Patent Publication Number: US-11639339-B2

Title: Materials for organic electroluminescent devices

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a U.S. national phase application under 35 U.S.C. § 371 of International Application No. PCT/EP2018/082161, filed on Nov. 22, 2018, which claims priority to European Patent Application No. 17203571.9, filed Nov. 24, 2017, the disclosures of each of which are hereby being incorporated by reference in their entirety for all purposes. 
     The present invention relates to a compound of the formula (1), to the use of the compound in an electronic device, and to an electronic device comprising a compound of the formula (1). The present invention furthermore relates to a process for the preparation of a compound of the formula (1) and to a formulation comprising one or more compounds of the formula (1). 
     The development of functional compounds for use in electronic devices is currently the subject of intensive research. The aim is, in particular, the development of compounds with which improved properties of electronic devices in one or more relevant points can be achieved, such as, for example, power efficiency and lifetime of the device as well as colour coordinates of the emitted light. 
     In accordance with the present invention, the term electronic device is taken to mean, inter alia, organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs). 
     Of particular interest is the provision of compounds for use in the last-mentioned electronic devices called OLEDs. The general structure and the functional principle of OLEDs are known to the person skilled in the art and are described, for example, in U.S. Pat. No. 4,539,507. 
     Further improvements are still necessary with respect to the performance data of OLEDs, in particular with a view to broad commercial use, for example in display devices or as light sources. Of particular importance in this connection are the lifetime, the efficiency and the operating voltage of the OLEDs and as well as the colour values achieved. In particular, in case of blue-emitting OLEDs, there is potential for improvement with respect to the lifetime and the efficiency of the devices. 
     An important starting point for achieving the said improvements is the choice of the emitter compound and of the host compound employed in the electronic device. 
     Blue-fluorescent emitters known from the prior art are a multiplicity of compounds. Arylamines containing one or more condensed aryl groups like pyrene, anthracene or chrysene are known from the prior, for example in accordance with US 20160218294 A1, JP 2014177441, US 20110215715, WO2011071507 and US 20140117322. 
     However, there is still a need for further fluorescent emitters, especially blue-fluorescent emitters, which may be employed in OLEDs and lead to OLEDs having good properties in terms of lifetime, colour emission and efficiency. 
     Furthermore, it is known that an OLED may comprise different layers, which may be applied either by vapour deposition in a vacuum chamber or by processing from a solution. The processes based on vapour deposition lead to good results but such processes are complex and expensive. Therefore, there is a need for OLED materials that can be easily and reliably processed from solution. In this case, the materials should have good solubility properties in the solution that comprises them. Additionally, the OLED materials that are processed from a solution should be able to orientate themselves in the deposited film to improve the overall efficiency of the OLED. The term orientation means here the horizontal orientation of the transition dipole or the horizontal molecular orientation of the compounds, as explained in Zhao et al., Horizontal molecular orientation in solution-processed organic light-emitting diodes, Appl. Phys. Lett. 106063301, 2015. 
     The present invention is thus based on the technical object of providing compounds which are suitable for use in electronic devices, such as OLEDs, more particularly as blue-fluorescent emitters or matrix materials and, which are suitable for vacuum processing or for solution processing, more particularly for solution processing. 
     In investigations on novel compounds for use in electronic devices, it has now been found, that compounds of formula (1) as defined below are eminently suitable for use in electronic devices. In particular, they achieve one or more, preferably all, of the above-mentioned technical objects. 
     The invention thus relates to compounds of formula (1), 
                         
where the following applies to the symbols and indices used:
 
     Ar 4  stands for a croup of formula (Ar 4 -1), 
                         
where the dashed bond in formula (Ar4-1) indicates the bonding to the structure of formula (1);
         G is a condensed aryl group having 10 to 50 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 ;   Ar 1 , Ar 2  and Ar 3  stand on each occurrence, identically or differently, for Ar 4 , or for 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 R 3 ;       

     Ar S  is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case also be substituted by one or more radicals R 3 ; 
     Ar 5 , Ar 6  stand on each occurrence, identically or differently, for an aryl or heteroaryl group having 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R 4 ; 
     X stands for CR 1  or N; or X stands for C, if it is bonded to Ar 5 , Ar 6 , R 4  or to an adjacent fluorene derivative unit; 
     R, R 0 , R 1 , R 2 , R 3 , R 4  stand on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar 7 ) 2 , C(═O)Ar 7 , P(═O)(Ar 7 ) 2 , S(═O)Ar 7 , S(═O) 2 Ar 7 , NO 2 , Si(R 5 ) 3 , B(OR 5 ) 2 , OSO 2 R 5 , a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 5 , where in each case one or more non-adjacent CH 2  groups may be replaced by R 5 C═CR 5 , CEO, Si(R 5 ) 2 , Ge(R 5 ) 2 , Sn(R 5 ) 2 , C═O, C═S, C═Se, P(═O)(R 5 ), SO, SO 2 , O, S or CONR 5  and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 , or an aryloxy groups having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 5 , where two adjacent substituents R, two adjacent substituents R 0 , two adjacent substituents R 1 , two adjacent substituents R 2 , two adjacent substituents R 3  and/or two adjacent substituents R 4 , may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 5 ; 
     R 5  stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar 7 ) 2 , C(═O)Ar 7 , P(═O)(Ar 7 ) 2 , S(═O)Ar 7 , S(═O) 2 Ar 7 , NO 2 , Si(R 6 ) 3 , B(OR 6 ) 2 , OSO 2 R 6 , a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 6 , where in each case one or more non-adjacent CH 2  groups may be replaced by R 6 C═CR 6 , C≡O, Si(R 6 ) 2 , Ge(R 6 ) 2 , Sn(R 6 ) 2 , C═O, C═S, C═Se, P(═O)(R 6 ), SO, SO 2 , O, S or CONR 6  and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 6 , or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 6 , where two adjacent substituents R 5  may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 6 ; 
     Ar 7  is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case also be substituted by one or more radicals R 6 ; 
     R 6  stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 C atoms, where in each case one or more non-adjacent CH 2  groups may be replaced by SO, SO 2 , O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 C atoms;
         n is equal to 0 or 1;   r is equal to 0, 1 or 2;   m, q are, identically or differently, an integer selected from 1 to 10;   p, s are on each occurrence, identically or differently, an integer selected from 0 to 10;   with the proviso that, if the group G is a pyrene group, then the compound of formula (1) bears at least one group R, R 0 , R 2  or R 3 , which stands for a straight-chain alkyl group having 3 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 6 .       

     Adjacent substituents in the sense of the present invention are substituents which are bonded to atoms which are linked directly to one another or which are bonded to the same atom. 
     The fact that Ar 1 , Ar 2  and Ar 3  stand on each occurrence, identically or differently, for Ar 4  or for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, means that Ar 1 , Ar 2  and Ar 3  correspond, independently, to a group of formula (Ar4-1) or to another aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms. 
     Furthermore, the following definitions of chemical groups apply for the purposes of the present application: 
     An aryl group in the sense of this invention contains 6 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, more preferably 6 to 20 aromatic ring atoms; a heteroaryl group in the sense of this invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms are preferably selected from N, O and S. This represents the basic definition. If other preferences are indicated in the description of the present invention, for example with respect to the number of aromatic ring atoms or the heteroatoms present, these apply. 
     An aryl group or heteroaryl group here is taken to mean either a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine or thiophene, or a condensed (annellated) aromatic or heteroaromatic polycycle, for example naphthalene, phenanthrene, quinoline or carbazole. A condensed (annellated) aromatic or heteroaromatic polycycle in the sense of the present application consists of two or more simple aromatic or heteroaromatic rings condensed with one another. 
     An aryl or heteroaryl group, which may in each case be substituted by the above-mentioned radicals and which may be linked to the aromatic or heteroaromatic ring system via any desired positions, is taken to mean, in particular, groups derived from 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, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, 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-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. 
     An aryloxy group in accordance with the definition of the present invention is taken to mean an aryl group, as defined above, which is bonded via an oxygen atom. An analogous definition applies to heteroaryloxy groups. 
     An aromatic ring system in the sense of this invention contains 6 to 60 C atoms in the ring system, preferably 6 to 40 C atoms, more preferably 6 to 20 C atoms. A heteroaromatic ring system in the sense of this invention contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the sense of this invention is intended to be taken to mean a system which does not necessarily contain only aryl or heteroaryl groups, but instead in which, in addition, a plurality of aryl or heteroaryl groups may be connected by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as, for example, an spa-hybridised C, Si, N or O atom, an sp 2 -hybridised C or N atom or an sp-hybridised C atom. Thus, for example, systems such as 9,9′-spirobifluorene, 9,9′-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are also intended to be taken to be aromatic ring systems in the sense of this invention, as are systems in which two or more aryl groups are connected, for example, by a linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group. Furthermore, systems in which two or more aryl or heteroaryl groups are linked to one another via single bonds are also taken to be aromatic or heteroaromatic ring systems in the sense of this invention, such as, for example, systems such as biphenyl, terphenyl or diphenyltriazine. 
     An aromatic or heteroaromatic ring system having 5-60 aromatic ring atoms, which may in each case also be substituted by radicals as defined above and which may be linked to the aromatic or heteroaromatic group via any desired positions, is taken to mean, in particular, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, 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, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 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-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, or combinations of these groups. 
     For the purposes of the present invention, a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, in which, in addition, individual H atoms or CH 2  groups may be substituted by the groups mentioned above under the definition of the radicals, is preferably taken to mean the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, neopentyl, 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 or octynyl. An alkoxy or thioalkyl group having 1 to 40 C atoms is preferably taken to mean 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-heptylthio, 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. 
     The formulation that two or more radicals may form a ring with one another is, for the purposes of the present application, intended to be taken to mean, inter alia, that the two radicals are linked to one another by a chemical bond. This is illustrated by the following schemes: 
     
       
         
         
             
             
         
       
     
     Furthermore, however, the above-mentioned formulation is also intended to be taken to mean that, in the case where one of the two radicals represents hydrogen, the second radical is bonded at the position to which the hydrogen atom was bonded, with formation of a ring. This is illustrated by the following scheme: 
     
       
         
         
             
             
         
       
     
     In accordance with a preferred embodiment, the index s is an integer selected from 1 to 10. More preferably, the index s in an integer selected from 1 to 5. Particularly preferably, the index s in an integer selected from 1, 2 and 3. Very particularly preferably, the index s is equal to 1. 
     The group Ar S  is preferably, identically or differently on each occurrence, selected from aromatic or heteroaromatic ring systems having 6 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R 3 . More preferably, the group Ar S  is, identically or differently on each occurrence, selected from benzene, biphenyl, naphthalene, fluorene, dibenzofuran, dibenzothiophene or carbazole, each of which may be substituted by one or more radicals R 3 . Particularly preferably, the group Ar S  is, identically or differently on each occurrence, selected from benzene or biphenyl, each of which may be substituted by one or more radicals R 3 . 
     Examples of particularly suitable groups Ar S  are the groups of formulae (Ar S -1) to (Ar S -17) below: 
                                                             
where the dashed bonds indicate the bonds to the group G and to the adjacent diarylamine group —NAr 1 Ar 2  or —NAr 3 Ar 4 , and where the groups (Ar S -1) to (Ar S -17) may be substituted at each free position by a group R 3 .
 
     According to the present invention, the index r is equal to 0, 1 or 2. When r is equal to 0, then the corresponding group Ar S  is absent and the groups adjacent to Ar S  are directly bonded with one another. In accordance with a preferred embodiment, the index r is 0. In accordance with another preferred embodiment, the index r is 1. 
     In accordance with a preferred embodiment, the compounds of formula (1) are selected from the compounds of formulae (2) to (5), preferably from compounds of formulae (2), (3) and (4), 
                         
where the symbols and indices have the same meaning as above.
 
     Preferably, the groups Ar 1 , Ar 2  and Ar 3  stand on each occurrence, identically or differently, for Ar 4 , or for an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R 3 . More preferably, the groups Ar 1 , Ar 2  and Ar 3  stand on each occurrence, identically or differently, for Ar 4 , or for benzene, biphenyl, fluorene, terphenyl, quaterphenyl, dibenzothiophene, dibenzofuran or carbazole; which may in each case be substituted by one or more radicals R 3 . 
     In accordance with a preferred embodiment, the groups Ar 5  and Ar 6  are selected, identically or differently, from the group consisting of the groups of formulae (Ar5-1) to (Ar5-26), 
                                                                               
where
 
     the dashed bonds indicate the bonding to the adjacent groups in formula (1); 
     the groups of formulae (Ar5-1) to (Ar5-26) may be substituted at each free position by a group R 4 , which has the same meaning as above; and E 1  is selected from —B(R 0 —), —C(R 0 ) 2 —, —C(R 0 ) 2 —C(R 0 ) 2 —, —Si(R 0 ) 2 —, —C(═O)—, —C(═NR 0 )—, —C═(C(R 0 )) 2 —, —O—, —S—, —S(═O)—, —SO 2 —, —N(R 0 )—, —P(R 0 )— and —P((═O)R 0 )—, where the substituent R 0  has the same meaning as above. 
     Among groups of formulae (Ar5-1) to (Ar5-26), groups of formulae (Ar5-1), (Ar5-2), (Ar5-3), (Ar5-18), (Ar5-19), (Ar5-20), (Ar5-21), (Ar5-22) and (Ar5-23) are preferred. 
     In accordance with a very preferred embodiment, the groups Ar 5  and Ar 6  are selected, identically or differently, from the group consisting of the groups of formulae (Ar5-27) to (Ar5-35), 
                                           
where
 
     the dashed bonds indicate the bonding to the adjacent groups depicted in formula (1); 
     the groups of formulae (Ar5-27) to (Ar5-35) may be substituted at each free position by a group R 4 , which has the same meaning as above; and the substituent E 1  in formulae (Ar5-28) to (Ar5-30) has the same meaning as above. 
     In accordance with a preferred embodiment, the group Ar 4  is selected from the groups of formulae (Ar4-2) to (Ar4-6), 
                         
where the dashed bond indicates the bonding to the structure of formula (1) and where the symbols and indices X, E 1 , R, R 0 , R 4 , Ar 6 , m, p, q and s have the same meaning as above.
 
     In accordance with a very preferred embodiment, the group Ar 4  is selected from the groups of formulae (Ar4-2-1) to (Ar4-6-1), 
                         
where the dashed bond indicates the bonding to the structure of formula (1) and where the symbols and indices have the same meaning as above.
 
     In accordance with a particularly preferred embodiment, the group Ar 4  is selected from the groups of formulae (Ar4-2-2) to (Ar4-6-2), 
                         
where the dashed bond indicates the bonding to the structure of formula (1) and where the symbols and indices have the same meaning as above.
 
     In accordance with a preferred embodiment, at least two adjacent groups R 0  and/or two adjacent groups R, in formulae (Ar4-1), (Ar4-2) to (Ar4-6), (Ar4-2-1) to (Ar4-2-6) and (Ar4-2-2) to (Ar4-2-6) stand for a straight-chain alkyl group having 3 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 6 . More preferably, at least two adjacent groups R 0  and/or two adjacent groups R in formulae (Ar4-1), (Ar4-2) to (Ar4-6), (Ar4-2-1) to (Ar4-2-6) and (Ar4-2-2) to (Ar4-2-6) stand for a straight-chain alkyl group having 3 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, each of which may be substituted by one or more radicals R 6 . Particularly preferably, at least two adjacent groups R 0  and/or two adjacent groups R in formulae (Ar4-1), (Ar4-2) to (Ar4-6), (Ar4-2-1) to (Ar4-2-6) and (Ar4-2-2) to (Ar4-2-6) stand for a straight-chain alkyl group having 3 to 10, preferably 6 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10, preferably 6 to 10 C atoms, each of which may be substituted by one or more radicals R 6 . 
     In accordance with a preferred embodiment, the indices m and q are on each occurrence, identically or differently, equal to 1, 2 or 3. 
     In accordance with a preferred embodiment, Ar 6  stands on each occurrence, identically or differently, for an aryl group having 6 to 14 aromatic ring atoms, which may in each case be substituted by one or more radicals R 4 . More preferably, Ar 6  stands on each occurrence, identically or differently, for a benzene, naphthalene, biphenyl or fluorene group, which may in each case be substituted by one or more radicals R 4 . 
     In accordance with a preferred embodiment, the index p is on each occurrence, identically or differently, equal to 0 or 1. More preferably, the index p is equal to 0. In this case, the corresponding Ar 6  is absent and the groups adjacent to Ar 6  are directly bonded with one another. 
     In accordance with a preferred embodiment, the group G is selected from the group consisting of naphthalene, anthracene, phenanthrene, tetracene, chrysene, benzophenanthracene, pyrene, perylene, triphenylene, benzopyrene, fluoranthene, each of which may be substituted by one or more radicals R 2  at any free positions. More preferably, the group G is selected from pyrene, chrysene and anthracene. 
     In accordance with a preferred embodiment, the index n is equal to 1 and the group G is selected from the group consisting of the groups of formulae (G-1) to (G-11), 
                                           
where
 
     the dashed bonds indicate the bonding to the adjacent groups in formula (1); and the groups of formulae (G-1) to (G-11) may be substituted at each free position by a group R 2 , which has the same meaning as above. 
     More preferably, the group G is selected from the groups of formulae (G-12) to (G-23). 
                                                             
where the dashed bonds indicate the bonding to the adjacent groups as depicted in formula (1);
         and where R 2  has the same meaning as above.       

     Compound according to one or more of the preceding claims, characterized in that the group G is selected from the groups of formulae (G-24) to (G-39), 
                                                             
where the dashed bonds indicate the bonding to the adjacent groups as depicted in formula (1) and where R 2  has the same meaning as above.
 
     In accordance with a preferred embodiment, the group R 2  stands on each occurrence, identically or differently, for H, D, F, a straight-chain alkyl group having 1 to 10 C atoms or branched or a cyclic alkyl groups having 3 to 10 C atoms, each of which may be substituted by one or more radicals R 5 , an aromatic ring systems having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 , where two adjacent substituents R 2  may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 5 , where R 5  has the same meaning as above. 
     In accordance with a preferred embodiment, the groups R 1 , R 3  and R 4  stand on each occurrence, identically or differently, for H, D, F, CN, N(Ar 7 ) 2 , a straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, preferably 1 to 10 C atoms, or branched or a cyclic alkyl or alkoxy groups having 3 to 20 C atoms, preferably 3 to 10 C atoms, each of which may be substituted by one or more radicals R 5 , where in each case one or more non-adjacent CH 2  groups may be replaced by R 5 C═CR 5 , C═O, C═S, SO, SO 2 , O or S and where one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring systems having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 , where two adjacent substituents R 1 , two adjacent substituents R 3  and/or two adjacent substituents R 4 , may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 5 . 
     In accordance with a preferred embodiment, the group R 5  stands on each occurrence, identically or differently, for H, D, F, CN, N(Ar 7 ) 2 , a straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, preferably 1 to 10 C atoms or branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, preferably 3 to 10 C atoms, each of which may be substituted by one or more radicals R 6 , where in each case one or more non-adjacent CH 2  groups may be replaced by R 6 C═CR 6 , C═O, C═S, SO, SO 2 , O or S and where one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring systems having 5 to 40, preferably 5 to 30, more preferably 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R 6 , where two adjacent substituents R 5  may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 6 . 
     In accordance with the preferred embodiment, Ar 7  is an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R 6 . 
     In accordance with a preferred embodiment, the group R 6  stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl group having 1 to 10 C atoms or branched or cyclic alkyl group having 3 to 10 C atoms, or an aromatic or heteroaromatic ring system having 5 to 24 C atoms. 
     The following compounds are examples of compounds of the formula (1): 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     The compounds according to the invention can be prepared by synthesis steps known to the person skilled in the art, such as, for example, bromination, Suzuki coupling, Ullmann coupling, Hartwig-Buchwald coupling, etc. An example of a suitable synthesis process is depicted in general terms in Schemes 1 and 2 below. 
     
       
         
         
             
             
         
       
     
                         
where in Schemes 1 and 2, the group G correspond to a group G as defined above, the group Ar is a group Ar 4  as defined above or another aromatic or heteroaromatic group, and the group X is a halogen atom (like Br, Cl, I) or another leaving group.
 
     The compounds of formula (1) may be synthesized as described above: 
     At least one diarylamine group comprising at least one group Ar 4  as defined above is bonded via a C—N coupling to a condensed aryl group G as defined above, substituted with at least one halogen or another leaving group (for example via a Hartwig-Buchwald coupling). 
     The present invention therefore relates to a process for the synthesis of the compounds according to the invention, in which at least one diarylamine group comprising at least one group Ar 4  as defined above is bonded via a C—N coupling to a condensed aryl group G as defined above, substituted with at least one halogen or another leaving group. 
     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-phenoxytoluene, (−)-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, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, 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. 
     The present invention therefore 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, in particular a phosphorescent dopant, and/or a further matrix material. Suitable emitting compounds and further matrix materials are indicated below in connection with the organic electroluminescent device. This further compound may also be polymeric. 
     The compounds and mixtures according to the invention are suitable for use in an electronic device. An electronic device here is taken to mean a device which comprises at least one layer which comprises at least one organic compound. However, the component here may also comprise inorganic materials or also layers built up entirely from inorganic materials. 
     The present invention therefore furthermore relates to the use of the compounds or mixtures according to the invention in an electronic device, in particular in an organic electroluminescent device. 
     The present invention again furthermore relates to an electronic device comprising at least one of the compounds or mixtures according to the invention mentioned above. The preferences stated above for the compound also apply to the electronic devices. 
     The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic dye-sensitised solar cells, 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” (D. M. Koller et al.,  Nature Photonics  2008, 1-4), preferably organic electroluminescent devices (OLEDs, PLEDs), in particular phosphorescent OLEDs. 
     The organic electroluminescent device comprises a cathode, an 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. It is likewise possible for interlayers, which have, for example, an exciton-blocking function, to 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 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). These can be fluorescent or phosphorescent emission layers or hybrid systems, in which fluorescent and phosphorescent emission layers are combined with one another. 
     The compound according to the invention in accordance with the embodiments indicated above can be employed in various layers, depending on the precise structure and on the substitution. Preference is given to an organic electroluminescent device comprising a compound of the formula (1) or in accordance with the preferred embodiments as fluorescent emitters, emitters showing TADF (Thermally Activated Delayed Fluorescence), matrix material for fluorescent emitters. Particularly preferred is an organic electroluminescent device comprising a compound of the formula (1) or in accordance with the preferred embodiments as fluorescent emitters, more particularly blue-emitting fluorescent compound. 
     The compounds of formula (1) can also be employed in an electron-transport layer and/or in an electron-blocking or exciton-blocking layer and/or in a hole-transport layer, depending on the precise substitution. The preferred embodiments indicated above also apply to the use of the materials in organic electronic devices. 
     The compound according to the invention is particularly suitable for use as blue-emitting emitter compound. The electronic device concerned may comprise a single emitting layer comprising the compound according to the invention or it may comprise two or more emitting layers. The further emitting layers here may comprise one or more compounds according to the invention or alternatively other compounds. 
     If the compound according to the invention is employed as a fluorescent emitting compound in an emitting layer, it is preferably employed in combination with one or more matrix materials. A matrix material here is taken to mean a material which is present in the emitting layer, preferably as the principal component, and which does not emit light on operation of the device. 
     The proportion of the emitting compound in the mixture of the emitting layer is between 0.1 and 50.0%, preferably between 0.5 and 20.0%, particularly preferably between 1.0 and 10.0%. Correspondingly, the proportion of the matrix material or matrix materials is between 50.0 and 99.9%, preferably between 80.0 and 99.5%, particularly preferably between 90.0 and 99.0%. 
     The specifications of the proportions in % are, for the purposes of the present application, taken to mean % by vol. if the compounds are applied from the gas phase and % by weight if the compounds are applied from solution. 
     Preferred matrix materials for use in combination with fluorescent emitting compounds are selected from the classes of the oligoarylenes (for example 2,2′,7,7′-tetraphenylspirobifluorene in accordance with EP 676461 or dinaphthylanthracene), in particular the oligoarylenes containing condensed aromatic groups, the oligoarylenevinylenes (for example DPVBi or spiro-DPVBi in accordance with EP 676461), the polypodal metal complexes (for example in accordance with WO 2004/081017), the hole-conducting compounds (for example in accordance with WO 2004/058911), the electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides, etc. (for example in accordance with WO 2005/084081 and WO 2005/084082), the atropisomers (for example in accordance with WO 2006/048268), the boronic acid derivatives (for example in accordance with WO 2006/117052) or the benzanthracenes (for example in accordance with WO 2008/145239). Particularly preferred matrix materials are selected from the classes of the oligoarylenes, comprising naphthalene, anthracene, benzanthracene and/or pyrene or atropisomers of these compounds, the oligoarylenevinylenes, the ketones, the phosphine oxides and the sulfoxides. Very particularly preferred matrix materials are selected from the classes of the oligoarylenes, comprising anthracene, benzanthracene, benzophenanthrene and/or pyrene or atropisomers of these compounds. An oligoarylene in the sense of this invention is intended to be taken to mean a compound in which at least three aryl or arylene groups are bonded to one another. 
     Particularly preferred matrix materials for use in combination with the compounds of the formula (1) in the emitting layer are depicted in the following table. 
     
       
         
           
               
             
               
                   
               
             
            
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
         
       
     
     If the compound according to the invention is employed as a fluorescent emitting compound in an emitting layer, it may be employed in combination with one or more other fluorescent emitting compounds. 
     Preferred fluorescent emitters, besides the compounds according to the invention, are selected from the class of the arylamines. An arylamine in the sense of this invention is taken to mean a compound which contains three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to the nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a condensed ring system, particularly preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenediamines. An aromatic anthracenamine is taken to mean a compound in which one diarylamino group is bonded directly to an anthracene group, preferably in the 9-position. An aromatic anthracenediamine is taken to mean a compound in which two diarylamino groups are bonded directly to an anthracene group, preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediamines are defined analogously thereto, where the diarylamino groups are preferably bonded to the pyrene in the 1-position or in the 1,6-position. Further preferred emitters are indenofluorenamines or indenofluorenediamines, for example in accordance with WO 2006/108497 or WO 2006/122630, benzoindenofluorenamines or benzoindenofluorenediamines, for example in accordance with WO 2008/006449, and dibenzoindenofluorenamines or dibenzoindenofluorenediamines, for example in accordance with WO 2007/140847, and the indenofluorene derivatives containing condensed aryl groups which are disclosed in WO 2010/012328. Still further preferred emitters are benzanthracene derivatives as disclosed in WO 2015/158409, anthracene derivatives as disclosed in WO 2017/036573, fluorene dimers like in WO 2016/150544 or phenoxazine derivatives as disclosed in WO 2017/028940 and WO 2017/028941. Preference is likewise given to the pyrenarylamines disclosed in WO 2012/048780 and WO 2013/185871. Preference is likewise given to the benzoindenofluorenamines disclosed in WO 2014/037077, the benzofluorenamines disclosed in WO 2014/106522 and the indenofluorenes disclosed in WO 2014/111269 or WO 2017/036574. 
     Examples of preferred fluorescent emitting compounds, besides the compounds according to the invention, which can be used in combination with the compounds of the invention in an emitting layer or which can be used in another emitting layer of the same device are depicted in the following table: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     The compounds according to the invention can also be employed in other layers, for example as hole-transport materials in a hole-injection or hole-transport layer or electron-blocking layer or as matrix materials in an emitting layer, preferably as matrix materials for phosphorescent emitters. 
     If the compound of the formula (I) is employed as hole-transport material in a hole-transport layer, a hole-injection layer or an electron-blocking layer, the compound can be employed as pure material, i.e. in a proportion of 100%, in the hole-transport layer, or it can be employed in combination with one or more further compounds. According to a preferred embodiment, the organic layer comprising the compound of the formula (I) then additionally comprises one or more p-dopants. The p-dopants employed in accordance with the present invention are preferably organic electron-acceptor compounds which are able to oxidise one or more of the other compounds of the mixture. 
     Particularly preferred embodiments of p-dopants are the compounds disclosed in WO 2011/073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, U.S. Pat. Nos. 8,044,390, 8,057,712, WO 2009/003455, WO 2010/094378, WO 2011/120709, US 2010/0096600 and WO 2012/095143. 
     If the compound of the formula (I) is employed as matrix material in combination with a phosphorescent emitter in an emitting layer, the phosphorescent emitter is preferably selected from the classes and embodiments of phosphorescent emitters indicated below. Furthermore, one or more further matrix materials are preferably present in the emitting layer in this case. 
     So-called mixed-matrix systems of this type preferably comprise two or three different matrix materials, particularly preferably two different matrix materials. It is preferred here for one of the two materials to be a material having hole-transporting properties and for the other material to be a material having electron-transporting properties. The compound of the formula (I) is preferably the material having hole-transporting properties. 
     However, the desired electron-transporting and hole-transporting properties of the mixed-matrix components may also be combined mainly or completely in a single mixed-matrix component, where the further mixed-matrix component or components satisfy other functions. The two different matrix materials may be present here in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1 and very particularly preferably 1:4 to 1:1. Mixed-matrix systems are preferably employed in phosphorescent organic electroluminescent devices. Further details on mixed-matrix systems are contained, inter alia, in the application WO 2010/108579. 
     Particularly suitable matrix materials which can be used as matrix components of a mixed-matrix system in combination with the compounds according to the invention are selected from the preferred matrix materials for phosphorescent emitters indicated below or the preferred matrix materials for fluorescent emitters, depending on what type of emitter compound is employed in the mixed-matrix system. 
     Generally preferred classes of material for use as corresponding functional materials in the organic electroluminescent devices according to the invention are indicated below. 
     Suitable phosphorescent 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. 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. 
     For the purposes of the present invention, all luminescent iridium, platinum or copper complexes are regarded as phosphorescent compounds. 
     Examples of the phosphorescent emitters described above are revealed by the 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 US 2005/0258742. In general, all phosphorescent complexes as 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 electroluminescent devices are suitable for use in the devices according to the invention. The person skilled in the art will also be able to employ further phosphorescent complexes without inventive step in combination with the compounds according to the invention in OLEDs. Preferred matrix materials for phosphorescent emitters 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-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851, 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 or WO 2013/041176, 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 2010/015306, WO 2007/063754 or WO 2008/056746, zinc complexes, for example in accordance with EP 652273 or WO 2009/062578, diazasilole or tetraazasilole derivatives, for example in accordance with WO 2010/054729, diazaphosphole derivatives, for example in accordance with WO 2010/054730, bridged carbazole derivatives, for example in accordance with US 2009/0136779, WO 2010/050778, WO 2011/042107, WO 2011/088877 or WO 2012/143080, triphenylene derivatives, for example in accordance with WO 2012/048781, or lactams, for example in accordance with WO 2011/116865 or WO 2011/137951. 
     Besides the compounds according to the invention, suitable charge-transport materials, as can be used in the hole-injection or hole-transport layer or electron-blocking layer or in the electron-transport layer of the electronic device according to the invention, are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials as are employed in these layers in accordance with the prior art. 
     Materials which can be used for the electron-transport layer are all materials as are used in accordance with the prior art as electron-transport materials in the electron-transport layer. Particularly suitable are aluminium complexes, for example Alq 3 , zirconium complexes, for example Zrq 4 , lithium complexes, for example Liq, 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 derivatives of the above-mentioned compounds, as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300. 
     Preferred hole-transport materials which can be used in a hole-transport, hole-injection or electron-blocking layer in the electroluminescent device according to the invention are indenofluorenamine derivatives (for example in accordance with WO 06/122630 or WO 06/100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (for example in accordance with WO 01/049806), amine derivatives containing condensed aromatic rings (for example in accordance with U.S. Pat. No. 5,061,569), the amine derivatives disclosed in WO 95/09147, monobenzoindenofluorenamines (for example in accordance with WO 08/006449), dibenzoindenofluorenamines (for example in accordance with WO 07/140847), spirobifluorenamines (for example in accordance with WO 2012/034627 or WO 2013/120577), fluorenamines (for example in accordance with the as yet unpublished applications EP 12005369.9, EP 12005370.7 and EP 12005371.5), spirodibenzopyranamines (for example in accordance with WO 2013/083216) and dihydroacridine derivatives (for example in accordance with WO 2012/150001). The compounds according to the invention can also be used as hole-transport materials. 
     The cathode of the organic electroluminescent device preferably comprises metals having a low work function, metal alloys or multilayered structures comprising various metals, such as, for example, alkaline-earth metals, alkali metals, main-group metals or lanthanoids (for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys comprising an alkali metal or alkaline-earth metal and silver, for example an alloy comprising magnesium and silver. In the case of multilayered structures, further metals which have a relatively high work function, such as, for example, Ag or Al, can also be used in addition to the said metals, in which case combinations of the metals, such as, for example, Ca/Ag, Mg/Ag or Ag/Ag, are generally used. It may also be preferred to introduce a thin interlayer of a material having a high dielectric constant between a metallic cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal fluorides or alkaline-earth metal fluorides, but also the corresponding oxides or carbonates (for example LiF, Li 2 O, BaF 2 , MgO, NaF, CsF, Cs 2 CO 3 , etc.). Furthermore, lithium quinolinate (LiQ) can be used for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm. 
     The anode preferably comprises materials having a high work function. The anode preferably has a work function of greater than 4.5 eV vs. vacuum. Suitable for this purpose are on the one hand metals having a high redox potential, such as, for example, Ag, Pt or Au. On the other hand, metal/metal oxide electrodes (for example Al/Ni/NiO x , Al/PtO x ) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent in order to facilitate either irradiation of the organic material (organic solar cells) or the coupling-out of light (OLEDs, O-lasers). Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is furthermore given to conductive, doped organic materials, in particular conductive doped polymers. 
     The device is appropriately (depending on the application) structured, provided with contacts and finally sealed, since the lifetime of the devices according to the invention is shortened in the presence of water and/or air. 
     In a preferred embodiment, the organic electroluminescent device according to the invention is 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 here 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 of 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, nozzle printing or offset printing, but particularly preferably LITI (light induced thermal imaging, thermal transfer printing) or ink-jet printing. Soluble compounds of the formula (I) are necessary for this purpose. High solubility can be achieved through suitable substitution of the compounds. 
     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. Thus, it is possible, for example, to apply the emitting layer from solution and to apply the electron-transport layer by vapour deposition. 
     These processes are generally known to the person skilled in the art and can be applied by him without inventive step to organic electroluminescent devices comprising the compounds according to the invention. 
     In accordance with the invention, the electronic devices comprising one or more compounds according to the invention can be employed in displays, as light sources in lighting applications and as light sources in medical and/or cosmetic applications (for example light therapy). 
     The invention will now be explained in greater detail by the following examples, without wishing to restrict it thereby. 
    
    
     A) SYNTHESES EXAMPLES 
     Following Building blocks can be used to synthesize compounds according to the invention: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     Synthesis of Compound BB-001 
     
       
         
         
             
             
         
       
     
     30 g (97.5 mmol) 2-Bromo-7-Chloro-9,9-dimethyl-9H-fluorene (see JP 2003277305 A), 25.5 g (107.3 mmol) (9,9-dimethylfluoren-2-yl)boronic acid 90 g (390 mmol) potassium phosphate monohydrate, 0.9 g (4 mmol) palladium(II)acetate and 3.6 g (11.7 mmol) tri(o-tolyl)-phosphine are dissolved in 1 l toluene, dioxane, water (1:1:1) and stirred at reflux overnight. After cooling to room temperature 200 mL toluene is added and the organic phase is separated and washed with water (2×200 ml). The combined organic phases are concentrated under reduced pressure. The residue is purified by recrystallization from toluene/heptane. 
     Yield: 39.1 g (93 mmol; 96%) 
     The following compounds can be synthesized in an analogous manner: 
     
       
         
           
               
               
               
             
               
                   
               
               
                 Compound 
                 Boronates 
                 Compound structure 
               
               
                   
               
             
            
               
                 BB-002 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
         
       
     
     Compound BB-003 
     
       
         
         
             
             
         
       
     
     40 g (95 mmol) BB-001, 38.6 g (152 mmol) bis-(pinacolato)-diboron, 4.2 g (5.7 mmol) trans-dichloro(tricyclohexylphosphine)palladium(II) and 28 g (285 mmol) potassium acetate are dissolved in 400 ml dioxane and stirred for 16 h at reflux. The reaction mixture is allowed to cool to room temperature and 400 ml toluene are added. The organic phase is separated, washed with water (2×200 mL) and filtered through Celite. The solution is concentrated to dryness under reduced pressure. The residue is purified by recrystallization from toluene/heptane. 
     Yield: 36 g (70 mmol; 74%) 
     The following compound can be synthesized in an analogous manner: 
     
       
         
           
               
               
               
             
               
                   
               
               
                   
                 Starting 
                   
               
               
                 Compound 
                 material 
                 Compound structure 
               
               
                   
               
             
            
               
                 BB-004 
                 BB-002 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
         
       
     
     Compound BB-005 
     
       
         
         
             
             
         
       
     
     5.5 g (17.8 mmol) 2-Bromo-5-iodo-1,3-dimethylbenzene, 6.5 g (12.7 mmol) BB-003, 366 mg (0.3 mmol) tetrakis(triphenylphosphin)-palladium(0) and 2.7 g (13 mmol) sodium carbonate are dissolved in 200 ml toluene, ethanol and water (2:1:1) and stirred for 16 hours at 90° C. After cooling to room temperature, 100 ml toluene are added, the organic phase is separated and washed with water (2×50 ml). The organic phase is concentrated to dryness under reduced pressure. The residue is purified by recrystallization from toluene/heptane. 
     Yield: 6.2 g (11 mmol; 86%) 
     The following compound can be synthesized in an analogous manner: 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                 Compound 
                 Educt A 
                 Educt B 
                 Product 
               
               
                   
               
             
            
               
                 BB-006 
                 BB-002 
                 CAS 844856-42-4 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 BB-015 
                 BB-004 
                 CAS 23055-77-8 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 BB-016 
                 BB-002 
                 CAS 106-40-1 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
         
       
     
     Compound BB-007: 
     The following compound can be synthesized in an analogous manner to BB-005: 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                 Compound 
                 Educt A 
                 Educt B 
                 Product 
               
               
                   
               
             
            
               
                 BB-007 
                 CAS 1679-18-1 
                 BB-004 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
         
       
     
     Compounds BB-008 to BB-009: 
     Compounds BB-008 to BB-009 can be synthesized in an analogous manner to BB-003: 
     
       
         
           
               
               
               
             
               
                   
               
               
                 Compound 
                 Reactant 
                 Compound structure 
               
               
                   
               
             
            
               
                 BB-008 
                 BB-006 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 BB-009 
                 BB-007 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
            
           
         
       
     
     Compound BB-010: 
     
       
         
         
             
             
         
       
     
     12.2 g (37.3 mmol) bis-(4-bromo-phenyl)-amine, 55.5 g (78.4 mmol) BB-004, 37.8 g (164.2 mmol) potassiumphosphate monohydrate and 1.2 g (1.5 mmol) XPhos Pd Gen 3 (CAS 1445085-55-1) are added to 600 mL THF/water (2:1) and stirred at 65° C. After 16 h the mixture is cooled to room temperature diluted with toluene and H2O. The organic phase is collected, the aqueous phase extracted further with toluene. The combined organics are washed with brine, collected, dried with Na2SO4, filtered and concentrated. The resulting residue is deposited in 1 L EtOH and stirred vigorously until a free flowing precipitate is formed. The precipitate is collected by filtration, washing with EtOH. The material is taken up in DCM and filtered through SiO 2 . The filtrate is concentrated to dryness. 
     Yield: 44.7 g (33.6 mmol; 90%) 
     The following compounds BB-011 to BB-012 can be synthesized in analogous manner: 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                   
                 Educt 1 
                 Educt 2 
                 Compound structure 
               
               
                   
               
             
            
               
                 BB-011 
                 BB-003 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   
                   
                 CAS 1383254-17-8 
                   
               
               
                   
               
               
                 BB-012 
                 BB-003 
                 CAS 27996-13-0 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 BB-013 
                 BB-008 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   
                   
                 CAS 16929-17-4 
                   
               
               
                   
               
               
                 BB-014 
                 BB-009 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   
                   
                 CAS 16929-17-4 
                   
               
               
                   
               
               
                 BB-017 
                 BB-016 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   
                   
                 CAS 106-40-1 
                   
               
               
                   
               
               
                 BB-018 
                 BB-004 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                   
                   
                 CAS 1863111-68-5 
               
               
                   
               
            
           
         
       
     
     Synthesis of Compounds According to the Invention: 
     Sample Synthesis of P-001 
     
       
         
         
             
             
         
       
     
     25.5 g (27.2 mmol) BB-010, 5.0 g (12.95 mmol) BB-500, 1.3 ml (1.3 mmol) tri-tert-butylphosphine (1M in toluene), 3.72 g (22.3 mmol) sodium-tert-butylate and 250.5 mg (1.11 mmol) palladium(II)diacetate are added to 750 ml toluene and stirred at 100° C. After 16 h the reaction mixture is allowed to cool down to room temperature, diluted with toluene and H2O. The organic phase are collected, the aqueous phase extracted further with toluene. The combined organic phases are washed with brine, collected, dried with Na 2 SO 4 , filtered and concentrated. The resulting residue is dissolved in toluene and filtered through silica and concentrated. The precipitate is further purified by recrystallisation from toluene/heptane and tempering (250° C., &lt;10 −4  mbar). 
     Yield: 10.1 g (4.79 mmol; 37%) 
     The following compounds can be synthesized in analogous manner: 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                 Educt A  
                 Educt B  
                 Compound structure  
                 Comp. 
               
               
                   
               
             
            
               
                 BB-500  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-001  
               
               
                   
               
               
                 BB-500  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-002  
               
               
                   
               
               
                 BB-500  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-003  
               
               
                   
               
               
                 BB-500  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-004  
               
               
                   
               
               
                 BB-501  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-005  
               
               
                   
               
               
                 BB-501  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-006  
               
               
                   
               
               
                 BB-501  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-007  
               
               
                   
               
               
                 BB-501  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-008  
               
               
                   
               
               
                 BB-502  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-009  
               
               
                   
               
               
                 BB-502  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-010  
               
               
                   
               
               
                 BB-502  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-011  
               
               
                   
               
               
                 BB-502  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-012  
               
               
                   
               
               
                 BB-503  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-013  
               
               
                   
               
               
                 BB-503  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-014  
               
               
                   
               
               
                 BB-503  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-015  
               
               
                   
               
               
                 BB-503  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-016  
               
               
                   
               
               
                 BB-504  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-017  
               
               
                   
               
               
                 BB-504  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-018  
               
               
                   
               
               
                 BB-504  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-019  
               
               
                   
               
               
                 BB-504  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-020  
               
               
                   
               
               
                 BB-505  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-021  
               
               
                   
               
               
                 BB-505  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-022  
               
               
                   
               
               
                 BB-505  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-023  
               
               
                   
               
               
                 BB-505  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-024  
               
               
                   
               
               
                 BB-506  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-025  
               
               
                   
               
               
                 BB-506  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-026  
               
               
                   
               
               
                 BB-506  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-027  
               
               
                   
               
               
                 BB-506  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-028  
               
               
                   
               
               
                 BB-507  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-031  
               
               
                   
               
               
                 BB-508  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-035  
               
               
                   
               
               
                 BB-509  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-039  
               
               
                   
               
               
                 BB-510  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-043  
               
               
                   
               
               
                 BB-511  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-047  
               
               
                   
               
               
                 BB-511  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-048  
               
               
                   
               
               
                 BB-512  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-051  
               
               
                   
               
               
                 BB-513  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-055  
               
               
                   
               
               
                 BB-514  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-059  
               
               
                   
               
               
                 BB-515  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-063  
               
               
                   
               
               
                 BB-516  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-067  
               
               
                   
               
               
                 BB-517  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-071  
               
               
                   
               
               
                 BB-518  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-073  
               
               
                   
               
               
                 BB-518  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-074  
               
               
                   
               
               
                 BB-518  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-075  
               
               
                   
               
               
                 BB-518  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-076  
               
               
                   
               
               
                 BB-519  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-077  
               
               
                   
               
               
                 BB-519  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-078  
               
               
                   
               
               
                 BB-519  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-079  
               
               
                   
               
               
                 BB-519  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-080  
               
               
                   
               
               
                 BB-520  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-081  
               
               
                   
               
               
                 BB-520  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-082  
               
               
                   
               
               
                 BB-520  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-083  
               
               
                   
               
               
                 BB-520  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-084  
               
               
                   
               
               
                 BB-521  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-085  
               
               
                   
               
               
                 BB-521  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-086  
               
               
                   
               
               
                 BB-521  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-087  
               
               
                   
               
               
                 BB-521  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-088  
               
               
                   
               
               
                 BB-522  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-089  
               
               
                   
               
               
                 BB-522  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-090  
               
               
                   
               
               
                 BB-522  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-091  
               
               
                   
               
               
                 BB-522  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-092  
               
               
                   
               
               
                 BB-523  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-093  
               
               
                   
               
               
                 BB-523  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-094  
               
               
                   
               
               
                 BB-523  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-095  
               
               
                   
               
               
                 BB-523  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-096  
               
               
                   
               
               
                 BB-524  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-097  
               
               
                   
               
               
                 BB-524  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-098  
               
               
                   
               
               
                 BB-524  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-099  
               
               
                   
               
               
                 BB-524  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-100  
               
               
                   
               
               
                 BB-525  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-101  
               
               
                   
               
               
                 BB-525  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-102  
               
               
                   
               
               
                 BB-525  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-103  
               
               
                   
               
               
                 BB-525  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-104  
               
               
                   
               
               
                 BB-526  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-105  
               
               
                   
               
               
                 BB-526  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-106  
               
               
                   
               
               
                 BB-526  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-107  
               
               
                   
               
               
                 BB-526  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-108  
               
               
                   
               
               
                 BB-527  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-109  
               
               
                   
               
               
                 BB-527  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-110  
               
               
                   
               
               
                 BB-527  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-111  
               
               
                   
               
               
                 BB-527  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-112  
               
               
                   
               
               
                 BB-528  
                 BB-011  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-113  
               
               
                   
               
               
                 BB-528  
                 BB-012  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-114  
               
               
                   
               
               
                 BB-528  
                 BB-013  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-115  
               
               
                   
               
               
                 BB-528  
                 BB-014  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-116  
               
               
                   
               
               
                 BB-550  
                 BB-018  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-155 
               
               
                   
               
            
           
         
       
     
     Synthesis of P-117 
     
       
         
         
             
             
         
       
     
     5.0 g (12.2 mmol) BB-529, 15.8 g (26.8 mmol) BB-002, 1.35 ml (1.35 mmol) tri-tert-butylphosphine (1M in toluene), 7.73 g (80.4 mmol) sodium-tert-butylate and 150.5 mg (0.67 mmol) palladium(II)-diacetate are added to 450 ml toluene and stirred at 100° C. After 16 h the reaction mixture is allowed to cool down to room temperature, diluted with toluene and H2O. The organic phase is collected, the aqueous phase extracted further with toluene. The combined organic phases are washed with brine, collected, dried with Na2SO4, filtered and concentrated. The resulting residue is dissolved in toluene and filtered through silica and concentrated. The precipitate is further purified by recrystallization from toluene/heptane and tempering (250° C., &lt;10 −4  mbar). 
     Yield: 4.2 g (3.5 mmol; 29%) 
     The following compounds can be synthesized in analogous manner: 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                 Educt A  
                 Educt B  
                 Compound structure  
                 Comp. 
               
               
                   
               
             
            
               
                 BB-529  
                 BB-002  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-117  
               
               
                   
               
               
                 BB-530  
                 BB-002  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-118  
               
               
                   
               
               
                 BB-531  
                 BB-002  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-119  
               
               
                   
               
               
                 BB-532  
                 BB-002  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-120  
               
               
                   
               
               
                 BB-533  
                 BB-002  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-121  
               
               
                   
               
               
                 BB-534  
                 BB-002  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-122  
               
               
                   
               
               
                 BB-535  
                 BB-002  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-123  
               
               
                   
               
               
                 BB-536  
                 BB-002  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-124  
               
               
                   
               
               
                 BB-537  
                 BB-002  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-125  
               
               
                   
               
               
                 BB-529  
                 BB-005  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-126  
               
               
                   
               
               
                 BB-530  
                 BB-005  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-127  
               
               
                   
               
               
                 BB-531  
                 BB-005  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-128  
               
               
                   
               
               
                 BB-533  
                 BB-005  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-130  
               
               
                   
               
               
                 BB-534  
                 BB-005  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-131  
               
               
                   
               
               
                 BB-535  
                 BB-005  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-132  
               
               
                   
               
               
                 BB-536  
                 BB-005  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-133  
               
               
                   
               
               
                 BB-537  
                 BB-005  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-134  
               
               
                   
               
               
                 BB-529  
                 BB-006  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-135  
               
               
                   
               
               
                 BB-530  
                 BB-006  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-136  
               
               
                   
               
               
                 BB-531  
                 BB-006  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-137  
               
               
                   
               
               
                 BB-532  
                 BB-006  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-138  
               
               
                   
               
               
                 BB-533  
                 BB-006  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-139  
               
               
                   
               
               
                 BB-534  
                 BB-006  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-140  
               
               
                   
               
               
                 BB-535  
                 BB-006  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-141  
               
               
                   
               
               
                 BB-536  
                 BB-006  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-142  
               
               
                   
               
               
                 BB-537  
                 BB-006  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-143  
               
               
                   
               
               
                 BB-529  
                 BB-007  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-144  
               
               
                   
               
               
                 BB-530  
                 BB-007  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-145  
               
               
                   
               
               
                 BB-531  
                 BB-007  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-146  
               
               
                   
               
               
                 BB-533  
                 BB-007  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-148  
               
               
                   
               
               
                 BB-534  
                 BB-007  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-149  
               
               
                   
               
               
                 BB-535  
                 BB-007  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-150  
               
               
                   
               
               
                 BB-536  
                 BB-007  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-151  
               
               
                   
               
               
                 BB-537  
                 BB-007  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-152  
               
               
                   
               
               
                 BB-539  
                 BB-015  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-153  
               
               
                   
               
               
                 BB-540  
                 BB-017  
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 P-154 
               
               
                   
               
            
           
         
       
     
     B) FABRICATION OF OLEDS 
     The production of solution-based OLEDs has already been described many times in the literature, for example in WO 2004/037887 and WO 2010/097155. The process is adapted to the circumstances described below (layer-thickness variation, materials). 
     The inventive material combinations are used in the following layer sequence:
         substrate,   ITO (50 nm),   Buffer (20 nm),   hole transport layer (20 nm),   emission layer (EML) (40 nm),   electron-transport layer (ETL) (20 nm),   electron injection layer (EIL) (3 nm),   cathode (Al) (100 nm).       

     Glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm serve as substrate. These are coated with the buffer (PEDOT) Clevios P VP AI 4083 (Heraeus Clevios GmbH, Leverkusen). The spin coating of the buffer is carried out from water in air. The layer is subsequently dried by heating at 180° C. for 10 minutes. The hole transport layers and the emission layers are applied to the glass plates coated in this way. 
     The hole-transport layer is the polymer of the structure shown in Table 1, which was synthesised based on monomers in accordance with CAS 374934-77-7, WO2013156130 and WO2010/097155. The polymer is dissolved in toluene, so that the solution typically has a solid content of approx. 5 g/l if, as here, the layer thickness of 20 nm which is typical for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 220° C. for 30 min. 
     The emission layer is composed of the matrix material (host material) H1 and the emitting dopant (emitter) D1. Both material are present in the emission layer in a proportion of 97% by weight H1 and 3% by weight D1. The mixture for the emission layer is dissolved in toluene. The solids content of such solutions is about 14 mg/ml if, as here, the layer thickness of 40 nm which is typical for a device is to be achieved by means of spin coating. The layers are applied by spin coating in an inert-gas atmosphere, and dried by heating at 120° C. for 10 minutes. The materials used in the present case are shown in table 1. 
     
       
         
           
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Structural formulae of the materials used for the OLEDs 
               
               
                   
               
             
            
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   HTL  
               
               
                   
               
               
                                   
   H1  
               
               
                   
               
               
                                   
   SdT1  
               
               
                   
               
               
                                   
   SdT2  
               
               
                   
               
               
                                   
   SdT3  
               
               
                   
               
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   D1 P-154  
               
               
                   
               
               
                                   
   D2 P-155  
               
               
                   
               
               
                                   
   D3 P-153 
               
               
                   
               
            
           
         
       
     
     The materials for the electron-transport layer and the electron injection layer are likewise applied by thermal vapour deposition in a vacuum chamber and are shown in table 2. The electron-transport layer consists of the material ETM and the electron injection layer consists of LiQ. The cathode is formed by the thermal evaporation of an aluminium layer with a thickness of 100 nm. 
     
       
         
           
               
             
               
                 TABLE 2 
               
               
                   
               
               
                 ETL and EIL materials used 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
                   
               
               
                   
                 ETM 
                 LiQ 
               
               
                   
                   
               
            
           
         
       
     
     The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra are recorded, the current efficiency (measured in cd/A) and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density assuming Lambert emission characteristics are calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines). The electroluminescence spectra are recorded at a luminous density of 1000 cd/m 2 , and the CIE 1931 x and y colour coordinates are calculated from this data. The term EQE1000 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m 2 . 
     The properties of the various OLEDs are summarised in table 3. Example V01, V02 and V03 are the comparative examples for the state-of-the-art, whereas E1, E2 and E3 show properties of OLEDs containing materials of the present invention. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Device data of solution processed OLEDs 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                 EML 
                 EML 
                   
                   
               
               
                   
                 Example 
                 host 
                 dopant 
                 EQE1000 [%] 
                 CIE x/y 
               
               
                   
                   
               
               
                   
                 V01 
                 H1 
                 SdT1 
                 3.8 
                 0.14/0.10 
               
               
                   
                 V02 
                 H1 
                 SdT2 
                 3.7 
                 0.14/0.14 
               
               
                   
                 V03 
                 H1 
                 SdT3 
                 3.0 
                 0.17/0.15 
               
               
                   
                 E01 
                 H1 
                 D1 
                 4.7 
                 0.15/0.11 
               
               
                   
                 E02 
                 H1 
                 D2 
                 4.7 
                 0.14/0.15 
               
               
                   
                 E03 
                 H1 
                 D3 
                 4.4 
                 0.17/0.15 
               
               
                   
                   
               
            
           
         
       
     
     Table 3 shows, that use of materials (D1, D2 and D3) according to the present invention give rise to improvements over the prior art (SdT, SdT2 and SdT3) when used as fluorescent blue emitters, in particular with respect to efficiency.