Metal complexes

Abstract

The present invention relates to metal complexes and to electronic devices, in particular organic electroluminescent devices, comprising these metal complexes.

1 - 15 . (canceled) 
     
     
         16 . A compound of the formula (1), 
       
         
           
           
               
               
           
         
         where L 1  stands, identically or differently on each occurrence, for a part-ligand of the following formula (2), 
       
       
         
           
           
               
               
           
         
         where the dashed bond indicates the bond to V, * denotes the position of the coordination to M and the following applies to the symbols and indices used: 
         M is Pt; 
         V is selected from the group consisting of NR 7 , N − , BR 7 , B(R 7 ) 2   − , S and Se; 
         X is on each occurrence, identically or differently, C or N, where all X in the part-ligand of the formula (2) together form a 14 π electron system, with the proviso that at least two groups X and at most 6 groups X in each part-ligand of the formula (2) stand for N; 
         R 1  to R 6  is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R 8 ) 2 , CN, NO 2 , Si(R 8 ) 3 , B(OR 8 ) 2 , C(═O)R 8 , P(═O)(R 8 ) 2 , S(═O)R 8 , S(═O) 2 R 8 , OSO 2 R 8 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 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 8 , where one or more non-adjacent CH 2  groups is optionally replaced by R 8 C═CR 8 , C≡C, Si(R 8 ) 2 , C═O, C═S, C═NR 8 , P(═O)(R 8 ), SO, SO 2 , NR 8 , O, S or CONR 8  and where one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 8 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 8 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 8 , or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 8 ; R 4  and R 5  and/or R 5  and R 6  and/or R 1  and R 7  here may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; furthermore, R 2  and R 3  may form a mono- or polycyclic, aliphatic ring system with one another;
 with the proviso that R 1  to R 6  represents a free electron pair if the group X to which this radical R 1  to R 6  is bonded is a nitrogen atom with a saturated valence; 
 
         R 7  is on each occurrence, identically or differently, H, D, Si(R 8 ) 3 , C(═O)R 8 , a straight-chain alkyl or alkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 8 , where one or more non-adjacent CH 2  groups is optionally replaced by R 8 C═CR 8 , C≡C, Si(R 8 ) 2 , C═O, C═S, C═NR 8 , P(═O)(R 8 ), SO, SO 2 , NR 8 , O, S or CONR 8  and where one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 8 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 8 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 8 ; R 1  and R 7  here may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; 
         R 8  is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R 9 ) 2 , CN, NO 2 , Si(R 9 ) 3 , B(OR 9 ) 2 , C(═O)R 9 , P(═O)(R 9 ) 2 , S(═O)R 9 , S(═O) 2 R 9 , OSO 2 R 9 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 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 9 , where one or more non-adjacent CH 2  groups is optionally replaced by R 9 C═CR 9 , C≡C, Si(R 9 ) 2 , C═O, C═S, C═NR 9 , P(═O)(R 9 ), SO, SO 2 , NR 9 , O, S or CONR 9  and where one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 9 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 9 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 9 , or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 9 ; two or more adjacent radicals R 8  here may form a mono- or polycyclic, aliphatic or aromatic ring system with one another; 
         R 9  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, in which, in addition, one or more H atoms is optionally replaced by F; two or more substituents R 9  here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; 
         L 2  is a bidentate part-ligand which is bonded to V; 
         n is 1 or 2; and 
         m is (2−n). 
       
     
     
         17 . The compound according to  claim 16 , wherein the part-ligand of the formula (2) is selected from structures of the formula (4), 
       
         
           
           
               
               
           
         
         where the symbols used have the meanings given in  claim 16  and at least one symbol X and at most 5 symbols X stand for N. 
       
     
     
         18 . The compound according to  claim 16 , wherein the part-ligand of the formula (2) is selected from the part-ligands of the formulae (5), (6) or (7), 
       
         
           
           
               
               
           
         
         where the symbols used have the meanings given in  claim 16 , in the case of the use of the part-ligands of the formula (7) the bridging unit V is selected from BR 7  and B(R 7 ) 2  and the part-ligands contain two, three, four, five or six nitrogen atoms. 
       
     
     
         19 . The compound according to  claim 16 , wherein the part-ligands of the formula (2) are selected from the part-ligands of the formulae (5a) to (5r), (6a) to (6r) or (7a) to (7r), 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         where the symbols used have the meanings given in  claim 16 . 
       
     
     
         20 . The compound according to  claim 16 , wherein, if the part-ligand of the formula (2) contains 3 or more nitrogen atoms, a bulky radical which is selected, identically or differently on each occurrence, from the group consisting of N(R 8 ) 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or an alkenyl or alkynyl group having 2 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 8 , where one or more non-adjacent CH 2  groups is optionally replaced by R 8 C═CR 8 , C≡C, Si(R 8 ) 2 , C═O, C═S, C═NR 8 , P(═O)(R 7 ), SO, SO 2 , NR 8 , O, S or CONR 8  and where one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 8 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 8 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 8 , or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 8 , is bonded to a carbon atom which is adjacent to a nitrogen atom which is not coordinated to the metal and which is not simultaneously bonded in a five-membered ring and a six-membered ring, 
     
     
         21 . The compound according to  claim 20 , wherein the bulky radical is selected from the structures of the formulae (R-1) to (R-112): 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         where Lig denotes the link from the group to the ligand and the aromatic and heteroaromatic groups may each be substituted by one or more radicals R 8 . 
       
     
     
         22 . The compound according to  claim 16 , wherein the index n=2 and the two part-ligands of the formula (2) are identical. 
     
     
         23 . The compound according to  claim 16 , wherein V stands for NR 7  and R 7  is selected from the group consisting of a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, each of which is optionally substituted by one or more radicals R 8 , where one or more H atoms is optionally replaced by D, F or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 8 . 
     
     
         24 . The compound according to  claim 23 , wherein R 7  is selected from the groups of the formulae (36) to (45), 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         where the dashed bond represents the bond to the boron atom or the nitrogen atom and the terminal phenyl groups in formula (44) may also be substituted by one or more alkyl groups having 1 to 5 C atoms. 
       
     
     
         25 . A process for the preparation of a compound according to  claim 16  which comprises reacting the corresponding free ligand with metal alkoxides of the formula (46), with metal ketoketonates of the formula (47) or with metal halides of the formula (48), 
       
         
           
           
               
               
           
         
         where the symbols M and R 8  have the meanings indicated in  claim 16 , Hal=F, Cl, Br or I and p stands for 1, 2 or 3, depending on the valence of the metal M. 
       
     
     
         26 . A formulation comprising one or more compounds according to  claim 16  and at least one solvent. 
     
     
         27 . The formulation as according to  claim 26 , wherein the formulation is a solution, suspension or mini-emulsion. 
     
     
         28 . An electronic device which comprises the compound according to  claim 16 . 
     
     
         29 . The electronic device as claimed in  claim 28 , wherein the electronic device is selected from the group consisting of an organic electroluminescent device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, a light-emitting electrochemical cell or an organic laser diode. 
     
     
         30 . An organic electroluminescent device which comprises the compound according to  claim 16  as emitting compound in one or more emitting layers. 
     
     
         31 . An electronic device which comprises the compound according to  claim 16  is employed in combination with a matrix material which is selected from the group consisting of ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, azaboroles, boronic esters, diazasilole derivatives, diazaphosphole derivatives, triazine derivatives, zinc complexes, dibenzofuran derivatives or bridged carbazole derivatives.