MONONUCLEAR IRIDIUM COMPLEXES CONTAINING THREE ORTHO-METALLATED BIDENTATE LIGANDS AND OPTICAL ORIENTATING ANISTROPHY
The present invention relates to iridium complexes suitable for use in organic electroluminescent devices, especially as emitters.
1 .- 18 . (canceled)
19 . A mononuclear iridium complex that exhibits oriented emission with an optical orientation anisotropy Θ≤0.24, containing three ortho-metallated bidentate ligands or three ortho-metallated bidentate sub-ligands, characterized in that the angle α(μ act ,d) between the transition dipole moment μ act and the electrical dipole moment d is ≤40°;
where the following compounds are excluded from the invention:
20 . The mononuclear iridium complex according to claim 19 , wherein the complex is a heteroleptic complex containing at least two different ligands or sub-ligands.
21 . The mononuclear iridium complex according to claim 19 , wherein the complex has two identical bidentate ligands or sub-ligands and a further bidentate ligand or sub-ligand different from the two other bidentate ligands or sub-ligands.
22 . The mononuclear iridium complex according to claim 19 , wherein the complex has exactly one optically active ligand or sub-ligand L act which is characterized in that the triplet energy is subject to the following condition: Ir(L act )<Ir(L) where L is the optically inactive ligand.
23 . The mononuclear iridium complex according to claim 22 , wherein the triplet energy of the ligand Ir(L) is at least 0.05 eV greater than that of the ligand Ir(L act ).
24 . The mononuclear iridium complex according to claim 19 , wherein the optically active ligand or sub-ligand is extended in the direction of the transition dipole moment with an aromatic or heteroaromatic ring system.
25 . The mononuclear iridium complex according to claim 19 , wherein the optical orientation anisotropy Θ is ≤0.22.
26 . The mononuclear iridium complex according to claim 19 , wherein the angle α(μ act ,d) between the transition dipole moment μ act and the electrical dipole moment d is ≤35°.
27 . The mononuclear iridium complex according to claim 19 , wherein the complex has a photoluminescence quantum efficiency of more than 0.85.
28 . The mononuclear iridium complex according to claim 19 , wherein the complex is one of the formulae (1) and (2)
where L act in formula (1) is an optically active ortho-metallated bidentate ligand and in formula (2) is an optically active ortho-metallated bidentate sub-ligand, L is different from L act and is the same or different at each instance and is ortho-metallated bidentate ligands in formula (1) and ortho-metallated bidentate sub-ligands in formula (2), and V in formula (2) is a bridging unit that joins the sub-ligands L act and L covalently to form a tripodal hexadentate ligand.
29 . The mononuclear iridium complex according to claim 28 , wherein L act and L each coordinate to the iridium via one carbon atom and one nitrogen atom or via two carbon atoms.
30 . The mononuclear iridium complex according to claim 28 , wherein L act and L each represent a structure of the formulae (L-1) or (L-2), where the two ligands or sub-ligands L may be the same or different,
where the dotted bond represents the bond of the sub-ligand in formula (2) to V and is absent for formula (1) and where the other symbols used are as follows:
CyC is the same or different at each instance and is a substituted or unsubstituted aryl or heteroaryl group which has 5 to 14 aromatic ring atoms and coordinates in each case to the metal via a carbon atom and which is bonded to CyD via a covalent bond;
CyD is the same or different at each instance and is a substituted or unsubstituted heteroaryl group which has 5 to 14 aromatic ring atoms and coordinates to the metal via a nitrogen atom or via a carbene carbon atom and which is bonded to CyC via a covalent bond;
at the same time, two or more of the optional substituents together may form a ring system.
31 . The mononuclear iridium complex according to claim 28 , wherein L act and L are each a structure of one of the formulae (L-1-1), (L-1-2), (L-2-1), (L-2-2), (L-2-3) or (L-2-4)
where “o” for compounds of the formula (2) represents the position of the bond to V, in which case the corresponding X is C, and where “o” is undefined for compounds of the formula (1), and in addition:
X is the same or different at each instance and is CR or N, with the proviso that at most two symbols X per ring are N;
R is the same or different at each instance and is H, D, F, Cl, Br, I, N(R 1 ) 2 , OR 1 , SR 1 , CN, NO 2 , COOR 1 , C(═O)N(R 1 ) 2 , Si(R 1 ) 3 , B(OR 1 ) 2 , C(═O)R 1 , P(═O)(R 1 ) 2 , S(═O)R 1 , S(═O) 2 R 1 , OSO 2 R 1 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R 1 radicals and where one or more nonadjacent CH 2 groups may be replaced by Si(R 1 ) 2 , C═O, NR 1 , O, S or CONR 1 , or 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 nonaromatic R 1 radicals; at the same time, two R radicals together may also form a ring system;
R 1 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R 2 ) 2 , OR 2 , SR 2 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)R 2 , P(═O)(R 2 ) 2 , S(═O)R 2 , S(═O) 2 R 2 , OSO 2 R 2 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R 2 radicals and where one or more nonadjacent CH 2 groups may be replaced by Si(R 2 ) 2 , C═O, NR 2 , O, S or CONR 2 , or 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 2 radicals; at the same time, two or more R 1 radicals together may form a ring system;
R 2 is the same or different at each instance and is H, D, F or an aliphatic organic radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F.
32 . The mononuclear iridium complex according to claim 28 , wherein L act is a ligand or sub-ligand of the formula (L-39) that coordinates to the iridium via the two D groups and which, when the complex is one of the formula (2), is bonded to V via the dotted bond, in which case the corresponding X is C,
Wherein
X is the same or different at each instance and is CR or N, with the proviso that at most two symbols X per ring are N;
R is the same or different at each instance and is H, D, F, Cl, Br, I, N(R 1 ) 2 , OR 1 , SR 1 , CN, NO 2 , COOR 1 , C(═O)N(R 1 ) 2 , Si(R 1 ) 3 , B(OR 1 ) 2 , C(═O)R 1 , P(═O)(R 1 ) 2 , S(═O)R 1 , S(═O) 2 R 1 , OSO 2 R 1 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R 1 radicals and where one or more nonadjacent CH 2 groups may be replaced by Si(R 1 ) 2 , C═O, NR 1 , O, S or CONR 1 , or 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 nonaromatic R 1 radicals; at the same time, two R radicals together may also form a ring system;
R 1 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R 2 ) 2 , OR 2 , SR 2 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)R 2 , P(═O)(R 2 ) 2 , S(═O)R 2 , S(═O) 2 R 2 , OSO 2 R 2 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R 2 radicals and where one or more nonadjacent CH 2 groups may be replaced by Si(R 2 ) 2 , C═O, NR 2 , O, S or CONR 2 , or 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 2 radicals; at the same time, two or more R 1 radicals together may form a ring system;
R 2 is the same or different at each instance and is H, D, F or an aliphatic organic radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F;
D is C or N, with the proviso that one D is C and the other D is N;
Z is CR′, CR or N, with the proviso that exactly one Z is CR′ and the other Z is CR or N;
where a maximum of one symbol X or Z per cycle is N;
R′ is a group of the following formula (14) or (15):
where the dotted bond indicates the attachment of the group;
R″ is the same or different at each instance and is H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms may also be replaced by D or F, or a branched or cyclic alkyl group having 3 to 10 carbon atoms in which one or more hydrogen atoms may also be replaced by D or F, or an alkenyl group having 2 to 10 carbon atoms in which one or more hydrogen atoms may also be replaced by D or F; at the same time, two adjacent R″ radicals or two R″ radicals on adjacent phenyl groups together may also form a ring system; or two R″ on adjacent phenyl groups together are a group selected from C(R 1 ) 2 , NR 1 , O and S, such that the two phenyl rings together with the bridging group are a carbazole, dibenzofuran or dibenzothiophene, and the further R″ are as defined above;
n is 0, 1, 2, 3, 4 or 5.
33 . The mononuclear iridium complex according to claim 28 , wherein V represents a group of the formula (16), where the dotted bonds represent the position of the attachment of the sub-ligands L act and L,
wherein
R is the same or different at each instance and is H, D, F, Cl, Br, I, N(R 1 ) 2 , OR 1 , SR 1 , CN, NO 2 , COOR 1 , C(═O)N(R 1 ) 2 , Si(R 1 ) 3 , B(OR 1 ) 2 , C(═O)R 1 , P(═O)(R 1 ) 2 , S(═O)R 1 , S(═O) 2 R 1 , OSO 2 R 1 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R 1 radicals and where one or more nonadjacent CH 2 groups may be replaced by Si(R 1 ) 2 , C═O, NR 1 , O, S or CONR 1 , or 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 nonaromatic R 1 radicals; at the same time, two R radicals together may also form a ring system;
R 1 is the same or different at each instance and is H, D, F, Cl, Br, I, N(R 2 ) 2 , OR 2 , SR 2 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)R 2 , P(═O)(R 2 ) 2 , S(═O)R 2 , S(═O) 2 R 2 , OSO 2 R 2 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl, alkenyl or alkynyl group may in each case be substituted by one or more R 2 radicals and where one or more nonadjacent CH 2 groups may be replaced by Si(R 2 ) 2 , C═O, NR 2 , O, S or CONR 2 , or 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 2 radicals; at the same time, two or more R 1 radicals together may form a ring system;
R 2 is the same or different at each instance and is H, D, F or an aliphatic organic radical, having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by F;
X 1 is the same or different at each instance and is CR or N;
A is the same or different at each instance and is CR 2 —CR 2 , CR 2 —O, CR 2 —NR, C(═O)—O, C(═O)—NR or a group of the formula (17):
where the dotted bond represents the position of the bond of the bidentate sub-ligands L act and L to this structure, * represents the position of the attachment of the unit of the formula (17) to the central trivalent aryl or heteroaryl group and X 2 is the same or different at each instance and is CR or N.
34 . An electronic device comprising at least one mononuclear iridium complex according to claim 19 .
35 . Electronic device according to claim 34 , the device is an organic electroluminescent device and the mononuclear iridium complex is used as emitting compound in an emitting layer.