Materials for electronic devices

Abstract

The invention relates to a compound according to formula (I), to the use thereof in an electronic device, to a method for the production thereof, and to an electronic device comprising a compound according to formula (I).

Description

[0001] This application relates to an aromatic amine compound containing a heteroaryl group selected from dibenzofuranyl, dibenzothiopheneyl, and carbazoleyl groups, and a biphenyl moiety having an amine substituent bonded thereto. The compound is suitable for use in electronic devices.

[0002] In the context of this application, "electronic device" is understood to mean a so-called organic electronic device that contains organic semiconductor materials as functional materials. More specifically, these are understood to mean OLED (Organic Light Emitting Device). The term OLED is understood to mean an electronic device having one or more layers containing organic compounds and emitting light when a voltage is applied. The general principles of the construction and function of OLEDs are known to those skilled in the art.

[0003] There is great interest in improving performance data in electronic devices, especially OLEDs. However, no completely satisfactory solution has yet been found in these areas.

[0004] The light-emitting layer and the hole-transporting layer have a significant impact on the performance data of electronic devices. There is also a search for novel compounds for use in these layers, particularly hole-transporting compounds and compounds that can be used as hole-transporting matrix materials in the light-emitting layer, especially for hole-transporting matrix materials in phosphorescent emitters. To this end, compounds with high glass transition temperatures, high stability, and high hole conductivity are particularly sought. High stability of the compounds is a prerequisite for achieving long lifetimes in electronic devices. Furthermore, it is necessary to find compounds whose use in electronic devices leads to improvements in device performance data, particularly compounds that result in high efficiency, long lifetime, and low operating voltage.

[0005] In the prior art, triarylamine compounds, particularly spirodifluoreneamine and fluoreneamine, are known as hole transport materials and hole transport matrix materials for electronic devices. Heteroaryl-substituted benzidines are also known, as disclosed in WO2023 / 025971, WO2019 / 206292, CN110577510, and CN116478115. Nevertheless, there is still room for improvement regarding the aforementioned properties.

[0006] Aromatic amines of formula (I) below have been found to have excellent suitability for electronic devices, characterized by comprising a heteroaryl-substituted benzidine moiety. They are particularly suitable for use in OLEDs, and even more specifically, as hole transport materials and as hole transport matrix materials, particularly for hole transport matrix materials in phosphorescent emitters. These compounds result in devices with high lifetime, high efficiency, and low operating voltage. More preferably, the discovered compounds possess high glass transition temperature, high stability, low sublimation temperature, good solubility, good synthetic accessibility, and high hole conductivity.

[0007] Therefore, this application relates to a compound according to formula (I).

[0008]

[0009] Formula (I),

[0010] The following applies to variables present in the formula:

[0011] Z 1 Selected from CR in each occurrence, either identically or differently. 1 and N;

[0012] If introduced into containing Z 11 Z 12 Z 13 Z 14 The bond in the ring is not with Z 11 Z 12 Z 13 Z 14 Connect, then Z 11 Z 12 Z 13 Z 14 Each is selected from CR, either the same or different. 11 and N, and if introduced into containing Z 11 Z 12 Z 14 The bond in the ring and Z 11 Z 12 Z 14 Connect, then Z 11 Z 12 Z 14 It is C;

[0013] Z 15 Selected from CR in each occurrence, either identically or differently. 11 and N;

[0014] Y is selected from O, S, and NR. 2 ;

[0015] Ar 1 Each occurrence may be identical or different from phenyl, biphenyl, terphenyl, and tetraphenyl, as well as fluorene, wherein each of the phenyl, biphenyl, terphenyl, and tetraphenyl groups R 31 The fluorene group is replaced by a group R at one of its 1 to 4 positions. 3 replace;

[0016] R 1 Each time it appears, it is selected from H, D, F, C (=O)R, either the same or different. 4 CN, Si(R)4 3. N(R) 4 2. P(=O)(R) 4 2. OR 4 S(=O)R 4 S(=O)2R 4 Straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms; branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms; alkenyl or alkynyl groups having 2 to 20 carbon atoms; aromatic ring systems having 6 to 40 aromatic ring atoms; and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more groups R 1 They can be linked together to form rings; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are bound by the R group. 4 Substitution, and wherein one or more CH2 groups of the alkyl, alkoxy, alkenyl, and alkynyl groups are in each case -R 4 C=CR 4 -、-C≡C-、Si(R 4 2. C=O, C=NR 4 -C(=O)O-, -C(=O)NR 4 -、NR 4 P(=O)(R) 4 Replace with -O-, -S-, SO or SO2;

[0017] R 11 Each time it appears, it is selected from H, D, F, C (=O)R, either the same or different. 4 CN, Si(R) 4 3. N(R) 4 2. P(=O)(R) 4 2. OR 4 S(=O)R 4 S(=O)2R 4 Straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms; branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms; alkenyl or alkynyl groups having 2 to 20 carbon atoms; aromatic ring systems having 6 to 40 aromatic ring atoms; and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more groups R 11 They can be linked together to form rings; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are bound by the R group. 4 Substitution, and wherein one or more CH2 groups of the alkyl, alkoxy, alkenyl, and alkynyl groups are in each case -R 4 C=CR 4 -、-C≡C-、Si(R 42. C=O, C=NR 4 -C(=O)O-, -C(=O)NR 4 -、NR 4 P(=O)(R) 4 Replace with -O-, -S-, SO or SO2;

[0018] R 2 Each time it appears, it is selected from straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein the alkyl groups and the aromatic ring systems and heteroaromatic ring systems are surrounded by the group R. 4 replace;

[0019] R 3 Each time it appears, it is selected from H, D, F, C (=O)R, either the same or different. 4 CN, Si(R) 4 3. N(R) 4 2. P(=O)(R) 4 2. OR 4 S(=O)R 4 S(=O)2R 4 Straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms; branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms; alkenyl or alkynyl groups having 2 to 20 carbon atoms; aromatic ring systems having 6 to 40 aromatic ring atoms; and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more groups R 3 They can be linked together to form rings; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are bound by the R group. 4 Substitution, and wherein one or more CH2 groups of the alkyl, alkoxy, alkenyl, and alkynyl groups are in each case -R 4 C=CR 4 -、-C≡C-、Si(R 4 2. C=O, C=NR 4 -C(=O)O-, -C(=O)NR 4 -、NR 4 P(=O)(R) 4 Replace with -O-, -S-, SO or SO2;

[0020] R 31 Each time it appears, it is selected from H, D, F, C (=O)R, either the same or different. 4 CN, Si(R) 4 3. N(R)4 2. P(=O)(R) 4 2. OR 4 S(=O)R 4 S(=O)2R 4 A straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms; a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms; an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein two or more groups R 31 They can be linked together to form a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups are connected by the group R. 4 Substitution, and wherein one or more CH2 groups of the alkyl, alkoxy, alkenyl, and alkynyl groups are in each case -R 4 C=CR 4 -、-C≡C-、Si(R 4 2. C=O, C=NR 4 -C(=O)O-, -C(=O)NR 4 -、NR 4 P(=O)(R) 4 Replace with -O-, -S-, SO or SO2;

[0021] R 4 Each time it appears, it is selected from H, D, F, C (=O)R, either the same or different. 5 CN, Si(R) 5 3. N(R) 5 2. P(=O)(R) 5 2. OR 5 S(=O)R 5 S(=O)2R 5 Straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms; branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms; alkenyl or alkynyl groups having 2 to 20 carbon atoms; aromatic ring systems having 6 to 40 aromatic ring atoms; and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more groups R 4 They can be linked together to form rings; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are bound by the R group. 5 Substitution, and wherein one or more CH2 groups of the alkyl, alkoxy, alkenyl, and alkynyl groups are in each case -R 5 C=CR 5 -、-C≡C-、Si(R 5 2. C=O, C=NR 5 -C(=O)O-, -C(=O)NR 5 -、NR5 P(=O)(R) 5 Replace with -O-, -S-, SO or SO2;

[0022] R 5 Each time it appears, it is selected from H, D, F, CN, alkyl groups having 1 to 20 carbon atoms, aromatic ring systems having 6 to 40 carbon atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, either identically or differently; wherein two or more groups R 5 They can be linked together to form a ring; and said alkyl groups, aromatic ring systems and heteroaromatic ring systems can be substituted by one or more groups selected from F and CN;

[0023] The inclusion of Z 11 Z 12 Z 13 and Z 14 The bond in the ring and Z 11 Z 12 and Z 14 One of the connections, and

[0024] If introduced into a system containing Z 11 Z 12 Z 13 and Z 14 The bond in the ring and Z 14 If connected, the two Ar groups 1 One of them is selected from the R group 3 The substituted fluorene group, and the two Ar groups 1 Another one selected from each of the R 31 Substituted phenyl, biphenyl, terphenyl, and tetraphenyl; and

[0025] Where Y is O or S, then it is introduced into the case of Z. 11 Z 12 Z 13 and Z 14 The bond in the ring and Z 11 and Z 14 One of the connections.

[0026] The first four bits of the fluorene group are shown below:

[0027]

[0028] The following definitions apply to chemical groups used as general definitions. They still apply unless a more specific definition is given.

[0029] The aryl group referred to herein is a simple aromatic ring, such as benzene, or a fused aromatic polycyclic ring, such as naphthalene, phenanthrene, or anthracene. A fused aromatic polycyclic ring in the sense of this application consists of two or more simple aromatic rings fused together. The aryl group in the sense of this invention contains 6 to 40 aromatic ring atoms. The aryl group does not contain any heteroatoms as aromatic ring atoms, but only carbon atoms as aromatic ring atoms.

[0030] The heteroaryl group referred to herein refers to a simple heteroaromatic ring, such as pyridine, pyrimidine, or thiophene, or a fused heteroaromatic polycyclic ring, such as quinoline or carbazole. A fused heteroaromatic polycyclic ring in the sense of this application consists of two or more simple aromatic or heteroaromatic rings fused together, wherein at least one of the two or more simple aromatic or heteroaromatic rings is a heteroaromatic ring. The heteroaryl group in the sense of this invention contains 5 to 40 aromatic ring atoms, wherein at least one is a heteroatom. The heteroatom is preferably selected from N, O, and S.

[0031] In each case, aryl or heteroaryl groups that can be substituted by the aforementioned groups, particularly those derived from the following substances: benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, leucine, perylene, fluoranthene, benzo[a]anthracene, benzo[a]phenanthrene, tetraphenylene, pentaphenylene, benzo[a]pyrene, furan, benzo[a]furan, isobenzo[a]furan, dibenzo[a]furan, thiophene, benzo[a]thiophene, isobenzo[a]thiophene, dibenzo[a]thiophene, pyrrole, indole, isoindole, carbamate, etc. Azole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenanthridine, pyrazole, indazole, imidazole, benzimidazole, benzimidazole[1,2-a]benzimidazole, naphthiamidazole, phenanthridineimidazole, pyrazinimidazole, quinoxalineimidazole, pyrazole, benzo[2]pyridineimidazole, naphthiamidazole Anthrazoazole, phenanthreneazole, isothrazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthidine, azacarbazole, benzocarbline, phenanthrene, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-diazole, 1,2,4-diazole, 1,2,5-diazole 1,3,4-thiadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indoleazine, and benzothiadiazole.

[0032] In the context of this invention, an aromatic ring system is a system that does not necessarily contain only aryl groups, but may additionally contain one or more non-aromatic rings fused to at least one aryl group. Such non-aromatic rings contain only carbon atoms as ring atoms. Examples of groups covered by this definition are tetrahydronaphthalene, fluorene, and spirodifluorene. Furthermore, the term aromatic ring system is understood to encompass systems consisting of two or more aromatic rings interconnected by single bonds, such as biphenyl, terphenyl, 7-phenyl-2-fluorenyl, and tetraphenyl. An aromatic ring system in the context of this invention contains 6 to 40 carbon atoms as ring atoms and no heteroatoms as ring atoms. An aromatic ring system in the context of this application does not contain any heteroaryl groups as defined above.

[0033] Heteroaromatic ring systems are defined similarly to the aromatic ring systems described above, but differ in that they must contain at least one heteroatom as one of the ring atoms. As with aromatic ring systems, they do not necessarily contain only aryl and heteroaryl groups; rather, they may additionally contain one or more non-aromatic rings fused with at least one aryl or heteroaryl group. The non-aromatic rings may contain only carbon atoms as ring atoms, or they may additionally contain one or more heteroatoms, wherein the heteroatoms are preferably selected from N, O, and S. An example of such a heteroaromatic ring system is benzopyranyl. Furthermore, the term heteroaromatic ring system is understood to include systems consisting of two or more aromatic or heteroaromatic ring systems linked together by single bonds, such as 4,6-diphenyl-2-triazineyl. The heteroaromatic ring system in the sense of this invention contains 5 to 40 ring atoms selected from carbon and heteroatoms, wherein at least one ring atom is a heteroatom. The heteroatoms are preferably selected from N, O, or S.

[0034] The terms "heteroaromatic ring system" and "aromatic ring system" as defined in this application differ in that an aromatic ring system cannot contain any heteroatom as a ring atom, while a heteroaromatic ring system must contain at least one heteroatom as a ring atom. Such a heteroatom can exist as a ring atom of a non-aromatic heterocycle in the system, or as a ring atom of an aromatic heterocycle in the system.

[0035] Based on the above, any aryl group as defined above is covered by the term "aromatic ring system" as defined above, and any heteroaryl group as defined above is covered by the term "heteroaromatic ring system" as defined above.

[0036] A group having 6 to 40 aromatic ring atoms or a heteroaromatic ring having 5 to 40 aromatic ring atoms, particularly a group derived from the above-mentioned aryl or heteroaromatic groups, or a group derived from the following substances: biphenyl, terphenyl, tetraphenyl, fluorene, spirofluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, indofluorene, trimerin, isotrimerinin, spirotrimerinin, spiroisotrimerinin and indocarbazole, or any combination of these groups.

[0037] For the purposes of this invention, wherein individual H atoms or CH2 groups may be replaced by groups mentioned above under the definition of groups, preferably straight-chain alkyl groups having 1 to 20 C atoms, branched or cyclic alkyl groups having 3 to 20 C atoms, or alkenyl or alkynyl groups having 2 to 20 C atoms, preferably meaning the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl alkyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, or ocynyl.

[0038] Alkoxy or thioalkyl groups having 1 to 20 carbon atoms are preferably considered to be methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-... Butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethylenethio, propylenethio, butenethio, pentenethio, cyclopentenethio, hexylthio, cyclohexenethio, hepenethio, cycloheptenethio, octenenethio, cyclooctenenethio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, hepynylthio, or octyynylthio.

[0039] The phrase "two or more groups may be linked to each other to form a ring" should be understood to include cases where two groups are linked by chemical bonds. Additionally, this phrase should be understood to include cases where one of the two groups is H, that H group is removed, and the other of the two groups forms a ring by attaching to the position where the H group was originally bonded.

[0040] Preferably, formula (I) conforms to one of the following formulas (IA) to (IC).

[0041]

[0042] Z 11 Z 12 Z 13 Z 14 Each is selected from CR, either the same or different.11 and N; and

[0043] In formula (IB), the two Ar groups 1 One of them is selected from fluorene group, which is surrounded by group R. 3 Substitution, and both Ar groups 1 The other one is selected from phenyl, biphenyl, terphenyl, and tetraphenyl, each of which is R 31 replace;

[0044] Furthermore, the other variable groups are the same as those defined above.

[0045] Of the above formulas (IA) to (IC), formula (IA) is preferred.

[0046] The preferred embodiments of formulas (IA) to (IC) are as follows:

[0047]

[0048]

[0049] In each of formulas (IB-1), (IB-2), and (IB-3), two Ar groups are present. 1 One of them is selected from fluorene group, which is surrounded by group R. 3 Substitution, and both Ar groups 1 The other one is selected from phenyl, biphenyl, terphenyl, and tetraphenyl, each of which is R 31 replace;

[0050] And where p is 3, q ​​is 5, m is 3 and n is 4;

[0051] Furthermore, the other variable groups are the same as those defined above.

[0052] According to the above, according to a preferred embodiment, preferred forms (IAa) and (IAba), wherein the most preferred form is (IAa). According to the above, according to another preferred embodiment, preferred forms (IAa), (IAb), and (IAc), wherein the most preferred form is (IAa).

[0053] The following is a drawing of the functional groups.

[0054]

[0055] This should be understood as the group R representing the number of markings (5 in this case). 1 Bonded to a benzene ring, wherein the group R 1 Each occurrence may be the same or different and bonded to the benzene ring, as shown below:

[0056] .

[0057] This drawing method is also used elsewhere in this application, and in each case is similar to the understanding described above.

[0058] The preferred embodiment of the compound of formula (I) conforms to the following formula, wherein in formula (I), the part marked with a box is A.

[0059]

[0060] Selected from the following groups shown in the right column:

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] Each free position on the aromatic ring of the phenyl, biphenyl, and terphenyl groups is represented by the group R. 31 Substitution, group R 31 In this case, H or D are preferred, whether they are the same or different, with H being the most preferred.

[0067] Similarly, this also applies to the preferred formulas (IA), (IB), (IC), (IAa) to (IAc), (IBa) to (IBc) and (ICa).

[0068] In the above preferred embodiments of A, the groups of formulas (A-1), (A-3), and (A-10) are most preferred.

[0069] Therefore, the preferred embodiment of equation (I) conforms to the following equation:

[0070]

[0071] Each free position on the aromatic ring of the phenyl, biphenyl, and terphenyl groups is represented by the group R. 31 Replace, R 31 In this case, H or D are preferred, whether they are the same or different, with H being the most preferred; and

[0072] Among them, it is introduced into containing Z 11 Z 12 Z 13 and Z 14 The bond in the ring, in the cases of equations (I-1) to (I-5), is related to Z.11 Z 12 and Z 14 One of the connections, and in the cases of equations (I-6) to (I-15), with Z 11 and Z 12 One of the connections; and

[0073] Where Y is O or S, then it is introduced into the case of Z. 11 Z 12 Z 13 and Z 14 The bond in the ring and Z 11 and Z 14 One of the connections.

[0074] A further preferred embodiment of formula (I) conforms to the following formula:

[0075]

[0076]

[0077] Z 11 Z 12 Z 13 Z 14 Each is selected from CR, either the same or different. 11 and N;

[0078] Furthermore, the other variable groups are the same as those defined above.

[0079] A further preferred embodiment of formula (I) conforms to the following formula:

[0080]

[0081]

[0082]

[0083]

[0084] The variable groups mentioned therein are the same as those defined above.

[0085] Preferably, Z 1 It is CR 1 Furthermore, preferably, CR 13 It is CR 11 Furthermore, preferably, if introduced into a system containing Z... 11 Z 12 Z 14 The key in the ring is not connected to Z. 11 Z 12 Z 14 Then Z11 Z 12 Z 14 Each is CR 11 And if introduced into containing Z 11 Z 12 Z 14 The key in the ring is connected to Z 11 Z 12 Z 14 Then Z 11 Z 12 Z 14 It is C. Furthermore, preferably, CR 15 It is CR 11 .

[0086] Furthermore, preferably, each aromatic six-membered ring contains no more than one element selected from group Z. 1 Z 11 Z 12 Z 13 Z 14 and Z 15 The group is N.

[0087] Y is preferably selected from O and S; more preferably Y is O.

[0088] Preferably, the Ar group 1 Selected, either identically or differently, from phenyl, biphenyl, terphenyl, and tetraphenyl groups, each without substituents, and those attached at one of their 1 to 4 positions and bound by a group R. 3 Substituted fluorene group. Even more preferably, Ar group. 1 Selected, either identically or differently, from biphenyl groups without substituents and attached at one of its 1 to 4 positions and bound by a group R. 3 Substituted fluorene groups. "Without substituents" means, in the case of this application, that the rings only have H groups bonded to them. Most preferably, both Ar groups... 1 Both are unsubstituted biphenyl groups; or two Ar groups 1 They are all attached at one of its positions 1 to 4 and bound by the group R. 3 Substituted fluorenyl group. In this case, "biphenyl" is preferably p-biphenyl, and "the fluorenyl group attached at one of its 1 to 4 positions" is preferably 2-fluorenyl.

[0089] According to the highly preferred group Ar of this application 1 As shown below:

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] Of these groups, Ar is particularly preferred. 1 -1 to Ar 1 -7、Ar 1 -15, Ar 1 -17, Ar 1 -41, Ar 1 -42, Ar 1 -139 to Ar 1 -142, Ar 1 -173, Ar 1 -174, Ar 1 -177, Ar 1 -242, Ar 1 -242, Ar 1 -260, Ar 1 -262, Ar 1 -264 to Ar 1 -266. Optimal Ar 1 -2 and Ar 1 -141.

[0096] Preferably, it is introduced into a system containing Z 11 Z 12 Z 13 and Z 14 The bond in the ring and Z 11 and Z 14 One of the connections. Preferably, it is connected to Z. 11 connect.

[0097] Preferably, R 1 Selected from H, D, F, CN, Si(R) or different 4 3. N(R) 4 2. A straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl and alkoxy groups and the aromatic and heteroaromatic ring systems are surrounded by a group R. 4 Substitution, and wherein one or more CH2 groups of the alkyl and alkoxy groups are in each case -C≡C-, -R 4 C=CR 4 -、Si(R 4 2. C=O, C=NR 4 -NR4 -, -O-, -S-, -C(=O)O- or -C(=O)NR 4 - Instead. Particularly preferred, R 1 The same or different from H, D, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, and a ring group R. 4 Substituted aromatic ring systems with 6 to 40 aromatic ring atoms and the R group 4 Substituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms. Even more preferably, R 1 Selected from H and D, either identically or differently. Most preferably, R... 1 It is H.

[0098] Preferably, R 11 Selected from H, D, F, CN, Si(R) or different 4 3. N(R) 4 2. A straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl and alkoxy groups and the aromatic and heteroaromatic ring systems are surrounded by a group R. 4 Substitution, and wherein one or more CH2 groups of the alkyl and alkoxy groups are in each case -C≡C-, -R 4 C=CR 4 -、Si(R 4 2. C=O, C=NR 4 -NR 4 -, -O-, -S-, -C(=O)O- or -C(=O)NR 4 - Instead. Particularly preferred, R 11 Selected from H, D and R, either the same or different 4 Substituted aromatic ring systems having 6 to 40 aromatic ring atoms and the R-substituted group 4 Substituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms. Even more preferably, R 11 Selected from H and D, either identically or differently. Most preferably, R... 11 It is H.

[0099] R 2 Preferably, the R group is selected from the same or different groups each time it appears. 4 Substituted aromatic ring systems with 6 to 40 aromatic ring atoms and the R group 4 Substituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms. More preferably, R 2 Selected from the subunit R 4Aromatic ring systems with 6 to 40 substituted aromatic ring atoms. Most preferably, R... 2 Selected from the same or different groups R 4 Substituted phenyl, naphthyl, or fluorenyl groups.

[0100] Preferably, R 3 Selected from H, D, F, CN, Si(R) or different 4 3. N(R) 4 2. A straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl and alkoxy groups and the aromatic and heteroaromatic ring systems are surrounded by a group R. 4 Substitution, and wherein one or more CH2 groups of the alkyl and alkoxy groups are in each case replaced by -C≡C-, -R 4 C=CR 4 -、Si(R 4 2. C=O, C=NR 4 -NR 4 -, -O-, -S-, -C(=O)O- or -C(=O)NR 4 - Instead. Particularly preferred, R 3 Selected from H, D, F, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, and R-terminated groups. 4 Substituted aromatic ring systems with 6 to 40 aromatic ring atoms and the R group 4 Substituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms. Furthermore, preferably, in Ar... 1 R on the aromatic ring of the fluorene group 3 The groups are selected from H, D, F, straight-chain alkyl groups having 1 to 20 carbon atoms, and branched or cyclic alkyl groups having 3 to 20 carbon atoms, either identically or differently; most preferably, those groups are H or D, with H being preferred. Furthermore, it is preferable that, in the case of Ar... 1 R on the bridgehead aliphatic carbon atom of the fluorenyl group 3 The same or different from F, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, and a ring group R. 4 Substituted aromatic ring systems with 6 to 40 aromatic ring atoms.

[0101] Preferably, R 31 Selected from H, D, F, CN, Si(R) or different 4 3. N(R) 42. A straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms; wherein the alkyl and alkoxy groups are surrounded by a group R. 4 Substitution, and wherein one or more CH2 groups of the alkyl and alkoxy groups are in each case -C≡C-, -R 4 C=CR 4 -、Si(R 4 2. C=O, C=NR 4 -NR 4 -, -O-, -S-, -C(=O)O- or -C(=O)NR 4 - Instead. More preferably, R 31 Selected from H, D, F, and R (different from H, D, F, and R groups) 4 Substituted straight-chain alkyl groups having 1 to 20 carbon atoms and the R-substituted group 4 Substituted alkyl groups having 3 to 20 carbon atoms, either branched or cyclic. Even more preferably, R 31 Selected from H and D, either identically or differently. Most preferably, R... 31 It is H.

[0102] Preferably, R 4 Selected from H, D, F, CN, Si(R) or different 5 3. N(R) 5 2. A straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl and alkoxy groups and the aromatic and heteroaromatic ring systems are surrounded by a group R. 5 Replacement. Particularly preferred, R 4 Selected from H and D. Most preferably, R 4 It is H.

[0103] Preferably, R 5 The same or different are selected from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 C atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein the alkyl groups, aromatic ring systems, and heteroaromatic ring systems may be substituted by one or more groups selected from F and CN.

[0104] Preferably, the compound satisfies the following conditions:

[0105] - The compound conforms to formula (I), preferably conforming to one of formulas (IAa), (IAb) and (IAc), with formula (IAa) being the most preferred; and

[0106] -Y is selected from O and S, with Y preferably being O; and

[0107] -Z 1 It is CR 1 ;and

[0108] -If introduced into containing Z 11 Z 12 Z 13 Z 14 The bond in the ring is not with Z 11 Z 12 Z 13 Z 14 Connect, then Z 11 Z 12 Z 13 Z 14 It is CR 11 And if introduced into containing Z 11 Z 12 Z 14 The bond in the ring and Z 11 Z 12 Z 14 Connect, then Z 11 Z 12 Z 14 It is C; and

[0109] -Z 15 It is CR 11 ;and

[0110] -Ar 1 Selected, either identically or differently, from phenyl, biphenyl, terphenyl, and tetraphenyl, each without substituents, and fluorene, wherein the fluorene group is attached at one of its 1 to 4 positions and is surrounded by a group R. 3 Replace; and

[0111] -R 1 Selected from H, D and the subunit R 4 Substituted aromatic ring systems having 6 to 40 aromatic ring atoms and the R-substituted group 4 Substituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; and

[0112] -R 11 Selected from H, D and R, either the same or different 4 Substituted aromatic ring systems having 6 to 40 aromatic ring atoms and the R-substituted group 4 Substituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; and

[0113] -R 2 Selected from the subunit R 4Substituted aromatic ring systems having 6 to 40 aromatic ring atoms; and

[0114] -R 3 The same or different from H, D, F, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, and a ring group R. 4 Substituted aromatic ring systems with 6 to 40 aromatic ring atoms and the R group 4 Substituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; and

[0115] -R 31 Selected from H, D, F, and R (different from H, D, F, and R groups) 4 Substituted straight-chain alkyl groups having 1 to 20 carbon atoms and the R-substituted group 4 Substituted alkyl groups having 3 to 20 carbon atoms, either branched or cyclic; and

[0116] -R 4 Selected from H, D, F, CN, Si(R) or different 5 3. N(R) 5 2. A straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl and alkoxy groups and the aromatic and heteroaromatic ring systems are surrounded by a group R. 5 Replace; and

[0117] -R 5 The same or different are selected from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 C atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein the alkyl groups, aromatic ring systems, and heteroaromatic ring systems may be substituted by one or more groups selected from F and CN.

[0118] The preferred specific compounds according to formula (I) are the following compounds:

[0119]

[0120]

[0121]

[0122]

[0123]

[0124] Compounds according to formula (I) can be prepared by synthetic methods such as Buchwald coupling and Suzuki coupling. Technicians, based on their general knowledge of organic synthetic chemistry, are familiar with several feasible synthetic routes.

[0125] A preferred synthetic route for preparing a compound according to formula (I) is described below: To prepare a compound of formula (I), a biphenyl derivative having two reactive groups (one at position 3 and one at position 4) on the biphenyl moiety is first reacted in a Suzuki coupling reaction with a dibenzofuranyl, dibenzothiophenyl, or carbazoleyl group, wherein the dibenzofuranyl, dibenzothiophenyl, or carbazoleyl group has a reactive group on one of its aromatic nuclei. The reactive groups are preferably chosen differently. The reaction occurs at the reactive group present at position 4 of the biphenyl moiety. The resulting intermediate is then further reacted at position 3 of the biphenyl moiety with a secondary amine having two aromatic groups in a Buchwald coupling reaction to give the compound of formula (I). Further reactions may be carried out. The described intermediates are commercially available in many cases. Specific, non-commercially available intermediates required to obtain a particular compound according to formula (I) can be prepared using methods known to those skilled in the art.

[0126] The above synthesis scheme is shown below:

[0127] Option 1

[0128]

[0129] The first line represents the first step, and the second line represents the second step, with the variable groups defined as follows:

[0130] X1 and X2 may be the same or different, preferably different, selected from reactive groups, and preferably selected from Cl, Br, I and sulfonyl groups;

[0131] X3 is a reactive group, preferably a boric acid or borate ester group;

[0132] Y is O, S, or NR;

[0133] R is an organic group, preferably an optionally substituted aromatic group;

[0134] Ar is selected from the same or different aromatic groups that are substituted by choice.

[0135] Therefore, the object of this patent application is a method for preparing a compound according to formula (I) as defined above, wherein in a first step, a biphenyl derivative having two reactive groups is reacted with a dibenzofuranyl, dibenzothiophenyl, or carbazoleyl derivative in a Suzuki coupling reaction, wherein one of the two reactive groups is located at the 3 position and the other is located at the 4 position of the biphenyl derivative, the dibenzofuranyl, dibenzothiophenyl, or carbazoleyl derivative having a reactive group on one of its aromatic nuclei, wherein the reactive group at the 4 position reacts in the coupling reaction.

[0136] The reactive groups are preferably selected differently. The resulting intermediate is preferably further reacted with a secondary amine with two aromatic groups at the 3-position of the biphenyl moiety in a Buchwald coupling reaction to give the compound of formula (I).

[0137] The compounds of the present invention, particularly those substituted with reactive leaving groups such as bromine, iodine, chlorine, boric acid, or borate esters, can be used as monomers for the preparation of corresponding oligomers, dendritic macromolecules, or polymers. Suitable reactive leaving groups are, for example, bromine, iodine, chlorine, boric acid, borate esters, amines, alkenyl or alkynyl groups having terminal C / C double or triple bonds, ethylene oxide, oxetane, groups that enter cycloadditions such as 1,3-dipolar cycloadditions such as dienes or azides, carboxylic acid derivatives, alcohols, and silanes.

[0138] Therefore, the present invention also provides oligomers, polymers, or dendritic macromolecules containing one or more compounds of formula (I), wherein one or more bonds connected to said polymer, oligomer, or dendritic macromolecule may be located in formula (I) by R. 1 R 11 R 2 R 3 R 31 R 4 Or R 5 Replace any desired position. According to the linkage of compounds of formula (I), the compound is part of the side chain or main chain of an oligomer or polymer.

[0139] Further technical details of such oligomers, polymers, and dendritic macromolecules containing one or more compounds of formula (I) are disclosed on page 49, line 26 to page 51, line 17 of WO2020 / 109434 A1. The entire disclosure cited herein is incorporated herein by reference.

[0140] To process the compounds of the present invention from the liquid phase, such as by spin coating or printing, formulations of the compounds of the present invention are required. These formulations may be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents are preferred. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-, or p-xylene, methyl benzoate, mesitylene, naphthylene, veratrine, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenazine, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α- - Terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or mixtures of these solvents.

[0141] Therefore, the present invention also provides a formulation, particularly a solution, dispersion, or emulsion, said formulation comprising at least one compound of formula (I) or at least one polymer, oligomer, or dendritic macromolecule comprising at least one unit of formula (I) and at least one solvent, preferably an organic solvent. Methods for preparing such solutions are known to those skilled in the art.

[0142] Compounds of formula (I) are suitable for use in electronic devices, particularly organic light-emitting diodes (OLEDs). Depending on the substitutions, compounds of formula (I) can be used in different functions and layers. They are preferably used as hole-transporting materials in hole-transporting layers and / or as matrix materials in light-emitting layers, and more preferably in combination with phosphorescent emitters.

[0143] Therefore, the present invention also provides the use of the compound of formula (I) in electronic devices. These electronic devices are preferably selected from organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photosensors, organic field quenching devices (OFQDs), organic light-emitting electrochemical cells (OLECs), and organic laser diodes (O-lasers), and more preferably organic electroluminescent devices (OLEDs).

[0144] The present invention also provides an electronic device comprising at least one compound of formula (I). This electronic device is preferably selected from the above-described devices.

[0145] Particularly preferred are organic electroluminescent devices comprising an anode, a cathode, and at least one light-emitting layer, characterized in that the device contains at least one organic layer comprising at least one compound of formula (I). Preferably, an organic electroluminescent device comprising an anode, a cathode, and at least one light-emitting layer is characterized in that at least one organic layer selected from a hole transport layer and a light-emitting layer, preferably selected from a hole transport layer, comprises at least one compound of formula (I).

[0146] The hole transport layer is understood herein to refer to all layers disposed between the anode and the light-emitting layer, preferably a hole injection layer, a hole transport layer, and an electron blocking layer. The hole injection layer is understood herein to mean a layer directly adjacent to the anode. The hole transport layer is understood herein to mean a layer between the anode and the light-emitting layer but not directly adjacent to the anode, and preferably not directly adjacent to the light-emitting layer. The electron blocking layer is understood herein to mean a layer between the anode and the light-emitting layer and directly adjacent to the light-emitting layer. The electron blocking layer preferably has a high-energy LUMO and thus prevents electrons from leaving the light-emitting layer.

[0147] In addition to the cathode, anode, and light-emitting layer, electronic devices may also include additional layers. These are selected in each case from, for example, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge generation layers, and / or organic or inorganic p / n junctions. However, it should be noted that not every one of these layers is necessary, and the choice of layers always depends on the compound used, and especially on whether the device is a fluorescent or phosphorescent photoluminescent device.

[0148] The preferred layer sequence in electronic devices is as follows:

[0149] -anode-

[0150] -Hollow Injection Layer-

[0151] -Hole transport layer-

[0152] -Optional additional hole transport layer-

[0153] -Optional electron blocking layer-

[0154] -Emitting Layer-

[0155] -Optional Cavity Blocking Layer-

[0156] -Electron transport layer-

[0157] -Electron Injection Layer-

[0158] cathode-.

[0159] At the same time, it should be pointed out again that not all of the mentioned layers need to exist and / or other layers may exist.

[0160] The organic electroluminescent device of the present invention may comprise two or more emitting layers. More preferably, these emitting layers generally have multiple luminescence maximum values ​​between 380 nm and 750 nm, such that the overall result is white light emission; in other words, a variety of luminescent compounds that can fluoresce or phosphorize and emit blue, green, yellow, orange, or red light are used in the emitting layers. Particularly preferred is a three-layer system, i.e., a system having three emitting layers, wherein one of the three layers exhibits blue light emission in each case, one of the three layers exhibits green light emission in each case, and one of the three layers exhibits orange or red light emission in each case. The compounds of the present invention are preferably present in the hole transport layer or the emitting layer. It should be noted that, in order to produce white light, it is also suitable to use a single luminescent compound that emits light over a wide wavelength range instead of a variety of colored luminescent compounds.

[0161] Preferably, the compound of formula (I) is used as a hole transport material. The luminescent layer here can be a fluorescent luminescent layer or a phosphorescent luminescent layer. The luminescent layer is preferably a blue fluorescent layer or a green phosphorescent layer.

[0162] When a device containing a compound of formula (I) contains a phosphorescent emitting layer, this layer preferably contains two or more, more preferably exactly two, different matrix materials (a mixed matrix system). Preferred embodiments of the mixed matrix system are described in further detail below.

[0163] If the compound of formula (I) is used as a hole transport material in a hole transport layer, hole injection layer or electron blocking layer, the compound can be used as a pure material, i.e., used in the hole transport layer at a 100% ratio, or it can be used in combination with one or more other compounds.

[0164] In a preferred embodiment, the hole-transporting layer comprising the compound of formula (I) further comprises one or more other hole-transporting compounds. These other hole-transporting compounds are preferably selected from triarylamine compounds, more preferably from monotriarylamine compounds. They are most preferably selected from preferred embodiments of the hole-transporting materials further specified below. In the preferred embodiment, the compound of formula (I) and one or more other hole-transporting compounds are preferably present in a proportion of at least 10%, more preferably in a proportion of at least 20%.

[0165] In a preferred embodiment, the hole-transporting layer comprising the compound of formula (I) further contains one or more p-type dopants. The p-type dopants used according to the invention are preferably organic electron acceptor compounds capable of oxidizing one or more other compounds in the mixture.

[0166] Particularly preferred as p-type dopants are quinone dimethane compounds, azidoindrone dione, azidobenznaphthalene, azidotriphenylide, I2, metal halides, preferably transition metal halides, metal oxides, preferably metal oxides containing at least one transition metal or a metal from Group 3, and transition metal complexes, preferably complexes of Cu, Co, Ni, Pd, and Pt with ligands containing at least one oxygen atom as a binding site. Transition metal oxides are further preferred as dopants, preferably oxides of rhenium, molybdenum, and tungsten, more preferably Re2O7, MoO3, WO3, and ReO3. Bismuth complexes in the (III) oxidation state are even more preferred, particularly bismuth (III) complexes with electron-deficient ligands, and even more particularly bismuth (III) complexes with carboxylic acid anion ligands.

[0167] The p-type dopant is preferably distributed substantially uniformly in the p-type doped layer. This can be achieved, for example, by co-evaporation of the p-type dopant and the hole transport material matrix. The p-type dopant is preferably present in the p-type doped layer at a proportion of 1% to 10%.

[0168] Preferred p-type dopants are also compounds explicitly disclosed in the tables on pages 86-87 of WO2021 / 156323 A1.

[0169] In a preferred embodiment, the device contains a hole injection layer that conforms to one of the following embodiments: a) it comprises a triarylamine and a p-type dopant; or b) it comprises a single electron-deficient material (electron acceptor). In a preferred embodiment of embodiment a), the triarylamine is a monotriarylamine, particularly one of the preferred triarylamine derivatives further mentioned below. In a preferred embodiment of embodiment b), the electron-deficient material is a hexaazatriphenylide derivative as described in US 2007 / 0092755.

[0170] The compound of formula (I) may be present in the hole injection layer, hole transport layer, and / or electron blocking layer of the device. When the compound is present in the hole injection layer or hole transport layer, it is preferably p-type doped, which means that it exists in the layer in a mixed form with the p-type dopant as described above.

[0171] The compound of formula (I) is preferably present in the electron blocking layer. In this case, it is preferably not p-type doped. More preferably, in this case, it is preferably present in the layer as a single compound without the addition of other compounds.

[0172] In an optional preferred embodiment, the compound of formula (I) is used as a matrix material in combination with one or more luminescent compounds, preferably phosphorescent compounds, in the luminescent layer. The phosphorescent compounds here are preferably selected from red-phosphorescent and green-phosphorescent compounds.

[0173] In this case, the proportion of matrix material in the light-emitting layer is 50.0 vol% to 99.9 vol%, preferably 80.0 vol% to 99.5 vol%, and more preferably 85.0 vol% to 97.0 vol%.

[0174] Accordingly, the proportion of the luminescent compound is from 0.1 vol% to 50.0 vol%, preferably from 0.5 vol% to 20.0 vol%, and more preferably from 3.0 vol% to 15.0 vol%.

[0175] The luminescent layer of an organic electroluminescent device may also contain a system comprising multiple matrix materials (mixed matrix system) and / or multiple luminescent compounds. In this case, the luminescent compounds are typically those compounds in a smaller proportion of the system, and the matrix materials are those compounds in a larger proportion of the system. However, in some cases, the proportion of a single matrix material in the system may be less than the proportion of a single luminescent compound.

[0176] The compound of formula (I) is preferably used as a component of the mixed matrix system, and more preferably as a component of the mixed matrix system for phosphorescent emitters. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material with hole transport properties, and the other is a material with electron transport properties. Further preferably, one of the materials is a compound selected from those having a large energy difference between HOMO and LUMO (wide bandgap material). The compound of formula (I) in the mixed matrix system is preferably a matrix material with hole transport properties. Accordingly, when the compound of formula (I) is used as the matrix material for the phosphorescent emitter in the light-emitting layer of an OLED, a second matrix compound with electron transport properties is present in the light-emitting layer. The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, and most preferably 1:4 to 1:1.

[0177] However, the desired electron transport and hole transport properties of the mixed matrix components can also be primarily or entirely combined in a single mixed matrix component, in which case one or more additional mixed matrix components fulfill other functions.

[0178] The following material categories are preferably used in the above-mentioned layers of the device:

[0179] Phosphorescent light source:

[0180] The term "phosphorescent luminescent material" generally refers to compounds in which luminescence is achieved through spin-forbidden transitions, such as from an excited triplet state or from a state with a higher spin quantum number, such as a quintet state.

[0181] Suitable phosphorescent emitters are, in particular, compounds that emit light when properly excited, preferably in the visible light region, and further contain at least one atom with an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. Compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium are preferred as phosphorescent emitters, especially compounds containing iridium, platinum, or copper.

[0182] In the context of this invention, all luminescent iridium, platinum, or copper complexes are considered phosphorescent compounds.

[0183] Generally, all phosphorescent complexes, such as those used in phosphorescent OLEDs according to existing technology and as known to those skilled in the art of organic electroluminescent devices, are suitable for the devices of the present invention. Other examples of suitable phosphorescent emitters are those shown in the tables on pages 100-104 of WO2023 / 025971 A2.

[0184] Fluorescent light source:

[0185] Preferred fluorescent compounds are selected from the arylamine class. In the context of this invention, arylamines or aromatic amines should be understood to mean compounds containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, more preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthraceneamines, aromatic anthracene diamines, aromatic pyreneamines, aromatic pyrene diamines, aromatic pyrine amines, or aromatic pyrine diamines. Aromatic anthraceneamines are understood to mean compounds in which a diaryl amino group is directly bonded to anthracene group, preferably at the 9-position. Aromatic anthracene diamines should be understood to mean compounds in which two diaryl amino groups are directly bonded to anthracene group, preferably at the 9 or 10-position. Similarly, aromatic pyreneamines, pyrene diamines, pyrine amines, and pyrine diamines are defined, wherein the diaryl amino groups are preferably bonded to pyrene at the 1-position or 1,6-position. Other preferred luminescent compounds are indenefluoreneamine or indenefluorene diamine, benzo[a]indenefluoreneamine or benzo[a]indenefluorene diamine, and dibenzo[a]indenefluoreneamine or dibenzo[a]indenefluorene diamine, as well as indenefluorene derivatives having fused aryl groups. Pyrene arylamines are also preferred. Benzo[a]indenefluoreneamine, benzo[a]fluoreneamine, extended benzo[a]indenefluorene, phenazine, and fluorene derivatives linked to furan units or thiophene units are also preferred.

[0186] Matrix materials for phosphors:

[0187] Preferred matrix materials for phosphors are selected from the following categories: oligomeric aromatic compounds (e.g., 2,2',7,7'-tetraphenylspirodifluorene), especially oligomeric aromatic compounds containing fused aromatic groups, oligomeric aromatic vinyl compounds, multi-legged metal complexes, hole-conducting compounds, electron-conducting compounds, especially ketones, phosphine oxides, and sulfoxides; transisomers, boric acid derivatives, or benzanthracene. Particularly preferred matrix materials are selected from the following categories: oligomeric aromatic compounds, including naphthalene, anthracene, benzanthracene, and / or pyrene, or transisomers of these compounds, oligomeric aromatic vinyl compounds, ketones, phosphine oxides, and sulfoxides. Very particularly preferred matrix materials are selected from the following categories: oligomeric aromatic compounds, including anthracene, benzanthracene, benzo[a]phenanthrene, and / or pyrene, or transisomers of these compounds. In the context of this invention, oligomeric aromatic compounds should be understood to refer to compounds in which at least three aryl or aromatic vinyl groups are bonded to each other.

[0188] Matrix materials for phosphorescent emitters:

[0189] In addition to compounds of formula (I), preferred matrix materials for phosphorescent emitters are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or aromatic sulfones, triarylamines, carbazole derivatives (e.g., CBP(N,N-biscarbazole biphenyl) or carbazole derivatives), indole-carbazole derivatives, indo-carbazole derivatives, azirazole derivatives, bipolar matrix materials, silanes, borazine or borate esters, triazine derivatives, zinc complexes, diazacyclopentane or tetrazacyclopentane derivatives, phosphazacyclopentane derivatives, bridged carbazole derivatives, biphenylide derivatives, or lactams.

[0190] Electron transport materials:

[0191] Suitable electron transport materials are, for example, compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials used in these layers according to the prior art.

[0192] The material used for the electron transport layer can be any material that can be used as an electron transport material in the electron transport layer according to the prior art. Particularly suitable are aluminum complexes, such as Alq3, zirconium complexes, such as Zrq4, lithium complexes, such as Liq, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, diazole derivatives, aromatic ketones, lactams, boranes, phosphazacyclopentane derivatives, and phosphine oxide derivatives.

[0193] Preferred electron transport and electron injection materials are those shown in the tables on pages 73-75 of WO2020 / 109434 A1.

[0194] Hole transport materials:

[0195] In addition to the compounds of formula (I), other compounds preferably used in the hole transport layer of the OLED of the present invention are indene-fluoreneamine derivatives, amine derivatives, hexaaza-triphenylene derivatives, amine derivatives having a fused aromatic system, monobenzo-indenefluoreneamine, dibenzo-indenefluoreneamine, spirodifluoreneamine, fluoreneamine, spirodibenzopyranamine, dihydroacridine derivatives, spirodibenzofuran and spirodibenzothiophene, phenanthrene diarylamine, spirotribenzocycloheptatrienolone, spirodifluorene having a m-phenylenediamine group, spirodiacridine, xanthondiarylamine, and 9,10-dihydroanthracene spirospirone having a diarylamino group. Preferred hole transport compounds are those shown in the tables on pages 76-80 of WO2020 / 109434 A1.

[0196] Preferred cathodes for electronic devices are metals with low work function, metal alloys composed of multiple metals, or multilayer structures. These metals are, for example, alkaline earth metals, alkali metals, group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Furthermore, alloys composed of alkali metals or alkaline earth metals and silver are suitable, such as alloys composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, other metals with relatively high work function, such as Ag or Al, can be used. In this case, combinations of these metals are typically used, such as Ca / Ag, Mg / Ag, or Ba / Ag. It is also preferable to introduce a thin interlayer of material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials suitable for this purpose are alkali metal fluorides or alkaline earth metal fluorides, and their corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.). Lithium quinoline (LiQ) can also be used for this purpose. The thickness of this layer is preferably between 0.5 nm and 5 nm.

[0197] The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, for this purpose, metals with high redox potentials, such as Ag, Pt, or Au, are suitable. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are also preferred. x Al / PtO x For some applications, at least one of the electrodes must be transparent or partially transparent to allow for the illumination of organic materials (organic solar cells) or light emission (OLEDs, O-lasers). The preferred anode material here is a conductive mixed metal oxide. Indium tin oxide (ITO) or indium zinc oxide (IZO) is particularly preferred. Conductive doped organic materials, especially conductive doped polymers, are also preferred. Furthermore, the anode may also consist of two or more layers, for example, an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide, or vanadium oxide.

[0198] In a preferred embodiment, the electronic device is characterized by coating one or more layers via a sublimation process. In this case, the layers are applied in a vacuum sublimation system at a temperature of less than 10... -5 millibars, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of millibars. However, in this case, even lower, for example, less than 10... -7 An initial pressure of millibars is also feasible.

[0199] Another preferred electronic device is characterized by coating one or more layers using OVPD (organic vapor deposition) or by means of carrier gas sublimation. In this case, at 10-5 The material is applied at a pressure between millibar and 1 bar. A special case of this method is OVJP (organic vapor phase spraying), in which the material is applied directly through a nozzle and thus structured (e.g., MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0200] Another preferred electronic device is characterized by producing one or more layers from a solution, for example, by spin coating, or by any printing method such as screen printing, flexographic printing, nozzle printing, or offset printing, but more preferably by LITI (photoinitiated thermal imaging, thermal transfer) or inkjet printing. For this purpose, a soluble compound of formula (I) is required. High solubility can be achieved by appropriate substitution of the compound.

[0201] Furthermore, the electronic device of the present invention is preferably manufactured by applying one or more layers from a solution and by applying one or more layers by sublimation.

[0202] After applying the layer, the device is structured according to its intended use, contact connections are established, and it is finally sealed to eliminate the damaging effects of water and air.

[0203] According to the present invention, electronic devices comprising one or more compounds of formula (I) can be used in displays, as light sources in lighting applications, and as light sources in medical and / or cosmetic applications.

[0204] Example

[0205] A) Synthesis Examples

[0206] Synthesis of intermediate Int-1.1

[0207]

[0208] 45.0 g (125.3 mmol) of 3-chloro-[1,1'-biphenyl]-4-yltrifluoromethanesulfonate (CAS 175153-76-1) and 31.9 g (188.0 mmol) of {8-oxatricyclo[7.4.0.0] 2 [7] Tridecano-1(13),2,4,6,9,11-hexene-3-yl}boronic acid and 39.9 g (376.0 mmol) sodium carbonate were dissolved in 1000 mL dialkyl / toluene / water (1:2:1). 2.9 g (2.5 mmol) tetrakis(triphenylphosphine)-palladium(0) was added, and the mixture was refluxed overnight. After complete conversion, the reaction mixture was brought to room temperature, 500 mL of brine was added, and the two phases were separated. The organic phase was reduced under reduced pressure, and the residue was purified by column chromatography (heptane / toluene 5:1; SiO2), and further purified by crystallization from heptane.

[0209] Yield: 35.4g (96.8mmol, 77%)

[0210] The following compounds can be synthesized in a similar manner:

[0211]

[0212]

[0213]

[0214] Synthesis of Compound 1

[0215]

[0216] 33.7 g (92.1 mmol) of Int-1.1 and 36.99 g (92.1 mmol) of bis(9,9-dimethyl-9-H-fluorene-2-yl)amine were dissolved in 600 mL of toluene. 1.3 g (81.84 mmol) of bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) and 41.36 mL of sodium tert-amyloxide solution (138.2 mmol; 40%, in toluene) were added. The mixture was stirred at 60 °C for 18 hours. After complete conversion, the reaction mixture was allowed to reach room temperature, and 500 mL of water was added to separate the two phases. The organic phase was washed twice with 400 mL of water and twice with 300 mL of brine. The organic phase was reduced under reduced pressure, and the residue crystallized from ethyl acetate. The solid was further purified by crystallization from toluene / heptane until HPLC purity >99.9%, and by sublimation (310 °C; <10 mmol / L). -5 Remove the remaining solvent.

[0217] Yield: 36.8g (51.1mmol, 66.3%)

[0218] The following compounds can be synthesized in a similar manner:

[0219]

[0220]

[0221] B) Device Examples

[0222] 1) General manufacturing process and characterization of OLEDs

[0223] A glass plate coated with 50nm thick structured ITO (indium tin oxide) is the substrate for applying OLEDs.

[0224] OLEDs generally have the following layer structure: substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / emitting layer (EML) / electron transport layer, optionally with a second layer (HBL, ETL1 / ETL) / electron injection layer (EIL), and finally a cathode. The cathode is formed of an aluminum layer with a thickness of 100 nm. The exact structure of an OLED can be found in the table below. The materials used to produce OLEDs are shown in the table below. Compound "EBM" is a spirodifluoreneamine derivative. Compound "HTM" is a bis-2-fluoreneamine derivative.

[0225] All materials are applied via thermal vapor deposition in a vacuum chamber. In this case, the light-emitting layer consists of at least one matrix material (host material) and a light-emitting dopant, which is added to one or more matrix materials by co-evaporation in a specific volume ratio. Details given in the form H:SEB (95%:5%) mean that material H is present in the layer at a volume ratio of 95%, and SEB is present in the layer at a ratio of 5%. Similarly, the electron transport layer and hole injection layer are also composed of mixtures of two materials. The structures of the materials used in OLEDs are shown in Table 1.

[0226] OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectrum, external quantum efficiency (EQE, measured as a percentage), calculated as a function of luminescence density from the current-voltage-luminescence density characteristics assuming Lambertian light emission properties, and lifetime were determined. The parameter EQE@10 mA / cm² was used. 2 This refers to 10 mA / cm 2 The external quantum efficiency obtained at 10 mA / cm². Parameter U@10mA / cm² 2 This refers to 10 mA / cm 2 The operating voltage at this point. Eff.Lum.@5000 cd / m² is in cd / A and U@5000 cd / m² is in V. 2 It depicts 5000 cd / m 2 The efficiency and voltage at a constant luminous density. Lifetime LT is defined as the time elapsed after the luminous density decreases from its initial value to a certain percentage during operation at a constant current density. The LT80 value here means that the reported lifetime corresponds to the time elapsed after the luminous density has decreased to 80% of its initial value. Value @ 60 mA / cm² 2 or 40mA / cm 2 This means that the lifetime being discussed is 60 mA / cm². 2 or 40mA / cm 2The measurement is taken below. In addition, for the commercial success of OLEDs, it is also important to consider their lifetime at a specific light intensity. If an OLED is more efficient, it achieves the same light intensity at a lower current density. Therefore, a smaller stress needs to be applied to the OLED to obtain the same result. Thus, another aspect of lifetime, namely "light output adjustment lifetime," is determined to evaluate the performance of the OLED. The lifetime LT90, as described above, is converted to the same initial luminous density L. 5000 cd / m 2 Or 30000cd / m 2 The lifespan is determined by Calculations show that 1.5 is the acceleration factor used for the conversion. Value @ 5000 cd / m 2 Or 30000cd / m 2 This means that LT here This is given at the corresponding initial luminescence density.

[0227]

[0228]

[0229] 1) The OLED of the present invention containing a compound of formula (I) in the EBL of a green phosphorescent OLED

[0230] Manufacture the devices shown in the table below:

[0231]

[0232] In the above-described device configuration, the compounds Inv-1 to Inv-3 of this invention exhibit very good efficiency and lifetime:

[0233]

[0234] 2) The OLEDs of the present invention containing the compound of formula (I) in the HIL and HTL of blue fluorescent OLEDs, compared with OLEDs containing comparative compounds.

[0235] The devices shown in the table below were fabricated:

[0236]

[0237] The compound Inv-1 according to the invention provides very good efficiency and lifetime, wherein the lifetime is significantly improved compared with the comparative compound CE-1, and the efficiency is at a comparable level.

[0238]

Claims

1. A compound according to the following formula (I) Formula (I), The following applies to variables present in the formula: Z 1 Selected from CR in each occurrence, either identically or differently. 1 and N; If introduced into containing Z 11 Z 12 Z 13 Z 14 The bond in the ring is not with Z 11 Z 12 Z 13 Z 14 Connect, then Z 11 Z 12 Z 13 Z 14 Each is selected from CR, either the same or different. 11 and N, and if introduced into containing Z 11 Z 12 Z 14 The bond in the ring and Z 11 Z 12 Z 14 Connect, then Z 11 Z 12 Z 14 It is C; Z 15 Selected from CR in each occurrence, either identically or differently. 11 and N; Y is selected from O, S, and NR. 2 ; Ar 1 Each occurrence may be identical or different from phenyl, biphenyl, terphenyl, and tetraphenyl, as well as fluorene, wherein each of the phenyl, biphenyl, terphenyl, and tetraphenyl groups R 31 The fluorene group is replaced by a group R at one of its 1 to 4 positions. 3 replace; R 1 Each time it appears, it is selected from H, D, F, C (=O)R, either the same or different. 4 CN, Si(R) 4 3. N(R) 4 2. P(=O)(R) 4 2. OR 4 S(=O)R 4 S(=O)2R 4 Straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms; branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms; alkenyl or alkynyl groups having 2 to 20 carbon atoms; aromatic ring systems having 6 to 40 aromatic ring atoms; and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more groups R 1 They can be linked together to form rings; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are bound by the R group. 4 Substitution, and wherein one or more CH2 groups of the alkyl, alkoxy, alkenyl, and alkynyl groups are in each case -R 4 C=CR 4 -、-C≡C-、Si(R 4 2. C=O, C=NR 4 -C(=O)O-, -C(=O)NR 4 -、NR 4 P(=O)(R) 4 Replace with -O-, -S-, SO or SO2; R 11 Each time it appears, it is selected from H, D, F, C (=O)R, either the same or different. 4 CN, Si(R) 4 3. N(R) 4 2. P(=O)(R) 4 2. OR 4 S(=O)R 4 S(=O)2R 4 Straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms; branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms; alkenyl or alkynyl groups having 2 to 20 carbon atoms; aromatic ring systems having 6 to 40 aromatic ring atoms; and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more groups R 11 They can be linked together to form rings; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are bound by the R group. 4 Substitution, and wherein one or more CH2 groups of the alkyl, alkoxy, alkenyl, and alkynyl groups are in each case -R 4 C=CR 4 -、-C≡C-、Si(R 4 2. C=O, C=NR 4 -C(=O)O-, -C(=O)NR 4 -、NR 4 P(=O)(R) 4 Replace with -O-, -S-, SO or SO2; R 2 Each time it appears, it is selected from straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein the alkyl groups and the aromatic ring systems and heteroaromatic ring systems are surrounded by the group R. 4 replace; R 3 Each time it appears, it is selected from H, D, F, C (=O)R, either the same or different. 4 CN, Si(R) 4 3. N(R) 4 2. P(=O)(R) 4 2. OR 4 S(=O)R 4 S(=O)2R 4 Straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms; branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms; alkenyl or alkynyl groups having 2 to 20 carbon atoms; aromatic ring systems having 6 to 40 aromatic ring atoms; and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more groups R 3 They can be linked together to form rings; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are bound by the R group. 4 Substitution, and wherein one or more CH2 groups of the alkyl, alkoxy, alkenyl, and alkynyl groups are in each case -R 4 C=CR 4 -、-C≡C-、Si(R 4 2. C=O, C=NR 4 -C(=O)O-, -C(=O)NR 4 -、NR 4 P(=O)(R) 4 Replace with -O-, -S-, SO or SO2; R 31 Each time it appears, it is selected from H, D, F, C (=O)R, either the same or different. 4 CN, Si(R) 4 3. N(R) 4 2. P(=O)(R) 4 2. OR 4 S(=O)R 4 S(=O)2R 4 A straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms; a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms; an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein two or more groups R 31 They can be linked together to form a ring; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups are connected by the group R. 4 Substitution, and wherein one or more CH2 groups of the alkyl, alkoxy, alkenyl, and alkynyl groups are in each case -R 4 C=CR 4 -、-C≡C-、Si(R 4 2. C=O, C=NR 4 -C(=O)O-, -C(=O)NR 4 -、NR 4 P(=O)(R) 4 Replace with -O-, -S-, SO or SO2; R 4 Each time it appears, it is selected from H, D, F, C (=O)R, either the same or different. 5 CN, Si(R) 5 3. N(R) 5 2. P(=O)(R) 5 2. OR 5 S(=O)R 5 S(=O)2R 5 Straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms; branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms; alkenyl or alkynyl groups having 2 to 20 carbon atoms; aromatic ring systems having 6 to 40 aromatic ring atoms; and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein two or more groups R 4 They can be linked together to form rings; wherein the alkyl, alkoxy, alkenyl, and alkynyl groups, as well as the aromatic and heteroaromatic ring systems, are bound by the R group. 5 Substitution, and wherein one or more CH2 groups of the alkyl, alkoxy, alkenyl, and alkynyl groups are in each case -R 5 C=CR 5 -、-C≡C-、Si(R 5 2. C=O, C=NR 5 -C(=O)O-, -C(=O)NR 5 -、NR 5 P(=O)(R) 5 Replace with -O-, -S-, SO or SO2; R 5 Each time it appears, it is selected from H, D, F, CN, alkyl groups having 1 to 20 carbon atoms, aromatic ring systems having 6 to 40 carbon atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms, either identically or differently; wherein two or more groups R 5 They can be linked together to form a ring; and said alkyl groups, aromatic ring systems and heteroaromatic ring systems can be substituted by one or more groups selected from F and CN; The inclusion of Z 11 Z 12 Z 13 and Z 14 The bond in the ring and Z 11 Z 12 and Z 14 One of the connections, and in, If introduced into containing Z 11 Z 12 Z 13 and Z 14 The bond in the ring and Z 14 If connected, the two Ar groups 1 One of them is selected from the R group 3 The substituted fluorene group, and the two Ar groups 1 Another one selected from each of the R 31 Substituted phenyl, biphenyl, terphenyl, and tetraphenyl; and in, If Y is O or S, then it is introduced into the case of Z. 11 Z 12 Z 13 and Z 14 The bond in the ring and Z 11 and Z 14 One of the connections.

2. The compound according to claim 1, characterized in that... The compound conforms to one of the following formulas: In each of formulas (IB-1), (IB-2), and (IB-3), two Ar groups are present. 1 One of them is selected from the R group 3 The substituted fluorene group, and the two Ar groups 1 Another one selected from each of the R 31 Substituted phenyl, biphenyl, triphenyl, and tetraphenyl; And where p is 3, q ​​is 5, m is 3 and n is 4; Furthermore, the other variable groups therein are the same as those defined in claim 1; Formulas (IAa), (IAb), and (IAc) are preferred, with formula (IAa) being the most preferred.

3. The compound according to claim 1 or 2, characterized in that... Y is selected from O and S, with O being preferred.

4. The compound according to one or more of claims 1 to 3, characterized in that... Ar group 1 Selected, either identically or differently, from phenyl, biphenyl, terphenyl, and tetraphenyl groups, each without substituents, and those attached at one of their 1 to 4 positions and bound by a group R. 3 Replaced fluorene.

5. The compound according to one or more of claims 1 to 4, characterized in that... Applicable to one of the following cases a) and b): a) Both groups Ar 1 Both are unsubstituted biphenyl groups; and b) both groups Ar 1 All are fluorene groups, wherein the fluorene group is attached at one of its 1 to 4 positions and is surrounded by a group R. 3 replace.

6. The compound according to one or more of claims 1 to 5, characterized in that it incorporates... To include Z 11 Z 12 Z 13 and Z 14 The bond in the ring and Z 11 and Z 14 A connection in one of them, and preferably characterized in that the key is with Z 11 connect.

7. The compound according to one or more of claims 1 to 6, characterized in that... R 1 The same or different from H, D, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, and a ring group R. 4 Substituted aromatic ring systems having 6 to 40 aromatic ring atoms and the R-substituted group 4 Substituted heteroaromatic ring systems with 5 to 40 aromatic ring atoms.

8. The compound according to one or more of claims 1 to 7, characterized in that... R 11 Selected from H, D and R, either the same or different 4 Substituted aromatic ring systems having 6 to 40 aromatic ring atoms and the R-substituted group 4 Substituted heteroaromatic ring systems with 5 to 40 aromatic ring atoms.

9. The compound according to one or more of claims 1 to 8, characterized in that... R 31 It is H.

10. The compound according to one or more of claims 1 to 9, characterized in that... The compound satisfies the following conditions: - The compound conforms to formula (I), preferably conforming to one of formulas (IAa), (IAb) and (IAc), with formula (IAa) being the most preferred; and -Y is selected from O and S, with Y preferably being O; and -Z 1 It is CR 1 ;and -If introduced into containing Z 11 Z 12 Z 13 Z 14 The bond in the ring is not with Z 11 Z 12 Z 13 Z 14 Connect, then Z 11 Z 12 Z 13 Z 14 It is CR 11 And if introduced into containing Z 11 Z 12 Z 14 The bond in the ring and Z 11 Z 12 Z 14 Connect, then Z 11 Z 12 Z 14 It is C; and -Z 15 It is CR 11 ;and -Ar 1 Selected, either identically or differently, from phenyl, biphenyl, terphenyl, and tetraphenyl, each without substituents, and fluorene, wherein the fluorene group is attached at one of its 1 to 4 positions and is surrounded by a group R. 3 Replace; and -R 1 Selected from H, D and the subunit R 4 Substituted aromatic ring systems having 6 to 40 aromatic ring atoms and the R-substituted group 4 Substituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; and -R 11 Selected from H, D and R, either the same or different 4 Substituted aromatic ring systems having 6 to 40 aromatic ring atoms and the R-substituted group 4 Substituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; and -R 2 Selected from the subunit R 4 Substituted aromatic ring systems having 6 to 40 aromatic ring atoms; and -R 3 The same or different from H, D, F, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, and a ring group R. 4 Substituted aromatic ring systems with 6 to 40 aromatic ring atoms and the R group 4 Substituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; and -R 31 Selected from H, D, F, and R (different from H, D, F, and R groups) 4 Substituted straight-chain alkyl groups having 1 to 20 carbon atoms and the R-substituted group 4 Substituted alkyl groups having 3 to 20 carbon atoms, either branched or cyclic; and -R 4 Selected from H, D, F, CN, Si(R) or different 5 3. N(R) 5 2. A straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein the alkyl and alkoxy groups and the aromatic and heteroaromatic ring systems are surrounded by a group R. 5 Replace; and -R 5 The same or different are selected from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 C atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; wherein the alkyl groups, aromatic ring systems, and heteroaromatic ring systems may be substituted by one or more groups selected from F and CN.

11. A method for preparing a compound according to one or more of claims 1 to 10, characterized in that, In the first step, a biphenyl derivative having two reactive groups is reacted with a dibenzofuranyl, dibenzothiophenyl, or carbazoleyl derivative in a Suzuki coupling reaction, wherein one of the two reactive groups is located at the 3-position and the other is located at the 4-position of the biphenyl derivative, and the dibenzofuranyl, dibenzothiophenyl, or carbazoleyl derivative has a reactive group on one of its aromatic nuclei, wherein the reactive group at the 4-position reacts in the coupling reaction.

12. A formulation comprising at least one compound according to one or more of claims 1 to 10 and at least one solvent.

13. An electronic device comprising at least one compound according to one or more of claims 1 to 10.

14. The electronic device according to claim 13, characterized in that... The electronic device is an organic electroluminescent device and includes an anode, a cathode and at least one light-emitting layer, and is characterized in that the compound is present in the hole transport layer or the light-emitting layer of the device.

15. Use of the compound according to one or more of claims 1 to 10 in an electronic device.

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