The present invention relates to materials for use in electronic devices, in particular in organic electroluminescent devices, and to electronic devices, in particular organic electroluminescent devices, comprising these materials.

The structure of organic electroluminescent devices (OLEDs) in which organic semiconductors are employed as functional materials is described, for example, in US 4539507, US 5151629, EP 0676461 and WO 98/27136. The emitting materials employed here are increasingly organometallic complexes which exhibit phosphorescence instead of fluorescence. For quantum-mechanical reasons, an up to four-fold increase in the energy and power efficiency is possible using organometallic compounds as

phosphorescence emitters. In general, however, there is still a need for improvement in the case of OLEDs, in particular also in the case of OLEDs which exhibit triplet emission (phosphorescence), for example with respect to efficiency, operating voltage and lifetime.

The properties of phosphorescent OLEDs are not only determined by the triplet emitters employed. In particular, the other materials used, such as matrix materials, hole-blocking materials, electron-transport materials, hole- transport materials and electron- or exciton-blocking materials, are also of particular importance here. Improvements in these materials can thus also result in significant improvements in the OLED properties.

There are many materials that can be employed as matrix materials for phosphorescent emitters in organic electroluminescent devices. Further improvements are desirable here, in particular with respect to the efficiency, the lifetime and the thermal stability of the materials. The object of the present invention is the provision of compounds which are suitable for use in an OLED, in particular as matrix material for phosphorescent emitters, but also as electron-transport materials although other uses such as hole- transport and/or electron-blocking materials are also possible. A further object of the present invention is to provide further organic semiconductors for organic electroluminescent devices so as to provide the person skilled in the art with a greater possible choice of materials for the production of OLEDs.

It is known that compounds with aromatic heterocyclic groups such as carbazoles, dibenzofurans, dibenzothiophenes, fluorenes, quinazolines, quinoxalines and benzimidazoles are useful in OLEDs, generally as hosts for light emitting materials or for their charge-carrying properties.

Compounds with combinations of at least three of these classes are known.

WO 2012/134124, WO 2012/169821, WO 2013/187689, WO 2012/121561, WO 2012/050371, WO 2012/036482, WO 2012/141499, KR 201310263, KR 2012132815, KR 2012116272, KR 2012109744, KR 2012038060, KR 2013102673 and KR 20120033017 describe OLEDs with quinazolone groups substituted with (among others) dibenzofuran, dibenzothiophene or fluorene groups as well as carbazoyl groups.

US 2014/0114069 discloses OLEDs with quinazoline substituted (either directly or through a link) through the nitrogen of a carbazole group which may be further substituted with dibenzofuran, dibenzothiophene or fluorene groups.

US 2013/0306959 discloses OLED with compounds of the formula A-B- (Cz)n where A, B and C are all aromatic heterocyclic groups, where A and B can include (among many others) quinazolines, quinoxalines, benzimidazoles, dibenzofurans and dibenzothiophenes and Cz can also include carbazoles as well.

CN 103467447 discloses OLEDs with quinazoline compounds substituted with carbazole groups and can be further substituted with (among others) dibenzofuran, dibenzothiophene and fluorene groups.

WO 2013/154325 and WO 2014/104585 disclose OLEDs with bis-carbazolyl groups that may be substituted with (among others) quinazolines, dibenzofurans, dibenzothiophenes and fluorenes. WO 2014/088290 discloses OLEDs with carbazole groups that have an annulated benzene ring which can be substituted with quinazolines, quinoxalines, dibenzofurans, dibenzothiophenes and fluorenes.

KR 2014013351, US 2014/0027744 and US 2012/0133274 describe OLEDs with compounds that may contain combinations of 2-(N-phenylbenz- imidazole), N-phenylcarbazole, dibenzofuran and dibenzothiophene groups.

JP 2012-222268 discloses OLEDs with compounds with combinations of carbazole, dibenzofuran, dibenzothiophene and N-benzimidazole groups.

WO 2013/022145 discloses OLEDs with compounds with N-phenylbenz- imidazole and carbazole groups which may be substituted with (among other) dibenzofuran and dibenzothiophene groups.

WO 2010/044607 discloses OLEDs with compounds with N-phenylbenz- imidazole and carbazole groups which may be substituted with (among other) dibenzofuran, dibenzothiophene and fluorene groups.

JP 2012-049518 discloses OLEDs with substituted dibenzofuran, dibenzothiophene and N-phenylcarbazole groups.

KR 2012104067 discloses dibenzothiophene derivatives substituted in the 1- position with quinoline and N-(l-phenylbenzimidazole) groups. The benzimidazole may be connected either directly through the nitrogen or through an aryl linking group to the nitrogen.

WO 2011/106344 discloses dibenzofuran, dibenzothiophene or fluorene compounds substituted in the 1- or 4- positions with a N-(1-phenylbenz- imidazole) as ligands for phosphorescent metal complexes.

Begoin er a/., Helv. Chem. Acta., 96, 853 (2013) discloses 1-(N-(1-phenyl- benzimidazole)) substituted dibenzofurans and dibenzothiophenes.

Additional general disclosures for compounds with a combination of three different kinds of aromatic heterocyclic groups can be found in WO 2012/033108; JP 20141883315; US 2011/0147792; KR 2014122680; KR 2014127073; US 2014/0284584; WO 2012/033108; US 2014/001460; KR 2014080002 and US 8685543.

US 7651790 discloses OLEDs with a compound of A-C-B where A is a hole- transporting group (including, among others, carbazoles), B is an electron- transporting group (including triazines, fluorenes and spirofluorenes among others) and C is a bond or a linking group.

Lee et al., Chem. Europ. J., 19, 1194 (2013) compares the effects on OLED performance of attaching a N-phenylcarbazole group (through the phenyl group) in the 2, 3 or 4 positions of a dibenzofuran.

Surprisingly, it has been found that certain compounds described in greater detail below achieve this object, are highly suitable for use in OLEDs and result in improvements in the organic electroluminescent device. The improvements here relate, in particular, to the lifetime of the device, although other characteristics can also be improved. The present invention therefore relates to these compounds and to electronic devices, in particular organic electroluminescent devices, which comprise compounds of this type.

The present invention relates to a compound according to Formula (1) or

(2):

Formula (1)

Formula (2) where:

X is an oxygen, sulfur or CZ1Z2;

Y is an oxygen, sulfur, CZ1Z2 or NAn; Zi and Z2 are on each occurrence, identically or differently, H, D, F, a straight-chain alky], alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R5, where one or more, preferably non-adjacent Chb groups may be replaced by

(R5)C=C(R ₅ ), C≡C, Si(R ₅ ) ₂ , Ge(Rs)2, Sn(R ₅ ) ₂ , C=0, C=S, C=Se, C=N(R ₅ ), P(=O)(Rs), SO, SO2, N(Rs)2, O, S or CON(Rs)2 and where one or more H atoms may be replaced by D, F, CI, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R5, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R5, where Zi and Z2 may be connected together to form a spiro ring system;

Ri, R2, R3 and R4 is on each occurrence, identically or differently, selected from the group consisting of H, D, F, CI, Br, I, CN, Si(Rs)3, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl with 3-40 C atoms which may be substituted by one or more radicals R5, wherein each one or more non- adjacent CH2 groups by may be replaced Si(Rs)2, C=NR5, P(=O)(Rs), SO,

SO2, NRs, O, S or CONR5 and where one or more H atoms may be replaced by D, F, CI, Br or I, an aromatic or heteroaromatic ring system having 6 to 40 carbon atoms which may be substituted by one or more radicals Rs, an aryloxy group having 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R5, or an aralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R5, where two or more adjacent substituents Ri, R2, R3 and R4 can form a mono- or poly- cyclic, aliphatic, aromatic or heteroaromatic ring system with one another and which may be substituted with one or more radicals R5; where R5 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 C atoms; R6 is the same as Ri but excluding H or D;

An and Ar2 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R5 and where optionally two or more adjacent substituents Rs can form a mono- or polycyclic- aliphatic, aromatic or heteroaromatic ring system with one another;

a, b, c are on each occurrence, identically or differently, are 0, 1, 2 or 3 where a is not 3 in Formula (2) and d is independently 0, 1, 2, 3 or 4;

Li and l_2 are on each occurrence, identically or differently, a direct bond or an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals Rs;

A is a heterocyclic group a ula Ai:

where only one or two of B are nitrogen atoms and the others are carbon atoms, Ri and R2 are as previously defined, e is 0, 1 , 2 or 3, f is 0, 1 , 2, 3 or 4, and wherein Ai is connected to the remainder of the compound through a carbon atom; or A is a heterocyclic group selected from the group of

Formula A2 or A3:

where Ar2, Ri, R2, e and f are as previously defined; or A is a heterocyclic group according to A4:

where Ar2, R2, R6, e and f are as previously defined.

In the sense of this invention, the following numbering system for the central nucleus to which A is attached (X = 0, S or CZ1Z2) will be used: For convenience, the same numbering system will also be used for a carbazole substituent (X=NAn).

The compounds of Formulae (1) or (2) can be generally described as having a central nucleus that is a dibenzofuran (X=0), a dibenzothiophene (X=S) or a fluorene (X=CZiZ2). The 1-position of the compound of Formulae (1) and (2) is connected (either directly or through a linking group Li) to a carbon atom of a heteroaromatic group with one or two nitrogen atoms in a bicyclic 6/6 core. Alternatively, the 1-position is connected (either directly or through a linking group Li) to a carbon or nitrogen atom of a heteroaromatic group with two nitrogen atoms in a bicyclic 5/6 core, which is a benzimidazole. In either of these alternatives, the compounds of Formulae (1) and (2) also have at least one substituent selected from a dibenzofuran (Y=0), dibenzothiophene (Y=S), fluorene attached via any of its 1- to 8- positions to any of the 2- to 8- positions of the central nucleus.

In the sense of the invention, the terms "dibenzofuran, dibenzothiophene, fluorene (including spirofluorene), or carbazole" include not only the parent heterocycle but also include any analogues that have annulated monocyclic- or polycyclic-, aliphatic, aromatic or heteroaromatic rings. An annulated ring is one that has two adjacent ring atoms in common with another ring.

An aryl group in the context of this invention contains from 6 to 24 carbon atoms; a heteroaryl group within the meaning of this invention containing from 2 to 24 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and hetero atoms is at least 5. The heteroatoms are preferably selected from N, O and S. Among an aryl or heteroaryl group is either a simple aromatic ring, for example benzene, or a simple

heteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

An aromatic ring system in the sense of this invention contains from 6 to 40 carbon atoms in the ring system. A heteroaromatic ring system in the sense of this invention contains 1 to 40 carbon atoms and at least one heteroatom in the ring system, with the proviso that the sum of carbon atoms and hetero atoms is at least 5 results. The heteroatoms are preferably selected from N, O and S. An aromatic or heteroaromatic ring system in the context of this invention is to be understood as a system that does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups are connected by a non-aromatic moiety, such as, for example, a C, N or O atom or a carbonyl group. For example, systems such as 9,9 -spiro- bifluorene, 9,9-diarylfluorene, triarylamine, stilbene, etc., are aromatic ring systems for the purposes of this invention. Also included are systems in which two or more aryl groups are connected, for example, by a linear or cyclic alkyl group or by a silyl group. Furthermore, to systems in which two or more aryl or heteroaryl groups are directly bonded to each other, such, for example, biphenyl, terphenyl or quaterphenyl be understood also as an aromatic or heteroaromatic ring system.

For the purposes of this invention, a cyclic alkyl, alkoxy or thioalkoxy means a monocyclic, bicyclic or a polycyclic group.

In the present invention, a C1 to C40 alkyl group, in which individual H atoms or CH2 groups may be substituted by the above-mentioned groups, include methyl, ethyl, n-propyl, i -propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo- pentyl, cyclopentyl, n hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl , 1 -methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo [2,2,2] octyl, 2-bicyclo [2.2.2] octyl, 2- (2,6-dimethyl) octyl, 3- (3,7- dimethyl) octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoro- ethyl, 1 ,1-dimethyl-n-hex-l-yl, 1,1-dimethyl-n-hept- 1-yl, 1 ,1-dimethyl-n-oct- 1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n- tetradec-1-yl, 1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1- diethyl-n-hex-1-yl, 1 , 1 -diethyl-n-hept-1 -yl, 1 ,1-diethyl-n-oct-1-yl, 1,1-diethyl- n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyln- n-hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl, 1 -(n-propyl) cyclohex- 1-yl, 1- (n- butyl)cyclohex-1-yl, l-(N-hexyl) -cyclohex-1-yl, 1-(n-octyl)-cyclohex-1-yl and 1-(n-decyl)cyclohex-1-yl. Examples of an alkenyl group include ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. Examples of an alkynyl group include, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. An alkoxy group having 1 to 40 C atoms is preferably taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy,

1- propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy,

2- methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2- trifluoroethoxy. A thioalkyi group having 1 to 40 C atoms is taken to mean, in particular, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butyl- thio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclo- hexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethyl- hexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynyl- thio, heptynylthio or octynylthio. In general, alkyl, alkoxy or thioalkyi groups in accordance with the present invention may be straight-chain, branched or cyclic, where one or more non-adjacent Chb groups may be replaced by the above-mentioned groups; furthermore, one or more H atoms may also be replaced by D, F, CI, Br, I, CN or NO2, preferably F, CI or CN, further preferably F or CN, particularly preferably CN..

An aromatic or heteroaromatic ring system having 5-60 aromatic ring atoms which may be substituted with residues above yet and which can be linked via any position on the aromatic or heteroaromatic compounds, for example, groups are understood to be derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthen, naphthacene, penta- cene, benzopyrene, biphenyl, biphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, c/s- or trans- indenofluorene, c/s- or frans-Monobenzoindenofluoren, c/s- or trans- dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothio- phene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, iso- quinoline, acridine, phenanthridine, benzo-5,6-quino!ine, benzo-6,7- quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, chinoxalinimidazole, oxazole, benz- oxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1 ,2- thiazole, 1 ,3-thiazole, benzothiazole, pyridazine, benzopyridazin, pyrimidine, benzpyrimidine, quinoxaline, 1 ,5-diaza-anthracene, 2,7-diazapyrene, 2,3- diazapyrene, 1 ,6-diazapyrene, 1 ,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10- tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1 ,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadi- azole, 1,2,5-oxadiazole, 1 ,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadi- azole, 1 ,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2, 4-triazine, 1 ,2,3-triazine, tetrazole, 1 ,2,4,5-tetrazine, 1 ,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

In the above, Ri to R4 refers to a first substituent and R5 is a secondary substituent on Ri - R ₄ or in the case of structure A4, a first substituent. Any of Ri - R ₄ and R5 can be chosen independently from the groups as described. Adjacent radicals or adjacent substituents in the sense of the present application are taken to mean substituents which are bonded to C atoms which are in turn bonded directly to one another or substituents which are bonded to the same C atom.

In compounds which are processed by vacuum evaporation, the alkyl groups preferably have not more than five C atoms, particularly preferably not more than 4 C atoms, very particularly preferably not more than 1 C atom. For compounds which are processed from solution, suitable compounds are also those which are substituted by alkyl groups, in particular branched alkyl groups, having up to 10 C atoms or which are substituted by oligoarylene groups, for example ortho-, meta-, para- or branched terphenyl or quaterphenyl groups.

If the compounds of the formula (1) or (2) or the preferred embodiments are used as matrix material for a phosphorescent emitter or in a layer which is directly adjacent to a phosphorescent layer, it is furthermore preferred for Ri - R6, Zi, Z2, An and Arc of the compound to contain no condensed aryl or heteroaryl groups in which more than two six-membered rings are condensed directly onto one another. It is generally advantageous for the triplet energy of the compound used as a matrix material or in an adjacent layer to be the same or greater than the phosphorescent material in the emitting layer.

The compounds according to the invention described above, in particular compounds which are substituted by reactive leaving groups, such as bromine, iodine, chlorine, boronic acid or boronic acid ester, or by reactive, polymerisable groups, such as olefins, styrenes, acrylates or oxetanes, can be used as monomers for the generation of corresponding oligomers, dendrimers or polymers. The oligomerisation or polymerisation here preferably takes place via the halogen functionality or the boronic acid functionality or via the polymerisable group. It is furthermore possible to crosslink the polymers via groups of this type. The compounds and polymers according to the invention can be employed as crosslinked or uncrosslinked layer.

The invention therefore furthermore relates to oligomers, polymers or dendrimers containing one or more of the compounds according to the invention indicated above, where one or more bonds from the compound according to the invention to the polymer, oligomer or dendrimer are present at one or more positions instead of substituents. Depending on the linking of the compound according to the invention, this forms a side chain of the oligomer or polymer or is linked in the main chain or forms the core of a dendrimer. The polymers, oligomers or dendrimers may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers may be linear, branched or dendritic. The same preferences as described above apply to the recurring units of the compounds according to the invention in oligomers, dendrimers and polymers.

For the preparation of the oligomers or polymers, the monomers according to the invention are homopolymerised or copolymerised with further monomers. Preference is given to homopolymers or copolymers in which the units of the formula (1) or the preferred embodiments indicated above are present to the extent of 0.01 to 99.9 mol%, preferably 5 to 90 mol%, particularly preferably 20 to 80 mol%. Suitable and preferred comonomers which form the polymer backbone are selected from fluorenes (for example in

accordance with EP 842208 or WO 2000/22026), spirobifluorenes (for example in accordance with EP 707020, EP 894107 or WO 2006/061181), para-phenylenes (for example in accordance with WO 92/18552),

carbazoles (for example in accordance with WO 2004/070772 or WO 2004/ 113468), thiophenes (for example in accordance with EP 1028136), dihydro- phenanthrenes (for example in accordance with WO 2005/014689), cis- and trans-indenofluorenes (for example in accordance with WO 2004/041901 or WO 2004/113412), ketones (for example in accordance with

WO 2005/040302), phenanthrenes (for example in accordance with

WO 2005/104264 or WO 2007/017066) or also a plurality of these units. The polymers, oligomers and dendrimers may also contain further units, for example hole-transport units, in particular those based on triarylamines, and/or electron-transport units. In addition, the polymers may contain triplet emitters, either copolymerised or mixed in as a blend. In particular, the combination of the oligomers, polymers or dendrimers according to the invention with triplet emitters leads to particularly good results.

X and Y may be the same or different in any combination. In particular, all of the following combinations (shown for Formula (1), but it should be understood that the same combinations apply to Formula (2) as well) are possible:

It is preferred that X is oxygen or sulfur and Y is oxygen, sulfur, CZ1Z2 or NAn in both Formulae (1) and (2). It is also preferred that Y is NAn and X is oxygen, sulfur or CZ1Z2 in both Formulae (1) and (2). It is most preferred that X is oxygen and Y is NAn as shown in Formulae (3) and (4):

In any of Formulae (1)-(4), it is preferred that c is 0, d is 0, 1 or 2 and when d is 2, the two R4 groups are adjacent and form a monocyclic- or polycyclic, aromatic or heteroaromatic annulated ring system.

Whenever X or Y (or both) is CZ1Z2 (a fluorene derivative), it is perferred that Zi and Z2 are on each occurence, identically or differently, an alkyl group of 1-10 carbon atoms or an aryl group of between 6-30 carbon atoms. For both alkyl and aryl groups, the two Z groups may be attached together to form a spiro ring system. Examples of suitable alkyl groups for Zi and Z2 are methyl, ethyl, hexyl and decyl. Of these, methyl groups are highly preferred. Examples of aryl groups are phenyl and naphthyl. The aryl groups may be further substituted with additional alkyl, aryl or heteroatoms. Of these, substituted or unsubstituted phenyl groups such as p-methylphenyl are preferred. Particularly preferred are 9,9'-diphenyl groups. It is preferred for both X and Y that Zi and Z2 are identical, although X and Y may individually have the same or different identical Z groups.

Two identical or different Zi and Z2 groups may also be connected together to form a 9,9'-spiro ring system. For example, two alkyl Z groups can be connected to form spiro compounds such as 9,9'-cyclopentyl or 9,9'-cyclo- hexyl:

Alternatively, two aryl Z groups may be connected to form spiro compounds such as a 9,9'-spirobifluorene:

which may be further substituted. Particularly preferred are unsubstituted 9,9'-spirobifluorenes. Also contemplated are unsymmetrical spiro

compounds where Zi is an alkyl and Z2 is an aryl such as:

Further contemplated are spirofluorene derivatives where the spiro group is further elaborated with additional substituents or forms heterocyclic spiro groups. Some examples of this type of heterocyclic spirofluorene derivative are:

where W is oxygen, sulfur, N-Aryl, SO2 or C=O. The group containing Y is connected through any of the 1- to 8- positions to the central nucleus (which contains X and the -Li-A group) and not through the 9-position. It is understood that when Y is NAn, the carbazole group is not connected to the central nucleus through the An group or the nitrogen of the carbazole group either. It is preferred for Formulae (1) and (2) that the 7- position of the group containing X is connected (either directly or through L2) to the 2-position of the group containing Y. l_2 is a linking group that connects the group containing X to the group containing Y. It may be a direct bond so that a carbon atom of the group containing X (in any of the 2- to 8- postions) is connected via a single bond to a carbon atom in the group containing Y (in any of the 1- to 8- positions). If L.2 is not a direct bond, then it is an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R5. For example, L2 can be a meta- or para- phenylene group, a polycyclic aromatic group such as naphthyl or a fluorene, or a polycyclic heteroaromatic group such as dibenzofuran or dibenzothiophene, any of which can be further substituted. If L2 is an aromatic or heteroaromatic ring system, then L2 is connected to both the group containing X and the group containing Y by single bonds. Thus, it is understood that the group containing X and the group containing Y are not annulated to each other. It is preferred that L2 is a direct bond as shown in Formulae (5) and (

The group containing X may be substituted with Ri and R2 substituents. The group containing Y may be substituted with R3 and R ₄ substituents. If there are any two adjacent Ri - R ₄ groups, they may be combined to form an annulated monocyclic or polycyclic aromatic or heteroaromatic ring. For example, any two adjacent R3 or R4 groups may be representated by the

The group -L1-A is located in the 1- position of the group containing X and Li is selected independently of L2. It may be a direct bond so that a carbon atom in the 1 -position of the group containing X is connected to A by a single bond. Alternatively, if Li is not a direct bond, then it is an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R5. For example, Li can be a meta- or para-phenylene group, a polycyclic aromatic group such as naphthyl or a fluorene, or a polycyclic heteroaromatic group such as dibenzofuran or dibenzothiophene, any of which can be further substituted. If Li is an aromatic or heteroaromatic ring system, then Li is connected to both the group containing X and A by single bonds. It is preferred that Li is a single bond as in Formulae (7) and (8):

One option for A is a heterocyclic group according to Formula Ai:

where only one or two of B are nitrogen atoms and the others are carbon atoms. If there is no substituent on the carbon atom, an H atom is bound to the corresponding carbon atom. The site where Ai is connected to Li or the group containing X is where B is a carbon atom and not a nitrogen. A

preferred version of Ai is acco la W:

W

where at least one but at most only two Q are nitrogen and the others are carbon and h and i are independently 0, 1 or 2. This embodiment

corresponds to

where at most only two Q are nitrogen and the others are carbon and h and i are independently 0, 1 or 2.

In one embodiment of Formulae (9) and ( 0) where only one Q is nitrogen, then W is a quinoline derivative according to formula Ai-a:

In this embodiment, one preferred structure for the quinoline derivative is:

and a specific example of a suitable structure for a quinoline derivative of this embodiment is:

In this embodiment of Formulae (9) and (10) with Ai-a, the most preferred structure is where f is 0.

In another embodiment of Formulae (9) and (10) where one Q is nitrogen, then W is an isoquinoline derivative according to formula Ai-b:

In this embodiment, two preferred structures for the isoquinoline derivative are:

and the most preferred structures for Formulae (9) and (10) with Ai-b are where f is 0. In Formulas (9) and (10) when two Q are nitrogen, then W can be a quinazoline derivative accordin

where i is 0 or 1. In this embodiment, three preferred structures for Ai-c are:

and some s ecific exam les of referred structures include

In this embodiment of Formulae (9) and ( 0) with Ai-c, it is most preferred that f is 0.

In another embodiment when two Q of W are nitrogen, then W can be a naphthyridine derivative according to Ai-d:

i-d

In this embodiment, a preferred structure for Ai-d is:

and the most preferred for Formulae (9) and (10) with Ai-d are where e is 0.

In yet another embodiment when two Q of W are nitrogen, then W can be a pyrido[3,2-b]-pyridine derivativ according to Ai-e:

and where preferred structures are

and the most preferred for Formulae (9) and (10) with A1-e are where e is 0.

In Ai-a, Ai-b, Ai-c, Ai-d or Ai-e, it is understood any two adjacent Ri or R2 groups may be combined to form an annulated monocyclic or polycyclic aromatic or heteroaromatic ring. In the sense of the invention, it is

understood that a derivative emcompasses such annulated groups.

Of these embodiments, the preferred are according to Formulae (11)-(12) with Ai-a, Formulae (13) - (14) with Ai-c, Formulae (15)-(16) with Ai-d and Formulae (17)-(18) with Ai-e :

-22-

In Formulae (11) - (18), it is preferred that f is 0.

In some embodiments, A can be a benzimidazole derivative as illustrated in A2, A3 and A4. The benzimidazole derivative can be attached to the 1- position of the group containing X (either directly or via Li) by a carbon atom as in A2 or A3, or through the 1 -nitrogen as in A4.

One preferred embodiment is according to A2 as shown in Formulae (19) and (20):

For Formula (19) and (20), it is preferred that f is 0. In another embodiment related to (19) and (20), it is preferred that Ar2 is phenyl. In yet another embodiment related to (19) and (20), it is preferred that Li is a direct bond or a phenyl group.

Another preferred embodiment is according to A4 as shown in Formulae (21) and (22):

For Formula (21) and (22), it is preferred that f is 0. In another embodiment related to (21) and (22), it is preferred that Ri is phenyl. In yet another embodiment related to (21) and (22), it is preferred that Li is a direct bond or a phenyl group. It is preferred in another embodiment of (21) and (22) that R6 is an alkyl group of 1 to 12 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, and most preferably, phenyl. Other preferred embodiments are where the A group is attached to a different ring of the group containing X than the group containing Y as in Formulae (1), (3), (5), (7), (9), (11), (13), (15), (17), (19) or (21). In any of these embodiments, it is preferred that a and b are both 0, and more preferred that a, b and c are all 0. It is most preferred that a, b and c is 0, d is 0 or 2 and when d is 2, the two R4 groups are adjacent and form a monocyclic- or polycyclic- aromatic or heteroaromatic annulated ring system

The preferred embodiments mentioned above can be combined with one another in any combination as desired. In a particularly preferred embodiment of the invention, multiple preferences mentioned above can occur simultaneously. For example, the following formulae include some preferred combinations of features.

In one embodiment according to Formula (22), it is most preferred that X is oxygen and Y is NAn. In another embodiment according to Formula (22), it is most preferred that L2 is a direct bond. In yet another embodiment according to Formula (22), it is most preferred that c is 0, d is 0 or 2 and when d is 2, the two R4 groups are adjacent and form a monocyclic- or polycyclic- aromatic or heteroaromatic annulated ring system. In yet another embodiment according to Formula (22), it is most preferred that A is a quinazoline group according to Ai-b.

In one embodiment according to Formula (23), it is preferred that c is 0. In another embodiment according to Formula (23), it is preferred that L2 is a direct bond. In yet another embodiment according to Formula (23), it is most preferred that c is 0, d is 0 or 2 and when d is 2, the two R4 groups are adjacent and form a monocyclic- or polycyclic- aromatic or heteroaromatic annulated ring system. In yet another embodiment according to Formula (23), it is preferred that A is a quinazoline group, and more preferrably, A is a quinoline derivative according to Ai-a, and even more preferrably where h and f are 0. In yet another embodiment according to Formula (23), it is preferred that A is a quinazoline group according to Ai-b, and more preferably where i and f are 0.

In one embodiment according to Formula (24), it is preferred that X is oxygen and Y is NAn. In yet another embodiment according to Formula (23), Li is a meta- or para- phenyl group. In yet another embodiment according to Formula (23), it is most preferred that c is 0, d is 0 or 2 and when d is 2, the two R4 groups are adjacent and form a monocyclic- or polycyclic, aromatic or heteroaromatic annulated ring system. In yet another embodiment according to Formula (24), it is most preferred that A is a quinazoline group according to Ai-b where f is 0 or a benzimidazole according to A ₄ where Li is a direct bond or a meta- or para- phenyl group and f is 0. For Formula (24), if A is according to A4, it is most preferred that Li is a meta- or para- phenyl group and An is a phenyl group.

In one embodiment according to Formula (25), it is preferred that A is according to A2. A3 or A4, and more preferred where e and f are 0. In yet another embodiment according to Formula (25), Li is a meta- or para- phenyl group. In yet another embodiment according to Formula (25), it is most preferred that c is 0, d is 0 or 2 and when d is 2, the two R4 groups are adjacent and form a monocyclic- or polycyclic- aromatic or heteroaromatic annulated ring system. In yet another embodiment according to Formula (25), it is most preferred that A is a benzimidazole according to A4 where Li is a direct bond or a meta- or para- phenyl group and f is 0. For Formula (25), if A is according to A ₄₎ it is most preferred that Li is a meta- or para- phenyl group and Ar2 is a phenyl group.

Examples of compounds in accordance with the embodiments indicated above are the compounds shown in the following table.

^' d



ό

o^S ⁰ 

-35-

CN -38-

-39-

The compounds according to the invention are suitable for use in an electronic device, in particular in an organic electroluminescent device. The present invention therefore furthermore relates to the use of a compound according to the invention in an electronic device, in particular in an organic electroluminescent device. The present invention still furthermore relates to an electronic device comprising at least one compound according to the invention. An electronic device in the sense of the present invention is a device which comprises at least one layer which comprises at least one organic compound. The component may also comprise inorganic materials or also layers which are built up entirely from inorganic materials.

The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs), 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), dye-sensitised organic solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and "organic plasmon emitting devices", but preferably organic electroluminescent devices (OLEDs), particularly preferably phosphorescent OLEDs.

The organic electroluminescent device comprises cathode, anode and at least one emitting layer. Apart from these layers, it may also comprise further layers, for example in each case 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. Interlayers, which have, for example, an exciton- blocking function, may likewise be introduced between two emitting layers. However, it should be pointed out that each of these layers does not necessarily have to be present. The organic electroluminescent device here may comprise one emitting layer, or it may comprise a plurality of emitting layers. If a plurality of emission layers are present, these preferably have in total a plurality of emission maxima between 380 nm and 750 nm, resulting overall in white emission, i.e. various emitting compounds which are able to fluoresce or phosphoresce are used in the emitting layers. Particular preference is given to systems having three emitting layers, where the three layers exhibit blue, green and orange or red emission (for the basic structure see, for example, WO 2005/011013). The organic electroluminescent device according to the invention may also be a tandem OLED, in particular also for white-emitting OLEDs.

The compound according to the invention in accordance with the embodiments indicated above can be employed in various layers, depending on the precise structure. Preference is given to an organic electroluminescent device comprising a compound of the formulae (1) or (2) or the preferred embodiments indicated above as matrix material for phosphorescent or fluorescent emitters, in particular for phosphorescent emitters, and/or in an electron-blocking or exciton-blocking layer and/or in a hole-transport layer and/or in a hole-blocking layer and/or in a hole-blocking or electron-transport layer, depending on the precise substitution.

In a preferred embodiment of the invention, the compound according to the invention is employed as matrix material for a phosphorescent compound in an emitting layer. The organic electroluminescent device here may comprise one emitting layer, or it may comprise a plurality of emitting layers, where at least one emitting layer comprises at least one compound according to the invention as matrix material.

If the compound according to the invention is employed as matrix material for a phosphorescent compound in an emitting layer, it is preferably employed in combination with one or more phosphorescent materials (triplet emitters). Phosphorescence in the sense of this invention is taken to mean the luminescence from an excited state having relatively high spin multiplicity, i.e. a spin state > 1 , in particular from an excited triplet state. In the sense of this application, all luminescent complexes containing transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.

The mixture of the compound according to the invention and the emitting compound comprises between 99 and 1% by vol., preferably between 98 and 10% by vol., particularly preferably between 97 and 60% by vol., in particular between 95 and 80% by vol., of the compound according to the invention, based on the entire mixture comprising emitter and matrix material. Correspondingly, the mixture comprises between 1 and 99% by vol., preferably between 2 and 90% by vol., particularly preferably between 3 and 40% by vol., in particular between 5 and 20% by vol., of the emitter, based on the entire mixture comprising emitter and matrix material.

A further preferred embodiment of the present invention is the use of the compound according to the invention as matrix material for a phosphorescent emitter in combination with a further matrix material. Particularly suitable matrix materials which can be employed in combination with the compounds according to the invention are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example in accordance with WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/ 006680, triarylamines, carbazole derivatives, for example CBP (N,N-bis- carbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005/ 039246, US 2005/0069729, JP 2004/288381, EP 1205527, WO 2008/ 086851 or WO 2013/041176, indolocarbazole derivatives, for example in accordance with WO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, for example in accordance with WO 2010/136109, WO 2011/ 000455, WO 2013/041176 or WO 2013/056776, azacarbazole derivatives, for example in accordance with EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrix materials, for example in accordance with WO 2007/137725, silanes, for example in accordance with WO 2005/ 111172, azaboroles or boronic esters, for example in accordance with WO 2006/117052, triazine derivatives, for example in accordance with WO 2007/063754, WO 2008/056746, WO 2010/015306, WO 2011/057706, WO 2011/060859 or WO 2011/060877, zinc complexes, for example in accordance with EP 652273 or WO 2009/062578, diazasilole or tetraaza- silole derivatives, for example in accordance with WO 2010/054729, diaza- phosphole derivatives, for example in accordance with WO 2010/054730, bridged carbazole derivatives, for example in accordance with WO

2011/042107, WO 2011/060867, WO 2011/088877 and WO 2012/143080, or triphenylene derivatives, for example in accordance with WO

2012/048781. A further phosphorescent emitter which emits at shorter wavelength than the actual emitter may likewise be present in the mixture as co-host, or a compound which does not participate in the charge transport to a significant extent, if at all, as described, for example, in WO 2010/108579.

Suitable phosphorescent compounds (= triplet emitters) are, in particular, compounds which emit light, preferably in the visible region, on suitable excitation and in addition contain at least one atom having an atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80, in particular a metal having this atomic number. The phosphorescence emitters used are preferably compounds which contain copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds which contain iridium or platinum.

Examples of the emitters described above are revealed by the applications WO 00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645,

EP 1191613, EP 1191612, EP 1191614, WO 2005/033244, WO 2005/ 019373, US 2005/0258742, WO 2010/086089, WO 2011/157339, WO 2012/ 007086, WO 2012/163471, WO 2013/000531 and WO 2013/020631. Also suitable are, for example, the metal complexes disclosed in the unpublished applications EP 12005187.5 and EP 12005715.3. In general, all

phosphorescent complexes as are used in accordance with the prior art for phosphorescent OLEDs and as are known to the person skilled in the art in the area of organic electroluminescence are suitable, and the person skilled in the art will be able to use further phosphorescent complexes without inventive step.

The compounds according to the invention are also suitable, in particular, as matrix materials for phosphorescent emitters in organic electroluminescent devices, as described, for example, in US 20 1/0248247 and

US 2012/0223633. In these multicoloured display components, an additional blue emission layer is applied by vapour deposition over the entire area to all pixels, also those having a colour other than blue. It has been found here, surprisingly, that the compounds according to the invention, when employed as matrix materials for the red and/or green pixels, continue to result in very good lifetime and emission together with the vapour-deposited blue emission layer. In a further embodiment of the invention, the organic electroluminescent device according to the invention does not comprise a separate hole- injection layer and/or hole-transport layer and/or hole-blocking layer and/or electron-transport layer, i.e. the emitting layer is directly adjacent to the hole- injection layer or the anode, and/or the emitting layer is directly adjacent to the electron-transport layer or the electron-injection layer or the cathode, as described, for example, in WO 2005/053051. It is furthermore possible to use a metal complex which is the same as or similar to the metal complex in the emitting layer as hole-transport or hole-injection material directly adjacent to the emitting layer, as described, for example, in WO

2009/030981.

In a further embodiment of the invention, the compound according to the invention is employed in a hole-transport layer or in an electron-blocking layer or exciton-blocking layer.

In still a further preferred embodiment of the invention, the compound according to the invention is employed as electron-transport material in an electron-transport or electron-injection layer. The emitting layer here may be fluorescent or phosphorescent. If the compound is employed as electron- transport material, it may be preferred for it to be doped, for example with alkali-metal complexes, such as, for example, LiQ (lithium hydroxy- quinolinate) or with an alkali metal, such as Li.

In still a further preferred embodiment of the invention, the compound according to the invention is employed in a hole-blocking layer. A hole- blocking layer is taken to mean a layer which is directly adjacent to an emitting layer on the cathode side.

In the further layers of the organic electroluminescent device according to the invention, all materials can be used as are usually employed in accordance with the prior art. The person skilled in the art will therefore be able to employ all materials which are known for organic electroluminescent devices in combination with the compounds of the formula (1) according to the invention or the preferred embodiments indicated above without inventive step.

Preference is furthermore given to an organic electroluminescent device, characterised in that one or more layers are coated by means of a sublimation process, in which the materials are applied by vapour deposition in vacuum sublimation units at an initial pressure of less than 10 ^"5 mbar, preferably less than 10 ^"6 mbar. However, it is also possible for the initial pressure to be even lower, for example less than 10 ^"7 mbar.

Preference is likewise given to an organic electroluminescent device, characterised in that one or more layers are coated by means of the OVPD (organic vapour phase deposition) process or with the aid of carrier-gas sublimation, in which the materials are applied at a pressure between 10 ^"5 mbar and 1 bar. A special case of this process is the OVJP (organic vapour jet printing) process, in which the materials are applied directly through a nozzle and are thus structured (for example M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device, characterised in that one or more layers are produced from solution, such as, for example, by spin coating, or by means of any desired printing process, such as, for example, screen printing, flexographic printing, offset printing, LITI (light induced thermal imaging, thermal transfer printing), ink-jet printing or nozzle printing. Soluble compounds, which are obtained, for example, by suitable substitution, are necessary for this purpose. Also possible are hybrid processes, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapour deposition.

For the processing of the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the compounds according to the invention are necessary. These formulations can be, for example, solutions, dispersions or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose.

Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxy- toluene, hexamethylindane, (-)-fenchone, 1 ,2,3,5-tetramethylbenzene, 1 ,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4- dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzo- thiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexyl- benzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole, 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, tetra- ethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)- ethane or mixtures of these solvents.

The present invention furthermore relates to a formulation comprising a compound according to the invention and at least one further compound. The further compound may be, for example, a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents. However, the further compound may also be at least one further organic or inorganic compound which is likewise employed in the electronic device, for example an emitting compound and/or a further matrix material. Suitable emitting compounds and further matrix materials are indicated above in connection with the organic electroluminescent device. This further compound may also be polymeric. dibenzofuran, dibenzothiophene or a fluorene group substituted in the 1- position, either directly or through a linking group, to a carbon atom of a heteroaromatic group with one or two nitrogen atoms in a bicyclic 6/6 core, or to a carbon or nitrogen atom of a heteroaromatic group with two nitrogen atoms in a bicyclic 5/6 core and are further substituted with a group selected from dibenzofuran, dibenzothiophene, fluorene or carbazole. All of the above processes are generally known to the person skilled in the art and can be applied without inventive step to organic electroluminescent devices comprising the compounds according to the invention.

The compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished by one or more of the following surprising advantages over the prior art:

1. The compounds according to the invention, employed as matrix material for fluorescent or phosphorescent emitters, result in long lifetimes. This applies, in particular, if the compounds are employed as matrix material for a phosphorescent emitter.

2. The compounds according to the invention result in very low operating voltages. This applies, in particular, if the compounds are employed as matrix material for a phosphorescent emitter.

These above-mentioned advantages are not accompanied by an impairment in the other electronic properties.

The invention is explained in greater detail by the following examples without wishing to restrict it thereby. The person skilled in the art will be able to use the descriptions to carry out the invention throughout the range disclosed and prepare further compounds according to the invention without inventive step and use them in electronic devices or apply the process according to the invention.

Examples

The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere in dried solvents. The solvents and reagents can be purchased from ALDRICH or ABCR. The numbers indicated in the case of the starting materials which are not commercially available are the corresponding CAS numbers.

Generally, there are two general processes for forming compounds of formulae (1) or (2). The first (illustrated in Scheme 2) is where an intermediate with a group containing X (i.e. dibenzofuran, dibenzothiophene or a fluorene group) and the group containing Y (i.e. dibenzofuran, dibenzothiophene, fluorene or carbazole) is obtained by a C-C coupling, such as Suzuki, Negishi, Yamamoto, Grignard-Cross, Stille, Hartwig- Buchwald or Ulimann, between the two groups. The heterocyclic A (or Li-A) group is added to this intermediate by subsequent functionization (i.e.

halogenation, followed by formation of a boron containing group) and another C-C coupling reaction with A (or Li-A) compound. In the case where A is a benzotriazole attached via nitrogen, the coupling reaction is by any known C-N coupling reactions including both a nucleophilic aromatic substitution reaction or a Pd-catalysed coupling reaction. Alternatively, a second process (illustrated in Schemes 1 and 3) is where the A (or Li-A) group is attached to the group containing X by any of same methods described above. The resulting intermediate is then functionized by any of the methods described for the first process, and the group containing Y is then added to the intermediate by a C-C coupling reaction. For example, some of the compounds of the invention may be made by the following synthetic schemes:

Scheme 1 :

cheme 2:

Synthesis Examples:

a) 4-bromo-

30 g (94 mmol) of 2,2'-dibromobiphenyl are dissolved in 200 ml of dried THF in a flask which has been dried by heating. The reaction mixture is cooled to -78°C. 37.7 ml of a 2.5 M solution of n-butyllithium in hexane (94 mmol) are slowly added dropwise (duration: about 1 h) at this temperature. The batch is stirred at -70°C for a further 1 h. 11.1 ml of acetophenone (94 mmol) are subsequently dissolved in 100 ml of THF and added dropwise at -70°C. When the addition is complete, the reaction mixture is slowly warmed to room temperature, quenched using NhUCI and subsequently evaporated in a rotary evaporator. 300 ml of acetic acid are carefully added to the evaporated solution, and 50 ml of fuming HCI are subsequently added. The batch is heated to 75°C and kept there for 6 h, during which a white solid precipitates out. b) 4-bromo-9,

37 g (152 mmol) of 2,2'-dibromobiphenyl are dissolved in 300 ml of dried THF in a flask which has been dried by heating. The reaction mixture is cooled to -78°C. 75 ml of a 5% solution of n-butyllithium in hexane

(119 mmol) are slowly added dropwise (duration: about 1 hour) at this temperature. The batch is stirred at -70°C for a further 1 h. 21.8 g of benzo- phenone (119 mmol) are subsequently dissolved in 100 ml of THF and added dropwise at -70°C. When the addition is complete, the reaction mixture is slowly warmed to room temperature, quenched using NH4CI and subsequently evaporated in a rotary evaporator. 510 ml of acetic acid are carefully added to the evaporated solution, and 100 ml of fuming HCI are subsequently added. The batch is heated to 75°C and kept at this temperature for 4 h, during which a white solid precipitates out. The batch is then cooled to room temperature, and the solid which has precipitated out is filtered off with suction and rinsed with methanol. The residue is dried at 40°C in vacuo. The yield is 33.2 g (83 mmol) (70% of theory).

The following brominated compounds b1-b3 were prepared analogously: c) 6-Bromo-2-fluoro-2'-methoxy-biphenyl

200 g (664 mmol) of 1-bromo-3-fluoro-2-iodobenzene, 101 g (664 mmol) of 2-methoxyphenylboronic acid and 137.5 g (997 mmol) of sodium tetraborate are dissolved in 1000 ml of THF and 600 ml of water and degassed. 9.3 g (13.3 mmol) of bis(triphenylphosphine)palladium(ll) chloride and 1 g (20 mmol) of hydrazinium hydroxide are added. The reaction mixture is subsequently stirred at 70°C for 48 h under a protective-gas atmosphere. The cooled solution is diluted with toluene, washed a number of times with water, dried and evaporated. The product is purified by column

chromatography on silica gel with toluene/heptane (1:2). Yield: 155 g (553 mmol), 83% of theory.

The following compound c1 was prepared analogously: d) 6'-bromo-2'-fluoro-biphenyl-2-ol

112 g (418 mmol) of 6-bromo-2-fluoro-2'-methoxybiphenyl are dissolved in 2 I of dichloromethane and cooled to 5°C. 41.01 ml (431 mmol) of boron tribromide are added dropwise to this solution over the course of 90 min., and stirring is continued overnight. Water is subsequently slowly added to the mixture, and the organic phase is washed three times with water, dried over Na2SO4, evaporated in a rotary evaporator and purified by

chromatography. Yield: 104 g (397 mmol), 98% of theory.

The following compound d1 was prepared analogously:

e) 1-Bromo-dibenzofuran

111 g (416 mmol) of 6'-bromo-2'-fluorobiphenyl-2-ol are dissolved in 2 I of SeccoSolv® DMF (max 0.003% of H2O) and cooled to 5°C. 20 g (449 mmol) of sodium hydride (60% suspension in paraffin oil) are added in portions to this solution, and the mixture is stirred for a further 20 min. after the addition is complete and then heated at 100°C for 45 min. After cooling, 500 ml of ethanol are slowly added to the mixture, which is then evaporated to dryness in a rotary evaporator and purified by chromatography. Yield: 90 g (367 mmol), 88.5% of theory.

The followin com ound e1 was re ared analo ousl :

f) 1-bromo-8-iodo-dibenzofuran

20 g (80 mmol) of dibenzofuran-1-boronic acid, 2.06 g (40.1 mmol) of iodine, 3.13 g (17.8 mmol) of iodic acid, 80 ml of acetic acid, 5 ml of sulfuric acid, 5 ml of water and 2 ml of chloroform are stirred at 65° for 3 hours. After cooling, water is added to the mixture, and the solid which has precipitated out is filtered off with suction and washed three times with water. The residue is recrystallised from toluene and from dichloromethane/heptane. The yield is 25.6 g (68 mmol), corresponding to 85% of theory.

The following compounds were prepared analogously:

Reactant Product Yield

[1265215-55-1] [854952-58-2]

22 g (66 mmol) of 1,3-dibromodibenzothiophene, 17 g (664 mmol) of 2-N-phenylcarbazole-3-boronic acid and 13.7 g (100 mmol) of sodium tetraborate are dissolved in 100 ml of THF and 60 ml of water and degassed. 0. g (1.3 mmol) of bis(triphenylphosphine)palladium(ll) chloride and 1 g (20 mmol) of hydrazinium hydroxide are added. The reaction mixture is subsequently stirred at 70°C for 48 h under a protective-gas atmosphere. The cooled solution is diluted with toluene, washed a number of times with water, dried and evaporated. The product is purified by column chromatography on silica gel with toluene/heptane (1:2). Yield: 13.2 g (26 mmol), 40% of theory.

The following compounds were prepared analogously: h) dibenzofuran-1-boronic acid

180 g (728 mmol) of 1-bromodibenzofuran are dissolved in 1500 ml of dry THF and cooled to -78°C. 305 ml (764 mmol / 2.5 M in hexane) of

n-butyllithium are added over the course of about 5 min. at this temperature, and the mixture is subsequently stirred at -78°C for a further 2.5 h. 151 g (1456 mmol) of trimethyl borate are added as rapidly as possible at this temperature, and the reaction is slowly allowed to come to room temperature (about 18 h). The reaction solution is washed with water, and the solid which has precipitated out and the organic phase are dried azeotropically with toluene. The crude product is washed by stirring with toluene/methylene chloride at about 40°C and filtered off with suction. Yield: 146 g (690 mmol), 95% of theory.

The following compounds were prepared analogously:

j) 2

23 g (110.0 mmol) of dibenzofuran-1-boronic acid, 29.5 g (110.0 mmol) of 2-chloro-4-phenyl-quinazoline and 26 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg

(0.5 mmol) of palladium(ll) acetate are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene and from dichloromethane/heptane. The yield is 32 g (86 mmol), corresponding to 80% of theory.

The following compounds were prepared analogously:

-61 -

-(8-bromo-dibenzofuran-1-yl)-4-phenyl-quinazoline

70.6 g (190.0 mmol) of 2-dibenzofuran-1-yl-4-phenylquinazoline are suspended in 2000 ml of acetic acid (100%) and 2000 ml of sulfuric acid (95-98%). 34 g (190 mmol) of NBS are added in portions to this suspension, and the mixture is stirred in the dark for 2 hours. Water/ice are then added, and the solid is separated off and rinsed with ethanol. The residue is recrystallised from toluene. The yield is 59 g (130 mmol), corresponding to 69% of theory. In the case of the thiophene derivatives, nitrobenzene is employed instead of sulfuric acid and elemental bromine is employed instead of NBS.

70.3 g (156 mmol) of 2-(8-bromodibenzofuran-1-yl)-4-phenylquinazoline, 50 g (172 mmol) of N-phenylcarbazole-3-boronic acid and 36 g (340 mmol) of sodium carbonate are suspended in 1000 ml of ethylene glycol diamine ether and 280 ml of water. 1.8 g (1.5 mmol) of tetrakis(triphenylphosphine)- palladium(O) are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The product is purified by column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed in a high vacuum (p = 5 x 10 ^"7 mbar) (purity 99.9%). The yield is 68 g (112 mmol), corresponding to 72% of theory.

-69-

I

20 g (182 mmol) of 3-(9-bromodibenzofuran-2-yl)-9-phenyl-9H-carbazole are dissolved in 400 ml of dry THF and cooled to -78°C. 77 ml (190 mmol / 2.5 M in hexane) of n-butyllithium are added over the course of about 5 min. at this temperature, and the mixture is subsequently stirred at -78°C for a further 2.5 h. 38 g (365 mmol) of trimethyl borate are added as rapidly as possible at this temperature, and the reaction is slowly allowed to come to RT (about 18 h). The reaction solution is washed with water, and the solid which has precipitated out and the organic phase are dried azeotropically with toluene. The crude product is washed by stirring with toluene/methylene chloride at about 40°C and filtered off with suction. Yield: 16.7 g (690 mmol), 90% of theory.

The following compounds were prepared analogously: m) 3-[9-(4-biphenyl-4-yl-quinazolin-2-yl)-dibenzofuran-2-yl]-9- phenyl-9H- carbazole

49.8 g (110.0 mmol) of 8-(9-phenyl-9H-carbazol-3-yl)dibenzofuran-1-boronic acid, 34 g (110.0 mmol) of 4-biphenyl-4-yl-2-chloroquinazoline and 26 g (210.0 mmol) of sodium carbonate are suspended in 500 ml of ethylene glycol diamine ether and 500 ml of water. 913 mg (3.0 mmol) of tri-o- tolylphosphine and then 112 mg (0.5 mmol) of palladium(ll) acetate are added to this suspension, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, filtered through silica gel, washed three times with 200 ml of water and subsequently evaporated to dryness. The product is purified by column chromatography on silica gel with toluene/heptane (1:2) and finally sublimed in a high vacuum (p = 5 x 10 ^{" 7} mbar) (purity 99.9%). The yield is 60 g (87 mmol), corresponding to 80% of theory.

-76-

k21

10 g (84.7 mmol) of benzimidazole, 42 g (127.4 mmol) of CsC03, 2.4 g (14.7 mmol) of Cul and 30.7 g (63 mmol) of 3-(9-bromodibenzofuran-2-yl)-9- phenyl-9H-carbazole are suspended in 100 ml of degassed DMF under a protective gas, and the reaction mixture is heated under reflux at 120°C for 40 h. After cooling, the solvent is removed in vacuo, the residue is dissolved in dichloromethane, and water is added. The organic phase is then separated off and filtered through silica gel. The yield is 28 g (53 mmol), corresponding to 87% of theory.

The followin com ounds are re ared analo ousl

o) 9-phenyl-3-[9-(2-phenyl-benzimidazol-1-yl)-dibenzofuran-2-yl ]-9H- carbazole

26 g (50 mmol) of 3-(9-benzimidazol-1-yldibenzofuran-2-yl)-9-phenyl-9H- carbazole, 560 mg (25 mmol) of Pd(OAc)2, 19.3 g (118 mmol) of Cul and 20.8 g (100 mmol) of iodobenzene are suspended in 300 ml of degassed DMF under a protective gas, and the reaction mixture is heated under reflux at 140°C for 24 h. After cooling, the solvent is removed in vacuo, the residue is dissolved in dichloromethane, and water is added. The organic phase is then separated off and filtered through silica gel. The product is purified by column chromatography on silica gel with toluene/heptane (1 :2) and finally sublimed in a high vacuum (p = 5 x 10 ^~7 mbar) (purity 99.9%). The yield is 17.8 g (30 mmol), corresponding to 60% of theory.

The following compounds were prepared analogously:

Fabrication of OLEDs

The following examples V1-V7 and E1-E11 (see Table 1 and 2) show data for various OLEDs.

Substrate pre-treatment of examples V1-7 and E1-E1a: Glass plates with structured ITO (50 nm, indium tin oxide) form the substrates on which the OLEDs are processed. Before evaporation of the OLED materials, the substrates are pre-baked for 15 minutes at 250°C, followed by an O2 plasma treatment for 130 seconds.

The OLEDs have in principle the following layer structure: substrate / optional hole-injection layer (HIL) / hole-transport layer (HTL) / optional interlayer (IL) / electron-blocking layer (EBL) / emission layer (EML) / optional hole-blocking layer (HBL) / electron-transport layer (ETL) / optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The exact layer structure (and layer thickness) is denoted in Table 1. The materials used for the OLED fabrication are presented in Table 3.

All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as IC1 :M1 :TEG1 (55%:35%:10%) here means that material IC1 is present in the layer in a proportion by volume of 55%, M1 is present in the layer in a proportion of 35% and TEG1 is present in the layer in a proportion of 10%. Analogously, the electron- transport layer may also consist of a mixture of two materials.

The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (CE1000, measured in cd/A at 1000 cd/m ² ), the luminous efficacy (LE1000, measured in Im/W at 1000 cd/m ² ), the external quantum efficiency (EQE1000, measured in % at 1000 cd/m ² ) and the voltage (U1000, measured at 1000 cd/m ² in V) are determined from current/ voltage/luminance characteristic lines (IUL characteristic lines) assuming a Lambertian emission profile. The

electroluminescence (EL) spectra are recorded at a luminous density of 10 ³ (1000) cd/m ² and the CIE 1931 x and y coordinates are then calculated from the EL spectrum.

For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminous density has dropped to a certain proportion from a certain initial luminous density Li when the OLED is driven at a constant current. The starting condition Lo; jo = 4000 cd/m ² and Li = 70% in Table 2 indicates that the in column LT denoted lifetime corresponds to the time in hours (h) needed to fade the OLED from a starting luminous density of 4000 cd/m ² to 2800 cd/m ² . Accordingly, the lifetime of the starting condition Lo;jo = 20mA/cm ² , Li= 80% is the time needed to fade the OLED operated at the constant current of 20mA cm ² to 80% of the initial luminous density. The device data of various OLEDs is summarized in Table 2. The examples V1-V7 are comparison examples according to the state-of-the-art using comparison compounds XXCE1 to XXCE7. The examples E1-E11 show data of inventive OLEDs using inventive examples lnv-1 to lnv-11.

Table 1: OLED structure

No. HTL IL EBL EML HBL ETL

V1 SpMA1 — — XXCE1:TER4 — ST2:LiQ 140nm (95%:5%) 40nm (50%: 50%) 35nm

V2 SpA1 HATCN SpMA1 IC1:TEG1 XXCE2 ST2:LiQ 70nm 5nm 110nm (90%: 10%) 30nm 10nm (50%:50%) 30nm

V3 SpA1 HATCN SpMA1 IC1 EG1 XXCE3 ST2:LiQ 70nm 5nm 110nm (90%: 10%) 30nm 10nm (50%:50%) 30nm

V4 SpMA1 — — XXCE4 ER4 — ST2:LiQ 140nm (95%:5%) 40nm (50%:50%) 35nm

V5 Sp A1 — — XXCE5.TER4 — ST2:LiQ 140nm (95%:5%) 40nm (50%:50%) 35nm

V6 SpMA1 — — XXCE6 ER4 — ST2:LiQ 140nm (95%:5%) 40nm (50%:50%) 35nm

V7 SpMA1 — — IC1:TER4 XXCE7 ST2:LiQ 140nm (95%:5%) 40nm 10nm (50%:50%) 25nm

E1 SpMA1 — — lnv-1 :TER4 — ST2:LiQ 140nm (95%:5%) 40nm (50%:50%) 35nm

E2 SpMA1 — — lnv-2:TER4 — ST2:LiQ 140nm (95%:5%) 40nm (50%:50%) 35nm

E3 SpMA1 — — lnv-3:TEG1:TER4 ST2:LiQ 140nm (80%:15%:5%) 40nm (50%:50%) 35nm

E4 SpMA1 — — lnv-4:SpMA1:TER4 ST2:LiQ 140nm (65%:30%:5%) 40nm (50%:50%) 35nm

E5 SpMA1 — — lnv-5:TEG1:TER4 ST2:LiQ 140nm (85%:10%:5%) 40nm (50%:50%) 35nm

E6 SpMA1 — — lnv-6:TER4 — ST2:LiQ 140nm (97%:3%) 40nm (50%:50%) 35nm

E7 SpMA1 — — lnv-7:TEG1:TER4 ST2:LiQ 140nm (85%:10%:5%) 40nm (50%:50%) 35nm

E8 SpMA1 — — lnv-8:TER4 — ST2:LiQ 140nm (95%:5%) 40nm (50%:50%) 35nm

E9 SpA1 HATCN SpMA1 IC1:TEG1 lnv-9 ST2:LiQ 70nm 5nm 110nm (90%: 10%) 30nm 10nm (50%:50%) 30nm

E10 SpA1 HATCN SpMA1 IC1:TEG1 — lnv-10:LiQ 70nm 5nm 110nm (90%: 10%) 30nm (50%:50%) 30nm

E11 SpMA1 — — lnv-11:TER4 IC1 ST2:LiQ 140nm (97%:3%) 40nm 10nm (50%:50%) 25nm Table 2: OLED device data

Table 3: Materials

HATCN SpA1

SpMA1 LiQ

As can been seen in Table 2, OLEDs containing the compounds of the invention provide improved performance, without regard to whether it is located in the light-emitting layer as a host (i.e. E1-E8), in a hole-blocking layer (i.e. E9) or in an electron-transporting layer (i.e. E10). For example, inventive OLEDs E1 , E2, E6 and E8, using inventive compounds as a host for a red phosphorescent emitter, are the same as comparative OLEDs V1 and V4-6 but have improved lifetime. In particular, comparison compound XXCE4 (V4), which has a diazine heterocycle in the 2-position, has a LT of 870 h. However, E1 , which is identical to V4 except for using the inventive compound lnv-1, which is identical for XXCE4 except that the diazine is located in the 1 -position, has a LT of 1120 h, for an improvement of 29%. Likewise, E9, where an inventive compound is used as a host for a green phosphorescent emitter, shows better lifetime than V2 and V3. Even better results are seen when an inventive compound is used in more than one layer (i.e. E11) is compared to a comparative (i.e. V7) without the inventive compound.