Transition metal complexes comprising carbene ligands serving as emitters for organic light-emitting diodes (OLED's)
Use of transition metal complexes of the formula (I) in organic light-emitting diodes where: M 1 is a metal atom; carbene is a carbene ligand; L is a monoanionic or dianionic ligand; K is an uncharged monodentate or bidentate ligand selected from the group consisting of phosphines; CO; pyridines; nitrites and conjugated dienes which form a π complex with M 1 ; n is the number of carbene ligands and is at least 1; m is the number of ligands L, where m can be 0 or ≧1; o is the number of ligands K, where o can be 0 or ≧1; where the sum n+m+o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands carbene and L, with the proviso that n is at least 1, and also an OLED comprising these transition metal complexes, a light-emitting layer comprising these transition metal complexes, OLEDs comprising this light-emitting layer, devices comprising an OLED according to the present invention, and specific transition metal complexes comprising at least two carbene ligands.
1. An organic light-emitting diode comprising at least one uncharged transition metal complex of the formula (I) comprising at least one carbene ligand
wherein the symbols have the following meanings:
M 1 is Ir in any oxidation state possible;
carbene is a carbene ligand selected from the group consisting of the following formulae
wherein Z, Z′ are identical or different and are each CH or N;
R 12 ,R 12′ are identical or different and are each an alkyl, aryl, heteroaryl or alkenyl radical, or 2 radicals R 12 or R 12′ together form a fused-on ring which may contain at least one heteroatom, or R 12 or R 12′ is a radical which acts as a donor or acceptor;
t and t′ are identical or different and are each from 0 to 3, and when t or t′>1 the radicals R 12 or R 12′ can be identical or different;
R 4 , R 5 , R 6 , and R 7 are each hydrogen, alkyl, aryl, heteroaryl or alkenyl or a radical which acts as a donor or acceptor;
R 10 is alkyl, aryl, heteroaryl or alkenyl or 2 radicals R 10 together form a fused-on ring which may contain at least one heteroatom, or R 10 is a radical which acts as a donor or acceptor; and
v is from 0 to 4 and when v is 0 the four carbon atoms of the aryl radical in the formula c which may be substituted by R 10 bear hydrogen atoms;
L is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
K is an uncharged monodentate or bidentate ligand selected from the group consisting of phosphines; phosphonates and derivatives thereof, arsenates and derivatives thereof; phosphites; CO; pyridines; nitriles and conjugated dienes which form a π complex with M 1 ;
n is the number of carbene ligands, wherein n is at least 1 and when n>1 the carbene ligands in the complex of the formula I can be identical or different;
m is the number of ligands L, wherein m can be 0 or ≧1 and when m>1 the ligands L can be identical or different;
o is the number of ligands K, wherein o can be 0 or ≧1 and when o>1 the ligands K can be identical or different;
wherein the sum n+m+o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands carbene and L, with the proviso that n is at least 1.
2. The organic light-emitting diode as claimed in claim 1 , wherein the uncharged transition metal complexes are employed as emitter molecules.
3. The organic light-emitting diode as claimed in claim 1 , wherein the carbene ligand is:
4. An uncharged transition metal complex of the formula:
wherein the symbols have the following meanings:
M 1 is Ir in any oxidation state possible;
L is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
K is an uncharged monodentate or bidentate ligand;
n is the number of carbene ligands, wherein n is at least 2 and the carbene ligands in the transition metal complex can be identical or different;
m is the number of ligands L, wherein m can be 0 or ≧1 and when m>1 the ligands L can be identical or different;
o is the number of ligands K, wherein o can be 0 or ≧1 and in the case of o>1 the ligands K can be identical or different;
wherein the sum n+m+o is dependent on the oxidation state and coordination number of the metal atom used and the denticity of the ligands and also on the charge on the ligands, with the proviso that n is at least 2; and
wherein the following symbols have the following meanings:
Z, Z′ are identical or different and are each CH or N;
R 12 , R 12′ are identical or different and are each an alkyl, aryl, heteroaryl or alkenyl radical, or 2 radicals R 12 or R 12′ together form a fused-on ring which may contain at least one heteroatom, or R 12 or R 12′ is a radical which acts as a donor or acceptor;
t and t′ are identical or different and are each from 0 to 3, and when t or t′>1 the radicals R 12 or R 12′ can be identical or different;
R 10 is alkyl, aryl, heteroaryl or alkenyl or 2 radicals R 10 together form a fused-on ring which may contain at least one heteroatom, or R 10 is a radical which acts as a donor or acceptor; and
v is from 0 to 4 and when v is 0 the four carbon atoms of the aryl radical in the formula c which may be substituted by R 10 bear hydrogen atoms.
5. The uncharged transition metal complex as claimed in claim 4 , wherein M 1 is Ir(III), n is 3 and m and o are each 0, and wherein the three carbene ligands are identical.
6. A process for preparing transition metal complexes as claimed in claim 4 by the deprotonation of the ligand precursors corresponding to the appropriate carbene ligands and subsequent reaction with suitable metal complexes in which the desired metal is present.
7. An OLED comprising at least one transition metal complex as claimed in claim 4 .
8. A light-emitting layer comprising at least one transition metal complex of the formula (I) comprising at least one carbene ligand
wherein the symbols have the following meanings:
M 1 is Ir in any oxidation state possible;
carbene is a carbene ligand selected from the group consisting of the following formulae
wherein Z, Z′ are identical or different and are each CH or N;
R 12 ,R 12′ are identical or different and are each an alkyl, aryl, heteroaryl or alkenyl radical, or 2 radicals R 12 or R 12′ together form a fused-on ring which may contain at least one heteroatom, or R 12 or R 12′ is a radical which acts as a donor or acceptor;
t and t′ are identical or different and are each from 0 to 3, and when t or t′ >1 the radicals R 12 or R 12′ can be identical or different;
R 4 , R 5 , R 6 , and R 7 are each hydrogen, alkyl, aryl, heteroaryl or alkenyl or a radical which acts as a donor or acceptor;
R 10 is alkyl, aryl, heteroaryl or alkenyl or 2 radicals R 10 together form a fused-on ring which may contain at least one heteroatom, or R 10 is a radical which acts as a donor or acceptor; and
v is from 0 to 4 and when v is 0 the four carbon atoms of the aryl radical in the formula c which may be substituted by R 10 bear hydrogen atoms;
L is a monoanionic or dianionic ligand, which may be monodentate or bidentate;
K is an uncharged monodentate or bidentate ligand selected from the group consisting of phosphines; phosphonates and derivatives thereof, arsenates and derivatives thereof; phosphites; CO; pyridines; nitriles and conjugated dienes which form a π complex with M 1 ;
n is the number of carbene ligands, wherein n is at least 1 and when n>1 the carbene ligands in the complex of the formula I can be identical or different;
m is the number of ligands L, wherein m can be 0 or ≧1 and when m>1 the ligands L can be identical or different;
o is the number of ligands K, wherein o can be 0 or ≧1 and when o>1 the ligands K can be identical or different;
wherein the sum n+m+o is dependent on the oxidation state and coordination number of the metal atom and on the denticity of the ligands carbene, L and K and also on the charge on the ligands carbene and L, with the proviso that n is at least 1.
9. An OLED comprising a light-emitting layer as claimed in claim 8 .
10. A device selected from the group consisting of stationary VDUs, VDUs in printers, kitchen appliances and advertising signs, lighting units, information signs, and mobile VDUs comprising an organic light-emitting diode as claimed in claim 1 .
11. A light-emitting layer comprising at least one transition metal complex as claimed in claim 4 .
12. An OLED comprising a light-emitting layer as claimed in claim 11 .
13. A device selected from the group consisting of stationary VDUs, VDUs in printers, kitchen appliances and advertising signs, lighting units, information signs, and mobile VDUs comprising an OLED as claimed in claim 7 .
14. A device selected from the group consisting of stationary VDUs, VDUs in printers, kitchen appliances and advertising signs, lighting units, information signs, and mobile VDUs comprising an OLED as claimed in claim 9 .
15. A device selected from the group consisting of stationary VDUs, VDUs in printers, kitchen appliances and advertising signs, lighting units, information signs, and mobile VDUs comprising an OLED as claimed in claim 12 .
16. The organic light-emitting diode as claimed in claim 1 , wherein the carbene ligand is :