemical formula (I):

[0010]

[0011] Wherein: X and Y are independently selected from N or CR, and 1 to 2 Xs are N, and 1 to 3 Ys are N;

[0012] L is selected from a single bond or a second-order linking unit;

[0013] Ar is selected from a substituted or unsubstituted aromatic group 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 groups;

[0014] R, when it occurs multiple times, may be selected, identically or differently, from H, D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a carbamoyl, haloformyl, formyl, isocyanate, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, where one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which they are bonded.

[0015] The present invention also relates to an organic mixture comprising a first compound H1 and a second compound H2, wherein the first compound H1 is selected from the chemical formula (II-1) or (II-2), and the second compound H2 is selected from the organic compounds according to the present invention:

[0016]

[0017] Ar1-Ar3 are 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 groups, wherein one or more of these groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded;

[0018] R1-R4 are substituents which, on each occurrence, may be identical or different and are selected from a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, wherein one or more of the groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded;

[0019] n1, n3, and n4 are each independently selected from integers from 0 to 7;

[0020] n2 is selected from integers of 0 to 8.

[0021] The present invention also relates to a composition comprising an organic compound or organic mixture as described above, and at least one organic solvent.

[0022] The present invention further relates to an optoelectronic device comprising an organic compound or organic mixture as described above.

[0023] Preferably, the above-mentioned optoelectronic device is an organic electroluminescent device, and comprises a substrate, an anode, at least one light-emitting layer and a cathode arranged in sequence, wherein the light-emitting layer comprises at least one organic compound or organic mixture as described above, or is prepared using the composition as described above.

[0024] The present invention further relates to an organic compound II having the following structure:

[0025]

[0026] Wherein: X and Y are selected from CR or N, and at least one Y is selected from N;

[0027] Ar 1 Having the structure shown in chemical formula (III-1); Ar 2 and Ar 3 are independently selected from the structures shown in chemical formula (III-1) or (III-2) or the combination of chemical formula (III-1) and (III-2); when Ar 2 and Ar 3 When it is carbazole, X is selected from CR;

[0028] Ring A is a 5-membered or 6-membered aromatic ring or a heteroaromatic ring;

[0029] Y1 is selected from single bond, O, S, Se, CR a R b NR a 、SiR a R b and BR a ;

[0030] R A At each occurrence, it independently represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0031] R, R a , R b , R A In each occurrence, each is independently selected from H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted silyl group, or a substituted or unsubstituted keto group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups; one or more H in the above-mentioned various groups may be further substituted by D.

[0032] Beneficial Effects: The organic compound or organic mixture according to the present invention, when applied to organic electronic devices, can provide high luminous efficiency and device life, for example, electroluminescent devices. Possible reasons for this are as follows, but not limited to: the use of an n-type compound containing an azadibenzofuran has a large electron-withdrawing property, resulting in a large delocalized frontier electron orbital (LUMO) for the entire molecule; on the other hand, the azadibenzofuran may also increase the dissociation energy of the CN bond between the intermediate six-membered ring and the carbazole, thereby improving the device life and stability. Through another experiment, we found that replacing the dibenzofuran with an electron-donating group such as those represented by Chemical Formulas (III-1) and (III-2) can achieve similar effects as azadibenzofuran, and can also improve the device life and stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1It is a diagram of a heterojunction structure, showing two possible types of relative positions of the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) when two organic semiconductor materials H1 and H2 are in contact, among which the type II semiconductor heterojunction structure is the energy level structure of the organic mixture according to the present invention. DETAILED DESCRIPTION

[0034] The present invention provides an organic compound based on azadibenzofuran; the present invention further provides an organic mixture, i.e., a co-host material, comprising a first compound H1 and a second compound H2, wherein the first compound H1 is a p-type material with a bicarbazole core structure, and the second compound H2 is an n-type material, selected from the organic compounds according to the present invention.

[0035] To make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0036] In the description of the embodiments of the present invention, a numerical range represented by “~” refers to a range that includes the numerical values ​​described before and after “~” as the lower limit and the upper limit.

[0037] In the description of the embodiments of the present invention, a substituent may be further substituted by a substituent, and "substituted group a" may refer to group a being substituted by a substituent, and the substituent may be substituted by at least one further substituent or may be unsubstituted.

[0038] In this disclosure, the term "and / or" describes the relationship between associated objects, indicating that three possible relationships exist. For example, "A and / or B" can represent: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0039] In the present invention, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can each be single or plural.

[0040] It should be understood that in various embodiments of the present invention, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present invention.

[0041] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The singular forms "a", "an", "the" and "the" used in the embodiments of the present invention and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0042] The term "OLED" is an abbreviation for "Organic Light Emitting Diode," which stands for organic electroluminescent diode, also known as organic electric laser display or organic light-emitting semiconductor (Organic Electroluminescence Display, OLED). OLED is a current-type organic light-emitting device that emits light through the injection and recombination of carriers, and the luminous intensity is proportional to the injected current. Under the action of the electric field, the holes generated by the anode and the electrons generated by the cathode will move, and are injected into the hole transport layer and the electron transport layer respectively, and migrate to the light-emitting layer. When the two meet in the light-emitting layer, energy excitons are generated, which excite the light-emitting molecules and ultimately produce visible light.

[0043] The term "TADF," short for "Thermally Activated Delayed Fluorescence," refers to thermally activated delayed fluorescence, which occurs when the triplet excited state and singlet excited state are close in energy, allowing the triplet excited state to transition to the singlet excited state through thermally activated reverse intersystem crossing (ISC). Conventional luminescence occurs as fluorescence and phosphorescence, respectively, where the exciton returns to the ground state via radiative emission from the singlet and triplet states. Furthermore, the energy difference between the lower singlet and triplet states is typically large, resulting in an inability to return the exciton to the singlet state once it reaches the triplet state through ISC.

[0044] In the present invention, main material, matrix material, host or matrix material have the same meaning and can be interchanged.

[0045] In the present invention, metal organic complex, metal organic complex and organometallic complex have the same meaning and can be used interchangeably.

[0046] In the present invention, the term "substituted or unsubstituted" means that a hydrogen atom in the compound is replaced by a substituent, and "unsubstituted" means that a hydrogen atom on the group is not replaced by a substituent. The substituent may be selected from the following groups: D, F, CN, alkenyl, alkynyl, amine, nitro, acyl, alkoxy, carbonyl, sulfone, boron-containing group, silicon-containing group, alkyl group having 1 to 50 carbon atoms (preferably 1 to 18, more preferably 1 to 8), cycloalkyl group having 3 to 50 ring atoms (preferably 3 to 10, more preferably 3 to 8, and even more preferably 5 or 6), aromatic hydrocarbon group or aromatic heterocyclic group having 3 to 50 ring atoms (preferably 3 to 25, more preferably 3 to 18).

[0047] 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.

[0048] For purposes of the present invention, an "aromatic hydrocarbon group" refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic and polycyclic ring systems. An "aromatic heterocyclic group" refers to a hydrocarbon group (containing heteroatoms) containing at least one aromatic heterocyclic ring, including monocyclic and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these polycyclic rings is aromatic or heteroaromatic. For the purposes of the present invention, an aromatic or heteroaromatic ring system includes not only aromatic or heteroaromatic groups, but also groups in which multiple aromatic or heteroaromatic groups are interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% non-H atoms, such as C, N, or O atoms). Thus, groups such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, and diaryl ethers are also considered aromatic ring systems for the purposes of this invention.

[0049] Specific examples of the aromatic hydrocarbon group include benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.

[0050] Specific examples of aromatic heterocyclic 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.

[0051] In the present invention, the energy level structure of the organic material, the singlet energy level E S1 , triplet energy level E T1 , HOMO, and LUMO play a key role. The following is an introduction to the determination of these energy levels.

[0052] 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.

[0053] The singlet energy level E of organic materials S1 It can be measured by fluorescence luminescence spectrum at room temperature or low temperature; the triplet energy level E T1 It 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 09W (Gaussian Inc.). The specific simulation method can be found in WO2011141110 or as described below in the examples.

[0054] It should be noted that HOMO, LUMO, E S1 、E T1 The absolute value of depends on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as the starting point and peak point on the CV curve, can give different HOMO / LUMO values. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. S1 、E T1 The value is based on the Time-dependent DFT simulation and does not affect the application of other measurement or calculation methods.

[0055] 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.

[0056] The present invention provides an organic compound having the following chemical formula (I):

[0057]

[0058] Wherein: X and Y are independently selected from N or CR, and 1 to 2 Xs are N, and 1 to 3 Ys are N;

[0059] L is selected from a single bond or a di-order linking unit (a di-order linking unit is a linking unit that connects two groups); Ar is selected from a substituted or unsubstituted aromatic group 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 groups;

[0060] R, when it occurs multiple times, may be selected, identically or differently, from H, D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a carbamoyl, haloformyl, formyl, isocyanate, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, where one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which they are bonded.

[0061] In a preferred embodiment, L is selected from a single bond.

[0062] In other preferred embodiments, L is selected from benzene, biphenyl, pyridine or dibenzofuran.

[0063] In a particularly preferred embodiment, all R in formula (I) are selected from H or D.

[0064] Preferably, Ar is selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 35 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 35 ring atoms, or a combination of these groups; more preferably, Ar is selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 30 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups; more preferably, Ar is selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 25 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 25 ring atoms, or a combination of these groups.

[0065] In a more preferred embodiment, the organic compound has the following chemical formula (I-1):

[0066]

[0067] Wherein, the definitions of X, Y, L, and Ar are the same as above.

[0068] In certain preferred embodiments, the aforementioned Ar is selected from benzene, naphthalene or carbazole.

[0069] In a more preferred embodiment, the above-mentioned Ar is selected from electron-donating groups.

[0070] Suitable electron donating groups may be selected from any of the following groups:

[0071]

[0072] Wherein, Ar0 represents an aromatic group or heteroaromatic group having 5 to 40 ring atoms;

[0073] Z 1 、Z 2 、Z 3 Each independently represents a single bond, CR 3 R 4 、SiR 5 R 6 NR 7 , O, C=O, S, S=O or SO2, but Z 2 and Z 3 Not single bond at the same time; R 1 -R 7 The definition of R is the same as above.

[0074] In some more preferred embodiments, the electron-donating group comprises any of the following groups:

[0075]

[0076] R 1 、R 2The definition of is the same as above.

[0077] In other embodiments, the Ar is selected from electron-withdrawing groups.

[0078] Examples of suitable groups having electron-withdrawing properties are shown below, but are not limited thereto, which may be further substituted optionally:

[0079]

[0080] Where n0 is any integer from 1 to 3; X 1 -X 8 Selected from CR or N, at least one of which is N, Z1, Z2, and Z3 are independently NR 8 , CR 9 R 10 、SiR 9 R 10 、O、C=N(R 8 ), C=C(R 9 R 10 ), PR 8 、P(=O)R 8 , S, S=O, SO2 or none, but at least one of them is not none; where R 8 -R 10 The group may be selected from the following: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.

[0081] Further electron withdrawing groups may be selected from F, cyano or a structure comprising the following groups, which may be further substituted with any desired group:

[0082]

[0083] In some particularly preferred embodiments, the electron-withdrawing group is selected from CN or one or more combinations of the structures shown below:

[0084]

[0085] In a particularly preferred embodiment, the organic compound has the following chemical formulas (I-2) to (I-4):

[0086]

[0087] Wherein: X, Yr are as defined above; Z is selected from N or CR 01 , R 01 The definition of R is the same as above; A is selected from O, S, SO2 or NR 02 ;

[0088] R 02is selected from a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, wherein one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which the group is bonded.

[0089] In a particularly preferred embodiment, the organic compound has the following chemical formulas (I-5) to (I-8):

[0090]

[0091] wherein: X and Y are independently selected from N or CR, 1 to 2 Xs are N, and 1 to 3 Ys are N; and R is as defined above.

[0092] In a particularly preferred embodiment, the organic compound has the structure of chemical formula (I-5)-(I-6), wherein: X is independently selected from N or CR, and one X is N.

[0093] The present invention also provides an organic compound II having the following structure:

[0094]

[0095] Wherein: X and Y are independently selected from CR or N, and at least one Y is selected from N;

[0096] Ar 1 Having the structure shown in chemical formula (III-1); Ar 2 and Ar 3 are independently selected from the structures shown in chemical formula (III-1) or (III-2), or a combination of chemical formula (III-1) or (III-2); when Ar 2 and Ar 3 When it is carbazole, X is selected from CR;

[0097] Ring A is a 5-membered or 6-membered aromatic ring or heteroaromatic ring; if Ring A contains nitrogen atoms, the nitrogen atoms cannot be directly bonded to each other;

[0098] Y1 is selected from single bond, O, S, Se, CR a R b NR a 、SiR a R b and BR a ;

[0099] R A At each occurrence, it independently represents a single substitution to the maximum number of substitutions allowed, or no substitution;

[0100] R, R a , R b , R, at each occurrence, is independently selected from H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted silyl group, or a substituted or unsubstituted keto group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups; one or more H in the above-mentioned various groups may be further substituted by D.

[0101] In a more preferred embodiment, the organic compound II has the following chemical formulas (IV-1) to (IV-16):

[0102]

[0103] Wherein: X and Y are defined as above.

[0104] In a preferred embodiment, the organic compound or organic compound II according to the present invention has ((LUMO+1)-LUMO) ≥ 0.1 eV, preferably ≥ 0.15 eV, more preferably ≥ 0.20 eV, even better ≥ 0.25 eV, and most preferably ≥ 0.30 eV.

[0105] In a more preferred embodiment, the organic compound or organic compound II according to the present invention has (HOMO-(HOMO+1))≥0.1eV, preferably ≥0.15eV, better still ≥0.20eV, even better still ≥0.25eV, and most preferably ≥0.30eV.

[0106] In another preferred embodiment, the organic compound or organic compound II according to the present invention has a ΔE ST (=E S1 -E T1 )≤0.4eV, preferably ≤0.3eV, more preferably ≤0.2eV, most preferably ≤0.1eV.

[0107] In a more preferred embodiment, the organic compound or organic compound II according to the present invention is at least partially deuterated, preferably ≥10% of the H is deuterated, more preferably ≥20% of the H is deuterated, most preferably ≥30% of the H is deuterated, and most preferably ≥40% of the H is deuterated.

[0108] Examples of organic compounds or organic compounds II according to the present invention are listed below, but are not limited to:

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] The present invention also provides an organic mixture comprising a first compound H1 and a second compound H2, wherein the second compound H2 is selected from the organic compounds according to the present invention.

[0118] In a preferred embodiment, the first compound H1 is selected from chemical formula (II-1) or (II-2):

[0119]

[0120] Ar1-Ar3 are 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 groups, wherein one or more of these groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded;

[0121] R1-R4 are substituents which, on each occurrence, may be identical or different and are selected from a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, wherein one or more of the groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded;

[0122] n1, n3, and n4 are independently selected from integers of 0 to 7; and n2 is selected from integers of 0 to 8.

[0123] In a preferred embodiment, the lowest unoccupied molecular orbital (LUMO) energy level (H1) of the first compound H1 is higher than the LUMO (H2) of the second compound H2.

[0124] In a preferred embodiment, the organic mixture, wherein the first compound H1 and the second compound H2 form a type II heterojunction structure, i.e., the highest occupied molecular orbital energy level (HOMO) (H1) of the first compound H1 is higher than the HOMO (H2) of the second compound H2, and the lowest unoccupied molecular orbital energy level (LUMO) (H1) of the first compound H1 is higher than the LUMO (H2) of the second compound H2. In certain embodiments, the energy gap of the first compound H1 is smaller than that of the second compound H2. In certain more preferred embodiments, the energy gap of the first compound H1 is larger than that of the second compound H2.

[0125] In certain embodiments, the organic mixture has HOMO(H1)≥HOMO(H2)+0.10 eV, and / or LUMO(H1)≥LUMO(H2)+0.10 eV.

[0126] In a more preferred embodiment, for the organic mixture, HOMO(H1)≥HOMO(H2)+0.20 eV, and / or LUMO(H1)≥LUMO(H2)+0.20 eV.

[0127] In a more preferred embodiment, for the organic mixture, HOMO(H1)≥HOMO(H2)+0.25eV, and / or LUMO(H1)≥LUMO(H2)+0.25eV.

[0128] In a most preferred embodiment, for the organic mixture, HOMO(H1)≥HOMO(H2)+0.30 eV, and / or LUMO(H1)≥LUMO(H2)+0.30 eV.

[0129] In certain embodiments, the first compound H1 and the second compound H2, wherein E ex =min(LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(E T1 (H1),E T1 (H2))+0.2eV, where HOMO(H1), LUMO(H1) and E T1 (H1) are the highest occupied molecular orbital, lowest unoccupied molecular orbital and triplet energy level of the first compound H1, HOMO (H2), LUMO (H2) and E T1 (H2) are the highest occupied molecular orbital, lowest unoccupied molecular orbital and triplet energy level of the second compound H2, respectively.

[0130] In a more preferred embodiment, E ex ≤min(E T1 (H1),E T1 (H2))+0.1eV, preferably ≤min(E T1 (H1),E T1 (H2)), particularly preferably ≤min(E T1 (H1),E T1 (H2))-0.1eV, the best is ≤min(E T1 (H1),E T1 (H2))-0.2eV.

[0131] In certain embodiments, E ex ≥2.6eV, preferably E ex ≥2.7eV, preferably E ex ≥2.75eV, especially E ex ≥2.8eV, the best is E ex ≥2.85eV.

[0132] In another preferred embodiment, the first compound H1 is selected from chemical formula (II-3):

[0133]

[0134] Ar4, Ar5, Ar6, and Ar7 independently represent an aromatic group or aromatic hetero group having 5 to 30 ring atoms;

[0135] X1 represents a single bond, NR7, CR8R9, SiR8R9, O, C=N(R7), C=C(R8R9), PR7, P(=O)R7, S,

[0136] S=O or SO2; X2 and X3 independently represent a single bond, NR7, CR8R9, SiR8R9, O, C=N(R7), C=C(R8R9), PR7, P(=O)R7, S, S=O or SO2, but X2 and X3 are not single bonds at the same time; R5-R9 independently represent H, D, F, CN, alkenyl, alkynyl, amine, nitro, acyl, alkoxy, carbonyl, sulfone, alkyl with 1 to 30 C atoms, cycloalkyl with 3 to 30 C atoms, aromatic hydrocarbon group or aromatic heterocyclic group with 5 to 60 ring atoms, wherein the connection position of R5 and R6 can be on any carbon atom on the condensed ring, and there can be any number of C atoms substituted by R5 and R6.

[0137] In a more preferred embodiment, the first compound H1 is selected from any one of chemical formulas (II-1a), (II-1b) or (II-2a):

[0138]

[0139] wherein Ar1-Ar3, R1-R4, and n1-n4 are as defined above.

[0140] In a particularly preferred embodiment, the first compound H1 is selected from chemical formula (II-1a) or (II-2a).

[0141] In a more preferred embodiment, the first compound H1 is selected from chemical formulas (II-3a) to (II-3e).

[0142]

[0143] X4 represents NR7, CR8R9, SiR8R9, O, C=N(R7), C=C(R8R9), PR7, P(=O)R7, S, S=O

[0144] Or SO2; X4 is preferably selected from NR7 or O; wherein Ar4, R7-R9 are as defined above.

[0145] In certain preferred embodiments, the above-mentioned Ar1, Ar2, and Ar3 are independently represented by substituted or unsubstituted aromatic groups or aromatic hetero groups with 5 to 30 ring atoms; in more preferred embodiments, Ar1, Ar2, and Ar3 are independently represented by substituted or unsubstituted aromatic groups or aromatic hetero groups with 5 to 20 ring atoms; in the most preferred embodiment, Ar1, Ar2, and Ar3 are independently represented by substituted or unsubstituted aromatic groups or aromatic hetero groups with 5 to 15 ring atoms.

[0146] In some preferred embodiments, the above-mentioned Ar1, Ar2, and Ar3 may comprise one or more combinations of the following structural groups:

[0147]

[0148] Among them, A 1 、A 2 、A 3 、A 4 、A 5 、A 6 、A 7 、A 8 Each independently represents CR 10 or N;

[0149] W 1 、W 2 Independently selected from CR 11 R 12 、SiR 11 R 12 NR 10 , C(=O), S or O;

[0150] R 10 、R 11 、R 12 The radicals may be selected, at each occurrence, identically or differently, from H, D, or straight-chain alkyl, alkoxy or thioalkoxy radicals having 1 to 20 C atoms, or branched or cyclic alkyl, alkoxy, thioalkoxy or silyl radicals having 3 to 20 C atoms, or keto radicals having 1 to 20 C atoms, or alkoxycarbonyl radicals having 2 to 20 C atoms, or aryloxycarbonyl radicals having 7 to 20 C atoms, or cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these radicals, where one or more of the radicals can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which the radicals are bonded.

[0151] In a more preferred embodiment, the above-mentioned Ar1, Ar2, and Ar3 comprise one of the following structural groups, wherein the H on the ring can be arbitrarily substituted:

[0152]

[0153] Furthermore, the above-mentioned Ar1, Ar2, and Ar3 are selected from benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, pyridine, pyrimidine, triazine, fluorene, dibenzothiazolidine, silylation, carbazole, thiophene, furan, thiazole, triphenylamine, triphenylphosphine, tetraphenylsilane, spirofluorene, spirosilicon fluorene and other groups and any combination thereof; more preferably, benzene, biphenyl, pyridine, pyrimidine, triazine, furan, carbazole and other groups and any combination thereof.

[0154] In a preferred embodiment, Ar2 or Ar3 in formula (II-2) or formula (II-2a) comprises an electron-withdrawing group, in particular a weak electron-withdrawing group, preferably selected from pyridine, pyrimidine or pyrazine.

[0155] In a more preferred embodiment, n1, n3, and n4 are 0, that is, there is no corresponding substitution.

[0156] In certain preferred embodiments, the substituents R1-R4 are independently selected from cyano, substituted or unsubstituted alkyl groups with 1 to 18 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3 to 18 carbon atoms, or substituted or unsubstituted aromatic or heteroaromatic ring systems with 5 to 30 ring atoms; in more preferred embodiments, R1-R4 are independently selected from substituted or unsubstituted alkyl groups with 1 to 12 carbon atoms, or substituted or unsubstituted aromatic or heteroaromatic ring systems with 5 to 20 ring atoms; in the most preferred embodiments, R1-R4 are independently selected from substituted or unsubstituted alkyl groups with 1 to 6 carbon atoms, or substituted or unsubstituted aromatic or heteroaromatic ring systems with 5 to 15 ring atoms.

[0157] In certain embodiments, E T1 (H1) ≥ 2.7 eV, preferably ≥ 2.8 eV, more preferably ≥ 2.85 eV, most preferably ≥ 2.9 eV.

[0158] In a preferred embodiment, the exciplex formed between the first compound H1 and the second compound H2 has a singlet energy level E S1 and triplet energy level E T1 The difference is ≤0.3 eV, preferably ≤0.25 eV, more preferably ≤0.2 eV, particularly preferably ≤0.15 eV.

[0159] Preferred examples of the first compound H1 according to the chemical formula (II-1), (II-1a), (II-1b), (II-2) and (II-2a) are shown below, but are not limited to:

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166] In certain embodiments, E T1 (H2) ≥ 2.65 eV, preferably ≥ 2.7 eV, more preferably ≥ 2.75 eV, most preferably ≥ 2.85 eV.

[0167] In certain embodiments, the aforementioned Ar, Ar1-Ar3, R, R1-R4 may further comprise the following chemical formula (A):

[0168]

[0169] Wherein L1 is selected from a single bond or any divalent linking group; the dotted line represents the linking bond; Ar8-Ar 10 is selected from a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 30 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 30 ring atoms, or a combination of these groups; preferably a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these groups; more preferably a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 15 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 15 ring atoms, or a combination of these groups.

[0170] In a very preferred embodiment, the organic mixture is used for the light-emitting layer of an organic electroluminescent device. In some embodiments, due to stability or process considerations, there may be some special requirements for the first compound H1 and the second compound H2.

[0171] In a preferred embodiment, according to the organic mixture of the present invention, at least one of the first compound H1 and the second compound H2 has ((LUMO+1)-LUMO) ≥ 0.1eV, preferably ≥ 0.15eV, better ≥ 0.20eV, even better ≥ 0.25eV, and most preferably ≥ 0.30eV.

[0172] In a more preferred embodiment, according to the organic mixture of the present invention, the second compound H2 has ((LUMO+1)-LUMO) ≥ 0.1eV, preferably ≥ 0.15eV, better ≥ 0.20eV, even better ≥ 0.25eV, and most preferably ≥ 0.30eV.

[0173] In another preferred embodiment, according to the organic mixture of the present invention, at least one of the first compound H1 and the second compound H2 has a (HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.25 eV, better ≥ 0.30 eV, even better ≥ 0.35 eV, and most preferably ≥ 0.40 eV.

[0174] In another more preferred embodiment, according to the organic mixture of the present invention, the first compound H1 has (HOMO-(HOMO-1)) ≥ 0.2eV, preferably ≥ 0.25eV, better ≥ 0.30eV, even better ≥ 0.35eV, and most preferably ≥ 0.40eV.

[0175] In a preferred embodiment, in the organic mixture, the molar ratio of the first compound H1 to the second compound H2 is from 2:8 to 8:2; the preferred molar ratio is 3:7 to 7:3; and the more preferred molar ratio is 4:6 to 6:4.

[0176] In a preferred embodiment, at least one of the first compound H1 and the second compound H2 in the organic mixture of the present invention has a glass transition temperature (Tg) ≥ 100°C; in a more preferred embodiment, at least one has a Tg ≥ 120°C; in a more preferred embodiment, at least one has a Tg ≥ 140°C; in a further more preferred embodiment, at least one has a Tg ≥ 160°C; in a most preferred embodiment, at least one has a Tg ≥ 180°C.

[0177] In a more preferred embodiment, at least one of the first compound H1 and the second compound H2 in the organic mixture according to the present invention is partially H-deuterated, preferably ≥10% H-deuterated, more preferably ≥20% H-deuterated, most preferably ≥30% H-deuterated, and most preferably ≥40% H-deuterated.

[0178] In a preferred embodiment, in the organic mixture according to the present invention, both the first compound H1 and the second compound H2 are small molecule materials.

[0179] One object of the present invention is to provide a material solution for vapor deposition type OLEDs.

[0180] In a preferred embodiment, the organic mixture according to the present invention is used in an evaporation-type OLED device. For this purpose, the molecular weight of the first compound H1 and the second compound H2 in the organic mixture material according to the present invention is ≤1000 g / mol, preferably ≤900 g / mol, very preferably ≤850 g / mol, more preferably ≤800 g / mol, and most preferably ≤700 g / mol.

[0181] The following are more important preferred embodiments:

[0182] Embodiment I: The organic mixture, wherein the difference in molecular weight between the first compound H1 and the second compound H2 does not exceed 80 Dalton; preferably, the difference in molecular weight does not exceed 60 Dalton; more preferably, the difference in molecular weight does not exceed 30 Dalton.

[0183] Embodiment II: The organic mixture, wherein the difference in sublimation temperature between the first compound H1 and the second compound H2 is no more than 30K; preferably, the difference in sublimation temperature is no more than 20K; more preferably, the difference in sublimation temperature is no more than 10K.

[0184] Example III: The organic mixture, wherein the difference in evaporation rate between the first compound H1 and the second compound H2 at a certain vacuum degree and a certain evaporation temperature does not exceed 5% (based on the evaporation rate of the first compound H1), more preferably does not exceed 4%, and most preferably does not exceed 3%.

[0185] The present invention also relates to an organic mixture, in particular to a preparation method (premix preparation method) according to Example I and / or Example II and / or Example III: a first compound H1 and a second compound H2 in a certain mass ratio are mixed as uniformly as possible, and then the mixture is placed in a temperature less than or equal to 10 -3 In a vacuum environment of Torr, the temperature in the vacuum environment is increased to completely melt the two main materials, and after being mixed evenly, the mixture is cooled to room temperature to solidify, and then ground into powder using a ball mill for standby use.

[0186] Another object of the present invention is to provide a material solution for printed OLEDs.

[0187] For this purpose, at least one, preferably both, of the first compound H1 and the second compound H2 in the organic mixture according to the invention have a molecular weight of ≥700 g / mol, preferably ≥800 g / mol, more preferably ≥900 g / mol, even more preferably ≥1000 g / mol, and most preferably ≥1100 g / mol.

[0188] In a premixed co-host in vapor-deposited OLEDs, the two host materials are required to have 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 may enhance film-forming performance, thereby improving device performance. In addition to molecular weight and sublimation temperature, these properties may also include other properties, such as glass transition temperature and molecular volume. Therefore, for printed OLEDs, preferred embodiments of the organic mixture according to the present invention include:

[0189] The difference in molecular weight between the first compound H1 and the second compound H2 is ≥120 g / mol, preferably ≥140 g / mol, more preferably ≥160 g / mol, most preferably ≥180 g / mol.

[0190] The difference in sublimation temperature between the first compound H1 and the second compound H2 is ≥60K, preferably ≥70K, more preferably ≥75K, most preferably ≥80K.

[0191] The difference in glass transition temperature between the first compound H1 and the second compound H2 is ≥20K, preferably ≥30K, more preferably ≥40K, most preferably ≥45K.

[0192] The difference in molecular volume between the first compound H1 and the second compound H2 is ≥20%, preferably ≥30%, more preferably ≥40%, and most preferably ≥45%.

[0193] In other embodiments, at least one, and preferably both, of the first compound H1 and the second compound H2 in the organic 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.

[0194] 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 most preferably ≤1500 g / mol.

[0195] 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.].

[0196] Conjugated polymer is a polymer whose main chain backbone is mainly composed of sp 2 Hybrid orbitals are formed. Famous examples include polyacetylene and poly(phenylene vinylene). The C atoms on the main chain can also be replaced by other non-C atoms, and when the sp 2 When hybridization is interrupted by some natural defects, it is still considered a conjugated polymer. In addition, the conjugated polymers in the present invention also include those containing aryl amines, aryl phosphine, other heteroaromatics, organometallic complexes, etc. in the main chain.

[0197] In a particularly preferred embodiment, the organic mixture further comprises another organic functional material. The another organic functional material comprises a hole (also known as an electron hole) injection or transport material (HIM / HTM), a hole blocking material (HBM), an electron injection or transport material (EIM / ETM), an electron blocking material (EBM), an organic host material (Host), a singlet light emitter (fluorescent light emitter), a triplet light emitter (phosphorescent light emitter), an organic thermally excited delayed fluorescence material (TADF material), and in particular a luminescent organometallic complex. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1, and WO2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein by reference. The organic functional material can be a small molecule or a polymer material.

[0198] In certain preferred embodiments, the organic mixture further comprises a light-emitting body, and the light-emitting body is selected from phosphorescent light-emitting bodies or TADF materials.

[0199] In a preferred embodiment, the organic mixture further comprises a phosphorescent light emitting body, wherein the weight percentage of the phosphorescent light emitting body is ≤20 wt%, preferably ≤15 wt%, and more preferably ≤10 wt%.

[0200] Phosphorescent emitters are also called triplet emitters. In a preferred embodiment, the phosphorescent emitter has the general formula M(L): n wherein M is a metal atom, L can be the same or different at each occurrence, is an organic ligand, which is bonded or coordinated to the metal atom M through one or more positions, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Optionally, these metal complexes are linked to a polymer through one or more positions, preferably through the organic ligand.

[0201] In a preferred embodiment, the metal atom M is selected from transition metal elements, lanthanides or actinides, preferably from Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, particularly preferably from Os, Ir, Ru, Rh, Re, Pd or Pt, most preferably from Ir, Pt.

[0202] Typically, phosphorescent emitters contain chelating ligands, i.e., ligands that coordinate to the metal via at least two binding sites. Triplet emitters are particularly preferred, containing two or three identical or different bidentate or multidentate ligands. Chelating ligands contribute to improving the stability of the metal complex.

[0203] 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, by fluorine-containing or trifluoromethyl groups. The auxiliary ligand may preferably be selected from acetic acid, acetone or picric acid.

[0204] In a preferred embodiment, the metal complex useful as triplet emitter has the following form:

[0205]

[0206] The metal atom M1 is selected from transition metal elements, lanthanides or actinides, preferably from Ir, Pt, Pd, Au, Rh, Ru, Os, Re, Cu, Ag, Ni, Co, W or Eu, and particularly preferably from Ir, Au, Pt, W or Os.

[0207] Ar 01 、Ar 02 Each occurrence may be the same or different and is a cyclic group wherein Ar 01Contains at least one donor atom, that is, an atom with a lone pair of electrons, such as nitrogen, through which the cyclic group is coordinated with the metal; 02 Contains at least one carbon atom through which the cyclic group is connected to the metal; Ar 01 and Ar 02 They are linked together by covalent bonds and may each carry one or more substituents, which may be further linked together by substituents. L' may be the same or different at each occurrence and is a bidentate chelating auxiliary ligand, preferably a monoanionic bidentate chelating ligand. q1 may be 0, 1, 2, or 3, preferably 2 or 3; q2 may be 0, 1, 2, or 3, preferably 1 or 0. Examples of organic ligands may be selected from phenylpyridine derivatives or 7,8-benzoquinoline derivatives. All of these organic ligands may be substituted, for example, with alkyl chains or fluorine- or silicon-containing substitutions. The auxiliary ligand may preferably be selected from acetone acetate or picric acid.

[0208] In a particularly preferred embodiment, the phosphorescent emitter is a transition metal complex (preferably a metal complex of Ir or Pt) and comprises at least one ligand or part of a ligand selected from the group consisting of:

[0209]

[0210]

[0211]

[0212] Wherein, T is selected from B, Al, Ga or In; K 1’ Is a direct bond selected from NR e PR e , O, S or Se; Y 1 -Y 15 are selected from C or N; Y' is selected from BR e NR e PR e ,O,S,Se,C=O,C=S,C=Se,C=NR e 、C=CR e R f 、S=O、SO2、CR e R f 、P(O)R e 、SiR e R f or GeR e R f ; R e and R f Can be fused or linked to form a ring; R a , R b , R c and Rd are represented as a single to the maximum possible number of substituents or unsubstituted, respectively;

[0213] R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f are independently selected from H, D, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, arylalkyl, alkoxy, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfonamide, sulfoxide, phosphorus, seleno or a combination thereof; and R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d Any two adjacent substituents may be fused or linked to form a ring or to form a multidentate ligand.

[0214] Examples of some phosphorescent materials and their applications can be found in the following patent documents and literature: WO200070655, WO200141512, WO200202714, WO200215645, EP1191613, EP1191612, EP1191614, WO2005033244, WO2005019373, US20050258742, WO2009146 770, WO2010015307, WO2010031485, WO2010054731, WO2010054728, WO2010086089, WO20100998 52, WO2010102709, US20070087219A1, US20090061681A1, US20010053462A1, Baldo, Thompsonnet al.Nature 403,(2000),750-753, Adachi et al.Appl.Phys.Lett.78(2001),1622-1624, J.Kido et al.Appl.Phys.Lett.65(1994),2124, Kido et al. al.Chem.Lett.657,1990,US20070252517A1,Johnson et al.,JACS105,1983,1795,Wrighton,JACS 96,1974,998,Maet al.,Synth.Metals The entire contents of the above-listed patent documents and literature are hereby incorporated by reference into this document.

[0215] Some examples of suitable metal complexes as phosphorescent emitters are listed below, but are not limited to:

[0216]

[0217]

[0218]

[0219] In another preferred embodiment, the organic mixture further comprises a fluorescent light emitting body, wherein the weight percentage of the fluorescent light emitting body is ≤15 wt%, preferably ≤10 wt%, and more preferably ≤8 wt%.

[0220] In another preferred embodiment, the organic mixture further comprises a TADF luminescent material, wherein the weight percentage of the TADF luminescent material is ≤15 wt%, preferably ≤10 wt%, and more preferably ≤8 wt%.

[0221] The following is a more detailed description of fluorescent luminescent materials (singlet luminophores) and TADF luminescent materials (but not limited to these).

[0222] 1. Singlet Emitter

[0223] Singlet emitters often have longer conjugated π-electron systems. To date, there have been many examples, such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729A1, and indenofluorene and its derivatives disclosed in WO2008 / 006449 and WO2007 / 140847.

[0224] In a preferred embodiment, the singlet emitter can be selected from monostyrylamine, distyrylamine, tertiary styrylamine, tetrastyrylamine, styrylphosphine, styryl ether and aromatic amine.

[0225] 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 pyrenamines, 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.

[0226] Examples of singlet emitters based on vinylamine and aromatic amine, which are also preferred examples, can be found in the following patent documents: WO2006 / 000388, WO2006 / 058737, WO2006 / 000389, WO2007 / 065549, WO2007 / 115610, US7250532B2, DE102005058557A1, CN1583691A, JP08053397A, US6251531B1, US2006 / 210830A, EP1957606A1 and US2008 / 0113101A1. The entire contents of the above-mentioned patent documents are hereby incorporated herein by reference.

[0227] Examples of singlet emitters based on stilbene and its derivatives are disclosed in US Pat. No. 5,121,029.

[0228] Further preferred singlet emitters can be selected from indenofluorene-amine and indenofluorene-diamine, as disclosed in WO2006 / 122630; benzoindenofluorene-amine and benzoindenofluorene-diamine, as disclosed in WO2008 / 006449; dibenzoindenofluorene-amine and dibenzoindenofluorene-diamine, as disclosed in WO2007 / 140847.

[0229] Other materials that can be used as singlet emitters include polycyclic aromatic hydrocarbon compounds, especially derivatives of the following compounds: anthracenes such as 9,10-di(2-naphthyl)anthracene, naphthalene, tetracene, xanthene, phenanthrene, pyrene (such as 2,5,8,11-tetra-t-butylperylene), indenopyrene, benzo-fused rings such as (4,4'-bis(9-ethyl-3-carbazolylvinyl)-1,1'-biphenyl), diindenopyrene, decacycloene, hexabenzophenone, fluorene, spirobifluorene, arylpyrene (such as US20060222886), arylenevinylene (such as US5121 [029, US5130603]), cyclopentadienes such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyrans such as 4-(dicyanomethylene)-6-(4-(p-dimethylaminophenyl)-2-methyl)-4H-pyran (DCM), thiopyrans, bis(azinyl)imine boron compounds (US2007 / 0092753A1), bis(azinyl)methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles, and diketopyrrolopyrroles. Some materials for singlet emitters can be found in the following patent documents: US20070252517A1, US4769292, and US6020078. The entire contents of the above-listed patent documents are hereby incorporated herein by reference.

[0230] Some examples of suitable singlet emitters are listed below:

[0231]

[0232] 2. Thermally activated delayed fluorescence materials (TADF materials)

[0233] Traditional organic fluorescent materials can only utilize 25% of singlet excitons formed by electrical excitation to emit light, and the internal quantum efficiency of the device is low (up to 25%). Although phosphorescent materials enhance intersystem crossing due to the strong spin-orbit coupling of heavy atom centers, they can effectively utilize singlet excitons and triplet excitons formed by electrical excitation to emit light, so that the internal quantum efficiency of the device reaches 100%. However, the high cost of phosphorescent materials, poor material stability, and severe device efficiency roll-off limit their application in OLEDs. Thermally activated delayed fluorescence luminescent materials are the third generation of organic light-emitting materials developed after organic fluorescent materials and organic phosphorescent materials. This type of material generally has a small singlet-triplet energy level difference (ΔE ST ), triplet excitons can be converted to singlet excitons through antisystem crossing to emit light. This fully utilizes both singlet and triplet excitons formed by electrical excitation, achieving a device internal quantum efficiency of 100%. Furthermore, the material boasts controllable structure, stable properties, low cost, and the absence of precious metals, promising broad application prospects in the OLED field.

[0234] TADF materials need to have a small singlet-triplet energy level difference, preferably ΔE ST <0.3eV, the next best is ΔE ST <0.25eV, preferably ΔE ST <0.20eV, preferably ΔE ST <0.1 eV. In a 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.,49,2013,10385,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.

[0235] Some examples of suitable TADF emitters are listed below:

[0236]

[0237] In certain embodiments, the organic mixture according to the present invention has a solubility in toluene at 25° C. of ≥10 mg / mL, preferably ≥15 mg / mL, and most preferably ≥20 mg / mL.

[0238] The present invention further relates to a composition or ink comprising an organic compound or organic mixture as described above, and at least one organic solvent.

[0239] 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.

[0240] In a preferred embodiment, the surface tension of the ink according to the present invention at operating temperature or at 25°C is approximately in the range of 19 dyne / cm to 50 dyne / cm; more preferably in the range of 22 dyne / cm to 35 dyne / cm; and most preferably in the range of 25 dyne / cm to 33 dyne / cm.

[0241] In another preferred embodiment, the viscosity of the ink according to the present invention at operating temperature or 25° C. is in the range of about 1 cps to 100 cps; preferably, in the range of 1 cps to 50 cps; more preferably, in the range of 1.5 cps to 20 cps; and most preferably, in the range of 4.0 cps to 20 cps. Such a formulated composition will facilitate inkjet printing.

[0242] 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 containing the organic compound or mixture 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 contained in the composition of the present invention is in the range of 0.3 wt% to 30 wt%, preferably in the range of 0.5 wt% to 20 wt%, more preferably in the range of 0.5 wt% to 15 wt%, even more preferably in the range of 0.5 wt% to 10 wt%, and most preferably in the range of 1 wt% to 5 wt%.

[0243] In some embodiments, according to the ink of the present invention, the at least one organic solvent is selected from aromatic or heteroaromatic based solvents, in particular aliphatic chain / ring substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

[0244] Examples of solvents suitable for the present invention include, but are not limited to: aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4- ... ,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, etc.; ketone-based solvents: 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, isophorone, 2,6,8-trimethyl-4-nonanone, fenchone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, phorone, di-n-amyl ketone; aromatic ether solvents: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, 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-ethylphenyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene , glycidyl phenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, 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; ester solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc.

[0245] Further, according to the ink 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, phorone, 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.

[0246] In some other embodiments, the printing ink further comprises another organic solvent. Examples of the other organic solvent include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, 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.

[0247] In a preferred embodiment, the composition according to the present invention is a solution.

[0248] In another preferred embodiment, the composition according to the present invention is a suspension.

[0249] The composition in the embodiment of the present invention may include 0.01wt% to 20wt% of the organic compound or organic mixture according to the present invention, preferably 0.1wt% to 15wt%, more preferably 0.2wt% to 10wt%, and most preferably 0.25wt% to 5wt% of the organic compound or organic mixture.

[0250] The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, and particularly preferably a preparation method by printing or coating.

[0251] Among them, suitable printing or coating techniques include (but are not limited to) gravure printing, inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, twist roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing or pad printing, slot extrusion coating, etc. Gravure printing, nozzle printing and inkjet printing are preferred. The solution or suspension may further include one or more components such as surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, adhesives, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. For detailed information on printing techniques and their requirements for relevant solutions, such as solvents and concentrations, viscosity, etc., please refer to "Handbook of Print Media: Technologies and Production Methods" edited by Helmut Kipphan, ISBN 3-540-67326-1.

[0252] Based on the above-mentioned organic mixture and organic compound, the present invention further provides an application of the above-mentioned organic mixture and organic compound, i.e., applying the organic mixture or organic compound to an organic electronic device. The organic electronic device may be selected from, but not limited to, an organic light-emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light-emitting cell (OLEEC), an organic field-effect transistor (OFET), an organic light-emitting field-effect transistor (OLED), an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode (OPED), in particular an OLED. In an embodiment of the present invention, the organic mixture or organic compound is preferably used in the light-emitting layer of an OLED device.

[0253] The present invention further provides a photovoltaic device comprising at least one organic compound or organic mixture as described above.

[0254] In some preferred embodiments, the optoelectronic device is an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic sensor or an organic plasmon emitting diode (Organic Plasmon Emitting Diode).

[0255] In some more preferred embodiments, the optoelectronic device is an organic electroluminescent device and comprises a substrate, an anode, at least one light-emitting layer, a cathode, and optionally a hole transport layer or an electron transport layer. In certain embodiments, the hole transport layer comprises an organic compound, organic mixture, or polymer according to the present invention. In a preferred embodiment, the light-emitting layer comprises an organic compound or organic mixture according to the present invention. More preferably, the light-emitting layer comprises an organic compound or organic mixture according to the present invention and at least one light-emitting material, wherein the light-emitting material may be a fluorescent emitter, a phosphorescent emitter, or a TADF material.

[0256] The device structure of the organic electroluminescent device is described below, but is not limited thereto.

[0257] The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting device. 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).

[0258] 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), 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, 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.

[0259] 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 are possible 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 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.

[0260] 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.

[0261] In a preferred embodiment, in the organic electroluminescent device according to the present invention, the light-emitting layer thereof comprises the organic compound or organic mixture of the present invention.

[0262] In another preferred embodiment, the light-emitting layer of the organic electroluminescent device can be formed by one of the following two methods: (1) the first compound H1 and the second compound H2 containing a co-host are deposited as one source; (2) the first compound H1 and the second compound H2 are evaporated as two separate sources.

[0263] In another preferred embodiment, in the organic electroluminescent device according to the present invention, the electron transport layer thereof comprises the organic compound or organic mixture of the present invention.

[0264] According to the organic electroluminescent device of the present invention, the emission wavelength is between 300nm and 1000nm, preferably between 350nm and 900nm, and more preferably between 400nm and 800nm.

[0265] 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.

[0266] Example

[0267] 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.

[0268] 1. Synthesis of compounds

[0269] Synthesis of compound 1:

[0270]

[0271] Under nitrogen, a three-necked flask was charged with 1a (50g), 1b (50g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (1g), and 300mL of toluene / 50mL of ethylene glycol ethyl ether / 50mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12 hours, and the temperature was cooled. The product was extracted with ethyl acetate and deionized water, the organic phase was washed twice, dried, filtered, and the filtrate was evaporated to dryness to obtain 25g of crude intermediate 1c. Column chromatography (petroleum ether / ethyl acetate = 15:1) was used to collect 20g of intermediate 1c. The yield was 40%. The molecular mass of the ion was determined by mass spectrometry to be 267.8 (calculated value: 267.78).

[0272] In a dry three-necked flask, intermediate 1c (20 g) and dichloromethane (250 mL) were added, the temperature was lowered to below 0°C, 50 mL of boron tribromide was added dropwise, the temperature was naturally raised after the addition, and the reaction was stopped by heating under reflux for 12 h. Ethanol was added dropwise under ice bath to quench the reaction, and the mixture was extracted with dichloromethane and deionized water. The mixture was washed twice with deionized water, dried, filtered, and the filtrate was spin-dried to obtain 18.9 g of crude intermediate 1d, which was used directly in the next reaction without other treatment.

[0273] In a dry three-necked flask, intermediate 1d (50 g), DMF (500 mL) and cesium carbonate (15 g) were added and heated under reflux for 24 h to stop the reaction. The mixture was extracted with dichloromethane and deionized water, washed twice with deionized water, dried, filtered, and the filtrate was spin-dried to obtain 30 g of crude intermediate 1e, which was used directly in the next reaction without further treatment.

[0274] To a dry three-necked flask, add intermediate 1e (20 g), dichloromethane (300 mL), and triethylamine (15 g). Cool the mixture to below 0°C and dropwise add 100 g of trifluoromethanesulfonic anhydride. Once the addition is complete, allow the mixture to warm to room temperature. Monitor the reaction progress by MS (ethanol quenching and injection) and stop the reaction. Quench the mixture dropwise with ethanol in an ice bath. Extract the mixture with dichloromethane and deionized water, wash three times with water, dry, filter, and spin-dry the filtrate. Prepare the sample for column chromatography. Use petroleum ether / ethyl acetate as the eluent, concentrate, collect, and dry to yield 18 g of intermediate 1f.

[0275] Under nitrogen, a three-necked flask was charged with intermediate 1f (50g), phenylboronic acid (60g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (1g), and 300mL of toluene / 50mL of ethylene glycol ethyl ether / 50mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12 hours, and the temperature was cooled. The reaction was extracted with ethyl acetate and deionized water, the organic phase was washed twice, dried, filtered, and the filtrate was spin-dried to obtain 40g of crude product 1h. Column chromatography (petroleum ether / ethyl acetate = 15:1) was used to collect 38g of the product intermediate 1h. The yield was 76%, and mass spectrometry analysis determined the molecular mass of 279 (calculated value: 279.72).

[0276] To a dry three-necked flask, add intermediate 1h (12 g), pinacol diboronate (15 g), potassium acetate (15 g), catalyst Pd(dppf)Cl2 (1 g), and toluene (300 mL). The atmosphere was replaced with nitrogen three times, and the temperature was raised to 100°C. The reaction was stirred and refluxed for 24 h. The reaction was terminated and separated by column chromatography (petroleum ether / ethyl acetate = 25:1). The product, intermediate 1i, was collected to yield 10.1 g. The yield was 90%. The molecular mass determined by mass spectrometry was 371 (calculated value: 371.24).

[0277] Under nitrogen, a three-necked flask was charged with intermediate 1i (10g), intermediate 1j (13g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (1g), and 300mL toluene / 50mL ethanol / 50mL water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12 hours, and the temperature was cooled. The product was extracted with ethyl acetate and deionized water, the organic phase was washed twice, dried, filtered, and the filtrate was spin-dried to obtain 10.2g of crude compound 1. Column chromatography (petroleum ether / ethyl acetate = 15:1) collected compound 1 to yield 9g. The yield was 90%, and the molecular mass determined by mass spectrometry was 565 (calculated value: 565.64).

[0278] Synthesis of compound 2:

[0279]

[0280] Under nitrogen, a three-necked flask was charged with 2a (50 g), 2b (50 g), potassium carbonate (25 g), tetrakistriphenylphosphine palladium (1 g), and 300 mL of toluene / 50 mL of ethylene glycol ethyl ether / 50 mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12 h, and the temperature was cooled. The product was extracted with ethyl acetate and deionized water, the organic phase was washed twice, dried, filtered, and the filtrate was spin-dried to obtain 20 g of crude intermediate 2c. Column chromatography (petroleum ether / ethyl acetate = 15:1) was used to collect intermediate 2c to yield 18 g. The yield was 36%. Mass spectrometry analysis determined the molecular mass of 282 (calculated value: 282.11).

[0281] In a dry three-necked flask, intermediate 2c (20 g) and dichloromethane (250 mL) were added, the temperature was lowered to below 0°C, 50 mL of boron tribromide was added dropwise, the temperature was naturally raised after the addition, and the reaction was stopped by heating under reflux for 12 h. Ethanol was added dropwise under ice bath to quench the reaction, and the mixture was extracted with dichloromethane and deionized water. The mixture was washed twice with deionized water, dried, filtered, and the filtrate was spin-dried to obtain 18.9 g of crude intermediate 2d, which was used directly in the next reaction without other treatment.

[0282] To a dry three-necked flask, intermediate 2d (50 g), DMF (500 mL), and cesium carbonate (15 g) were added. The reaction was terminated by heating under reflux for 24 h. The mixture was extracted with dichloromethane and deionized water, washed twice with deionized water, dried, filtered, and the filtrate was spin-dried to obtain 30 g of crude intermediate 2e. This was separated by column chromatography (petroleum ether / ethyl acetate = 15:1) to obtain 26 g of intermediate 2e. The yield was 52%. Mass spectrometry analysis determined the molecular mass of 248 (calculated value: 248.08).

[0283] To a dry three-necked flask, intermediate 2e (15 g), pinacol diboronate (15 g), potassium acetate (15 g), catalyst Pd(dppf)Cl2 (1 g), and toluene (300 mL) were added. The atmosphere was replaced with nitrogen three times, and the temperature was raised to 100°C. Stirring and refluxed for 24 h, the reaction was terminated. The product, intermediate 2f, was collected by column chromatography (petroleum ether / ethyl acetate = 25:1), yielding 12 g. The yield was 80%. The molecular mass of the product, determined by mass spectrometry, was 295 (calculated value: 295.15).

[0284] Under nitrogen, a three-necked flask was charged with intermediate 2f (10g), intermediate 2h (13g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (1g), and 300mL toluene / 50mL ethanol / 50mL water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12 hours, and the temperature was cooled. The product was extracted with ethyl acetate and deionized water, the organic phase was washed twice, dried, filtered, and the filtrate was evaporated to dryness to obtain 11g of crude compound 2. Column chromatography (petroleum ether / ethyl acetate = 15:1) collected compound 2 to yield 9.5g. The yield was 95%. The molecular mass of the product was 578 (calculated value: 578.64) as determined by mass spectrometry.

[0285] Synthesis of compound 3:

[0286]

[0287] Under nitrogen, a three-necked flask was charged with 3a (50 g), 3b (50 g), potassium carbonate (25 g), tetrakistriphenylphosphine palladium (1 g), and 300 mL of toluene / 50 mL of ethylene glycol ethyl ether / 50 mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12 h, and the temperature was cooled. The product was extracted with ethyl acetate and deionized water, the organic phase was washed twice, dried, filtered, and the filtrate was spin-dried to obtain 22 g of crude intermediate 3c. Column chromatography (petroleum ether / ethyl acetate = 15:1) was performed to collect 20 g of intermediate 3c. The yield was 40%. Mass spectrometry analysis determined the molecular mass of 282 (calculated value: 282.11).

[0288] In a dry three-necked flask, intermediate 3c (20 g) and dichloromethane (250 mL) were added, and the temperature was lowered to below 0°C. 50 mL of boron tribromide was added dropwise. After the addition was complete, the temperature was naturally raised and the reaction was stopped by heating under reflux for 12 h. Ethanol was added dropwise under ice bath to quench the reaction. The mixture was extracted with dichloromethane and deionized water, washed twice with deionized water, dried, filtered, and the filtrate was spin-dried to obtain 17.6 g of crude intermediate 3d, which was used directly in the next reaction without further treatment.

[0289] To a dry three-necked flask, intermediate 3d (50 g), DMF (500 mL), and cesium carbonate (15 g) were added. The reaction was terminated by heating under reflux for 24 h. The mixture was extracted with dichloromethane and deionized water, washed twice with deionized water, dried, filtered, and the filtrate was evaporated to dryness to obtain 40 g of crude intermediate 3e. This product was separated by column chromatography (petroleum ether / ethyl acetate = 15:1) to obtain 18 g of intermediate 3e. The yield was 36%. Mass spectrometry analysis determined the molecular mass of 248 (calculated value: 248.08).

[0290] To a dry three-necked flask, intermediate 3e (15 g), pinacol diboronate (15 g), potassium acetate (15 g), catalyst Pd(dppf)Cl2 (1 g), and toluene (300 mL) were added. The atmosphere was replaced with nitrogen three times, and the temperature was raised to 100°C. The reaction was stirred and refluxed for 24 h. The reaction was terminated and separated by column chromatography (petroleum ether / ethyl acetate = 25:1). The product, intermediate 3f, was collected to yield 14 g. The yield was 93.3%. The molecular mass determined by mass spectrometry was 295 (calculated value: 295.15).

[0291] Under nitrogen, a three-necked flask was charged with intermediate 3f (10g), intermediate 3h (synthesized according to literature: DOI: 10.1039 / D0TC05395C) (13g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (1g), and 300mL toluene / 50mL ethanol / 50mL water. The atmosphere was replaced with nitrogen three times, and the reaction temperature was raised to 100°C. The reaction was stopped by heating under reflux for 12 hours, and the temperature was then cooled. The product was extracted with ethyl acetate and deionized water. The organic phase was washed twice with water, dried, filtered, and the filtrate was spin-dried to obtain 10g of crude compound 3. Column chromatography (petroleum ether / ethyl acetate = 15:1) collected compound 3 to yield 9g. The yield was 90%, and the molecular mass determined by mass spectrometry was 577 (calculated value: 577.65).

[0292] Synthesis of compound 4:

[0293]

[0294] To a dry three-necked flask, add intermediate 4a (20 g), pinacol diboronate (15 g), potassium acetate (15 g), catalyst Pd(dppf)Cl2 (1 g), and toluene (300 mL). The atmosphere was replaced with nitrogen three times, and the temperature was raised to 100°C. Stirring and refluxed for 24 h allowed the reaction to terminate. The product 4b was separated by column chromatography (petroleum ether / ethyl acetate = 25:1) to yield 10 g. The yield was 5%.

[0295] Under nitrogen, a three-necked flask was charged with 4b (50g), intermediate 2h (50g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (1g), and 300mL of toluene / 50mL of ethylene glycol ethyl ether / 50mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was stopped by heating under reflux for 12h. The temperature was then lowered. The product was extracted with ethyl acetate and deionized water, and the organic phase was washed twice with water, dried, filtered, and the filtrate was evaporated to dryness to obtain 30g of crude intermediate 4d. Column chromatography (petroleum ether / ethyl acetate = 15:1) was used to collect 25g of intermediate 4d. The yield was 50%.

[0296] To a dry three-necked flask were added intermediate 4d (20 g), carbazole (30 g), sodium tert-butoxide (2 g), catalyst Pd(dppf)Cl2 (1 g), tri-tert-butylphosphine (1 g), and toluene (300 mL). The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the mixture was stirred and refluxed for 24 h. The reaction was terminated and separated by column chromatography (petroleum ether / ethyl acetate = 25:1) to obtain 9 g of compound 4. The yield was 45%. Mass spectrometry analysis determined the molecular ion mass to be 742 (calculated value: 742.84).

[0297] Synthesis of compound 5:

[0298]

[0299] The synthesis method of compound 5 is similar to that of compound 4, except that intermediate 5a is used instead of intermediate 4a to obtain compound 5 with a yield of 65%.

[0300] Synthesis of compound 6:

[0301]

[0302] The synthesis method of compound 6 is similar to that of compound 4, except that intermediate 6a is used instead of intermediate 2h to obtain compound 6 with a yield of 47%.

[0303] Synthesis of compound 7:

[0304]

[0305] The synthesis method of compound 7 is similar to that of compound 5, except that intermediate 7b is used instead of intermediate carbazole to obtain compound 7 with a yield of 78%.

[0306] Synthesis of compound 8:

[0307]

[0308] The synthesis method of compound 8 is similar to that of compound 4, except that intermediate 8a is used instead of intermediate 2h to obtain compound 8 with a yield of 63%.

[0309] Synthesis of compound 9:

[0310]

[0311] In a dry three-necked flask, add 9a (20g), diboronic acid pinacol ester (15g), potassium acetate (15g), catalyst Pd(dppf)Cl2 (1g), and toluene (300mL). Replace the atmosphere with nitrogen three times, raise the temperature to 100°C, and stir under reflux for 24h to terminate the reaction. Separate by column chromatography (petroleum ether / ethyl acetate = 25:1) to collect the product 9b, yielding 11g. Yield: 51%.

[0312] Under nitrogen, a three-necked flask was charged with 9b (50g), intermediate 2h (50g), potassium carbonate (25g), tetrakistriphenylphosphine palladium (1g), and 300mL of toluene / 50mL of ethylene glycol ethyl ether / 50mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the reaction was stopped by heating under reflux for 12 hours. The temperature was then lowered. The product was extracted with ethyl acetate and deionized water, and the organic phase was washed twice with water, dried, filtered, and the filtrate was evaporated to dryness to obtain 40g of crude intermediate 9c. Column chromatography (petroleum ether / ethyl acetate = 15:1) was used to collect 30g of intermediate 9c, yielding 60%.

[0313] To a dry three-necked flask were added intermediate 9c (20 g), carbazole (30 g), sodium tert-butoxide (2 g), catalyst Pd(dppf)Cl2 (1 g), tri-tert-butylphosphine (1 g), and toluene (300 mL). The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, and the mixture was stirred and refluxed for 24 h. The reaction was terminated and separated by column chromatography (petroleum ether / ethyl acetate = 25:1) to obtain 5 g of compound 9. The yield was 25%. Mass spectrometry analysis determined the molecular ion mass to be 742 (calculated value: 742.84).

[0314] Synthesis of compound 10:

[0315]

[0316] In a dry three-necked flask, 4a (30 g), carbazole (30 g), sodium tert-butoxide (2 g), catalyst Pd(dppf)Cl2 (1 g), tri-tert-butylphosphine (1 g), and toluene (300 mL) were added. The atmosphere was replaced with nitrogen three times, and the temperature was raised to 100°C. After stirring and refluxing for 24 h, the reaction was stopped. The intermediate 10b was collected by column chromatography (petroleum ether / ethyl acetate = 25:1) to obtain 15 g of the product. Yield: 50%

[0317] To a dry three-necked flask, add intermediate 10b (20 g), pinacol diboronate (15 g), potassium acetate (15 g), catalyst Pd(dppf)Cl2 (1 g), and toluene (300 mL). The atmosphere was replaced with nitrogen three times, and the temperature was raised to 100°C. The reaction was stirred and refluxed for 24 h. The reaction was terminated and separated by column chromatography (petroleum ether / ethyl acetate = 25:1). The product 10c was collected to yield 8 g. The yield was 40%.

[0318] Under nitrogen, a three-necked flask was charged with 10c (50 g), intermediate 2h (50 g), potassium carbonate (25 g), tetrakistriphenylphosphine palladium (1 g), and 300 mL of toluene / 50 mL of ethylene glycol ethyl ether / 50 mL of water. The atmosphere was replaced with nitrogen three times, the temperature was raised to 100°C, the reaction was stopped by heating under reflux for 12 h, and the temperature was cooled. The organic phase was extracted with ethyl acetate and deionized water, washed twice with water, dried, filtered, and the filtrate was spin-dried to obtain 10 g of crude compound 10. Column chromatography (petroleum ether / ethyl acetate = 15:1) yielded 9.5 g of compound 10, with a yield of 20%. Mass spectrometry confirmed the molecular mass of 742 (calculated value: 742.84).

[0319] Synthesis of compound 11:

[0320]

[0321] The synthesis method of compound 11 is similar to that of compound 10, except that intermediate 11a is used instead of intermediate 4a to prepare compound 11 with a yield of 63%.

[0322] Synthesis of compound 12:

[0323]

[0324] The synthesis method of compound 12 is similar to that of compound 4, except that intermediate 12a is used instead of intermediate 4a to prepare compound 12 with a yield of 35%.

[0325]

[0326] The synthesis method of compound 13 is similar to that of compound 4, except that intermediate 13a is used instead of intermediate 4a to prepare compound 13 with a yield of 43%.

[0327] 2. Energy structure of compounds

[0328] The energy levels of compounds 1 to 13 and the following H1-1 and H1-2 can be obtained by quantum calculation, for example, using TD-DFT (time-dependent density functional theory) through Gaussian 09W (Gaussian Inc.). The specific simulation method can be found in WO2011141110. First, the semi-empirical method "Ground State / Semi-empirical / Default Spin / AM1" (Charge 0 / Spin Singlet) is used to optimize the molecular geometry. Then, the energy structure of the organic molecule is calculated by the TD-DFT (time-dependent density functional theory) method using "TD-SCF / DFT / Default Spin / B3PW91" and the basis set "6-31G(d)" (Charge0 / Spin Singlet). The HOMO and LUMO energy levels are calculated according to the following calibration formula, E S1 , E T1 and the resonance factor f(S1) are used directly.

[0329] HOMO(eV)=((HOMO(G)×27.212)-0.9899) / 1.1206

[0330] LUMO(eV)=((LUMO(G)×27.212)-2.0041) / 1.385

[0331] The HOMO(G) and LUMO(G) are the direct calculation results of Gaussian 09W, and the unit is Hartree. The results are shown in Table 1:

[0332] Table 1

[0333]

[0334]

[0335] 3. Preparation of the Mixture

[0336] H1-1 and H1-2 as shown below will be used as the first compound H1 in the mixture:

[0337]

[0338] The first compound H1 and the second compound H2 in Table 2 were mixed as evenly as possible according to a mass ratio of 1:1, and then the mixture was placed in a -3 In a 100-torr vacuum environment, the temperature is raised to completely melt the two host materials. Once mixed, the mixture is cooled to room temperature to solidify, and then ground into a powder using a ball mill. The resulting mixtures 1-3 can be used as blue or green phosphorescent hosts.

[0339] Table 2: Composition of the mixture

[0340] mixture First compound H1 Second compound H2 Mixture 1 H1-1 Compound 1 Mixture 2 H1-2 Compound 2 Mixture 3 H1-2 Compound 3

[0341] 4. Preparation and Characterization of Blue Light Devices

[0342]

[0343] The preparation process of the above-mentioned OLED device is described in detail below through a specific embodiment. The blue phosphorescent device structure is HT:PD=97:3(10nm) / HT(50nm) / BP(5nm) / PBH:NBH:BD=52:38:10(35nm) / HB(5nm) / ET:LiQ=50:50(30nm) / LiQ(2nm) / Al(100nm).

[0344] 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 ultraviolet ozone treatment.

[0345] b. Evaporation: Move the ITO substrate into the vacuum vapor deposition equipment and place it in a high vacuum (1×10 -6 At 100 mbar (100 mbar), two evaporation sources were used to vaporize the materials at different rates, resulting in a 97:3 HT-1:PD ratio, forming a 10nm thick hole injection layer. Compound HT-1 was then evaporated on the HI layer to form a 50nm hole transport layer, followed by a 5nm BP electron blocking layer on the hole transport layer. Three evaporation sources were then used to vaporize the materials at different rates, resulting in a 52:38:10 weight ratio of PBH:NBH:BD, forming a 35nm light-emitting layer. A hole blocking layer (HB, 5nm) was then evaporated, followed by a 50wt% co-deposition of the electron transport material and LiQ in separate evaporation units for 30nm, each at a 50wt% ratio, to form the electron transport layer. A 2nm LiQ electron injection layer was then deposited, and finally a 100nm thick Al cathode was deposited on the electron injection layer.

[0346] c. Packaging: The device is encapsulated with UV curable resin in a nitrogen glove box.

[0347] The device performance of the above embodiments and comparative examples was tested, as shown in Table 3; wherein EQE is the external quantum efficiency of the device, BI (Blue Index) @ 1000 nits is defined as the ratio of the device current efficiency (Cd / A) to CIE-y at a brightness of 1000 nits; Comparative Compound A to Comparative Compound F are referred to as pairs (AF); and the device lifespan T95 @ 1000 nits is defined as the time it takes for the brightness to decay to 95% of the initial value under constant current conditions when the initial brightness of the device is 1000 nits (the results of the embodiments and other comparative examples in the table are uniformly compared relative to the values ​​of the device comparative example 3).

[0348] Table 3

[0349]

[0350]

[0351] The device data results in Table 3 show that the device examples using the organic compound of the present invention as the NBH (N-type blue light host) show improved overall performance in external quantum efficiency, color coordinates, blue light index (BI), and lifetime compared to the comparative examples using the comparative compound as the NBH. A comparison of Device Example 1 and Comparative Example 3 shows that by further attaching an electron-donating carbazole to the dibenzofuran linked to the triazine, higher external quantum efficiency, BI, and lower CIE-y can be achieved, while also significantly improving device lifetime. Without being limited by a specific principle, this improvement may be related to the improved carrier balance in the light-emitting layer achieved by the organic compound of the present invention. A comparison of Device Example 1 and Comparative Example 1 shows that, compared to directly attaching carbazole to all positions on the triazine ring, attaching carbazole via dibenzofuran as a bridge at one position can achieve higher efficiency and lifetime. Without being limited by a specific principle, this improvement may be related to the dibenzofuran helping to expand the distribution of the triazine ring LUMO, thereby achieving more stable electron transport and exciton recombination. Comparison of Device Example 1 and Comparative Example 2 shows that, compared to the comparative compound using biphenyl-bridged triazine and carbazole, the organic compound according to the present invention as an NBH can simultaneously achieve more ideal blue light color coordinates (smaller CIE-y value), higher external quantum efficiency, and longer device life. Without being limited by a specific principle, this may be related to the rigid dibenzofuran structure reducing intramolecular non-radiative energy loss and improving the film-forming properties and morphological stability of the organic compound.

[0352] 5. Preparation and Characterization of Red OLED Devices

[0353]

[0354] The preparation process of the above-mentioned OLED device is described in detail below through a specific embodiment (device embodiment 9).

[0355] The structure of the green OLED device is: ITO / HI (30 nm) / HT-1 (50 nm) / HT-3 (10 nm) / EML (40 nm) / ET:Liq (30 nm) / Liq (1 nm) / Al (100 nm). The preparation steps of device Example 9 are as follows:

[0356] 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 ultraviolet ozone treatment.

[0357] b. In high vacuum (1×10 -6 mbar) by thermal evaporation: the ITO substrate was moved into the vacuum vapor deposition equipment and heated in a high vacuum (1×10 -6 At 100 mbar, a resistive heating evaporation source was used to form a 30nm thick HI layer. A 50nm thick HT-1 layer and a 10nm thick HT-3 layer were then formed on the HI layer. A 40nm thick luminescent layer (EL) was then formed on the hole transport layer, controlling the weight ratio of compound 5:PH-1:Dopant to 50:50:10. ET and LiQ were then co-deposited at 50 wt% each in separate evaporation units to form a 30nm thick electron transport layer (ETL) on the EL. A 1nm thick LiQ layer was then deposited on the ETL as an electron injection layer (EIL). Finally, a 100nm thick Al cathode was deposited on the EIL.

[0358] c. Packaging: The device is encapsulated with UV curable resin in a nitrogen glove box.

[0359] The implementation method of device examples 10 to 13 is the same as that of device example 9, except that different co-hosts are used instead. The co-hosts refer to two compounds placed in different evaporation units, and the weight ratio of the materials is controlled to be 50:50.

[0360] Table 4

[0361] OLED devices main body CE(cd / A)@1000nits T95@1000nits Device Example 9 Compound 5: PH-1 = 5:5 171％ 160％ Device Example 10 Compound 7: PH-1 = 5:5 169％ 146％ Device Example 11 Compound 13: PH-1 = 5:5 158％ 147％ Device Example 12 Compound 5: H1-1 = 5:5 175％ 250％ Device Example 13 Compound 7: H1-1 = 5:5 175％ 247％ Comparative Example G1 CBP 100％ 100％ Comparative Example G2 Comparative compound A: PH-1 = 5:5 110％ 132％ Comparative Example G3 Comparative compound B: PH-1 = 5:5 108％ 125％ Comparative Example G4 Comparative compound C: PH-1 = 5:5 86％ 124％ Comparative Example G5 Comparative compound D: H1-1 = 5:5 75％ 150％ Comparative Example G6 Comparative compound E: H1-1 = 5:5 90％ 156％

[0362] The current-voltage-luminescence (IVL) characteristics of the green OLED devices were characterized using a characterization system, with key parameters such as efficiency, lifetime, and driving voltage recorded. The performance of the green OLED devices is summarized in Table 4. The lifetime and CE values ​​are relative to the comparative example (with the lifetime of comparative example G1 as 100%). Testing shows that the organic mixture of the present invention exhibits significant improvements in performance as a green light host, particularly lifetime.

[0363] It should be noted that the above are only specific embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. The embodiments of the present invention and the features within the embodiments can be combined with each other unless there is a conflict. Therefore, the scope of protection of the present invention shall be based on the scope of protection of the claims.

Claims

1. An organic compound having the structure of the following chemical formula (I): in, X and Y are independently selected from N or CR, and 1 to 2 Xs are N and 1 to 3 Ys are N; L is selected from a single bond or a second-order linking unit; Ar is selected from a substituted or unsubstituted aromatic group 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 groups; R, when it occurs multiple times, may be selected, identically or differently, from H, D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a carbamoyl, haloformyl, formyl, isocyanate, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, where one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which they are bonded.

2. The organic compound according to claim 1, having the structure of the following chemical formula (I-1):

3. The organic compound according to claim 1 or 2, having the structure of the following chemical formula (I-2) to (I-4): in, Z is selected from N or CR 01 , R 01 The definition of is the same as R in claim 1; A is selected from O, S, SO2 or NR 02 ; R 02 is selected from a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, wherein one or more of the groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring to which the group is bonded.

4. An organic mixture comprising a first compound H1 and a second compound H2, characterized in that: The first compound H1 is selected from the chemical formula (II-1) or (II-2), and the second compound H2 is selected from the organic compound according to any one of claims 1 to 3: Ar1-Ar3 are 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 groups, wherein one or more of these groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which they are bonded; R1-R4 are substituents which, on each occurrence, may be identical or different and are selected from a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy or silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups, wherein one or more of the groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded; n1, n3, and n4 are each independently selected from integers from 0 to 7; n2 is selected from integers of 0 to 8.

5. The organic mixture according to claim 4, characterized in that The first compound H1 and the second compound H2 form a type II heterojunction structure, and min(LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(E T1 (H1),E T1 (H2))+0.1eV, where HOMO(H1), LUMO(H1) and E T1 (H1) are the highest occupied molecular orbital, lowest unoccupied molecular orbital and triplet energy level of the first compound H1, HOMO (H2), LUMO (H2) and E T1 (H2) are the highest occupied molecular orbital, lowest unoccupied molecular orbital and triplet energy level of the second compound H2, respectively.

6. The organic mixture according to claim 4 or 5, characterized in that The first compound H1 is selected from any one of chemical formulas (II-1a), (II-1b) or (II-2a):

7. The organic mixture according to any one of claims 4 to 6, characterized in that 1) The difference in molecular weight between the first compound H1 and the second compound H2 does not exceed 80 Dalton, and / or 2) The difference in sublimation temperature between the first compound H1 and the second compound H2 does not exceed 30K, and / or 3) At a certain vacuum degree and a certain evaporation temperature, the difference in evaporation rates between the first compound H1 and the second compound H2 does not exceed 5%, with the evaporation rate of the first compound H1 being used as a standard.

8. The organic mixture according to any one of claims 4 to 7, characterized in that The organic mixture further comprises a light emitter, which is selected from phosphorescent light emitters or TADF materials.

9. The organic mixture according to claim 8, characterized in that The phosphorescent emitter is a transition metal complex and comprises at least one ligand or partial ligand selected from the following: Wherein, T is selected from B, Al, Ga or In; K 1’ Is a direct bond selected from NR e PR e , O, S or Se; Y 1 -Y 15 are selected from C or N; Y' is selected from BR e NR e PR e ,O,S,Se,C=O,C=S,C=Se,C=NR e 、C=CR e R f 、S=O、SO2、CR e R f 、P(O)R e 、SiR e R f or GeR e R f ; R e and R f Can be fused or linked to form a ring; R a , R b , R c and R d are represented as a single to the maximum possible number of substituents or unsubstituted, respectively; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f are independently selected from H, D, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, arylalkyl, alkoxy, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfonamide, sulfoxide, phosphorus, seleno or a combination thereof; and R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d Any two adjacent substituents may be fused or linked to form a ring or to form a multidentate ligand.

10. A composition comprising an organic compound according to any one of claims 1 to 3 or an organic mixture according to any one of claims 4 to 9, and at least one organic solvent.

11. A photovoltaic device comprising an organic compound according to any one of claims 1 to 3 or an organic mixture according to any one of claims 4 to 9.

12. The optoelectronic device according to claim 11, wherein: The optoelectronic device is an organic electroluminescent device and comprises a substrate, an anode, a light-emitting layer and a cathode arranged in sequence, wherein the light-emitting layer comprises at least one organic compound according to any one of claims 1 to 3 or an organic mixture according to any one of claims 4 to 9, or is prepared using the composition according to claim 10.

13. An organic compound II having the structure of the following chemical formula (III): in: X and Y are independently selected from CR or N, and at least one Y is selected from N; Ar 1 Having the structure shown in chemical formula (III-1); Ar 2 and Ar 3 are independently selected from the structures shown in chemical formula (III-1) or (III-2) or the combination of chemical formula (III-1) and (III-2); when Ar 2 and Ar 3 When it is carbazole, X is selected from CR; Ring A is a 5-membered or 6-membered aromatic ring or a heteroaromatic ring; Y1 is selected from single bond, O, S, Se, CR a R b NR a 、SiR a R b and BR a ; R A At each occurrence, it independently represents a single substitution to the maximum number of substitutions allowed, or no substitution; R, R a , R b , R A In each occurrence, each is independently selected from H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, or a substituted or unsubstituted silyl group, or a substituted or unsubstituted keto group having 1 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 20 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyanate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these groups; one or more H in the above-mentioned various groups may be further substituted by D.

Images