Organic Electroluminescent Element And Novel Iridium Complex

Abstract

An organic electronic device comprising at least one hole-transport material and/or at least one electron/exciton blocker material, wherein said at least one hole-transport material and/or said at least one electron/exciton blocker material is an Ir metal-carbene complex comprising one, two or three specific bidentate azabenzimidazole ligands; a hole transport layer or an electron/exciton blocking layer, comprising at least one Ir metal-carbene complex, comprising one, two or three specific bidentate azabenzimidazole ligands; an apparatus selected from the group consisting of stationary visual display units, mobile visual display units, illumination units, units in items of clothing, units in furniture and units in wallpaper, comprising the organic electronic device of the present invention or the hole transport layer or the electron/exciton blocking layer of the present invention; and the use of an Ir metal-carbene complex comprising one, two or three specific bidentate azabenzimidazole ligands according to the present invention as hole-transport material and/or electron/exciton blocker material.

1 .- 15 . (canceled) 
     
     
         16 . An organic electronic device comprising at least one hole-transport material and/or at least one electron/exciton blocker material, wherein said at least one hole-transport material and/or said at least one electron/exciton blocker material is an Ir metal-carbene complex comprising one, two or three bidentate ligands of formula (I) and/or (I′) 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2  and R 3    
         are each independently hydrogen, deuterium, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 1 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted cycloalkyl radical optionally bearing at least one functional group and having from 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclo alkyl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 3 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted aryl radical optionally bearing at least one functional group and having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 5 to 18 carbon atoms and/or heteroatoms, or a group with donor or acceptor action; 
         or 
         R 1  and R 2 , or R 2  and R 3 , form, independently of each other, together with a carbon atom to which they are bonded, an optionally substituted saturated, unsaturated, or aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms; 
         A 1  is CR 4  or N; 
         A 2  is CR 5  or N; 
         A 3  is CR 6  or N; 
         A 4  is CR 7  or N; 
         A 1′  is CR 4′  or N; 
         A 2′  is CR 5′  or N; 
         A 3′  is CR 6′  or N; 
         A 4′  is CR 7′  or N; 
         R 4 , R 5 , R 6 , R 7 , R 4′ , R 5′ , R 6′ , and R 7′   
         are each independently hydrogen, deuterium, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 1 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted cycloalkyl radical optionally bearing at least one functional group and having from 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclo alkyl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 3 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted aryl radical optionally bearing at least one functional group and having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 5 to 18 carbon atoms and/or heteroatoms, or a group with donor or acceptor action; 
         or 
         R 4  and R 5 , R 5  and R 6 , R 6  and R 7 , R 4′  and R 5′ , R 5′  and R 6′ , or R 6′  and R 7′ , form, independently of each other, together with the carbon atoms to which they are bonded, an optionally substituted saturated, unsaturated, or aromatic ring, which has a total of from 5 to 18 carbon atoms and/or heteroatoms, is optionally interrupted by at least one heteroatom, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms. 
       
     
     
         17 . The organic electronic device according to  claim 16 , wherein the at least one hole-transport material comprising the Ir metal-carbene complex comprising one, two or three bidentate ligands of formula (I) and/or (I′) is present in a hole transport layer of the organic electronic device and/or the at least one electron/exciton blocker material, comprising the Ir metal-carbene complex comprising one, two or three bidentate ligands of formula (I) and/or (I′) is present in an electron/exciton-blocking layer of the organic electronic device. 
     
     
         18 . The organic electronic device according to  claim 16 , wherein the organic electronic device is selected from organic light-emitting diodes (OLED), light-emitting electrochemical cells (LEEC), organic photovoltaic cells (OPV) and organic field-effect transistors (OFET). 
     
     
         19 . The organic electronic device according to  claim 18 , wherein the OLED comprises
 (a) an anode,   (b) a cathode,   (c) a light-emitting layer between the anode and the cathode,   (d) at least one layer, selected from a hole-transport layer (d1) and an electron/exciton blocking layer (d2),   wherein the at least one hole-transport material, comprising the Ir metal-carbene complex comprising one, two or three bidentate ligands of formula (I) and/or (I′) is present in the hole-transport layer of the OLED and/or the at least one electron/exciton blocker material, comprising the Ir metal-carbene complex comprising one, two or three bidentate ligands of formula (I) and/or (I′) is present in the electron/exciton blocking layer of the OLED.   
     
     
         20 . The organic electronic device according to  claim 16 , wherein the radicals, groups and symbols in the at least two ligands of formulae (I) and (I′) have the following meanings:
 R 1 , R 2  and R 3    
 are each independently hydrogen, a linear or branched alkyl radical having from 1 to 6 carbon atoms, a substituted or unsubstituted aryl radical having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical having a total of from 5 to 18 carbon atoms and/or heteroatoms, or a group with donor or acceptor action selected from the group consisting of halogen radicals, CF 3 , CN, SiPh 3  and SiMe 3 ; 
 or 
 R 1  and R 2 , or R 2  and R 3 , form, independently of each other, together with a carbon atom to which they are bonded, an optionally substituted saturated, unsaturated, or aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms; 
 A 1  is CR 4 ; 
 A 2  is CR 5 ; 
 A 3  is CR 6 ; 
 A 4  is CR 7 ; 
 A 1′  is CR 4′  or N; 
 A 2′  is CR 5′  or N; 
 A 3′  is CR 6′  or N; 
 A 4′  is CR 7′  or N; 
 R 4 , R 5 , R 6 , R 7 , R 4′ , R 5′ , R 6′  and R 7′   
 are each independently hydrogen, deuterium, a linear or branched alkyl radical optionally bearing at least one functional group, optionally interrupted by at least one heteroatom, and having a total of from 1 to 20 carbon and/or heteroatoms, a substituted or unsubstituted aryl radical, having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical, having a total of from 5 to 18 carbon atoms and/or heteroatoms, a group with donor or acceptor action selected from halogen radicals, CF 3 , CN and SiMe 3 ; 
 or 
 R 4  and R 5 , R 5  and R 6 , R 6  and R 7 , R 4′  and R 5′ , R 5′  and R 6′ , or R 6′ and R 7′ , form, independently of each other, with the carbon atoms to which they are bonded, an optionally substituted saturated, unsaturated, or aromatic ring, which is optionally interrupted by at least one heteroatom, has a total of from 5 to 18 carbon atoms and/or heteroatoms, and may optionally be fused by at least one further optionally substituted saturated or unsaturated aromatic ring optionally interrupted by at least one heteroatom, and having a total of from 5 to 18 carbon atoms and/or heteroatoms. 
 
     
     
         21 . The organic electronic device according to  claim 16 , wherein the Ir metal-carbene complex has one of the following formulae (II), (II′) or (II″) 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2  and R 3    
         are each independently hydrogen, deuterium, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 1 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted cycloalkyl radical optionally bearing at least one functional group and having from 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclo alkyl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 3 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted aryl radical optionally bearing at least one functional group and having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 5 to 18 carbon atoms and/or heteroatoms, or a group with donor or acceptor action; 
         or 
         R 1  and R 2 , or R 2  and R 3 , form, independently of each other, together with a carbon atom to which they are bonded, an optionally substituted saturated, unsaturated, or aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms, which may optionally be fused to at least one further optionally substituted saturated, unsaturated, aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms; 
         A 1  is CR 4  or N; 
         A 2  is CR 5  or N; 
         A 3  is CR 6  or N; 
         A 4  is CR 7  or N; 
         A 1′  is CR 4′  or N; 
         A 2′  is CR 5′  or N; 
         A 3′  is CR 6′  or N; 
         A 4′  is CR 7′  or N; 
         R 4 , R 5 , R 6 , R 7 , R 4′ , R 5′ , R 6′ , and R 7′   
         are each independently hydrogen, deuterium, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 1 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted cycloalkyl radical optionally bearing at least one functional group and having from 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclo alkyl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 3 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted aryl radical optionally bearing at least one functional group and having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 5 to 18 carbon atoms and/or heteroatoms, or a group with donor or acceptor action; 
         or 
         R 4  and R 5 , R 5  and R 6 , or R 6  and R 7 , form, independently of each other, together with the carbon atoms to which they are bonded, an optionally substituted saturated, unsaturated, aromatic ring, which has a total of from 5 to 18 carbon atoms and/or heteroatoms, is optionally interrupted by at least one heteroatom, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms; 
         n is 1, 2 or 3; 
         L is a monoanionic bidentate ligand; 
         o is 0, 1 or 2, where, when o=2, the L ligands may be the same or different; 
         n′ is 1 or 2; 
         n″ is 1 or 2; 
         wherein the sum of n′+n″ is 2 or 3; 
         o′ is 0 or 1; and 
         wherein the sum of n+o in formulae (II) and (II′) and the sum of n′+n″+and o′ in formula (II″) is 3, with the proviso that n in formula (II) and (II′) is at least 1 and n′, as well as n″ in formula (II″) are at least 1. 
       
     
     
         22 . The organic electronic device according to  claim 21 , wherein
     n′ is 1 or 2; and   n″ is 1 or 2;   wherein the sum of n′+n″ is 3.   
     
     
         23 . The organic electronic device according to  claim 22 , wherein the Ir metal-carbene complex has one of the following formulae (IIa), (II′a), (II″a) or (II″a′) 
       
         
           
           
               
               
           
         
       
     
     
         24 . The organic electronic device according to  claim 16 , wherein the Ir metal-carbene complex is employed in combination with at least one metal oxide. 
     
     
         25 . The organic electronic device according to  claim 19 , wherein the light-emitting layer comprises at least one emitter material, which has an emission maximum λ max  of from 400 to 500 nm. 
     
     
         26 . The organic electronic device according to  claim 19 , wherein the light-emitting layer comprises at least one phosphorescent emitter material. 
     
     
         27 . The organic electronic device according to  claim 25 , wherein the at least one emitter material is a compound of formula (IV) 
       
         
           
           
               
               
           
         
         wherein 
         M is Ir; 
         n′″ is 1, 2 or 3; 
         A 9  is CR 9  or N; 
         A 10  is CR 10  or N; 
         A 11  is CR 11  or N; 
         A 12  is CR 12  or N; 
         where 2 of A 9 , A 10 , A 11  and A 12  are nitrogen atoms and at least one carbon atom is present between two nitrogen atoms in the ring; 
         R 8  is a linear or branched alkyl radical having from 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl radical having from 3 to 20 carbon atoms, a substituted or unsubstituted aryl radical having from 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl radical having a total of from 5 to 18 carbon atoms and/or heteroatoms, 
         R 9 , R 10 , R 11  and R 12  are each independently hydrogen, a linear or branched alkyl radical having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl radical having from 3 to 20 carbon atoms, a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl radical having a total of 5 to 18 carbon atoms and/or heteroatoms, 
         or 
         R 10  and R 11  form, together with the carbon atoms to which they are bonded, an optionally substituted, unsaturated ring optionally interrupted by at least one heteroatom and having a total of 5 to 18 carbon atoms and/or heteroatoms; 
         A 5  is CR 13  or N; 
         A 6  is CR 14  or N; 
         A 7  is CR 15  or N;, 
         A 8  is CR 16  or N; 
         R 13 , R 14 , R 15  and R 16  are each independently hydrogen, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 1 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted cycloalkyl radical optionally bearing at least one functional group and having from 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclo alkyl radical, interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 3 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted aryl radical optionally bearing at least one functional group and having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 5 to 18 carbon atoms and/or heteroatoms, or a group with donor or acceptor action; 
         L′ is a monoanionic bidentate ligand; 
         o″ is 0, 1 or 2; and 
         n″′+o″ is 3. 
       
     
     
         28 . The organic electronic device according to  claim 16 , wherein the at least one hole transport material and/or at least one electron/exciton blocker material is in a hole transport layer or an electron/exciton blocking layer. 
     
     
         29 . An apparatus selected from the group consisting of stationary visual display units, mobile visual display units, illumination units, units in items of clothing, units in furniture and units in wallpaper, wherein the apparatus comprises the organic electronic device according to  claim 16 . 
     
     
         30 . A hole-transport and/or electron/exciton blocker material, wherein said at least one hole-transport material and/or said at least one electron/exciton blocker material is an Ir metal-carbene complex comprising one, two or three bidentate ligands of formula (I) and/or (I′) 
       
         
           
           
               
               
           
         
         wherein 
         R 1 , R 2  and R 3    
         are each independently hydrogen, deuterium, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 1 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted cycloalkyl radical optionally bearing at least one functional group and having from 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclo alkyl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 3 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted aryl radical optionally bearing at least one functional group and having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 5 to 18 carbon atoms and/or heteroatoms, or a group with donor or acceptor action; 
         or 
         R 1  and R 2 , or R 2  and R 3 , form, independently of each other, together with a carbon atom to which they are bonded, an optionally substituted saturated, unsaturated, or aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms; 
         A 1  is CR 4  or N; 
         A 2  is CR 5  or N; 
         A 3  is CR 6  or N; 
         A 4  is CR 7  or N; 
         A 1′  is CR 4′  or N; 
         A 2′  is CR 5′  or N; 
         A 3′  is CR 6′  or N; 
         A 4′  is CR 7′  or N; 
         R 4 , R 5 , R 6 , R 7 , R 4′ , R 5′ , R 6′ , and R 7′   
         are each independently hydrogen, deuterium, a linear or branched alkyl radical optionally interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 1 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted cycloalkyl radical optionally bearing at least one functional group and having from 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclo alkyl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 3 to 20 carbon atoms and/or heteroatoms, a substituted or unsubstituted aryl radical optionally bearing at least one functional group and having from 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl radical interrupted by at least one heteroatom, optionally bearing at least one functional group, and having a total of from 5 to 18 carbon atoms and/or heteroatoms, or a group with donor or acceptor action; 
         or 
         R 4  and R 5 , R 5  and R 6 , R 6  and R 7 , R 4′  and R 5′ , R 5′  and R 6′ , or R 6′  and R 7′ , form, independently of each other, together with the carbon atoms to which they are bonded, an optionally substituted saturated, unsaturated, or aromatic ring, which has a total of from 5 to 18 carbon atoms and/or heteroatoms, is optionally interrupted by at least one heteroatom, and may optionally be fused to at least one further optionally substituted saturated or unsaturated or aromatic ring optionally interrupted by at least one heteroatom and having a total of from 5 to 18 carbon atoms and/or heteroatoms. 
       
     
     
         31 . A hole transport layer or an electron/exciton blocking layer comprising the hole-transport and/or electron/exciton blocker material of  claim 30 . 
     
     
         32 . An apparatus selected from the group consisting of stationary visual display units; mobile visual display units, illumination units, units in items of clothing, units in furniture and units in wallpaper, wherein the apparatus comprises the hole-transport and/or electron/exciton blocker material of  claim 30 .