Compound and application thereof in photoelectric field

Abstract

The invention discloses a pyrazine cyclic azine compound and application thereof in an organic electronic device. The compound has a general formula represented by a chemical formula (I). The light-emitting spectrum of the compound has narrower half-peak width, and the peak position of the photoluminescence spectrum of the compound can be adjusted through the molecular structure, so that spectrums with different colors can be emitted respectively. These narrow half-peak width light emitting devices of different colors can be used to fabricate display devices with high color gamut and high efficiency. # imgabs0 #

Description

Technical Field

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

[0002] Due to the diversity of organic semiconductor materials in chemical synthesis, relatively low manufacturing costs during large-scale production, and excellent optical and electrical properties, etc., their optoelectronic devices, especially organic light-emitting diodes (OLEDs), have great application potential in the display field.

[0003] In an OLED display, various colors are represented by mixing the emissions of the three primary colors of light, namely red, green, and blue. However, if the color purity of each of the three primary colors is low, many colors cannot be reproduced, resulting in a reduction in the image quality of the display. Therefore, in commercially available displays, unwanted colors are removed from the emission spectrum by using an optical filter to improve the color purity. If the original spectral width is wide, the proportion of removal increases. Thus, even when the luminous efficiency is high, the actual luminous efficiency is significantly reduced. For example, the full width at half maximum (FWHM) of the blue emission spectrum of commercially available smartphones is about 20 nm to 25 nm, but the FWHM value of general fluorescent materials is about 40 nm to 60 nm, the FWHM value of phosphorescent materials is about 60 nm to 90 nm, and if it is a TADF material, the FWHM value is about 70 nm to 100 nm. In the case of using a fluorescent material, since the FWHM width is relatively narrow, it is sufficient to remove only a part of the unwanted colors. However, in the case of using a phosphorescent material or a TADF material, more than half of the colors need to be removed, and the actual luminous efficiency is significantly reduced.

[0004] US2023128708A1 discloses an indolecarbazole compound with relatively strong rigidity and a relatively narrow full width at half maximum (FWHM) of the emission spectrum, but its stability, especially the lifetime of OLED devices using it as a light-emitting body, still needs to be improved. Since Hatakeyama et al. first reported a blue-light BN compound with a narrow emission spectrum (DOI: 10.1002 / adma.201505491) in 2016, such compounds have received extensive attention. Boron nitride compounds have a multiple resonance effect, that is, the molecular structure is maintained in a special planar rigid conjugated structure, and the different electronegativities brought by the empty orbitals on the boron atom that can participate in the electron cloud conjugation and the lone pair electrons on the nitrogen atom that can participate in the electron cloud conjugation are enhanced through the conjugation effect with each other, thereby forming an intramolecular short-range charge transfer state, and thus realizing highly efficient emission with thermally activated delayed fluorescence (TADF) properties. However, the synthesis of BN compounds is complex, and the lifetime of the devices still needs to be improved.

[0005] Therefore, novel and stable compounds with a narrow emission spectrum still need to be developed. SUMMARY OF THE INVENTION

[0006] In view of the deficiencies of the above prior art, the object of the present invention is to provide a compound, a polymer, a composition, a mixture, an organic electronic device and their applications containing the same, aiming to provide a novel class of stable compounds with a narrow emission spectrum.

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

[0008] A compound having a structure represented by the following chemical formula (I):

[0009]

[0010] Wherein: A and B are condensed ring systems having 5 to 20 ring atoms; Ar1 and Ar2 may be the same or different and are selected from linear alkyl, alkoxy groups having 1 to 20 C atoms, or branched or cyclic alkyl, alkoxy groups having 3 to 20 C atoms, or substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or arylamino or heteroarylamino groups having 5 to 40 ring atoms, or combinations of these groups;

[0011] X is CR 1 or N, and when both A and B are non-N hetero-condensed ring systems, at least one X is N;

[0012] R 1 Each time it appears, it may be the same or different and is selected from H, D, or linear alkyl, haloalkyl, alkoxy, thioalkoxy groups having 1 to 20 C atoms, or branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy, silyl groups having 3 to 20 C atoms, or keto groups having 1 to 20 C atoms, or alkoxycarbonyl groups having 2 to 20 C atoms, or aryloxycarbonyl groups having 7 to 20 C atoms, or cyano, carbamoyl, halocarbonyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I, crosslinkable groups, or substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or arylamino or heteroarylamino groups having 5 to 40 ring atoms, disubstituted units at any position of the above groups or combinations of these groups, wherein one or more groups may form monocyclic or polycyclic aliphatic or aromatic ring systems with each other and / or with the ring to which the group is bonded.

[0013] The present invention also relates to a polymer comprising at least one first repeating unit, and the first repeating unit comprises a structure corresponding to at least one compound as described above.

[0014] The present invention also relates to a composition comprising a compound as described above or at least one polymer as described above, and at least one organic solvent.

[0015] The present invention further relates to a mixture comprising a compound as described above or a polymer as described above, and at least one organic functional material, and the organic functional material can be selected from at least one of a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitter, and a host material.

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

[0017] Advantageous effects: By applying the compound to an organic light-emitting device, the organic light-emitting device can have high color purity, relatively high device stability, and a relatively long device operating life, etc. Compared with the indolocarbazole compound with relatively strong rigidity (US2023128708A1), an N heteroatom is introduced into the core structure of the indolocarbazole compound according to the compound of the present invention, thereby significantly improving the electron-withdrawing ability of the pyrazine ring core structure. The D-A-D or D-A type light-emitting material based on this core structure has a narrow emission spectrum line and relatively high stability, thereby enabling the organic light-emitting device to have high luminous efficiency, high color purity, and a relatively long device operating life, etc. Detailed embodiments

[0018] The present invention provides a compound, which can be used as an organic light-emitting material in an organic light-emitting device, but not limited thereto. Through optimized selection, the compound has at least high luminous efficiency, a narrow emission spectrum FWHM, and a relatively long luminous life, etc.

[0019] To make the objectives, technical solutions, and effects of the present invention clearer and more definite, the following further describes the present invention in detail with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. The data ranges involved in the present invention should include the end values unless otherwise specified.

[0020] In the description of the embodiments of the present invention, the numerical range represented by "~" means a range including the numerical values recorded before and after "~" as the lower limit value and the upper limit value.

[0021] In the description of the embodiments of the present invention, a substituent may be further substituted by a substituent. "Substituted group a" may mean that group a is substituted by a substituent, and the substituent may be substituted by at least one further substituent or may be unsubstituted.

[0022] In the present invention, the term "and / or" describes the association relationship of associated objects and indicates that three relationships may exist. For example, A and / or B may represent: A exists alone, A and B exist simultaneously, and B exists alone. Wherein A and B may be singular or plural. The character " / " generally indicates that the associated objects before and after are an "or" relationship.

[0023] In the present invention, "at least one" means one or more, and "a plurality" means two or more. "At least one of the following items (pieces)" or similar expressions refer to any combination of these items, including any combination of single items (pieces) or plural items (pieces). For example, "at least one of a, b, or c", or, "at least one of a, b, and c" can both represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or plural respectively.

[0024] It should be understood that in various embodiments of the present invention, the magnitude of the sequence numbers of the above processes does not mean the order of execution. Some or all of the steps may 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 to the implementation process of the embodiments of the present invention.

[0025] 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", "the", and "said" used in the embodiments of the present invention and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0026] The term "OLED" is an abbreviation for "Organic Light Emitting Diode", which represents an organic electroluminescent diode, also known as organic electro-laser display, organic light-emitting semiconductor (Organic Electroluminescence Display, OLED). OLED belongs to a current-type organic light-emitting device, and is a phenomenon of luminescence caused by the injection and recombination of carriers. The luminescence intensity is proportional to the injected current. Under the action of an electric field, the holes generated by the anode and the electrons generated by the cathode in OLED will move, and are respectively injected into the hole transport layer and the electron transport layer, and migrate to the light-emitting layer. When the two meet in the light-emitting layer, energy excitons are generated, which excite the luminescent molecules to finally generate visible light.

[0027] The term "TADF" is an abbreviation for "Thermally Activated Delayed Fluorescence", which represents thermally activated delayed fluorescence. In essence, when the energy of the triplet excited state is close to that of the singlet excited state, the triplet excited state can return to the singlet excited state through thermally activated reverse intersystem crossing. Traditional luminescence includes fluorescence and phosphorescence, where excitons in the singlet state and triplet state return to the ground state in the form of radiative luminescence respectively. Moreover, generally, the energy level difference between the lower singlet state and the lower triplet state is relatively large, resulting in the fact that once an exciton reaches the triplet state through the intersystem crossing (ISC) process from the singlet state, it cannot return to the singlet state anymore.

[0028] In the present invention, the host material, matrix material, Host material, and Matrix material have the same meaning and can be interchanged.

[0029] In the present invention, the guest material, luminescent material, Emitter material have the same meaning and can be interchanged.

[0030] In the present invention, the color converter, color conversion layer, and CCL have the same meaning and can be interchanged.

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

[0032] In the present invention, "substituted" means that a hydrogen atom in a compound is replaced by a substituent.

[0033] In the present invention, when the same substituent appears multiple times, it can be independently selected from different groups respectively.

[0034] In the present invention, "substituted or unsubstituted" means that the defined group can be substituted or unsubstituted. When the defined group is substituted by a substituent, it should be understood that it is optionally substituted by a substituent acceptable in the art, and the above-mentioned substituent can also be further substituted by a substituent acceptable in the art.

[0035] In the present invention, "the number of ring atoms" refers to the number of atoms that form a ring structure by bonding atoms in a cyclic compound (for example, monocyclic compound, fused ring compound, crosslinked compound, carbocyclic compound, heterocyclic compound). When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below under the condition of no special explanation. For example, the number of ring atoms in a benzene ring is 6, the number of ring atoms in a naphthalene ring is 10, and the number of ring atoms in a thiophenyl group is 5.

[0036] An aromatic group refers to a hydrocarbon group containing at least one aromatic ring. A heteroaromatic group refers to an aromatic hydrocarbon group containing at least one heteroatom. The heteroatom is preferably selected from Si, N, P, O, S, and / or Ge, and particularly preferably selected from Si, N, P, O, and / or S. A polycyclic aromatic group means that the rings of the aromatic group can have two or more rings, where two carbon atoms are shared by two adjacent rings, that is, a fused ring. A polycyclic heteroaromatic group refers to a polycyclic aromatic hydrocarbon group containing at least one heteroatom. For the purposes of the present invention, an aromatic group or a heteroaromatic group includes not only the system of aromatic rings but also non-aromatic ring systems. Thus, groups such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene, etc. are also considered aromatic groups or heteroaromatic groups for the purposes of this invention. For the purposes of the present invention, a polycyclic aromatic or polycyclic heteroaromatic ring system includes not only the system of aromatic groups or heteroaromatic groups, but also, where multiple aromatic groups or heteroaromatic groups can also be interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% non-H atoms, such as C, N, or O atoms). Thus, groups such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc. are also considered aromatic ring systems for the purposes of this invention.

[0037] In the embodiments of the present invention, the energy level structure of the organic material, the singlet energy level S1, the oscillator factor f1, the triplet energy level T1, HOMO, and LUMO play a crucial role. The determination of these energy levels will be introduced below.

[0038] The 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 (hereinafter referred to as CV). Recently, quantum chemical methods, such as density functional theory (hereinafter referred to as DFT), have also become effective methods for calculating the energy levels of molecular orbitals.

[0039] The singlet energy level S1 of the organic material can be determined by emission spectroscopy, and the triplet energy level T1 can be measured by low-temperature time-resolved emission spectroscopy. S1 and T1 can also be obtained by quantum simulation calculations (such as through Time-dependent DFT), such as through commercial software Gaussian 09W (Gaussian Inc.). The specific simulation method can be referred to WO2011141110 or as described in the following examples. ΔE ST Is defined as (S1 - T1).

[0040] It should be noted that the absolute values of HOMO, LUMO, S1, f1, and T1 depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as the starting point and peak point on the CV curve, can give different HOMO / LUMO values. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, S1, f1, and T1 are based on simulations using Time-dependent DFT, but this does not affect the application of other measurement or calculation methods.

[0041] In the invention, (HOMO-1) is defined as the second-highest occupied orbital energy level, (HOMO-2) is the third-highest occupied orbital energy level, and so on. (LUMO+1) is defined as the second-lowest unoccupied orbital energy level, (LUMO+2) is the third-lowest unoccupied orbital energy level, and so on.

[0042] The present invention relates to a compound having a structure represented by the following chemical formula (I):

[0043]

[0044] Wherein: A and B are fused ring systems having 5 to 20 ring atoms; Ar1 and Ar2 may be the same or different and are selected from linear alkyl or alkoxy groups having 1 to 20 C atoms, or branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, or substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or arylamino or heteroarylamino groups having 5 to 40 ring atoms, or combinations of these groups; X is CR 1 or N, and when both A and B are non-N hetero fused ring systems, at least one of X is N;

[0045] R 1Each occurrence may be the same or different and is selected from H, D, or a straight-chain alkyl, haloalkyl, alkoxy, thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy, silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or cyano, carbamoyl, halocarbonyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF3, Cl, Br, F, I, 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 an arylamino or heteroarylamino group having 5 to 40 ring atoms, a disubstituted unit at any position of the above groups or a combination of these groups, wherein one or more 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.

[0046] In a preferred embodiment, A or B is selected from a fused polycyclic aromatic group or a fused polycyclic heteroaromatic group having 5 to 20 ring atoms. The fused polycyclic aromatic group is preferably selected from: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, benzophenanthrene, dibenzo[a,h]anthracene, tetracene, pyrene, benzopyrene, acenaphthene, fluorene, and their N-hetero derivatives, etc.; the fused polycyclic heteroaromatic group is preferably selected from benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thiophenopyrrole, thiophenothiophene, furanopyrrole, furanofuran, thiophenofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, perimidine, quinazoline, quinazolinone, pyridine, pyrimidine, and their derivatives, etc.

[0047] In a particularly preferred embodiment, A or B is selected from benzene, naphthalene, pyridine, pyrimidine.

[0048] In a preferred embodiment, A and B are selected from the same structure.

[0049] In a preferred embodiment, the compound has a structure shown by the following chemical formulas (I-a)-(I-d):

[0050]

[0051] wherein, Ar3 - Ar 10 is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms.

[0052] In a preferred embodiment, the compound has a structure shown by the chemical formula (I-1):

[0053]

[0054] wherein X is CR 1 or N, and at least one of them is N; Ar1 and Ar2 are defined as above.

[0055] In some embodiments, each occurrence of Ar1 and Ar2 may be the same or different and is independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 30 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 30 ring atoms, or arylamino or heteroarylamino groups having 5 to 30 ring atoms, or combinations of these groups. In some preferred embodiments, each occurrence of Ar1 and Ar2 may be the same or different and is independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 20 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 20 ring atoms, or arylamino or heteroarylamino groups having 5 to 20 ring atoms, or combinations of these groups. In some more preferred embodiments, each occurrence of Ar1 and Ar2 may be the same or different and is independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 18 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 18 ring atoms, or arylamino or heteroarylamino groups having 5 to 18 ring atoms, or combinations of these groups. In some even more preferred embodiments, each occurrence of Ar1 and Ar2 may be the same or different and is independently selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 15 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 15 ring atoms, or arylamino or heteroarylamino groups having 5 to 15 ring atoms, or combinations of these groups.

[0056] In some embodiments, in formula (I) or (I-1), one of X is N.

[0057] In some other more preferred embodiments, in formula (I) or (I-1), two of X are N; more preferably, the two Ns are symmetrically located, as shown in the following example structures:

[0058]

[0059] In a preferred embodiment, one or two of the Xs in formula (I-1) are selected from N, and the rest are CH.

[0060] In certain embodiments, for the compounds according to formula (I) or (I-1), at least one R 1 is selected from F, Cl, cyano, phenoxy, p-methoxyphenylthio, a partially or fully fluorinated alkyl chain, or one of the following groups:

[0061]

[0062] Wherein: m1 is 1, 2 or 3; X1-X8 are selected from CR 2 or N, and no two adjacent Ns among X1-X8; M 1 、M 2 、M 3 each independently represents NR 2 、CR 2 R 3 、SiR 2 R 3 、O、C═NR 2 、C═CR 2 R 3 、PR 2 、P(═O)R 2 、S、S═O、SO2 or none;

[0063] R 2 、R 3 、R 4 、R 5 each occurrence may be the same or different and is selected from H, D, or a straight-chain alkyl, haloalkyl, alkoxy, thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy, silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or cyano, carbamoyl, halocarbonyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF3, Cl, Br, F, I, 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 an arylamino or heteroarylamino group having 5 to 40 ring atoms, a disubstituted unit at any position of the above groups or a combination of these groups, wherein one or more 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.

[0064] In certain more preferred embodiments, the compound is selected from chemical formulas (I-1a)-(I-1d):

[0065]

[0066] wherein, the definitions of X, Ar3-Ar 10 are as described above.

[0067] In certain embodiments, the compounds of chemical formulas (I-1), chemical formulas (I-a)-(I-d), chemical formulas (I-1a)-(I-1d), wherein the Ar1-Ar 10may be the same or different and each independently selected from one of the following groups:

[0068]

[0069] wherein: each occurrence of w is independently selected from CR 6 R 7 , NR 6 , O, S, SiR 6 R 7 , PR 6 , P(=O)R 6 , S=O, S(=O)2 or C=O; each occurrence of v is independently selected from CR 8 or N;

[0070] R 6 -R 8 each occurrence is independently selected from H, D, or a straight-chain alkyl, alkoxy, thioalkoxy having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy, silyl having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or cyano, carbamoyl, halocarbonyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF3, Cl, Br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

[0071] In certain embodiments, Ar1 - Ar 10 are each independently selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 6 to 20 ring atoms. In other embodiments, Ar1 - Ar 10 are each independently selected from a substituted or unsubstituted aromatic or heteroaromatic ring system having 8 to 13 ring atoms.

[0072] In a preferred embodiment, the aromatic or heteroaromatic ring system is selected from the following groups:

[0073]

[0074] wherein: the definitions of v and w are as described above.

[0075] More preferably, the aromatic or heteroaromatic ring system is selected from the following groups:

[0076]

[0077] Wherein: v and w are defined as above.

[0078] In a preferred embodiment, the polycyclic aromatic group is selected from: benzene, naphthalene, anthracene, fluoranthene, phenanthrene, benzo[a]phenanthrene, dibenzo[a,h]anthracene, tetracene, pyrene, benzo[a]pyrene, acenaphthene, fluorene, and their derivatives, etc.; the polycyclic heteroaromatic group is selected from benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thiophenopyrrole, thiophenothiophene, furanopyrrole, furanofuran, thiophenofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, perimidine, quinazoline, quinazolinone, and their derivatives, etc.

[0079] In certain embodiments, R 1 -R 8 each time it appears, may be independently selected from the following groups:

[0080]

[0081] Wherein: v and w are defined as above; n1, n2, n3, and n4 are all integers greater than or equal to 1.

[0082] Furthermore, R 1 -R 8 each time it appears, is independently selected from the following groups:

[0083]

[0084] Wherein: the H atoms on the ring may be further substituted.

[0085] In certain embodiments, in the compound of formula (I), Ar1 and Ar2 each time they appear, are independently selected from the following structural units or their combinations:

[0086]

[0087] Wherein n5 is 1 or 2 or 3 or 4.

[0088] In certain preferred embodiments, the compound is selected from formula (I-2a)-(I-2d):

[0089]

[0090] Wherein, the definition of Ar1-Ar 10 is as above.

[0091] In some other preferred embodiments, the compound is selected from formula (I-3a)-(I-3b):

[0092]

[0093] Among them, Ar3 - Ar6 are defined as described above.

[0094] In some other preferred embodiments, the compound is selected from the chemical formula (I - 4):

[0095]

[0096] Among them, X is defined as described above; Y is selected from the group consisting of CR 9 R 10 , SiR 9 R 10 , NR 9 , O or S. Among them, R 9 , R 10 are defined the same as R 1 above.

[0097] In some other more preferred embodiments, the compound is selected from the chemical formulas (I - 5a) - (I - 5b):

[0098]

[0099] R 9 , R 10 are defined as described above.

[0100] In a relatively preferred embodiment, at least part of the H in the compound is deuterated, preferably 10% or more of the H is deuterated, more preferably 20% or more of the H is deuterated, very preferably 30% or more of the H is deuterated, and most preferably 40% or more of the H is deuterated.

[0101] Specific examples of the compounds according to the present invention are listed below, but are not limited thereto:

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115] The compounds according to the present invention can be used as organic functional materials in electronic devices, especially in light-emitting devices. The light-emitting devices can be a color converter, or an electroluminescent device, such as an OLED, an OLEEC, an organic light-emitting field effect transistor; an OLED device is particularly preferred. Organic functional materials can be classified into color conversion materials (CCM), hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injection materials (EIM), electron blocking materials (EBM), hole blocking materials (HBM), light-emitting materials (Emitter), host materials (Host), and organic dyes. In a preferred embodiment, the compounds according to the present invention can be used as light-emitting materials. In another preferred embodiment, the compounds according to the present invention can be used as light-emitting materials in electroluminescent devices.

[0116] In a preferred embodiment, the light-emitting wavelength of the light-emitting device is 300 nm to 1500 nm, preferably 400 nm to 1000 nm, more preferably 400 nm to 800 nm.

[0117] In a preferred embodiment, the compounds according to the present invention can be used as fluorescent guest materials (i.e., fluorescent light-emitting materials).

[0118] As a fluorescent guest material, it must have an appropriate singlet energy level, i.e., S1. In some embodiments, for the compounds according to the present invention, S1 ≥ 2.1 eV, preferably ≥ 2.3 eV, more preferably ≥ 2.5 eV, even more preferably ≥ 2.7 eV, and most preferably ≥ 2.8 eV.

[0119] As a fluorescent guest material, it must have a high photoluminescence quantum efficiency, i.e., PLQY. In some embodiments, for the compounds according to the present invention, PLQY ≥ 40%, preferably ≥ 50%, more preferably ≥ 60%, and most preferably ≥ 70%.

[0120] In some embodiments, for the compounds according to the present invention, the resonance factor f1 ≥ 0.2, preferably ≥ 0.3, more preferably ≥ 0.4, and most preferably ≥ 0.5.

[0121] As an organic functional material, good thermal stability is desired. Generally, for the compounds according to the present invention, their glass transition temperature (Tg) ≥ 100 °C, preferably Tg ≥ 140 °C, more preferably Tg ≥ 180 °C.

[0122] In some preferred embodiments, for the compounds according to the present invention, (HOMO-(HOMO-1)) ≥ 0.2 eV, preferably ≥ 0.3 eV, more preferably ≥ 0.4 eV, and most preferably ≥ 0.45 eV.

[0123] In some other preferred embodiments, for the compounds according to the present invention, ((LUMO + 1)-LUMO) ≥ 0.15 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.30 eV, and most preferably ≥ 0.35 eV.

[0124] The present invention also provides a polymer comprising at least one first repeating unit, and the first repeating unit comprises a structure corresponding to at least one compound of the present invention.

[0125] In some embodiments, the polymer further comprises at least one second repeating unit different from the first repeating unit.

[0126] In certain embodiments, the polymer is a conjugated polymer; in some preferred embodiments, the conjugated polymer comprises a second repeating unit, and the second repeating unit is selected from one of the following repeating units:

[0127]

[0128] wherein R' are each independently selected from one or more combinations of H, D, C1-C20 linear alkyl, C1-C20 alkoxy, C1-C20 thioalkoxy, C3-C20 branched alkyl, C3-C20 cyclic alkyl, C3-C20 branched alkoxy, C3-C20 cyclic alkoxy, C3-C20 branched thioalkoxy, C3-C20 cyclic thioalkoxy, silyl, C1-C20 keto, C2-C20 alkoxycarbonyl, C7-C20 aryloxycarbonyl, cyano, carbamoyl, halocarbonyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I, crosslinkable groups, substituted or unsubstituted aryl having 5 to 60 ring atoms, substituted or unsubstituted heteroaryl having 5 to 60 ring atoms, aryloxy having 5 to 60 ring atoms, and heteroaryloxy having 5 to 60 ring atoms.

[0129] In some other preferred embodiments, the polymer includes a polymer molecular main chain and side chains connected to the polymer molecular main chain, and the side chains are derived from the compounds of the present invention. Preferably, the polymer further includes at least one third repeating unit different from the first repeating unit and the second repeating unit. More preferably, the polymer is a non-conjugated polymer, which contains a third repeating unit selected from one of the following repeating units:

[0130]

[0131] wherein each R” is independently selected from one or more combinations of H, D, C1-C20 straight-chain alkyl, C1-C20 alkoxy, C1-C20 thioalkoxy, C3-C20 branched-chain alkyl, C3-C20 cyclic alkyl, C3-C20 branched-chain alkoxy, C3-C20 cyclic alkoxy, C3-C20 branched-chain thioalkoxy, C3-C20 cyclic thioalkoxy, silyl, C1-C20 keto, C2-C20 alkoxycarbonyl, C7-C20 aryloxycarbonyl, cyano, carbamoyl, halocarbonyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF3, Cl, Br, F, I, crosslinkable groups, substituted or unsubstituted aryl having 5 to 60 ring atoms, substituted or unsubstituted heteroaryl having 5 to 60 ring atoms, aryloxy having 5 to 60 ring atoms, and heteroaryloxy having 5 to 60 ring atoms.

[0132] In a preferred embodiment, the synthesis method of the polymer is selected from SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

[0133] In a preferred embodiment, for the polymer according to the present invention, its glass transition temperature (Tg) ≥ 100 °C, preferably ≥ 120 °C, more preferably ≥ 140 °C, still more preferably ≥ 160 °C, and most preferably ≥ 180 °C.

[0134] In a preferred embodiment, for the polymer according to the present invention, the value range of its molecular weight distribution (PDI) is preferably 1 to 5, more preferably 1 to 4, still more preferably 1 to 3, even more preferably 1 to 2, and most preferably 1 to 1.5.

[0135] In a preferred embodiment, for the polymer according to the present invention, the weight-average molecular weight (Mw) preferably ranges from 10,000 to 1,000,000, more preferably from 50,000 to 500,000, still more preferably from 100,000 to 400,000, even more preferably from 150,000 to 300,000, and most preferably from 200,000 to 250,000.

[0136] In certain embodiments, the compound or polymer according to the present invention has a light-emitting function, and its emission wavelength is between 300 nm and 1000 nm, preferably between 350 nm and 900 nm, and more preferably between 400 nm and 800 nm. The light emission referred to here means photoluminescence or electroluminescence.

[0137] The present invention also relates to a mixture comprising a compound or polymer as described above and at least one organic functional material. The organic functional material is selected from at least one of a color conversion material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitter, and a host material. The light emitter is selected from a singlet light emitter (fluorescent light emitter), a triplet light emitter (phosphorescent light emitter), and an organic thermally activated delayed fluorescence material (TADF material). For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1, and WO2011110277A1, and the entire contents of these 3 patent documents are hereby incorporated herein by reference. The organic functional material can be a small molecule and polymer material.

[0138] In some preferred embodiments, the mixture comprises at least one compound or polymer according to the present invention and a fluorescent host material. The compound according to the present invention can be used as a fluorescent guest material, and the weight percentage of the fluorescent guest is ≤10 wt%, preferably ≤9 wt%, more preferably ≤8 wt%, particularly preferably ≤7 wt%, and most preferably ≤5 wt%.

[0139] In another preferred embodiment, the mixture comprises at least one compound or polymer according to the present invention, a TADF material, and a fluorescent host material.

[0140] In another preferred embodiment, the mixture comprises at least one compound or polymer according to the present invention, a phosphorescent light-emitting material, and a phosphorescent host material.

[0141] The following provides a detailed introduction to the phosphorescent host material (triplet host material), fluorescent host material (singlet host material), TADF material, and phosphorescent light emitter (triplet light emitter).

[0142] 1. Triplet Host:

[0143] Examples of the triplet host material are not particularly limited, and any metal complex or organic compound may be used as the host, as long as its triplet energy level is higher than that of the luminescent material, particularly the triplet luminescent material or the phosphorescent material.

[0144] Examples of the metal complex that can be used as the triplet host include (but are not limited to) the following general structures:

[0145]

[0146] M1 is a metal; (Y 1 -Y 2 ) is a bidentate ligand, and Y 1 and Y 2 are independently selected from C, N, O, P or S; L is a auxiliary ligand; m is an integer, and its value ranges from 1 to the maximum coordination number of this metal; in a preferred embodiment, the metal complex that can be used as the triplet host has the following form:

[0147]

[0148] (O-N) is a bidentate ligand, in which the metal coordinates with O and N atoms. m is an integer, and its value ranges from 1 to the maximum coordination number of this metal.

[0149] In one embodiment, M1 can be selected from Ir and Pt.

[0150] Examples of the organic compound that can be used as a triplet host are selected from compounds containing a cyclic aromatic hydrocarbon group, such as benzene, biphenyl, triphenylbenzene, benzofluorene; compounds containing an aromatic heterocyclic group, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, dibenzocarbazole, indolocarbazole, pyridoindole, pyrrolodipyridine, pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, oxazole, dibenzooxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthalene, phthal, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furanopyridine, benzothiophenpyridine, thiophenpyridine, benzoselenophenpyridine and selenophenobenzodipyridine; groups having a 2- to 10-ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups and are linked to each other directly or through at least one of the following groups, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group. Among them, each Ar may be further substituted, and the substituents may be selected from hydrogen, deuterium, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

[0151] In a preferred embodiment, the triplet host material may be selected from compounds containing at least one of the following groups:

[0152]

[0153] Wherein: when Y0 appears multiple times, Y0 is independently selected from C(R)2, NR, O or S; when X0 appears multiple times, X0 is independently selected from CR or N, Ar 1 -Ar 3 is selected from an aryl group or a heteroaryl group, and R may be selected from the following groups: hydrogen, deuterium, halogen atoms (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl, and n6 is an integer from 1 to 20.

[0154] Examples of suitable triplet host materials are listed below, but are not limited to:

[0155]

[0156]

[0157] 2. Singlet Host:

[0158] Examples of the singlet host material are not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of the luminescent body, especially the singlet luminescent body or fluorescent luminescent body.

[0159] Examples of the organic compound used as the singlet host material may be selected from compounds containing a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenylbenzene, benzophenanthrene, naphthalene, anthracene, perylene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, pyrrolodipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furandipyridine, benzothiophenpyridine, thiophenedipyridine, benzoselenophenpyridine and selenophenedipyridine; groups having a 2- to 10-ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups and are linked to each other directly or through at least one of the following groups such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group.

[0160] In a preferred embodiment, the singlet host material may be selected from compounds containing at least one of the following groups:

[0161]

[0162] Y 10 Each occurrence is independently selected from C(R1)2 or NR1 or O or S, X 10 Each occurrence is independently selected from CR1 or N, and each occurrence of R1 is independently selected from the following groups: hydrogen, deuterium, halogen atom (F, Cl, Br, I), cyano group, alkyl group, alkoxy group, amino group, alkenyl group, alkynyl group, aralkyl group, heteroalkyl group, aryl group and heteroaryl group, and n7 is an integer selected from 1 to 20.

[0163] In some preferred embodiments, the singlet host is selected from derivatives of anthracene, such as those disclosed in patent documents such as CN102224614B, CN100471827C, CN1914293B, WO2015033559A1, US2014246657A1, WO2016117848A1, WO2016117861A1, WO2016171429A2, CN102369256B, CN102428158B, etc.

[0164] Examples of anthracene-based singlet host materials are listed below:

[0165]

[0166]

[0167] In some more preferred embodiments, the anthracene-based singlet host material is deuterated, that is, the host material molecule contains at least one deuterium atom. Such examples are disclosed in patent documents such as CN102369256B, CN102428158B, CN102639671B, US2015021586A1, etc. Specific examples are:

[0168]

[0169] 3. Thermally activated delayed fluorescence (TADF) materials:

[0170] Traditional organic fluorescent materials can only utilize 25% of the singlet excitons formed by electrical excitation for luminescence, and the internal quantum efficiency of the device is relatively low (up to 25%). Although phosphorescent materials enhance intersystem crossing due to the strong spin-orbit coupling of heavy atom centers and can effectively utilize singlet excitons and triplet excitons formed by electrical excitation for luminescence, enabling the internal quantum efficiency of the device to reach 100%, the problems such as high cost of phosphorescent materials, poor material stability, and serious device efficiency roll-off limit their application in OLEDs. Thermally activated delayed fluorescence materials are the third generation of organic light-emitting materials developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔE ST ), and triplet excitons can be converted into singlet excitons for luminescence through reverse intersystem crossing. This can make full use of singlet excitons and triplet excitons formed under electrical excitation. The internal quantum efficiency of the device can reach 100%. At the same time, the material structure is controllable, the properties are stable, the price is cheap and no precious metals are required, and it has broad application prospects in the field of OLEDs.

[0171] TADF materials need to have a small singlet-triplet energy level difference, preferably ΔE ST <0.3 eV, preferably ΔE ST <0.25 eV, more preferably ΔE ST <0.20 eV, and most preferably ΔE ST <0.1 eV. In a preferred embodiment, the TADF material has a relatively small ΔE ST, in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF-emitting materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064(A1), Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et.al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et.al. Appl. Phys. Lett., 101, 2012, 093306, Adachi, et.al. Chem. Commun., 48, 2012, 11392, Adachi, et.al. Nature Photonics, 6, 2012, 253, Adachi, et.al. Nature, 492, 2012, 234, Adachi, et.al. J. Am. Chem. Soc, 134, 2012, 14706, Adachi, et.al. Angew. Chem. Int. Ed, 51, 2012, 11311, Adachi, et.al. Chem. Commun., 48, 2012, 9580, Adachi, et.al. Chem. Commun., 49, 2013, 10385, Adachi, et.al. Adv. Mater., 25, 2013, 3319, Adachi, et.al. Adv. Mater., 25, 2013, 3707, Adachi, et.al. Chem. Mater., 25, 2013, 3038, Adachi, et.al. Chem. Mater., 25, 2013, 3766, Adachi, et.al. J. Mater. Chem. C., 1, 2013, 4599, Adachi, et.al. J. Phys. Chem. A., 117, 2013, 5607. The entire contents of the above-listed patents or article documents are hereby incorporated herein by reference.

[0172] Examples of some suitable TADF-emitting materials are listed below:

[0173]

[0174]

[0175] 4. Triplet Emitter

[0176] The triplet emitter is also called a phosphorescent emitter. In a preferred embodiment, the triplet emitter is a metal complex having the general formula M(L)n, where M is a metal atom, and L may be the same or different each time it appears and is an organic ligand that is bonded or coordinatively linked to the metal atom M through one or more positions, and n is an integer between 1 and 6. Preferably, the triplet emitter contains a chelating ligand, that is, a ligand that coordinates with the metal through at least two binding points. Particularly preferred is that the triplet emitter contains two or three identical or different bidentate or polydentate ligands. The chelating ligand is beneficial to improving the stability of the metal complex. In a preferred embodiment, the metal complex that can be used as a triplet emitter has the following form:

[0177]

[0178] The metal atom M2 is selected from transition metal elements, lanthanide elements or actinide elements, preferably selected from Ir, Pt, Pd, Au, Rh, Ru, Os, Re, Cu, Ag, Ni, Co, W or Eu, and particularly preferably selected from Ir, Au, Pt, W or Os.

[0179] Ar1 and Ar2 may be the same or different each time they appear and are a cyclic group, where Ar1 contains at least one donor atom, that is, an atom with a lone pair of electrons, such as nitrogen, through which the cyclic group is coordinatively linked to the metal; where Ar2 contains at least one carbon atom, through which the cyclic group is linked to the metal; Ar1 and Ar2 are covalently linked together, and each may carry one or more substituents, and they may also be linked together through the substituents; L' may be the same or different each time it appears and is a bidentate chelating auxiliary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0, 1, 2 or 3, preferably 2 or 3; q2 may be 0, 1, 2 or 3, preferably 1 or 0. 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, by an alkyl chain or a fluorine- or silicon-containing substituent. The auxiliary ligand may preferably be selected from acetylacetone or picric acid.

[0180] Examples of materials and applications of some triplet emitters can be found in the following patent documents and literature: WO200070655, WO200141512, WO200202714, WO200215645, WO2005033244, WO2005019373, US20050258742, US20070087219, US20070252517, US2008027220, WO2009146770, US20090061681, WO2009118087, WO2010015307, WO2010054731, WO2011157339, WO2012007087, WO201200708, WO2013107487, WO2013094620, WO2013174471, WO2014031977, WO2014112450, WO2014007565, WO2014024131, Baldo et al. Nature(2000), 750, Adachi et al. Appl. Phys. Lett.(2001), 1622, Kido et al. Appl. Phys. Lett.(1994), 2124, Wrighton et al. J. Am. Chem. Soc.(1974), 998, Ma et al. Synth. Metals(1998), 245. The entire contents of the above-listed patent documents and literature are hereby incorporated herein by reference. Examples of some suitable triplet emitters are listed below:

[0181]

[0182] An object of the present invention is to provide a material solution for vapor-deposited OLEDs.

[0183] In certain embodiments, for the compounds according to the present invention, the molecular weight ≤ 1200 g / mol, preferably ≤ 1100 g / mol, more preferably ≤ 1000 g / mol, still more preferably ≤ 950 g / mol, and most preferably ≤ 900 g / mol.

[0184] Another object of the present invention is to provide a material solution for printed OLEDs.

[0185] In certain embodiments, for the compounds according to the present invention, the molecular weight ≥ 800 g / mol, preferably ≥ 1000 g / mol, more preferably ≥ 1100 g / mol, and most preferably ≥ 1200 g / mol.

[0186] In other embodiments, the solubility of the compounds according to the invention in toluene at 25 °C is ≥ 10 mg / mL, preferably ≥ 15 mg / mL, and most preferably ≥ 20 mg / mL.

[0187] The present invention further relates to a composition or an ink comprising a compound according to the invention or at least one polymer, and at least one organic solvent.

[0188] When used in a printing process, the viscosity and surface tension of the ink are important parameters. The surface tension parameter of a suitable ink is suitable for a specific substrate and a specific printing method.

[0189] In a preferred embodiment, the surface tension of the ink according to the invention at the working temperature or at 25 °C is in the range of about 19 dyne / cm to 50 dyne / cm; more preferably in the range of 22 dyne / cm to 35 dyne / cm; most preferably in the range of 25 dyne / cm to 33 dyne / cm.

[0190] In another preferred embodiment, the viscosity of the ink according to the invention at the working 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; most preferably in the range of 4 cps to 20 cps. The composition formulated in this way will facilitate inkjet printing.

[0191] The viscosity can be adjusted by different methods, such as by selecting a suitable solvent and the concentration of the functional materials in the ink. The ink containing the metal-organic complex or polymer according to the invention can facilitate the adjustment of the printing ink within an appropriate range according to the printing method used. Generally, the weight ratio of the functional materials contained in the composition according to the 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%.

[0192] In some embodiments, for the ink according to the invention, the at least one organic solvent is selected from aromatic or heteroaromatic-based solvents, especially aliphatic chain / ring-substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

[0193] Examples of solvents suitable for the present invention include, but are not limited to: aromatic or heteroaromatic-based solvents: p-diisopropylbenzene, amylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene, tripentylbenzene, amyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, 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-(phenyloxiranyl)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-nonanone, fenchone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, phorone, di-n-pentyl ketone; aromatic ether solvents: 3-phenoxytoluene, butoxybenzene, benzyl butylbenzene, 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-ethylphenetole, 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, pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; ester solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolactone, alkyl oleate, etc.

[0194] Furthermore, for the ink according to the present invention, the at least one organic solvent may be selected from: aliphatic ketones, such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, phorone, di-n-amyl ketone, etc.; or aliphatic ethers, such as pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.

[0195] In some other embodiments, the printing ink further comprises another organic solvent. Examples of the another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetralin, decalin, indene and / or their mixtures.

[0196] In a preferred embodiment, the composition according to the present invention is a solution.

[0197] In another preferred embodiment, the composition according to the present invention is a suspension.

[0198] The composition in the embodiments of the present invention may include 0.01 wt% to 20 wt% of the compound or its polymer or mixture according to the present invention, preferably 0.1 wt% to 15 wt%, more preferably 0.2 wt% to 10 wt%, and most preferably 0.25 wt% to 5 wt% of the compound or its polymer or mixture.

[0199] 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 a preparation method by printing or coating is particularly preferred.

[0200] Among them, suitable printing or coating techniques include (but are not limited to) gravure printing, inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, knife coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brush coating or pad printing, slot die coating, etc. Preference is given to inkjet printing, nozzle printing and gravure printing. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, water repellents, adhesives, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. For detailed information on printing techniques and their related requirements for relevant solutions, such as solvents and concentrations, viscosities, etc., please refer to "Handbook of Print Media: Technologies and Production Methods" edited by Helmut Kipphan, ISBN 3-540-67326-1.

[0201] Based on the above compounds or polymers, the present invention further provides an application of the above-mentioned compounds or polymers, that is, applying the compounds or polymers to organic electronic devices, which may be selected from, but not limited to, color converters, organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light-emitting electrochemical cells (OLEECs), organic field-effect transistors (OFETs), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes, etc. Particularly preferred are organic electroluminescent devices, such as OLEDs, OLEECs, and organic light-emitting field-effect transistors. In the embodiments of the present invention, it is preferred to use the compounds in the light-emitting layer of electroluminescent devices.

[0202] The present invention further relates to an organic electronic device comprising at least one of the above-mentioned compounds or polymers or mixtures. Generally, such an organic electronic device at least comprises a cathode, an anode, and a functional layer located between the cathode and the anode, wherein the functional layer at least comprises one of the above-mentioned compounds or polymers. The organic electronic device may be selected from, but not limited to, color converters, organic light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs), organic light-emitting electrochemical cells (OLEECs), organic field-effect transistors (OFETs), organic light-emitting field-effect transistors, organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes, etc. Particularly preferred are organic electroluminescent devices, such as OLEDs, OLEECs, and organic light-emitting field-effect transistors.

[0203] In some particularly preferred embodiments, the organic electronic device comprises a light-emitting layer, and the light-emitting layer comprises one of the compounds, or comprises one of the compounds and a host material, or comprises one of the compounds, a phosphorescent emitter and a host material.

[0204] In some preferred embodiments, the organic electronic device is an organic light-emitting device, which comprises a light-emitting layer, and the guest material of the light-emitting layer comprises at least one of the above-mentioned compounds, polymers or mixtures.

[0205] In the above-mentioned organic electronic device, particularly in an OLED, it includes a substrate, an anode, at least one light-emitting layer, and a cathode.

[0206] The substrate can be opaque or transparent. A transparent substrate can be used to fabricate a transparent light-emitting component. For example, see Bulovic et al., Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or flexible. The substrate can be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate without surface defects is a particularly ideal choice. In a preferred embodiment, the substrate is flexible and can be selected from polymer films or plastics with a glass transition temperature (Tg) of 150 °C or higher, preferably exceeding 200 °C, more preferably exceeding 250 °C, and most preferably exceeding 300 °C. Examples of suitable flexible substrates include polyethylene terephthalate (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

[0207] The anode can include a conductive metal, metal oxide, or conductive polymer. The anode can easily inject holes into the hole injection layer (HIL), hole transport layer (HTL), or light-emitting layer. In a preferred embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light-emitting layer or the p-type semiconductor material serving as the HIL, HTL, or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), etc. Other suitable anode materials are known, and those of ordinary skill in the art can easily select and use them. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc. In some embodiments, the anode is pattern-structured. Patterned ITO conductive substrates are commercially available and can be used to fabricate the devices according to the present invention.

[0208] The cathode may include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light-emitting layer. In a preferred embodiment, the absolute value of the difference between the work function of the cathode and the LUMO energy level or the conduction band energy level of the light-emitting substance in the light-emitting layer or the n-type semiconductor material serving as the electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials that can be used as the cathode of an OLED may be used as the cathode material of the device of the present invention. Examples of cathode materials include, but are not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.

[0209] The OLED 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, and the entire contents of these three patent documents are hereby incorporated herein by reference.

[0210] In a preferred embodiment, in the organic light-emitting device according to the present invention, the light-emitting layer is prepared from the composition according to the present invention.

[0211] The light-emitting device according to the present invention, particularly an OLED, has a light-emitting wavelength between 300 nm and 1500 nm, preferably between 350 nm and 1200 nm, and more preferably between 400 nm and 800 nm.

[0212] The present invention also relates to the application of the organic electronic 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.

[0213] The present invention also relates to an electronic device comprising the organic electronic device according to the present invention, including, but not limited to, a display device, a lighting device, a light source, a sensor, etc. In certain embodiments, the electronic device includes a housing and the device as described above provided on the housing. The electronic device may be various terminal devices equipped with an OLED display screen, including, but not limited to, a smart phone, a tablet computer, a personal laptop computer, a smart TV, a vehicle-mounted display, a smart watch, etc. In some embodiments, the electronic device is a smart phone.

[0214] Embodiment

[0215] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims define the scope of the present invention. Under the guidance of the inventive concept of the present invention, those skilled in the art should realize that certain changes made to the embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0216] 1. Compound synthesis

[0217] Synthesis of Compound 1:

[0218]

[0219] For the synthesis of Compound 1-1, see US10249832B1, April 2019, R. Takahashi, H. Ikeda, K. Seda, Y. Nakano.

[0220] For the synthesis of Compound 1-2, see F. Kreuzer, Dissertation, University of Ulm, 2020.

[0221] Synthesis of Compound 1-3 (2,5-bis(4-methoxycarbazol-1-yl)-3,6-dichloropyrazine):

[0222] Under inert conditions, 18.77 g (2.2 eq, 58.1 mmol) of 1-(4,4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4-methoxy-9H-carbazole (Compound 1-1), 8.11 g (1.0 eq, 26.4 mmol) of 2,5-dibromo-3,6-dichloropyrazine (Compound 1-2), 15.31 g (4.2 eq, 110.9 mmol) of potassium carbonate and 3.05 g (10 mol%, 2.64 mmol) of tetrakis(triphenylphosphine)palladium were dissolved in a mixed solvent of toluene, ethanol and water (5:1:1, 250 mL). The resulting mixture was stirred at 100 °C for two days. After the reaction was completed and cooled to room temperature, the reaction mixture was diluted with dichloromethane, the organic phase was washed with water, and dried over anhydrous magnesium sulfate. The solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography using hexane and ethyl acetate (8:2) as the eluent. The product Compound 1-3 as a white solid (11.3 g, 79%) was obtained, and the success of the reaction was confirmed by mass spectrometry, with the obtained m / z being 538, which was consistent with the calculated m / z 538.

[0223] Synthesis of Compound 1 (Pyrazine Ringazine):

[0224] Under inert conditions, 17.3 g (1.0 eq, 32.1 mmol) of 2,5-bis(4-methoxycarbazol-1-yl)-3,6-dichloropyrazine (Compound 1-3), 11.07 g (2.5 eq, 80.2 mmol) of potassium carbonate, 0.61 g (10 mol%, 3.21 mmol) of copper(I) iodide and 0.74 g (20 mol%, 6.43 mmol) of L-proline were stirred in 125 mL of dimethyl sulfoxide at 150 °C overnight. After cooling to room temperature, the precipitate was filtered out and subjected to short silica gel chromatography to remove the catalyst residue, and the product Compound 1 as a light yellow powder (10.7 g, 72%) was obtained. The success of the reaction was confirmed by mass spectrometry, and the experimental result of m / z 466 was in agreement with the calculated m / z 466.

[0225] Synthesis of Compound 2:

[0226]

[0227] Compound 1 (4.7 g, 10 mmol) was dispersed in 100 mL of dichloromethane (DCM), and BBr3 (1 M DCM solution, 25 mL) was added dropwise at 0°C. The mixture was stirred for 16 hours and then poured into water. The precipitate was collected by filtration, washed with water and dried in vacuo. The obtained white solid 2-1 was directly dissolved in a mixed solvent (50 mL / 50 mL) of dry pyridine and DCM without further purification. Subsequently, trifluoromethanesulfonic anhydride (14.1 g, 50 mmol) was added thereto in portions, and the resulting mixture was stirred at room temperature for 24 hours to fully react. After the reaction was completed, the organic phase was washed with hydrochloric acid and water in sequence, dried with anhydrous sodium sulfate, and evaporated under reduced pressure to remove the solvent. The crude product was purified by silica gel column chromatography using a mixture of hexane and DCM as an eluent (6:4) to obtain a white solid product compound 2-2 (2.45 g, 35%). The success of the reaction was confirmed by mass spectrometry, with a measured m / z of 702, consistent with the calculated m / z of 702.

[0228] Under inert conditions, a mixture of compound 2-2 (703 mg, 1 mmol), (4-isopropylphenyl)aniline (844 mg, 4 mmol), sodium tert-butyrate (576 mg, 6 mmol), palladium acetate (11 mg, 0.05 mmol) and tri-tert-butylphosphine (20 mg, 0.1 mmol) was dissolved in toluene and stirred at 120°C for 24 hours. After the reaction was completed and cooled to room temperature, the mixture was diluted with DCM, the organic phase was washed with water, and dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (eluent hexane: DCM = 8: 2) to obtain compound 2 as a yellow solid (685 mg, 83%). The product was confirmed by mass spectrometry, and the measured m / z was 824, which was consistent with the calculated m / z 824.

[0229] Synthesis of compound 3:

[0230]

[0231] Under inert conditions, compound 3-1 (93.2 g, 0.5 mol), compound 3-2 (111.6 g, 0.55 mol), potassium carbonate (152 g, 1.1 mol) and Pd(PPh3)4 (2.54 g, 2%) were dissolved in a mixture of toluene, ethanol and water (5:2:1, 1000 mL) and stirred at 100 ° C for 24 hours. After the reaction was completed and cooled to room temperature, the mixture was diluted with DCM, the organic phase was washed with water, and dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography with hexane and ethyl acetate (8:2) as eluents, and the product compound 3-3 (109.8 g, 83%) was obtained as a yellow solid. The product was confirmed by mass spectrometry, and the measured m / z was 264, which was consistent with the calculated m / z 264.

[0232] In a round-bottom flask, compound 3-3 (100 g, 0.38 mol) and 1,2-bis(diphenylphosphino)ethane (751 g, 1.9 mol) were stirred at 150 °C under a nitrogen atmosphere for 5 hours. The mixture was cooled to room temperature, diluted with DCM, the organic phase was washed with water and dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting crude product was purified by silica gel column chromatography using n-hexane and ethyl acetate as the eluent (8:2). The product was a yellow solid compound 3-4 (29.2 g, 33%). The product was confirmed by mass spectrometry, and the measured m / z was 232, which was consistent with the calculated m / z 232.

[0233] Under inert conditions, compound 3-4 (25 g, 107.4 mmol), bis(pinacolato)diboron (40.9 g, 161.2 mmol), potassium acetate (26.4 g, 268.5 mmol), Pd2dba3 (2.46 g, 2.5%) and XPhos (2.56 g, 5%) were dissolved in 1,4-dioxane (500 mL) and stirred at 110 °C for 16 hours. After the reaction was completed and cooled to room temperature, the mixture was diluted with DCM, the organic phase was washed with water, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The resulting crude product was subjected to silica gel column chromatography using n-hexane and ethyl acetate as the eluent (8:2) to obtain a yellow solid compound 3-5 (28.9 g, 83%). The product was confirmed by mass spectrometry, and the measured m / z was 324, which was consistent with the calculated m / z 324.

[0234] Under a nitrogen atmosphere, compound 3-5 (25 g, 77.1 mmol), 1,4-dibromo-2,5-diiodobenzene (18.8 g, 38.6 mmol), potassium carbonate (22.4 g, 162 mmol) and Pd(PPh3)4 (2.23 g, 5%) were dispersed in a mixture of toluene, ethanol and water (5:2:1, 250 mL) and stirred at 100 °C. After the reaction was completed and cooled to room temperature, the mixture was diluted with DCM, the organic phase was washed with water and dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate 7:3) to obtain a yellow solid compound 3-6 (17.9 g, 74%). The product was confirmed by mass spectrometry, and the measured m / z was 628, which was consistent with the calculated m / z 628.

[0235] A mixture of compound 3-6 (15 g, 23.9 mmol), CuI (909 mg, 4.8 mmol), L-proline (1.4 g, 11.9 mol) and potassium carbonate (8.2 g, 59.8 mmol) was dissolved in 100 mL DMSO under inert conditions and stirred at 150 ° C for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, diluted with DCM, and the organic phase was washed with water and dried over anhydrous sodium sulfate. After the solvent was removed by rotary evaporation, the crude product was purified by silica gel chromatography with hexane and ethyl acetate (9:1) as eluent to obtain compound 3-7 as a yellow solid (10.1 g, 91%). The product was confirmed by mass spectrometry, and the measured m / z was 466, which was consistent with the calculated m / z 466.

[0236] Compound 3-7 (9 g, 19.3 mmol) was dispersed in ultra-dry DCM and cooled to 0°C. Boron tribromide solution (50 mL, 1 M) was added dropwise at 0°C, followed by stirring at room temperature overnight. After the reaction was completed, the solution was poured into 1000 mL of water, filtered, the precipitate was washed with water, and vacuum dried to obtain compound 3-8 as a white solid. Without further purification, the obtained compound 3-8 was directly dissolved in a mixture of 200 mL DCM and 200 mL pyridine. Then propionic anhydride (20 mL) was slowly added and stirred at room temperature for 24 hours. After the reaction was completed, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography with hexane and ethyl acetate (9:1) as eluent to obtain yellow solid compound 3-9 (5 g, 37%). The product was confirmed by mass spectrometry, and the measured m / z was 702, which was consistent with the calculated m / z 702.

[0237] Under inert conditions, compound 3-9 (703 mg, 1 mmol), N-(4-isopropylphenyl)aniline (528 mg, 2.5 mmol), palladium acetate (11 mg, 0.05 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and sodium tert-butoxide (576 mg, 6 mmol) were dissolved in 50 mL of toluene and stirred at 120 ° C for 24 hours. After the reaction was completed, the solution was cooled to room temperature and diluted with DCM, the organic phase was washed with water, and dried over anhydrous sodium sulfate. After the solvent was removed by rotary evaporation, the crude product was purified by silica gel column chromatography (hexane / ethyl acetate 9:1) to obtain a yellow solid compound 3 (718 mg, 87%). The product was confirmed by mass spectrometry, and the measured m / z was 824, which was consistent with the calculated m / z 824.

[0238] Synthesis of compound 4:

[0239]

[0240] Under inert conditions, a mixture of compound 2-2 (703 mg, 1 mmol), bis(4-isopropylphenyl)aniline 4-1 (1052 mg, 2.5 mmol), sodium tert-butoxide (576 mg, 6 mmol), palladium acetate (11 mg, 0.05 mmol) and tri-tert-butylphosphine (20 mg, 0.1 mmol) was dissolved in 50 mL of toluene and heated to 120°C while stirring vigorously. Subsequently, the mixture was cooled to room temperature and diluted with DCM, the organic phase was washed with water, dried over anhydrous sodium sulfate, and the solvent was removed by evaporation under reduced pressure. The crude product was purified by silica gel column chromatography using hexane and ethyl acetate (9:1) as eluent to obtain a yellow solid compound 4 (982 mg, 79%). The product was confirmed by mass spectrometry, and the measured m / z was 1243, which was consistent with the calculated m / z 1243.

[0241] Synthesis of compound 5:

[0242]

[0243]

[0244] A mixture of compound 5-1 (50 g, 0.123 mol), compound 1-2 (37.8 g, 0.123 mol), potassium carbonate (37.3 g, 0.27 mol) and Pd (PPh 3) 4 (3.6 g, 2.5%) was dissolved in a mixture of toluene, ethanol and water (5: 2: 1, 1000 mL) and heated to 100 ° C with stirring. After 16 hours, the reaction was cooled to room temperature and diluted with DCM, the organic phase was washed with water and dried over anhydrous sodium sulfate. After the solvent was removed by rotary evaporation, the crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate 8: 2) to obtain a white solid product compound 5-2 (35.4 g, 57%). The product was confirmed by mass spectrometry, and the measured m / z was 503, which was consistent with the calculated m / z 503.

[0245] Under inert conditions, compound 5-2 (33 g, 65 mmol), compound 1-1 (25.3 g, 78 mmol), potassium carbonate (23.7 g, 172 mmol) and Pd (PPh3) 4 (1.9 g, 2.5%) were dissolved in a mixture of toluene, ethanol and water (5:2:1, 500 mL). The resulting two-phase system was stirred at 100 ° C for 24 hours. After cooling to room temperature, DCM was added, the organic phase was washed with water and dried with sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was subjected to silica gel column chromatography (hexane / ethyl acetate 8:2) to obtain yellow solid compound 5-3 (29.5 g, 73%). The product was confirmed by mass spectrometry, and the measured m / z was 620, which was consistent with the calculated m / z 620.

[0246] Under nitrogen atmosphere, compound 5-3 (25 g, 40.2 mmol), CuI (1.5 g, 8 mmol), L-proline (1.8 g, 16 mol) and potassium carbonate (13.9 g, 100.5 mmol) were dissolved in 170 mL DMSO and heated to 150 ° C overnight. After the reaction, the mixture was cooled to room temperature and then poured into water. After filtration, the precipitate was washed with water and then dried in vacuo to obtain white solid compound 5-4 (12.4 g, 56%). The product was confirmed by mass spectrometry, and the measured m / z was 548, which was consistent with the calculated m / z 548.

[0247] Compound 5-4 (10 g, 18.2 mmol) was dispersed in 200 mL of dry DCM, and BBr3 (1 M, 36 mL) was added dropwise at 0 ° C. After stirring for 4 hours, the solution was poured into water, filtered, the precipitate was washed with water, and vacuum dried to obtain white solid compound 5-5. Without further purification, compound 5-5 was dissolved in a mixture of 100 mL of DCM and 100 mL of pyridine. Trifluoromethanesulfonic anhydride (20 mL) was added and stirred for 24 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (hexane / ethyl acetate 8:2) to obtain yellow solid compound 5-6 (5.0 g, 41%). The product was confirmed by mass spectrometry, and the measured m / z was 666, which was consistent with the calculated m / z 666.

[0248] Under inert conditions, compound 5-6 (667 mg, 1 mmol), N-(4-isopropylphenyl)aniline (264 mg, 1.3 mmol), palladium acetate (11 mg, 0.05 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and sodium tert-butoxide (288 mg, 3 mmol) were dissolved in 50 mL of toluene and stirred at 120 ° C for 24 hours. After the reaction was completed, it was cooled to room temperature, the reaction mixture was diluted with DCM, the organic phase was washed with water and dried over anhydrous sodium sulfate. After the solvent was removed by rotary evaporation, the crude product was purified by silica gel column chromatography (hexane / ethyl acetate 9:1) to obtain yellow solid compound 5 (633 mg, 87%). The product was confirmed by mass spectrometry, and the measured m / z was 727, which was consistent with the calculated m / z 727.

[0249] Synthesis of compound 6:

[0250]

[0251] In a Shrek tube filled with nitrogen, compound 5-6 (667 mg, 1 mmol), compound 4-1 (526 mg, 1.3 mmol), palladium acetate (11 mg, 0.05 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and naphthyl ethyl ester (288 mg, 3 mmol) were dissolved in 50 mL of toluene and stirred overnight at 120 ° C. The reaction was cooled to room temperature, diluted with DCM, and the organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (hexane / ethyl acetate 9:1) to obtain yellow solid compound 6 (619 mg, 66%). The product was confirmed by mass spectrometry, and the measured m / z was 936, which was consistent with the calculated m / z 936.

[0252] Synthesis of compound 7:

[0253]

[0254] A mixture of compound 7-1 (111.2 g, 0.5 mol), compound 7-2 (100 g, 0.6 mol), potassium carbonate (138 g, 1 mol) and Pd(PPh3)4 (5.8 g, 1%) was dissolved in a mixture of toluene, ethanol and water (5:2:1, 1000 mL) under inert conditions, heated to 100 ° C, and stirred for 24 hours. After the reaction was completed, the solution was cooled to room temperature and diluted with DCM. The organic phase was washed with water, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate 8:2) to obtain a white solid compound 7-3 (111.2 g, 84%). The product was confirmed by mass spectrometry, and the measured m / z of 264 was consistent with the calculated m / z 264.

[0255] Under inert conditions, a mixture of compound 7-3 (100 g, 0.38 mol) and 1,2-bis(diphenylphosphine)ethane (751 g, 1.9 mol) was heated to 150 ° C and reacted for 12 hours. After the reaction was completed, it was cooled to room temperature and then washed with ethanol. The residue was purified by silica gel column chromatography (hexane / ethyl acetate 7:3) to obtain a yellow solid compound 7-4 (37.1 g, 42%). The product was confirmed by mass spectrometry, and the measured m / z was 232, which was consistent with the calculated m / z 232.

[0256] Compound 7-4 (35 g, 150.4 mmol), bis(pinacolato)diboron (57.3 g, 225.6 mmol), potassium acetate (44.2 g, 451.2 mmol), Pd2dba3 (3.44 g, 2.5%), and XPhos (3.58 g, 5%) were stirred in 1,4-dioxane (700 mL) at 110 °C for 16 h. After the reaction was completed, the solvent was removed by rotary evaporation. The crude product was washed with hexane and purified by silica gel column chromatography using hexane and ethyl acetate (8:2) as the eluent to obtain yellow solid compound 7-5 (44.4 g, 91%). The product was confirmed by mass spectrometry, and the measured m / z was 324, which was consistent with the calculated m / z 324.

[0257] Compound 7-5 (40 g, 123.4 mmol), 1,4-dibromo-2,5-diiodobenzene (30.1 g, 61.8 mmol), potassium carbonate (35.8 g, 259 mmol), and Pd(PPh3)4 (3.57 g, 5%) were added to a mixture of toluene, ethanol, and water (5:2:1, 400 mL), and the mixture was stirred at 100 °C for 28 h. After the reaction was completed, the solution was cooled to room temperature, diluted with DCM, washed with water, and dried over anhydrous sodium sulfate. After the solvent was removed by rotary evaporation, the crude product was purified by silica gel column chromatography (hexane / ethyl acetate 8:2) to obtain yellow solid compound 7-6 (38.8 g, 57%). The product was confirmed by mass spectrometry, and the measured m / z was 628, which was consistent with the calculated m / z 628.

[0258] A mixture of compound 7-6 (30 g, 47.8 mmol), CuI (1.8 g, 9.6 mmol), L-proline (2.8 g, 23.8 mol), and potassium carbonate (16.4 g, 119.6 mmol) was added to 200 mL of DMSO, and the temperature was raised to 150 °C and stirred under inert conditions for 24 h. Then the solution was poured into cold ethanol for precipitation and filtered. The collected crude product was purified by silica gel column chromatography using hexane and ethyl acetate (9:1) as the eluent to obtain yellow solid compound 7-7 (16.1 g, 72%). The product was confirmed by mass spectrometry, and the measured m / z was 466, which was consistent with the calculated m / z 466.

[0259] Compound 7-7 (15 g, 32.2 mmol) was dispersed in 250 mL of dry DCM, and boron tribromide (1 M DCM solution, 80 mL) was carefully added at 0 ° C. After stirring at room temperature for 8 hours, the resulting mixture was poured into water. The solid was collected by filtration, washed with water and then dried in vacuo. Without further purification, the obtained compound 7-8 was directly used for the next step of the reaction. Compound 7-8 was dissolved in a mixture of DCM and pyridine (150 mL each) under inert conditions, and 30 mL of trifluoromethanesulfonic anhydride was carefully added thereto, and the reaction was stirred overnight. After the reaction was completed, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (hexane / ethyl acetate 9:1) to obtain a yellow solid compound 7-9 (9.7 g, 43%). The product was confirmed by mass spectrometry, and the measured m / z of 702 was consistent with the calculated m / z702.

[0260] Under inert conditions, compound 7-9 (703 mg, 1 mmol), N-(4-isopropylphenyl)aniline (528 mg, 2.5 mmol), palladium acetate (11 mg, 0.05 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and sodium tert-butoxide (576 mg, 6 mmol) were dissolved in 50 mL of toluene and stirred at 120 ° C for 24 hours. After the reaction was completed, the solution was cooled to room temperature and diluted with DCM, the organic phase was washed with water, and dried over anhydrous sodium sulfate. After the solvent was removed by rotary evaporation, the crude product was purified by silica gel column chromatography (hexane / ethyl acetate 9:1) to obtain yellow solid compound 7 (634 mg, 77%). The product was confirmed by mass spectrometry, and the measured m / z was 824, which was consistent with the calculated m / z 824.

[0261] Synthesis of compound 8:

[0262]

[0263] A mixture of compound 2-2 (703 mg, 1 mmol), compound 8-1 (861 mg, 3 mmol), potassium carbonate (911 mg, 6.6 mmol) and Pd(PPh3)4 (58 mg, 5%) was dissolved in a mixture of toluene, ethanol and water (5:2:1, 50 mL) in an inert atmosphere and heated to 100 ° C overnight with stirring. After cooling to room temperature, DCM was added, the organic phase was washed with water and dried over anhydrous sodium sulfate. After the solvent was removed by rotary evaporation, the crude product was purified by silica gel column chromatography (hexane / ethyl acetate 9:1) to obtain yellow solid compound 8 (649 mg, 73%). The product was confirmed by mass spectrometry, and the measured m / z of 888 was consistent with the calculated m / z 888.

[0264] Synthesis of compound 9:

[0265]

[0266] Under inert conditions, compound 2-2 (703 mg, 1 mmol), compound 9-1 (1081 mg, 3 mmol), potassium carbonate (911 mg, 6.6 mmol) and Pd(PPh3)4 (58 mg, 5%) were dissolved in a mixture of toluene, ethanol and water (5:2:1, 50 mL) at 100 °C and stirred for 24 hours. After the reaction, the mixture was cooled to room temperature, diluted with DCM, and the organic phase was washed with water in batches. After combination, it was dried over anhydrous sodium sulfate. After removing the solvent by rotary evaporation, the crude product was purified by silica gel column chromatography using n-hexane and ethyl acetate (9:1) as the eluent to obtain white solid compound 9 (663 mg, 64%). The product was confirmed by mass spectrometry, and the measured m / z was 1034, which was consistent with the calculated m / z 1034.

[0267] 2. Device Fabrication and Characterization

[0268] The following is a detailed description of the preparation process of the above OLED device through specific examples. The OLED device structure is HI(30) / HT-1(50) / HT-2(10) / BH-1:Dopant = 97:3(25) / ET:LiQ = 50:50(30) / LiQ(1) / Al(100).

[0269]

[0270] a. Cleaning of the ITO (indium tin oxide) conductive glass substrate: Clean it with various solvents (such as one or several of chloroform, acetone or isopropanol), and then perform ultraviolet ozone treatment.

[0271] b. Evaporation: Transfer the ITO substrate into a vacuum vapor deposition device. Under high vacuum (1×10 -6 mbar), a HI layer with a thickness of 30 nm is formed using a resistance heating evaporation source. A hole transport layer HT-1 with a thickness of 50 nm is evaporated on the HI layer, and then a 10 nm HT-2 layer is formed on the HT-1 layer. Subsequently, two evaporation sources are used, and the materials are vaporized at different rates to make the weight ratio of BH-1:Dopant 97:3, forming a 25 nm light-emitting layer. Then, the electron transport layer is evaporated. ET and LiQ are placed in different evaporation units and co-deposited at a ratio of 50 wt% each to obtain a 30 nm electron transport layer. Subsequently, 1 nm of LiQ is deposited as the electron injection layer, and finally, an Al cathode with a thickness of 100 nm is deposited on the electron injection layer.

[0272] c. Encapsulation: The device is encapsulated with ultraviolet curable resin in a nitrogen glove box.

[0273] The device performances of the above-mentioned examples and comparative examples were tested, as specifically shown in Table 1; among them, the external quantum efficiency (EQE) was tested at a current density of 10 mA / cm 2 and the device lifetime of T95 refers to the time when the device brightness decays to 95% at a constant current density of 50 mA / cm 2 , with the value of Comparative Example 1 as the reference (100%).

[0274] Table 1

[0275]

[0276] It can be seen from the device data results in Table 1 that the external quantum efficiency and lifetime of Device Examples 1 - 9 are improved compared with the comparative examples.

[0277] It should be noted that the above is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of changes or substitutions, which should all be covered within the protection scope of the present invention; without conflict, the implementation manners of the present invention and the features in the implementation manners can be combined with each other. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A compound having a structure shown in the following chemical formula (I): in: A and B are a fused ring system having 5 to 20 ring atoms; Ar1 and Ar2 may be the same or different and may be selected from a linear alkyl or alkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, 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 an arylamine or heteroarylamine group having 5 to 40 ring atoms, or a combination of these groups; X is CR 1 or N, when A and B are both non-N hetero-fused ring systems, at least one X is N; R 1 at each occurrence, may be identical or different and is selected from H, D, or a linear alkyl, haloalkyl, alkoxy, thioalkoxy radical having 1 to 20 C atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy, silyl radical having 3 to 20 C atoms, or a keto radical having 1 to 20 C atoms, or an alkoxycarbonyl radical having 2 to 20 C atoms, or an aryloxycarbonyl radical having 7 to 20 C atoms, or a cyano, carbamoyl, haloformyl, formyl, isocyano, Isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I, 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 an arylamine or heteroarylamine group having 5 to 40 ring atoms, a disubstituted unit at any position of the above groups or a combination of these groups, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded.

2. The compound according to claim 1, characterized in that The compounds have structures shown in the following chemical formulas (Ia)-(Id): Among them, Ar3-Ar 10 It is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms.

3. The compound according to claim 1, characterized in that The compound has a structure shown in chemical formula (I-1): Where X is CR 1 or N, and at least one of them is N.

4. The compound according to claim 1 or 3, characterized in that The compound has a structure shown by one of the chemical formulas (I-1a) to (I-1d):

5. The compound according to any one of claims 1 to 4, characterized in that At least one R 1 is selected from F, Cl, cyano, phenoxy, p-methoxyphenylthio, a partially or fully fluorinated alkyl chain or one of the following groups: Where: m1 is 1, 2 or 3; X1-X8 is selected from CR 2 or N, and no two adjacent ones among X1-X8 are N; M 1 、M 2 、M 3 Each independently represents NR 2 , CR 2 R 3 、SiR 2 R 3 、O、C=NR 2 、C=CR 2 R 3 , PR 2 、P(=O)R 2 , S, S=O, SO2 or none; R 2 , R 3 , R 4 , R 5 at each occurrence, may be identical or different and is selected from H, D, or a linear alkyl, haloalkyl, alkoxy, thioalkoxy radical having 1 to 20 C atoms, or a branched or cyclic alkyl, haloalkyl, alkoxy, thioalkoxy, silyl radical having 3 to 20 C atoms, or a keto radical having 1 to 20 C atoms, or an alkoxycarbonyl radical having 2 to 20 C atoms, or an aryloxycarbonyl radical having 7 to 20 C atoms, or a cyano, carbamoyl, haloformyl, formyl, isocyano, Isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, I, 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 an arylamine or heteroarylamine group having 5 to 40 ring atoms, a disubstituted unit at any position of the above groups or a combination of these groups, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or with the ring to which the groups are bonded.

6. The compound according to any one of claims 1 to 5, characterized in that Ar1-Ar 10 Can be the same or different, and independently selected from one of the following groups: in: w is independently selected from CR at each occurrence 6 R 7 NR 6 、O、S、SiR 6 R 7 , PR 6 、P(=O)R 6 , S=O, S(=O)2 or C=O; v is independently selected from CR at each occurrence 8 or N; R 6 -R 8 At each occurrence, it is independently selected from H, D, or a straight-chain alkyl, alkoxy, thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy, thioalkoxy, silyl group having 3 to 20 C atoms, or a keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, CF3, Cl, Br, F, I, a crosslinkable group, or a substituted or unsubstituted aromatic group or heteroaromatic group having 5 to 60 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

7. A polymer comprising at least one first repeating unit, characterized in that The first repeating unit comprises at least one structure corresponding to the compound according to any one of claims 1 to 6.

8. A composition, characterized in that Contains a compound as claimed in any one of claims 1 to 6 or at least one polymer as claimed in claim 7, and at least one organic solvent.

9. A mixture, characterized in that It comprises a compound as described in any one of claims 1 to 6 or a polymer as described in claim 7, and at least one organic functional material, wherein the organic functional material is selected from at least one of a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a luminophore and a host material.

10. An organic electronic device comprising a compound as claimed in any one of claims 1 to 6 or a polymer as claimed in claim 7 or a mixture as claimed in claim 9.

11. The organic electronic device according to claim 10, characterized in that: The organic electronic device is selected from a color converter, an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spin electronic device, an organic sensor or an organic plasmon emission diode.

12. The organic electronic device according to claim 10, characterized in that: The organic electronic device is an organic light-emitting device, which comprises a light-emitting layer, wherein the guest material of the light-emitting layer comprises at least one compound according to any one of claims 1 to 6, a polymer according to claim 7, or a mixture according to claim 9.

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