Heterocyclic spiro compounds

Abstract

The present invention relates to spiro compounds containing electron-conducting groups and to electronic devices, in particular organic electroluminescent devices, comprising these compounds.

1 - 31 . (canceled) 
     
     
         32 . A mixture comprising at least one compound of the formula (I), 
       
         
           
           
               
               
           
         
         wherein 
         X is O, S, or C(R 1 ) 2 ; 
         Ar is on each occurrence, identically or differently, an aryl group having 6 to 40 C atoms or a heteroaryl group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 1 ; 
         R 1  is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, C(═O)Ar 1 , P(═O)(Ar 1 ) 2 , S(═O)Ar 1 , S(═O) 2 Ar 1 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , OSO 2 R 2 , a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , and wherein one or more non-adjacent CH 2  groups are optionally replaced by R 2 C═CR 2 , C≡C, Si(R 2 ) 2 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, P(═O)(R 2 ), SO, SO 2 , O, S, or CONR 2 , and wherein one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN, or NO 2 , an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or a combination of these systems; and wherein two or more adjacent substituents R 1  optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another; 
         R 2  is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, C(═O)Ar 1 , P(═O)(Ar 1 ) 2 , S(═O)Ar 1 , S(═O) 2 Ar 1 , CN, NO 2 , Si(R 3 ) 3 , B(OR 3 ) 2 , OSO 2 R 3 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 3 , wherein one or more non-adjacent CH 2  groups are optionally replaced by C≡C, Si(R 3 ) 2 , Ge(R 3 ) 2 , Sn(R 3 ) 2 , C═O, C═S, C═Se, P(═O)(R 3 ), SO, SO 2 , O, S, or CONR 3 , and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO 2 , or a combination of these systems; and wherein two or more adjacent substituents R 2  optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another; 
         Ar 1  is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 ; wherein two radicals Ar 1  bonded to the same phosphorus atom are also optionally linked to one another by a single bond or a bridge selected from the group consisting of B(R 3 ), C(R 3 ) 2 , Si(R 3 ) 2 , C═O, C═NR 3 , C═C(R 3 ) 2 , O, S, S═O, SO 2 , N(R 3 ), P(R 3 ), and P(═O)R 3 ; 
         R 3  is on each occurrence, identically or differently, H, D, F, or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, wherein one or more H atoms of the hydrocarbon radical are optionally replaced by F; and wherein two or more adjacent substituents R 3  optionally define a mono- or polycyclic, aliphatic or aromatic ring system with one another; 
         n is on each occurrence, identically or differently, 0, 1, 2, 3, or 4; 
         m is on each occurrence, identically or differently, 0, 1, 2, or 3; 
         o is on each occurrence, identically or differently, 0, 1, or 2; 
         p, q, r, and u are on each occurrence, identically or differently, 0 or 1; 
         s and t are, on each occurrence, 0; 
         E is an electron-transporting group, which is optionally substituted by one or more radicals R 1 , 
         R a  is, independently, H, D, or F; 
         R b  is, independently, H, D, or F; 
         with the proviso that 
         the compound of formula (I) contains only one electron-transporting group E; 
         the sum of all indices m, s and, t is less than 7; 
         the sum of all indices n, q and, u is less than 9; 
         the sum of the indices r and o is less than 3; and 
         at least one further compound wherein the further compound is a matrix material. 
       
     
     
         33 . The mixture according to  claim 32 , wherein p is 0, so that E is bonded directly to the benzofuran or spiro group. 
     
     
         34 . The mixture according to  claim 32 , wherein at least one radical containing the electron-transporting group E is bonded in position 1, 3, 4, 5, 6, or 8 of the spirobifluorene skeleton. 
     
     
         35 . The mixture according to  claim 32 , wherein the electron-transporting group E is a heteroaryl group having 5 to 60 aromatic ring atoms. 
     
     
         36 . The mixture according to  claim 32 , wherein the electron-transporting group E comprises at least one structure selected from the group consisting of triazines, pyrimidines, pyrazines, imidazoles, benzimidazoles, and pyridines. 
     
     
         37 . The mixture according to  claim 32 , wherein the electron-transporting group E comprises at least one structure selected from the group consisting of formulae (E-1) through (E-10): 
       
         
           
           
               
               
           
         
         wherein 
         the dashed bond marks the bonding position, 
         Q′ is on each occurrence, identically or differently, CR 1  or N, and 
         Q″ is NR 1 , O, or S, and 
         wherein at least one Q′ is N and/or at least one Q″ is NR 1 . 
       
     
     
         38 . The mixture according to  claim 35 , wherein the electron-transporting group E comprises at least one structure selected from the group consisting of formulae (E-11) through (E-19): 
       
         
           
           
               
               
           
         
       
       wherein the dashed bond marks the bonding position. 
     
     
         39 . The mixture according to  claim 37 , wherein at least one of the radicals R 1  in the structures of formulae (E-1) through (E-10) is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 . 
     
     
         40 . The mixture according to  claim 32 , wherein the compound comprises a compound of formulae (II), (III), (IV), (V), (VI), and/or (VII): 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         41 . The mixture according to  claim 32 , wherein the matrix material has hole-transporting properties. 
     
     
         42 . The mixture according to  claim 32 , wherein the hole transporting compound is a carbazole, bridged carbazoles biscarbazole, indenocarbazole and indolocarbazole derivative. 
     
     
         43 . The mixture according to  claim 32 , wherein the carbazole derivative is a biscarbazole. 
     
     
         44 . The mixture according to  claim 32 , wherein the compound of formula (I) is selected from the group of compounds 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         45 . An organic electroluminescent device comprising the mixture according to  claim 32 . 
     
     
         46 . An organic electroluminescent device comprising the mixture according to  claim 42 . 
     
     
         47 . An organic electroluminescent device comprising the mixture according to  claim 43 . 
     
     
         48 . An organic electroluminescent device comprising the mixture according to  claim 32  wherein the mixture is employed in an emitting layer, in combination with a phosphorescent dopant. 
     
     
         49 . An organic electroluminescent device comprising the mixture according to  claim 42  wherein the mixture is employed in an emitting layer, in combination with a phosphorescent dopant. 
     
     
         50 . An organic electroluminescent device comprising the mixture according to  claim 43  wherein the mixture is employed in an emitting layer, in combination with a phosphorescent dopant.