Oxygen-containing heterocyclic compounds for organic electroluminescent devices

Abstract

This invention relates to oxygen-containing heterocyclic compounds suitable for use in electronic devices, and to electronic devices containing these heterocyclic compounds, particularly organic electroluminescent devices.

Description

[0001] This invention relates to oxygen-containing heterocyclic compounds for use in electronic devices, particularly for use in organic electroluminescent devices, and electronic devices comprising these materials, particularly organic electroluminescent devices.

[0002] The luminescent materials used in organic electroluminescent devices are typically phosphorescent organometallic complexes. For quantum mechanical reasons, using organometallic compounds as phosphorescent emitters can achieve up to four times the energy efficiency and power efficiency. However, improvements are still generally needed in electroluminescent devices, especially those exhibiting triplet emission (phosphorescence). The properties of phosphorescent electroluminescent devices depend not only on the triplet emitter used, but also, more specifically, on other materials used, such as the matrix material. Therefore, improvements in these materials can lead to significant improvements in the performance of the electroluminescent device.

[0003] In addition, many electroluminescent devices contain other layers besides the light-emitting layer, such as one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers. These layers have a significant impact on the performance of the electroluminescent device.

[0004] In addition, electroluminescent devices that use fluorescent emitters or emitters exhibiting TADF are also known. These electroluminescent devices also face corresponding challenges.

[0005] Typically, improvements are still needed even when these materials are used as matrix materials, particularly in terms of device lifespan, efficiency, and operating voltage.

[0006] Therefore, one object of the present invention is to provide compounds and corresponding electronic devices, said compounds being suitable for use in organic electronic devices, particularly organic electroluminescent devices, and when used in such devices, said compounds cause good device performance.

[0007] More specifically, the problem addressed by this invention is to provide compounds that result in long lifetimes, good efficiency, and low operating voltages. These properties are contributed not only by the light emitter but also, in particular, by hole-conducting materials, hole-injecting materials, electron-blocking materials, electron-injecting materials, electron-transporting materials, and hole-blocking materials. Furthermore, the properties of the matrix material, also referred to herein as the host material, have a significant impact on the lifetime and efficiency of organic electroluminescent devices.

[0008] Furthermore, an object of the present invention is to provide a compound characterized by a low refractive index (RI).

[0009] Another object of the present invention is to provide compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, particularly as matrix materials. In particular, one object of the present invention is to provide matrix materials suitable for green or blue phosphorescent electroluminescent devices, and also suitable for red or yellow phosphorescent electroluminescent devices.

[0010] Furthermore, the compounds, especially when used as light emitters, host materials, hole conduction materials, hole injection materials, electron blocking materials, electron injection materials, electron transport materials, or hole blocking materials in organic electroluminescent devices, should enable the devices to have excellent color purity.

[0011] Another objective can be considered as providing electronic devices with excellent performance that are very inexpensive and of stable quality.

[0012] Furthermore, electronic devices should be usable or modified for a wide range of purposes. More specifically, the performance of electronic devices should be maintained over a wide temperature range.

[0013] It has been surprisingly found that certain compounds, described in more detail below, achieve this objective and are highly suitable for use in electroluminescent devices, resulting in organic electroluminescent devices exhibiting excellent performance, particularly in terms of lifetime, color purity, efficiency, operating voltage, and refractive index. Therefore, the present invention provides these compounds and electronic devices comprising these compounds, particularly organic electroluminescent devices.

[0014] This invention provides a compound comprising at least one structure of formula (Ia) or (Ib), preferably a compound of formula (Ia) or (Ib):

[0015]

[0016] The symbols are as follows:

[0017] Z is the same or different in various cases and is -(CR) b 2) n - a group, wherein n is an integer in the range of 1 to 6, preferably 1 to 4;

[0018] W is the same or different in various situations and is -(CR) b 2) m - A group, wherein m is an integer in the range of 1 to 6, preferably 1 to 4, wherein the W group may be bridged to the Z group via one or more V groups, wherein V may be the same or different in various cases and is a single bond or has 1 to 40 carbon atoms and may be connected to one or more R groups. 2 A substituted alkyl subunit, wherein one or more non-adjacent CH2 groups may be -R2 C=CR 2 -、-C≡C-、Si(R 2 2. C=O, C=S, C=Se, C=NR 2 -C(=O)O-, -C(=O)NR 2 -、NR 2 P(=O)(R) 2 The V group is replaced by -O-, -S-, SO or SO2, and one or more of the hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, wherein the V group is preferably a single bond; -(CR c 2) o -A group, wherein o is an integer in the range of 1 to 5, preferably 1 to 3; or -(CR c 2) p -C=C-、-(CR c 2) p C=C(CR c 2) p - a group, wherein p is an integer in the range of 1 to 4, preferably 1 to 3;

[0019] Ar may be the same or different in various cases and is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and being substituted by one or more R groups; Ar is preferably an aryl or heteroaromatic group having 6 to 40 aromatic ring atoms and being substituted by one or more R groups, or an aromatic or heteroaromatic ring system having 6 to 13 aromatic ring atoms and being substituted by one or more R groups, wherein the Ar group may coordinate with a transition metal;

[0020] R a In various cases, they may be the same or different and are: H, D, F; straight-chain alkyl groups having 1 to 40 carbon atoms, branched or cyclic alkyl groups having 3 to 40 carbon atoms, each of which may be represented by one or more R b Group substitution; or having 5 to 60 aromatic ring atoms and, in various cases, being substituted with one or more R groups; 1 The substituted aromatic or heteroaromatic ring system is preferably a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group, wherein two R groups are substituted. a Groups can form ring systems together;

[0021] R b In various cases, they may be the same or different and are: H, D, F; a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of which may be represented by one or more R2 Group substitution is preferably H, D, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 15 carbon atoms, more preferably H or D, wherein two or more R b Groups can form ring systems together;

[0022] R c In various cases, they may be the same or different and are: H, D, F; a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of which may be represented by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 2. C=O, C=S, C=Se, C=NR 2 -C(=O)O-, -C(=O)NR 2 -、NR 2 P(=O)(R) 2 The alkyl group is replaced by -O-, -S-, SO or SO2, preferably H, D, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 15 carbon atoms, more preferably H or D, wherein two or more R c Groups can form ring systems together;

[0023] R is the same or different in various cases and is: H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R) 1 )2、C(=O)N(Ar')2、C(=O)N(R 1 )2、C(Ar')3、C(R 1 )3、Si(Ar')3、Si(R 1 )3、B(Ar')2、B(R 1 )2、C(=O)Ar'、C(=O)R 1 、P(=O)(Ar')2、P(=O)(R 1 )2、P(Ar')2、P(R 1 )2、S(=O)Ar'、S(=O)R 1 S(=O)2Ar', S(=O)2R 1 OSO2Ar', OSO2R 1A straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein each of the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group may be derived from one or more R... 1 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 1 C=CR 1 C≡C, Si(R) 1 2. C=O, C=S, C=Se, C=NR 1 -C(=O)O-, -C(=O)NR 1 -、NR 1 P(=O)(R) 1 ), -O-, -S-, SO or SO2 substituted; or having 5 to 60 aromatic ring atoms and, in various cases, being substituted by one or more R 1 Aromatic or heteroaromatic ring systems with substituted groups; or having 5 to 60 aromatic ring atoms and being substituted by one or more R groups. 1 The aryloxy or heteroaryloxy group is substituted with a group, wherein the two R groups can form a cyclic system with each other, or one R group can form a cyclic system with other groups, especially with R b The groups form a ring system, in which the R group can coordinate with a transition metal;

[0024] Ar' can be the same or different in various cases and has 5 to 60 aromatic ring atoms and can be denoted by one or more R. 1 Aromatic or heteroaromatic ring systems with substituted groups, wherein the two Ar' groups bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom can also be bonded by a single bond or selected from B(R) 1 ), C(R 1 )2、Si(R 1 2. C=O, C=NR 1 C=C(R) 1 )2、O、S、S=O、SO2、N(R 1 ), P(R 1 ) and P(=O)R 1 The bridging groups in the structure are connected to each other, and the Ar' group can coordinate with transition metals;

[0025] R 1 The following are the same or different under various conditions: H, D, F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R) 2 )2、C(=O)Ar''、C(=O)R 2,P(=O)(Ar'')2,P(Ar'')2,B(Ar'')2,B(R 2 )2、C(Ar'')3、C(R 2 )3、Si(Ar'')3、Si(R 2 )3; a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be generated by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 2. C=O, C=S, C=Se, C=NR 2 -C(=O)O-, -C(=O)NR 2 -、NR 2 P(=O)(R) 2 ), -O-, -S-, SO or SO2, and one or more of the hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2; or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be replaced by one or more R 2 Group substitution; or having 5 to 60 aromatic ring atoms and being substituted with one or more R groups. 2 A group-substituted aryloxy or heteroaryloxy group; or a group having 5 to 60 aromatic ring atoms and being substituted with one or more R groups. 2 Group-substituted aralkyl or heteroaralkyl groups; or combinations of these systems; wherein two or more, preferably adjacent, R groups 1 Groups can form cyclic systems with each other, wherein one or more R groups 1 The group can form a ring system with other parts of the compound, wherein R 1 The group can coordinate with transition metals;

[0026] Ar'' can be the same or different in various cases and has 5 to 30 aromatic ring atoms and can be denoted by one or more R''. 2 Aromatic or heteroaromatic ring systems with substituted groups, wherein the two Ar'' groups bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom can also be bonded by a single bond or selected from B(R) 2 ), C(R 2 )2、Si(R 2 2. C=O, C=NR 2 C=C(R) 2 )2、O、S、S=O、SO2、N(R 2 ), P(R2 ) and P(=O)R 2 The bridging groups in the structure are connected to each other, and the Ar'' group can coordinate with transition metals;

[0027] R 2 In various cases, they may be the same or different and selected from: H, D, F, CN; an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and said aromatic or heteroaromatic ring system may be replaced by one or more alkyl groups each having 1 to 4 carbon atoms, wherein two or more, preferably adjacent, substituents R 2 They can form a ring system together.

[0028] In the context of this invention, aryl groups contain 6 to 40 carbon atoms; heteroaryl groups contain 3 to 40 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatom is at least 5. The heteroatom is preferably selected from N, O, and / or S. Here, aryl groups or heteroaryl groups refer to simple aromatic rings, i.e., benzene; or simple heteroaromatic rings such as pyridine, pyrimidine, thiophene, etc.; or fused (enhanced) aryl or heteroaryl groups such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Conversely, aromatic compounds linked together by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.

[0029] In the context of this invention, an electron-deficient heteroaryl group is a heteroaryl group having at least one heteroaryl six-membered ring having at least one nitrogen atom. Other aromatic or heteroaryl five-membered or six-membered rings may be fused to the six-membered ring. Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline, or quinoxaline.

[0030] In the context of this invention, an aromatic ring system contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms. In the context of this invention, a heteroaromatic ring system contains 3 to 60 carbon atoms, 3 to 40 carbon atoms, and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. In the context of this invention, an aromatic or heteroaromatic ring system should refer to a system that does not necessarily contain only aryl or heteroaromatic groups, but in which two or more aryl or heteroaromatic groups can also be linked by non-aromatic units, such as carbon, nitrogen, or oxygen atoms. For example, in the context of this invention, systems such as fluorene, 9,9'-spirodifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, piracene, etc., should also be considered aromatic ring systems, as should systems in which two or more aryl groups are linked, for example, by short alkyl groups. Preferably, the aromatic ring system is selected from fluorene, 9,9'-spirodifluorene, 9,9-diarylamine, or groups in which two or more aryl and / or heteroaryl groups are linked to each other by single bonds.

[0031] In the context of this invention, the aliphatic hydrocarbon group or alkyl group or alkenyl or ynyl group containing 1 to 20 carbon atoms, wherein some hydrogen atoms or CH2 groups may be replaced by the aforementioned groups, preferably refers to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, 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, heptenyl, or octyynyl groups. The alkoxy group having 1 to 40 carbon atoms is preferably alkoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexoxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, pentafluoroethoxy, and 2,2,2-trifluoroethoxy. The thioalkyl group having 1 to 40 carbon atoms should, in particular, be thioyl, ethyl thioyl, n-propyl thioyl, isopropyl thioyl, n-butyl thioyl, isobutyl thioyl, sec-butyl thioyl, tert-butyl thioyl, n-pentyl thioyl, sec-pentyl thioyl, n-hexyl thioyl, cyclohexyl thioyl, n-heptyl thioyl, cycloheptyl thioyl, 2-ethylhexyl thioyl, trifluoromethyl thioyl, pentafluoroethyl thioyl, 2,2,2-trifluoroethyl thioyl, ethylene thioyl, propylene thioyl, butene thioyl, pentene thioyl, cyclopentene thioyl, hexene thioyl, cyclohexene thioyl, hepten thioyl, cycloheptene thioyl, octenene thioyl, cyclooctenene thioyl, ethynyl thioyl, propynyl thioyl, butynyl thioyl, pentynyl thioyl, hexynyl thioyl, heptenyl thioyl, or octyynyl thioyl. Typically, the alkyl, alkoxy, or thioalkyl groups according to the invention can be straight-chain, branched, or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the aforementioned groups; furthermore, one or more hydrogen atoms can be replaced by D, F, Cl, Br, I, CN, or NO2, preferably by F, Cl, or CN, even more preferably by F or CN, and especially preferably by CN.

[0032] Aromatic or heteroaromatic ring systems having 5 to 60 or 5 to 40 aromatic ring atoms, and which can be substituted by the aforementioned groups in various cases, and which can be linked to aromatic or heteroaromatic systems via any desired position, should be understood to specifically refer to groups derived from the following substances: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, pyrene, celestene, perylene, fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, diphenylidene, terphenyl, terphenylidene, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorene, cis or trans indo[a]carbazole, cis or trans indo[a]carbazole. Zyrazole, terpinene, isoterpinene, spiroterpinene, spiroisoterpinene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenothiazine, pyrazole, indazole, imidazole, benzimidazole, naphthiazole, phenanthridine, pyridinium pyridimazole, pyrazinium pyridimazole, quinoxalineium pyridimazole, pyrazole, benzopyridimazole, naphthiazole Anthrazoazole, anthrazoazole, phenanthreneazole, isothiazoazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatribenzide, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazathracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenanthrene, phenothiazine, fluorescein ring, naphthidine, azacarbazole, benzocarbline, phenanthrene, 1,2,3-triazole, 1,2,4- Triazoles, benzotriazoles, 1,2,3-diazoles, 1,2,4-diazoles, 1,2,5-diazoles, 1,3,4-diazoles, 1,2,3-thiadiazoles, 1,2,4-thiadiazoles, 1,2,5-thiadiazoles, 1,3,4-thiadiazoles, 1,3,5-triazines, 1,2,4-triazines, 1,2,3-triazines, tetraazoles, 1,2,4,5-tetraazines, 1,2,3,4-tetraazines, 1,2,3,5-tetraazines, purines, pteridines, indoleazines, and benzothiadiazoles, or groups derived from combinations of these systems.

[0033] In the context of this specification, the phrase "two or more groups can form a ring with each other" should specifically refer to the two groups being connected to each other by chemical bonds under conditions that formally eliminate two hydrogen atoms. This is illustrated by the following scheme:

[0034] .

[0035] However, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group bonds to the position where the hydrogen atom is bonded, thereby forming a ring. This will be illustrated by the following scheme:

[0036] .

[0037] Preferably, the Ar group may be the same or different in various cases and is selected from phenyl, biphenyl, terphenyl, tetraphenyl, fluorene, spirodifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, triphenylamine, diphenyl ether, dibenzofuran, dibenzothiophene, indobenzocarbazole, indolebenzocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or biphenylene oxide, each of which may be substituted by one or more R groups, preferably phenyl, biphenyl, fluorene, dibenzofuran, biphenylene oxide, or indolebenzocarbazole.

[0038] It is also feasible, especially in the structures of formula (Ia) and / or (Ib) and structures based thereon, that the sum of the markers m and n is 3 to 6 and / or the sum of the markers p, o, m and n is preferably 3 to 8.

[0039] The Ar group, together with the carbon atom bonded to the Ar group and the oxygen atom bonded to the same carbon atom, preferably forms a ring having 5, 6, 7, 8, 9 or 10 atoms, more preferably having 5, 6, 7, 8 or 9 atoms, and even more preferably having 5, 6, 7 or 8 atoms.

[0040] In a preferred configuration, the compounds of the present invention may preferably comprise at least one structure of formula (Ia-1) to (Ib-7), more preferably compounds selected from formulas (Ia-1) to (Ib-7):

[0041]

[0042] Equation (Ia-1) Equation (Ia-2)

[0043]

[0044] Equation (Ia-3) Equation (Ia-4)

[0045]

[0046] Equation (Ia-5) Equation (Ia-6)

[0047]

[0048] Equation (Ia-7) Equation (Ib-1)

[0049]

[0050] Equation (Ib-2) Equation (Ib-3)

[0051]

[0052] Equation (Ib-4) Equation (Ib-5)

[0053]

[0054] Equation (Ib-6) Equation (Ib-7)

[0055] Among them, the symbols R and R a R b W and Z have the definitions given above, especially for equations (Ia) and (Ib), and the other symbols are as follows:

[0056] Y may be the same or different in various cases and is O, S, NR, Si(R)2, C(R)2 or an ortho-bonded benzene group that can be replaced by one or more R groups, preferably O or NR, more preferably NR;

[0057] Y 1 In various cases, the same or different and of the following types are C(R)2, Si(R)2, C=O, P(O)R, P(R), O, S, NR, or BR, preferably NR or BR, more preferably NR; and

[0058] X may be the same or different in various cases and is either CR or N, preferably CR.

[0059] Herein are preferred structures / compounds of formulas Ia-1, Ia-2, Ia-5, Ia-6, Ib-1 and Ib-2, with particularly preferred structures / compounds of formulas Ia-1 and Ib-1.

[0060] In a preferred and feasible manner, particularly in the structures / compounds of formulas (Ia-1) to (Ib-7), no more than two X groups in each ring are N, and preferably all X are CR; preferably at least one, more preferably at least two X groups in each ring are selected from CH and CD.

[0061] Even more preferably, in particular in the structures / compounds of formulas (Ia-1) to (Ib-7), no more than four, preferably no more than two, X groups are N; more preferably, all X groups are CR, wherein no more than four, more preferably no more than three, and especially preferably no more than two of the CR groups represented by X are not CH or CD groups.

[0062] In another preferred embodiment, it is feasible for the compounds of the present invention to comprise structures of formulas (IIa-1) to (IIb-7), wherein the compounds of the present invention may more preferably be selected from compounds of formulas (IIa-1) to (IIb-7):

[0063]

[0064] Equation (IIa-1) Equation (IIa-2)

[0065]

[0066] Equation (IIa-3) Equation (IIa-4)

[0067]

[0068] Equation (IIa-5) Equation (IIa-6)

[0069]

[0070] Equation (IIa-7) Equation (IIb-1)

[0071]

[0072] Equation (IIb-2) Equation (IIb-3)

[0073]

[0074] Equation (IIb-4) Equation (IIb-5)

[0075]

[0076] Equation (IIb-6) Equation (IIb-7)

[0077] Among them, the symbols R and R a R b W and Z have the definitions given above, especially for the definitions given in equations (Ia) and (Ib), and the symbols Y and Y 1 It has the definitions given above, especially for the definitions given in equations (Ia-1) to (Ib-7), and the other symbols are as follows:

[0078] j can be 0, 1, 2 or 3 independently in various cases, preferably 0, 1 or 2;

[0079] h can be independently 0, 1, 2, 3, or 4 in various cases, preferably 0, 1, or 2; and

[0080] g is independently 0, 1, 2, 3, 4 or 5 in various cases, preferably 0, 1 or 2.

[0081] Preferred structures / compounds are those of formulas IIa-1, IIa-2, IIa-5, IIa-6, IIb-1, and IIb-2, with particularly preferred structures / compounds of formulas IIa-1 and IIb-1.

[0082] In a preferred and feasible case, especially in the structures / compounds of formulas (IIa-1) to (IIb-7), the sum of the designations j, h and g preferably does not exceed 6, more preferably does not exceed 4, and more preferably does not exceed 2.

[0083] In another preferred embodiment, it is feasible for the compounds of the present invention to comprise structures of formulas (III-1) to (III-4), wherein the compounds of the present invention may more preferably be selected from compounds of formulas (III-1) to (III-4):

[0084]

[0085] Equation (III-1) Equation (III-2)

[0086]

[0087] Equation (III-3) Equation (III-4)

[0088] Among them, the symbols R and R a R b W and Z have the definitions given above, especially for equations (Ia) and (Ib), and the other symbols are as follows:

[0089] Y 2 Same or different in various cases and is B(R) 1 ), C(R 1 )2、Si(R 1 2. C=O, C=NR 1 C=C(R) 1 )2、O、S、S=O、SO2、N(R 1 ), P(R 1 ) and P(=O)R 1 B(R) is preferred. 1 ), C=O or P(=O)R 1 More preferably B(R) 1 );

[0090] Y 3 Same or different in various cases and is B(R) 1 ), C(R 1 )2、Si(R 1 2. C=O, C=NR 1 C=C(R) 1 )2、O、S、S=O、SO2、N(R 1 ), P(R 1 ) and P(=O)R 1 Preferably O, N(R) 1 ) or P(R 1 ), more preferably O or N(R) 1 The optimal choice is N(R). 1 );and

[0091] j can be 0, 1, 2 or 3 independently in various cases, preferably 0, 1 or 2.

[0092] Furthermore, especially in the structures / compounds of formulas (III-1) to (III-4), it is feasible for the sum of the designations j to be no more than 8, preferably no more than 6, especially preferably no more than 5, and more preferably no more than 3.

[0093] In a preferred embodiment of the invention, it is feasible that the Z and W groups, together with CR b Group or CR b Groups and CR b 2 groups and CR b The carbon atoms bonded together by the groups form substructures of formulas (RC-1) to (RC-10):

[0094]

[0095] Formula (RC-1) Formula (RC-2) Formula (RC-3)

[0096]

[0097] Formula (RC-4) Formula (RC-5) Formula (RC-6)

[0098]

[0099] Formula (RC-7) Formula (RC-8)

[0100]

[0101] Formula (RC-9) Formula (RC-10)

[0102] Where R b With the definitions given above, especially for formulas (Ia) and (Ib), the dashed bond represents the bond connected to the oxygen atom and the Ar group, and the other symbols are defined as follows:

[0103] r is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0104] s is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0105] t is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0106] v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2.

[0107] The preferred structures here are (RC-4), (RC-6), (RC-8), and (RC-9).

[0108] In another preferred embodiment, it is feasible for the compounds of the present invention to comprise structures of formulas (IV-1) to (IV-16), wherein the compounds of the present invention may more preferably be selected from compounds of formulas (IV-1) to (IV-16):

[0109]

[0110] Formula (IV-1) Formula (IV-2)

[0111]

[0112] Formula (IV-3) Formula (IV-4)

[0113]

[0114] Formula (IV-5) Formula (IV-6)

[0115]

[0116] Formula (IV-7) Formula (IV-8)

[0117]

[0118] Formula (IV-9) Formula (IV-10)

[0119]

[0120] Formula (IV-11) Formula (IV-12)

[0121]

[0122] Formula (IV-13) Formula (IV-14)

[0123]

[0124] Formula (IV-15) Formula (IV-16)

[0125] Among them, the symbols R and R a and R b With the definitions given above, especially for the definitions given in equations (Ia) and (Ib), the symbols Y and Y 1 It has the definitions given above, especially for the definitions given in equations (Ia-1) to (Ib-7), and the other symbols are as follows:

[0126] j can be 0, 1, 2 or 3 independently in various cases, preferably 0, 1 or 2;

[0127] h can be independently 0, 1, 2, 3 or 4 in various cases, preferably 0, 1 or 2;

[0128] r is 0, 1, 2, 3, 4, 5, or 6, preferably 0, 1, 2, 3, or 4, more preferably 0, 1, or 2; and

[0129] v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2.

[0130] The preferred structures / compounds are IV-2, IV-3, IV-4, IV-6, IV-7, IV-8, IV-15 and IV-16, with particularly preferred structures / compounds being IV-2, IV-7 and IV-15.

[0131] Furthermore, particularly in the structures / compounds of formulas (Ia) and (Ib) and their associated structures / compounds such as (Ia-1) to (Ib-7), (IIa-1) to (IIb-7), (III-1) to (III-4), and (IV-1) to (IV-16), it is feasible that two Ra The group forms a substructure of (RC-1) to (RC-10), preferably a substructure of (RC-4), (RC-6), (RC-8) or (RC-9).

[0132] In another preferred embodiment, it is feasible for the compounds of the present invention to comprise structures of formulas (V-1) to (V-5), wherein the compounds of the present invention may more preferably be selected from compounds of formulas (V-1) to (V-5):

[0133]

[0134] Equation (V-1) Equation (V-2)

[0135]

[0136] Equation (V-3) Equation (V-4)

[0137]

[0138] Equation (V-5)

[0139] Where the symbols R and R b With the definitions given above, especially for the definitions given in equations (Ia) and (Ib), the symbols Y and Y 1 It has the definitions given above, especially for the definitions given in equations (Ia-1) to (Ib-7), and the other symbols are as follows:

[0140] h can be independently 0, 1, 2, 3 or 4 in various cases, preferably 0, 1 or 2;

[0141] r is 0, 1, 2, 3, 4, 5, or 6, preferably 0, 1, 2, 3, or 4, more preferably 0, 1, or 2; and

[0142] v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2.

[0143] In a preferred embodiment of the invention, it is feasible for at least two, preferably adjacent, R groups to form a fused ring together with other groups bonded to the two R groups, wherein the two R groups form at least one structure of formula (RA-1) to (RA-12):

[0144]

[0145] Formula RA-1 Formula RA-2 Formula RA-3

[0146]

[0147] Type RA-4, Type RA-5, Type RA-6

[0148]

[0149] Type RA-7, Type RA-8, Type RA-9

[0150]

[0151] Type RA-10, Type RA-11, Type RA-12

[0152] Where R 1 As defined above, a dashed bond represents a site where atoms of a group bonded to two R groups are connected, and other symbols have the following definitions:

[0153] Y 4 The same or different in various cases and is C(R) 1 )2、(R 1 )2C-C(R 1 )2、(R 1 C=C(R) 1 ), NR 1 , NAr', O or S, preferably C(R) 1 )2、(R 1 )2C-C(R 1 )2、(R 1 C=C(R) 1 ), O or S;

[0154] R d In various cases, they may be the same or different and are: F; a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group may in various cases be one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 C≡C, Si(R) 2 2. C=O, C=S, C=Se, C=NR 2 -C(=O)O-, -C(=O)NR 2 -、NR 2 P(=O)(R) 2 ), -O-, -S-, SO or SO2 substitution; or having 5 to 60 aromatic ring atoms and, in various cases, being replaceable by one or more R2 Aromatic or heteroaromatic ring systems with substituted groups; or having 5 to 60 aromatic ring atoms and being substituted by one or more R groups. 2 The aryloxy or heteroaryloxy group is substituted with two R groups. d Groups can also form cyclic systems with each other, or an R d Groups can react with R 1 The group together or with other groups forms a cyclic system, wherein R 2 It has the definitions given above, especially for equations (Ia) and (Ib);

[0155] s is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0156] t is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0157] v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2.

[0158] Herein are preferred structures RA-1, RA-3, RA-4 and RA-5, with particularly preferred structures RA-4 and RA-5.

[0159] In a preferred embodiment of the invention, preferably at least two, preferably adjacent, R groups together with other groups bonded to the two R groups form a fused ring, wherein the two R groups form a structure of formula (RA-1a) to (RA-4f):

[0160]

[0161] Formula RA-1a, Formula RA-1b, Formula RA-1c

[0162]

[0163] Formula RA-2a Formula RA-2b Formula RA-2c

[0164]

[0165] Formula RA-3a Formula RA-3b

[0166]

[0167] Formula RA-4a, Formula RA-4b, Formula RA-4c

[0168]

[0169] Formula RA-4d, Formula RA-4e, Formula RA-4f

[0170] The dashed bond represents the site of atomic connection to the group bonded to the two R groups, and m is marked as 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the symbol R 1 R 2 R d And the notations s and t have the definitions given above, especially for the definitions given in equation (Ia) or (Ib) and / or equations (RA-1) to (RA-12).

[0171] The preferred structure here is RA-4f.

[0172] Another feasible scenario is that at least two R groups forming the structures of formulas (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) and forming fused rings are R groups derived from adjacent X groups, or R groups each bonded to adjacent carbon atoms, wherein these carbon atoms are preferably connected by bonds.

[0173] In another preferred configuration, preferably at least two, preferably adjacent, R groups together with other groups bonded to the two R groups form a fused ring, wherein the two R groups form a structure of formula (RB):

[0174]

[0175] RB

[0176] Where R 1 With the definitions given above, especially for formula (Ia) or (Ib), the dashed bond represents the linking site where the two R groups are bonded, and m is labeled as 0, 1, 2, 3, or 4, preferably 0, 1, or 2, Y 5 For C(R) 1 2. NR 1 ,NAr',BR 1 , BAr', O or S, preferably C(R) 1 )2, NAr' or O, more preferably C(R) 1 )2 or O, where Ar' has the definition given above, especially for the definitions given in equations (Ia) or (Ib).

[0177] Another feasible scenario is that the structure forming the (RB) and the at least two R groups forming the fused ring are R groups derived from the adjacent X group, or R groups each bonded to an adjacent carbon atom, wherein these carbon atoms are preferably connected by bonds.

[0178] More preferably, the compound comprises at least one structure of formula (VI-1) to (VI-12); more preferably, the compound is selected from compounds of formula (VI-1) to (VI-12), wherein the compound has at least one fused ring:

[0179]

[0180]

[0181] Among them, the symbols R and R a and R b With the definitions given above, especially for the definitions given in equations (Ia) and (Ib), the symbol o represents the fusion site of at least one fused ring, and the other notations used are as follows:

[0182] i can be 0, 1, or 2 independently in various cases, preferably 0 or 1;

[0183] r is 0, 1, 2, 3, 4, 5, or 6, preferably 0, 1, 2, 3, or 4, more preferably 0, 1, or 2; and

[0184] v is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2.

[0185] Another feasible scenario is that, particularly for structures / compounds of formulas (VI-1) to (VI-12), the fused ring is formed by the structures of formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) and / or (RB) as shown above, preferably by the structure of formula (RB).

[0186] Furthermore, in the structures / compounds of formulas (VI-1) to (VI-12), it is feasible for the sum of the designations i, r, and v to not exceed 10, preferably not exceed 8, especially preferably not exceed 6, and more preferably not exceed 4.

[0187] Preferably, the compound has at least two fused rings, wherein at least one fused ring is formed by a structure of formula (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f), and the other ring is formed by a structure of formula (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB).

[0188] Another feasible scenario is that the substituent R in the above formula does not interact with the substituents R and R. 1 The bonded ring atoms form fused aromatic or heteroaromatic ring systems. This includes systems that can be bonded to substituents R and R. 1 Feasible substituents for bonding R 1 and R2 It forms fused aromatic or heterocyclic aromatic ring systems.

[0189] R a R b R c The substituent group preferably does not form any ring system with other groups. If the substituent R a If they form a ring system, then the ring is preferably composed of exactly two R atoms bonded to one carbon atom. a Group formation.

[0190] When the compounds of the present invention are reacted with aromatic or heteroaromatic R, R 1 Or R 2 When substituting groups, in one embodiment, it is preferred that these groups do not have any of the following aryl or heteroaryl groups having more than two directly fused aromatic six-membered rings. More preferably, the substituents do not have any of the following aryl or heteroaryl groups having six-membered rings directly fused to each other. The reason for this preference is that this structure has a low triplet energy. Fused aryl groups having more than two directly fused aromatic six-membered rings but still suitable according to the invention are phenanthrene and biphenylide, because these also have high triplet energy levels.

[0191] Another feasible scenario is R, R 1 Or R 2 The groups do not contain any aromatic or heteroaromatic ring systems having three linearly fused aromatic 6-membered rings, wherein preferably, the R groups do not contain any aromatic or heteroaromatic ring systems having three linearly fused aromatic 6-membered rings.

[0192] Another feasible scenario is that, according to the above formula, the substituents R and R 1 It does not form fused aromatic or heteroaromatic ring systems with the ring atoms of the ring system, and preferably does not form any fused ring systems. This includes reactions with R, R 1 Feasible substituents R for group bonding 1 and R 2 A fused ring system is formed.

[0193] When it can be selected especially from R, R 1 and / or R 2 When two groups form a ring system with each other, the ring system can be a monocyclic or polycyclic aliphatic, heteroaliphatic, aromatic, or heteroaromatic ring system. In this case, the groups forming the ring system together can be adjacent, meaning that these groups are bonded to the same carbon atom or to carbon atoms directly bonded to each other, or they can be further apart from each other. Furthermore, the groups having substituents R, R... 1 and / or R 2 The ring systems can also be connected to each other via bonds, thus enabling ring closure.

[0194] Another feasible scenario is that at least two R groups are fused rings, preferably fused rings of the structures (RA-1) to (RA-12) or (RB), or at least one R group may be the same or different in various cases and is selected from aromatic or heteroaromatic ring systems selected from Ar-1 to Ar-76, and / or the Ar' group may be the same or different in various cases and is selected from Ar-1 to Ar-76:

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224] Where R 1 As defined above, a dashed bond represents a bond connected to the corresponding group. Furthermore:

[0225] Ar 1 In various cases, they may be the same or different and have 6 to 18 aromatic ring atoms and can be one or more R in various cases. 1 Divalent aromatic or heteroaromatic ring systems with substituted groups;

[0226] A is the same or different in various situations and is C(R) 1 2. NR 1 , O or S;

[0227] p is either 0 or 1, where p = 0 means Ar 1 The functional group is absent, and the corresponding aromatic or heteroaromatic functional group is directly bonded to the corresponding functional group;

[0228] q is 0 or 1, where q=0 means that no A group is bonded to that position, but R is bonded there. 1 The functional group is bonded to the corresponding carbon atom.

[0229] The structures of formulas (Ar-1) to (Ar-76) detailed above are preferred configurations of the Ar group as defined in, for example, formulas (Ia) or (Ib), in which case the substituent R in formulas (Ar-1) to (Ar-76) 1 It should be replaced with R, where R has the above definition, especially for the definition given in formula (Ia) or (Ib). Furthermore, the Ar group contains other linkage sites, in which case, in formulas (Ar-1) to (Ar-76), one R... 1 A group can represent a bonding site.

[0230] Here, preferred formulas are (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (Ar -45), (Ar-46), (Ar-69), (Ar-70), and (Ar-76) structures, particularly preferably the structures of formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16).

[0231] When the structures of formulas (Ar-1) to (Ar-76) have two or more A groups, these feasible options include all combinations derived from the definition of A. In this case, a preferred embodiment is that one of the A groups is NR. 1 And the other A group is C(R) 1 )2 or both A groups are NR 1 Or those cases where both A groups are O.

[0232] When A is NR 1 When the substituent R is bonded to the nitrogen atom 1 Preferably, it has 5 to 24 aromatic ring atoms and can also be divided by one or more R 2 Aromatic or heteroaromatic ring systems with substituted groups. In a particularly preferred embodiment, the R... 1 The substituents may be the same or different in various cases and are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, especially 6 to 18 aromatic ring atoms, which do not have any fused aryl groups and any fused heteroaromatic groups in which two or more of the aromatic or heteroaromatic 6-membered ring groups are directly fused to each other, and in various cases may also be replaced by one or more R 2 Group substitution. Phenyl, biphenyl, terphenyl, and tetraphenyl are preferred. More preferred are triazine, pyrimidine, and quinazoline as listed above for Ar-47 to Ar-50, Ar-57, and Ar-58, wherein these structures may be substituted with one or more R groups. 2 Group substitution instead of being R 1 replace.

[0233] When A is C(R) 1 At 2, the substituent R bonded to the carbon atom 1 Preferably, in various cases, they are the same or different and are straight-chain alkyl groups having 1 to 10 carbon atoms, or branched or cyclic alkyl groups having 3 to 10 carbon atoms, or aromatic or heteroaromatic ring systems having 5 to 24 aromatic ring atoms, which may also be composed of one or more R 2Group substitution. Most preferably, R 1 It is a methyl group or a phenyl group. In this case, R 1 The groups together can also form ring systems, which result in spirocyclic systems.

[0234] The preferred substituents R and R are described below. d .

[0235] The preferred and feasible approach is to use the following symbols, particularly in equations (Ia), (Ib), (Ia-1) to (Ib-7):

[0236] R is the same or different in various cases and is: H, D, N(Ar')2, N(R) 1 )2、C(Ar')3、C(R 1 )3、Si(Ar')3、Si(R 1 )3、B(Ar')2、B(R 1 )2; a straight-chain alkyl group having 1 to 40 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group may, in various cases, be one or more R 1 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 1 C=CR 1 C≡C, Si(R) 1 2. C=O, C=S, C=Se, C=NR 1 -C(=O)O-, -C(=O)NR 1 -、NR 1 P(=O)(R) 1 ), -O-, -S-, SO or SO2 substitution; or having 5 to 30 aromatic ring atoms and, in various cases, being replaceable by one or more R 1 Aromatic or heteroaromatic ring systems with substituted R groups, wherein the two R groups can also form a ring system with each other, or one R group can form a ring system with other groups, especially with R b The groups form a ring system.

[0237] In a preferred embodiment of the invention, R may be the same or different in various cases and is selected from: H, D, F, CN, NO2, Si(R) 1 3. B(OR) 1 )2; a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group may, in various cases, be one or more R 1 Group substitution; or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in various cases can be replaced by one or more R groups. 1Aromatic or heteroaromatic ring systems with substituted groups.

[0238] In another preferred embodiment of the invention, the substituent R may be the same or different in various cases and is selected from: H, D, F; a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group may be one or more R in various cases. 1 Group substitution; or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in various cases can be replaced by one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups.

[0239] Another feasible scenario is that at least one R group, preferably one substituent R, is the same or different in various cases and is selected from: H, D, having 6 to 30 aromatic ring atoms and being substituted by one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups, or N(Ar') rings. 2 Group, more preferably, at least one substituent R, R d In various cases, they may be the same or different and are selected from those having 6 to 30 aromatic ring atoms and can be generated by one or more R... 1 Aromatic or heteroaromatic ring systems or N(Ar')2 groups with substituted groups. Particularly preferably, at least one substituent R may be the same or different in various cases and is selected from those having 6 to 30 aromatic ring atoms and may be substituted by one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups. In another preferred embodiment of the invention, the substituent R forms a ring according to the structure of formulas (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), or the substituent R may be the same or different in various cases and selected from H, D, having 6 to 30 aromatic ring atoms and may be substituted by one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups, or N(Ar') rings. 2 Group. More preferably, the R group, preferably the substituent R, may be the same or different in various cases and is selected from H, D; or has 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, and in various cases may be one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups.

[0240] Another feasible scenario is that at least one R group is an aromatic ring group having 5 to 13 atoms and can be generated by one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups.

[0241] Preferably, at least one group, preferably one substituent R, may be the same or different in various cases and is selected from phenyl, biphenyl, terphenyl, tetraphenyl, fluorene, spirodifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indole-carbazole, indolo-carbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or biphenylide, each of which may be replaced by one or more Rs. 1 Group substitution.

[0242] The term "substituent" here specifically refers to R not being H. Furthermore, if two or more substituents selected from the mentioned aromatic or heteroaromatic groups are present, the substituents R may be the same or different.

[0243] Another feasible scenario is that R is bonded to a single carbon atom. a The functional groups are the same.

[0244] Another feasible scenario is R bonded to different carbon atoms. a The functional groups are the same.

[0245] In a particularly preferred embodiment, it is feasible that the two R atoms bonded to the carbon atom... a Group formation and bonding to R b The Z and W groups of these groups have the same structure as the carbon atom. This produces symmetry with respect to the oxygen atom and the Ar group. Therefore, a more preferable scenario is that the Z and W groups are attached to the CR group. b Group or CR b Groups, and CR b 2 groups and CR b The carbon atoms bonded to the groups form substructures of formulas (RC-1) to (RC-10) as described above, and R a The groups form the same substructures of formulas (RC-1) to (RC-10).

[0246] Another feasible scenario is R bonded to different carbon atoms. a The functional groups are different.

[0247] The preferred and feasible scenario is that R is bonded to a carbon atom. a The group is selected from a straight-chain alkyl group having 1 to 10 carbon atoms or having 3 to 10 carbon atoms and, in various cases, can be one or more R groups. b Group-substituted branched or cyclic alkyl groups, or in various cases, one or more R groups. 1 Group substitution, preferably deuterated phenyl groups, wherein the R group bonded to the carbon atom a Groups can form a ring system together, wherein if R aIn various cases, the phenyl group represents a phenyl group, which can be formed via a single bond or selected from C(R) 1 )2、Si(R 1 2. C=O, C=NR 1 C=C(R) 1 )2、O、S、S=O、SO2、N(R 1 ), P(R 1 ) and P(=O)R 1 Preferred selection from C(R) 1 )2、Si(R 1 The bridge bases in )2 or O are bridged to each other.

[0248] Another preferred and feasible scenario is that R a The group is methyl, ethyl, propyl, or phenyl, or two R groups bonded to the same carbon atom. a The group forms a cycloalkyl group having 5 or 6, preferably 5, carbon atoms, wherein R a The group is preferably methyl, wherein these groups may be deuterated. Preferably, in addition to D, the group R a It has not been replaced.

[0249] In a preferred and feasible scenario, at least one R a The group is a phenyl group, or two R groups bonded to the same carbon atom. a Each group represents a phenyl group, wherein the phenyl group may be formed by a single bond or selected from C(R) 1 )2、Si(R 1 2. C=O, C=NR 1 C=C(R) 1 )2、O、S、S=O、SO2、N(R 1 ), P(R 1 ) and P(=O)R 1 Preferred selection from C(R) 1 )2、Si(R 1 The bridging groups in )2 or O are bridged to each other. Preferably, in addition to D, the group R a It has not been replaced.

[0250] The preferred and feasible scenario is that R b The functional groups are H, D, methyl, ethyl, and propyl, among which these groups can be deuterated, and R... b The radical is preferably H or D.

[0251] The preferred and feasible scenario is that R c The functional groups are H, D, methyl, ethyl, and propyl, among which these groups can be deuterated, and R... c The radical is preferably H or D.

[0252] In a preferred embodiment of the present invention, R d In various cases, they may be the same or different and are selected from straight-chain alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, wherein the alkyl group may in various cases be one or more R 1 Group substitution; or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and in various cases can be replaced by one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups.

[0253] In another preferred embodiment of the invention, R d In various cases, they may be the same or different and are selected from straight-chain alkyl groups having 1 to 10 carbon atoms or branched or cyclic alkyl groups having 3 to 10 carbon atoms, wherein the alkyl group may in various cases be one or more R 2 Group substitution, having 6 to 30 aromatic ring atoms and being substituted by one or more R groups 2 Aromatic or heteroaromatic ring systems with substituted groups. More preferably, R d In various cases, they may be the same or different and are selected from straight-chain alkyl groups having 1 to 5 carbon atoms or branched or cyclic alkyl groups having 3 to 5 carbon atoms, wherein the alkyl group may in various cases be one or more R 2 Group substitution; or having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, and in various cases may be substituted with one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups.

[0254] In a preferred embodiment of the present invention, R d In various cases, they may be the same or different and are selected from straight-chain alkyl groups having 1 to 6 carbon atoms or cyclic alkyl groups having 3 to 6 carbon atoms, wherein the alkyl group may in various cases be one or more R 2 Group substitution; or having 6 to 24 aromatic ring atoms and, in various cases, being substituted with one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups... d The groups can also form a ring system together. More preferably, R d In various cases, they may be the same or different and are selected from straight-chain alkyl groups having 1, 2, 3, or 4 carbon atoms, or branched or cyclic alkyl groups having 3 to 6 carbon atoms, wherein the alkyl group may in various cases be one or more R 2The group is substituted, but preferably unsubstituted, or has 6 to 12 aromatic ring atoms, especially 6 aromatic ring atoms, and in various cases can be replaced by one or more preferably non-aromatic R groups. 2 Aromatic ring systems with substituted groups, but preferably unsubstituted; wherein two R groups are present. d The groups can form a ring system together. Most preferably, R d In various cases, they may be the same or different and are selected from straight-chain alkyl groups having 1, 2, 3, or 4 carbon atoms or branched alkyl groups having 3 to 6 carbon atoms. Most preferably, R d It is a methyl group or a phenyl group, wherein two phenyl groups can form a ring system together, and a methyl group is preferred over a phenyl group.

[0255] Substituents R, R a R d R e R d Alternatively, the preferred aromatic or heteroaromatic ring system represented by Ar or Ar' is selected from phenyl; biphenyl, especially ortho-biphenyl, meta-biphenyl, or para-biphenyl; terphenyl, especially ortho-terphenyl, meta-terphenyl, or para-terphenyl, or branched terphenyl; tetraphenyl, especially ortho-tetraphenyl, meta-tetraphenyl, or para-tetraphenyl, or branched tetraphenyl; fluorene that can be linked via the 1, 2, 3, or 4 position; spirodifluorene that can be linked via the 1, 2, 3, or 4 position; naphthalene, especially 1- or 2-bonded naphthalene; indole; benzofuran; benzothiophene; carbazole linked via the 1, 2, 3, or 4 position; dibenzofuran linked via the 1, 2, 3, or 4 position; dibenzothiophene linked via the 1, 2, 3, or 4 position; indocarbazole; indolecarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; isoquinoline; quinazoline; quinoxaline; anthracene; pyrene; perylene; fentanyl; or biphenylide, each of which can be linked via one or more R, R 1 Or R 2 Group substitution. Structures Ar-1 to Ar-76 listed above are particularly preferred, especially those with formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), and (Ar-76). Structures with formulas (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16) are particularly preferred. Regarding structures Ar-1 to Ar-76, it should be noted that these structures are formed using substituent R. 1 As shown. In the case of the cyclic Ar system, these substituents R 1 It should be replaced with R, and in R d In the case of these substituents R1 It should be replaced with R 2 .

[0256] Other suitable R groups are of the formula -Ar 4 -N(Ar 2 (Ar) 3 ) groups, wherein Ar 2 Ar 3 and Ar 4 In various cases, they may be the same or different and have 5 to 24 aromatic ring atoms and can be one or more R in various cases. 1 Aromatic or heteroaromatic ring systems with substituted groups. Here, Ar... 2 Ar 3 and Ar 4 The total number of aromatic ring atoms in the sample should not exceed 60, preferably not exceeding 40.

[0257] Here, Ar 4 and Ar 2 It can also be selected from C(R) 1 2. NR 1 The O and S groups are bonded to each other, and / or Ar 2 and Ar 3 Selected from C(R) 1 2. NR 1 The O and S groups are bonded to each other. Preferably, Ar 4 and Ar 2 Each adjacent position bonded to the nitrogen atom is connected to the others, and Ar 2 and Ar 3 Each adjacent position bonded to a nitrogen atom is connected to the others. In another embodiment of the invention, Ar 2 Ar 3 and Ar 4 The groups are not bonded to each other.

[0258] Preferably, Ar 4 It has 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, and in various cases can be substituted by one or more R atoms. 1 Aromatic or hybrid aromatic ring systems that are replaced by groups. More preferably, Ar 4 Selected from o-phenylene, m-phenylene, or p-phenylene, or o-biphenyl, m-biphenyl, or p-biphenyl, each of which can be soluble in one or more R... 1 The group is replaced, but preferably not replaced. Most preferably, Ar... 4 It is an unsubstituted benzene group.

[0259] Preferably, Ar 2 and Ar 3In various cases, they may be the same or different and have 6 to 24 aromatic ring atoms and can be converted by one or more R atoms in various cases. 1 Aromatic or heteroaromatic ring systems with substituted groups. Ar is particularly preferred. 2 and Ar 3 The functional groups may be the same or different in various cases and are selected from: benzene; o-phenyl, m-phenyl, or p-phenyl; o-terphenyl, m-terphenyl, or p-terphenyl or branched terphenyl; o-tetraphenyl, m-tetraphenyl, or p-tetraphenyl or branched tetraphenyl; 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, or 4-fluorenyl; 1-spirodifluorenyl, 2-spirodifluorenyl, 3-spirodifluorenyl, or 4-spirodifluorenyl; 1-naphthyl or 2-naphthyl; indole; benzofuran; benzothiazolyl Phenyl; 1-carbazole, 2-carbazole, 3-carbazole or 4-carbazole; 1-dibenzofuran, 2-dibenzofuran, 3-dibenzofuran or 4-dibenzofuran; 1-dibenzothiophene, 2-dibenzothiophene, 3-dibenzothiophene or 4-dibenzothiophene; indobenzocarbazole; indolocarbazole; 2-pyridine, 3-pyridine or 4-pyridine; 2-pyrimidine, 4-pyrimidine or 5-pyrimidine; pyrazine; pyridazine; triazine; phenanthrene or biphenylide, each of which may be oxidized by one or more R 1 Group substitution. Most preferably, Ar 2 and Ar 3 In various cases, they may be the same or different and selected from: benzene; biphenyl, especially ortho-biphenyl, meta-biphenyl or para-biphenyl; terphenyl, especially ortho-terphenyl, meta-terphenyl or para-terphenyl or branched terphenyl; tetraphenyl, especially ortho-tetraphenyl, meta-tetraphenyl or para-tetraphenyl or branched tetraphenyl; fluorene, especially 1-fluorene, 2-fluorene, 3-fluorene or 4-fluorene; or spirodifluorene, especially 1-spirodifluorene, 2-spirodifluorene, 3-spirodifluorene or 4-spirodifluorene.

[0260] In another preferred embodiment of the invention, R 1 In various cases, they may be the same or different and are selected from H, D, F, CN, having a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group may in various cases be one or more R 2 Group substitution, or having 6 to 24 aromatic ring atoms and, in various cases, being substituted by one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups. In a particularly preferred embodiment of the invention, R 1 In various cases, they may be the same or different and selected from H, having 1 to 6 carbon atoms, especially straight-chain alkyl groups having 1, 2, 3 or 4 carbon atoms, or branched or cyclic alkyl groups having 3 to 6 carbon atoms, wherein the alkyl group may be converted by one or more R 2The group is substituted, but preferably unsubstituted; or has 6 to 13 aromatic ring atoms and in various cases can be replaced by one or more R groups. 5 Aromatic or heteroaromatic ring systems that are substituted, but preferably unsubstituted.

[0261] In another preferred embodiment of the invention, R 2 In various cases, the same or different is: H, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, said group may be substituted with an alkyl group having 1 to 4 carbon atoms, but preferably unsubstituted.

[0262] Furthermore, in the compounds of the present invention processed by vacuum evaporation, the alkyl group preferably has no more than 5 carbon atoms, more preferably no more than 4 carbon atoms, and most preferably no more than 1 carbon atom. For compounds processed from solution, suitable compounds are also those substituted with alkyl groups having at most 10 carbon atoms, especially branched alkyl groups, or those substituted with oligomeric aromatic subunits such as o-terphenyl, m-terphenyl, or p-terphenyl, or branched terphenyl, or tetraphenyl groups.

[0263] When the compound of formula (Ia) or (Ib) or a preferred embodiment is used as a matrix material for a phosphorescent emitter or in a layer directly adjacent to the phosphorescent layer, it is also preferred that the compound does not contain any fused aryl or heteroaryl groups in which more than two six-membered rings are directly fused to each other. Phenanthrene and biphenylide are exceptions because of their high triplet energy; they may still be preferred despite the presence of fused aromatic six-membered rings.

[0264] In one preferred embodiment, the compound does not contain any aromatic or heteroaromatic ring system having three mutually fused aromatic 6-membered rings.

[0265] In another embodiment, it is feasible for the compound to comprise an aromatic or heteroaromatic ring system having three mutually fused aromatic 6-membered rings. This is particularly suitable for use in combination with a phosphor, or as a phosphor itself.

[0266] Another possible scenario is that the following compounds are excluded from the scope of protection:

[0267] .

[0268] The compounds of the present invention are preferably used as components in electronic devices, and more preferably as functional components, and therefore may preferably contain functional groups. These include hole transport groups, electron transport groups, and luminescent groups as described above and below.

[0269] Preferably, the compound contains at least one hole-transporting group.

[0270] Hole transport groups are well known in the field. These include, in particular, diarylamine or triarylamine groups, carbazole groups, and groups with similar properties. Preferred groups include, for example, the Ar-76 group as defined above.

[0271] Preferably, the compound contains at least one electron transport group.

[0272] Electron-transporting groups are well known in the art and enhance the ability of compounds to transport and / or conduct electrons. These particularly include nitrogen-containing heteroaryl groups having 5 to 12 ring atoms, more preferably 6 to 12 ring atoms, wherein these are typically electron-deficient heteroaryl groups.

[0273] Preferably, the compound comprises at least one electron transport group selected from the following groups: pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole, and / or benzimidazole groups, preferably pyrimidine, pyrazine, triazine, quinazoline, quinoxaline, and / or benzimidazole groups, more preferably pyrimidine, triazine, quinazoline, and / or quinoxaline groups, very particularly preferably pyrimidine and / or triazine groups, and most preferably can be substituted by one or more R, R 1 Or R 2 The triazine group is substituted by a group, depending on the position where the group is formed or bonded.

[0274] In one embodiment, it is feasible that the compound does not contain any carbazole group, preferably not containing any carbazole group and / or any N(Ar')2, N(R)2, or N(R)2. 1 The substituents of )2 are preferably not containing any hole transport groups.

[0275] Compounds having one or more electron transport groups and not containing any hole transport groups are particularly suitable as electron injection materials, electron transport materials or hole blocking materials for use in corresponding layers, wherein the layers typically do not contain any luminescent compounds.

[0276] In another implementation scheme, it is feasible for L to... 1 The group comprises a hole transport group, preferably a carbazole group and / or a substituent of the formula N(Ar')2, more preferably a carbazole group.

[0277] Furthermore, it is permissible for the compound to not contain any triazine groups, preferably not any pyrimidine and / or triazine groups, and more preferably not any electron transport groups.

[0278] Compounds having one or more hole transport groups but not containing any electron transport groups are particularly suitable as hole injection materials, hole transport materials or electron blocking materials for use in corresponding layers, wherein the layer typically does not contain any luminescent compounds.

[0279] In another embodiment, it is feasible for the compound to contain at least one electron transport group and at least one hole transport group, preferably at least one carbazole group and / or at least one substituent of the formula N(Ar')2, more preferably a carbazole group.

[0280] Compounds having one or more electron transport groups and including at least one hole transport group are particularly suitable as host materials for use in combination with luminescent compounds.

[0281] A compound as described in at least one of the preceding claims, characterized in that the compound comprises at least one luminescent group.

[0282] Light-emitting groups are also well known and lead to fluorescent light emitters, phosphorescent light emitters, light emitters exhibiting TADF, etc.

[0283] It is common knowledge that groups that cause phosphors are often found to be reactive, and these groups can be converted into phosphors by R in many cases. 1 Or R 2 Fused aromatic rings with substituent groups, such as fluorene, anthracene, and / or pyrene groups. Phosphorescent emitters are widely known to those skilled in the art, and metal complexes are used specifically for this purpose, which will be described later herein. Emitters exhibiting TADF have also been well described. Preferred emitters include DABNA-type compounds and compounds with similar properties, including, for example, compounds detailed in formulas (III-1) to (III-4), which preferably have at least one boron atom and at least one nitrogen atom.

[0284] It is also possible for the compound to contain exactly two, exactly three, or exactly four structures of formula (Ia) or (Ib).

[0285] In a preferred configuration, the compound is selected from compounds of formula (D-1), (D-2), or (D-3):

[0286]

[0287] Equation (D-1)

[0288]

[0289] Equation (D-2)

[0290]

[0291] Equation (D-3)

[0292] Where L 1 The group is a linking group, preferably a bond or an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, aromatic ring atoms that can be substituted by one or more R groups, and other symbols and designations used have the definitions given above, especially for the definitions given in formula (Ia) or (Ib), where L 1 Groups replace hydrogen atoms or substituents form bonds with the basic structure; preferably, L 1 The group is bonded to the Ar group, or the Ar group is bonded to the L group. 1 The groups together form an aromatic or heteroaromatic ring system having 5 to 60, preferably 10 to 40, aromatic ring atoms that can be substituted by one or more R groups.

[0293] In another preferred embodiment of the invention, L 1 It is an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, said ring system may be substituted with one or more R groups, but preferably not substituted, wherein R may have the definition given above, especially for the definition given in formula (Ia) or (Ib). More preferably, L 1 It is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which can be generated by one or more R 1 Group substitution, but preferably unsubstituted, wherein R 1 It may have the definitions given above, especially for the definitions given in equation (Ia) or (Ib).

[0294] Alternatively, preferably, the symbol L shown in formula (D1) 1 Especially in various cases, the same or different aryl or heteroaryl groups with 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, such that the aromatic or heteroaryl groups of the aromatic or heteroaryl ring system are directly, i.e., via atoms of the aromatic or heteroaryl groups to the corresponding atoms of other groups.

[0295] Another feasible scenario is that L shown in equation (D1) 1 The group comprises an aromatic ring system having no more than four, preferably no more than three, more preferably no more than two fused aromatic and / or heteroaromatic 6-membered rings, and preferably does not contain any fused aromatic or heteroaromatic ring system. Therefore, a naphthyl structure is preferred over anthracene structure. Furthermore, fluorenyl, spirodifluorenyl, dibenzofuranyl, and / or dibenzothiopheneyl structures are preferred over a naphthyl structure.

[0296] Particularly preferred are unfused structures, such as phenyl, biphenyl, triphenyl, and / or tetraphenyl structures.

[0297] Suitable aromatic or heteroaromatic ring systems L 1 Examples are selected from: o-phenylene, m-phenylene, or p-phenylene; o-biphenylene, m-biphenylene, or p-biphenylene; terphenylene, especially branched terphenylene; tetraphenylene, especially branched tetraphenylene; fluorene; spirodifluorene; dibenzofuran; dibenzothiophene; and carbazole, each of which can be derived from one or more R 1 Group substitution is preferred, but unsubstituted groups are preferred.

[0298] In a preferred configuration, the compound is selected from compounds of formulas (D-1-1) to (D-3-2):

[0299]

[0300]

[0301]

[0302] Among them, the symbols R and R a R b W and Z have the definitions given above, especially for the definitions given in equation (Ia) or (Ib), and the other notations used are as follows:

[0303] i can be 0, 1, or 2 independently in various cases, preferably 0 or 1;

[0304] j can be 0, 1, 2 or 3 independently in various cases, preferably 0 or 1;

[0305] h can be independently 0, 1, 2, 3, or 4 in various cases, preferably 0, 1, or 2; and

[0306] g is independently 0, 1, 2, 3, 4 or 5 in various cases, preferably 0, 1 or 2.

[0307] In a preferred configuration, the compound of the present invention preferably has a high degree of deuteration. Preferably, the degree of deuteration is at least 50%, more preferably at least 80%, particularly preferably at least 90%, and most preferably at least 95%. The degree of deuteration is determined by the combination of deuterium and deuterium. 1 The ratio of the total number of hydrogen atoms (D / (D+H)×100) is used to determine the compound. The compound is particularly preferably fully deuterated.

[0308] In a preferred configuration, the compounds of the present invention can be represented by at least one structure of formula (Ia), (Ib), (Ia-1) to (Ib-7), (IIa-1) to (IIb-7), (III-1) to (III-4), (IV-1) to (IV-16), (V-1) to (V-5) and / or (VI-1) to (VI-12). Preferably, the compounds of the present invention comprising the structures of formulas (Ia), (Ib), (Ia-1) to (Ib-7), (IIa-1) to (IIb-7), (III-1) to (III-4), (IV-1) to (IV-16), (V-1) to (V-5) and / or (VI-1) to (VI-12) have a molecular weight not exceeding 5000 g / mol, preferably not exceeding 4000 g / mol, particularly preferably not exceeding 3000 g / mol, especially preferably not exceeding 2000 g / mol, even more preferably not exceeding 1200 g / mol, and most preferably not exceeding 900 g / mol.

[0309] Furthermore, a preferred compound of the present invention is characterized by its sublimation capability. These compounds typically have a molar mass of less than about 1200 g / mol.

[0310] Preferably, the compound does not contain any alkoxy, thioalkoxy, or hydroxyl groups.

[0311] Another feasible scenario is that the compound containing the structure of formula (Ia) or (Ib), preferably the compound of formula (Ia) or (Ib) or a preferred embodiment of these structures / compounds, does not directly contact the metal atom and is preferably not a ligand of a metal complex.

[0312] In another preferred configuration, it is feasible to include a compound comprising a structure of (Ia) or (Ib), preferably a compound of (Ia) or (Ib) or a preferred embodiment of such structures / compounds, coordinated with a transition metal, preferably a ligand of a metal complex.

[0313] Therefore, the present invention also provides a metal complex comprising one or more compounds according to any one of claims 1 to 36, wherein the metal complex conforms to general formula (1):

[0314] M(L) n (L') m Equation (1)

[0315] The symbols and markings used are as follows:

[0316] M is a transition metal, preferably Cu, Mo, W, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au or Eu, and more preferably Pt or Ir;

[0317] L is a bidentate ligand;

[0318] L' may be the same or different in various cases and is a ligand;

[0319] n is 1, 2 or 3, preferably 2, and more preferably 3;

[0320] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, more preferably 0;

[0321] Two or more ligands L can be linked together, or L can be connected to L' via a single bond or a divalent or trivalent bridging group, thereby forming a tridentate, tetradentate, pentadentate or hexadentate ligand system;

[0322] At least one of the ligands L and L' represents the structure of formula (Ia) or (Ib) or a preferred embodiment of these structures / compounds.

[0323] Another feasible scenario is that the metal complex of general formula (1) contains the substructure M(L) of formula (2). n :

[0324]

[0325] Equation (2)

[0326] Wherein M has the definition given in claim 37, and the symbols and notations used are as follows:

[0327] CyC is an aryl or heteroaryl group or a fluorene or azirmonofluorene group having 5 to 18 aromatic ring atoms, each group being coordinated with Ir via a carbon atom, and each group being substituted by one or more R groups and covalently bonded to CyD in various cases, wherein R has the definition given above, especially for the definitions given in formulas (Ia) and (Ib);

[0328] CyD is a heteroaryl group having 5 to 18 aromatic ring atoms coordinated with Ir via an uncharged nitrogen atom or via a carbene carbon atom and which can be substituted by one or more R groups and covalently bonded to CyC, wherein R has the definition given above, especially for the definitions given in formulas (Ia) and (Ib);

[0329] n is 1, 2 or 3, preferably 2, and more preferably 3;

[0330] Two or more ligands L can also be connected to each other via single bonds or divalent or trivalent bridging groups to form tridentate, tetradentate, pentadentate or hexadentate ligand systems;

[0331] The substituents can also coordinate with M in addition;

[0332] At least one of the CyC or CyD groups represents a structure of formula (Ia) or (Ib), or a preferred embodiment of these structures / compounds.

[0333] The disclosures of patent application WO 2018 / 001990 A1 (application number PCT / EP 2017 / 065763), which are related to this application, particularly those relating to the metal complexes described in formulas (1) and (2), are incorporated herein by reference for purposes of disclosure; although this application is limited to Ir complexes, it covers other complexes and is extended accordingly. In particular, CyC and CyD groups are described in detail in this application by way of example.

[0334] The preferred embodiments described above can be combined with each other as needed within the limitations defined in claim 1. In a particularly preferred embodiment of the invention, the above-mentioned preferences occur simultaneously.

[0335] Examples of preferred compounds according to the above detailed embodiments are the compounds detailed in the table below:

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347] The basic structures of the compounds of the present invention can be prepared via the routes outlined below. The various synthetic steps described herein, such as coupling reactions that induce C / C bond formation and / or CN bond formation, are known in principle to those skilled in the art. These include Buchwald, Suzuki, Yamamoto, Stiller, Heck, Negishi, Sonogashira, and Hiyama reactions.

[0348] More information related to the synthesis of the compounds of the present invention can be found in the synthesis examples.

[0349] The compounds of the present invention can be prepared from unfunctionalized or functionalized, especially chlorinated, 1,2-dibromobenzene (1a), 1,8-dibromonaphthalene (1b), and 2,2'-dibromobiphenyl and their derivatives (1c), as shown by way of example in Scheme 1. The compounds of the present invention can also be obtained by methods other than those shown in Scheme 1. Furthermore, Scheme 1 presents the use of a specific ketone K2, but this is not absolutely necessary. Instead, open-chain or monocyclic ketones can also be used. The same applies to the aromatic or heteroaromatic compounds Ar shown.

[0350] These compounds can be monolithiated first by reacting with n-butyllithium, and then reacted with a bicyclic ketone K1, a tricyclic ketone K1, or a polycyclic ketone K1 to generate an alcohol (2), as described by example in step 1. The isolated bromine-functionalized alcohol (2) can be sequentially lithiated with 2 equivalents of n-butyllithium, and then the intermediate aryllithium can be reacted with a bicyclic ketone K1, a tricyclic ketone K1, or a polycyclic ketone K1, as described by example in step 2. As an alternative to K2, an open-chain or monocyclic ketone can be used.

[0351] Steps 1 and 2 can also be carried out continuously without separating the intermediate alcohol (2). Then, the diol (3) can be cyclized into an ether (4) under acid catalysis, preferably by removing the water formed, optionally by physical methods (distillation, e.g., distillation on a water separator) or by chemical methods (water-absorbing agents, e.g., organic or inorganic anhydrides, acetals, orthoesters, etc.), as shown by example in step 3. Finally, the ether (4) can be converted into the compound (5) of the present invention.

[0352] Unfunctionalized aromatic compounds Ar can be activated by deprotonation and boration; see, for example, T. E. Hurst et al., Chem. Eur. J., 2010, Vol. 16 (No. 27), p. 8155 or DN Coventry et al., Chem. Commun., 2005, (No. 16), p. 2172. The resulting boronic esters can be coupled with suitable aryl / heteroaryl halides via functionalization reactions familiar to those skilled in the art, such as Suzuki-type CC coupling, to obtain the materials of the present invention. Functionalized, especially chlorofunctionalized ethers (4) can be prepared by reacting suitable aryl / heteroaryl boronic acids or esters or secondary amines via functionalization reactions familiar to those skilled in the art, such as Suzuki-type, Negishi-type, Yamamoto-Grindard cross-coupling type, Buchwald-Hartwig type, Ullmann type, etc., via CC or CN coupling, to obtain the materials of the present invention.

[0353] Option 1:

[0354]

[0355] X: CR, N; Y: single bond, BR, CR2, SiR2, NR, O, S

[0356] The definitions of the symbols used in the scheme presented above are essentially the same as those for formulas (Ia) and / or (Ib). For clarity, all symbol numbers and full representations have been omitted, and preferred groups of the Ar group are shown.

[0357] Therefore, the present invention also provides a method for preparing the compounds of the present invention, wherein a compound having an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms is synthesized, and the compound is reacted with a ketone having a bicyclic alkyl group at the α-position. In addition to bicyclic ketones, tricyclic or polycyclic ketones may also be used.

[0358] These methods, if necessary, can then be purified, for example, by recrystallization or sublimation, to obtain high purity, preferably greater than 99% (using [methods]). 1 The compounds of the present invention are determined by ¹H NMR and / or HPLC.

[0359] The compounds of the present invention can also be mixed with polymers. Similarly, these compounds can be covalently incorporated into polymers. This is particularly applicable to compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boric acid, or borate esters, or substituted with reactive polymerizable groups such as olefins or oxetanes. These have been found to be suitable as monomers for the manufacture of corresponding oligomers, dendritic macromolecules, or polymers. Oligopolymerization or polymerization preferably occurs via halogen or boric acid functional groups or via polymerizable groups. Furthermore, such groups can crosslink the polymer. The compounds and polymers of the present invention can be used in the form of crosslinked or uncrosslinked layers.

[0360] Therefore, the present invention also provides an oligomer, polymer, or dendritic macromolecule containing one or more of the structures of formulas (Ia) and / or (Ib) detailed above and preferred embodiments of those formulas, or compounds of the present invention, wherein one or more bonds of the compounds of the present invention or the structures of formulas (Ia) and / or (Ib) and preferred embodiments of those formulas are present and linked to the polymer, oligomer, or dendritic macromolecule. According to the structures of formulas (Ia) and / or (Ib) and preferred embodiments of those formulas, or the linkage of the compounds, these thus form side chains of the oligomer or polymer or are bonded within the main chain. The polymer, oligomer, or dendritic macromolecule may be conjugated, partially conjugated, or non-conjugated. The oligomer or polymer may be linear, branched, or dendritic. The same preferences as described above apply to the repeating units of the compounds of the present invention in the oligomer, dendritic macromolecule, and polymer.

[0361] To prepare oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with other monomers. Preferably, copolymers are used in which the units of formula (Ia) and / or (Ib) or the preferred embodiments described above and below are present in an amount from 0.01 mol% to 99.9 mol%, preferably from 5 mol% to 90 mol%, more preferably from 20 mol% to 80 mol%. Suitable and preferred comonomers forming the basic polymer backbone are selected from: fluorene (e.g., according to EP 842208 or WO 2000 / 022026), spirodifluorene (e.g., according to EP 707020, EP 894107 or WO 2006 / 061181), p-phenylene (e.g., according to WO 92 / 18552), carbazole (e.g., according to WO 2004 / 070772 or WO 2004 / 113468), thiophene (e.g., according to EP 1028136), dihydrophenanthrene (e.g., according to WO 2005 / 014689), cis and trans-indenofluorene (e.g., according to WO 2004 / 041901 or WO 2004 / 113412), ketones (e.g., according to WO 2005 / 040302), phenanthrene (e.g., according to WO 92 / 18552), cis and trans-indenofluorene (e.g., according to WO 2004 / 041901 or WO 2004 / 113412), ketones (e.g., according to WO 2005 / 040302), and phenanthrenes (e.g., according to WO 92 / 18552). (e.g., 2005 / 104264 or WO2007 / 017066) or other various units. Polymers, oligomers and dendritic macromolecules may also contain other units, such as: hole transport units, especially those based on triarylamines; and / or electron transport units.

[0362] Furthermore, compounds of the present invention characterized by high glass transition temperatures are of particular interest. In this regard, compounds of the present invention comprising the structures of formulas (Ia) and / or (Ib) or the preferred embodiments described above and below are especially preferred, having a glass transition temperature of at least 70°C, more preferably at least 110°C, even more preferably at least 125°C, and particularly preferably at least 150°C, as measured according to DIN 51005 (2005-08 edition).

[0363] For example, by spin coating or printing, formulations of the compounds of the present invention are required for processing from the liquid phase. These formulations can 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-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthalene, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methyl anisole, 4-methyl anisole, 3,4-dimethyl anisole, 3,5-dimethyl anisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol. Cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, 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, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate, or mixtures of these solvents.

[0364] Therefore, the present invention also provides a formulation or composition comprising at least one compound of the present invention and at least one other compound. The other compound may be, for example, a solvent, particularly one of the solvents described above or a mixture of these solvents. If the other compound contains a solvent, the mixture is referred to herein as a formulation. The other compound may also be at least one other organic or inorganic compound also used in electronic devices, such as a luminescent compound and / or a matrix material. Preferably, the at least one other compound is selected from phosphorescent emitters, phosphorescent emitters, emitters exhibiting TADF, host materials, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, electron blocking materials, and hole blocking materials, preferably host materials.

[0365] The present invention also provides the use of the inventive compounds in electronic devices, particularly in organic electroluminescent devices. Preferably, the compounds of the present invention are used in electronic devices as light emitters, host materials, hole conducting materials, hole injecting materials, electron blocking materials, electron transport materials, electron injection materials, or hole blocking materials. Preferred uses herein depend on the functional groups present in the compound, and reference is made in this context to the description of the functional groups that the compound may have.

[0366] The present invention also provides an electronic device comprising at least one compound of the present invention. In the context of the present invention, an electronic device is a device comprising at least one layer containing at least one organic compound. The assembly may also comprise other layers of inorganic materials or materials entirely composed of inorganic materials.

[0367] The electronic device is more preferably selected from: organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), and more preferably organic light-emitting diodes (OLED), small molecule-based organic light-emitting diodes (sOLED), polymer-based organic light-emitting diodes (PLED), light-emitting electrochemical cells (LEC), organic laser diodes (O-lasers), and organic plasma light-emitting devices (DM Koller et al.). Nature Photonics 2008, 1-4); organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photosensors, organic field quenching devices (O-FQDs), and organic electrical sensors, preferably organic electroluminescent devices (OLEDs, sOLEDs, PLEDs, LECs, etc.), more preferably organic light-emitting diodes (OLEDs), small molecule-based organic light-emitting diodes (sOLEDs), polymer-based organic light-emitting diodes (PLEDs), especially phosphorescent OLEDs.

[0368] An organic electroluminescent device comprises a cathode, an anode, and at least one emitting layer. In addition to these layers, the organic electroluminescent device may also include other layers, such as one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, and / or charge generation layers in various cases. An intermediate layer having, for example, exciton blocking functionality may also be introduced between two emitting layers. However, it should be noted that each of these layers is not necessarily present. In this case, the organic electroluminescent device may contain one emitting layer, or it may contain multiple emitting layers. If multiple emitting layers are present, it is preferable that these emitting layers collectively have multiple emission peaks between 380 nm and 750 nm, such that the overall result is white emission; in other words, multiple luminescent compounds capable of fluorescence or phosphorescence are used in the emitting layers. A system having three emitting layers is particularly preferred, wherein the three layers exhibit blue, green, and orange or red emission. The organic electroluminescent device of the present invention can also be a tandem electroluminescent device, particularly a white-emitting OLED.

[0369] The compounds of the present invention can be used in different layers depending on their specific structure. Preferably, organic electroluminescent devices contain compounds of formula (Ia) and / or (Ib) or the preferred embodiments described above in the emitting layer as matrix materials for phosphorescent emitters or emitters exhibiting TADF (thermally activated delayed fluorescence), particularly for phosphorescent emitters. Furthermore, the compounds of the present invention can also be used in electron transport layers and / or hole blocking layers. More preferably, the compounds of the present invention are used in the emitting layer as matrix materials for phosphorescent emitters, particularly for red, orange, blue, green, or yellow phosphorescent emitters, preferably for blue or green phosphorescent emitters, as host materials, electron transport materials, electron injection materials, or hole blocking materials. In another preferred embodiment, the compounds of the present invention in the emitting layer can be used as matrix materials for phosphorescent emitters, particularly red, orange, blue, green, or yellow phosphorescent emitters, preferably for blue or green phosphorescent emitters, as host materials, hole conduction materials, hole injection materials, or electron blocking materials. Furthermore, the compounds of the present invention can be used as fluorescent emitters, emitters exhibiting TADF, or phosphorescent emitters in organic electroluminescent devices, with the aforementioned metal complexes preferably used as phosphorescent emitters, which also constitutes part of the subject matter of the present invention.

[0370] Preferably, the organic electroluminescent device comprises at least one light-emitting layer and at least one electron transport layer, wherein the electron transport layer is an electron transport layer containing a compound according to the present invention.

[0371] When the compounds of the present invention are used as matrix materials for phosphorescent compounds in the luminescent layer, they are preferably used in combination with one or more phosphorescent materials (triple-state emitters). In the context of this invention, phosphorescence should be understood as the emission of light from excited states with high spin multiplicity, i.e., spin >1, particularly from excited triplet states. In the context of this application, all luminescent complexes having transition metals or lanthanides, particularly all iridium, platinum, and copper complexes, should be considered phosphorescent compounds.

[0372] Based on the overall mixture of the luminescent material and the matrix material, the mixture of the compound and the luminescent compound of the present invention contains the compound of the present invention in the range of 99 vol% to 1 vol%, preferably between 98 vol% and 10 vol%, more preferably between 97 vol% and 60 vol%, and particularly between 95 vol% and 80 vol%. Accordingly, based on the overall mixture of the luminescent material and the matrix material, the mixture contains the luminescent material in the range of 1 vol% to 99 vol%, preferably between 2 vol% and 90 vol%, more preferably between 3 vol% and 40 vol%, and particularly between 5 vol% and 20 vol%.

[0373] In one embodiment of the invention, the compound of the invention is used herein as the sole matrix material (“single host”) for the phosphorescent emitter.

[0374] Another embodiment of the present invention is to use the compounds of the present invention as a matrix material for a fluorescent emitter. Fluorescent emitters are well known in the art, and preferred examples of fluorescent emitters are listed in the table below.

[0375]

[0376]

[0377]

[0378]

[0379]

[0380] The phosphors described in detail above by way of example are preferably having the structures of formula (Ia) and / or (Ib) or preferred embodiments of these structures, wherein these compounds having the structures of the present invention are particularly preferred phosphors of the present invention.

[0381] Another embodiment of the present invention is to use the compounds of the present invention as a matrix material for a TADF-exhibiting luminescent material. Another embodiment of the present invention is to use the compounds of the present invention as a matrix material for a fluorescent luminescent material. Luminescent materials exhibiting TADF are well known to those skilled in the art, and preferred examples of fluorescent luminescent materials are listed in the table below.

[0382]

[0383]

[0384]

[0385]

[0386] The luminescent material exhibiting TADF and shown by way of example above may preferably have the structure of formula (Ia) and / or (Ib) or preferred embodiments of these structures, wherein these compounds having the structure according to the invention are particularly preferred luminescent materials exhibiting TADF according to the invention.

[0387] Another embodiment of the present invention is to combine the compound of the present invention with other matrix materials and use it as a matrix material for phosphorescent emitters. Suitable matrix materials that can be used in combination with the compounds of the present invention are aromatic ketones, aromatic phosphine oxides, or aromatic sulfoxides or sulfones, such as those according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO2010 / 006680; triarylamines; carbazole derivatives, such as CBP (N,N-dicarbazolylbiphenyl) or carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176; indolecarbazole derivatives, such as those according to WO 2007 / 063754 or WO 2008 / 056746; indobenzocarbazole derivatives, such as those according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, such as those according to EP 1617710, EP 1617711, EP 1731584, JP2005 / 347160; bipolar matrix materials, such as those according to WO 2007 / 137725; silanes, such as those according to WO 2005 / 111172; borazolacine or borate esters, such as those according to WO 2006 / 117052; triazine derivatives, such as those according to WO2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO WO 2011 / 060859 or WO 2011 / 060877; zinc complexes, for example according to EP 652273 or WO 2009 / 062578; silylated diazacyclopentane or silylated tetrazacyclopentane derivatives, for example according to WO 2010 / 054729; phosphorus diazacyclopentane derivatives, for example according to WO 2010 / 054730; bridged carbazole derivatives, for example according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; triphenylide derivatives, for example according to WO 2012 / 048781; dibenzofuran derivatives, for example according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO2017 / 148565; or cyclocarbazole, for example, according to JP 3139321 B2.

[0388] Similarly, it is also feasible to include other phosphorescent emitters that emit light at wavelengths shorter than the actual emitter in the mixture as co-substrate. Particularly good results were obtained when the emitter used was a red phosphorescent emitter and the co-substrate used in combination with the compound of the present invention was a yellow phosphorescent emitter.

[0389] Furthermore, the co-matrix used can be a compound that participates in charge transport but not to a significant degree, such as those described, for example, in WO 2010 / 108579. Compounds with large band gaps and which themselves participate in charge transport of the luminescent layer but not to a significant degree are particularly suitable as co-matrix materials in combination with the compounds of the present invention. Such materials are preferably pure hydrocarbons. Examples of such materials can be found, for example, in WO 2009 / 124627 or WO 2010 / 006680. In this case, it should be emphasized that the compounds of the present invention have the advantageous property of lacking specific functional groups such as hole transport groups and / or electron transport groups.

[0390] Suitable phosphorescent compounds (= triplet emitters) are especially those that emit light when properly excited, preferably in the visible region; and also 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, especially a metal having that atomic number. Preferred phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, or europium, especially compounds containing iridium or platinum.

[0391] Examples of the aforementioned luminescent materials can be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626、WO 2011 / 066898、WO 2011 / 157339、WO 2012 / 007086、WO 2014 / 008982、WO 2014 / 023377、WO 2014 / 094961、WO 2014 / 094960、WO 2015 / 036074, WO 2015 / 104045, WO 2015 / 117718, WO 2016 / 015815, WO 2016 / 124304, WO 2017 / 032439 and WO 2018 / 011186. Generally, all phosphorescent complexes for phosphorescent devices that are known to those skilled in the art and to those skilled in the art of organic electroluminescence are suitable, and those skilled in the art will be able to use other phosphorescent complexes without inventive effort.

[0392] Examples of phosphorescent dopants are listed in the table below:

[0393]

[0394]

[0395]

[0396]

[0397] The phosphorescent dopants detailed above by way of example are preferably having structures of formula (Ia) and / or (Ib) or preferred embodiments of these structures, wherein these compounds having the structures of the present invention are particularly preferred metal complexes of the present invention.

[0398] The compounds of this invention are also particularly suitable as matrix materials for phosphorescent emitters in organic electroluminescent devices, as described, for example, in WO 98 / 24271, US 2011 / 0248247, and US 2012 / 0223633. In these multicolor display components, an additional blue emitting layer is applied to all pixels, including pixels with non-blue colors, by vapor deposition over the entire area.

[0399] In another embodiment of the invention, the organic electroluminescent device of the present invention does not contain any separate hole injection layer and / or hole transport layer and / or hole blocking layer and / or electron transport layer, meaning that the light-emitting layer is directly adjacent to the hole injection layer or anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode, as described, for example, in WO2005 / 053051. Alternatively, a metal complex identical or similar to the metal complex in the light-emitting layer can be used as the hole transport or hole injection material directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0400] In the other layers of the organic electroluminescent device of the present invention, any material commonly used in the prior art can be used. Therefore, those skilled in the art will be able to combine any known material for organic electroluminescent devices with the compounds of the present invention of formula (Ia) and / or (Ib) or the preferred embodiments described above without inventive effort.

[0401] Another preferred organic electroluminescent device is characterized by coating one or more layers via a sublimation method. In this case, by using 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, the initial pressure can be even lower, for example, less than 10. -7 millibar.

[0402] Also preferred is an organic electroluminescent device, characterized by coating one or more layers by 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 inkjet printing), in which the material is applied directly through a nozzle and thus structured.

[0403] Another preferred organic electroluminescent 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, offset printing, LITI (photoinduced thermal imaging), thermal transfer, inkjet printing, or nozzle printing. For this purpose, a soluble compound, for example, obtained through suitable substitution, is required.

[0404] Formulations using compounds of formula (Ia) and / or (Ib) or the preferred embodiments thereof detailed above are novel. Therefore, the present invention also provides a formulation comprising at least one solvent and a compound of formula (Ia) and / or (Ib) or the preferred embodiments thereof detailed above.

[0405] Furthermore, a hybrid approach is feasible, for example, in which one or more layers are applied from a solution and one or more other layers are applied by vapor deposition.

[0406] These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices containing the compounds of the present invention without any inventive effort.

[0407] The compounds of the present invention and the organic electroluminescent devices of the present invention are particularly significant compared to the prior art in that they have a low refractive index (RI). Furthermore, these compounds and the resulting organic electroluminescent devices exhibit improved lifetime. Meanwhile, other electronic properties of the electroluminescent devices, such as efficiency or operating voltage, remain at least as good. In another variation, the compounds of the present invention and the organic electroluminescent devices of the present invention are particularly characterized by improved efficiency and / or operating voltage and a longer lifetime compared to the prior art.

[0408] The electronic devices of the present invention, especially organic electroluminescent devices, have one or more of the following surprising advantages compared with the prior art:

[0409] 1. Compounds comprising the preferred embodiments of formula (Ia) and / or (Ib) or the context thereof, particularly as light emitters, as matrix materials, as hole-conducting materials, or as electron-conducting materials, exhibit excellent efficiency in electronic devices, especially organic electroluminescent devices. In this case, the compounds of the present invention having the structure of the preferred embodiments of formula (Ia) and / or (Ib) or the context thereof, when used in electronic devices, can produce low operating voltages.

[0410] 2. Compounds comprising the preferred embodiments of formulas (Ia) and / or (Ib) or described in the context, particularly as light emitters, as matrix materials, as hole-conducting materials, or as electron-conducting materials, exhibit very good lifetimes in electronic devices, especially organic electroluminescent devices. In this case, these compounds particularly contribute to low roll-off, i.e., a small decrease in power efficiency of the device at high luminous density.

[0411] 3. The compounds of the present invention according to the preferred embodiments of formula (Ia) and / or (Ib) or the context thereof exhibit very high stability and lifetime.

[0412] 4. Compounds comprising the preferred embodiments of formula (Ia) and / or (Ib) or the context thereof, particularly electronic devices, especially organic electroluminescent devices, having very low refractive indices, as light emitters, as matrix materials, as hole-conducting materials, or as electron-conducting materials.

[0413] 5. Electronic devices comprising compounds of formula (Ia) and / or (Ib) or the preferred embodiments described in the context, particularly organic electroluminescent devices, having very high color purity, especially as light emitters or matrix materials.

[0414] 6. The compounds of formulas (Ia) and / or (Ib) or the preferred embodiments described in the context can avoid the formation of optical loss channels in electronic devices, particularly organic electroluminescent devices. As a result, these devices are characterized by high PL efficiency of the light emitter and the resulting high EL efficiency, as well as excellent energy transfer from the matrix to the dopant.

[0415] 7. The compounds of the preferred embodiments described in formula (Ia) and / or (Ib) or in the context of the present invention have excellent glass film formation.

[0416] 8. The compounds of the preferred embodiments described in formula (Ia) and / or (Ib) or in the context form very well films from solutions.

[0417] These advantages are not accompanied by a very serious deterioration in other electronic properties.

[0418] It should be noted that the scope of this invention covers variations of the embodiments described herein. Unless explicitly excluded, any feature disclosed herein may be substituted with an alternative feature having the same or equivalent / similar purpose. Therefore, unless otherwise stated, any feature disclosed herein should be considered an example of a general series or an equivalent / similar feature.

[0419] Unless specific features and / or steps are mutually exclusive, all features of the invention can be combined with each other in any way. This is especially true of preferred features of the invention. Similarly, features that are not necessarily combined can be used individually (and not in combination).

[0420] It should also be noted that many features of the invention, especially those of the preferred embodiments, should be considered inventive in themselves, and not merely as embodiments of the invention. Independent protection may be sought for these features as supplements to or alternatives to any currently claimed invention.

[0421] The technical teachings disclosed in this invention can be refined and combined with other embodiments.

[0422] The invention is illustrated in more detail by way of the following examples, but is not intended to limit the invention. Those skilled in the art will be able to use the information given to practice the invention throughout the entire scope of the disclosure, prepare other compounds of the invention and use them in electronic devices, or employ the methods of the invention without inventive effort.

[0423] Example

[0424] Unless otherwise specified, the following synthesis is carried out in an anhydrous solvent under a protective gas atmosphere. Solvents and reagents are available from, for example, Sigma-Aldrich or ABCR. The corresponding numbers in square brackets or the numbers cited for individual compounds relate to the CAS numbers of the compounds known from the literature. In the case of compounds that may have multiple isomers, enantiomers, diastereomers, or tautomers, one form is shown in a representative manner.

[0425] A: Synthetons, bromides (LB), and ketones (LK) known from the literature:

[0426]

[0427]

[0428]

[0429] B: Preparation of synthon S:

[0430] Example S1:

[0431]

[0432] a) S1a:

[0433]

[0434] To a well-stirred mixture of 24.1 g (100 mmol) LB1, 250 mL tetrahydrofuran (THF), and 250 mL diethyl ether cooled to -110 °C, 40.0 mL of a 2.5 M n-butyllithium solution in n-hexane was added dropwise over approximately 10 minutes while maintaining the temperature below -100 °C. The mixture was stirred at -110 °C for 30 minutes, followed by the dropwise addition of 15.0 g (100 mmol) LK7 in 50 mL THF over approximately 20 minutes while maintaining the temperature below -100 °C. The reaction mixture was stirred at -110 °C for another 1 hour, the cooling bath was removed, and the mixture was gradually warmed to room temperature. The organic phase was removed by quenching with 200 mL of saturated ammonium chloride solution, and the mixture was concentrated to dryness. The residue was subjected to column chromatography (Torrent automated column system from A. Semrau). Yield: 24.2 g (78 mmol), 78%. Purity: as per [reference needed]. 1 The H NMR spectroscopy result was 97%.

[0435] b) S1b:

[0436]

[0437] To a well-stirred mixture of 24.1 g (100 mmol) S1a, 250 ml tetrahydrofuran (THF), and 250 ml diethyl ether cooled to -78 °C, 80.0 ml (200 mmol) of a 2.5 M n-hexane solution of n-butyllithium was added dropwise over approximately 20 minutes while maintaining the temperature below -70 °C. The mixture was stirred at -78 °C for 30 minutes, followed by the dropwise addition of 15.0 g (100 mmol) of a solution of LK7 in 50 ml THF over approximately 15 minutes while maintaining the temperature below -70 °C. The reaction mixture was stirred at -78 °C for another 1 hour, the cooling bath was removed, and the mixture was gradually warmed to room temperature. Quenching was performed by adding 200 ml of saturated ammonium chloride solution. The organic phase was dried over magnesium sulfate and concentrated to dryness under reduced pressure at a maximum temperature of 30 °C. The residue was dissolved in approximately 250 ml of warm n-heptane, scraped, and frozen overnight at -25 °C. The crystals were filtered off, washed once with a small amount of n-heptane, and dried under reduced pressure. A second crystalline fraction was obtained from the mother liquor. Yield: 20.6 g (54 mmol), 54%. Purity: as per [previous treatment / method / etc.]. 1 The H NMR spectroscopy result was 97%.

[0438] c) S1:

[0439] A well-stirred mixture of 37.9 g (100 mmol) S1b, 3.0 g of Amberlyst R 15 in hydrogen form, and 500 ml of toluene was heated on a water separator until the reaction was complete (approximately 2 hours). The mixture was allowed to cool to room temperature, Amberlyst was filtered off, the filtrate was concentrated to dryness, and the residue was subjected to column chromatography (from A. Semrau's Torrent automated column system). Yield: 16.6 g (82 mmol), 82%. Purity: as indicated by... 1 The H NMR spectroscopy result was 98%.

[0440] The following compounds can be prepared similarly:

[0441]

[0442]

[0443]

[0444]

[0445]

[0446]

[0447] Example S100:

[0448]

[0449] The process is similar to WO 2012 / 068589. In the case of chloride, S-Phos can be used instead of PCy3. 36.0 g (100 mmol) of S2 was used. Yield: 45.3 g (93 mmol), 93%; Purity: as per [unspecified standard]. 1 H NMR confirmed it to be approximately 97%.

[0450] The following compounds can be prepared similarly:

[0451]

[0452] Example S200:

[0453]

[0454] Preparation was similar to that of Y. Hu et al., ACS Appl. Polymer Mater., 2019, Vol. 1 (Issue 2), p. 221, compound 8. 1.05 equivalents of NBS were used; the crude product was purified by column chromatography (Torrent automated column system from A. Semrau). Starting material: 52.8 g (100 mmol) of S15. Yield: 56.8 g (90 mmol), 90%. Purity: as determined by… 1 The HNMR result was 97%.

[0455] C: Preparation of synthon S and inventive compound E:

[0456] Example E1:

[0457]

[0458] Preparations are similar to: a) JF Hartwig et al., J. Org. Chem., 1999, Vol. 64 (Issue 15), 5575 pages; b) M. Watanabe et al., Tetrahedron Lett., 2000, Vol. 41 (Issue 4), 481 pages; c) Y. Zhang et al., Chem. Sci., 2023, Vol. 14 (Issue 19), 5125 pages. Other electron-rich phosphines such as SPhos, AmPhos, and RuPhos can be used as an alternative to tri-tert-butylphosphine. The starting materials are similar to a): 39.5 g (100 mmol) of S2 and 32.1 g (100 mmol) of bis(4-biphenyl)amine [102113-98-4]. Purification was carried out under various conditions by repeated hot extraction crystallization (using conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, volume ratio 1:3 to 3:1) or column chromatography and fractional sublimation or high-vacuum heat treatment. Yield: 57.0 g (84 mmol), 84%; Purity: >99.9% as determined by HPLC.

[0459] The following compounds can be prepared similarly:

[0460]

[0461]

[0462]

[0463]

[0464]

[0465]

[0466]

[0467]

[0468]

[0469]

[0470]

[0471]

[0472]

[0473]

[0474]

[0475]

[0476]

[0477]

[0478]

[0479] Example E200:

[0480]

[0481] A well-stirred solution of 39.4 g (100 mmol) S2, 44.1 g (110 mmol) β-[4-[bis([1,1'-biphenyl]-4-yl)amino]phenyl]boronic acid [943836-24-6], 42.4 g (200 mmol) tripotassium phosphate [7778-53-2], 1.64 g (4 mmol) SPhos [657408-07-6], 449 mg (2 mmol) palladium(II) acetate, 400 ml toluene, 100 ml dimethyl ether, and 300 ml water was heated to reflux for 24 hours. After cooling, the organic phase was removed, and the solution was washed three times with 300 ml of water each time and once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The drying agent was filtered off, the filtrate was concentrated to dryness, and the residue was subjected to column chromatography (from A. Semrau's Torrent automated column system). The crude product was further purified under various conditions by column chromatography and / or repeated thermal extraction crystallization (using conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, volume ratio 1:3 to 3:1) and fractional sublimation or high-vacuum heat treatment. Yield: 52.3 g (69 mmol), 69%; Purity: approximately 99.9% as determined by HPLC.

[0482] The following compounds can be prepared similarly, with adjustments made to the stoichiometry of the reactants:

[0483]

[0484]

[0485]

[0486]

[0487]

[0488]

[0489]

[0490]

[0491]

[0492]

[0493]

[0494]

[0495]

[0496]

[0497] Example E300:

[0498]

[0499] Add 2.4 g (100 mmol) of sodium hydride in portions to a solution of 45.2 g (105 mmol) of S16 in 300 ml of DMF (Caution: Hydrogen gas escapes!). Then add 37.8 g (110 mmol) of 2-[1,1'-biphenyl]-4-yl-4-chloro-6-phenyl-1,3,5-triazine [1472062-94-4], and stir the mixture at room temperature for 2 hours, then at 50°C for 3 hours. While stirring, add 2000 ml of water dropwise, filter the precipitated solid, wash three times with 100 ml of water each time, and twice with 100 ml of ethanol each time, and dry under reduced pressure. Dissolve the solid in dichloromethane, filter as a DCM slurry through a silica gel bed, and gradually concentrate the filtrate on a rotary evaporator, continuously replacing the distilled DCM with ethanol. Filter the crystalline product, wash twice with 50 ml of ethanol each time, and dry under reduced pressure. The crude product was further purified under various conditions by column chromatography and / or repeated thermal extraction crystallization (using conventional organic solvents or combinations thereof, preferably acetonitrile-DCM, volume ratio 1:3 to 3:1) and fractional sublimation or high-vacuum heat treatment. Yield: 53.0 g (70 mmol), 70%; Purity: approximately 99.9% as determined by HPLC.

[0500] The following compounds can be prepared similarly:

[0501]

[0502]

[0503] Example E400:

[0504]

[0505] Preparation was similar to that described by S. Oda et al., Angew. Chem. Int. Ed., 2021, Vol. 60, p. 2882, compound “CzDABNA-NP-M / TB”. Starting material: 9.8 g (10 mmol) of S300; yield: 4.0 g (4.1 mmol), 41%; purity: >99.5% as determined by HPLC.

[0506] The following compounds can be prepared similarly:

[0507]

[0508] Example: OLED Manufacturing

[0509] The OLEDs of the present invention and the OLEDs according to the prior art are manufactured by a general method according to WO 2004 / 058911, with said method adapted to the environment described herein (variations in layer thickness, materials used).

[0510] Subsequent examples present results for various OLEDs. Clean glass plates coated with a 50 nm thick layer of structured ITO (indium tin oxide) (cleaned in a Miele laboratory glass washer with Merck Extran detergent) were pretreated with UV ozone for 25 minutes (UVP PR-100 UV ozone generator). These coated glass plates form the substrate for applying the OLED.

[0511] a) Blue fluorescent OLED module - BF:

[0512] The compounds of this invention can be used in hole transport layers (HTL), electron blocking layers (EBL), and electron transport layers (ETL). All materials are applied by thermal vapor deposition in a vacuum chamber. The light-emitting layer (EML) here always consists of at least one matrix material (host material) SMB (see Table 1) and a light-emitting dopant (dopant, emitting element) D, which is added to (one or more) matrix materials by co-evaporation in a specific volume ratio. Details given herein in the form of SMB:D (95%:5%) mean that material SMB is present in the layer at a volume ratio of 95% and dopant D at a volume ratio of 5%. Similarly, the electron transport layer can also consist of a mixture of two materials; see Table 1. Materials used for producing OLEDs are shown in Table 5 or related to the synthesis examples detailed above.

[0513] The OLED was characterized using standard methods. For this purpose, the electroluminescence spectrum was determined, and the current efficiency (measured in cd / A), power efficiency (measured in lm / W), and external quantum efficiency (EQE, measured as a percentage) as a function of luminescence density were calculated using the current-voltage-luminescence density characteristics (IUL characteristics) under the assumption of Lambertian luminescence properties. At 1000 cd / m²... 2 The EQE is reported in (%) and the voltage in (V) at the luminous density.

[0514] OLEDs have the following layer structure:

[0515] base

[0516] Hole injection layer (HIL) composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0517] Hole transport layer (HTL), composed of HTM1, 180 nm

[0518] Electron blocking layer (EBL), see Table 1

[0519] Emissive layer (EML), see Table 1

[0520] Hole blocking layer (HBL), see Table 1

[0521] Electron transport layer (ETL), see Table 1

[0522] Electron injection layer (EIL) composed of ETM2, 1 nm

[0523] Aluminum cathode, 100 nm

[0524] Table 1: Structure of Blue Fluorescent OLED Module

[0525]

[0526] Table 2: Results of Blue Fluorescent OLED Module

[0527]

[0528] b) Phosphorescent OLED modules:

[0529] Compound E can be used as a hole-conducting or electron-conducting matrix material (host material) (hTMM / eTMM) in hole transport layers (HTL), electron blocking layers (EBL), electron transport layers (ETL), and emissive layers (EML). For this purpose, all materials are applied by thermal vapor deposition in a vacuum chamber. The emissive layer here always consists of at least one or more matrix materials M and a phosphorescent dopant Ir, which is added to the matrix material(s) in a specific volume ratio by co-evaporation. Details given here in the form of M1:M2:Ir (55%:35%:10%) mean that material M1 is present in the layer at a volume ratio of 55%, M2 at a volume ratio of 35%, and Ir at a volume ratio of 10%. Similarly, the electron transport layer can also consist of a mixture of the two materials. The exact structure of the OLED can be found in Table 3. Materials used to produce the OLED are shown in Table 5 or related to the synthesis examples detailed above.

[0530] The OLED was characterized using standard methods. For this purpose, the electroluminescence spectrum was determined, and the current efficiency (measured in cd / A), power efficiency (measured in lm / W), and external quantum efficiency (EQE, measured in %) as a function of luminescence density were calculated using the current-voltage-luminescence density characteristics (IUL characteristics) under the assumption of Lambertian luminescence properties. At 1000 cd / m²... 2 The EQE is reported in (%) and the voltage in (V) at the luminous density.

[0531] OLEDs have the following layer structure:

[0532] base

[0533] Hole injection layer (HIL) composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm

[0534] The hole transport layer (HTL) composed of HTM1 has a wavelength of 180 nm for blue and 50 nm for green, yellow, and red.

[0535] Electron blocking layer (EBL), see Table 3

[0536] Emissive Layer (EML), see Table 3

[0537] Hole blocking layer (HBL), see Table 3

[0538] Electron transport layer (ETL), see Table 3

[0539] Electron injection layer (EIL) composed of ETM2, 1 nm

[0540] Aluminum cathode, 100 nm

[0541] Table 3: Structure of Phosphorescent OLED Modules

[0542]

[0543] Table 4: Results of phosphorescent OLED modules

[0544]

[0545] Table 5: Structural Formulas of Materials Used

[0546]

[0547]

[0548]

Claims

1. A compound comprising at least one structure of formula (Ia) or formula (Ib): The symbols are as follows: Z is the same or different in various cases and is -(CR) b 2) n -group, where n is an integer in the range of 1 to 6; W is the same or different in various situations and is -(CR) b 2) m - A group, wherein m is an integer in the range of 1 to 6, wherein the W group can be bridged to the Z group via one or more V groups, wherein V may be the same or different in various cases and is a single bond or has 1 to 40 carbon atoms and can be connected to one or more R groups. 2 A substituted alkyl subunit, wherein one or more non-adjacent CH2 groups may be -R 2 C=CR 2 -、-C≡C-、Si(R 2 2. C=O, C=S, C=Se, C=NR 2 -C(=O)O-, -C(=O)NR 2 -、NR 2 P(=O)(R) 2 (), -O-, -S-, SO or SO2, and one or more of the hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2; Ar can be the same or different in various cases and is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms that can be substituted by one or more R groups, wherein the Ar group can coordinate with a transition metal; R a In various cases, they may be the same or different and are: H, D, F; straight-chain alkyl groups having 1 to 40 carbon atoms, branched or cyclic alkyl groups having 3 to 40 carbon atoms, each of which may be represented by one or more R b Group substitution; or having 5 to 60 aromatic ring atoms and, in various cases, being substituted with one or more R groups; 1 Aromatic or heteroaromatic ring systems with substituted groups, wherein two R groups are present. a Groups can form ring systems together; R b In various cases, they may be the same or different and are: H, D, F; a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of which may be represented by one or more R 2 Group substitution, wherein two or more R groups are substituted. b Groups can form ring systems together; R c In various cases, they may be the same or different and are: H, D, F; a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 40 carbon atoms, each of which may be represented by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 2. C=O, C=S, C=Se, C=NR 2 -C(=O)O-, -C(=O)NR 2 -、NR 2 P(=O)(R) 2 ), -O-, -S-, SO or SO2 substitution, where two or more of the R c Groups can form ring systems together; R is the same or different in various cases and is: H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R) 1 )2、C(=O)N(Ar')2、C(=O)N(R 1 )2、C(Ar')3、C(R 1 )3、Si(Ar')3、Si(R 1 )3、B(Ar')2、B(R 1 )2、C(=O)Ar'、C(=O)R 1 、P(=O)(Ar')2、P(=O)(R 1 )2、P(Ar')2、P(R 1 )2、S(=O)Ar'、S(=O)R 1 S(=O)2Ar', S(=O)2R 1 OSO2Ar', OSO2R 1 A straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or an alkenyl or alkynyl group having 2 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 20 carbon atoms, wherein each of the alkyl, alkoxy, thioalkoxy, alkenyl, or alkynyl group may be derived from one or more R... 1 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 1 C=CR 1 C≡C, Si(R) 1 2. C=O, C=S, C=Se, C=NR 1 -C(=O)O-, -C(=O)NR 1 -、NR 1 P(=O)(R) 1 ), -O-, -S-, SO or SO2 substituted; or having 5 to 60 aromatic ring atoms and, in various cases, being substituted by one or more R 1 Aromatic or heteroaromatic ring systems with substituted groups; or having 5 to 60 aromatic ring atoms and being substituted by one or more R groups. 1 The aryloxy or heteroaryloxy group is substituted with a group, wherein the two R groups can form a cyclic system with each other, or one R group can form a cyclic system with other groups, especially with R b The groups form a cyclic system, in which the R group can coordinate with a transition metal; Ar' can be the same or different in various cases and has 5 to 60 aromatic ring atoms and can be denoted by one or more R. 1 Aromatic or heteroaromatic ring systems with substituted groups, wherein the two Ar' groups bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom can also be bonded by a single bond or selected from B(R) 1 ), C(R 1 )2、Si(R 1 2. C=O, C=NR 1 C=C(R) 1 )2、O、S、S=O、SO2、N(R 1 ), P(R 1 ) and P(=O)R 1 The bridging groups in the structure are connected to each other, and the Ar' group can coordinate with transition metals; R 1 The following are the same or different under various conditions: H, D, F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R) 2 )2、C(=O)Ar''、C(=O)R 2 ,P(=O)(Ar'')2,P(Ar'')2,B(Ar'')2,B(R 2 )2、C(Ar'')3、C(R 2 )3、Si(Ar'')3、Si(R 2 )3; a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms, or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be generated by one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 2. C=O, C=S, C=Se, C=NR 2 -C(=O)O-, -C(=O)NR 2 -、NR 2 P(=O)(R) 2 ), -O-, -S-, SO or SO2, and one or more of the hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2; or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be replaced by one or more R 2 Group substitution; or having 5 to 60 aromatic ring atoms and being substituted with one or more R groups. 2 A group-substituted aryloxy or heteroaryloxy group; or a group having 5 to 60 aromatic ring atoms and being substituted with one or more R groups. 2 Group-substituted aralkyl or heteroaralkyl groups; or combinations of these systems; wherein two or more R groups are substituted with aralkyl or heteroaralkyl groups; or combinations thereof; wherein two or more R groups are substituted with aralkyl or heteroaralkyl groups. 1 Groups can form cyclic systems with each other, wherein one or more R groups 1 The group can form a ring system with other parts of the compound, wherein R 1 The group can coordinate with transition metals; Ar'' can be the same or different in various cases and has 5 to 30 aromatic ring atoms and can be denoted by one or more R''. 2 Aromatic or heteroaromatic ring systems with substituted groups, wherein the two Ar'' groups bonded to the same carbon, silicon, nitrogen, phosphorus, or boron atom can also be bonded by a single bond or selected from B(R) 2 ), C(R 2 )2、Si(R 2 2. C=O, C=NR 2 C=C(R) 2 )2、O、S、S=O、SO2、N(R 2 ), P(R 2 ) and P(=O)R 2 The bridging groups in the structure are connected to each other, and the Ar'' group can coordinate with transition metals; R 2 In various cases, they may be the same or different and selected from: H, D, F, CN; an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and said aromatic or heteroaromatic ring system may be replaced by one or more alkyl groups each having 1 to 4 carbon atoms, wherein two or more substituents R 2 They can form a ring system together.

2. The compound according to claim 1, characterized in that... The sum of the labels m and n is between 3 and 6.

3. The compound according to claim 1 or 2, wherein the compound comprises at least one structure of formula (Ia-1) to (Ib-7): Among them, the symbols R and R a R b W and Z have the definitions given in claim 1, and other symbols used are as follows: Y may be the same or different in various cases and is O, S, NR, Si(R)2, C(R)2 or an ortho-bonded phenylene group that can be substituted by one or more R groups; Y 1 In various cases, they may be the same or different and are C(R)2, Si(R)2, C=O, P(O)R, P(R), O, S, NR, or BR; and X is the same or different in various cases and is CR or N.

4. The compound according to one or more of claims 1 to 3, wherein the compound comprises at least one structure of formula (IIa-1) to (IIb-7): Among them, the symbols R and R a R b W and Z have the definitions given in claim 1, and the symbols Y and Y 1 It has the definition given in claim 3, and the other symbols are as follows: j can be 0, 1, 2 or 3 independently in all cases; h can be independently 0, 1, 2, 3, or 4 in various cases; and g can be 0, 1, 2, 3, 4, or 5 independently in various cases.

5. The compound according to one or more of claims 1 to 4, wherein the compound comprises at least one structure of formula (III-1) to (III-4): Among them, the symbols R and R a R b W and Z have the definitions given in claim 1, and other symbols used are as follows: Y 2 Same or different in various cases and is B(R) 1 ), C(R 1 )2、Si(R 1 2. C=O, C=NR 1 C=C(R) 1 )2、O、S、S=O、SO2、N(R 1 ), P(R 1 ) and P(=O)R 1 ; Y 3 Same or different in various cases and is B(R) 1 ), C(R 1 )2、Si(R 1 2. C=O, C=NR 1 C=C(R) 1 )2、O、S、S=O、SO2、N(R 1 ), P(R 1 ) and P(=O)R 1 ;and j can be 0, 1, 2, or 3 independently in all cases.

6. The compound according to one or more of claims 1 to 5, characterized in that... Z and W groups, with CR b Group or CR b Groups and CR b 2 groups and the CR b The carbon atoms bonded to the groups together form substructures of formulas (RC-1) to (RC-10): Where R b As defined in claim 1, the dashed bond represents the site of connection with the oxygen atom and the Ar group, and the other symbols are defined as follows: r can be 0, 1, 2, 3, 4, 5, or 6; s can be 0, 1, 2, 3, 4, 5, 6, 7, or 8; t can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; v can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

7. The compound according to one or more of claims 1 to 6, wherein the compound comprises at least one structure of formula (IV-1) to (IV-16): Among them, the symbols R and R a and R b With the definition given in claim 1, the symbols Y and Y 1 It has the definition given in claim 3, and the other symbols are as follows: j can be 0, 1, 2 or 3 independently in all cases; h can be 0, 1, 2, 3 or 4 independently in various cases; r is 0, 1, 2, 3, 4, 5, or 6; and v can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

8. The compound according to claim 6 or 7, characterized in that... Two Rs a Group formation of substructures of formulas (RC-1) to (RC-10).

9. The compound according to at least one of claims 1 to 8, characterized in that... R bonded to carbon atoms a The group is selected from: a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which can be generated by one or more R groups. b Group substitution; or phenyl group, wherein the phenyl group may be replaced by one or more R groups in various cases. 1 Group substitution, preferably deuteration, wherein the R group bonded to the carbon atom a Groups can form a ring system together, wherein, in R a In various cases where the phenyl group is represented, the phenyl group may be via a single bond or selected from C(R) 1 )2、Si(R 1 2. C=O, C=NR 1 C=C(R) 1 )2、O、S、S=O、SO2、N(R 1 ), P(R 1 ) and P(=O)R 1 In O, the bridge bases are connected to each other.

10. The compound according to at least one of claims 1 to 9, characterized in that... R b The groups are H, D, methyl, ethyl, and propyl, among which these groups can be deuterated.

11. An oligomer, polymer, or dendritic macromolecule, said oligomer, polymer, or dendritic macromolecule comprising one or more compounds according to any one of claims 1 to 10, wherein, One or more bonds of the compound connected to the polymer, oligomer, or dendritic macromolecule are present in place of hydrogen atoms or substituents.

12. A formulation comprising at least one compound according to one or more of claims 1 to 10 or an oligomer, polymer or dendritic macromolecule according to claim 11 and at least one other compound, wherein the other compound is preferably selected from one or more solvents.

13. A composition comprising at least one compound according to one or more of claims 1 to 10 or an oligomer, polymer or dendritic macromolecule according to claim 11 and at least one other compound selected from phosphors, phosphorescents, emitting sources exhibiting TADF, host materials, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, electron blocking materials and hole blocking materials.

14. A method for preparing a compound according to one or more of claims 1 to 10, characterized in that... A compound having an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms is synthesized, and the compound is reacted with a ketone having a bicyclic alkyl group at the α-position.

15. Use of the compound according to one or more of claims 1 to 10 or the oligomer, polymer or dendritic macromolecule according to claim 11 in electronic devices, preferably as a light emitter, host material, hole conducting material, hole injection material, electron blocking material, electron transport material, electron injection material or hole blocking material.

16. An electronic device comprising at least one compound according to one or more of claims 1 to 10 or an oligomer, polymer or dendritic macromolecule according to claim 11.

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