Metal complexes

Information

  • Patent Grant
  • 9169282
  • Patent Number
    9,169,282
  • Date Filed
    Thursday, January 14, 2010
    15 years ago
  • Date Issued
    Tuesday, October 27, 2015
    9 years ago
Abstract
The present invention relates to metal complexes and to electronic devices, in particular organic electroluminescent devices, comprising these metal complexes.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. §371) of PCT/EP2010/000177, filed Jan. 14, 2010, which claims benefit of Germany application 10 2009 007 038.9, filed Feb. 2, 2009.


BACKGROUND OF THE INVENTION

The structure of organic electroluminescent devices (OLEDs) in which organic semiconductors are employed as functional materials is described, for example, in U.S. Pat. No. 4,539,507, 5,151,629, EP 0676461 and WO 98/27136. The emitting materials employed here are increasingly organometallic complexes which exhibit phosphorescence instead of fluorescence (M. A. Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). For quantum-mechanical reasons, an up to four-fold increase in energy and power efficiency is possible using organometallic compounds as phosphorescence emitters. In general, however, there is still a need for improvement in OLEDs which exhibit triplet emission, in particular with respect to efficiency, operating voltage and lifetime. This applies, in particular, to OLEDs which emit in the relatively short-wave range, i.e. green and in particular blue. Thus, no blue-emitting triplet emitters which meet the technical requirements for industrial use are known to date.


In accordance with the prior art, the triplet emitters employed in phosphorescent OLEDs are, in particular, iridium complexes. An improvement in these OLEDs has been achieved by employing metal complexes containing polypodal ligands or cryptates, as a consequence of which the complexes have higher thermal stability, which results in a longer lifetime of the OLEDs (WO 04/081017, WO 05/113563, WO 06/008069). However, these complexes are not suitable for blue emission, in particular for saturated deep-blue emission.


The prior art furthermore discloses iridium complexes which contain imidazophenanthridine derivatives or diimidazoquinazoline derivatives as ligands (WO 07/095,118). These complexes can result in blue phosphorescence on use in organic electroluminescent devices, depending on the precise structure of the ligand. Here too, further improvements are desirable with respect to efficiency, operating voltage and lifetime. In particular, there is also a need for improvement here with respect to the colour coordinates in order to be able to achieved deep-blue emission.


BRIEF SUMMARY OF THE INVENTION

The object of the present invention is therefore to provide novel metal complexes which are suitable as emitters for use in OLEDs. In particular, the object is to provide emitters which are suitable for blue-phosphorescent OLEDs.


Surprisingly, it has been found that certain metal chelate complexes described in greater detail below achieve this object and result in improvements in the organic electroluminescent device, in particular with respect to the operating voltage, the efficiency and the emission colour. The present invention therefore relates to these metal complexes and to organic electroluminescent devices which comprise these complexes.


The invention thus relates to a compound of the formula (1)

M(L)n(L′)m  formula (1)

where the compound of the general formula (1) contains a moiety M(L)n of the formula (2) or formula (3):




embedded image



where the following applies to the symbols and indices used:

  • M is a metal;
  • X is selected on each occurrence, identically or differently, from the group consisting of C, N and B; and all X together represent a 14π electron system;
  • R1 to R7 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R8)2, CN, NO2, Si(R8)3, B(OR8)2, C(═O)R8, P(═O)(R8)2, S(═O)R8, S(═O)2R8, OSO2R8, 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 may be substituted by one or more radicals R8, where one or more non-adjacent CH2 groups may be replaced by R8C═CR8, C≡C, Si(R8)2, Ge(R8)2, Sn(R8)2, C═O, C═S, C═Se, C═NR8, P(═O)(R8), SO, SO2, NR8, O, S or CONR8 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, 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 R8, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R8, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R8, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R8; R1 and R2 and/or R2 and R3 and/or R4 and R5 and/or R8 and R6 and/or R6 and R7 here may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; furthermore, R3 and R4 may form a mono- or polycyclic, aliphatic ring system with one another;
    • with the proviso that R1 to R7 represent a free electron pair if the group X to which these radicals R1 to R7 are bonded is a nitrogen atom with a saturated valence;
  • R8 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R9)2, CN, NO2, Si(R9)3, B(OR9)2, C(═O)R9, P(═O)(R9)2, S(═O)R9, S(═O)2R9, OSO2R9, 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 may be substituted by one or more radicals R9, where one or more non-adjacent CH2 groups may be replaced by R9C═CR9, C≡C, Si(R9)2, Ge(R9)2, Sn(R9)2, C═O, C═S, C═Se, C═NR9, P(═O)(R9), SO, SO2, NR9, O, S or CONR9 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, 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 R9, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R9, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R9, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R9; two or more adjacent radicals R8 here may form a mono- or polycyclic, aliphatic or aromatic ring system with one another;
  • R9 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 may be replaced by F; two or more substituents R9 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another;
  • L′ is, identically or differently on each occurrence, any desired co-ligand;
  • n is 1, 2, 3 or 4;
  • m is 0, 1, 2, 3, 4, 5 or 6;


    a plurality of ligands L here may also be linked to one another or L may be linked to L′ via any desired bridge V, thus forming a tridentate, tetradentate, pentadentate or hexadentate ligand system.


A DETAILED DESCRIPTION OF THE INVENTION

Both the ligand L as a whole and also individual atoms X in the ligand L may also be charged here.


The indices n and m here are selected so that the coordination number on the metal M corresponds overall, depending on the metal, to the usual coordination number for this metal. This is usually the coordination number 4, 5 or 6 for transition metals, depending on the metal. It is generally known that metal coordination compounds have different coordination numbers, i.e. bind a different number of ligands, depending on the metal and on the oxidation state of the metal. Since the preferred coordination numbers of metals and metal ions in various oxidation states belong to the general expert knowledge of the person skilled in the art in the area of organometallic chemistry or coordination chemistry, it is readily possible for the person skilled in the art to use a suitable number of ligands, depending on the metal and its oxidation state and depending on the precise structure of the ligand L, and thus to select the indices n and m suitably.


The ligands L are bidentate ligands, which bond to the metal M via one carbon atom and one nitrogen atom or via two carbon atoms or via two nitrogen atoms. If the ligand bonds to the metal via two carbon atoms, the ligand preferably contains precisely two nitrogen atoms in the coordinating carbene ring. In a preferred embodiment of the invention, the ligand L bonds to the metal M via one carbon atom and one nitrogen atom.


All atoms X together form a 14π electron system. Each carbon atom here contributes 1π electron to the overall electron system. Each nitrogen atom which is only bonded in a 6-membered ring likewise contributes 1π electron to the overall electron system. Each nitrogen atom which is bonded simultaneously in a 5-membered ring and a 6-membered ring contributes 2π electrons to the overall electron system. Each nitrogen atom which is only bonded in a 5-membered ring contributes 1 or 2π electrons to the overall electron system. It depends on the bonding of the nitrogen in the 5-membered ring whether this nitrogen atom contributes 1 or 2π electrons to the overall electron system. Each boron atom contributes 0 or 1π electron to the overall electron system, depending on whether the boron atom is neutral or negatively charged. The circle in a ring in formulae (2) and (3) represents a 6π electron system, as is usually used for the representation of aromatic or heteroaromatic structures in organic chemistry. The following structures again explain when the nitrogen contributes 1 or 2π electrons (shown only as electrons in the scheme) to the overall π electron system:




embedded image


For the purposes of this invention, a nitrogen atom with a saturated valence is taken to mean a nitrogen atom which formally forms either one single bond and one double bond or three single bonds within the aromatic skeleton. In these cases, the radical R1 to R7 which is bonded to this nitrogen atom represents a free electron pair. For the purposes of this invention, a nitrogen atom with an unsaturated valence is taken to mean, by contrast, a nitrogen atom which formally only forms two single bonds within the aromatic skeleton. In these cases, the radical from R1 to R7 which is bonded to this nitrogen atom represents a radical as defined above and not a free electron pair. The following structures again explain what is taken to mean by a nitrogen atom with a saturated valence:




embedded image


For the purposes of this invention, an aryl group contains 6 to 40 C atoms; for the purposes of this invention, a heteroaryl group contains 2 to 40 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aryl group or heteroaryl group here is taken to mean either a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc., or a condensed aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.


The ligands may also bond to the metal via a carbene carbon atom. For the purposes of this invention, a cyclic carbene is a cyclic group which bonds to the metal via a neutral C atom. Preference is given here to Arduengo carbenes, i.e. carbenes in which two nitrogen atoms are bonded to the carbene C atom. A five-membered Arduengo carbene ring or another unsaturated five-membered carbene ring is likewise regarded as an aryl group for the purposes of this invention. In a preferred embodiment of the invention, the cyclic carbene which coordinates to the metal contains precisely two nitrogen atoms which bond to the carbene C atom, but no further nitrogen atoms.


For the purposes of this invention, an aromatic ring system contains 6 to 60 C atoms in the ring system. For the purposes of this invention, a heteroaromatic ring system contains 1 to 60 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. For the purposes of this invention, an aromatic or heteroaromatic ring system is intended to be taken to mean a system which does not necessarily contain only aryl or heteroaryl groups, but instead in which, in addition, a plurality of aryl or heteroaryl groups may be interrupted by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as, for example, an sp3-hybridised C, N or O atom or a carbonyl group. Thus, for example, systems such as 9,9′-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc., are also intended to be taken to mean aromatic ring systems for the purposes of this invention, as are systems in which two or more aryl groups are interrupted, for example, by a linear or cyclic alkyl group or by a silyl group.


For the purposes of this invention, a cyclic alkyl, alkoxy or thioalkoxy group is taken to mean a monocyclic, bicyclic or polycyclic group.


For the purposes of the present invention, a C1- to C40-alkyl group, in which, in addition, individual H atoms or CH2 groups may be substituted by the above-mentioned groups, is taken to mean, for example, the radicals methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methyl-butyl, n-pentyl, s-pentyl, tert-pentyl, 2-pentyl, cyclopentyl, n-hexyl, s-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, trifluoromethyl, pentafluoroethyl or 2,2,2-trifluoroethyl. An alkenyl group is taken to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. An alkynyl group is taken to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. A C1- to C40-alkoxy group is taken to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy. An aromatic or heteroaromatic ring system having 5-60 aromatic ring atoms, which may also in each case be substituted by the radicals R mentioned above and which may be linked to the aromatic or heteroaromatic ring system via any desired positions, is taken to mean, for example, groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzofluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.


Preference is given to compounds of the formula (1), characterised in that they are uncharged, i.e. are electrically neutral. This is achieved in a simple manner by selecting the charge of the ligands L and L′ in such a way that they compensate for the charge of the complexed metal atom M.


Preference is furthermore given to compounds of the formula (1), characterised in that the sum of the valence electrons around the metal atom is 16 in tetracoordinated complexes and 16 or 18 in pentacoordinated complexes and 18 in hexacoordinated complexes. This preference is due to the particular stability of these metal complexes.


In a preferred embodiment of the invention, M stands for a transition metal or for a main-group metal. If M stands for a main-group metal, it preferably stands for a metal from the third, fourth or fifth main group, in particular for tin.


Preference is given to compounds of the formula (1) in which M stands for a transition metal, in particular for a tetracoordinated, pentacoordinated or hexacoordinated transition metal, particularly preferably selected from the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum, copper, silver and gold, in particular molybdenum, tungsten, rhenium, ruthenium, osmium, iridium, copper, platinum and gold. Very particular preference is given to iridium and platinum. The metals here can be in various oxidation states. The above-mentioned metals are preferably in the oxidation states Cr(0), Cr(II), Cr(III), Cr(IV), Cr(VI), Mo(0), Mo(II), Mo(III), Mo(IV), Mo(VI), W(0), W(II), W(III), W(IV), W(VI), Re(I), Re(II), Re(III), Re(IV), Ru(II), Ru(III), Os(II), Os(III), Os(IV), Rh(I), Rh(III), Ir(I), Ir(III), Ir(IV), Ni(0), Ni(II), Ni(IV), Pd(II), Pt(II), Pt(IV), Cu(I), Cu(II), Cu(III), Ag(I), Ag(II), Au(I), Au(III) and Au(V); particular preference is given to Mo(0), W(0), Re(I), Ru(II), Os(II), Rh(III), Cu(I), Ir(III) and Pt(II).


In a preferred embodiment of the invention, M is a tetracoordinated metal, and the index n stands for 1 or 2. If the index n=1, one bidentate or two monodentate ligands L′, preferably one bidentate ligand L′, is (are) also coordinated to the metal M. If the index n=2, the index m=0.


In a further preferred embodiment of the invention, M is a hexacoordinated metal, and the index n stands for 1, 2 or 3, preferably for 2 or 3. If the index n=1, four monodentate or two bidentate or one bidentate and two monodentate or one tridentate and one monodentate or one tetradentate ligand L′, preferably two bidentate ligands L′, are also coordinated to the metal. If the index n=2, one bidentate or two monodentate ligands L′, preferably one bidentate ligand L′, are also coordinated to the metal. If the index n=3, the index m=0.


In a preferred embodiment of the invention, the central ring of the ligand L contains at least one nitrogen atom. Preferred moieties of the formula (2) and of the formula (3) are thus the structures of the following formulae (2a) and (3a):




embedded image



where the symbols and indices used have the meanings given above and furthermore:

  • X1 is, identically or differently on each occurrence, C or N, with the proviso that at least one group X1 stands for N.


In a particularly preferred embodiment of the invention, the central ring of the ligand L contains at least one nitrogen atom which is bonded in two rings. Preferred moieties of the formula (2a) and of the formula (3a) are thus the structures of the following formulae (2b) and (3b):




embedded image



where the symbols and indices used have the meanings given above.


In a preferred embodiment of the invention, the moieties of the formula (2) are selected from the structures of the following formulae (4), (5) and (6), and the moieties of the formula (3) are selected from the structures of the following formulae (7) and (8):




embedded image



where the symbols and indices have the meanings indicated above.


In a particularly preferred embodiment of the invention, the moieties of the formulae (4) to (8) are selected from the structures of the following formulae (4a) to (8a) in which the central ring of the ligand has at least one nitrogen atom which is bonded in two rings:




embedded image



where the symbols and indices have the meanings indicated above.


A particularly preferred embodiment of the moieties of the formulae (4) to (8) and (4a) to (8a) are the structures of the following formulae (9) to (77):




embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image



where the symbols and indices used have the meanings indicated above.


In a preferred embodiment of the invention, at least one of the substituents R1, R2, R3 and/or R4, particularly preferably R2, R3 and/or R4, is not equal to hydrogen or deuterium. The substituent R2 is very particularly preferably not equal to hydrogen or deuterium. In a very particularly preferred embodiment of the invention, the substituent R2 is therefore not equal to hydrogen or deuterium and the substituents R3 and R4 are equal to hydrogen or deuterium or the substituent R3 is equal to hydrogen or deuterium and the substituent R4 is not equal to hydrogen or deuterium or the substituent R3 is not equal to hydrogen or deuterium and the substituent R4 is equal to hydrogen or deuterium. This preference is due to the higher stability of the corresponding metal complexes.


Furthermore, larger condensed structures are possible through cyclisation of the substituents. Thus, for example, structures of the following formulae (78) to (89) are obtainable:




embedded image


embedded image


embedded image



where the symbols and indices used have the meanings given above. R8 in the formulae (78) to (89) preferably stands for H or an alkyl group having 1 to 5 C atoms, in particular for H or methyl.


The formulae (78) to (89) show merely by way of example on a specific ligand how corresponding larger condensed ring systems are accessible through cyclisation. Cyclisation is possible entirely analogously with the other structures according to the invention, for example with the structures of the formulae (9) to (77), without further inventive step.


It is furthermore possible for the substituent R6 or R7 which is in the orthoposition to the metal coordination to represent a coordinating group which likewise coordinates to the metal M. Preferred coordinating groups R7 are aryl and heteroaryl groups, for example phenyl or pyridyl, aryl or alkyl cyanides, aryl or alkyl isocyanides, amines or amides, alcohols or alcoholates, thioalcohols or thioalcoholates, phosphines, phosphites, carbonyl functions, carboxylates, carbamides or aryl- or alkylacetylides. The moieties ML of the following formulae (90) to (97), for example, are accessible here:




embedded image


embedded image



where the symbols used have the meanings given above. The preferences given above apply to the ligands.


The formulae (90) to (97) show merely by way of example how the substituent R6 or R7 can additionally coordinate to the metal. Other groups R6 and R7 which coordinate to the metal are also possible entirely analogously without further inventive step.


As described above, a bridging unit V which links this ligand L to one or more further ligands L or L′ may also be present instead of one of the radicals R1 to R7. In a preferred embodiment of the invention, a bridging unit V is present instead of one of the radicals R1 to R7, in particular instead of R1, R2, R6 or R7, so that the ligands have a tridentate or polydentate or polypodal character. Formula (2) preferably contains a bridging unit V instead of R1 or R7 and formula (3) preferably contains a bridging unit V instead of R1 or R6. It is also possible for two such bridging units V to be present. This results in the formation of macrocyclic ligands or in the formation of cryptates.


Preferred structures containing polydentate ligands are the metal complexes of the following formulae (98) to (105):




embedded image


embedded image



where the symbols used have the meanings given above, and V preferably represents a bridging unit containing 1 to 80 atoms from the third, fourth, fifth and/or sixth main group (IUPAC group 13, 14, 15 or 16) or a 3- to 6-membered homo- or heterocycle which covalently bonds the part-ligands L to one another or covalently bonds L to L′. The bridging unit V here may also have an asymmetrical structure, i.e. the linking of V to L and L′ need not be identical. The bridging unit V can be neutral, singly, doubly or triply negatively charged or singly, doubly or triply positively charged. V is preferably neutral or singly negatively charged or singly positively charged. The charge of V is preferably selected so that overall a neutral complex forms. The preferences given above for the moiety MLn apply to the ligands.


The precise structure and chemical composition of the group V do not have a significant influence on the electronic properties of the complex since it is, in particular, the task of this group to increase the chemical and thermal stability of the complexes by bridging L to one another or to L′.


If V is a trivalent group, i.e. bridges three ligands L to one another or two ligands L to L′ or one ligand L to two ligands L′, V is preferably selected, identically or differently on each occurrence, from the group consisting of B, B(R8), B(C(R8)2)3, (R8)B(C(R8)2)3, B(O)3, (R8)B(O)3, B(C(R8)2C(R8)2)3, (R8)B(C(R8)2C(R8)2)3, B(C(R8)2O)3, (R8)B(C(R8)2O)3, B(OC(R8)2)3, (R8)B(OC(R8)2)3, C(R8), CO, CN(R8)2, (R8)C(C(R8)2)3, (R8)C(O)3, (R8)C(C(R8)2C(R8)2)3, (R8)C(C(R8)2O)3, (R8)C(OC(R8)2)3, (R8)C(Si(R8)2)3, (R8)C(Si(R8)2C(R8)2)3, (R8)C(C(R8)2Si(R8)2)3, (R8)C(Si(R8)2Si(R8)2)3, Si(R8), (R8)Si(C(R8)2)3, (R8)Si(O)3, (R8)Si(C(R8)2C(R8)2)3, (R8)Si(OC(R8)2)3, (R8)Si(C(R8)2O)3, (R8)Si(Si(R8)2)3, (R8)Si(Si(R8)2C(R8)2)3, (R8)Si(C(R8)2Si(R8)2)3, (R8)Si(Si(R8)2Si(R8)2)3, N, NO, N(R8)+, N(C(R8)2)3, (R8)N(C(R8)2)3+, N(C═O)3, N(C(R8)2C(R8)2)3, (R8)N(C(R8)2C(R8)2)+, P, P(R8)+, PO, PS, PSe, PTe, P(O)3, PO(O)3, P(OC(R8)2)3, PO(OC(R8)2)3, P(C(R8)2)3, P(R8)(C(R8)2)3+, PO(C(R8)2)3, P(C(R8)2C(R8)2)3, P(R8) (C(R8)2C(R8)2)3+, PO(C(R8)2C(R8)2)3, As, As(R8)+, AsO, AsS, AsSe, AsTe, As(O)3, AsO(O)3, As(OC(R8)2)3, AsO(OC(R8)2)3, As(C(R8)2)3, As(R8)(C(R8)2)3+, AsO(C(R8)2)3, As(C(R8)2C(R8)2)3, As(R8)(C(R8)2C(R8)2)3+, AsO(C(R8)2C(R8)2)3, Sb, Sb(R8)+, SbO, SbS, SbSe, SbTe, Sb(O)3, SbO(O)3, Sb(OC(R8)2)3, SbO(OC(R8)2)3, Sb(C(R8)2)3, Sb(R8)(C(R8)2)3+, SbO(C(R8)2)3, Sb(C(R8)2C(R8)2)3, Sb(R8)(C(R8)2C(R8)2)3+, SbO(C(R8)2C(R8)2)3, Bi, Bi(R8)+, BiO, BiS, BiSe, BiTe, Bi(O)3, BiO(O)3, Bi(OC(R8)2)3, BiO(OC(R8)2)3, Bi(C(R8)2)3, Bi(R8)(C(R8)2)3+, BiO(C(R8)2)3, Bi(C(R8)2C(R8)2)3, Bi(R8)(C(R8)2C(R8)2)3+, BiO(C(R8)2C(R8)2)3, S+, S(C(R8)2)3+, S(C(R8)2C(R8)2)3+, Se+, Se(C(R8)2)3+, Se(C(R8)2C(R8)2)3+, Te+, Te(C(R8)2)3+, Te(C(R8)2C(R8)2)3+,


or a unit of the formula (106), (107), (108) or (109):




embedded image



where the dashed bonds in each case indicate the bond to the part-ligands L or L′, and Z is selected, identically or differently on each occurrence, from the group consisting of a single bond, O, S, S(═O), S(═O)2, NR8, PR8, P(═O)R8, P(═NR8), C(R8)2, C(═O), C(═NR8), C(═C(R8)2), Si(R8)2 and BR8. The other symbols used have the meanings given above.


If V is a divalent group, i.e. bridges two ligands L to one another or one ligand L to U, V is preferably selected, identically or differently on each occurrence, from the group consisting of BR8, B(R8)2, C(R8)2, C(═O), Si(R8)2, NRB, PR8, P(R8)2+, P(═O)(R8), P(═S)(R8), AsR8, As(═O)(R8), As(═S)(R8), O, S, Se, or a unit of the formulae (110) to (119):




embedded image


embedded image



where the dashed bonds in each case indicate the bond to the part-ligands L or L′, Y stands on each occurrence, identically or differently, for C(R8)2, N(R8), O or S, and the other symbols used each have the meanings mentioned above.


Preferred ligands L′ as occur in formula (1) are described below. The ligand groups L′ can also be selected correspondingly if they are bonded to L via a bridging unit V, as indicated in formulae (98) to (105).


The ligands L′ are preferably neutral, monoanionic, dianionic or trianionic ligands, particularly preferably neutral or monoanionic ligands. They can be monodentate, bidentate, tridentate or tetradentate and are preferably bidentate, i.e. preferably have two coordination sites. As described above, the ligands L′ can also be bonded to L via a bridging group V.


Preferred neutral, monodentate ligands L′ are selected from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, such as, for example, acetonitrile, aryl cyanides, such as, for example, benzonitrile, alkyl isocyanides, such as, for example, methyl isonitrile, aryl isocyanides, such as, for example, benzoisonitrile, amines, such as, for example, trimethylamine, triethylamine, morpholine, phosphines, in particular halophosphines, trialkylphosphines, triarylphosphines or alkylarylphosphines, such as, for example, trifluorophosphine, trimethylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, triphenylphosphine, tris(pentafluorophenyl)phosphine, dimethylphenylphosphine, methyldiphenylphosphine, bis(tert-butyl)phenylphosphine, phosphites, such as, for example, trimethyl phosphite, triethyl phosphite, arsines, such as, for example, trifluoroarsine, trimethylarsine, tricyclohexylarsine, tri-tert-butylarsine, triphenylarsine, tris(pentafluorophenyl)arsine, stibines, such as, for example, trifluorostibine, trimethylstibine, tricyclohexylstibine, tri-tert-butylstibine, triphenylstibine, tris(pentafluorophenyl)stibine, nitrogen-containing heterocycles, such as, for example, pyridine, pyridazine, pyrazine, pyrimidine, triazine, and carbenes, in particular Arduengo carbenes.


Preferred monoanionic, monodentate ligands L′ are selected from hydride, deuteride, the halides F, Cl, Br and I, alkylacetylides, such as, for example, methyl-C≡C, tert-butyl-C≡C, arylacetylides, such as, for example, phenyl-C≡C, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic or aromatic alcoholates, such as, for example, methanolate, ethanolate, propanolate, iso-propanolate, tert-butylate, phenolate, aliphatic or aromatic thioalcoholates, such as, for example, methanethiolate, ethanethiolate, propanethiolate, iso-propanethiolate, tert-thiobutylate, thiophenolate, amides, such as, for example, dimethylamide, diethylamide, di-iso-propylamide, morpholide, carboxylates, such as, for example, acetate, trifluoroacetate, propionate, benzoate, aryl groups, such as, for example, phenyl, naphthyl, and anionic, nitrogen-containing heterocycles, such as pyrrolide, imidazolide, pyrazolide. The alkyl groups in these groups are preferably C1-C20-alkyl groups, particularly preferably C1-C10-alkyl groups, very particularly preferably C1-C4-alkyl groups. An aryl group is also taken to mean heteroaryl groups. These groups are as defined above.


Preferred di- or trianionic ligands are O2−, S2−, carbides, which result in coordination in the form R—C≡M, and nitrenes, which result in coordination in the form R—N═M, where R generally stands for a substituent, or N3−.


Preferred neutral or mono- or dianionic bidentate or polydentate ligands L′ are selected from diamines, such as, for example, ethylenediamine, N,N,N′,N′-tetramethylethylenediamine, propylenediamine, N,N,N′,N′-tetramethylpropylenediamine, cis- or trans-diaminocyclohexane, cis- or transN,N,N′,N′-tetramethyldiaminocyclohexane, imines, such as, for example, 2-[1-(phenylimino)ethyl]pyridine, 2-[1-(2-methylphenylimino)ethyl]pyridine, 2-[1-(2,6-di-iso-propylphenylimino)ethyl]pyridine, 2-[1-(methylimino)ethyl]-pyridine, 2-[1-(ethylimino)ethyl]pyridine, 2-[1-(iso-propylimino)ethyl]pyridine, 2-[1-(tert-butylimino)ethyl]pyridine, diimines, such as, for example, 1,2-bis(methylimino)ethane, 1,2-bis(ethylimino)ethane, 1,2-bis(iso-propylimino)ethane, 1,2-bis(tert-butylimino)ethane, 2,3-bis(methylimino)butane, 2,3-bis(ethylimino)butane, 2,3-bis(iso-propylimino)butane, 2,3-bis(tert-butylimino)butane, 1,2-bis(phenylimino)ethane, 1,2-bis(2-methylphenylimino)ethane, 1,2-bis(2,6-di-iso-propylphenylimino)ethane, 1,2-bis(2,6-di-tert-butylphenylimino)ethane, 2,3-bis(phenylimino)butane, 2,3-bis(2-methylphenylimino)butane, 2,3-bis(2,6-di-iso-propylphenylimino)butane, 2,3-bis(2,6-di-tert-butylphenylimino)butane, heterocycles containing two nitrogen atoms, such as, for example, 2,2′-bipyridine, o-phenanthroline, diphosphines, such as, for example, bis(diphenylphosphino)methane, bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane, bis(diphenylphosphino)butane, bis(dimethylphosphino)methane, bis(dimethylphosphino)ethane, bis(dimethylphosphino)propane, bis(diethylphosphino)-methane, bis(diethylphosphino)ethane, bis(diethylphosphino)propane, bis(di-tert-butylphosphino)methane, bis(di-tert-butylphosphino)ethane, bis(tert-butylphosphino)propane, 1,3-diketonates derived from 1,3-diketones, such as, for example, acetylacetone, benzoylacetone, 1,5-diphenylacetylacetone, dibenzoylmethane, bis(1,1,1-trifluoroacetyl)-methane, 3-ketonates derived from 3-ketoesters, such as, for example, ethyl acetoacetate, carboxylates derived from aminocarboxylic acids, such as, for example, pyridine-2-carboxylic acid, quinoline-2-carboxylic acid, glycine, N,N-dimethylglycine, alanine, N,N-dimethylaminoalanine, salicyliminates derived from salicylimines, such as, for example, methylsalicylimine, ethylsalicylimine, phenylsalicylimine, dialcoholates derived from dialcohols, such as, for example, ethylene glycol, 1,3-propylene glycol, and dithiolates derived from dithiols, such as, for example, 1,2-ethylenedithiol, 1,3-propylenedithiol.


Preferred tridentate ligands are borates of nitrogen-containing heterocycles, such as, for example, tetrakis(1-imidazolyl) borate and tetrakis(1-pyrazolyl) borate.


Preference is furthermore given to bidentate monoanionic, neutral or dianionic ligands L′, in particular monoanionic ligands, which, with the metal, form a cyclometallated five- or six-membered ring with at least one metal-carbon bond, in particular a cyclometallated five-membered ring. These are, in particular, ligands as are generally used in the area of phosphorescent metal complexes for organic electroluminescent devices, i.e. ligands of the type phenylpyridine, naphthylpyridine, phenylquinoline, phenylisoquinoline, etc., each of which may be substituted by one or more radicals R1 to R6. A multiplicity of such ligands is known to the person skilled in the art in the area of phosphorescent electroluminescent devices, and he will be able, without inventive step, to select further ligands of this type as ligand L′ for compounds of the formula (1). The combination of two groups as depicted by the following formulae (120) to (147) is generally particularly suitable for this purpose, where one group is preferably bonded via a neutral nitrogen atom or a carbene atom and the other group is preferably bonded via a negatively charged carbon atom or a negatively charged nitrogen atom. The ligand L′ can then be formed from the groups of the formulae (120) to (147) through these groups bonding to one another in each case at the position denoted by #. The position at which the groups coordinate to the metal is denoted by *. These groups may also be bonded to the ligand L via one or two bridging units V.




embedded image


embedded image


embedded image


embedded image


The symbols used here have the same meaning as described above, and preferably a maximum of three symbols X in each group stand for N, particularly preferably a maximum of two symbols X in each group stand for N, very particularly preferably a maximum of one symbol X in each group stands for N, especially preferably all symbols X stand for C.


Likewise preferred ligands L′ are η5-cyclopentadienyl, η5-pentamethyl-cyclopentadienyl, η6-benzene or η7-cycloheptatrienyl, each of which may be substituted by one or more radicals R1.


Likewise preferred ligands L′ are 1,3,5-cis,cis-cyclohexane derivatives, in particular of the formula (148), 1,1,1-tri(methylene)methane derivatives, in particular of the formula (149), and 1,1,1-trisubstituted methanes, in particular of the formulae (150) and (151):




embedded image



where the coordination to the metal M is shown in each of the formulae, R1 has the meaning given above, and A stands, identically or differently on each occurrence, for O, S, COO, P(R1)2 or N(R1)2.


Preferred radicals R1 to R7 in the structures shown above are selected on each occurrence, identically or differently, from the group consisting of H, D, F, Br, N(R8)2, CN, B(OR8)2, C(═O)R8, P(═O)(R8)2, a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, each of which may be substituted by one or more radicals R8, where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 14 aromatic ring atoms, which may in each case be substituted by one or more radicals R8; R1 and R2 and/or R2 and R3 and/or R4 and R5 and/or R5 and R6 and/or R6 and R7 here may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; furthermore, R3 and R4 may form a mono- or polycyclic, aliphatic ring system with one another. Particularly preferred radicals R1 to R7 are selected on each occurrence, identically or differently, from the group consisting of H, D, F, Br, CN, B(OR8)2, a straight-chain alkyl group having 1 to 5 C atoms, in particular methyl, or a branched or cyclic alkyl group having 3 to 5 C atoms, in particular isopropyl or tert-butyl, where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 12 aromatic ring atoms, which may in each case be substituted by one or more radicals R8; R1 and R2 and/or R2 and R3 and/or R4 and R5 and/or R5 and R6 and/or R6 and R7 here may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; furthermore, R3 and R4 may form a mono- or polycyclic, aliphatic ring system with one another.


The complexes according to the invention can be facial or pseudofacial or they can be meridional or pseudomeridional.


The preferred embodiments indicated above can be combined with one another as desired. In a particularly preferred embodiment of the invention, the preferred embodiments indicated above apply simultaneously.


The metal complexes according to the invention can in principle be prepared by various processes. However, the processes described below have proven particularly suitable.


The present invention therefore furthermore relates to a process for the preparation of the metal complex compounds of the formula (1) by reaction of the corresponding free ligands with metal alkoxides of the formula (152), with metal ketoketonates of the formula (153) or with metal halides of the formula (154):




embedded image



where the symbols M, n and R8 have the meanings indicated above, and Hal=F, Cl, Br or I.


It is likewise possible to use metal compounds, in particular iridium compounds, which carry both alkoxide and/or halide and/or hydroxyl radicals as well as ketoketonate radicals. These compounds may also be charged. Corresponding iridium compounds which are particularly suitable as starting materials are disclosed in WO 04/085449. [IrCl2(acac)2], for example Na[IrCl2(acac)2], is particularly suitable. A particularly preferred starting material is furthermore Ir(acac)3.


Suitable platinum starting materials are, for example, PtCl2, K2[PtCl4], PtCl2(DMSO)2, Pt(Me)2(DMSO)2 or PtCl2(benzonitrile)2.


It is furthermore possible firstly to prepare a precursor of the metal complex and to introduce the bridge between the two coordinating aryl or heteroaryl rings in a further step. This is shown by way of example for a complex in the following scheme:




embedded image


The synthesis of the complexes is preferably carried out as described in WO 02/060910 and in WO 04/085449. Heteroleptic complexes can also be synthesised, for example, in accordance with WO 05/042548. The synthesis here can also be activated, for example, thermally, photochemically and/or by microwave radiation. In a preferred embodiment of the invention, the reaction is carried out in the melt without the use of an additional solvent. “Melt” here means that the ligand is in molten form, and the metal precursor is dissolved or suspended in this melt.


These processes give the compounds of the formula (1) according to the invention in high purity, preferably greater than 99% (determined by means of 1H-NMR and/or HPLC).


The synthetic methods explained here facilitate, inter alia, the preparation of structures 1 to 357 according to the invention depicted below.




embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


embedded image


The compounds according to the invention can also be solubilised by suitable substitution, for example by alkyl groups, in particular branched alkyl groups, or optionally substituted aryl groups, for example xylyl, mesityl or branched terphenyl groups. These soluble compounds are particularly suitable for processing from solution, for example by printing processes.


The compounds according to the invention described above can also be used as recurring units in conjugated, partially conjugated or non-conjugated oligomers, polymers or dendrimers. For the purposes of this invention, an oligomer is taken to mean a compound having about 3 to 10 recurring units, which may be identical or different. The polymerisation here is preferably carried out via a bromine or boronic acid functionality. Thus, compounds of this type can be copolymerised, inter alia, into polyfluorenes (for example in accordance with EP 842208 or WO 00/22026), polyspirobifluorenes (for example in accordance with EP 707020 or EP 894107), polydihydrophenanthrenes (for example in accordance with WO 05/014689), polyindenofluorenes (for example in accordance with WO 04/041901 and WO 04/113468), polyphenanthrenes (for example in accordance with WO 05/104264), poly-para-phenylenes (for example in accordance with WO 92/18552), polycarbazoles (for example in accordance with WO 04/070772 or WO 04/113468), polyketones (for example in accordance with WO 05/040302), polysilanes (for example in accordance with WO 05/111113) or polythiophenes (for example in accordance with EP 1028136) or also into copolymers which comprise various of these units. They can either be incorporated into the side chain or into the main chain of the polymer here or can represent branching points of the polymer chains (for example in accordance with WO 06/003000).


The invention thus furthermore relates to oligomers, polymers or dendrimers comprising one or more of the compounds of the formula (1), where at least one of the radicals R1 to R8 defined above represents a bond to the polymer or dendrimer. The oligomers, polymers or dendrimers may be conjugated, partially conjugated or non-conjugated. For units of the formula (1), the same preferences as already described above apply in polymers and dendrimers. Apart from the units mentioned above, the oligomers, polymers or dendrimers may comprise further units selected, for example, from recurring units which have hole-transport properties or electron-transport properties. The materials or recurring units known in the prior art are suitable for this purpose.


The oligomers, polymers, copolymers and dendrimers mentioned above are distinguished by good solubility in organic solvents and high efficiency and stability in electroluminescent devices.


The compounds of the formula (1) according to the invention, in particular those which are functionalised by halogens, may furthermore also be further functionalised by common reaction types and thus converted into extended compounds of the formula (1). An example which may be mentioned here is functionalisation with arylboronic acids by the Suzuki method or with amines by the Hartwig-Buchwald method.


The complexes of the formula (1) described above or the preferred embodiments mentioned above can be used as active component in the electronic device. An electronic device is taken to mean a device which comprises an anode, a cathode and at least one layer, where this layer comprises at least one organic or organometallic compound. The electronic device according to the invention thus comprises an anode, a cathode and at least one layer which comprises at least one compound of the formula (1) given above. Preferred electronic devices here are selected from the group consisting of organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs) and organic laser diodes (O-lasers), comprising at least one compound of the formula (1) given above in at least one layer. Particular preference is given to organic electroluminescent devices. Active components are generally the organic or inorganic materials which have been introduced between the anode and cathode, for example charge-injection, charge-transport or charge-blocking materials, but in particular emission materials and matrix materials. The compounds according to the invention exhibit particularly good properties as emission material in organic electroluminescent devices. Organic electroluminescent devices are therefore a preferred embodiment of the invention.


The organic electroluminescent device comprises a cathode, an anode and at least one emitting layer. Apart from these layers, it may also comprise further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers, charge-generation layers and/or organic or inorganic p/n junctions. Interlayers which have, for example, an exciton-blocking function and/or control the charge balance in the electroluminescent device may likewise be introduced between two emitting layers. However, it should be pointed out that each of these layers does not necessarily have to be present.


The organic electroluminescent device may comprise one emitting layer or a plurality of emitting layers. If a plurality of emission layers are present, these preferably have in total a plurality of emission maxima between 380 nm and 750 nm, resulting overall in white emission, i.e. various emitting compounds which are able to fluoresce or phosphoresce are used in the emitting layers. Particular preference is given to three-layer systems, where the three layers exhibit blue, green and orange or red emission (for the basic structure see, for example, WO 05/011013), or systems which have more than three emitting layers. A hybrid system is also possible, where one or more layers fluoresce and one or more other layers phosphoresce.


In a preferred embodiment of the invention, the organic electroluminescent device comprises the compound of the formula (1) or the preferred embodiments mentioned above as emitting compound in one or more emitting layers.


If the compound of the formula (1) is employed as emitting compound in an emitting layer, it is preferably employed in combination with one or more matrix materials. The mixture comprising the compound of the formula (1) and the matrix material comprises between 1 and 99% by vol., preferably between 2 and 90% by vol., particularly preferably between 3 and 40% by vol., especially between 5 and 15% by vol., of the compound of the formula (1), based on the mixture as a whole comprising emitter and matrix material. Correspondingly, the mixture comprises between 99 and 1% by vol., preferably between 98 and 10% by vol., particularly preferably between 97 and 60% by vol., especially between 95 and 85% by vol., of the matrix material, based on the mixture as a whole comprising emitter and matrix material.


In general, the matrix material employed can be all materials which are known for this purpose in accordance with the prior art. The triplet level of the matrix material is preferably higher than the triplet level of the emitter.


Suitable matrix materials for the compounds according to the invention are ketones, phosphine oxides, sulfoxides and sulfones, for example in accordance with WO 04/013080, WO 04/093207, WO 06/005627 or the unpublished application DE 102008033943.1, triarylamines, carbazole derivatives, for example CBP (N,N-biscarbazolylbiphenyl), m-CBP or the carbazole derivatives disclosed in WO 05/039246, US 2005/0069729, JP 2004/288381, EP 1205527, WO 08/086,851 or US 2009/0134784, indolocarbazole derivatives, for example in accordance with WO 07/063,754 or WO 08/056,746, indenocarbazole derivatives, azacarbazoles, for example in accordance with EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrix materials, for example in accordance with WO 07/137,725, silanes, for example in accordance with WO 05/111172, azaboroles or boronic esters, for example in accordance with WO 06/117052, diazasilole derivatives and diazaphosphole derivatives, for example in accordance with the unpublished application DE 102008056688.8, triazine derivatives, for example in accordance with the unpublished application DE 102008036982.9, WO 07/063,754 or WO 08/056,746, or zinc complexes, for example in accordance with EP 652273 or WO 09/062,578.


It may also be preferred to employ a plurality of different matrix materials as a mixture, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material. A preferred combination is, for example, the use of an aromatic ketone or a triazine derivative with a triarylamine derivative or a carbazole derivative as mixed matrix for the metal complex according to the invention.


It is furthermore preferred to employ a mixture of two or more triplet emitters together with a matrix. The triplet emitter having the shorter-wavelength emission spectrum serves as co-matrix for the triplet emitter having the longer-wavelength emission spectrum.


The compounds according to the invention can also be employed in other functions in the electronic device, for example as hole-transport material in a hole-injection or -transport layer, as charge-generation material or as electron-blocking material.


As cathode, preference is given to metals having a low work function, metal alloys or multilayered structures comprising various metals, such as, for example, alkaline-earth metals, alkali metals, main-group metals or lanthanoids (for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys comprising an alkali metal or alkaline-earth metal and silver, for example an alloy comprising magnesium and silver. In the case of multilayered structures, further metals which have a relatively high work function, such as, for example, Ag, may also be used in addition to the said metals, in which case combinations of the metals, such as, for example, Ca/Ag or Ba/Ag, are generally used. It may also be preferred to introduce a thin interlayer of a material having a high dielectric constant between a metallic cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal or alkaline-earth metal fluorides, but also the corresponding oxides or carbonates (for example LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). The layer thickness of this layer is preferably between 0.5 and 5 nm.


The anode preferably comprises materials having a high work function. The anode preferably has a work function of greater than 4.5 eV vs. vacuum. Suitable for this purpose are on the one hand metals having a high redox potential, such as, for example, Ag, Pt or Au. On the other hand, metal/metal oxide electrodes (for example Al/Ni/NiOx, Al/PtOx) may also be preferred. For some applications, at least one of the electrodes must be transparent in order either to facilitate irradiation of the organic material (O-SCs) or the coupling-out of light (OLEDs/PLEDs, O-LASERs). A preferred structure uses a transparent anode. Preferred anode materials here are conductive mixed metal oxides. Particular preference is given to indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is furthermore given to conductive, doped organic materials, in particular conductive doped polymers, for example PEDOT, PANI or derivatives of these polymers.


All materials as are used in accordance with the prior art for the layers can generally be used in the further layers, and the person skilled in the art will be able to combine each of these materials with the materials according to the invention in an electronic device without inventive step.


The device is correspondingly structured (depending on the application), provided with contacts and finally hermetically sealed, since the lifetime of such devices is drastically shortened in the presence of water and/or air.


Preference is furthermore given to an organic electroluminescent device, characterised in that one or more layers are applied by means of a sublimation process, in which the materials are vapour-deposited in vacuum sublimation units at an initial pressure of usually less than 10−5 mbar, preferably less than 10−6 mbar. It is also possible for the initial pressure to be even lower or even higher, for example less than 10−7 mbar.


Preference is likewise given to an organic electroluminescent device, characterised in that one or more layers are applied by means of the OVPD (organic vapour phase deposition) process or with the aid of carrier-gas sublimation, in which the materials are applied at a pressure of between 10−5 mbar and 1 bar. A special case of this process is the OVJP (organic vapour jet printing) process, in which the materials are applied directly through a nozzle and thus structured (for example M. S. Arnold et at., Appl. Phys. Lett. 2008, 92, 053301).


Preference is furthermore given to an organic electroluminescent device, characterised in that one or more layers are produced from solution, such as, for example, by spin coating, or by means of any desired printing process, such as, for example, screen printing, flexographic printing, offset printing or nozzle printing, but particularly preferably LITI (light induced thermal imaging, thermal transfer printing) or ink-jet printing. Soluble compounds are necessary for this purpose, which are obtained, for example, through suitable substitution.


The organic electroluminescent device may also be produced as a hybrid system by applying one or more layers from solution and applying one or more other layers by vapour deposition. Thus, for example, it is possible to apply an emitting layer comprising a compound of the formula (1) and a matrix material from solution and to apply a hole-blocking layer and/or an electron-transport layer on top by vacuum vapour deposition.


These processes are generally known to the person skilled in the art and can be applied by him without problems to organic electroluminescent devices comprising compounds of the formula (1) or the preferred embodiments mentioned above.


The electronic devices according to the invention, in particular organic electroluminescent devices, are distinguished by the following surprising advantages over the prior art:

  • 1. Organic electroluminescent devices comprising compounds of the formula (1) as emitting materials have an excellent lifetime.
  • 2. Organic electroluminescent devices comprising compounds of the formula (1) as emitting materials have excellent efficiency.
  • 3. The metal complexes according to the invention give access to organic electroluminescent devices which phosphoresce in the blue colour region. In particular, blue phosphorescence with good efficiencies and lifetimes can only be achieved with great difficulty in accordance with the prior art.


These advantages mentioned above are not accompanied by an impairment of the other electronic properties.


The invention is explained in greater detail by the following examples, without wishing to restrict it thereby. The person skilled in the art will be able to produce further electronic devices according to the invention from the descriptions without an inventive step and thus carry out the invention throughout the range claimed.







EXAMPLES

The following syntheses are, unless indicated otherwise, carried out under a protective-gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light. The solvents and reagents can be purchased from ALDRICH or ABCR.


A: Synthesis of the Ligands


1) Imidazo[2,1-a]isoquinoline systems


Synthesis of 1-aminoisoquinolines:


A mixture of 100 mmol of the 1-chloroisoquinoline derivative and 600 mmol of ammonium chloride in 100 ml of sulfolane is stirred at 200° C. for 20 h. 200 ml of water are added to the cooled mixture, and the mixture is stirred at room temperature for 1 h. The solid is filtered off with suction, washed once with 50 ml of water and subsequently suspended in a mixture of 50 ml of methanol and 150 ml of conc. ammonia solution. The suspension is stirred at room temperature for 20 h, and the solid is filtered off, washed three times with 50 ml of methanol/water 1:1, dried in vacuo and subjected to Kugelrohr distillation.
















1-Chloroisoquinoline
1-Aminoisoquinoline



Ex.
derivative
derivative
Yield







A1


embedded image

  24188-78-1



embedded image


74%





A2


embedded image

  15787-20-9



embedded image


67%





A3


embedded image

  55792-01-3



embedded image


61%










Ligand Synthesis Variant A:


A vigorously stirred mixture of 100 mmol of the 1-aminoisoquinoline derivative, 150 mmol of the carbonyl component, 130 mmol of sodium hydrogencarbonate, 80 ml of ethanol and 15 ml of water is heated under reflux until the 1-aminoisoquinoline has reacted (aldehydes about 3-8 h, ketones about 30-100 h). The solvent is subsequently removed in vacuo, the residue is taken up in 500 ml of dichloromethane, and the mixture is washed three times with 200 ml of water. After the organic phase has been dried and the solvent has been removed in vacuo, the residue is chromatographed on silica gel (eluent: ethyl acetate/heptane mixtures). The resultant oils/solids are freed from low-boiling components in an oil-pump vacuum, by bulb-tube distillation or sublimation.


Ligand Synthesis Variant B:


A mixture of 100 mol of the 1-aminoisoquinoline derivative, 300 mol of the carbonyl component, 150 mol of sodium hydrogencarbonate, 150 ml of DMF and 30 g of glass beads (diameter 3 mm) is stirred at 130° C. for 24 h. The glass beads and salts are subsequently filtered off, the DMF is removed in vacuo, and the residue is chromatographed on silica gel (eluent: ethyl acetate/heptane mixtures). The resultant oils/solids are freed from low-boiling components in an oil-pump vacuum, by bulb-tube distillation or sublimation.



















1-Amino-







isoquinoline
Carbonyl




Ex.
Variant
derivative
component
Product
Yield







L1 
A


embedded image

  1532-84-9



embedded image

  107-20-0



embedded image


84%





L2 
A


embedded image




embedded image

  683-50-1



embedded image


79%





L3 
A


embedded image




embedded image

  78-95-5



embedded image


81%





L4 
A


embedded image




embedded image

  28832-55-5



embedded image


83%





L5 
A


embedded image




embedded image

  4091-39-8



embedded image


65%





L6 
A


embedded image




embedded image

  29585-17-9



embedded image


76%





L7 
A


embedded image




embedded image

  29846-94-4



embedded image


70%





L8 
B


embedded image




embedded image

  61914-03-2



embedded image


54%





L9 
B


embedded image




embedded image




embedded image


85%





L10
A


embedded image




embedded image




embedded image


91%





L11
A


embedded image




embedded image




embedded image


90%





L12
B


embedded image




embedded image




embedded image


84%





L13
A


embedded image




embedded image

  4638-79-3



embedded image


86%





L14
A


embedded image




embedded image




embedded image


93%





L15
A


embedded image




embedded image




embedded image


80%





L16
B


embedded image




embedded image




embedded image


68%





L17
A


embedded image




embedded image




embedded image


77%





L18
A


embedded image




embedded image




embedded image


88%





L19
A


embedded image




embedded image




embedded image


35%





L20
B


embedded image




embedded image




embedded image


72%





L21
A


embedded image




embedded image




embedded image


31%





L22
A


embedded image

  58814-41-8



embedded image




embedded image


91%





L23
B


embedded image




embedded image




embedded image


73%





L24
A


embedded image

  55270-26-3



embedded image




embedded image


84%





L25
A


embedded image




embedded image




embedded image


84%





L26
B


embedded image




embedded image




embedded image


79%





L27
A


embedded image




embedded image




embedded image


80%





L28
B


embedded image

  58814-43-0



embedded image




embedded image


29%





L29
A


embedded image

  42398-74-3



embedded image




embedded image


89%





L30
A


embedded image




embedded image




embedded image


90%





L31
A


embedded image




embedded image




embedded image


82%





L32
B


embedded image




embedded image




embedded image


71%





L33
A


embedded image

  009034-72-3



embedded image




embedded image


87%





L34
A


embedded image

  58814-44-1



embedded image




embedded image


48%





L35
A


embedded image

  161468-33-3



embedded image




embedded image


69%





L36
A


embedded image




embedded image

  55756-20-2



embedded image


41%










Ligand Synthesis Variant C:


100 mmol of the 2-phenylimidazole derivative are initially introduced in 400 ml of triethylamine. 200 ml of the alkyne, 6 mmol of triphenylphosphine, 6 mmol of copper(I) iodide and 3 mmol of palladium(II) acetate are successively added with stirring. The reaction mixture is subsequently stirred at 80° C. for 20 h. After cooling, the reaction mixture is diluted with 400 ml of dichloromethane, the solids are separated off by filtration through a Celite bed, and the filtrate is evaporated to dryness. The residue is taken up in 300 ml of dichloromethane, and the solution is washed three times with 100 ml of conc. ammonia solution each time and three times with 100 ml of water each time and dried over magnesium sulfate. After the solvent has been removed in vacuo, the crude product is adsorbed onto silica gel (5 g per g of crude product) and packed into a silica-gel column. Byproducts are firstly removed using dichloromethane, then the solvent is switched to THF, and the product is eluted. The resultant oils/solids are freed from low-boiling components in an oil-pump vacuum, by bulb-tube distillation or sublimation.

















2-Phenylimidazole





Ex.
derivative
Alkyne
Product
Yield







L37


embedded image

  162356-38-9



embedded image

  536-74-3



embedded image


38%





L38


embedded image

  496807-43-3



embedded image




embedded image


51%





L39


embedded image




embedded image

  769-26-6



embedded image


44%





L40


embedded image




embedded image




embedded image


21%





L41


embedded image




embedded image

  40430-66-8



embedded image


17%










Ligand Synthesis Variant D:


Synthesis of 3-bromoimidazo[2,1-a]isoquinolines:


105 mmol of N-bromosuccinimide are added in portions to a vigorously stirred solution, cooled to +5° C., of 100 mmol of the imidazo[2,1-a]isoquinoline derivative in 300 ml of THF at such a rate that the temperature does not exceed +10° C. When the addition is complete and after the reaction mixture has been warmed to room temperature, the mixture is diluted with 300 ml of dichloromethane, and the org. phase is washed five times with 500 ml of sat. sodium carbonate solution and dried over magnesium sulfate. The solvent is substantially removed in vacuo, 200 ml of n-heptane are added to the residue, and the mixture is stirred for 12 h. The resultant solid is filtered off, washed with n-heptane and dried in vacuo.
















Imidazo[2,1-a]iso-
3-Bromoimidazo[2,1-a]-



Ex.
quinoline derivative
isoquinoline derivative
Yield







A4


embedded image




embedded image


81%





A5


embedded image




embedded image


79%





A6


embedded image




embedded image


76%





A7


embedded image




embedded image


64%





A8


embedded image




embedded image


80%





A9


embedded image




embedded image


45%










Suzuki Coupling:


20 mmol of dicyclohexyl(2′,6′-dimethoxy[1,1′-biphenyl]-2-yl)phosphine and 10 mmol of palladium(II) acetate are added to a vigorously stirred mixture of 100 mmol of the 3-bromoimidazo[2,1-a]isoquinoline derivative, 400 mmol of the boronic acid, 600 mmol of tripotassium phosphate (anhydrous) and 200 g of glass beads (diameter 3 mm) in 500 ml of toluene, and the mixture is stirred at 70° C. for 60 h. After cooling, the mixture is filtered through a Celite bed, and the organic phase is washed three times with 500 ml of water, dried over magnesium sulfate and then evaporated to dryness in vacuo. The residue is chromatographed on silica gel (eluent ethyl acetate/n-heptane). The resultant oils/solids are freed from low-boiling components and traces of metal in an oil-pump vacuum, by bulb-tube distillation or sublimation.

















3-Bromoimidazo-






[2,1-a]isoquinoline
Boronic




Ex.
derivative
acid
Product
Yield







L42


embedded image




embedded image

  98-80-6



embedded image


87%





L43


embedded image




embedded image

  16419-60-6



embedded image


80%





L44


embedded image




embedded image

  100379-00-8



embedded image


76%





L45


embedded image




embedded image

  5980-97-2



embedded image


59%





L46


embedded image




embedded image

  363166-79-4



embedded image


37%





L47


embedded image




embedded image

  1065663-52-6



embedded image


17%





L48


embedded image




embedded image

  197958-29-5



embedded image


83%





L49


embedded image




embedded image




embedded image


71%





L50


embedded image




embedded image




embedded image


66%





L51


embedded image




embedded image




embedded image


69%





L52


embedded image




embedded image




embedded image


57%





L53


embedded image




embedded image




embedded image


71%





L54


embedded image




embedded image




embedded image


23%










Ligand Synthesis Variant E:


105 mmol, 62.6 ml of n-butyllithium (1.6 M in hexane) are added dropwise over the course of 5 min. to a vigorously stirred solution, cooled to −78° C., of 100 mmol of the 3-bromoimidazo[2,1-a]isoquinoline derivative in 1000 ml of diethyl ether. The mixture is stirred for a further 15 min., and 120 mmol of the electrophile are then added over the course of 2 min. After the mixture has been warmed to room temperature, the organic phase is washed once with 500 ml of water and dried over magnesium sulfate, and the solvent is removed in vacuo. The residue is chromatographed on silica gel (eluent ethyl acetate/n-heptane). The resultant oils/solids are freed from low-boiling components in an oil-pump vacuum, by bulb-tube distillation or sublimation.

















3-Bromoimidazo-





Ex.
[2,1-a]isoquinoline derivative
Electrophile
Product
Yield







L55


embedded image


H3C—I


embedded image


87%





L56


embedded image


D3C—I


embedded image


83%





L57


embedded image




embedded image

  630-17-1



embedded image


70%





L58


embedded image




embedded image




embedded image


84%





L59


embedded image




embedded image

  The org. phase is not washed with water.



embedded image


57%





L60


embedded image




embedded image

  70892-81-8 The org. phase is not washed with water.



embedded image


36%





L61


embedded image




embedded image

  13154-24-0 The org. phase is not washed with water.



embedded image


21%





L62


embedded image




embedded image




embedded image


74%










Ligand Synthesis Variant F:


2 mmol of pentamethylcyclopentadienylrhodium(III) chloro dimer and 8 mmol of tetraphenylcyclopentadiene are added to a vigorously stirred mixture of 100 mmol of the 2-arylimidazole derivative, 120 mmol of the alkyne and 120 mmol of copper(II) acetate in 1000 ml of DMF, and the mixture is stirred at 80° C. for 20 h. After cooling, the mixture is filtered through a Celite bed, 1000 ml of dichloromethane are added to the organic phase, and the mixture is washed five times with 500 ml of water, dried over magnesium sulfate and then evaporated to dryness in vacuo. The residue is chromatographed on silica gel (eluent ethyl acetate/n-heptane). The resultant oils/solids are freed from low-boiling components in an oilpump vacuum, by bulb-tube distillation or sublimation.

















2-Arylimidazole





Ex.
derivative
Alkyne
Product
Yield







L63


embedded image

  670-96-2



embedded image

  501-65-5



embedded image


63%





L64


embedded image

  13682-20-7



embedded image




embedded image


54%





L65


embedded image




embedded image

  19339-46-9



embedded image


57%





L66


embedded image




embedded image

  5294-03-1



embedded image


61%





L67


embedded image

  21202-37-9



embedded image




embedded image


26%





L68


embedded image

  92437-07-5



embedded image




embedded image


57%










2) 1,2,4-Triazolo[3,4-a]isoquinoline systems














Ex.
Literature
Product







L69
G. S. Sidhu et al. J. Heterocyclic Chem. 1966, 3(2), 158.


embedded image







L70
H. Reimlinger et al. Chem. Ber. 1970, 103, 1960.


embedded image







L71
Analogous to Ex. L70, but pivalic anhydride [1538-75-6] is employed instead of acetic anhydride


embedded image







L72
H. Reimlinger et al. Chem. Ber. 1970, 103, 1960.


embedded image







L73
H. Reimlinger et al. Chem. Ber. 1970, 103, 1960.


embedded image












3) 1,2,4-Triazolo[5,1-a]isoquinoline systems














Ex.
Literature
Product







L74
Y. -I. Lin et al. J. Org. Chem., 1981, 46(15), 3123


embedded image







L75
C. N. Hoang et al. ARKIVOC, 2001, 2(2), 42-50


embedded image







L76
C. Hoogzand et al. Recueil des Travaux Chimiques des Pays- Bas 1971, 90(11), 1225-33


embedded image







L77
H. Reimlinger et al. Chem. Ber., 1971, 104(12), 3965-75


embedded image












Suzuki Coupling:


20 mmol of dicyclohexyl(2′,6′-dimethoxy[1,1′-biphenyl]-2-yl)phosphine and 10 mmol of palladium(II) acetate are added to a vigorously stirred mixture of 100 mmol of the bromo-1,2,4-triazolo[5,1-a]isoquinoline derivative, 400 mmol of the boronic acid, 600 mmol of tripotassium phosphate (anhydrous) and 200 g of glass beads (diameter 3 mm) in 500 ml of toluene, and the mixture is stirred at 70° C. for 60 h. After cooling, the mixture is filtered through a Celite bed, and the organic phase is washed three times with 500 ml of water, dried over magnesium sulfate and then evaporated to dryness in vacuo. The residue is chromatographed on silica gel (eluent ethyl acetate/n-heptane). The resultant oils/solids are freed from low-boiling components in an oil-pump vacuum, by bulb-tube distillation or sublimation.

















Bromo-1,2,4-tri-






azolo[5,1-a]iso-





Ex.
quinoline derivative
Boronic acid
Product
Yield







L78


embedded image




embedded image




embedded image


47%





L79


embedded image




embedded image




embedded image


23%










4) Tetraazolo[5,1-a]isoquinolines














Ex.
Literature
Product







L80
J. M. Keith, J. Org. Chem. 2006, 71(25), 9540.


embedded image







L81
H. Reimlinger, Chem. Ber. 1975, 108(12), 3780-6


embedded image







L82
From bromide in accordance with Ex. L79 by Suzuki coupling analogously to process 3) 1,2,4- triazolo[5,1-a]isoquinoline systems


embedded image












5) Benzimidazo[2,1-a]isoquinoline systems


Ligand Synthesis Variant A:


A vigorously stirred mixture of 500 mmol of the 1-chloroisoquinoline derivative, 600 mmol of the aniline, 1250 mmol of potassium carbonate, 200 g of glass beads (diameter 3 mm), 10 mmol of triphenylphosphine and 2 mmol of palladium(II) acetate in 1500 ml of o-xylene is heated under reflux for 3-48 h until the 1-chloroisoquinoline derivative has been consumed. After cooling, the mixture is filtered through a silica-gel bed and rinsed with 2000 ml of THF, and the filtrate is evaporated to dryness. The residue is dissolved in 100 ml of boiling ethyl acetate, and 800 ml of n-heptane are slowly added. After cooling, the solid that has crystallised out is filtered off with suction, washed twice with 100 ml of n-heptane each time and dried in vacuo. The resultant oils/solids are freed from low-boiling components in an oil-pump vacuum, by bulb-tube distillation or sublimation.

















1-Chloroiso-






quinoline





Ex.
derivative
Aniline
Product
Yield







L83


embedded image




embedded image




embedded image


73%





L84


embedded image




embedded image




embedded image


56%





L85


embedded image




embedded image




embedded image


67%





L86


embedded image




embedded image




embedded image


67%





L87


embedded image




embedded image




embedded image


65%





L88


embedded image




embedded image




embedded image


61%





L89


embedded image




embedded image




embedded image


72%





L90


embedded image




embedded image




embedded image


50%





L91


embedded image




embedded image




embedded image


69%





L92


embedded image




embedded image




embedded image


34%





L93


embedded image




embedded image




embedded image


41%





L94


embedded image




embedded image




embedded image


19%





L95


embedded image




embedded image




embedded image


64%





L96


embedded image




embedded image




embedded image


71%





L97


embedded image




embedded image




embedded image


29%





L98


embedded image




embedded image




embedded image


67%





L99


embedded image




embedded image




embedded image


71%





L100


embedded image




embedded image




embedded image


65%





L101


embedded image




embedded image




embedded image


34%





L102


embedded image




embedded image




embedded image


68%





L103


embedded image




embedded image




embedded image


60%





L104


embedded image




embedded image




embedded image


55%





L105


embedded image




embedded image




embedded image


69%





L106


embedded image




embedded image




embedded image


63%





L107


embedded image




embedded image




embedded image


28%





L108


embedded image




embedded image




embedded image


22%





L109


embedded image




embedded image




embedded image


62%





L110


embedded image




embedded image




embedded image


31%





L111


embedded image




embedded image




embedded image


74%





L112


embedded image




embedded image




embedded image


19%





L113


embedded image




embedded image




embedded image


59%





L114


embedded image




embedded image




embedded image


44%










Ligand Synthesis Variant B:


2 mmol of pentamethylcyclopentadienylrhodium(III) chloro dimer and 8 mmol of tetraphenylcyclopentadiene are added to a vigorously stirred mixture of 100 mmol of the 2-arylbenzimidazole derivative, 120 mmol of the alkyne and 120 mmol of copper(II) acetate in 1000 ml of DMF, and the mixture is stirred at 80° C. for 20 h. After cooling, the mixture is filtered through a Celite bed, 1000 ml of dichloromethane are added to the organic phase, and the mixture is washed five times with 500 ml of water, dried over magnesium sulfate and then evaporated to dryness in vacuo. The residue is chromatographed on silica gel (eluent ethyl acetate/n-heptane). The resultant oils/solids are freed from low-boiling components in an oil-pump vacuum, by bulb-tube distillation or sublimation.

















2-Arylbenz-






imidazole





Ex.
derivative
Alkyne
Product
Yield







L115


embedded image




embedded image




embedded image


43%





L116


embedded image




embedded image




embedded image


45%





L117


embedded image




embedded image




embedded image


37%





L118


embedded image




embedded image




embedded image


23%





L119


embedded image




embedded image




embedded image


45%





L120


embedded image




embedded image




embedded image


9%





L121


embedded image




embedded image




embedded image


23%





L122


embedded image




embedded image




embedded image


6%





L123


embedded image




embedded image




embedded image


29%





L124


embedded image




embedded image




embedded image


43%





L125


embedded image




embedded image




embedded image


13%





L126


embedded image




embedded image




embedded image


16%










Ligand Synthesis Variant C:


100 mmol of the 2-(2-bromophenyl)imidazole derivative are initially introduced in 300 ml of triethylamine and 200 ml of DMF. 200 ml of the alkyne, 5 mmol of triphenylphosphine, 5 mmol of copper(I) iodide and 2 mmol of palladium(II) acetate are successively added with stirring. The reaction mixture is subsequently stirred at 80° C. for 20 h. After cooling, the reaction mixture is diluted with 400 ml of dichloromethane, the solids are separated off by filtration through a Celite bed, and the filtrate is evaporated to dryness. The residue is taken up in 300 ml of dichloromethane, and the solution is washed three times with 100 ml of conc. ammonia solution each time and three times with 100 ml of water each time and dried over magnesium sulfate. The resultant oils/solids are freed from low-boiling components and traces of metal in an oil-pump vacuum, by bulb-tube distillation or sublimation.

















2-(2-Bromo-






phenyl)-





Ex.
imidazole
Alkyne
Product
Yield







L127


embedded image




embedded image




embedded image


37%





L128


embedded image




embedded image




embedded image


34%





L129


embedded image




embedded image




embedded image


38%





L130


embedded image




embedded image




embedded image


27%





L131


embedded image




embedded image




embedded image


9%










6) Heteroimidazo[2,1-a]isoquinoline systems


Ligand Synthesis Variant A:


A vigorously stirred mixture of 500 mmol of the 1-chloroisoquinoline derivative, 520 mmol of the amine, 1250 mmol of potassium carbonate (1800 mmol in the case of hydrobromides), 200 g of glass beads (diameter 3 mm), 10 mmol of triphenylphosphine and 2 mmol of palladium(II) acetate in 1500 ml of o-xylene is heated under reflux for 3-36 h until the 1-chloroisoquinoline has been consumed. After cooling, the mixture is filtered through a silica-gel bed and rinsed with 2000 ml of THF, and the filtrate is evaporated to dryness. The residue is dissolved in 100 ml of boiling ethyl acetate, and 800 ml of n-heptane are slowly added. After cooling, the solid that has crystallised out is filtered off with suction, washed twice with 100 ml of n-heptane each time and dried in vacuo. If necessary, the crude product is recrystallised again from ethyl acetate/heptane. The resultant oils/solids are freed from low-boiling components in an oil-pump vacuum, by bulb-tube distillation or sublimation.

















1-Chloro-





Ex.
isoquinoline
Amine
Product
Yield







L132


embedded image




embedded image




embedded image


56%





L133


embedded image




embedded image




embedded image


64%





L134


embedded image




embedded image




embedded image


82%





L135


embedded image




embedded image




embedded image


78%





L136


embedded image




embedded image




embedded image


26%





L137


embedded image




embedded image




embedded image


17%





L138


embedded image




embedded image




embedded image


45%





L139


embedded image




embedded image




embedded image


50%










Ligand Synthesis Variant B:


A vigorously stirred mixture of 500 mmol of 1-aminoisoquinoline, 520 mmol of the dibromide, 1250 mmol of potassium carbonate, 200 g of glass beads (diameter 3 mm), 10 mmol of triphenylphosphine and 2 mmol of palladium(II) acetate in 1500 ml of o-xylene is heated under reflux for 3-12 h until the 1-aminoisoquinoline has been consumed. After cooling, the mixture is filtered through a silica-gel bed and rinsed with 2000 ml of THF, and the filtrate is evaporated to dryness. The residue is dissolved in 100 ml of boiling ethyl acetate, and 800 ml of n-heptane are slowly added. After cooling, the solid that has crystallised out is filtered off with suction, washed twice with 100 ml of n-heptane each time and dried in vacuo. If necessary, the crude product is recrystallised again from ethyl acetate/heptane. The resultant oils/solids are freed from low-boiling components in an oil-pump vacuum, by bulb-tube distillation or sublimation.

















1-Aminoiso-





Ex.
quinoline
Dibromide
Product
Yield







L140


embedded image




embedded image




embedded image


22%





L141


embedded image




embedded image




embedded image


19%










7) 8H-Acenaphth[1′,2′:4,5]imidazo[2,1-a]benz[de]isoquinoline


Procedure analogous to 6) Heteroimidazo[2,1-a]isoquinoline systems, ligand synthesis variant B.

















1-Amino-





Ex.
isoquinoline
Dibromide
Product
Yield







L142


embedded image




embedded image




embedded image


25%





L143


embedded image




embedded image




embedded image


16%










8) Imidazo[2,1-a]phthalazine systems














Ex.
Literature
Product







L144
A. D. C. Parenty et al. Synthesis 2008, 9, 1479


embedded image







L145
A. Heim-Riether et al. Synthesis 2009, 10, 1715-1719


embedded image







L146
DE 2206012 The base is liberated from the hydrochloride using solid potassium carbonate in EtOH.


embedded image







L147
DE 2206012


embedded image







L148
U.S. Pat. No. 3,704,300


embedded image







L149
Analogously to Ex. L148 through the use of tert-butanol


embedded image







L150
S. El-Feky et al. Polish Journal of Chemistry 1991, 65(9-10), 1645-57


embedded image







L151
D. Catarzi et al. Farmaco 1993, 48(4), 447-57


embedded image







L152
M. Razvi et al. Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry 1992, 31B(11), 788-9


embedded image







L153
V. A. Kuznetsov et al. Tetrahedron 2006, 62(42), 10018


embedded image












9) Imidazo[1,2-c]quinazoline systems














Ex.
Literature
Product







L154
P. Franchetti et al. Journal of Heterocyclic Chemistry 1970, 7(6), 1295


embedded image







L155
P. Franchetti et al. Journal of Heterocyclic Chemistry 1970, 7(6), 1295


embedded image







L156
P. Franchetti et al. Journal of Heterocyclic Chemistry 1970, 7(6), 1295


embedded image







L157
P. Franchetti et al. Journal of Heterocyclic Chemistry 1970, 7(6), 1295


embedded image







L158
F. Claudi et al. Journal of Organic Chemistry 1974, 39(24), 3508


embedded image







L159
Analogously to Ex. 158 through the use of 2- mesitylaziridine [65855- 33-6] instead of 2-phenylaziridine, Yield: 23%


embedded image







L160
J. Kalinowska-Torz et al. Acta Poloniae Pharmaceutica 1984, 41(2), 161


embedded image







L161
M. Cardellini et al. Farmaco, Edizione Scientifica 1975, 30(7), 536


embedded image







L162
M. Davis et al. Journal of the Chemical Society 1962, 945


embedded image







L163
D. -Q. Shi et al. Gaodeng Xuexiao Huaxue Xuebao 2007, 28(10), 1889


embedded image







L164
M. Davis, Michael et al. Journal of the Chemical Society 1962, 945


embedded image







L165
A. V. Bogatskii et al. Ukrainskii Khimicheskii Zhurnal (Russian Edition) 1979, 45(3), 225


embedded image







L166
S. Vomero et al. Farmaco, Edizione Scientifica 1984, 39(5), 394


embedded image







L167
J. Padmaja et al. Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry 1988, 27B(10), 909


embedded image







L168
J. Padmaja et al. Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry 1988, 27B(10), 909


embedded image












Ligand Synthesis:


Preparation analogous to 1) Imidazo[2,1-a]isoquinoline systems.



















Quinazol-4-
Carbonyl




Ex.
Variant
ylamine
comp.
Product
Yield







L169
A


embedded image




embedded image




embedded image


76%





L170
A


embedded image




embedded image




embedded image


65%





L171
A


embedded image




embedded image




embedded image


54%





L172
A


embedded image




embedded image




embedded image


51%





L173
B


embedded image




embedded image




embedded image


75%










10) Imidazo[2,1-f][1,6]naphthyridine systems

















Ex.
Literature
Product









L174
J. M. Chezal et al. Tetrahedron 2002, 58(2), 295


embedded image













11) Pyrazolo[1,5-a]quinoline systems














Ex.
Literature
Product







L175
D. Barrett et al. Recent Research Developments in Organic Chemistry 1997, 1, 137


embedded image







L176
H. Gnichtel et al. Liebigs Annalen der Chemie 1981, 10, 1751


embedded image







L177
R. E. Banks Journal of Fluorine Chemistry 1980, 15(2), 179


embedded image







L178
Y. P. Reddy et al. Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry 1988, 27B(6), 563


embedded image







L179
Y. P. Reddy et al. Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry 1988, 27B(6), 563


embedded image












12) 1,2,4-Triazolo[1,5-a]quinoline systems














Ex.
Literature
Product







L180
S. Batori et al. Heterocycles 1990, 31(2), 289


embedded image







L181
C. N. Hoang, et al. ARKIVOC 2001, 2(2), 42


embedded image












13) 1,2,3-Triazolo[1,5-a]quinoline systems














Ex.
Literature
Product







L182
Y. Tamura et al. Journal of Heterocyclic Chemistry 1975, 12(3), 481


embedded image







L183
Y. Tamura et al. Journal of Heterocyclic Chemistry 1975, 12(3), 481


embedded image







L184
R. Ballesteros-Garrido et al. Tetrahedron 2009, 65(22), 4410


embedded image












14) Tetraazolo[1,5-a]quinoline systems














Ex.
Literature
Product







L185
J. K. Laha Synthesis 2008, 24, 4002


embedded image







L186
U.S. Pat. No. 2743274


embedded image







L187
DE 2166398


embedded image







L188
C. W. Rees et al. Journal of the Chemistry Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999) 1976, 20, 2178


embedded image












15) Imidazo[1,2-a][1,8]naphthyridine systems

















Ex.
Literature
Product









L189
A. Gueiffier et al. Journal of Heterocyclic Chemistry 1997, 34(3), 765


embedded image









L190
A. Gueiffier et al. Journal of Heterocyclic Chemistry 1997, 34(3), 765


embedded image













16) 1,2,4-Triazolo[4,3-a][1,8]naphthyridine systems














Ex.
Literature
Product







L191
H. Shailaja Rani et al. Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry 1996, 35B(2), 106


embedded image












17) Pyrrolo[1,2-a][1,8]naphthyridine systems














Ex.
Literature
Product







L192
I. Cardinaud et al. Heterocycles 1993, 36(11), 2513


embedded image












18) 1H-Pyrrolo[3,2-h]quinoline systems














Ex.
Literature
Product







L193
M. Vlachou et al. Heterocycles 2002, 57(1), 129


embedded image







L194
Zh. F. Sergeeva et al. Khimiya Geterotsiklicheskikh Soedinenii 1975, 12, 1656


embedded image







L195
S. A. Yamashkin et al. Khimiya Geterotsiklicheskikh Soedinenii 1995, 1, 58


embedded image







L196
C. B. de Koning et al. Perkin 1 2000, 11, 1705


embedded image







L197
C. Galvez et al. Journal of Chemical Research, Synopses 1987, 1, 16


embedded image







L198
N. P. Buu-Hoi et al. Journal of the Chemical Society [Section] C: Organic 1966, 1, 47


embedded image







L199
E. P. Baberkina et al. Zhurnal Organicheskoi Khimii 1991, 27(5), 1110


embedded image












19) Imidazo[1,2-h][1,7]naphthyridine systems














Ex.
Literature
Product







L200
J. M. Chezal et al. Tetrahedron 2002, 58(2), 295


embedded image







L201
M. Andaloussi et al. European Journal of Medicinal Chemistry 2008, 43(11), 2505


embedded image












20) 1,8-Dihydropyrrolo[3,2-g]indoles














Ex.
Literature
Product







L202
A. Berlin et al. Journal of the Chemical Society, Chemical Communications 1987, 15, 1176


embedded image







L203
Schiavon, et al. Synthetic Metals 1989, 28(1-2), C199-C204


embedded image












21) 1,8-Dihydrobenzo[1,2-d:3,4-d′]diimidazoles














Ex.
Literature
Product







L204
A. Berlin et al. Journal of the Chemical Society, Chemical Communications 1987, 15, 1176


embedded image












22) Bridged imidazo[2,1-a]isoquinoline systems


The following ligands are prepared analogously to the imidazo[2,1-a]isoquinoline systems, variant A, from the 1-aminoisoquinoline derivatives and carbonyl components shown.

















1-Amino-






isoquinoline
Carbonyl




Ex.
derivative
component
Product
Yield







L205


embedded image




embedded image




embedded image


54%





L206


embedded image




embedded image




embedded image


55%





L207


embedded image




embedded image




embedded image


63%





L208


embedded image




embedded image




embedded image


37%










B: Synthesis of the Metal Complexes


1) Trishomoleptic Iridium Complexes:


Variant A:


A mixture of 12.5 mmol of the ligand, 2.5 mmol of sodium bis(acetylacetonato)dichloroiridate(III) [770720-50-8] in 5 ml of triethylene glycol is stirred at 240° C. for 24 h under a gentle stream of argon. After cooling, the mixture is diluted with 100 ml of 1N hydrochloric acid and extracted five times with 100 ml of dichloromethane. The org. phase is washed three times with 200 ml of water, dried over a mixture of sodium sulfate and sodium carbonate and then evaporated to dryness. The residue is chromatographed on silica gel (eluent dichloromethane), subsequently recrystallised from dichloromethane/hexane and then sublimed in vacuo.


















Ex.
Ligand
Ir complex
Yield









Ir(L1)3
L1 


embedded image



 19%








Ir(L74)3
L74


embedded image


23.9%







Ir(L69)3
L69


embedded image


12.0%







Ir(L80)3
L80


embedded image


 3.4%











Variant B:


A mixture of 10 mmol of tris(acetylacetonato)indium(III) [15635-87-7] and 60 mmol of the ligand is sealed in vacuo (10 mbar) in a 100 ml glass ampoule. The ampoule is conditioned for the stated time at the stated temperature, with the molten mixture being stirred with the aid of a magnetic stirrer. After cooling—ATTENTION: the ampoules are usually under pressure!—the ampoule is opened, and the sinter cake is stirred at 60° C. for 5 h with 200 g of glass beads (diameter 3 mm) in 500 ml of EtOH and mechanically digested in the process. After cooling, the fine suspension is decanted off from the glass beads, and the solid is filtered off with suction dried in vacuo. The dry solid is placed on a silica-gel bed with a depth of 10 cm in a hot extractor and then extracted with 1,2-dichloroethane or chlorobenzene. When the extraction is complete, the extraction medium is concentrated to about 50 ml in vacuo, 100 ml of methanol are added to the suspension, and the mixture is stirred for a further 1 h. After the metal complex has been filtered off with suction and dried, its purity is determined by means of NMR and/or HPLC. If the purity is less than 99.9%, the hot extraction step is repeated, when a purity of >99.9% has been reached, the metal complex is conditioned or sublimed. The conditioning is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from 200-300° C. The sublimation is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from about 300 to about 420° C.



















Reaction






temp./






reaction



Ex.
Ligand
Ir complex
time
Yield







Ir(L1)3
L1


embedded image


245° C./ 30 h
 5%





Ir(L2)3
L2
Ir(L2)3
245° C./
23%





30 h



Ir(L3)3
L3
Ir(L3)3
245° C./
13%





30 h



Ir(L4)3
L4
Ir(L4)3
245° C./
19%





30 h



Ir(L5)3
L5
Ir(L5)3
240° C./
65%





45 h



Ir(L6)3
L6
Ir(L6)3
240° C./
62%





48 h



Ir(L7)3
L7
Ir(L7)3
240° C./
38%





48 h



Ir(L8)3
L8
Ir(L8)3
240° C./
77%





48 h



Ir(L9)3
L9
Ir(L9)3
250° C./
59%





50 h



Ir(L10)3
L10
Ir(L10)3
245° C./
 9%





30 h



Ir(L11)3
L11
Ir(L11)3
245° C./
23%





30 h



Ir(L12)3
L12
Ir(L12)3
245° C./
47%





30 h



Ir(L13)3
L13
Ir(L13)3
245° C./
51%





30 h



Ir(L14)3
L14
Ir(L14)3
245° C./
42%





26 h



Ir(L15)3
L15
Ir(L15)3
245° C./
41%





30 h



Ir(L16)3
L16
Ir(L16)3
245° C./
45%





40 h



Ir(L17)3
L17
Ir(L17)3
240° C./
32%





48 h



Ir(L18)3
L18
Ir(L18)3
240° C./
11%





48 h



Ir(L19)3
L19
Ir(L19)3
240° C./
38%





48 h



Ir(L20)3
L20
Ir(L20)3
240° C./
61%





48 h



Ir(L21)3
L21
Ir(L21)3
240° C./
35%





44 h



Ir(L22)3
L22
Ir(L22)3
245° C./
 9%





20 h



Ir(L23)3
L23
Ir(L23)3
240° C./
40%





44 h



Ir(L24)3
L24
Ir(L24)3
245° C./
 5%





20 h



Ir(L25)3
L25
Ir(L25)3
245° C./
31%





28 h



Ir(L26)3
L26
Ir(L26)3
245° C./
36%





32 h



Ir(L27)3
L27
Ir(L27)3
250° C./
39%





32 h



Ir(L28)3
L28
Ir(L28)3
240° C./
28%





44 h



Ir(L29)3
L29
Ir(L29)3
240° C./
 4%





40 h



Ir(L30)3
L30
Ir(L30)3
240° C./
30%





40 h



Ir(L31)3
L31
Ir(L31)3
240° C./
43%





40 h



Ir(L32)3
L32
Ir(L32)3
240° C./
44%





40 h



Ir(L33)3
L33
Ir(L33)3
245° C./
27%





28 h



Ir(L34)3
L34
Ir(L34)3
240° C./
36%





35 h



Ir(L35)3
L35
Ir(L35)3
240° C./
20%





32 h



Ir(L36)3
L36
Ir(L36)3
260° C./
15%





60 h






Ir(L37)3
L3


embedded image


270° C./ 48 h
18%





Ir(L38)3
L38
Ir(L38)3
270° C./
48%





48 h



Ir(L39)3
L39
Ir(L39)3
270° C./
34%





48 h



Ir(L40)3
L40
Ir(L40)3
270° C./
76%





48 h



Ir(L41)3
L41
Ir(L41)3
270° C./
22%





48 h






Ir(L42)3
L42


embedded image


255° C./ 25 h
47%





Ir(L43)3
L43
Ir(L43)3
250° C./
43%





60 h



Ir(L44)3
L44
Ir(L44)3
250° C./
55%





60 h



Ir(L45)3
L45
Ir(L45)3
250° C./
60%





60 h



Ir(L46)3
L46
Ir(L46)3
250° C./
34%





60 h



Ir(L47)3
L47
Ir(L47)3
260° C./
46%





35 h



Ir(L48)3
L48
Ir(L48)3
240° C./
17%





55 h



Ir(L49)3
L49
Ir(L49)3
250° C./
58%





60 h



Ir(L50)3
L50
Ir(L50)3
250° C./
61%





60 h



Ir(L51)3
L51
Ir(L51)3
250° C./
40%





38 h



Ir(L52)3
L52
Ir(L52)3
250° C./
68%





60 h



Ir(L53)3
L53
Ir(L53)3
250° C./
48%





43 h



Ir(L54)3
L54
Ir(L54)3
255° C./
31%





52 h






Ir(L55)3
L55


embedded image


245° C./ 30 h
23%





Ir(L56)3
L56
Ir(L56)3
245° C./
21%





30 h



Ir(L57)3
L57
Ir(L57)3
245° C./
41%





50 h



Ir(L58)3
L58
Ir(L58)3
250° C./
34%





38 h



Ir(L59)3
L59
Ir(L59)3
240° C./
 7%





18 h



Ir(L60)3
L60
Ir(L60)3
240° C./
22%





18 h



Ir(L61)3
L61
Ir(L61)3
240° C./
21%





22 h



Ir(L62)3
L62
Ir(L62)3
250° C./
40%





42 h






Ir(L63)3
L63


embedded image


275° C./ 48 h
27%





Ir(L64)3
L64
Ir(L64)3
275° C./
61%





30 h



Ir(L65)3
L65
Ir(L65)3
275° C./
57%





30 h



Ir(L66)3
L66
Ir(L66)3
280° C./
44%





18 h



Ir(L67)3
L67
Ir(L67)3
280° C./
46%





22 h



Ir(L68)3
L68
Ir(L68)3
285° C./
41%





24 h






Ir(L69)3
L69


embedded image


250° C./ 32 h
 7%





Ir(L70)3
L70
Ir(L70)3
250° C./
11%





22 h



Ir(L71)3
L71
Ir(L71)3
275° C./
 2%





16 h



Ir(L72)3
L72
Ir(L72)3
260° C./
23%





26 h



Ir(L73)3
L73
Ir(L73)3
260° C./
15%





18 h






Ir(L74)3
L74


embedded image


240° C./ 24 h
13%





Ir(L75)3
L75
Ir(L75)3
240° C./
25%





24 h



Ir(L78)3
L78
Ir(L78)3
245° C./
15%





24 h



Ir(L79)3
L79
Ir(L79)3
245° C./
36%





30 h






Ir(L80)3
L80


embedded image


220° C./ 24 h
 3%





Ir(L82)3
L82
Ir(L82)3
230° C./
11%





24 h






Ir(L83)3
L83


embedded image


250° C./ 28 h
72%





Ir(L84)3
L84
Ir(L84)3
250° C./
74%





28 h



Ir(L85)3
L85
Ir(L85)3
250° C./
69%





28 h



Ir(L86)3
L86
Ir(L86)3
250° C./
63%





24 h



Ir(L87)3
L87
Ir(L87)3
250° C./
70%





32 h



Ir(L88)3
L88
Ir(L88)3
250° C./
75%





20 h



Ir(L89)3
L89
Ir(L89)3
255° C./
65%





18 h



Ir(L90)3
L90
Ir(L90)3
245° C./
79%





29 h



Ir(L91)3
L91
Ir(L91)3
250° C./
70%





30 h



Ir(L92)3
L92
Ir(L92)3
270° C./
35%





24 h



Ir(L93)3
L93
Ir(L93)3
270° C./
38%





26 h



Ir(L94)3
L94
Ir(L94)3
270° C./
53%





24 h



Ir(L95)3
L95
Ir(L95)3
280° C./
72%





28 h



Ir(L96)3
L96
Ir(L96)3
265° C./
68%





24 h



Ir(L97)3
L97
Ir(L97)3
250° C./
66%





32 h



Ir(L98)3
L98
Ir(L98)3
250° C./
71%





20 h



Ir(L99)3
L99
Ir(L99)3
250° C./
77%





22 h



Ir(L100)3
L100
Ir(L100)3
245° C./
68%





32 h



Ir(L101)3
L101
Ir(L101)3
260° C./
70%





22 h



Ir(L102)3
L102
Ir(L102)3
250° C./
71%





22 h



Ir(L103)3
L103
Ir(L103)3
250° C./
70%





22 h



Ir(L104)3
L104
Ir(L104)3
255° C./
73%





26 h



Ir(L105)3
L105
Ir(L105)3
250° C./
67%





20 h



Ir(L106)3
L106
Ir(L106)3
255° C./
67%





25 h



Ir(L107)3
L107
Ir(L107)3
250° C./
65%





24 h



Ir(L108)3
L108
Ir(L108)3
275° C./
63%





18 h



Ir(L109)3
L109
Ir(L109)3
275° C./
58%





22 h



Ir(L110)3
L110
Ir(L110)3
275° C./
43%





24 h



Ir(L111)3
L111
Ir(L111)3
275° C./
57%





20 h



Ir(L112)3
L112
Ir(L112)3
255° C./
23%





16 h



Ir(L113)3
L113
Ir(L113)3
255° C./
26%





18 h



Ir(L114)3
L114
Ir(L114)3
260° C./
 9%





16 h






Ir(L115)3
L115


embedded image


280° C./ 20 h
76%





Ir(L116)3
L116
Ir(L116)3
280° C./
72%





22 h



Ir(L117)3
L117
Ir(L117)3
280° C./
78%





30 h



Ir(L118)3
L118
Ir(L118)3
270° C./
26%





20 h



Ir(L119)3
L119
Ir(L119)3
270° C./
19%





18 h



Ir(L120)3
L120
Ir(L120)3
285° C./
75%





40 h



Ir(L121)3
L121
Ir(L121)3
280° C./
74%





30 h



Ir(L122)3
L122
Ir(L122)3
280° C./
11%





22 h



Ir(L123)3
L123
Ir(L123)3
285° C./
69%





40 h



Ir(L124)3
L124
Ir(L124)3
280° C./
73%





36 h



Ir(L125)3
L125
Ir(L125)3
265° C./
66%





40 h



Ir(L126)3
L126
Ir(L126)3
265° C./
64%





38 h






Ir(L127)3
L127


embedded image


265° C./ 40 h
67%





Ir(L128)3
L128
Ir(L128)3
265° C./
44%





30 h



Ir(L129)3
L129
Ir(L129)3
265° C./
57%





60 h



Ir(L130)3
L130
Ir(L130)3
260° C./
62%





55 h



Ir(L131)3
L131
Ir(L131)3
245° C./
52%





45 h






Ir(L132)3
L132


embedded image


270° C./ 20 h
15%





Ir(L133)3
L133
Ir(L133)3
275° C./
17%





30 h



Ir(L134)3
L134
Ir(L134)3
270° C./
34%





20 h



Ir(L135)3
L135
Ir(L135)3
270° C./
61%





20 h



Ir(L136)3
L136
Ir(L136)3
265° C./
56%





30 h



Ir(L137)3
L137
Ir(L137)3
275° C./
30%





24 h



Ir(L138)3
L138
Ir(L138)3
265° C./
23%





34 h



Ir(L139)3
L139
Ir(L139)3
270° C./
67%





47 h






Ir(L140)3
L140


embedded image


270° C./ 28 h
53%





Ir(L141)3
L141
Ir(L141)3
270° C./
28%





28 h






Ir(L142)3
L142


embedded image


270° C./ 48 h
47%





Ir(L143)3
L143
Ir(L143)3
265° C./
61%





64 h






Ir(L144)3
L144


embedded image


245° C./ 46 h
 7%





Ir(L145)3
L145
Ir(L145)3
250° C./
74%





36 h



Ir(L146)3
L146
Ir(L146)3
245° C./
13%





28 h



Ir(L147)3
L147
Ir(L147)3
265° C./
23%





35 h



Ir(L148)3
L148
Ir(L148)3
245° C./
 5%





16 h



Ir(L149)3
L149
Ir(L149)3
245° C./
10%





26 h



Ir(L150)3
L150
Ir(L150)3
250° C./
 7%





36 h



Ir(L151)3
L151
Ir(L151)3
255° C./
38%





42 h



Ir(L152)3
L152
Ir(L152)3
255° C./
77%





40 h



Ir(L153)3
L153
Ir(L153)3
245° C./
74%





46 h






Ir(L154)3
L154


embedded image


245° C./ 26 h
11%





Ir(L155)3
L155
Ir(L155)3
245° C./
14%





30 h



Ir(L156)3
L156
Ir(L156)3
245° C./
65%





36 h



Ir(L157)3
L157
Ir(L157)3
245° C./
63%





36 h



Ir(L158)3
L158
Ir(L158)3
250° C./
48%





28 h



Ir(L159)3
L159
Ir(L159)3
245° C./
54%





30 h



Ir(L160)3
L160
Ir(L160)3
245° C./
50%





30 h



Ir(L161)3
L161
Ir(L161)3
240° C./
32%





38 h



Ir(L162)3
L162
Ir(L162)3
255° C./
71%





30h



Ir(L163)3
L163
Ir(L163)3
250° C./
69%





34 h



Ir(L164)3
L164
Ir(L164)3
255° C./
70%





30 h



Ir(L165)3
L165
Ir(L165)3
250° C./
59%





30 h



Ir(L166)3
L166
Ir(L166)3
255° C./
25%





40 h



Ir(L167)3
L167
Ir(L167)3
265° C./
38%





30 h



Ir(L168)3
L168
Ir(L168)3
270° C./
55%





35 h



Ir(L169)3
L169
Ir(L169)3
250° C./
42%





36 h






Ir(L170)3
L170


embedded image


255° C./ 28 h
33%





Ir(L171)3
L171
Ir(L171)3
255° C./
68%





30 h



Ir(L172)3
L172
Ir(L172)3
255° C./
71%





30 h



Ir(L173)3
L173
Ir(L173)3
255° C./
36%





30 h






Ir(L174)3
L174


embedded image


245° C./ 30 h
 6%





Ir(L175)3
L175


embedded image


250° C./ 30 h
 3%





Ir(L176)3
L176
Ir(L176)3
250° C./
67%





34 h



Ir(L177)3
L177
Ir(L177)3
255° C./
48%





32 h



Ir(L178)3
L178
Ir(L178)3
260° C./
75%





30 h



Ir(L179)3
L179
Ir(L179)3
260° C./
74%





30 h






Ir(L180)3
L180


embedded image


250° C./ 24 h
26%





Ir(L181)3
L181
Ir(L181)3
250° C./
16%





24 h






Ir(L182)3
L182


embedded image


250° C./ 30 h
17%





Ir(L183)3
L183
Ir(L183)3
260° C./
31%





20 h



Ir(L184)3
L184
Ir(L184)3
230° C./
23%





25 h



Ir(L185)3
L185
Ir(L185)3
230° C./
 5%





18 h



Ir(L186)3
L186
Ir(L186)3
235° C./
 7%





20 h



Ir(L187)3
L187
Ir(L187)3
230° C./
 8%





25 h



Ir(L188)3
L188
Ir(L188)3
240° C./
13%





25 h






Ir(L189)3
L189


embedded image


245° C./ 35 h
 9%





Ir(L190)3
L190
Ir(L190)3
245° C./
12%





26 h






Ir(L191)3
L191


embedded image


250° C./ 26 h
26%





Ir(L192)3
L192


embedded image


250° C./ 36 h
 8%





Ir(L193)3
L193


embedded image


230° C./ 16 h
 6%





Ir(L194)3
L194
Ir(L194)3
230° C./
54%





16 h



Ir(L195)3
L195
Ir(L195)3
230° C./
71%





26 h



Ir(L196)3
L196
Ir(L196)3
250° C./
58%





36 h



Ir(L197)3
L197
Ir(L197)3
250° C./
27%





36 h



Ir(L198)3
L198
Ir(L198)3
255° C./
34%





46 h



Ir(L199)3
L199
Ir(L199)3
250° C./
17%





46 h










Variant C: Ligand Synthesis on the Complex


A mixture of 10 mmol of tris(acetylacetonato)iridium(III) [15635-87-7] and 60 mmol of the imidazole derivative is sealed in vacuo (10−3 mbar) in a 100 ml glass ampoule. The ampoule is conditioned for the stated time at the stated temperature, with the molten mixture being stirred with the aid of a magnetic stirrer. After cooling—ATTENTION: the ampoules are usually under pressure!—the ampoule is opened, and the sinter cake is stirred at 50° C. for 5 h with 100 g of glass beads (diameter 3 mm) in 300 ml of EtOH and mechanically digested in the process. After cooling, the fine suspension is decanted off from the glass beads, and the solid is filtered off with suction and dried in vacuo. The solid is suspended in a mixture of 90 ml of acetic acid and 10 ml of acetic anhydride, 1 ml of trifluoroacetic acid is added to the suspension, and the mixture is then heated under reflux for 1 h. After cooling, the solid is filtered off with suction, washed once with 20 ml of acetic acid and three times with 30 ml of ethanol each time and dried in vacuo. The dry solid is placed on a silicagel bed with a depth of 10 cm in a hot extractor and then extracted with 1,2-dichloroethane. When the extraction is complete, the extraction medium is concentrated to about 50 ml in vacuo, 100 ml of methanol are added to the suspension, and the mixture is stirred for a further 1 h. After the metal complex has been filtered off with suction and dried, its purity is determined by means of NMR and/or HPLC. If the purity is less than 99.9%, the hot extraction step is repeated, when a purity of >99.9% has been reached, the metal complex is sublimed. The sublimation is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from about 350 to about 370° C.
















Imidazole




Example
derivative
Ir complex
Yield







Ir(L83)3


embedded image




embedded image


20%





Ir(L88)3


embedded image




embedded image


35%










2) Heteroleptic Iridium Complexes:


Variant A:


A mixture of 10 mmol of sodium bis(acetylacetonato)dichloroiridate(III) [770720-50-8] and 21 mmol of the ligand is sealed in vacuo (10−3 mbar) in a 50 ml glass ampoule. The ampoule is conditioned at 220-250° C. for 6-12 h, with the molten mixture being stirred with the aid of a magnetic stirrer. After cooling—ATTENTION: the ampoules are usually under pressure!—the ampoule is opened, and the sinter cake is stirred at 60° C. for 5 h with 200 g of glass beads (diameter 3 mm) in 500 ml of EtOH and mechanically digested in the process. After cooling, the fine suspension is decanted off from the glass beads, and the corresponding chloro dimer of the formula [Ir(L)2Cl]2 is filtered off with suction and dried in vacuo. The resultant crude chloro dimer of the formula [Ir(L)2Cl]2 is suspended in a mixture of 75 ml of 2-ethoxyethanol and 25 ml of water, and 13 mmol of the co-ligand or co-ligand compound and 15 mmol of sodium carbonate are added. After 20 h under reflux, a further 75 ml of water are added dropwise, the mixture is cooled, and the solid is filtered off with suction, washed three times with 50 ml of water each time and three times with 50 ml of methanol each time and dried in vacuo. The solid is placed on a silica-gel bed with a depth of 10 cm in a hot extractor and then extracted with dichloromethane or 1,2-dichloroethane. When the extraction is cornplete, the extraction medium is concentrated to about 50 ml in vacuo, 100 ml of methanol are added to the suspension, and the mixture is stirred for a further 1 h. After the metal complex has been filtered off with suction and dried, its purity is determined by means of NMR and/or HPLC. If the purity is less than 99.9%, the hot extraction step is repeated, when a purity of >99.9% has been reached, the metal complex is conditioned or sublimed. The conditioning is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from 200-300° C. The sublimation is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from about 300 to about 420° C.
















Ex.
Ligand
Co-ligand
Ir complex
Yield







Ir(L5)2(CL1)
L5


embedded image




embedded image


51%





Ir(L5)2(CL2)
L5


embedded image




embedded image


55%





Ir(L5)2(CL3)
L5


embedded image




embedded image


56%





Ir(L5)2(CL4)
L5


embedded image




embedded image


43%





Ir(L5)2(L193)
L5
L193


embedded image


61%





Ir(L7)2(CL1)
L7
CL1
Ir(L7)2(CL1)
40%


Ir(L9)2(CL1)
L9
CL1
Ir(L9)2(CL1)
55%


Ir(L15)2(CL1)
L15
CL1
Ir(L15)2(CL1)
61%


Ir(L49)2(CL1)
L49
CL1
Ir(L49)2(CL1)
37%


Ir(L83)2(CL2)
L83
CL2
Ir(L83)2(CL1)
17%


Ir(L104)2(CL2)
L104
CL2
Ir(L104)2(CL2)
41%


Ir(L105)2(CL2)
L105
CL2
Ir(L105)2(CL2)
40%


Ir(L119)2(CL3)
L119
CL3
Ir(L119)2(CL3)
23%


Ir(L130)2(CL3)
L130
CL3
Ir(L130)2(CL3)
64%


r(L139)2(CL3)
L139
CL3
Ir(L139)2(CL3)
58%


Ir(L163)2(CL1)
L163
CL1
Ir(L163)2(CL1)
51%


Ir(L172)2(L199)
L172
L199
Ir(L172)2(L199)
44%










Variant B:


A mixture of 10 mmol of sodium bis(acetylacetonato)dichloroiridate(III) [770720-50-8] and 22 mmol of the ligand is sealed in vacuo (10−3 mbar) in a 50 ml glass ampoule. The ampoule is conditioned at 220-250° C. for 6-12 h, with the molten mixture being stirred with the aid of a magnetic stirrer. After cooling—ATTENTION: the ampoules are usually under pressure!—the ampoule is opened, and the sinter cake is stirred at 60° C. for 5 h with 200 g of glass beads (diameter 3 mm) in 500 ml of EtOH and mechanically digested in the process. After cooling, the fine suspension is decanted off from the glass beads, and the corresponding crude chloro dimer of the formula [Ir(L)2Cl]2 is filtered off with suction and dried in vacuo. The crude chloro dimer of the formula [Ir(L)2Cl]2 is reacted further in accordance with WO 2007/065523, Example 5, in the presence of 75 mmol of N,N-dimethylglycine in a dioxane/water mixture. The resultant solids are placed on a silica-gel bed with a depth of 10 cm in a hot extractor and then extracted with dichloromethane or 1,2-dichloroethane. When the extraction is complete, the extraction medium is concentrated to about 50 ml in vacuo, 100 ml of methanol are added to the suspension, and the mixture is stirred for a further 1 h. After the metal complex has been filtered off with suction and dried, its purity is determined by means of NMR and/or HPLC. If the purity is less than 99.9%, the hot extraction step is repeated, when a purity of >99.9% has been reached, the metal complex is conditioned or sublimed. The conditioning is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from 200-300° C. The sublimation is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from about 300 to about 420° C.
















Ex.
Ligand
Co-ligand
Ir complex
Yield







Ir(L1)2(CL5)
L1


embedded image




embedded image


51%





Ir(L7)2(CL5)
L7
CL5
Ir(L7)2(CL5)
72%





Ir(L7)2(CL6)
L7


embedded image




embedded image


48%





Ir(L14)2(CL7)
L14


embedded image




embedded image


53%





Ir(L49)2(CL7)
L49
CL7
Ir(L49)2(CL7)
57%





Ir(L83)2(CL8)
L83


embedded image




embedded image


77%





Ir(L104)2(CL8)
L104
CL8
Ir(L104)2(CL8)
82%


Ir(L105)2(CL8)
L105
CL8
Ir(L105)2(CL8)
80%


Ir(L119)2(CL8)
L119
CL8
Ir(L119)2(CL8)
69%





Ir(L119)2(CL9)
L119


embedded image




embedded image


73%





Ir(L130)2(CL10)
L130


embedded image




embedded image


42%





Ir(L139)2(CL7)
L139
CL7
Ir(L139)2(CL7)
55%










Variant C:


A mixture of 10 mmol of sodium bis(acetylacetonato)dichloroiridate(III) [770720-50-8] and 21 mmol of the ligand is sealed in vacuo (10−3 mbar) in a 50 ml glass ampoule. The ampoule is conditioned at 220-250° C. for 6-12 h, with the molten mixture being stirred with the aid of a magnetic stirrer. After cooling—ATTENTION: the ampoules are usually under pressure!—the ampoule is opened, and the sinter cake is stirred at 60° C. for 5 h with 200 g of glass beads (diameter 3 mm) in 500 ml of EtOH and mechanically digested in the process. After cooling, the fine suspension is decanted off from the glass beads, and the corresponding chloro dimer of the formula [Ir(L)2Cl]2 is filtered off with suction and dried in vacuo. The resultant crude chloro dimer of the formula [Ir(L)2Cl]2 is suspended in 100 ml of THF, 40 mmol of the co-ligand, 20 mmol of silver(I) trifluoroacetate and 80 mmol of potassium carbonate are added to the suspension, and the mixture is heated under reflux for 24 h. After cooling, the THF is removed in vacuo, and the solid is placed on a silica-gel bed with a depth of 10 cm in a hot extractor and then extracted with dichloromethane or 1,2-dichloroethane. When the extraction is complete, the extraction medium is concentrated to about 50 ml in vacuo, 100 ml of methanol are added to the suspension, and the mixture is stirred for a further 1 h. After the metal complex has been filtered off with suction and dried, its purity is determined by means of NMR and/or HPLC. If the purity is less than 99.9%, the hot extraction step is repeated, when a purity of >99.9% has been reached, the metal complex is conditioned or sublimed. The conditioning is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from 200-300° C. The sublimation is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from about 300 to about 420° C.
















Ex.
Ligand
Co-ligand
Ir complex
Yield







Ir(L1)2(CL5)
L1


embedded image




embedded image


83%





Ir(L12)2(L7)
L12
L7
Ir(L12)2(L7)
31%


Ir(L12)2(L32)
L32
L32
Ir(L12)2(L32)
43%


Ir(L12)2(L51)
L51
L51
Ir(L12)2(L51)
45%


Ir(L51)2(L12)
L51
L12
Ir(L51)2(L12)
32%


Ir(L79)2(CL7)
L79
CL7
Ir(L79)2(CL7)
50%


Ir(L99)2(L111)
L99
L111
Ir(L99)2(L111)
38%


Ir(L139)2(CL8)
L139
CL8
Ir(L139)2(CL8)
41%


Ir(L164)2(CL8)
L164
CL8
Ir(L164)2(CL8)
46%










3) Bishomoleptic Platinum Complexes:


A mixture of 5 mmol of bis(benzonitrile)di(chloro)platinum(II) [14873-63-3], 20 mmol of the ligand, 20 mmol of lithium acetate and 20 ml of acetic acid is initially introduced in an ampoule. This is degassed via freeze-pumpthaw cycles, sealed in vacuo and then subjected to microwave radiation (Discover™ unit from CEM-GmbH, Kamp-Lintfort, Germany, magnetron frequency 2450 MHz, 150 W per litre) at 130° C. for 20 min. The reaction mixture is cooled and stirred into a mixture of 80 ml of EtOH and 20 ml of water, and the fine solid is filtered off with suction, washed three times with 20 ml of ethanol and dried in vacuo. The dry solid is placed on a silica-gel bed with a depth of 10 cm in a hot extractor and then extracted with THF. When the extraction is complete, the extraction medium is concentrated to about 30 ml in vacuo, 75 ml of methanol are added to the suspension, and the mixture is stirred for a further 1 h. After the metal complex has been filtered off with suction and dried, its purity is determined by means of NMR and/or HPLC. If the purity is less than 99.9%, the hot extraction step is repeated, when a purity of >99.9% has been reached, the metal complex is conditioned or sublimed. The conditioning is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from 200-300° C. The sublimation is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from about 300 to about 420° C.















Example
Ligand
Pt complex
Yield







Pt (L12)2
L12


embedded image


 3%





Pt (L41)2
L41
Pt (L41)2
22%


Pt (L46)2
L46
Pt (L46)2
19%


Pt (L101)2
L101
Pt (L101)2
 8%


Pt (L165)2
L165
Pt (L165)2
24%










4) Platinum Complexes Containing Tetradentate Ligands:


A mixture of 5 mmol of bis(benzonitrile)di(chloro)platinum(II) [14873-63-3], 5 mmol of the ligand, 20 mmol of lithium acetate and 20 ml of acetic acid is initially introduced in an ampoule. This is degassed via freeze-pump-thaw cycles, sealed in vacuo and then subjected to microwave radiation (Discover™ unit from CEM-GmbH, Kamp-Lintfort, Germany, magnetron frequency 2450 MHz, 150 W per litre) at 130° C. for 20 min. The reaction mixture is cooled and stirred into a mixture of 80 ml of EtOH and 20 ml of water, and the fine solid is filtered off with suction, washed three times with 20 ml of ethanol and dried in vacuo. The dry solid is placed on a silica-gel bed with a depth of 10 cm in a hot extractor and then extracted with THF. When the extraction is complete, the extraction medium is concentrated to about 30 ml in vacuo, 75 ml of methanol are added to the suspension, and the mixture is stirred for a further 1 h. After the metal complex has been filtered off with suction and dried, its purity is determined by means of NMR and/or HPLC. If the purity is less than 99.9%, the hot extraction step is repeated, when a purity of >99.9% has been reached, the metal complex is conditioned or sublimed. The conditioning is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from 200-300° C. The sublimation is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from about 300 to about 420° C.















Example
Ligand
Pt complex
Yield







Pt (L205)
L205


embedded image


23%





Pt (L206)
L206


embedded image


17%





Pt (L207)
L207


embedded image


26%





Pt (L208)
L208


embedded image


31%










5) Heteroleptic Platinum Complexes:


A mixture of 5 mmol of platinum(II) chloride, 6 mmol of the ligand and 0.5 mmol of tetra-n-butylammonium chloride in 10 ml of dichloromethane is heated under reflux for 12 h. After 50 ml of methanol have been added dropwise, the fine solid is filtered off with suction, washed twice with 10 ml of methanol and dried in vacuo. The resultant crude chloro dimer of the formula [Pt(L)Cl]2 is suspended in a mixture of 45 ml of 2-ethoxyethanol and 15 ml of water, and 7 mmol of the co-ligand or co-ligand compound and 7 mmol of sodium carbonate are added. After 20 h under reflux, a further 75 ml of water are added dropwise, the mixture is cooled, and the solid is filtered off with suction, washed three times with 50 ml of water each time and three times with 50 ml of methanol each time and dried in vacuo. The dry solid is placed on a silica-gel bed with a depth of 10 cm in a hot extractor and then extracted with THF. When the extraction is cornplete, the extraction medium is concentrated to about 15 ml in vacuo, 75 ml of methanol are added to the suspension, and the mixture is stirred for a further 1 h. After the metal complex has been filtered off with suction and dried, its purity is determined by means of NMR and/or HPLC. If the purity is less than 99.9%, the hot extraction step is repeated, when a purity of >99.9% has been reached, the metal complex is conditioned or sublimed. The conditioning is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from 200-300° C. The sublimation is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from about 300 to about 420° C.


















Co-




Ex.
Ligand
ligand
Pt complex
Yield







Pt(L40)(CL1)
L40


embedded image




embedded image


32%





Pt(L66)(CL2)
L66
CL2
Pt(L66)(CL2)
22%


Pt(L107)(CL1)
L107
CL1
Pt(L107)(CL1)
13%


Pt(L107)(L196)
L107
L196
Pt(L107)(L196)
17%


Pt(L107)(L199)
L107
L199
Pt(L107)(L199)
28%










6) Heteroleptic Gold Complexes:


A mixture of 5 mmol of dichloro[2-(2-pyridinyl)phenyl-C,N]gold, 6 mmol of the ligand and 10 mmol of triethylamine in 50 ml of THF is stirred at 50° C. for 20 h. After the reaction mixture has been concentrated to 10 ml and 50 ml of methanol have been added dropwise, the fine solid is filtered off with suction, washed twice with 10 ml of methanol and dried in vacuo. The dry solid is placed on a Celite bed with a depth of 10 cm in a hot extractor and then extracted with THF. When the extraction is complete, the extraction medium is concentrated to about 15 ml in vacuo, 75 ml of methanol are added to the suspension, and the mixture is stirred for a further 1 h. After the metal complex has been filtered off with suction and dried, its purity is determined by means of NMR and/or HPLC. If the purity is less than 99.9%, the hot extraction step is repeated, when a purity of >99.9% has been reached, the metal complex is conditioned or sublimed. The conditioning is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from 200-300° C. The sublimation is carried out in a high vacuum (p about 10−6 mbar) in the temperature range from about 300 to about 420° C.




















Co-




Ex.
Ligand
ligand
Au complex
Yield





Au(L202)(CL5)
L202
CL5


embedded image


42%





Au(L203)(CL5)
L203
CL5
Au(L203)(CL5)
37%


Au(L204)(CL5)
L204
CL5
Au(L204)(CL5)
11%










7) Heteroleptic Copper Complexes:


A mixture of 5 mmol of tetrakis(acetonitrile)copper(I) tetrafluoroborate [15418-29-8], 5 mmol of the ligand, 5 mmol of the co-ligand and 6 mmol of triethylamine in 50 ml of THF is stirred at room temperature for 20 h. After the reaction mixture has been concentrated to 5 ml and 50 ml of methanol have been added dropwise, the fine solid is filtered off with suction, washed twice with 10 ml of methanol and dried in vacuo. The crude product is recrystallised twice from dichloromethane/methanol. The conditioning is carried out in a high vacuum (p about 10−6 mbar) at a temperature in the region of 200° C.


















Co-




Ex.
Ligand
ligand
Cu complex
Yield







Cu(L194)(CL11)
L194


embedded image




embedded image


63%





Cu(L196)(CL11)
L196
CL11
Cu(L196)(CL11)
48%





Cu(L195)(CL12)



embedded image




embedded image


71%










Production of OLEDs


OLEDs according to the invention and OLEDs in accordance with the prior art are produced by a general process in accordance with WO 04/058911, which is adapted to the circumstances described here (layer-thickness variation, materials used).


The results for various OLEDs are presented in the following Examples 1 to 250 (see Tables 1 and 2). Glass plates coated with structured ITO (indium tin oxide) in a thickness of 150 nm are coated with 20 nm of PEDOT (poly(3,4-ethylenedioxy-2,5-thiophene), spin-coated from water, purchased from H.C. Starck, Goslar, Germany) for improved processing. These coated glass plates form the substrates to which the OLEDs are applied. The OLEDs have in principle the following layer structure: substrate/optional hole-injection layer (HIL)/hole-transport layer (HTL)/optional interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm.


Firstly, vacuum-processed OLEDs are described. For this purpose, all materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or materials in a certain volume proportion by co-evaporaSon. Information such as M3:M2:Ir(L1)3 (55%:35%:10%) here means that the material M3 is present in the layer in a proportion by volume of 55%, M2 in a proportion of 35% and Ir(L1)3 in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials. The precise structure of the OLEDs is shown in Table 1. The materials used to produce the OLEDs are shown in Table 3.


The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A) and the voltage (measured in V at 1000 cd/m2) are determined from current-voltage-luminance characteristic lines (IUL characteristic lines). For selected experiments, the lifetime is likewise determined. The lifetime is defined as the time after which the luminous density has dropped to a certain proportion from a certain initial luminous density. The term LD50 means that the lifetime indicated is the time at which the luminous density has dropped to 50% of the initial luminous density, i.e. from, for example, 4000 cd/m2 to 2000 cd/m2. Depending on the emission colour, different initial luminances were selected. The values for the lifetime can be converted to a figure for other initial luminous densities with the aid of conversion formulae known to the person skilled in the art. The lifetime for an initial luminous density of 1000 cd/m2 is the usual figure here.


Use of Compounds According to the Invention as Emitter Materials And Hole-Transport Materials in Phosphorescent OLEDs


The compounds according to the invention can be employed, inter alia, as phosphorescent emitter materials in the emission layer in OLEDs. The metal complexes containing the central atoms Ir, Pt, Au and Cu are used here. The compound Ir(ref)3 is used as comparison in accordance with the prior art. It is furthermore shown that the compounds according to the invention can also be employed as hole-transporting materials. The results for the OLEDs are shown in Table 2.









TABLE 1







Structure of the OLEDs















HTL1
HTL2
EBL
EML
HBL
ETL
EIL


Ex.
thickness
thickness
thickness
thickness
thickness
thickness
thickness

















1
HTM1
EBM1
EBM3
M1:EBM3:Ir(L1)3
M1
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 m
(50%:50%)






40 nm

20 nm


2
HTM1
EBM1
EBM3
M3:Ir(L1)3

ETM1:LiQ




20 nm
5 m
15 nm
(90%:10%)

(50%:50%)






40 nm

20 nm


3
HTM1
EBM1
EBM3
M4:EBM3:Ir(L1)3
M4
ETM1:LiQ




20 nm
5 m
15 nm
(68%:30%:2%)
10 nm
(50%:50%)






40 m

20 nm


4
HTM1
EBM1
EBM3
M4:EBM3:Ir(L1)3
M4
ETM1:LiQ




20 nm
5 m
15 nm
(28%:70%:2%)
10 nm
(50%:50%)






40 m

20 nm


5
HTM1
EBM1
EBM3
M2:Ir(L1)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(85%15%)
10 nm
(50%:50%)






40 nm

20 nm


6
HTM1
EBM1
EBM2
M5:Ir(L1)3
M3
Alq3
LiF



20 nm
5 m
15 nm
(80%10%)
10 nm






40 nm


7
HTM1
EBM1
EBM3
M3:EBM3:Ir(L1)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


8
HTM1
EBM1
EBM3
M3:EBM3:Ir(L2)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


9
HTM1
EBM1
EBM3
M3:EBM3:Ir(L3)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


10
HTM1
EBM1
EBM3
M3:EBM3:Ir(L4)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


11
HTM1
EBM1
EBM3
M3:EBM3:Ir(L5)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


12
HTM1
EBM1
EBM3
M3:EBM3:Ir(L6)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


13
HTM1
EBM1
EBM3
M3:EBM3:Ir(L7)3
M3
ETM1:LIQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


14
HTM1
EBM1
EBM3
M3:EBM3:Ir(L8)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:60%)






40 nm

20 nm


15
HTM1
EBM1
EBM3
M3:EBM3:Ir(L9)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


16
HTM1
EBM1
EBM3
M3:EBM3:Ir(L10)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


17
HTM1
EBM1
EBM3
M3:EBM3:Ir(L11)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


18
HTM1
EBM1
EBM3
M3:EBM3:Ir(L12)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


19
HTM1
EBM1
EBM3
M3:EBM3:Ir(L13)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


20
HTM1
EBM1
EBM3
M3:EBM3:Ir(L14)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


21
HTM1
EBM1
EBM3
M3:EBM3:Ir(L15)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


22
HTM1
EBM1
EBM3
M3:EBM3:Ir(L16)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


23
HTM1
EBM1
EBM3
M3:EBM3:Ir(L17)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


24
HTM1
EBM1
EBM3
M3:EBM3:Ir(L18)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


25
HTM1
EBM1
EBM3
M3:EBM3:Ir(L19)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


26
HTM1
EBM1
EBM3
M3:EBM3:Ir(L20)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


27
HTM1
EBM1
EBM3
M3:EBM3:Ir(L21)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


28
HTM1
EBM1
EBM3
M3:EBM3:Ir(L22)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


29
HTM1
EBM1
EBM3
M3:EBM3:Ir(L23)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


30
HTM1
EBM1
EBM3
M3:EBM3:Ir(L24)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


31
HTM1
EBM1
EBM3
M3:EBM3:Ir(L25)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


32
HTM1
EBM1
EBM3
M3:EBM3:Ir(L26)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


33
HTM1
EBM1
EBM3
M3:EBM3:Ir(L27)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


34
HTM1
EBM1
EBM3
M3:EBM3:Ir(L28)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


35
HTM1
EBM1
EBM3
M3:EBM3:Ir(L29)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


36
HTM1
EBM1
EBM3
M3:EBM3:Ir(L30)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


37
HTM1
EBM1
EBM3
M3:EBM3:Ir(L31)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


38
HTM1
EBM1
EBM3
M3:EBM3:Ir(L32)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


39
HTM1
EBM1
EBM3
M3:EBM3:Ir(L33)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


40
HTM1
EBM1
EBM3
M3:EBM3:Ir(L34)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


41
HTM1
EBM1
EBM3
M3:EBM3:Ir(L35)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


42
HTM1
EBM1
EBM3
M3:EBM3:Ir(L36)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


43
HTM1
EBM1
EBM3
M3:EBM3:Ir(L37)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


44
HTM1
EBM1
EBM3
M3:EBM3:Ir(L38)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


45
HTM1
EBM1
EBM3
M3:EBM3:Ir(L39)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


46
HTM1
EBM1
EBM3
M3:EBM3:Ir(L40)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


47
HTM1
EBM1
EBM3
M3:EBM3:Ir(L41)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


48
HTM1
EBM1
EBM3
M3:EBM3:Ir(L42)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


49
HTM1
EBM1
EBM3
M3:EBM3:Ir(L43)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


50
HTM1
EBM1
EBM3
M3:EBM3:Ir(L44)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


51
HTM1
EBM1
EBM3
M3:EBM3:Ir(L45)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


52
HTM1
EBM1
EBM3
M3:EBM3:Ir(L46)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


53
HTM1
EBM1
EBM3
M3:EBM3:Ir(L47)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


54
HTM1
EBM1
EBM3
M3:EBM3:Ir(L48)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


55
HTM1
EBM1
EBM3
M3:EBM3:Ir(L49)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


56
HTM1
EBM1
EBM3
M3:EBM3:Ir(L50)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


57
HTM1
EBM1
EBM3
M3:EBM3:Ir(L51)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


58
HTM1
EBM1
EBM3
M3:EBM3:Ir(L52)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


59
HTM1
EBM1
EBM3
M3:EBM3:Ir(L53)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


60
HTM1
EBM1
EBM3
M3:EBM3:Ir(L54)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


61
HTM1
EBM1
EBM3
M3:EBM3:Ir(L56)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


62
HTM1
EBM1
EBM3
M3:EBM3:Ir(L58)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


63
HTM1
EBM1
EBM3
M3:EBM3:Ir(L59)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


64
HTM1
EBM1
EBM3
M3:EBM3:Ir(L60)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


65
HTM1
EBM1
EBM3
M3:EBM3:Ir(L61)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


66
HTM1
EBM1
EBM3
M3:EBM3:Ir(L62)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


67
HTM1
EBM1
EBM3
M3:EBM3:Ir(L63)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


68
HTM1
EBM1
EBM3
M3:EBM3:Ir(L64)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


69
HTM1
EBM1
EBM3
M3:EBM3:Ir(L65)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


70
HTM1
EBM1
EBM3
M3:EBM3:Ir(L66)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


71
HTM1
EBM1
EBM3
M3:EBM3:Ir(L69)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


72
HTM1
EBM1
EBM3
M3:EBM3:Ir(L70)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


73
HTM1
EBM1
EBM3
M3:EBM3:Ir(L71)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


74
HTM1
EBM1
EBM3
M3:EBM3:Ir(L72)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


75
HTM1
EBM1
EBM3
M3:EBM3:Ir(L73)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


76
HTM1
EBM1
EBM3
M3:EBM3:Ir(L74)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


77
HTM1
EBM1
EBM3
M3:EBM3:Ir(L75)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


78
HTM1
EBM1
EBM3
M3:EBM3:Ir(L78)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


79
HTM1
EBM1
EBM3
M3:EBM3:Ir(L79)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


80
HTM1
EBM1
EBM3
M3:EBM3:Ir(L80)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


81
HTM1
EBM1
EBM3
M3:EBM3:Ir(L82)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


82
HTM1
EBM1
EBM3
M3:EBM3:Ir(L83)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


83
HTM1
EBM1
EBM3
M3:Ir(L83)3
M3
Alq3
LiF



20 nm
5 m
15 nm
(90%:10%)
10 nm
20 nm






40 nm


84
HTM1
EBM1
EBM2
M4:Ir(L83)3
M3
Alq3
LiF



20 nm
5 m
15 nm
(90%:10%)
10 nm
20 nm






40 nm


85
HTM1
EBM1

M4:Ir(L83)3
M6
Alq3
LiF



20 nm
20 m 

(90%:10%)
10 nm
20 nm






40 nm


86
HTM1
EBM1

EBM3:Ir(L83)3
M6
Alq3
LiF



20 nm
20 m 

(90%:10%)
10 nm
20 nm






40 nm


87
HTM1
EBM1
EBM2
EBM2:M3:Ir(L83)3
M3
Alq3
LiF



20 nm
5 m
15 nm
(60%:30%:10%)
10 nm
20 nm






40 nm


88
HTM1
EBM1
EBM3
M6:Ir(L83)3
M3
Alq3
LiF



20 nm
5 m
15 nm
(90%:10%)
10 nm
20 nm






40 nm


89
HTM1
EBM1
EBM2
M6:EBM3:Ir(L83)3
M3
Alq3
LiF



20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
20 nm






40 nm


90
HTM1
EBM1
EBM3
M7:Ir(L83)3
M3
Alq3
LiF



20 nm
5 m
15 nm
(95%:5%)
10 nm
20 nm






40 nm


91
HTM1
EBM1
EBM3
M3:EBM3:Ir(L84)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


92
HTM1
EBM1
EBM3
M3:EBM3:Ir(L85)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


93
HTM1
EBM1
EBM3
M3:EBM3:Ir(L86)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


94
HTM1
EBM1
EBM3
M3:EBM3:Ir(L87)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


95
HTM1
EBM1
EBM3
M3:EBM3:Ir(L88)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


96
HTM1
EBM1
EBM3
M3:EBM3:Ir(L89)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


97
HTM1
EBM1
EBM3
M3:EBM3:Ir(L90)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


98
HTM1
EBM1
EBM3
M3:EBM3:Ir(L91)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


99
HTM1
EBM1
EBM3
M3:EBM3:Ir(L92)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


100
HTM1
EBM1
EBM3
M3:EBM3:Ir(L93)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


101
HTM1
EBM1
EBM3
M3:EBM3:Ir(L94)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


102
HTM1
EBM1
EBM3
M3:EBM3:Ir(L95)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


103
HTM1
EBM1
EBM3
M3:EBM3:Ir(L96)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


104
HTM1
EBM1
EBM3
M3:EBM3:Ir(L97)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


105
HTM1
EBM1
EBM3
M3:EBM3:Ir(L98)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


106
HTM1
EBM1
EBM3
M3:EBM3:Ir(L99)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


107
HTM1
EBM1
EBM3
M3:EBM3:Ir(L100)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


108
HTM1
EBM1
EBM3
M3:EBM3:Ir(L101)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


109
HTM1
EBM1
EBM3
M3:EBM3:Ir(L102)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


110
HTM1
EBM1
EBM3
M3:EBM3:Ir(L103)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


111
HTM1
EBM1
EBM3
M3:EBM3:Ir(L104)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


112
HTM1
EBM1
EBM3
M3:EBM3:Ir(L105)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


113
HTM1
EBM1
EBM3
M3:EBM3:Ir(L106)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


114
HTM1
EBM1
EBM3
M3:EBM3:Ir(L107)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


115
HTM1
EBM1
EBM3
M3:EBM3:Ir(L112)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


116
HTM1
EBM1
EBM3
M3:EBM3:Ir(L113)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


117
HTM1
EBM1
EBM3
M3:EBM3:Ir(L114)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


118
HTM1
EBM1
EBM3
M3:EBM3:Ir(L115)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


119
HTM1
EBM1
EBM3
M3:EBM3:Ir(L118)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


120
HTM1
EBM1
EBM3
M3:EBM3:Ir(L119)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


121
HTM1
EBM1
EBM3
M3:EBM3:Ir(L120)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


122
HTM1
EBM1
EBM3
M3:EBM3:Ir(L122)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


123
HTM1
EBM1
EBM3
M3:EBM3:Ir(L125)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


124
HTM1
EBM1
EBM3
M3:EBM3:Ir(L126)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


125
HTM1
EBM1
EBM3
M3:EBM3:Ir(L127)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


126
HTM1
EBM1
EBM3
M3:EBM3:Ir(L128)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


127
HTM1
EBM1
EBM3
M3:EBM3:Ir(L129)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


128
HTM1
EBM1
EBM3
M3:EBM3:Ir(L130)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


129
HTM1
EBM1
EBM3
M3:EBM3:Ir(L131)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


130
HTM1
EBM1
EBM3
M3:EBM3:Ir(L132)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


131
HTM1
EBM1
EBM3
M3:EBM3:Ir(L133)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


132
HTM1
EBM1
EBM3
M3:EBM3:Ir(L134)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


133
HTM1
EBM1
EBM3
M3:EBM3:Ir(L135)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


134
HTM1
EBM1
EBM3
M3:EBM3:Ir(L136)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


135
HTM1
EBM1
EBM3
M3:EBM3:Ir(L137)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


136
HTM1
EBM1
EBM3
M3:EBM3:Ir(L138)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


137
HTM1
EBM1
EBM3
M3:EBM3:Ir(L139)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


138
HTM1
EBM1
EBM3
M3:EBM3:Ir(L142)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


139
HTM1
EBM1
EBM3
M3:EBM3:Ir(L144)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


140
HTM1
EBM1
EBM3
M3:EBM3:Ir(L145)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


141
HTM1
EBM1
EBM3
M3:EBM3:Ir(L146)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


142
HTM1
EBM1
EBM3
M3:EBM3:Ir(L147)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


143
HTM1
EBM1
EBM3
M3:EBM3:Ir(L148)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


144
HTM1
EBM1
EBM3
M3:EBM3:Ir(L149)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


145
HTM1
EBM1
EBM3
M3:EBM3:Ir(L150)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


146
HTM1
EBM1
EBM3
M3:EBM3:Ir(L151)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


147
HTM1
EBM1
EBM3
M3:EBM3:Ir(L152)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


148
HTM1
EBM1
EBM3
M3:EBM3:Ir(L153)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


149
HTM1
EBM1
EBM3
M3:EBM3:Ir(L154)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


150
HTM1
EBM1
EBM3
M3:EBM3:Ir(L155)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


151
HTM1
EBM1
EBM3
M3:EBM3:Ir(L156)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


152
HTM1
EBM1
EBM3
M3:EBM3:Ir(L157)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


153
HTM1
EBM1
EBM3
M3:EBM3:Ir(L158)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


154
HTM1
EBM1
EBM3
M3:EBM3:Ir(L159)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


155
HTM1
EBM1
EBM3
M3:EBM3:Ir(L160)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


156
HTM1
EBM1
EBM3
M3:EBM3:Ir(L161)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


157
HTM1
EBM1
EBM3
M3:EBM3:Ir(L162)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


158
HTM1
EBM1
EBM3
M3:EBM3:Ir(L163)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


159
HTM1
EBM1
EBM3
M3:EBM3:Ir(L164)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


160
HTM1
EBM1
EBM3
M3:EBM3:Ir(L165)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


161
HTM1
EBM1
EBM3
M3:EBM3:Ir(L169)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


162
HTM1
EBM1
EBM3
M3:EBM3:Ir(L170)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


163
HTM1
EBM1
EBM3
M3:EBM3:Ir(L171)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


164
HTM1
EBM1
EBM3
M3:EBM3:Ir(L172)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


165
HTM1
EBM1
EBM3
M3:EBM3:Ir(L173)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


166
HTM1
EBM1
EBM3
M3:EBM3:Ir(L174)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


167
HTM1
EBM1
EBM3
M3:EBM3:Ir(L175)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


168
HTM1
EBM1
EBM3
M3:EBM3:Ir(L176)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


169
HTM1
EBM1
EBM3
M3:EBM3:Ir(L177)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


170
HTM1
EBM1
EBM3
M3:EBM3:Ir(L178)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


171
HTM1
EBM1
EBM3
M3:EBM3:Ir(L179)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


172
HTM1
EBM1
EBM3
M3:EBM3:Ir(L180)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


173
HTM1
EBM1
EBM3
M3:EBM3:Ir(L181)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


174
HTM1
EBM1
EBM3
M3:EBM3:Ir(L182)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


175
HTM1
EBM1
EBM3
M3:EBM3:Ir(L183)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


176
HTM1
EBM1
EBM3
M3:EBM3:Ir(L184)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


177
HTM1
EBM1
EBM3
M3:EBM3:Ir(L185)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


178
HTM1
EBM1
EBM3
M3:EBM3:Ir(L186)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


179
HTM1
EBM1
EBM3
M3:EBM3:Ir(L187)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


180
HTM1
EBM1
EBM3
M3:EBM3:Ir(L188)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


181
HTM1
EBM1
EBM3
M3:EBM3:Ir(L189)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


182
HTM1
EBM1
EBM3
M3:EBM3:Ir(L190)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


183
HTM1
EBM1
EBM3
M3:EBM3:Ir(L191)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


184
HTM1
EBM1

ETM1:Ir(L192)3

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


185
HTM1
EBM1

ETM1:Ir(L193)3

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


186
HTM1
EBM1

ETM1:Ir(L194)3

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


187
HTM1
EBM1

ETM1:Ir(L195)3

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


188
HTM1
EBM1
EBM3
M3:EBM3:Ir(L200)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


189
HTM1
EBM1
EBM3
M3:EBM3:Ir(L201)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


190
HTM1
EBM1

ETM1:Ir(L202)3

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


191
HTM1
EBM1

ETM1:Ir(L203)3

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


192
HTM1
EBM1
EBM3
M3:EBM3:Ir(L204)3
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


193
HTM1
EBM1
EBM3
M3:EBM3:Ir(L5)2(CL1)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


194
HTM1
EBM1
EBM3
M3:EBM3:Ir(L5)2(CL2)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


195
HTM1
EBM1
EBM3
M3:EBM3:Ir(L5)2(CL3)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


196
HTM1
EBM1
EBM3
M3:EBM3:Ir(L5)2(CL4)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


197
HTM1
EBM1

ETM1:Ir(L5)2(L193)

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


198
HTM1
EBM1
EBM3
M3:EBM3:Ir(L7)2(CL1)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


199
HTM1
EBM1
EBM3
M3:EBM3:Ir(L9)2(CL1)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


200
HTM1
EBM1
EBM3
M3:EBM3:Ir(L15)2(CL1)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


201
HTM1
EBM1
EBM3
M3:EBM3:Ir(L49)2(CL1)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


202
HTM1
EBM1
EBM3
M3:EBM3:Ir(L83)2(CL2)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


203
HTM1
EBM1
EBM3
M3:EBM3:Ir(L104)2(CL2)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


204
HTM1
EBM1
EBM3
M3:EBM3:Ir(L105)2(CL2)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


205
HTM1
EBM1
EBM3
M3:EBM3:Ir(L119)2(CL3)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


206
HTM1
EBM1
EBM3
M3:EBM3:Ir(L130)2(CL3)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


207
HTM1
EBM1
EBM3
M3:EBM3:Ir(L139)2(CL3)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


208
HTM1
EBM1
EBM3
M3:EBM3:Ir(L163)2(CL3)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


209
HTM1
EBM1
EBM3
M3:EBM3:Ir(L172)2(L199)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


210
HTM1
EBM1
EBM3
M3:EBM3:Ir(L1)2(CL5)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


211
HTM1
EBM1
EBM3
M3:EBM3:Ir(L7)2(CL5)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


212
HTM1
EBM1
EBM3
M3:EBM3:Ir(L7)2(CL6)
M3
ETM1:LiQ




20 nm
5 nm
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


213
HTM1
EBM1
EBM3
M3:EBM3:Ir(L15)2(CL7)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


214
HTM1
EBM1
EBM3
M3:EBM3:Ir(L49)2(CL7)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


215
HTM1
EBM1
EBM3
M3:EBM3:Ir(L83)2(CL8)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


216
HTM1
EBM1
EBM3
M3:EBM3:Ir(L104)2(CL8)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


217
HTM1
EBM1
EBM3
M3:EBM3:Ir(L105)2(CL8)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


218
HTM1
EBM1
EBM3
M3:EBM3:Ir(L119)2(CL8)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


219
HTM1
EBM1

ETM1:Ir(L119)2(CL9)

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


220
HTM1
EBM1

ETM1:Ir(L130)2(CL10)

ETM1:LiQ




20 nm
20 m 

90%:10%)

(50%:50%)






40 nm

20 nm


221
HTM1
EBM1
EBM3
M3:EBM3:Ir(L139)2(CL7)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


222
HTM1
EBM1
EBM3
M3:EBM3:Ir(L12)2(L7)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


223
HTM1
EBM1
EBM3
M3:EBM3:Ir(L12)2(L32)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


224
HTM1
EBM1
EBM3
M3:EBM3:Ir(L12)2(L51)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


225
HTM1
EBM1
EBM3
M3:EBM3:Ir(L51)2(L12)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


226
HTM1
EBM1
EBM3
M3:EBM3:Ir(L79)2(CL7)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


227
HTM1
EBM1
EBM3
M3:EBM3:Ir(L99)2(L111)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


228
HTM1
EBM1
EBM3
M3:EBM3:Ir(L139)2(CL8)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


229
HTM1
EBM1
EBM3
M3:EBM3:Ir(L164)2(CL8)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


230
HTM1
EBM1
EBM3
M3:EBM3:Pt(L12)2
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


231
HTM1
EBM1
EBM3
M3:EBM3:Pt(L41)2
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


232
HTM1
EBM1
EBM3
M3:EBM3:Pt(L46)2
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


233
HTM1
EBM1
EBM3
M3:EBM3:Pt(L101)2
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


234
HTM1
EBM1
EBM3
M3:EBM3:Pt(L165)2
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


235
HTM1
EBM1
EBM3
M3:EBM3:Pt(L205)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


236
HTM1
EBM1
EBM3
M3:EBM3:Pt(L206)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


237
HTM1
EBM1
EBM3
M3:EBM3:Pt(L207)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


238
HTM1
EBM1
EBM3
M3:EBM3:Pt(L208)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


239
HTM1
EBM1
EBM3
M3:EBM3:Pt(L40)(CL1)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


240
HTM1
EBM1
EBM3
M3:EBM3:Pt(L66)(CL2)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


241
HTM1
EBM1
EBM3
M3:EBM3:Pt(L107)(CL1)
M3
ETM1:LiQ




20 nm
5 m
15 nm
(80%:10%:10%)
10 nm
(50%:50%)






40 nm

20 nm


242
HTM1
EBM1

ETM1:Pt (L107)(L196)

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


243
HTM1
EBM1

ETM1:Pt(L107)(L199)

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


244
HTM1
EBM1

ETM1:Au(L202)(CL5)

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


245
HTM1
EBM1

ETM1:Pt(L203)(CL5)

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


246
HTM1
EBM1

ETM1:Pt(L204)(CL5)

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


247
HTM1
EBM1

ETM1:Cu(L194)(CL11)

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


248
HTM1
EBM1

ETM1:Pt (L196)(CL11)

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


249
HTM1
EBM1

ETM1:Pt(L195)(CL12)

ETM1:LiQ




20 nm
20 m 

(90%:10%)

(50%:50%)






40 nm

20 nm


250
Ir(L83)3
M2:Ir(L83)3

M2:Ir(L83)3
M3
Alq3
LiF



20 nm
(70%:30%)

(85%:15%)
10 nm
20 nm




20 nm

40 nm


comp.
HTM1
EBM1
EBM3
M2:Ir(ref)
M3
Alq3
LiF



20 nm
5 m
15 nm
(85%:15%)
10 nm
20 nm






40 nm
















TABLE 2







Use of compounds according to the invention as matrix


materials in phosphorescent OLEDs















Efficiency






Voltage (V)
(cd/A) at
CIE x/y at
LD50 (h) at



Ex.
1000 cd/m2
1000 cd/m2
1000 cd/m2
1000 cd/m2

















1
6.1
9.4
0.34/0.52
1300



2
5.2
8.1
0.52/0.47
600



3
14.0
7.5
0.18/0.32
300



4
14.2
7.2
0.18/0.31
400



5
8.1
9.8
0.19/0.35
400



6
6.5
8.2
0.19/0.35
700



7
5.1
8.9
0.34/0.52
1200



8
6.2
15.0
0.29/0.52




9
5.0
18.2
0.27/0.48




10
6.0
19.3
0.26/0.47




11
5.5
15.5
0.29/0.53




12
5.8
20.3
0.23/0.45




13
5.7
22.5
0.25/0.46




14
4.8
19.9
0.27/0.46




15
5.3
22.3
0.26/0.47




16
5.7
27.6
0.29/0.52




17
4.9
29.3
0.28/0.50




18
6.1
9.3
0.16/0.24
300



19
5.1
28.6
0.29/0.52




20
4.9
11.2
0.19/0.35




21
5.0
14.5
0.19/0.35




22
4.7
16.7
0.16/0.30
600



23
4.9
17.3
0.19/0.35




24
5.3
16.9
0.18/0.31




25
5.2
16.7
0.18/0.34




26
5.5
17.3
0.19/0.35




27
5.0
22.7
0.21/0.39




28
5.0
14.9
0.20/0.41




29
4.9
19.0
0.21/0.38




30
5.2
14.7
0.18/0.32
700



31
5.5
16.9
0.19/0.34




32
4.6
21.3
0.21/0.38




33
4.8
13.9
0.20/0.36




34
5.3
16.7
0.18/0.32
500



35
4.8
18.3
0.18/0.31




36
4.7
16.3
0.17/0.31
300



37
5.6
22.5
0.21/0.36




38
5.0
25.8
0.21/0.35
800



39
4.9
15.6
0.17/0.30




40
5.8
12.9
0.20/0.36




41
5.3
13.9
0.16/0.25




42
4.9
18.6
0.20/0.39




43
5.5
15.5
0.21/0.36




44
5.0
23.2
0.23/0.40




45
4.9
25.6
0.21/0.36




46
5.1
27.1
0.22/0.38




47
4.7
24.9
0.18/0.31




48
5.3
22.9
0.21/0.38




49
4.9
23.1
0.20/0.37




50
4.8
20.3
0.19/0.34




51
4.8
19.7
0.19/0.33
400



52
4.9
20.1
0.17/0.26




53
5.3
21.1
0.17/0.26




54
5.2
23.1
0.20/0.38




55
4.9
19.9
0.19/0.32




56
4.7
22.3
0.18/0.32




57
5.6
16.7
0.20/0.39




58
7.3
24.1
0.20/0.35




59
5.6
22.1
0.21/0.36




60
4.8
16.7
0.22/0.38




61
5.7
19.3
0.23/0.40
700



62
5.5
23.5
0.25/0.43




63
4.5
19.5
0.19/0.33




64
4.8
22.6
0.17/0.28




65
5.1
19.7
0.19/0.34
200



66
5.5
19.0
0.21/0.38




67
4.9
24.9
0.28/0.52
17000



68
5.8
19.6
0.26/0.49
22000



69
5.2
22.7
0.28/0.48




70
5.4
20.6
0.21/0.35




71
4.7
22.4
0.19/0.32
1800



72
4.9
24.7
0.20/0.35




73
5.2
23.9
0.20/0.34




74
4.8
19.7
0.18/0.30




75
5.5
18.7
0.21/0.35




76
4.8
22.7
0.20/0.30
2800



77
6.1
24.6
0.21/0.40




78
5.5
20.7
0.19/0.26




79
5.1
19.6
0.20/0.32




80
8.5
15.7
0.25/0.43
1500



81
8:3
16.9
0.19/0.28




82
5.4
24.7
0.33/0.51
12000



83
6.2
23.0
0.34/0.51
7000



84
5.7
18.8
0.19/0.45
1200



85
6.0
14.1
0.20/0.46
700



86
7.4
11.3
0.17/0.40
200



87
4.9
20.7
0.26/0.47
600



88
8.9
7.3
0.23/0.45
2100



89
7.4
8.6
0.21/0.44
2600



90
5.8
37.2
0.25/0.49
100



91
5.4
22.7
0.26/0.47




92
5.6
36.5
0.23/0.45




93
5.1
24.9
0.22/0.45




94
4.8
26.7
0.20/0.44
2400



95
5.6
22.7
0.29/0.45




96
4.9
25.0
0.23/0.39




97
5.8
22.9
0.21/0.37




98
5.2
24.7
0.22/0.43




99
4.9
22.0
0.25/0.49




100
5.5
21.9
0.25/0.43




101
5.3
19.7
0.23/0.39




102
5.9
30.9
0.29/0.52




103
4.7
26.9
0.20/0.43




104
6.7
33.5
0.23/0.39




105
5.8
23.8
0.21/0.32




106
5.3
18.9
0.22/0.32




107
4.7
25.7
0.23/042




108
4.5
25.6
0.19/0.43
2800



109
5.5
28.8
0.21/0.32




110
5.3
32.6
0.21/0.32




111
4.9
26.9
0.30/0.46




112
6.7
29.0
0.29/0.43




113
5.2
26.4
0.26/0.43




114
6.3
23.9
0.23/0.43




115
5.0
22.7
0.19/0.36




116
4.8
19.8
0.21/0.32




117
5.7
31.0
0.29/0.52




118
5.2
29.8
0.30/0.55
25000



119
5.4
29.6
0.21/0.35




120
5.6
26.8
0.30/0.49




121
4.7
33.8
0.21/0.34




122
4.9
30.2
0.22/0.38




123
5.1
24.8
0.20/0.37




124
4.6
29.8
0.19/0.34




125
5.8
32.2
0.28/0.55
23000



126
4.4
29.8
0.26/0.42




127
5.3
30.7
0.23/0.38




128
6.0
23.8
0.22/0.36




129
5.8
26.8
0.21/0.30




130
5.0
26.5
0.19/0.34
1700



131
4.8
25.6
0.20/0.38




132
4.2
36.6
0.26/0.38




133
4.6
33.3
0.23/0.38




134
5.2
30.5
0.26/0.47




135
5.3
34.8
0.23/0.37




136
4.3
35.7
0.19/0.32




137
4.7
34.5
0.25/40  




138
5.5
23.4
0.26/0.47




139
5.2
39.1
0.32/0.50
29000



140
4.6
40.3
0.35/0.59




141
4.3
32.0
0.30/0.50




142
4.8
29.9
0.29/0.59




143
5.3
33.5
0.28/0.50




144
5.1
29.8
0.27/0.45




145
4.9
38.9
0.30/0.55




146
4.7
37.6
0.26/0.46




147
5.0
38.6
0.33/0.60




148
4.7
35.6
0.30/0.55




149
5.5
27.3
0.26/0.49
23000



150
5.3
29.3
0.26/0.45




151
5.1
30.5
0.25/0.50




152
4.9
34.0
0.23/0.37




153
4.9
33.4
0.26/0.49




154
4.2
39.8
0.23/0.26




155
4.8
26.8
0.20/0.28




156
5.0
28.1
0.19/0.25
3100



157
6.0
22.0
0.26/0.47




158
4.9
25.6
0.23/0.35




159
5.1
26.4
0.23/0.39




160
5.5
20.2
0.19/0.26




161
5.1
30.6
0.27/0.50
12000



162
4.6
36.5
0.23/0.35




163
4.5
32.7
0.24/0.37




164
4.9
29.6
0.22/0.40




165
4.8
32.3
0.24/0.42




166
5.3
22.7
0.19/0.29
1600



167
5.3
26.4
0.26/0.49
4500



168
5.0
25.3
0.21/0.38




169
4.8
22.0
0.19/0.28




170
5.2
30.5
0.28/0.51




171
5.6
33.5
0.29/0.52




172
4.8
32.3
0.27/0.52
15000



173
5.4
26.7
0.22/0.42




174
6.2
28.4
0.29/0.52
800



175
5.3
33.7
0.28/0.51




176
4.4
36.1
0.27/0.51




177
5.7
30.6
0.24/0.48
300



178
5.9
38.9
0.23/0.38




179
6.2
35.7
0.24/0.40




180
5.8
33.6
0.29/0.58




181
4.6
28.3
0.23/0.42
400



182
4.3
26.8
0.21/0.35




183
5.7
37.2
0.19/0.26
500



184
5.3
8.1
0.64/0.36




185
4.5
16.6
0.62/0.38
19000



186
4.8
7.9
0.68/0.32




187
5.5
10.5
0.67/0.33
32000



188
4.3
19.7
0.20/0.28




189
4.1
18.0
0.18/0.24




190
4.5
16.7
0.19/0.27




191
5.1
17.2
0.61/0.39
16700



192
4.7
16.5
0.63/0.37
22000



193
5.7
23.6
0.26/0.45




194
5.2
25.1
0.24/0.38
900



195
5.9
22.0
0.37/0.61
10000



196
5.2
23.1
0.22/0.28




197
4.2
19.6
0.61/0.39
22000



198
4.9
16.4
0.23/0.38




199
5.3
14.2
0.21/0.29




200
5.2
18.9
0.19/0.35
3200



201
4.6
19.0
0.18/0.32




202
6.2
26.8
0.23/0.45




203
5.1
29.0
0.29/0.42




204
6.2
25.4
0.28/0.51




205
5.6
35.7
0.33/0.58
21000



206
5.7
19.7
0.21/0.32




207
4.9
29.4
0.25/0.50




208
4.7
24.1
0.24/0.35




209
5.5
10.9
0.55/0.43
26000



210
4.2
30.5
0.28/0.55




211
4.7
16.0
0.21/0.28




212
5.3
12.1
0.19/0.23




213
4.9
17.3
0.20/0.25




214
5.7
19.5
0.23/0.40




215
4.8
45.8
0.30/0.60




216
4.9
13.2
0.26/0.49




217
5.0
30.1
0.29/0.51




218
5.2
32.2
0.30/0.59




219
4.7
12.8
0.67/0.33
35000



220
4.3
14.7
0.66/0.34




221
5.1
39.0
0.35/0.62




222
5.8
15.6
0.17/0.26
600



223
5.8
20.4
0.20/0.29




224
4.7
13.9
0.18/0.24




225
4.8
14.0
0.19/0.25




226
5.2
16.5
0.17/0.22




227
4.6
31.2
0.29/0.56




228
4.3
38.4
0.30/0.59




229
4.4
36.7
0.32/0.57
29000



230
5.6
19.1
0.25/0.47
600



231
5.2
17.4
0.23/0.35




232
6.7
13.1
0.19/0.28
1200



233
5.8
17.9
0.22/0.42




234
6.4
18.6
0.23/0.39




235
5.1
16.5
0.19/0.24
1100



236
8.0
8.9
0.25/0.45
600



237
5.2
14.0
0.22/0.28




238
4.9
11.2
0.23/0.32




239
5.5
16.4
0.25/0.35
5000



240
5.1
12.1
0.23/0.33




241
4.9
13.1
0.35/0.58




242
4.2
13.1
0.65/035 
23000



243
5.9
11.1
0.66/0.33




244
6.3
20.5
0.62/0.38
1500



245
5.9
19.7
0.63/0.37
2500



246
5.3
14.3
0.59/0.37




247
4.8
17.3
0.58/0.36




248
5.2
14.2
0.63/0.37




249
4.7
8.6
0.64/0.36




250
6.2
21.4
0.34/0.51
500



comp.
6.7
9.6
0.18/0.30
300

















TABLE 3





Structural formulae of the materials used









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image









embedded image











Materials according to the invention can also be used from solution and in this case result in significantly simpler OLEDs compared with vacuum-processed OLEDs, but nevertheless having good properties.


The production of components of this type is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described a number of times in the literature (for example in WO 2004/037887 A2). The structure is composed of substrate/ITO/PEDOT (80 nm)/interlayer/emission layer (80 nm)/cathode. The interlayer used serves for hole injection; in this case, HIL-012 from Merck is used. In the present case, the emitters according to the invention for the emission layer are dissolved in toluene besides the matrices. The typical solids content of such solutions is between 16 and 25 g/l if, as here, the layer thickness of 80 nm which is typical for a device is to be achieved by means of spin coating. The emission layer is applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 120° C. for 10 min. Finally, a cathode comprising barium and aluminium is applied by vacuum vapour deposition. The layers HBL and ETL used in the above-mentioned examples can also be applied between the EML and the cathode by vapour deposition, and the interlayer may also be replaced by one or more layers, which merely have to satisfy the condition of not being re-detached by the downstream processing step of EML deposition from solution.


The solution-processed devices are also characterised by standard methods in the matrices PS (polystyrene):M8:M1:Ir(LX)3 (26%:14%:42%:20%), and the OLED examples given have not yet been optimised. Table 4 shows the data obtained. It is evident here that the materials according to the invention in the processed OLEDs result in efficient blue- to greenemitting OLEDs.









TABLE 4







Results with materials processed from solution














EML with
Voltage [V] at
Max. eff.
CIE



Ex.
emitter 80 nm
100 cd/m2
[cd/A]
(x, y)

















251
 Ir(L67)3
8.3
12.6
0.21/0.38



252
 Ir(L68)3
8.6
10.6
0.22/0.41



253
Ir(L108)3
7.9
13.4
0.23/0.39



254
Ir(L109)3
7.7
11.3
0.24/0.45



255
Ir(L110)3
8.6
9.1
0.25/0.49



256
Ir(L111)3
7.6
14.7
0.24/0.43



257
Ir(L116)3
6.9
16.4
0.28/0.52



258
Ir(L117)3
7.1
14.8
0.27/0.50



259
Ir(L121)3
8.6
19.1
0.30/0.50



260
Ir(L123)3
9.5
20.6
0.32/0.59



261
Ir(L124)3
8.1
17.6
0.31/0.54



262
Ir(L136)3
7.2
19.4
0.28/0.50



263
Ir(L137)3
8.6
23.4
0.33/0.62



264
Ir(L143)3
7.7
22.8
0.36/0.60



265
Ir(L166)3
8.3
18.6
0.35/0.60



266
Ir(L167)3
7.9
19.5
0.36/0.59



267
Ir(L168)3
8.4
16.4
0.33/0.62



268
Ir(L196)3
8.8
12.7
0.63/0.37



269
Ir(L197)3
8.7
19.8
0.58/0.38



270
Ir(L198)3
7.9
8.4
0.66/0.34



271
Ir(L199)3
8.3
7.2
0.67/0.33









Claims
  • 1. A compound of the formula (1) M(L)n(L′)m  formula (1)containing a moiety M(L)n of the formula (3):
  • 2. The compound according to claim 1, wherein the ligands L bond to the metal M via one carbon atom and one nitrogen atom.
  • 3. The compound according to claim 1, wherein the moiety of the formula (3) is selected from the formula (3b):
  • 4. The compound according to claim 1, wherein the moieties of the formulae (7) to (8) are selected from the structures of the following formulae (7a) to (8a):
  • 5. The compound according to claim 1, wherein the moieties of the formula (3) are selected from the structures of the formulae (27)-(30), (50)-(53) and (73)-(76):
  • 6. The compound according to claim 1, wherein at least one of the substituents R2, R3 and/or R4, is a substituent not equal to hydrogen or deuterium.
  • 7. The compound according to claim 1, wherein the substituent R6 which is in the ortho-position to the metal coordination represents a coordinating group which coordinates to the metal M, and is aryl or heteroaryl groups, aryl or alkyl cyanides, aryl or alkyl isocyanides, amines or amides, alcohols or alcoholates, thioalcohols or thioalcoholates, phosphines, phosphites, carbonyl functions, carboxylates, carbamides or aryl- or alkylacetylides.
  • 8. The compound according to claim 7, wherein the moiety of the formula (3) is selected from the structures of the formulae (94) to (97):
  • 9. The compound according to claim 1, wherein the complexes contain a polydentate ligand, wherein the metal complexes are selected from the formulae (102), (103) and (105):
  • 10. The compound according to claim 9, wherein V, if it is a trivalent group, which bridges three ligands L to one another or two ligands L to L′ or one ligand L to two ligands L′, is selected, identically or differently on each occurrence, from the group consisting of B, B(R8)−, B(C(R8)2)3, (R8)B(C(R8)2)3−, B(O)3, (R8)B(O)3−, B(C(R8)2C(R8)2)3, (R8)B(C(R8)2C(R8)2)3−, B(C(R8)2O)3, (R8)B(C(R8)2O)3−, B(OC(R8)2)3, (R8)B(OC(R8)2)3−, C(R8), CO−, CN(R8)2, (R8)C(C(R8)2)3, (R8)C(O )3, (R8)C(C(R8)2C(R8)2)3, (R8)C(C(R8)2O)3, (R8)C(OC(R8)2)3, (R8)C(Si(R8)2)3, (R8)C(Si(R8)2C(R8)2)3, (R8)C(C(R8)2Si(R8)2)3, (R8)C(Si(R8)2Si(R8)2)3, Si(R8), (R8)Si(C(R8)2)3, (R8)Si(O)3, (R8)Si(C(R8)2C(R8)2)3, (R8)Si(OC(R8)2)3, (R8)Si(C(R8)2O)3, (R8)Si(Si(R8)2)3, (R8)Si(Si(R8)2C(R8)2)3, (R8)Si(C(R8)2Si(R8)2)3, (R8)Si(Si(R8)2Si(R8)2)3, N, NO, N(R8)+, N(C(R8)2)3, (R8)N(C(R8)2)3+, N(C═O)3, N(C(R8)2C(R8)2)3, (R8)N(C(R8)2C(R8)2)+, P, P(R8)+, PO, PS, PSe, PTe, P(O)3, PO(O)3, P(OC(R8)2)3, PO(OC(R8)2)3, P(C(R8)2)3, P(R8)(C(R8)2)3+, PO(C(R8)2)3, P(C(R8)2C(R8)2)3, P(R8)(C(R8)2C(R8)2)3+, PO(C(R8)2C(R8)2)3, As, As(R8)+, AsO, AsS, AsSe, AsTe, As(O)3, AsO(O)3, As(OC(R8)2)3, AsO(OC(R8)2)3, As(C(R8)2)3, As(R8)(C(R8)2)3+, AsO(C(R8)2)3, As(C(R8)2C(R8)2)3, As(R8)(C(R8)2C(R8)2)3+, AsO(C(R8)2C(R8)2)3, Sb, Sb(R8)+, SbO, SbS, SbSe, SbTe, Sb(O)3, SbO(O)3, Sb(OC(R8)2)3, SbO(OC(R8)2)3, Sb(C(R8)2)3, Sb(R8)(C(R8)2)3+, SbO(C(R8)2)3, Sb(C(R8)2C(R8)2)3, Sb(R8)(C(R8)2C(R8)2)3+, SbO(C(R8)2C(R8)2)3, Bi, Bi(R8)+, BiO, BiS, BiSe, BiTe, Bi(O)3, BiO(O)3, Bi(OC(R8)2)3, BiO(OC(R8)2)3, Bi(C(R8)2)3, Bi(R8)(C(R8)2)3+, BiO(C(R8)2)3, Bi(C(R8)2C(R8)2)3, Bi(R8)(C(R8)2C(R8)2)3+, BiO(C(R8)2C(R8)2)3, S+, S(C(R8)2)3+, S(C(R8)2C(R8)2)3+, Se+, Se(C(R8)2)3+, Se(C(R8)2C(R8)2)3+, Te+, Te(C(R8)2)3+, Te(C(R8)2C(R8)2)3+,
  • 11. The compound according to claim 1, wherein the ligands L′ are selected, identically or differently on each occurrence, from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, aryl cyanides, alkyl isocyanides, aryl isocyanides, amines, phosphines, phosphites, arsines, stibines, nitrogen-containing heterocycles, carbenes, hydride, deuteride, F−, Cl−, Br− and I−, alkylacetylides, arylacetylides, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic or aromatic alcoholates, aliphatic or aromatic thioalcoholates, amides, carboxylates, aryl groups, O2−, S2−, carbides, nitrenes, N3−, diamines, imines, diimines, heterocycles containing two nitrogen atoms, diphosphines, 1,3-diketonates derived from 1,3-diketones, 3-ketonates derived from 3-ketoesters, carboxylates derived from aminocarboxylic acids, salicyliminates derived from salicylimines, dialcoholates derived from dialcohols, dithiolates derived from dithiols, borates of nitrogen-containing heterocycles, η5-cyclopentadienyl, η5-pentamethylcyclopentadienyl, η6-benzene and η7-cycloheptatrienyl, each of which is optionally substituted by one or more radicals R1; and/or the ligands L′ are, identically or differently on each occurrence, bidentate ligands L′ which, with the metal, form a cyclometal-lated five- or six-membered ring, the combination of two groups, as depicted by the formulae (120) to (147), where one group bonds via a neutral nitrogen atom or a carbene atom and the other group bonds via a negatively charged carbon atom or a negatively charged nitrogen atom, where the aromatic rings in these groups in each case bond to one another at the position denoted by #, and the position at which the groups coordinate to the metal is denoted by *:
  • 12. Process for the preparation of the compound according to claim 1 which comprises reacting the corresponding free ligands or a precursor of the ligand with metal alkoxides of the formula (152), with metal ketoketonates of the formula (153) or with metal halides of the formula (154):
  • 13. An oligomer, polymer or dendrimer comprising one or more of the compounds according to claim 1, where at least one of the radicals R1 to R6 and R8 defined above represents a bond to the polymer or dendrimer.
  • 14. An electronic device comprising at least one compound according to claim 1.
  • 15. The electronic device as claimed in claim 14, wherein the electronic device selected from the group consisting of organic electroluminescent device (OLED, PLED), organic integrated circuit (O-IC), organic field-effect transistor (O-FET), organic thin-film transistor (O-TFT), organic light-emitting transistor (O-LET), organic solar cells (O-SCs), organic optical detector, organic photoreceptor, organic field-quench device (O-FQD), light-emitting electrochemical cell (LEC) and organic laser diode (O-laser).
  • 16. An organic electroluminescent device which comprises the compound according to claim 1 is employed as emitting compound in one or more emitting layers.
  • 17. The organic electroluminescent device according to claim 16, wherein the matrix material of the emitting layer is selected from ketones, phosphine oxides, sulfoxides, sulfones, triarylarnines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, silanes, azaboroles, boronic esters, diazasilole derivatives, diazaphosphole derivatives, triazine derivatives and zinc complexes.
  • 18. A compound of the formula (1) M(L)n(L′)m   formula (1)containing a moiety M(L)n of the formula (5) or formula (6)
  • 19. The compound according to claim 18, wherein the moieties of the formulae (5) to (6) are selected from the structures of the following formulae (5a) to (6a):
  • 20. The compound according to claim 18, wherein the ligands L bond to the metal M via one carbon atom and one nitrogen atom.
  • 21. The compound according to claim 18, wherein at least one of the substituents R2, R3 and/or R4, is a substituent not equal to hydrogen or deuterium.
  • 22. The compound according to claim 18, wherein the ligands L′ are selected, identically or differently on each occurrence, from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, aryl cyanides, alkyl isocyanides, aryl isocyanides, amines, phosphines, phosphites, arsines, stibines, nitrogen-containing heterocycles, carbenes, hydride, deuteride, F−, Cl−, Br− and I−, alkylacetylides, arylacetylides, cyanide, cyanate, isocyanate, thio-cyanate, isothiocyanate, aliphatic or aromatic alcoholates, aliphatic or aromatic thioalcoholates, amides, carboxylates, aryl groups, O2−, S2−, carbides, nitrenes, N3−, diamines, imines, diimines, heterocycles containing two nitrogen atoms, diphosphines, 1,3-diketonates derived from 1,3-diketones, 3-ketonates derived from 3-ketoesters, carboxylates derived from aminocarboxylic acids, salicyliminates derived from salicylimines, dialcoholates derived from dialcohols, dithiolates derived from dithiols, borates of nitrogen-containing heterocycles, η5-cyclopenta-dienyl, η5-pentamethylcyclopentadienyl, η6-benzene and η7-cycloheptatrienyl, each of which is optionally substituted by one or more radicals R1; and/or the ligands L′ are, identically or differently on each occurrence, bidentate ligands L′ which, with the metal, form a cyclometal-lated five- or six-membered ring, the combination of two groups, as depicted by the formulae (120) to (147), where one group bonds via a neutral nitrogen atom or a carbene atom and the other group bonds via a negatively charged carbon atom or a negatively charged nitrogen atom, where the aromatic rings in these groups in each case bond to one another at the position denoted by #, and the position at which the groups coordinate to the metal is denoted by *:
  • 23. Process for the preparation of the compound according to claim 18 which comprises reacting the corresponding free ligands or a precursor of the ligand with metal alkoxides of the fommla (152), with metal ketoketonates of the formula (153) or with metal halides of the folumla (154):
  • 24. An oligomer, polymer or dendrimer comprising one or more of the compounds according to claim 18, where at least one of the radicals R1 to R8 defined above represents a bond to the polymer or dendrimer.
  • 25. An electronic device comprising at least one compound according to claim 18.
  • 26. The electronic device as claimed in claim 25, wherein the electronic device selected from the group consisting of organic electroluminescent device (OLED, PLED), organic integrated circuit (O-IC), organic field-effect transistor (O-FET), organic thin-film transistor (O-TFT), organic light-emitting transistor (O-LET), organic solar cells (O-SCs), organic optical detector, organic photoreceptor, organic field-quench device (O-FQD), light-emitting electrochemical cell (LEC) and organic laser diode (O-laser).
  • 27. An organic electroluminescent device which comprises the compound according to claim 18 is employed as emitting compound in one or more emitting layers.
  • 28. The organic electroluminescent device according to claim 27, wherein the one or more emitting layers further comprises a matrix material selected from ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, silanes, azaboroles, boronic esters, diazasilole derivatives, diazaphosphole derivatives, triazine derivatives and zinc complexes.
  • 29. A compound of the formula (1) M(L)n(L′)m  formula (1)containing a moiety M(L)n selected from the structures of the foimulae (9) to (12), (14)-(17), (25), (26) or (31) to (77):
  • 30. The compound according to claim 29, wherein at least one of the substituents R2, R3 and/or R4, is a substituent not equal to hydrogen or deuterium.
  • 31. The compound according to claim 29, wherein the ligands L′ are selected, identically or differently on each occurrence, from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, aryl cyanides, alkyl isocyanides, aryl isocyanides, amines, phosphines, phosphites, arsines, stibines, nitrogen-containing heterocycles, carbenes, hydride, deuteride, F−, Cl−, Br− and I−, alkylacetylides, arylacetylides, cyanide, cyanate, isocyanate, thio-cyanate, isothiocyanate, aliphatic or aromatic alcoholates, aliphatic or aromatic thioalcoholates, amides, carboxylates, aryl groups, O2−, S2−, carbides, nitrenes, N3−, diamines, imines, diimines, heterocycles containing two nitrogen atoms, diphosphines, 1,3-diketonates derived from 1,3-diketones, 3-ketonates derived from 3-ketoesters, carboxylates derived from aminocarboxylic acids, salicyliminates derived from salicylimines, dialcoholates derived from dialcohols, dithiolates derived from dithiols, borates of nitrogen-containing heterocycles, η5-cyclopenta-dienyl, η5-pentamethylcyclopentadienyl, η6-benzene and η7-cycloheptatrienyl, each of which is optionally substituted by one or more radicals R1; and/or the ligands L′ are, identically or differently on each occurrence, bidentate ligands L′ which, with the metal, form a cyclometal-lated five- or six-membered ring, the combination of two groups, as depicted by the folinulae (120) to (147), where one group bonds via a neutral nitrogen atom or a carbene atom and the other group bonds via a negatively charged carbon atom or a negatively charged nitrogen atom, where the aromatic rings in these groups in each case bond to one another at the position denoted by #, and the position at which the groups coordinate to the metal is denoted by *:
  • 32. Process for the preparation of the compound according to claim 29 which comprises reacting the corresponding free ligands or a precursor of the ligand with metal alkoxides of the formula (152), with metal ketoketonates of the formula (153) or with metal halides of the formula (154):
  • 33. An oligomer, polymer or dendrimer comprising one or more of the compounds according to claim 29, where at least one of the radicals R1 to R8 defined above represents a bond to the polymer or dendrimer.
  • 34. An electronic device comprising at least one compound according to claim 29.
  • 35. The electronic device as claimed in claim 34, wherein the electronic device selected from the group consisting of organic electroluminescent device (OLED, PLED), organic integrated circuit (O-IC), organic field-effect transistor (O-FET), organic thin-film transistor (O-TFT), organic light-emitting transistor (O-LET), organic solar cells (O-SCs), organic optical detector, organic photoreceptor, organic field-quench device (O-FQD), light-emitting electrochemical cell (LEC) and organic laser diode (O-laser).
  • 36. An organic electroluminescent device which comprises the compound according to claim 29 is employed as emitting compound in one or more emitting layers.
  • 37. The organic electroluminescent device according to claim 36, wherein the one or more emitting layers further comprises a matrix material selected from ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, silanes, azaboroles, boronic esters, diazasilole derivatives, diazaphosphole derivatives, triazine derivatives and zinc complexes.
  • 38. A compound of the formula (1) M(L)n(L′)m   formula (1)containing a moiety M(L)n selected from the structures of the formulae (90) to (93) or wherein the metal complexes are selected from the formulae (98) to (101) and (104):
Priority Claims (1)
Number Date Country Kind
10 2009 007 038 Feb 2009 DE national
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/EP2010/000177 1/14/2010 WO 00 8/2/2011
Publishing Document Publishing Date Country Kind
WO2010/086089 8/5/2010 WO A
US Referenced Citations (48)
Number Name Date Kind
2743274 VanSlyke et al. Apr 1956 A
3704300 Hardtmann Nov 1972 A
3887566 Rodway et al. Jun 1975 A
4539507 VanSlyke et al. Sep 1985 A
5151629 VanSlyke Sep 1992 A
5621131 Kreuder et al. Apr 1997 A
5840217 Lupo et al. Nov 1998 A
6169163 Woo et al. Jan 2001 B1
6458909 Spreitzer et al. Oct 2002 B1
6653438 Spreitzer et al. Nov 2003 B1
7345301 Gerhard et al. Mar 2008 B2
7723455 Becker et al. May 2010 B2
20050069729 Ueda et al. Mar 2005 A1
20050123795 Lussier et al. Jun 2005 A1
20050171076 Meggers et al. Aug 2005 A1
20050227112 Ise et al. Oct 2005 A1
20060019942 Meggers et al. Jan 2006 A1
20060058494 Busing et al. Mar 2006 A1
20060063027 Vestweber et al. Mar 2006 A1
20060142604 Bach et al. Jun 2006 A1
20060175958 Gerhard et al. Aug 2006 A1
20060220004 Stossel et al. Oct 2006 A1
20060252936 Stossel et al. Nov 2006 A1
20060284140 Breuning et al. Dec 2006 A1
20070135635 Stossel et al. Jun 2007 A1
20070176147 Buesing et al. Aug 2007 A1
20070205714 Busing et al. Sep 2007 A1
20070231598 Busing et al. Oct 2007 A1
20070249834 Stossel et al. Oct 2007 A1
20070281182 Schulte et al. Dec 2007 A1
20080027220 Stossel et al. Jan 2008 A1
20080312396 Stoessel et al. Dec 2008 A1
20090134384 Stoessel et al. May 2009 A1
20090134784 Lin et al. May 2009 A1
20090163545 Goldfarb Jun 2009 A1
20090167166 Bach et al. Jul 2009 A1
20090302742 Komori et al. Dec 2009 A1
20090302752 Parham et al. Dec 2009 A1
20100102305 Heun et al. Apr 2010 A1
20100141125 Otsu et al. Jun 2010 A1
20100141126 Otsu et al. Jun 2010 A1
20100187977 Kai et al. Jul 2010 A1
20100227978 Stoessel et al. Sep 2010 A1
20100244009 Parham et al. Sep 2010 A1
20110068304 Parham et al. Mar 2011 A1
20110105778 Stoessel et al. May 2011 A1
20110121274 Parham et al. May 2011 A1
20110140043 Stoessel et al. Jun 2011 A1
Foreign Referenced Citations (60)
Number Date Country
2206012 Aug 1972 DE
2166398 Jan 1974 DE
102008033943 Jan 2010 DE
102008036982 Feb 2010 DE
102008056688 May 2010 DE
652273 May 1995 EP
0 676 461 Oct 1995 EP
0 707 020 Apr 1996 EP
0 842 208 May 1998 EP
0 894 107 Feb 1999 EP
1 028 136 Aug 2000 EP
1205527 May 2002 EP
1617710 Jan 2006 EP
1617711 Jan 2006 EP
1731584 Dec 2006 EP
1327311 Aug 1973 GB
2002110357 Apr 2002 JP
2004131464 Apr 2004 JP
2004288381 Oct 2004 JP
2005317516 Nov 2005 JP
2005-347160 Dec 2005 JP
WO-9218552 Oct 1992 WO
WO-9827136 Jun 1998 WO
WO-0022026 Apr 2000 WO
WO-02060910 Aug 2002 WO
WO-2004013080 Feb 2004 WO
WO-2004037887 May 2004 WO
WO-2004041901 May 2004 WO
WO-2004058911 Jul 2004 WO
WO-2004070772 Aug 2004 WO
WO-2004081017 Sep 2004 WO
WO-2004085449 Oct 2004 WO
WO-2004093207 Oct 2004 WO
WO-2004113468 Dec 2004 WO
WO-2005011013 Feb 2005 WO
WO-2005014689 Feb 2005 WO
WO-2005039246 Apr 2005 WO
WO-2005040302 May 2005 WO
WO-2005042548 May 2005 WO
WO-2005104264 Nov 2005 WO
WO-2005111113 Nov 2005 WO
WO-2005111172 Nov 2005 WO
WO-2005113563 Dec 2005 WO
WO-2006003000 Jan 2006 WO
WO-2006005627 Jan 2006 WO
WO-2006008069 Jan 2006 WO
WO-2006117052 Nov 2006 WO
WO-2007063754 Jun 2007 WO
WO-2007065523 Jun 2007 WO
WO-2007095118 Aug 2007 WO
WO-2007095118 Aug 2007 WO
WO-2007137725 Dec 2007 WO
WO-2008056746 May 2008 WO
WO-2008086851 Jul 2008 WO
WO-2008140114 Nov 2008 WO
WO-2008143059 Nov 2008 WO
WO-2008140114 Nov 2008 WO
WO-2008143059 Nov 2008 WO
WO-2008156879 Dec 2008 WO
WO-2009062578 May 2009 WO
Non-Patent Literature Citations (7)
Entry
Hennig, H., et al., “Coordination tendencies of acidic amino groups. 12. EPR investigations on cationic copper(II) chelates of 5mino-2-methyl-3H-imidazo[4,5-h]quinoline,” Zeitschrift fuer Chemie (1971), vol. 11, No. 3, pp. 115-117, Sekt. Chem., Karl-Marx-Univ., Leipzig, Fed. Rep. Ger. XP-002589524. (Article is not in the English language but can be found in the International Search Report).
English Translation of Japanese Office Action for Application No. 2011-54668, dated Feb. 4, 2014.
Henning, H. et al., “Chelate-forming dye couplers, III. Synthesis and properties of blue-green couplers with imidazo[4,5-h]-quinoline as the complex-forming group”, Journal fuer Praktische Chemie (Leipzig), vol. 317, No. 5, (1975), pp. 853-860.
Henning, H. et al., Coordination tendencies of acidic amino groups. 12. EPR 5-amino-2-methyl-3H-imidazo[4,5-h]quinoline, Zeitschrift fuer Chemie, vol. 11, No. 3, (1971), pp. 115-117.
Karshtedt, D. et al., “Stoichiometric and Catalytic Arene Activations by Platinum Complexes Containing Bidentate Monoanionic Nitrogen-Based Ligands”, Organometallics, vol. 25, No. 7, (2006), pp. 1801-1811.
Lee, J. et al., “An Unusual Coordination Mode for Amides: Lone-Pair Binding via Nitrogen”, Inorganic Chemistry, vol. 34, No. 25, (1995), pp. 6295-6301.
Wu, F. et al., “Bidentate Ligands That Contain Pyrrole in Place of Pyridine”, Inorg. Chem., vol. 39, No. 3, (2000), pp. 584-590.
Related Publications (1)
Number Date Country
20110284799 A1 Nov 2011 US