Materials for electronic devices

Abstract

To provide a compound that is suitable for use in a fluorescent or phosphorescent OLED, for example, as a host material and / or matrix material, or as a hole transporting / electron blocking material or exciton blocking material, or as an electron transporting or hole blocking material, and that, when used in an OLED, results in good device properties, and to provide a corresponding electronic device. The present invention provides a tricyclic compound having functional substituents in a specific spatial arrangement of electron-conducting and hole-conducting groups, a device containing the functional substituents, a method for producing the device, and its use. For example, the compound represented by the following general formula (1) is shown. JPEG2023036578000083.jpg45170

Description

[Technical field]

[0001] The present invention relates to cyclic compounds having specific arrangements of electron-conducting and hole-conducting groups, their use in electronic devices, and methods for producing the same and electronic devices.

[0002] The structures of organic electroluminescent devices (for example OLED-organic light-emitting diodes or OLEC-organic light-emitting electrochemical cells) in which organic semiconductors are used as functional materials are described, for example, in US 4539507, US 5151629, EP0676461 and WO98 / 27136. The emitting materials used here are increasingly organometallic complexes that, in addition to fluorescent emission, also exhibit phosphorescent emission (MA Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). For quantum mechanical reasons, an increase in energy and power efficiency of up to four times is possible using organometallic compounds as phosphorescent emitters. In general, there is still a need for improvements, especially in terms of efficiency, driving voltage and lifetime, both in the case of OLEDs that exhibit singlet emission and in the case of OLEDs that exhibit triplet emission. This applies in particular to OLEDs that emit in the relatively shorter wavelength range, i.e. in the green and especially in the blue.

[0003] The properties of organic electroluminescent devices are not only determined by the emitter used. Other materials used are also of particular importance here, such as host and matrix materials, hole blocking materials, electron transport materials, hole transport materials and electron or exciton blocking materials. Improvements in these materials can also bring about significant improvements in electroluminescent devices.

[0004] According to the prior art, in particular ketones (for example according to 2004 / 093207 or WO 2010 / 006680) or phosphine oxides (for example according to WO 2005 / 003253) are used as matrix materials for phosphorescent emitters. Further matrix materials according to the prior art are triazines (for example WO 2008 / 056746, EP 0906947, EP 0908787, EP 0906948).

[0005] According to the prior art, for fluorescent OLEDs, condensed aromatic compounds, in particular anthracene derivatives, in particular 9,10-bis(2-naphthyl)anthracene (US 5935721), are used as host materials for blue-emitting electroluminescent devices. WO 03 / 095445 and CN 1362464 disclose 9,10-bis(1-naphthyl)anthracene derivatives for use in OLEDs. Further anthracene derivatives are disclosed in WO 01 / 076323, WO 01 / 021729, WO 2004 / 013073, WO 2004 / 018588, WO 2003 / 087023, or WO 2004 / 018587. Aryl-substituted pyrene and chrysene-based host materials are disclosed in WO 2004 / 016575. Benzanthracene derivative-based host materials are disclosed in WO 2008 / 145239. It is desirable to have improved host materials available for high quality applications.

[0006] The prior art discloses the use of compounds containing one or more carbazole groups in electronic devices, for example in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851.

[0007] The prior art further discloses the use of compounds containing one or more indenocarbazole groups in electronic devices, for example in WO 2010 / 136109 and WO 2011 / 000455.

[0008] The prior art further discloses the use of compounds containing one or more electron-deficient heteroaromatic six-membered rings in electronic devices, for example in WO 2010 / 015306, WO 2007 / 063754 and WO 2008 / 056746.

[0009] WO 2009 / 069442 discloses tricyclic compounds such as carbazole, dibenzofuran or dibenzothiophene that are highly substituted with electron-deficient heteroaromatic groups (e.g. pyridine, pyrimidine or triazine). The tricyclic compounds are not substituted with hole-conducting groups, i.e. electron-rich groups.

[0010] JP 2009-21336 discloses substituted dibenzofurans substituted at the 2-position with a carbazole and at the 8-position with a triazine.

[0011] WO 2011 / 057706 discloses as matrix materials some of which are substituted dibenzothiophenes and dibenzofurans, where the compounds are substituted in a specific manner by electron-conducting groups and by hole-conducting groups.

[0012] However, with regard to the use of these materials, as with other materials, there is still a need for improvement, particularly with regard to device efficiency and lifetime.

[0013] It is therefore an object of the present invention to provide compounds which are suitable for use in fluorescent or phosphorescent OLEDs, e.g. as host and / or matrix materials, or as hole transporting / electron blocking or exciton blocking materials, or as electron transporting or hole blocking materials, and which, when used in OLEDs, result in good device properties, and to provide corresponding electronic devices.

[0014] Surprisingly, it has been found that certain compounds, which are described in more detail below, achieve these objectives and provide good properties of organic electroluminescent devices, in particular with respect to lifetime, efficiency and driving voltage. The present invention therefore relates to electronic devices, in particular organic electroluminescent devices, containing compounds of this type and corresponding preferred compounds. The surprising effect is achieved by a specific arrangement of electron-conducting and hole-conducting groups in the compounds of the formula shown below.

[0015] The compounds according to the invention are furthermore characterised by a high temperature stability which allows them to be evaporated under high vacuum without decomposition, a property which is a fundamental premise for the reproducible production of organic electronic devices, such as organic electroluminescent devices, and which has a positive effect in particular on the operating life.

[0016] The compounds according to the invention also have a high glass transition temperature (T g ), which is advantageous in terms of the processability of the compound during the manufacture of electronic devices. The high glass transition temperature of the compound also enables the compound to be used in thin, amorphous organic layers.

[0017] Furthermore, the compounds according to the invention have sufficiently high triplet energies, which allow stabilization of charge carriers in the excited state, an important prerequisite for phosphorescent devices, and furthermore, the compounds according to the invention show improved properties in OLEDs compared to compounds from the prior art.

[0018] The compounds according to the invention are also characterized by an improved redox stability in solution compared to compounds from the prior art, which simplifies the purification of the compounds, simplifies their handling and improves their storage stability in solutions prepared for the manufacture of organic electronic devices from solutions by printing processes.

[0019] Finally, the compounds according to the invention are characterized by a very good solubility, which allows the compounds to be processed from solution.In this way, the inexpensive manufacture of organic electronic devices is realized.Therefore, the compounds according to the invention are also suitable for the mass production of organic electronic devices.

[0020] The present invention therefore relates to compounds of general formula (1)

[0021] [ka]

[0022] In the formulas, the following applies to the symbols and subscripts used: ETG is an organic electron transport group (ETG) from the group of electron-deficient heteroaromatic groups, where ETG is preferably a heteroaryl group having 5 to 60 aromatic ring atoms, where very preferred heteroatoms are N-atoms, and very particularly preferred ETGs are selected from the group of triazines, pyrimidines, pyrazines, pyridines, quinazolines, benzimidazoles, quinolines, isoquinolines and naphthyridines, especially preferred ETGs are selected from the group of triazines, pyrimidines, pyrazines and pyridines, where ETG is selected from the group of one or more groups R 1 may be replaced by, which may be identical or different at each occurrence; W is a hole conducting electron rich organic group, where W is preferably selected from the group of arylamines, triarylamines, bridged amines, where preferred bridged amines are dihydroacridine, dihydrophenazine, phenoxazine and phenothiazine, carbazole, bridged carbazole, biscarbazole, benzocarbazole, indenocarbazole and indolocarbazole; W is selected from one or more groups R 1 may be replaced by, which may be identical or different at each occurrence; V is O or S, preferably O; Y is a divalent bridge, Y is preferably an aromatic or heteroaromatic ring structure having 5 to 60 ring atoms; the divalent bridge Y very preferably has 5 to 30 ring atoms, particularly preferably 5 to 18 ring atoms, very preferably 5 to 12 ring atoms, especially preferably 5 to 10 aromatic ring atoms, more preferably the bridge has exactly 6 ring atoms, most preferably the bridge is a phenylene bridge; n is either 0 or 1, and is preferably 0, where n=0 means that ETG and ring B are directly bonded to each other via a single bond; r is an integer from 0, 1, 2 or 3, preferably 0 or 1, very preferably 0; s is an integer from 0, 1, 2 or 3, preferably 0 or 1, very preferably 0; R 1 are the same or different for each occurrence, H, D, F, Cl, Br, I, N(R 2 )2, CN, NO2, Si(R 2 )3, B(OR 2 )2, C(=O)R 2 , P(=O)(R 2 )2, S(=O)R 2 , S(=O)2R 2 , OSO2R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 C atoms (each of which is represented by one or more groups R 2 and one or more non-adjacent CH groups may be replaced by R 2 C=CR 2 , C≡C, Si(R 2 )2, Ge(R 2 )2, Sn(R 2 )2, C=O, C=S, C=Se, C=NR 2 , P(=O)(R 2 ), SO, SO2, NR 2 , O, S or CONR 2where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; or in each case one or more groups R 2 an aromatic or heteroaromatic ring structure having 5 to 60 aromatic ring atoms, optionally substituted by one or more groups R 2 an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more groups R 2 or a combination of two or more of these groups, or a crosslinkable group Q; 1 may together form a monocyclic or polycyclic aliphatic or aromatic ring structure; R 2 are the same or different for each occurrence, H, D, F, Cl, Br, I, N(R 3 )2, CN, NO2, Si(R 3 )3, B(OR 3 )2, C(=O)R 3 , P(=O)(R 3 )2, S(=O)R 3 , S(=O)2R 3 , OSO2R 3 , a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, a linear alkenyl or alkynyl group having 2 to 40 C atoms, a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 C atoms (each of which is one or more R 3 groups, and one or more non-adjacent CH groups may be substituted by R 3 C=CR 3 , C≡C, Si(R 3 )2, Ge(R 3 )2, Sn(R 3 )2, C=O, C=S, C=Se, C=NR 3 , P(=O)(R 3 ), SO, SO2, NR 3 , O, S or CONR 3where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2; or in each case one or more groups R 3 an aromatic or heteroaromatic ring structure having 5 to 60 aromatic ring atoms, optionally substituted by one or more groups R 3 an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more groups R 3 or a combination of two or more of these groups, each of which has 10 to 40 aromatic ring atoms, optionally substituted by 2 may together form a monocyclic or polycyclic aliphatic or aromatic ring structure; R 3 are identical or different at each occurrence and are H, D, F, an aliphatic, aromatic and / or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, one or more H atoms may be replaced by F; in which two or more substituents R 3 may together form a monocyclic or polycyclic aliphatic or aromatic ring structure; R 4 , R 5 are the same or different for each occurrence, H, D, F, Cl, Br, I, N(R 2 )2, CN, NO2, Si(R 2 )3, B(OR 2 )2, C(=O)R 2 , P(=O)(R 2 )2, S(=O)R 2 , S(=O)2R 2 , OSO2R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 C atoms.

[0023] In a further preferred embodiment of the invention, V in the compound of formula (1) is S.

[0024] Preferred electron-deficient heteroaromatic groups for the ETG are selected from the following groups:

[0025] [ka]

[0026] In the formula, the dashed bond indicates the bond position, and R 1 is as defined above, and Q' may be the same or different for each occurrence, and CR 1 or N; and Q" is NR 1 , O or S; wherein at least one Q' is N and / or at least one Q" is NR 1 It is.

[0027] Preferred electron-deficient heteroaromatic groups as ETG are pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-triazine, 1,3,5-triazine, quinoline, isoquinoline, quinoxaline, pyrazole, imidazole, benzimidazole, thiazole, benzothiazole, oxazole or benzoxazole, respectively, R 1 Even more preferably, the electron transport group may be substituted with one or more groups R 1 The pyridine, pyrazine, pyrimidine, pyridazine or 1,3,5-triazine may be substituted with

[0028] Compounds of formula (1) comprising an electron transport group preferably have a LUMO (Lowest Unoccupied Molecular Orbital) energy below −1.3 eV, very preferably below −2.5 eV and very particularly preferably below −2.7 eV.

[0029] The HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) energy levels of a material and the energy T1 of the lowest triplet state or S1 of the lowest excited singlet state can be determined by quantum chemical calculations. Here, the "Gaussian09W" (Gaussian Inc.) software package is used for this purpose. For calculations of organic substances, a geometric optimization is first performed using the "Ground State / Quasi-Empirical / Default Spin / AM1 / Charge 0 / Singlet Spin" method. An energy calculation is then performed on the basis of the geometric optimization. Here, the "TD-SCF / DFT / Default Spin / B3PW91" method is used with the "6-31G(d)" basis set (Charge 0 / Singlet Spin). The energy calculation gives the HOMO energy level HEh or the LUMO energy level LEh in Hartree units. The HOMO and LUMO energy levels in electron volts calibrated with reference to cyclic voltammetry measurements are determined therefrom as follows:

[0030] HOMO(eV)=((HEh*27.212)-0.9899) / 1.1206 LUMO(eV)=((LEh*27.212)-2.0041) / 1.385 These values, for purposes of this application, should be considered as the HOMO and LUMO energy levels of the material.

[0031] The lowest triplet level T1 is defined as the energy of the triplet state having the lowest energy as revealed by the above quantum chemical calculations.

[0032] The lowest excited singlet level S1 is defined as the energy of the excited singlet state having the lowest energy, which is evident from the above quantum chemical calculation.

[0033] More preferably, the compound of formula (1) is -6 cm 2 / (Vs) or more, highly preferably 10 -5 cm 2 / (Vs) or more, very particularly preferably 10-4 cm 2 Electron mobility μ above / (Vs) - has.

[0034] In the compound of formula (1), LUMO is preferably localized on the electron transport group, and a probability of staying of 0.9 is assumed for the orbital. LUMO is very preferably localized more than 80% on the electron transport group, and more preferably, LUMO is not localized at all on the group W (for example, carbazole group). It is especially preferred when the HOMO and LUMO of the compound according to the invention do not overlap at all. Those skilled in the art have no problem in determining the overlap of orbitals.

[0035] The overlap of molecular orbitals involved in a certain electronic transition (charge-transfer state) is described using the parameter Λ. The meaning of the parameter Λ is well known to the skilled artisan. The determination of the parameter by the methods described in the prior art does not pose any problem to the skilled artisan. For the purposes of the present invention, the parameter Λ is determined using the PBHT method according to DJ Tozer et al. (J. Chem. Phys. 128, 044118 (2008)), for example as implemented in the Q-Chem 4.1 software package from Q-Chem, Inc. The molecular orbitals are calculated here by the method described above. Occupied molecular orbitals ψ i and unoccupied (virtual) molecular orbital ψ a The spatial overlap for all possible pairs with is subsequently determined from the following formula:

[0036]

number

[0037] Here, the coefficients of the trajectory are used for the calculation.

[0038] The parameter Λ is then obtained from the weighted sum over all pairs of occupied and unoccupied molecular orbitals i according to the formula

[0039]

number

[0040] Here, the value of κ ia is determined from the orbital coefficients in the excitation vector of the decomposed TD (time-dependent) eigenvalue equation by the method of Tozer et al., where 0≦Λ≦1.

[0041] In a preferred embodiment, the present invention relates to compounds of general formula (1) that have a small spatial overlap of the molecular orbitals Λ involved in certain electronic transitions (charge-transfer states).

[0042] In the present application, a small overlap of molecular orbitals is such that the value of the parameter Λ is less than or equal to 0.3, preferably less than or equal to 0.2, very preferably less than or equal to 0.15, very particularly preferably less than or equal to 0.1 and especially preferably less than or equal to 0.05.

[0043] Compounds of formula (1) containing a hole transporting group W reduce the electron work function (Φ anode ) plus +1.5V or less, i.e.

[0044]

number

[0045] The HOMO energy (HOMO w ), preferably.

[0046] If the anode used has an electronic work function of -0.5 eV, the HOMO energy of the compound of formula (1) is less than or equal to -3.5 eV (i.e. more negative than -3.5 eV).The compound of formula (1) very preferably has a HOMO energy that is the same as or lower than the electronic work function of the anode, very particularly preferably lower.

[0047] More preferably, the compound of formula (1) is -6 cm2 / (Vs) or more, highly preferably 10 -5 cm 2 / (Vs) or more, very particularly preferably 10 -4 cm 2 Hole mobility μ above / (Vs) + It is characterized by:

[0048] Measurements of electron and hole mobility are performed by standard techniques by those skilled in the art.

[0049] In the compounds of formula (1), the HOMO is localized on a hole transport group, meaning that the HOMO is more than 80% localized on a hole conducting group or is substantially not localized on an electron deficient electron transport group, where a residence probability of 0.9 is assumed for the orbital.

[0050] For the purposes of the present invention, preference is given to compounds of the general formula (2):

[0051] [ka]

[0052] wherein the symbols and subscripts used are defined above, and further wherein X is N or CR 1 where at least one of the five groups X in ring A is an N atom, preferably two of the five groups X in ring A are an N atom, very preferably three of the five groups X in ring A are an N atom; ring A is very particularly preferably a triazine, especially preferably a 1,3,5-triazine; W is a group of formula (W-1),

[0053] [ka]

[0054] During the ceremony, U is N or CR 1 , preferably CR1 where the dashed line is the bond from group W to ring C in formula (2).

[0055] In one preferred embodiment, the group U=CR 1 Two or more adjacent groups R 1 may together form a monocyclic or polycyclic aliphatic or aromatic ring structure.

[0056] In a further preferred embodiment, the group U=CR 1 Two or more adjacent groups R 1 are incapable of forming a monocyclic or polycyclic aliphatic or aromatic ring structure with each other.

[0057] Group U=CR 1 at least one group R 1 But more preferably, it is not H.

[0058] For the purposes of the present invention, the group U=CR 1 R as 1 is H or, in each case, one or more radicals R 2 It is highly preferred that the aromatic or heteroaromatic ring system has 5 to 60 aromatic ring atoms, which may be substituted by the group U=CR 1 At least one R from 1 However, it is particularly preferred that it is not H.

[0059] R 1 in each case H or in each case one or more radicals R 2 It is highly preferred that the aromatic or heteroaromatic ring system has 5 to 60 aromatic ring atoms, which may be substituted by, 1 It is particularly preferred that at least one of is not H.

[0060] It is preferred that the compound has the general formula (1) where r is either 0 or 1 and s is either 0 or 1. Preferably, either only r or only s is 1 and each other parameter is 0, and highly preferably, both r and s are 0.

[0061] In a further preferred embodiment of the invention, n is always 1, such that a divalent bridge is always present between ring A and ring B.

[0062] It is further preferred if the compound has the general formula (4) wherein the symbols and indices used have the above definitions and the embodiments mentioned as preferred anywhere in the present invention are also preferred embodiments of formula (4),

[0063] [ka]

[0064] In the formula, the symbols and subscripts used are defined as above, where r is either 0 or 1, and s is either 0 or 1.

[0065] It is even more preferable that r+s=1.

[0066] It is also preferred when the compound has the general formula (6), wherein the symbols and indices used have the above definitions and the embodiments mentioned as preferred anywhere in the invention are also preferred embodiments of formula (6).

[0067] [ka]

[0068] More preferred is when the compound has the general formula (7), wherein the symbols and indices used have the above definitions and the embodiments mentioned as preferred anywhere in the invention are also preferred embodiments of formula (7).

[0069] [ka]

[0070] Preferred is when the group W is carbazole, indenocarbazole or indolocarbazole, where the groups may be substituted as disclosed herein. In one preferred embodiment of the invention, the group W is carbazole and is joined to one or more groups R 1 where the adjacent groups R 1 cannot form a ring closure with each other. The group W is indenocarbazole and is preferably a substituted or unsubstituted aryl group. 1 Or R 2 It is highly preferred if it may be substituted by:

[0071] The group W is an indolocarbazole and is represented by one or more groups R 1 Or R 2 It is highly preferred if it may be substituted by:

[0072] The group W of the following formula (W-2) is particularly preferred:

[0073] [ka]

[0074] Very particular preference is given to groups W of the formula (W-3),

[0075] [ka]

[0076] Very particular preference is given to the group W of formula (W-4).

[0077] [ka]

[0078] The group W has the formula (W-4), and the group R 1is more preferably not hydrogen, and in this case, R 1 in each case one or more groups R 2 More preferably, the aromatic ring structure is an aromatic or heteroaromatic ring structure having 5 to 60 aromatic ring atoms which may be substituted by:

[0079] In another highly preferred embodiment of the invention, the group W has the formula (W-4) 1 But it is also hydrogen.

[0080] It is particularly preferred if the group W is a group of formula (W-5):

[0081] [ka]

[0082] wherein the subscripts and symbols used are as defined above, and further wherein T p , T q is a bivalent bridge that may be the same or different for each occurrence; T p and T q is preferably N(R 2 )2, B(R 2 )2, O, C(R 2 )2, Si(R 2 )2, C=O, C=NR 2 , C=C(R 2 )2, S, S=O, SO2, P(R 2 )2 and P(=O)(R 2 )2; where N(R 2 )2, O, C(R 2 )2 and S are highly preferred, N(R 2 )2 and C(R 2 ) 2 is particularly preferred, U' may be the same or different for each occurrence, and CR 2 or N, preferably CR 2 is: p is 0 or 1, where p=0 means that ring E and ring D are bonded to each other via a single bond; q is 0 or 1, where q=0 means that ring E and ring D are bonded to each other via a single bond; and p+q=1 or 2, preferably 1; Here, T p and T q are each bonded to an adjacent group U of ring D in any possible orientation, and further, T p or T q Each group U attached to is a carbon atom.

[0083] Very particularly preferred radicals W are selected from the following radicals of the formulae (W-6) to (W-8), with the radical of the formula (W-7) being especially preferred.

[0084] [ka]

[0085] Particularly preferred groups W are groups of the formulae (W-9) to (W-14).

[0086] [ka]

[0087] In one preferred embodiment of the invention, the group W is an indenocarbazole, very preferably having one of the following formulae (W-15) to (W-20):

[0088] [ka]

[0089] In this formula, the indenocarbazole of formula (W-17), (W-18), (W-19), (W-15) and (W-16) are very particularly preferred.Particularly preferred are the indenocarbazole of formula (W-17), (W-18) and (W-19), more preferably the indenocarbazole of formula (W-17) and (W-18), and most preferably the indenocarbazole of formula (W-17).

[0090] In a further preferred embodiment of the invention, the group W is an indolocarbazole, very preferably having one of the following formulae (W-21) to (W-25):

[0091] [ka]

[0092] Indolocarbazoles of the formulae (W-21), (W-23) and (W-26) are very particularly preferred. Particularly preferred indolocarbazoles are those of the formulae (W-21) and (W-23), most preferably those of the formula (W-21).

[0093] For the purposes of the present invention, U in the groups of formulae (W-1) and (W-5) to (W-26) is always CR 1 It is highly preferred if, in which the group U=CR 1 Group R belonging to 1 It is particularly preferred that is always H.

[0094] For the purposes of the present invention, U' in the groups of formulae (W-5) to (W-26) is always CR 2 It is highly preferred that the group U'=CR 2 Group R belonging to 2 It is particularly preferred that is always H.

[0095] In the groups of formulae (W-5) to (W-26), U is CR 1 and U' is CR 2 It is particularly preferred when the group U=CR 1 Group R belonging to 1 and the group U'=CR 2 Group R belonging to 2 is very particularly preferably H.

[0096] In a further preferred embodiment, the present invention relates to compounds of formula (1), wherein W is defined as shown in formula (W-27):

[0097] [ka]

[0098] wherein the symbols and indices used are as defined above, and the embodiments mentioned as preferred anywhere in the present invention are also preferred embodiments of formula (W-27).

[0099] As already explained, the group X in the ring A of the compound of formula (2) is N or CR 1 wherein at least one of the five groups X in ring A is an N atom, preferably two of the five groups X in ring A are N, and very preferably three of the five groups X in ring A are N.

[0100] Preferred groups for ring A in formula (2) of formula (A-1)

[0101] [ka]

[0102] is a group of the following formulae (A-2) to (A-13), in which the dashed line represents the bond between ring A and Y in formula (2), or, in the case of n=0, represents the bond between ring A and ring B in formula (2);

[0103] [ka]

[0104] In the formula, the symbols and subscripts used are subject to the above definitions and preferred embodiments.

[0105] Particularly preferred here are groups of the formula (A-2):

[0106] Further preferred groups for ring A in formula (2) are the following groups of formula (A-14):

[0107] [ka]

[0108] Highly preferred groups for ring A in formula (2) of formula (A-1) are groups of formulae (A-2) to (A-11), where R 1 Ar 1 and Ar 1 may be identical or different on each occurrence and in each case represent one or more groups R 2 an aromatic or heteroaromatic ring structure having 5 to 60 aromatic ring atoms, which may be substituted by Ar 1 is preferably identical or different on each occurrence and in each case contains one or more groups R 2 is a phenyl, biphenyl, terphenyl, quaterphenyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, spirobifluorenyl, pyridyl or pyrimidyl group, optionally substituted by Ar 1 is very preferably identical or different on each occurrence and in each case contains one or more groups R 2 Particularly preferred are phenyl, biphenyl, terphenyl or quaterphenyl radicals, which in each case may be substituted by one or more radicals R 2 embedded image wherein the phenyl group is in the unsubstituted form is especially preferred.

[0109] Very particular preference is given here to R 1 Ar 1 is a group of formula (A-2).

[0110] Further highly preferred groups for ring A in formula (2) are R 1 Ar 1 is a group of formula (A-14).

[0111] Particularly preferred groups Ar 1 are also the following radicals having the formulae (Ar-1) to (Ar-24), in which the radicals are each independently selected from one or more radicals R 2 may be substituted by:

[0112] Very particularly preferred radicals Ar 1 is also a group of the formulae (Ar-1) to (Ar-9).

[0113] [ka]

[0114] [ka]

[0115] The expression that two or more groups may form a ring together is intended for the purposes of this application to be used in particular to mean that the two groups are linked together by a chemical bond, as illustrated by the following scheme:

[0116] [ka]

[0117] However, the above mentioned expressions are further intended to be used in the sense that when one of the two groups is hydrogen, the second group is attached at the position to which the hydrogen atom is attached to form a ring, which is illustrated by the following scheme:

[0118] [ka]

[0119] The following are general definitions of chemical groups within the meaning of this application:

[0120] An aryl group, in the sense of the present invention, contains 6 to 60 aromatic ring atoms, and a heteroaryl group, in the sense of the present invention, contains 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms are preferably selected from N, O and S. This is the basic definition. If other preferences are indicated in the description of the present invention, for example with regard to the number of aromatic ring atoms or heteroatoms, these also apply.

[0121] An aryl or heteroaryl group is used here to mean either a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, or a condensed (annulated) aromatic or heteroaromatic polycycle, such as naphthalene, phenanthrene, quinoline or carbazole, etc. A condensed (annulated) aromatic or heteroaromatic polycycle in the sense of the present application consists of two or more simple aromatic or heteroaromatic rings condensed together.

[0122] In the sense of the present invention, electron-deficient heteroaryl groups are defined as 5-membered heteroaryl ring groups containing at least two heteroatoms, such as imidazole, oxazole, oxadiazole, etc., or 6-membered heteroaryl ring groups containing at least one heteroatom, such as pyridine, pyrimidine, pyrazine, triazine, etc. Further 6-membered aryl or 6-membered heteroaryl groups may be condensed to these groups, such as benzimidazole, quinoline or phenanthroline.

[0123] The aryl or heteroaryl radicals may in each case be substituted by the above-mentioned groups and may be linked to the aromatic or heteroaromatic structure via any desired position, but in particular benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, 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, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, oxazo benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-o It is used to mean the radicals derived from oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0124] According to the definition of the present invention, an aryloxy group is used to mean an aryl group as defined above bonded via an oxygen atom. The same definition applies to heteroaryloxy groups.

[0125] An aromatic ring structure, in the sense of the present invention, contains 6 to 60 C atoms in the ring structure. A heteroaromatic ring structure, in the sense of the present invention, contains 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from N, O and / or S. An aromatic or heteroaromatic ring structure, in the sense of the present invention, is a structure which does not necessarily contain only aryl or heteroaryl groups, in addition, several aryl or heteroaryl groups may contain non-aromatic units (preferably less than 10% of atoms other than H), e.g. sp 3 Hybridized C, Si, N or O atoms, sp 2 It is intended to be used in the sense of aromatic ring structures in the sense of the present invention, since structures such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are structures in which two or more aryl groups are linked, for example, by linear or cyclic alkyl, alkenyl or alkynyl groups, or by silyl groups. Furthermore, structures in which two or more aryl or heteroaryl groups are linked to each other via single bonds, such as, for example, biphenyl, terphenyl or diphenyltriazine, are also intended to be used in the sense of aromatic or heteroaromatic ring structures in the sense of the present invention.

[0126] The aromatic or heteroaromatic ring structures having 5 to 60 aromatic ring atoms may in each case be substituted by groups defined above and may be linked to the aromatic or heteroaromatic structure in any desired position, but are in particular benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene, spirobifluorene, dihydrophenane, threne, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline , benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthriimidazole, pyridoimidazole, pyrazineimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazole zaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazapyrylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,It is used to mean the radicals derived from 3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole or combinations of these structures.

[0127] For the purposes of the present invention, linear alkyl groups having 1 to 40 C atoms or branched or cyclic alkyl groups having 3 to 40 C atoms or alkenyl or alkynyl groups having 2 to 40 C atoms, in which in addition the individual H atoms or CH2 groups may be substituted by the groups mentioned above under the definition of the groups, preferably the groups methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, It is used to mean pentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.An alkoxy or thioalkyl group having 1 to 40 C atoms is preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-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, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n -pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptthiol, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

[0128] Compounds according to the invention can be prepared according to Scheme 1. The corresponding monoboronic acids are commercially available and can be converted to the corresponding target compounds by Suzuki coupling followed by bromination and further Buchwald coupling.

[0129] [ka]

[0130] In the formula, Z is Cl, Br or I, and the other symbols and subscripts have the meanings given above. The reaction scheme can be used in exactly the same way to prepare compounds of formula (1).

[0131] The general processes shown for the synthesis of the compounds according to the invention are exemplary: those skilled in the art will be able to develop alternative synthetic routes within their general expertise.

[0132] The overview below contains examples of compounds according to the invention that can be prepared by one of the processes described herein.

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] The present invention further relates to the use of compounds of formula (1) in electronic devices, preferably in an electron transport layer and / or in an emissive layer.

[0143] The compounds according to the invention can also be used in a hole transport layer.

[0144] The electronic components according to the invention are preferably selected from the group consisting of organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (OLETs), organic solar cells (O-SCs), organic optical test elements, organic photoreceptors, organic field quenching elements (OFQDs), organic light emitting electrochemical cells (OLECs, LEECs, LECs), organic laser diodes (O-lasers) and organic light emitting diodes (OLEDs). Particularly preferred are organic electroluminescent elements, very particularly preferred are OLECs and OLEDs, especially preferred are OLEDs.

[0145] OLEDs in the sense of the present invention are used to mean both small organic molecule organic light emitting diodes (SMOLEDs) and also polymer light emitting diodes (PLEDs), whereby light emitting diodes (SMOLEDs) are the preferred OLEDs.

[0146] The organic layer containing the compound of formula (1) is preferably a layer having an electron transport function, particularly preferably an electron injection layer (EIL), an electron transport layer (ETL), a hole blocking layer (HBL) or an emissive layer (EML), and more preferably the compound is present in the emissive layer.

[0147] The hole transport layer according to the present application is a layer having a hole transport function located between the anode and the light emitting layer.

[0148] An electron transport layer according to the present application is a layer having electron transport functionality located between the cathode and the light emitting layer.

[0149] Hole injection layer and electron blocking layer are used in the sense of the present application as special embodiments of a hole transport layer. In the case of multiple hole transport layers between the anode and the light emitting layer, the hole injection layer is the hole transport layer that is directly adjacent to the anode or separated therefrom only by a single coating of the anode. In the case of multiple hole transport layers between the anode and the light emitting layer, the electron blocking layer is the hole transport layer that is directly adjacent to the light emitting layer on the anode side.

[0150] As already mentioned above, the compounds of formula (1) are used in a preferred embodiment as matrix materials in the light-emitting layer of an organic electronic device, in particular in an organic electroluminescent device, for example in an OLED or OLEC. The matrix material of formula (1) is present in the electronic device in combination with one or more dopants, preferably a phosphorescent dopant.

[0151] The term phosphorescent dopant typically encompasses compounds in which emission results from a spin-forbidden transition, such as an excited triplet state or a state having a relatively high spin quantum number, such as a quintet state.

[0152] Suitable phosphorescent dopants are in particular compounds which, upon suitable excitation, preferably emit in the visible range and additionally contain at least one atom with an atomic number greater than 20, preferably between 38 and 84, particularly preferably between 56 and 80. The phosphorescent 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, platinum or copper.

[0153] All luminescent iridium, platinum or copper complexes are considered phosphorescent compounds within the meaning of this application. Examples of phosphorescent dopants are given in the following section.

[0154] In a system comprising a matrix material and a dopant, the dopant is used to mean the component which is the minor component in the mixture. Correspondingly, in a system comprising a matrix material and a dopant, the matrix material is used to mean the component which is the major component in the mixture.

[0155] In this case, the ratio of the matrix material in the light-emitting layer is 50.0 to 99.9 volume %, preferably 80.0 to 99.5 volume %, and particularly preferably 92.0 to 99.5 volume % for the fluorescent-emitting layer, and 85.0 to 97.0 volume % for the phosphorescent-emitting layer.

[0156] Correspondingly, the proportion of the dopant is 0.1 to 50.0% by volume, preferably 0.5 to 20.0% by volume, and particularly preferably 0.5 to 8.0% by volume for the fluorescent-emitting layer, and 3.0 to 15.0% by volume for the phosphorescent-emitting layer.

[0157] The light-emitting layer of an organic electroluminescent device may also comprise a system that comprises several matrix materials (mixed matrix systems) and / or several dopants. In this case too, the dopants are generally the materials that are in the smaller proportion in the system, and the matrix materials are the materials that are in the larger proportion in the system. However, in individual cases, the proportion of each matrix material in the system may be smaller than the proportion of each dopant.

[0158] In a further preferred embodiment of the present invention, the compounds of formula (1) are used as components of a mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, particularly preferably two different matrix materials. Here, one of the two materials is preferably a material with hole transport properties, the other a material with electron transport properties. However, the desired electron transport and hole transport properties of the mixed matrix components may also be mainly or completely combined in a single mixed matrix component, where a further mixed matrix component performs the other function. Here, the two different matrix materials may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1, very particularly preferably 1:4 to 1:1. The mixed matrix system is preferably used in a phosphorescent organic electroluminescent device. More precise information on the mixed matrix system can be found, in particular, in application WO 2010 / 108579.

[0159] Particularly suitable matrix materials which can be used as matrix components in a mixed matrix system in combination with the compounds according to the invention are selected from the preferred matrix materials for phosphorescent dopants or the preferred matrix materials for fluorescent dopants given below, depending on which type of dopant is used in the mixed matrix system.

[0160] The present invention therefore also relates to a composition comprising at least one compound of formula (1) and at least one further matrix material. Preferred further matrix materials are the matrix materials mentioned below.

[0161] The present invention also relates to a composition comprising at least one compound of formula (1) and at least one wide band gap material, where wide band gap material is used in the sense of material as disclosed in US 7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices. It is particularly preferred when the band gap of the wide band gap material is 3.5 eV or more, where band gap is used in the sense of the energy difference between HOMO and LUMO. The orbital energy is determined by the method described above.

[0162] The present invention further relates to a composition comprising at least one compound of formula (1) and at least one further organic semiconducting material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials, hole blocking materials.

[0163] Preferred phosphorescent dopants for use in mixed matrix systems are the preferred phosphorescent dopants set forth below.

[0164] Examples of phosphorescent dopants can be found in applications WO 2000 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 2005 / 033244, WO 2005 / 019373 and US2005 / 0258742. In general, all phosphorescent complexes are suitable as used according to the prior art for phosphorescent OLEDs and known to those skilled in the art of organic electroluminescent devices.

[0165] Specific examples of phosphorescent dopants are shown in the table below.

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[0167]

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[0176] Preferred fluorescent dopants are selected from the class of arylamines. Arylamines or aromatic amines in the sense of the present invention are used to mean compounds that contain three substituted or unsubstituted aromatic or heteroaromatic ring structures directly bonded to nitrogen. At least one of these aromatic or heteroaromatic ring structures is preferably a fused ring structure, particularly preferably having at least 14 aromatic ring atoms. Preferred examples of these are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. Aromatic anthracenamines are used to mean compounds in which one diarylamino group is directly bonded to the anthracene group, preferably in the 9-position. Aromatic anthracenediamines are used to mean compounds in which two diarylamino groups are directly bonded to the anthracene group, preferably in the 9.10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined similarly, where the diarylamino group is preferably bonded to the pyrene in the 1-position or the 1.6-position. Further preferred dopants are indenofluoreneamines or indenofluorenediamines, for example according to WO 2006 / 108497 or WO 2006 / 122630, benzoindenofluoreneamines or benzoindenofluorenediamines, for example according to WO 2008 / 006449, and dibenzoindenofluoreneamines and dibenzoindenofluorenediamines, for example according to WO 2007 / 140847 and indenofluorene derivatives containing fused aryl groups, as disclosed in WO 2010 / 012328.

[0177] Preferably, suitable matrix materials for fluorescent dopants are materials from various classes of substances in addition to the compounds of formula (1). Preferred matrix materials are oligoarylenes (for example 2,2',7,7'-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), in particular oligoarylenes containing fused aromatic groups, oligoarylenevinylenes (for example DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes (for example according to WO 2004 / 081017), hole conducting compounds (for example according to WO 2004 / 058911), electron conducting compounds, in particular ketones, phosphine oxides, sulfoxides etc. (for example according to WO 2005 / 084081 and WO 2005 / 084082), atropisomers (for example according to WO 2006 / 048268), boronic acid derivatives (for example according to WO 2006 / 177052) or benzanthracenes (for example according to WO 2008 / 145239). Particularly preferred matrix materials are selected from the classes of oligoarylenes containing naphthalene, anthracene, benzanthracene and / or pyrene or atropisomers of these compounds, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides. Very particularly preferred matrix materials are selected from the classes of oligoarylenes containing anthracene, benzanthracene, benzophenanthrene and / or pyrene or atropisomers of these compounds. Oligoarylene in the sense of the present invention is used to mean a compound in which at least three aryl or arylene groups are bonded to one another.

[0178] Preferred matrix materials for phosphorescent dopants, in addition to the compounds of formula (1), are aromatic amines, in particular triarylamines, for example according to US 2005 / 0069729, carbazole derivatives (for example CBP, N,N-biscarbazolylbiphenyl) or compounds according to WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527 or WO 2008 / 086851, for example bridged carbazole derivatives according to WO 2011 / 088877 and WO 2011 / 128017, indenocarbazole derivatives according to WO 2010 / 136109 and WO 2011 / 000455, for example according to EP 1617710, EP 1617711, EP 1731584, azacarbazole derivatives according to JP 2005 / 347160, for example indolocarbazole derivatives according to WO 2007 / 063754 or WO 2008 / 056746, ketones, for example according to WO 2004 / 093207 or WO 2010 / 006680, phosphine oxides, sulfoxides and sulfones, oligoarylenes, for example according to WO 2005 / 003253, bipolar matrix materials, for example according to WO 2007 / 137725, for example according to WO silanes according to WO 2005 / 111172, azaboroles or boronic esters according to WO 2006 / 117052, triazine derivatives according to WO 2010 / 15306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes according to EP 652273 or WO 2009 / 062578, aluminium complexes such as BAlq, diazasilol and tetraazasilol derivatives according to WO 2010 / 054729, diazaphosphole derivatives according to WO 2010 / 054730, aluminium complexes such as BAlQ.

[0179] Apart from the cathode, the anode and the layer containing the compound of formula (1), the electronic device may contain further layers. These are, for example, selected from in each case one or more of a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, an exciton blocking layer, an intermediate layer, a charge generation layer (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J.Endo, K. Mori, N. Kawamura, A. Yokoi, J.Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and / or an organic or inorganic p / n junction. However, it must be pointed out that each of these layers does not necessarily have to be present.

[0180] The layer arrangement of the organic electroluminescent device is preferably as follows: Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode. It should be pointed out here again that not all of said layers necessarily have to be present and / or further layers may additionally be present.

[0181] The organic electroluminescent device according to the invention may comprise a plurality of light-emitting layers. In this case, these light-emitting layers particularly preferably have a plurality of maximum emission wavelengths between 380 nm and 750 nm, and as a whole, white light emission occurs, in other words, various light-emitting compounds that can emit fluorescence or phosphorescence and emit blue, yellow, orange or red light can be used in the light-emitting layers. Particularly preferred is a three-layer structure, i.e. a structure having three light-emitting layers, where the three layers exhibit blue, green and orange or red light emission (for basic structures, see, for example, WO 2005 / 011013). It should also be noted that for the generation of white light, individually used emitter compounds that emit in a broad wavelength range may be suitable instead of a plurality of color-emitting emitter compounds.

[0182] Suitable charge transport materials which can be used in the hole-injection or hole-transport layer, or in the electron-blocking layer or in the electron-transport layer of the organic electroluminescent device according to the present invention are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 or other materials used in these layers according to the prior art.

[0183] The materials that can be used for the electron transport layer are all materials that are used according to the prior art as electron transport material in the electron transport layer.Particularly suitable are aluminum complexes, such as Alq3, zirconium complexes, such as Zrq4, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, lactams, boranes, diazaphosphole derivatives and phosphine oxide derivatives.Furthermore, suitable materials are the derivatives of the above-mentioned compounds, as disclosed in JP2000 / 053957, WO2003 / 060956, WO 2004 / 028217, WO 2004 / 080975 and WO 2010 / 072300.

[0184] Preferred hole transport materials which can be used in the hole transport, hole injection or electron blocking layer are indenofluorene amine derivatives (e.g. according to WO 06 / 122630 or WO06 / 100896), the amine derivatives disclosed in EP1661888, hexaazatriphenylene derivatives (e.g. according to WO 01 / 049806), amine derivatives with condensed aromatic rings (e.g. according to US 5,061,569), the amine derivatives disclosed in WO95 / 09147, monobenzoindenofluorene amines (e.g. according to WO08 / 006449), dibenzoindenofluorene amines (e.g. according to WO 07 / 140847), spirobifluoreneamines (for example according to WO 2012 / 034627 or the unpublished EP 12000929.5), fluoreneamines (for example according to the unpublished applications EP 12005369.9, EP 12005370.7 and EP 12005371.5), spirodibenzopyranamines (for example according to the unpublished application EP 11009127.9) and dihydroacridine derivatives (for example according to the unpublished application EP 11007067.9).

[0185] The cathode of the electronic device preferably comprises a metal with a low work function, a metal alloy or a multilayer structure comprising various metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys comprising alkali metals or alkaline earth metals and silver, such as alloys comprising magnesium and silver. In the case of multilayer structures, further metals with relatively high work functions, such as Ag or Al, can also be used in addition to the metals, in which case combinations of metals such as Ca / Ag, Mg / Ag or Ba / Ag are commonly used. It may also be preferable to insert a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal or alkaline earth metal fluorides as well as the corresponding oxides or carbonates (e.g. LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Furthermore, lithium quinolinate (LiQ) can also be used for this purpose. The layer thickness of this layer is preferably 0.5 to 5 nm.

[0186] The anode is preferably a material with a high work function. The anode preferably has a work function higher than 4.5 eV vs. vacuum. Suitable for this purpose are metals with high reduction potentials, such as Ag, Pt or Au. On the other hand, metal / metal oxide electrodes (e.g. Al / Ni / NiO x , Al / PtO x) may also be preferred. For some applications, at least one electrode must be transparent or partially transparent to allow either irradiation of the organic material (organic solar cell) or outcoupling of light (OLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Further preferred are conductive doped organic materials, in particular conductive doped polymers. Furthermore, the anode may consist of several layers, for example an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium.

[0187] During manufacture, the electronic component is appropriately structured (depending on the application), provided with contacts and finally encapsulated, since the lifetime of the component according to the invention is shortened in the presence of water and / or air.

[0188] In a preferred embodiment, the electronic component according to the invention is characterized in that one or more layers are applied by a sublimation process, the material being 10 -5 Less than 10 mbar, preferably less than 10 -6 Vacuum vapor deposition is carried out in a vacuum sublimation unit at an initial pressure of less than 10 mbar. However, the initial pressure can also be much lower, e.g. -7 Even below mbar is possible.

[0189] Likewise preferred organic electroluminescent devices are characterized in that one or more layers are applied by OVPD (organic vapor phase deposition) or carrier gas sublimation, and the materials are -5 It is applied at pressures between mbar and 1 bar. A special case of this process is the OVJP (Organic Vapor Jet Printing) method, where the material is applied directly by a nozzle and thereby structured (see, for example, MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0190] Further preferred organic electroluminescent devices are characterized in that one or more layers are produced from solution, for example by spin-coating, or by any desired printing process, for example by screen printing, flexographic printing, nozzle printing or offset printing, particularly preferably by LITI (light-induced thermal imaging, thermal transfer printing), or inkjet printing.Soluble compounds of formula (1) are required for this purpose.High solubility can be achieved by suitable substitution of the compounds.

[0191] For the preparation of the organic electroluminescent device of the present invention it is further preferred to apply one or more layers from solution and one or more layers by a sublimation process.

[0192] The invention therefore relates to a method for the production of an electronic device according to the invention, characterized in that at least one organic layer is applied by vapor deposition or from solution.

[0193] According to the present invention, electronic devices comprising one or more compounds of formula (1) can be used as light sources for lighting applications, as light sources for medical and / or cosmetic applications (e.g. phototherapy), in display devices.

[0194] The present invention also relates to a formulation comprising at least one compound of formula (1) or at least one of the above mentioned compositions and at least one solvent.

[0195] 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-phenoxytoluene, (-)-phencone, 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, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanoate ... Examples of suitable solvents include benzene, cyclohexylbenzene, 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, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, or mixtures of these solvents.

[0196] The devices comprising the compounds of formula (1) can be used in a very versatile way. Thus, for example, electroluminescent devices comprising one or more compounds of formula (1) can be used in display devices for televisions, mobile phones, computers, cameras. However, the devices can also be used for lighting applications. Furthermore, electroluminescent devices comprising at least one compound of formula (1), for example in OLEDs or OLECs, can be used for medical or cosmetic phototherapy. Thus, a large number of diseases (psoriasis, atopic dermatitis, inflammation, acne, skin cancer, etc.) or the prevention or reduction of skin wrinkles, skin redness, skin aging can be treated. Furthermore, the light-emitting devices can be used to keep drinks, food or food fresh or to sterilize devices (for example medical equipment).

[0197] The present invention therefore also relates to an electronic device, preferably an organic electroluminescent device, very preferably an OLED or OLEC, very particularly preferably an OLED, comprising at least one compound of formula (1) for use in phototherapy in medicine.

[0198] The present invention therefore further relates to an electronic device, preferably an organic electroluminescent device, very preferably an OLED or OLEC, very particularly preferably an OLED, comprising at least one compound of formula (1) for use in the phototherapy of skin diseases.

[0199] The present invention therefore further relates to an electronic device, preferably an organic electroluminescent device, very preferably an OLED or OLEC, very particularly preferably an OLED, comprising at least one compound of formula (1) for use in phototherapy of psoriasis, atopic dermatitis, inflammation, acne, wound healing, skin cancer.

[0200] The present invention therefore furthermore relates to an electronic device, preferably an organic electroluminescent device, very preferably an OLED or OLEC, very particularly preferably an OLED, comprising at least one compound of formula (1) for cosmetic use for the treatment of acne, skin ageing and cellulite.

[0201] The compounds according to the invention or the organic electroluminescent devices according to the invention differ from the prior art by the following surprising advantages:

[0202] 1. The compounds according to the invention are extremely highly suitable for use in the light-emitting layer and show improved performance data compared to compounds from the prior art.

[0203] 2. The compounds according to the invention have a relatively low sublimation temperature, high temperature stability and therefore can be sublimated without decomposition and without residues.Furthermore, they have high oxidation stability and high glass transition temperatures, which are favorable both for processability, for example from solution or from the gas phase, and for use in electronic devices.

[0204] 3. The use of the compounds according to the invention in electronic devices leads to high efficiency, low driving voltage and long lifetime, especially when used as electron transport or electron injection materials as well as matrix materials.

[0205] It should be noted that variations of the embodiments described in the present invention fall within the scope of the present invention. Each feature disclosed in the present invention may be replaced by an alternative feature serving the same, equivalent or similar purpose, unless expressly excluded. Therefore, unless otherwise specified, each feature disclosed in the present invention should be considered as a generic series of examples or equivalent or similar features.

[0206] All features of the present invention may in any event be combined with one another, unless certain features and / or steps are mutually exclusive. This applies in particular to the preferred features of the present invention. Similarly, features of non-essential combinations may be used separately (and not in combination).

[0207] Many features, particularly those of the preferred embodiments of the invention, are inventive in their own right and must be considered as not merely part of an embodiment of the invention. Independent protection may be afforded to these features in addition to or as an alternative to the presently claimed invention.

[0208] The teachings regarding the technical functions disclosed in the present invention can be extracted and combined with other examples.

[0209] The present invention will now be described in more detail by the following examples, without however being limited thereby.

[0210] example: The following syntheses are carried out in anhydrous solvents under a protective gas atmosphere unless otherwise specified. Solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The numbers in brackets for compounds known from the literature refer to the CAS numbers.

[0211] Example 1 Synthesis of 2-dibenzofuran-4-yl-4,6-diphenyl-1,3,5-triazine

[0212] [ka]

[0213] 28.9 g (136 mmol) of dibenzofuran-4-boronic acid, 33 g (124.1 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 78.9 ml (158 mmol) of Na2CO3 (2M solution) are suspended in 120 ml of toluene, 120 ml of ethanol and 100 ml of water. 2.6 g (2.2 mmol) of Pd(PPh3)4 are added to the suspension and the reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is separated, filtered through silica gel, washed three times with 200 ml of water and then evaporated to dryness. The residue is recrystallized from toluene. The yield is 45 g (112 mmol), corresponding to 91% of theory.

[0214] In a similar manner, the following compounds can be obtained:

[0215] [ka]

[0216] [ka]

[0217] Example 2 Synthesis of 2-(8-bromobenzofuran-4-yl)-4,6-diphenyl-1,3,5-triazine

[0218] [ka]

[0219] 16 g (41 mmol) of 2-dibenzofuran-4-yl-4,6-diphenyl-1,3,5-triazine are initially placed in 100 ml of anhydrous dimethylformamide (DMF) together with 8 mg of N-bromosuccinimide (NBS) (45 mmol, 1.1 mol%). The reaction mixture is heated at 120° C. for 24 hours and then the solvent is removed in vacuo. The residue is purified by column chromatography on silica gel with heptane / DCM (2 / 1) as eluent. The yield is 14.6 g (30 mmol), corresponding to 75% of theory.

[0220] In a similar manner, the following compounds can be obtained:

[0221] [ka]

[0222] [ka]

[0223] Example 3 Synthesis of 9-[6-(4,6-diphenyl-1,3,5-triazin-2-yl)dibenzofuran-2-yl]-3-phenyl-9H-carbazole

[0224] [ka]

[0225] A degassed solution of 70 g (147 mmol) of 2-(8-bromobenzofuran-4-yl)-4,6-diphenyl-1,3,5-triazine and 35.7 g (147 mmol) of 3-phenyl-9H-carbazole in 600 ml of toluene is saturated with N2 for 1 h. Then, first, 2.09 ml (8.6 mmol) of P(tBu)3 and then 1.38 g (6.1 mmol) of palladium(II) acetate are added to the solution, and then 17.7 g (185 mmol) of NaOtBu in the solid state are added to the solution. The reaction mixture is heated under reflux for 1 h. After cooling to room temperature, 500 ml of water are carefully added. The aqueous phase is washed with 3 x 50 ml of toluene, dried over MgSO4 and the solvent is removed in vacuum. The crude product is then purified by column chromatography on silica gel with heptane / ethyl acetate (20 / 1). The residue is recrystallized from toluene and finally purified by high vacuum (p=5×10 -6 The mixture is sublimated at 1000 psi (mbar). The yield was 77.7 g (121 mmol), corresponding to 83% of theory.

[0226] In a similar manner, the following compounds can be obtained:

[0227] [ka]

[0228] [ka]

[0229] [ka]

[0230] [ka]

[0231] Example 4 Synthesis of 2-dibenzofuran-4-yl-4-phenylquinazoline

[0232] [ka]

[0233] 23 g (110.0 mmol) of dibenzofuran-4-boronic acid, 29.5 g (110.0 mmol) of 2-chloro-4-phenylquinazoline 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(II) acetate are added to this suspension. The reaction mixture is heated under reflux for 16 hours. After cooling, the organic phase is separated, filtered through silica gel, washed three times with 200 ml of water and then evaporated to dryness. The residue is recrystallized from toluene and from dichloromethane / heptane. The yield is 31 g (85 mmol), corresponding to 79% of theory.

[0234] In a similar manner, the following compounds can be obtained:

[0235] [ka]

[0236] [ka]

[0237] Example 5 Synthesis of 2-(8-bromodibenzofuran-4-yl)-4-phenylquinazoline

[0238] [ka]

[0239] 70.6 g (190.0 mmol) of 2-dibenzofuran-4-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 is then added, the solid is separated and rinsed with ethanol. The residue is recrystallized from toluene. The yield is 59 g (130 mmol), corresponding to 69% of theory.

[0240] In the case of thiophene derivatives, nitrobenzene is used in place of sulfuric acid and elemental bromine is used in place of NBS.

[0241] In a similar manner, the following compounds can be obtained:

[0242] [ka]

[0243] [ka]

[0244] Example 6 Synthesis of 3-phenyl-9-[6-(4-phenylquinazolin-2-yl)dibenzofuran-2-yl]-9H-carbazole

[0245] [ka]

[0246] A degassed solution of 70 g (147 mmol) of 2-(8-bromodibenzofuran-4-yl)-4-phenylquinazoline and 35.7 g (147 mmol) of 3-phenyl-9H-carbazole in 600 ml of toluene is saturated with N2 for 1 h. Then, first, 2.09 ml (8.6 mmol) of P(tBu)3 and then 1.38 g (6.1 mmol) of palladium(II) acetate are added to the solution, followed by 17.7 g (185 mmol) of NaOtBu in the solid state. The reaction mixture is heated under reflux for 1 h. After cooling to room temperature, 500 ml of water are carefully added. The aqueous phase is washed 3 times with 50 ml of toluene, dried over MgSO4 and the solvent is removed in vacuum. The crude product is then purified by column chromatography on silica gel with heptane / ethyl acetate (20 / 1). The residue is recrystallized from toluene and finally purified by high vacuum (p=5×10 -6 The mixture is sublimated at 1000 psi (mbar). The yield is 76 g (119 mmol), corresponding to 81% of theory.

[0247] In a similar manner, the following compounds can be obtained:

[0248] [ka]

[0249] [ka]

[0250] [ka]

[0251] [ka]

[0252] Example 16 OLED fabrication and characterization Data for various OLEDs is presented below in Examples V1-E12 (see Tables 1 and 2).

[0253] Pretreatment of Example V1-E12: Glass plates coated with 50 nm thick structured ITO (indium tin oxide) are coated with 20 nm PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) spin-coated from an aqueous solution, purchased as CLEVIOS® P VP AI 4083 from Heraeus Precious Metals GmbH Germany) for improved processing. These coated glass plates form the substrates on which the OLEDs are applied.

[0254] An OLED basically has the following layer structure: substrate / hole-transporting layer (HTL) / optionally an interlayer (IL) / electron-blocking layer (EBL) / emissive layer (EML) / optionally a hole-blocking layer (HBL) / electron-transporting layer (ETL) / optionally an electron-injecting layer (EIL) and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer. The exact structure of the OLED is shown in Table 1. The materials required for the manufacture of the OLED are shown in Table 3.

[0255] All materials are applied by thermal vapor deposition in a vacuum chamber. Here, the light-emitting layer always consists of at least one matrix material (host material) and a light-emitting dopant (emitter) that is premixed with one or more matrix materials in a certain volumetric proportion by coevaporation. Here, expressions such as IC1:IC3:TEG1 (55%:35%:10%) mean that the material IC1 is present in the layer in a proportion of 55% by volume, IC3 in a proportion of 35% by volume and TEG1 in a proportion of 10% by volume. Similarly, the electron-transporting layer may also consist of a mixture of two materials.

[0256] OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A) as a function of luminance, calculated from the current / voltage / luminance characteristic line (IUL characteristic line) assuming Lambertian emission characteristics, the power efficiency (measured in Im / W) and the external quantum efficiency (EQE, measured in percent) are measured. The electroluminescence spectrum is measured at a luminance of 1000 cd / m 2 The CIE 1931 x and y color coordinates are calculated from this. The term U1000 in Table 2 means a luminance of 1000 cd / m 2 The voltage required for CE1000 and PE1000 is 1000cd / m 2 Finally, the EQE1000 achieves a driving luminance of 1000cd / m 2 The external quantum efficiency at 1000 cd / m is shown. The lifetime LT is defined as the time it takes for the luminance to decrease from the initial luminance to a certain ratio L1 when operating at a constant current. L0;j0=4000 cd / m 2 and L1=70% means that the indicated lifetime is for an initial luminance of 4000cd / m 2 from 2800 cd / m 2 Similarly, L0;j0=20mA / cm 2 and L1=80%, the luminance is 20mA / cm 2 This means that after a time LT of operation, the LED will drop to 80% of its initial brightness.

[0257] The data for the different OLEDs are summarized in Table 2. Examples V1 to V5 are comparative examples according to the prior art, while Examples E1 to E12 show data for OLEDs according to the invention.

[0258] Some examples are described in more detail below to demonstrate the advantages of the OLED according to the present invention.

[0259] Use of the mixtures according to the invention in the emissive layer of a phosphorescent OLED When used as matrix materials in phosphorescent OLEDs, the materials according to the invention provide a significant improvement in terms of power efficiency compared to the prior art. By using the compounds EG1 and EG2 according to the invention in combination with the green-emitting dopant TEG1, an increase in power efficiency of up to 20% can be observed compared to the prior art (examples E1 vs. V1, E2 vs. V2, V3, V4, V5). Furthermore, the compounds according to the invention provide a significant improvement in terms of device lifetime. Thus, the lifetime of device E2, which contains the matrix EG2 according to the invention, is improved from 125 to 210 hours compared to prior art V4, which contains SdT4 (L0; j0=20 mA / cm2). 2 , L1=80%).

[0260] [Table 1]

[0261] [Table 2]

[0262] [Table 3-1]

[0263] [Table 3-2]

[0264] [Table 3-3]

[0265] [Table 3-4]

Claims

1. Compound of general formula (1): 【Chemistry 1】 where the following applies to the symbols and indices used: ETG is selected from the group consisting of triazine, pyrimidine, pyrazine, quinazoline, benzimidazole, quinoline, isoquinoline and naphthyridine, and is selected from the group consisting of one or more groups R １ may be the same or different at each occurrence; W is one or more groups R １ and selected from indenocarbazole and indolocarbazole, which may be the same or different at each occurrence: wherein indenocarbazole and indolocarbazole are bonded to ring atom C of formula (1) via a nitrogen atom; V is O; Y is an aromatic or heteroaromatic ring structure having 5 to 60 ring atoms; n is either 0 or 1, where n=0 means that ETG and ring B are directly bonded to each other via a single bond; r is an integer from 0 or 1; s is an integer from 0 to 1; R for ETG １ are the same or different for each occurrence, H, D, F, Cl, Br, I, N (R ２ ) ２ , C.N., N.O. ２ , Si(R ２ ) ３ , B(OR ２ ) ２ , C(=O)R ２ , P(=O)(R ２ ) ２ , S(=O)R ２ , S(=O) ２ R ２ , OSO ２ R ２ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 C atoms (each of which is represented by one or more groups R ２ and may be substituted by one or more non-adjacent CH ２ The group is R ２ C=CR ２ , C≡C, Si(R ２ ) ２ , Ge(R ２ ) ２ , Sn(R ２ ) ２ , C=O, C=S, C=Se, C=NR ２ , P(=O)(R ２ ), SO, SO ２ , N.R. ２ , O, S or CONR ２ where one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ or in each case one or more radicals R ２ an aromatic or heteroaromatic ring structure having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R ２ an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more groups R ２ or a combination of two or more of these groups; R against W １ are the same or different for each occurrence, H, D, F, Cl, Br, I, N (R ２ ) ２ , C.N., N.O. ２ , Si(R ２ ) ３ , B(OR ２ ) ２ , C(=O)R ２ , P(=O)(R ２ ) ２ , S(=O)R ２ , S(=O) ２ R ２ , OSO ２ R ２ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 C atoms (each of which is represented by one or more groups R ２ and may be substituted by one or more non-adjacent CH ２ The group is R ２ C=CR ２ , C≡C, Si(R ２ ) ２ , Ge(R ２ ) ２ , Sn(R ２ ) ２ , C=O, C=S, C=Se, C=NR ２ , P(=O)(R ２ ), SO, SO ２ , N.R. ２ , O, S or CONR ２ where one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ or in each case one or more radicals R ２ an aromatic or heteroaromatic ring structure having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R ２ an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more groups R ２ or a combination of two or more of these groups; R ２ are the same or different for each occurrence, H, D, F, Cl, Br, I, N (R ３ ) ２ , C.N., N.O. ２ , Si(R ３ ) ３ , B(OR ３ ) ２ , C(=O)R ３ , P(=O)(R ３ ) ２ , S(=O)R ３ , S(=O) ２ R ３ , OSO ２ R ３ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 C atoms (each of which is one or more R ３ groups, and may be substituted with one or more non-adjacent CH ２ The group is R ３ C=CR ３ , C≡C, Si(R ３ ) ２ , Ge(R ３ ) ２ , Sn(R ３ ) ２ , C=O, C=S, C=Se, C=NR ３ , P(=O)(R ３ ), SO, SO ２ , N.R. ３ , O, S or CONR ３ where one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO ２ or in each case one or more radicals R ３ an aromatic or heteroaromatic ring structure having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R ３ an aryloxy, arylalkoxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more groups R ３ or a combination of two or more of these groups; R ３ is identical or different at each occurrence and is H, D, F, an aliphatic, aromatic and / or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, where, in addition, one or more H atoms may be replaced by F; R ４ , R ５ are the same or different for each occurrence, H, D, F, Cl, Br, I, N (R ２ ) ２ , C.N., N.O. ２ , Si(R ２ ) ３ , B(OR ２ ) ２ , C(=O)R ２ , P(=O)(R ２ ) ２ , S(=O)R ２ , S(=O) ２ R ２ , OSO ２ R ２ , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, alkylalkoxy or thioalkoxy group having 3 to 40 C atoms.

2. 2. The compound of claim 1, wherein Y is a phenylene bridge.

3. The compound according to claim 1, wherein n is 0, where n=0 means that ETG and ring B are directly bonded to each other via a single bond.

4. The compound according to any one of claims 1 to 3, having the general formula (2): 【Chemistry 2】 During the ceremony, X is N or CR １ where at least two of the five groups X in ring A are N atoms.

5. 5. The compound according to claim 4, wherein three of the five groups X in ring A are N atoms.

6. 6. The compound according to claim 4 or 5, characterized in that the compound has the following formula: 【Chemistry 3】

7. 6. The compound according to claim 4 or 5, characterized in that the compound has the general formula (6). 【Chemistry 4】

8. The compound according to any one of claims 1 to 7, characterized in that the compound has the general formula (7): 【Chemistry 5】

9. The group W is a group of the formula (W-9) to (W-14), where Tp and Tq are N(R ２ 9. The compound according to claim 1 , 【Chemistry 6】 U is CR 1 ; U' is CR 2 ; p is 1; q is 1; Here, the dashed line indicates the bond from group W to ring C.

10. Compounds according to any one of claims 1 to 8, characterized in that the group W is a group of the formulae (W-21) to (W-26); 【Chemistry 7】 U is CR 1 ; U' is CR 2 ; Here, the dashed line indicates the bond from group W to ring C.

11. A composition comprising at least one compound according to any one of claims 1 to 10 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials and hole blocking materials.

12. The composition of claim 11, wherein the additional compound is a host material or a matrix material.

13. 13. The composition of claim 11 or 12, wherein the additional compound has a band gap of 2.5 eV or more.

14. 13. The composition of claim 11 or 12, wherein the additional compound has a band gap of 3.5 eV or more.

15. A formulation comprising at least one compound according to any one of claims 1 to 10 or at least one composition according to any one of claims 11 to 14 and at least one solvent.

16. Use of at least one compound according to any one of claims 1 to 10 or at least one composition according to any one of claims 11 to 14 in an electronic device.

17. An electronic device comprising at least one compound according to any one of claims 1 to 10 or at least one composition according to any one of claims 11 to 14.

18. 18. The electronic device according to claim 17, characterized in that it is selected from the group consisting of organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic electroluminescent devices, organic solar cells (O-SCs), organic optical inspection devices, and organic photoreceptors.

19. 19. The electronic device according to claim 17 or 18, characterized in that it is an organic electroluminescent device, which is also selected from organic light emitting transistors (OLETs), organic field quenched devices (OFQDs), organic light emitting electrochemical cells (OLECs, LEECs, LECs), organic laser diodes (O-lasers) and organic light emitting diodes (OLEDs).

20. Method for producing an electronic device according to any one of claims 17 to 19, characterized in that at least one organic layer is applied by vapor deposition or from solution.

21. 20. The electronic device of claim 19 for use in medical applications for light therapy.

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