Materials for organic electroluminescent devices

Abstract

The invention relates to compounds which are suitable for use in electronic devices, and electronic devices, in particular organic electroluminescent devices, containing said compounds.

1 .- 15 . (canceled) 
     
     
         16 . A compound of formula (1), formula (2) or formula (3) 
       
         
           
           
               
               
           
         
       
       where the symbols and indices used are as follows:
 X is the same or different at each instance and is CR 1  or N; or two adjacent Xs are a group of the following formula (4), (5) or (6): 
 
       
         
           
           
               
               
           
         
         
           where ̂ indicates the corresponding adjacent X groups in the formula (1) or (2) or (3); 
         
         V is the same or different at each instance and is C(R 1 ) 2 , NR 1 , O, S, BR 1 , Si(R 1 ) 2  or C═O; 
         Z is the same or different at each instance and is CR 1  or N; 
         Ar is the same or different at each instance and is an aromatic ring system which has 6 to 40 aromatic ring atoms and may be substituted by one or more R 2  radicals, or a heteroaromatic ring system which has 5 to 40 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted by one or more R 2  radicals; 
         R, R 1  is the same or different at each instance and is selected from the group consisting of H, D, F, Cl, Br, I, CN, NO 2 , N(Ar 1 ) 2 , N(R 3 ) 2 , C(═O)Ar 1 , C(═O)R 3 , P(═O)(Ar 1 ) 2 , P(Ar 1 ) 2 , B(Ar 1 ) 2 , Si(Ar 1 ) 3 , Si(R 3 ) 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, each of which may be substituted by one or more R 3  radicals, where one or more nonadjacent CH 2  groups may be replaced by R 3 C═CR 3 , Si(R 3 ) 2 , C═O, C═S, C═NR 3 , P(═O)(R 3 ), SO, SO 2 , NR 3 , O, S or CONR 3  and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R 3  radicals, an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R 3  radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R 3  radicals; at the same time, it is optionally possible for two R 1  substituents bonded to the same carbon atom to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more R 3  radicals; 
         R 2  is the same or different at each instance and is selected from the group consisting of H, D, F, Cl, Br, I, CN, NO 2 , N(Ar 1 ) 2 , N(R 3 ) 2 , C(═O)Ar 1 , C(═O)R 3 , P(═O)(Ar 1 ) 2 , P(Ar 1 ) 2 , B(Ar 1 ) 2 , Si(Ar 1 ) 3 , Si(R 3 ) 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, each of which may be substituted by one or more R 3  radicals, where one or more nonadjacent CH 2  groups may be replaced by R 3 C═CR 3 , Si(R 3 ) 2 , C═O, C═S, C═NR 3 , P(═O)(R 3 ), SO, SO 2 , NR 3 , O, S or CONR 3  and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted in each case by one or more R 3  radicals, an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted by one or more R 3  radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted by one or more R 3  radicals; at the same time, it is possible for two or more adjacent R 3  substituents together to form a mono- or polycyclic aliphatic ring system; 
         Ar 1  is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5-30 aromatic ring atoms and may be substituted by one or more nonaromatic R 3  radicals; at the same time, two Ar 1  radicals bonded to the same nitrogen atom, phosphorus atom or boron atom may also be bridged to one another by a single bond or a bridge selected from N(R 3 ), C(R 3 ) 2 , O and S; 
         R 3  is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms and an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, where two or more adjacent R 3  substituents together may form a mono- or polycyclic, aliphatic ring system; 
         p is the same or different at each instance and is 0, 1, 2, 3 or 4; 
         q is 0, 1 or 2;
 where the two following compounds are excluded from the invention: 
 
       
       
         
           
           
               
               
           
         
       
     
     
         17 . The compound as claimed in  claim 16 , wherein X is the same or different at each instance and is CR 1  or N, where not more than one X group per cycle is N, or in that two adjacent X groups are a group of the formula (4), where Z is the same or different at each instance and is CR 1  and V is the same or different at each instance and is NR 1 , C(R 1 ) 2 , O or S, and the rest of the X groups in the cycle are CR 1 . 
     
     
         18 . The compound as claimed in  claim 16 , wherein the compound is selected from the compounds of the formulae (7) to (15) 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       where the symbols and indices used have the definitions given in  claim 16 . 
     
     
         19 . The compound as claimed in  claim 16 , wherein the compound is selected from compounds of the formulae (7a) to (15a) 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       where the symbols and indices used have the definitions given in  claim 16 . 
     
     
         20 . The compound as claimed in  claim 16 , wherein R is the same or different at each instance and is selected from the group consisting of H, F, CN, N(Ar 1 ) 2 , a straight-chain alkyl group having 1 to 10 carbon atoms and a branched or cyclic alkyl group having 3 to 10 carbon atoms and an aromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more nonaromatic R 3  radicals. 
     
     
         21 . The compound as claimed in  claim 16 , wherein the compound is selected from compounds of the formulae (7b) to (15b) 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       where the symbols used have the definitions given in  claim 16 . 
     
     
         22 . The compound as claimed in  claim 16 , wherein the compounds of the formula (1) and (3) contain a total of at least 12 aromatic ring atoms in the Ar, R 1  and R 2  substituents, and in that the compounds of the formula (2) contain a total of at least 24 aromatic ring atoms in the Ar, R 1  and R 2  substituents. 
     
     
         23 . The compound as claimed in  claim 16 , wherein Ar is selected from the groups of the formulae Ar-1 to Ar-58 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       where R 2  has the definitions given in  claim 16 , the dotted bond represents the bond to the group of the formula (1) or (2) or (3) and, in addition:
 Ar 2  is the same or different at each instance and is a bivalent aromatic or heteroaromatic ring system which has 6 to 18 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted in each case by one or more R 2  radicals; 
 Ar 3  is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 18 aromatic ring atoms, does not contain any electron-deficient heteroaryl groups and may be substituted in each case by one or more R 2  radicals; 
 Y is the same or different at each instance and is C(R 2 ) 2 , NR 2 , O or S; 
 n is 0 or 1, where n=0 means that no Y group is bonded at this position and R 2  radicals thereof are bonded to the corresponding carbon atoms instead; 
 
       where the Ar-1 to Ar-57 groups can also bind via a bridging group to the nitrogen atom in formula (1) or formula (2) or formula (3). 
     
     
         24 . The compound as claimed in  claim 16 , wherein R 1  is the same or different at each instance and is selected from the group consisting of H, D, N(Ar 1 ) 2 , a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be substituted by one or more R 3  radicals, where one or more hydrogen atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted in each case by one or more R 3  radicals. 
     
     
         25 . The compound as claimed in  claim 16 , wherein R 1 , when it is an aromatic or heteroaromatic ring system, is selected from the groups R 1 -1 to R 1 -43 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       where R 3  has the definitions given in  claim 16 , the dotted bond represents the bond to the group of the formula (1) or (2) or (3) and, in addition:
 A is the same or different at each instance and is CR 3  or N, where not more than 3 X symbols per cycle are N; 
 Y is the same or different at each instance and is C(R 3 ) 2 , NR 3 , O or S; 
 Ar 2 , Ar 3  is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 18 aromatic ring atoms, each of which may be substituted in each case by one or more R 3  radicals; 
 n is 0 or 1, where n=0 means that no Y group is bonded at this position and R 3  radicals thereof are bonded to the corresponding carbon atoms instead; 
 
       where the R 1 -1 to R 1 -42 groups can also bind via a bridging group to the nitrogen atom in formula (1) or formula (2) or formula (3). 
     
     
         26 . An oligomer, polymer or dendrimer containing one or more compounds as claimed in  claim 16 , wherein one or more bonds of the compound to the polymer, oligomer or dendrimer are present in place of substituents at one or more positions. 
     
     
         27 . A formulation comprising at least one compound as claimed in  claim 16  and at least one further compound, especially a solvent. 
     
     
         28 . A formulation comprising at least one oligomer, polymer or dendrimer as claimed in  claim 26  and at least one further compound, especially a solvent. 
     
     
         29 . An electronic device comprising the compound as claimed in  claim 16 . 
     
     
         30 . An electronic device comprising the oligomer, polymer or dendrimer as claimed in  claim 26 . 
     
     
         31 . The electronic device as claimed in  claim 29 , wherein the device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitized organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon-emitting devices. 
     
     
         32 . An organic electroluminescent device which comprises the compound as claimed in  claim 16  is used as matrix material for phosphorescent or fluorescent emitters and/or in an electron-blocking or exciton-blocking layer and/or in a hole transport layer and/or in a hole blocker layer and/or in a hole blocker or electron transport layer.