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Definitions

• transition metal carbene complexes that do not contain cyclo-metallation via non-carbenes in OLEDs
• the present invention relates to the use of transition metal carbene complexes in which the linking of the carbene ligand or metals with the transition metal takes place exclusively via carbene carbon atoms, in organic light-emitting diodes, organic light emitting diodes containing at least one aforementioned transition metal carbene complex, a light-emitting layer containing at least an abovementioned transition metal carbene complex, organic light-emitting diodes containing at least one light-emitting layer according to the invention and devices which contain at least one organic light-emitting diode according to the invention.
• OLEDs organic light emitting diodes
• the property of materials is used to emit light when excited by electric current.
• OLEDs are of particular interest as an alternative to cathode ray tubes and liquid crystal displays for the production of flat panel displays. Due to the very compact design and the intrinsically low power consumption, the devices containing OLEDs are particularly suitable for mobile applications, eg. For applications such as cell phones, laptops, etc.
• WO 2005/019373 discloses for the first time the use of neutral transition metal complexes which contain at least one carbene ligand in OLEDs. These transition metal complexes can be used according to WO 2005/019373 in each layer of an OLED, wherein the ligand skeleton or central metal can be varied to adapt to desired properties of the transition metal complexes. For example, the use of the transition metal complexes in a block layer for electrons, a block layer for excitons, a block layer for holes or Light-emitting layer of the OLEDs possible, wherein the transition metal complexes are preferably used as emitter molecules in OLEDs.
• WO 2005/113704 relates to luminescent compounds which carry carbene ligands. According to WO 2005/1 13704, numerous transition metal complexes with various carbene ligands are mentioned, the transition metal complexes preferably being used as phosphorescent light-emitting material, particularly preferably as doping substance.
• Both the transition metal carbene complexes disclosed in WO 2005/019373 and in WO 2005/1 13704 have carbene ligands which are bonded to the transition metal atom by cyclometalation.
• the linking of the carbene ligand (s) with the transition metal takes place on the one hand via the carbene carbon atom and further via another carbon or heteroatom.
• the object of the present invention over the aforementioned prior art is to provide further transition metal carbene complexes for use in OLEDs which exhibit a balanced property spectrum, e.g. B. good efficiencies, improved durability and higher stability.
• M 1 metal atom selected from the group consisting of Group IIB, MIB, IVB, VB, VIB, VIIB, VIII transition metals of the Periodic Table of the Elements (CAS version) and Cu, in each of them possible for the corresponding metal atom
• L mono- or dianionic ligand, which may be mono- or bidentate
• m, o, n and p are dependent on the oxidation state and coordination number of the metal atom used and on the charge of the ligands and the total charge of the complex
• Do donor atom selected from the group consisting of N, C, P, O, S and Si;
• Y 1 , Y 2 each independently represent hydrogen or a carbon-containing group selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, alkenyl and alkynyl groups, the groups being substituted or may be unsubstituted; or
• Y 1 and Y 2 together form a saturated or unsaturated bridge between the donor atom Do and the nitrogen atom has at least two atoms, wherein one or more atoms of the bridge optionally With a medium alkyl or aryl groups, said groups may be substituted or unsubstituted NEN, and / or groups with donor or acceptor action may be substituted. NEN, and the bridge may optionally be fused with one or more rings;
• R 1 , R 2 are each independently of one another hydrogen, alkyl, cycloalkyl, heterocycloalkyl,
• - R 1 and / or R 2 may each independently form a bridge together with one of the radicals R 1 and / or R 2 of one or two further carbene ligands, wherein the bridge has the following meanings alkylene, arylene, heteroarylene, alkynylene, alkenylene, where the groups may be substituted or unsubstituted, NR 5 , PR 6 , BR 7 , BR 8 2 " , CR 9 (O " ), SO 2 ,
• SiR 10 R 11 , CO, CO-O, O-CO and (CR 12 R 13 ) X wherein one or more non-adjacent groups (CR 12 R 13 ) are substituted by arylene, heteroarylene, alkynylene, alkenylene, said groups being substituted or unsubstituted, NR 5 , PR 6 , BR 7 , BR 8 2 -, CR 9 (O " ), O, S, SO, SO 2 , SiR 10 R 11 , CO, CO-O, or O-CO can be;
• R 3 D 4 D 5 D 6 D 7 D 8 D 9 D 10 D 1 1 D 22 D 23 D 24 D 25 independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl,
• transition metal complexes of the formula I characterized in that in the transition metal complexes of the formula I, a linkage of the or of the carbene ligand with the transition metal takes place exclusively via carbene carbon atoms. It has surprisingly been found that sufficiently stable transition metal carbene complexes suitable for use in OLEDs can be provided without requiring cyclometalation of the carbene ligand (s) via another carbon or heteroatom.
• the present invention relates to the use of the transition metal carbene complexes of the general formula I, wherein the use of the following transition metal carbene complexes of the general formulas I 'and II'
• L monodentate monoanionic ligand preferably selected independently of one another from halides, pseudohalides, " alkoxy and OAc " , more preferably Br “ , I " and OAc " or bidentate dianionic ligand, preferably selected from bisphenolates, bis-alcoholates, bisthiolates, bisazolates, bisamides which may be unsubstituted or optionally mono- or polysubstituted by C 1 to C 6 alkyl radicals and / or donor / acceptor substituents, preferably unsubstituted bisphenolate;
• R 2 , R 3 , R 2 , R 3 independently of one another are hydrogen, alkyl, aryl, preferably hydrogen;
• W monoanionic counterion, preferably halide, pseudohalide or OAc " , more preferably Cl “ , Br “ , I “ , CN “ , OAc “ , very particularly preferably Br “ or I “ ;
• the present invention encompasses both the individual isomers of the transition metal carbene complexes of the formula I as well as mixtures of different isomers in any desired mixing ratio.
• various isomers of the metal complexes of the formula I can be prepared by methods known to the person skilled in the art, eg. Example, by chromatography, sublimation or crystallization, are separated.
• the transition metal carbene complexes of the formula I can be used in any layer of an OLED, wherein the ligand skeleton or central metal can be varied to adapt to desired properties of the metal complexes.
• the use of the transition metal carbene complexes of the formula I in a block layer for electrons, a block layer for excitons, a block layer for holes or the light-emitting layer of the OLED is possible.
• the compounds of the formula I are preferably used as emitter molecules in OLEDs.
• a bidentate ligand is to be understood as meaning a ligand which is coordinated in two places to the transition metal atom M 1 .
• the term "bidentate" is used synonymously with the term “bidentate”.
• a monodentate ligand is to be understood as meaning a ligand which coordinates at one point of the ligand with the transition metal atom M 1 .
• a tridentate ligand is to be understood as meaning a ligand which is coordinated at three sites to the transition metal atom M 1 .
• the term "tridentate” is used synonymously with the term “tridentate”.
• tetradentate ligand is to be understood as meaning a ligand which is coordinated at four sites to the transition metal atom M 1 .
• tetradentate is used synonymously with the term “tetradentate”.
• Transition metal carbene complexes which exclusively have a linkage of the carbene ligand (s) with the transition metal atom via carbene carbon atoms are known in the art.
• M. Albrecht et al. Inorganica Chimica Acta 2006, Vol. 359, 6, 1929-1938, relates to the synthesis and structural analysis of palladium-biscarbene complexes bearing bisimidazolium ligands.
• M. Albrecht et al. mechanistic investigations of the metallation of the bisimidazolium ligand.
• Ch.-M. Che et al., Organometallics 1998, 17, 1622-1630, relates to an investigation of the spectroscopic properties of luminescent rhenium (I) -N-heterocyclic carbene complexes bearing aromatic diimine ligands.
• the investigation of the spectroscopic properties of the complexes serves to better understand the electronic conditions in these complexes.
• An application of the N-heterocyclic rhenium (I) carbene complexes as well as possible electroluminescent properties are described in Ch.-M. Che not specified.
• N-heterocyclic biscarbene complexes of platinum and palladium their preparation and their use as a catalyst, in particular as a catalyst for the partial oxidation of hydrocarbons or hydrocarbonaceous feeds.
• DE-A 10 2005 058 206 contains no information regarding the luminescence properties of the disclosed complexes.
• transition metal carbene complexes of the formula I according to the present invention for use in OLEDs is not mentioned in any of the above-mentioned documents. It has thus been found that the transition metal carbene complexes of the formula I according to the present application are suitable for use in OLEDs.
• the transition metal carbene complexes of the formula I used according to the invention preferably have a metal atom M 1 selected from the group consisting of Ir, Co, Rh, Ni, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re and Cu, more preferably Ir, Os, Ru, Rh, Pd, Co, Ni and Pt, most preferably Ir, Pt, Rh, Ru and Os, in any oxidation state possible for the corresponding metal atom. Particular preference is given to using Pt (II), Pt (IV), Ir (I), Ir (III), Os (II) and Ru (II) in the transition metal carbene complexes of the formula I used according to the invention.
• Suitable mono- or dianionic ligands L which may be mono- or bidentate, are the ligands commonly used as mono- or bidentate mono- or dianionic ligands.
• monoanionic monodentate ligands or dianionic bidentate ligands are preferably used, if ligands L are present at all.
• non-photoactive ligands are used as ligands L.
• Suitable ligands are, for. B. monoanionic monodentate ligands such as halides, in particular Cl “ , Br “ , I “ , pseudohalides, in particular CN “ , OAc “ , alkyl radicals which are linked to the transition metal atom M 1 via a sigma, for example, CH 3 , alcohol late, thiolates, amides (R 26 2 N " , where R 26 is hydrogen or a substituted or unsubstituted alkyl or aryl radical); monoanionic bidentate ligands, such as acetylacetate and its derivatives, and the bidentate monionionic ligands and oxide mentioned in WO 02/15645.
• monoanionic monodentate ligands such as halides, in particular Cl “ , Br “ , I “ , pseudohalides, in particular CN “ , OAc “ , alkyl
• dianionic bidentate ligands such as bisphenolates, bis-alcoholates, bisthiolates, bisazolates, bisamides, which may be unsubstituted or optionally monosubstituted or polysubstituted with C 1 to C 6 -alkyl radicals and / or donor / acceptor substituents, are preferably unsubstituted, bisphenolate , are used as ligands L.
• Suitable neutral mono- or bidentate ligands K are those ligands commonly used as neutral mono- or bidentate ligands. In general, those in the transition metal carbene complexes of the formula (I) used ligand K to non-photoactive ligands.
• Suitable ligands K are z. B. phosphines, especially trialkylphosphines, z. PEt 3 , PnBu 3 , tri-arylphosphines, e.g. B.
• PPh 3 Phosphonates and derivatives thereof, arsenates and derivatives thereof, phosphites, CO, nitriles, amines, dienes which can form a ⁇ -complex with M 1 , eg. B. 2,4-hexadiene, ⁇ 4 -cyclooctadiene and ⁇ 2 -cyclooctadiene (each 1, 3 and 1, 5), AIIyI, methallyl, cyclooctene, norbornadiene.
• M 1 eg. B. 2,4-hexadiene, ⁇ 4 -cyclooctadiene and ⁇ 2 -cyclooctadiene (each 1, 3 and 1, 5), AIIyI, methallyl, cyclooctene, norbornadiene.
• Suitable monoanionic counterions W “ are, for example, halide, pseudohalide, BF 4 " , PF 6 “ , AsF 6 “ , SbF 6 “ or OAc “ , preferably Cl “ , Br “ , I “ , CN “ , OAc “ , particularly preferably Br “ or I “ .
• the number n of carbene ligands in the transition metal carbon complexes of the formula I is from 1 to 6.
• n is in the Sprintsme - tallcarbenekomplexen of formula I 4 to 6, more preferably 4 or 6.
• the number o of the neutral ligands K in the transition metal carbene complexes of the formula I is 0 to 5, preferably 0 to 2, particularly preferably 0. If o> 1, the ligands K may be identical or different, preferably they are the same.
• the number of ligands carbene, K and L and the number of monoanionic counterions W " , ie n, o, m and p, are dependent on the oxidation state and coordination number of the metal atom M 1 used and on the charge of the ligands and the total charge of the complex.
• the carbene ligand "carbene” in the transition metal carbene complexes of the formula I has the general formula (II):
• Do donor atom selected from the group consisting of N, C, P, O, S and
• Si preferably N, P, O and S, more preferably N;
• Y 1 , Y 2 are each independently of one another hydrogen or a carbon-containing group selected from the group consisting of alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralykl, alkenyl and alkynyl groups, the groups being substituted or may be unsubstituted; or
• Y 1 and Y 2 together form a saturated or unsaturated bridge between the donor atom Do and nitrogen atom, which, having at least two atoms preferably two or three atoms wherein one or more atoms of the bridge optionally said groups substituted with alkyl or aryl groups, or unsubstituted, and / or groups with Donor or acceptor may be substituted, and the bridge may optionally be fused with one or more rings;
• R 1 , R 2 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, alkynyl, alkenyl, wherein the groups may be substituted or unsubstituted, BR 3 2 , NR 22 2 , OR 23 2 , OR 24 , SR 25 or SiR 4 3, preferably hydrogen, substituted or unsubstituted alkyl, cycloalkyl, aralkyl radicals; or - in the event that n> 1 - R 1 and / or R 2 R 1 and / or R 2 of one or two carbene ligand of the formula Il each case independently form, together with one of the radicals a bridge, where the bridge may have the following meanings:
• R 3 D 4 D 5 D 6 D 7 D 8 D 9 D 10 D 1 1 D 22 D 23 D 24 D 25 independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, aralkyl, heteroaryl, alkenyl, alkynyl, alkoxy, where the groups may be substituted or unsubstituted, preferably hydrogen, alkyl, cycloalkyl, aryl, alkoxy, more preferably hydrogen, alkyl or alkoxy; and R 12 , R 13 independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, alkynyl, alkenyl, where the groups may be substituted or unsubstituted, or groups having donor or acceptor action, for example amino or alkoxy, preferably hydrogen, alkyl, cycloalkyl, aryl, amino or alkoxy, particularly preferably hydrogen, alkyl
• transition metal carbene complexes of the formula I it is essential that in the transition metal carbene complexes of the formula I, a linking of the or the carbene ligand of the formula II with the transition metal atom M 1 takes place exclusively via carbene carbon atoms. Cyclometalation of the carbene ligand (s) via non-carbene is not present in the transition metal carbene complexes of the formula I.
• the substituents of the groups Y 1 and Y 2 may together form a bridge having at least two atoms, preferably having a total of two to four, particularly preferably two to three atoms, of which one or more atoms, preferably one or two atoms, heteroatoms, preferably N or B, and the remaining atoms are carbon atoms, so that the group NCDo forms together with this bridge preferably a 5 to 7-membered, more preferably 5 to 6-membered ring, optionally 2 - or in the case of 6- or 7-membered rings - may have three double bonds, and optionally with alkyl or aryl groups, where the groups may be substituted or unsubstituted, and / or groups may be substituted with donor or acceptor and optionally heteroatoms, preferably N may contain, wherein a 5-membered or 6-membered aromatic ring containing alkyl or aryl groups, wherein the groups may be substituted or unsubstituted k and / or groups
• Preferred carbene ligands of the formula II thus have the formula IIa mentioned below:
• the curved line in structure IIa represents the bridge formed jointly of Y 1 and Y 2 , which is as defined above.
• the grouping NCDo together with this bridge forms a 5- to 6-membered ring which, as indicated above, may be saturated or unsaturated, substituted and / or fused, preferably benzo-fused.
• Y 1 and / or Y 2 or the bridge formed jointly by Y 1 and Y 2 may be linked to the radical R 1 and / or R 2 via a bridge, this bridge having the following meanings:
• x is 2 to 10, preferably 2 to 5, particularly preferably 2 to 3;
• the linking bridge to the group R 1 and / or R 2 may be directly linked to the 5- to 7-membered one Ring may be linked or attached to a substituent of this ring.
• the linking bridge may be linked to an atom of the fused ring.
• aryl radical or group heteroaryl radical or group, alkyl radical or group, cycloalkyl radical or group, heterocycloalkyl radical or group, alkenyl radical or group, alkynyl radical or group, aralkyl radical or group, amino group and donor and / or acceptor groups have the following meanings:
• aryl radical or group
• Suitable backbones are, for example, phenyl, naphthyl, anthracenyl or phenanthrenyl. This backbone may be unsubstituted (ie, all carbon atoms that are substitutable bear hydrogen atoms) or substituted at one, more, or all substitutable positions of the backbone.
• Suitable substituents are, for example, alkyl radicals, preferably alkyl radicals having 1 to 8 carbon atoms, more preferably methyl, ethyl or i-propyl, aryl radicals, preferably C 6 - aryl radicals which in turn may be substituted or unsubstituted, heteroaryl radicals, preferably heteroaryl radicals which contain at least one nitrogen atom particularly preferably pyridyl radicals, alkenyl radicals, preferably alkenyl radicals which carry a double bond, particularly preferably alkenyl radicals having a double bond and 1 to 8 carbon atoms, or groups having donor or acceptor action. Suitable groups with donor or acceptor action are mentioned below.
• the aryl radicals carry substituents selected from the group consisting of methyl, F, Cl, CN, aryloxy and alkoxy, sulfonyl, heteroaryl.
• the aryl radical or the aryl group is a C 6 -C 8 -aryl radical, particularly preferably a C 6 -aryl radical which is optionally substituted by at least one or more of the abovementioned substituents.
• the C 6 -C 8 -aryl radical preferably C 6 -aryl radical, has none, one, two or three of the abovementioned substituents, where in the case of a C 6 -aryl radical having a substituent in ortho, meta or para.
• Position to the further point of attachment of the aryl radical is arranged, and - in the case of two substituents - they can each be arranged in the meta position or ortho position to the further point of attachment of the aryl radical or a radical is in the ortho position and a radical in the meta position arranged or a remainder is arranged in ortho or meta position and the remainder is arranged in the para position.
• substituents these are preferably arranged in ortho- (two of the three substituents) and p-position (third substituent) to the further point of attachment of the aryl radical.
• a heteroaryl radical or a heteroaryl radical is to be understood as meaning radicals which differ from the abovementioned aryl radicals in that at least one carbon atom in the skeleton of the aryl radicals is replaced by a heteroatom.
• Preferred heteroatoms are N, O and S.
• one or two carbon atoms of the backbone of the aryl radicals are replaced by heteroatoms.
• the backbone is selected from systems such as pyridine and five-membered heteroaromatics such as pyrrole, furan, pyrazole, imidazole, thiophene, oxazole, thiazole.
• the backbone may be substituted at one, several or all substitutable positions of the backbone. Suitable substituents are the same as those already mentioned with respect to the aryl groups.
• alkyl radical or an alkyl group is to be understood as meaning a radical having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 8, very particularly preferably 1 to 4 carbon atoms.
• This alkyl radical may be branched or unbranched and may optionally be interrupted by one or more heteroatoms, preferably Si, N, O or S, more preferably N, O or S.
• this alkyl radical may be substituted by one or more of the substituents mentioned with respect to the aryl groups. It is also possible for the alkyl radical to carry one or more (hetero) -aryl groups. All of the (hetero) aryl groups listed above are suitable.
• the alkyl radicals are particularly preferably selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl and tert-butyl, very particularly preferred are methyl, isopropyl and n-butyl ,
• a cycloalkyl radical or a cycloalkyl radical is to be understood as meaning a radical having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, particularly preferably 3 to 8 carbon atoms.
• This backbone may be unsubstituted (i.e., all carbon atoms that are substitutable bear hydrogen atoms) or substituted at one, several, or all substitutable positions of the backbone.
• Suitable substituents are the groups already mentioned above with respect to the aryl radicals.
• suitable cycloalkyl radicals are cyclopropyl, cyclopentyl and cyclohexyl.
• a heterocycloalkyl radical or a heterocycloalkyl radical is to be understood as meaning radicals which differ from the above-mentioned cycloalkyl radicals in that in the skeleton of the cycloalkyl radicals at least one carbon atom is replaced by a heteroatom.
• Preferred heteroatoms are N, O and S. Very particular preference is given to one or two carbon atoms of the skeleton of the cycloadditions. substituted loalkyl radicals by heteroatoms.
• suitable heterocycloalkyl radicals are radicals derived from pyrrolidine, piperidine, piperazine, tetrahydrofuran, dioxane.
• An aralkyl radical (or group) is to be understood as meaning a radical having a skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, which may be unsubstituted or substituted by the radicals mentioned relative to the aryl groups.
• Suitable aralkyl groups are e.g. Benzyl, phenylethyl and phenylpropyl.
• alkenyl radical or an alkenyl group is to be understood as meaning a radical which corresponds to the abovementioned alkyl radicals having at least two carbon atoms, with the difference that at least one C-C single bond of the alkyl radical is replaced by a C-C double bond.
• the alkenyl radical preferably has one or two double bonds.
• alkynyl radical or an alkynyl radical is to be understood as meaning a radical which corresponds to the abovementioned alkyl radicals having at least two carbon atoms, with the difference that at least one C-C single bond of the alkyl radical has been replaced by a C-C triple bond.
• the alkynyl radical preferably has one or two triple bonds.
• An amino group is to be understood as meaning a group of the general formula -NR'R ", where R 'and R" independently of one another may denote hydrogen, alkyl or aryl. Furthermore, R 'and R "together with the N atom can form a ring, preferably a 5- or 6-membered ring The ring can be saturated or unsaturated and optionally substituted by alkyl or aryl groups. and aryl groups are mentioned above.
• alkylene, arylene, heteroarylene, alkynylene and alkenylene have the meanings mentioned with regard to the alkyl, aryl, heteroaryl, alkynyl and alkenyl radicals, with the difference that the alkylene, arylene, heteroarylene , Alkinylene and alkenylene groups have two binding sites to atoms of the ligand of the formula II.
• Preferred alkylene groups are (CR 1) n , where R 4 is H or alkyl, preferably H, methyl or ethyl, particularly preferably H and n is 1 to 3, preferably 1 or 2, particularly preferably 1. Most preferably, the alkylene group is CH 2 .
• a group or a substituent with donor or acceptor action is to be understood as meaning the following groups:
• Donor-action groups are to be understood as meaning groups having a + I and / or + M effect, and groups having acceptor action are to be understood as meaning groups having an -I and / or -M effect.
• Suitable groups with donor or acceptor action are halogen radicals, preferably F, Cl, Br, particularly preferably F, alkoxy radicals, aryloxy radicals, carbonyl radicals, ester radicals, both oxycarbonyl and carbonyloxy, amino groups, amide radicals, CH 2 F groups, CHF 2 groups, CF 3 groups, CN groups, thio groups, sulfonic acid groups, sulfonic acid ester groups, boronic acid groups, boronic acid ester groups, phosphonic acid groups, phosphonic acid ester groups, phosphine radicals, sulfoxide radicals, sulfonyl radicals, sulfide radicals, nitro groups, OCN, borane radicals, silyl groups, Stannate residues, imino groups, hydrazine residues, hydrazone residues, oxime residues, nitroso groups, diazo groups, phosphine oxide groups, hydroxy groups or SCN groups.
• aryl radicals or groups, heteroaryl radicals or groups, alkyl radicals or groups, cycloalkyl radicals or groups, heterocycloalkyl radicals or groups, alkenyl radicals or groups, alkynyl radicals or groups, aralkyl radicals or groups, amino groups and groups with donor and / or or acceptor action, as well as the alkylene, arylene, heteroaryl, alkynylene and alkenylene radicals or groups may be substituted or unsubstituted.
• an unsubstituted group is to be understood as meaning a group in which the substitutable atoms of the group carry hydrogen atoms.
• a substituted group is to be understood as meaning a group in which one or more substitutable atoms carry a substituent at least at one position instead of one hydrogen atom.
• Suitable substituents are the substituents mentioned above with respect to the aryl radicals or groups.
• radicals with the same numbering occur several times in the compounds according to the present application, these radicals can each independently have the stated meanings.
• the carbene ligand of the formula II is preferably a carbene ligand of the formula IIa as mentioned above.
• the carbene ligand of the formula II is particularly preferably selected from the group consisting of
• Z ' are independently CR i21 or N; preferably 0 to 3 groups Z 'N, more preferably 0 to 2, most preferably 0 or 1, wherein the remaining groups Z' is CR 21 ;
• R 21 is hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, alkynyl, alkenyl, where the groups may be substituted or unsubstituted, or a moiety with donor or acceptor action or in each case two radicals R 21 together form a fused ring which optionally may contain at least one heteroatom;
• the carbene ligands of the formula II are bridged carbene ligands, a bridging via the radical R 1 and / or the radical R 2 to form a further carbene ligand - likewise via the radical R 1 and / or R 2 of the other carbene ligands - takes place.
• the present invention relates to such transition metal carbene complexes of formula I wherein n> 1, which carry bridged carbene ligands.
• R 1 and / or R 2 each independently of one another together with one of the radicals R 1 and / or R 2 of one or two further carbene ligands form a bridge, the bridge having the following May have meanings:
• CH 2 , CH CH, 1, 2-phenylene, CH (amino), CH (O “ ), BR 8 2 " , in which
• Suitable bridged carbene ligands of the formula II are carbene ligands of the following structures:
• Do 'donor atom selected from the group consisting of N, C, P and Si;
• X 1 , X 2 , X 3 , X 4 are independent of each other
• Alkylene, arylene, heteroarylene, alkynylene, alkenylene, where the groups may be substituted or unsubstituted, NR 5 , PR 6 , BR 7 , BR 8 2 " , CR 9 (O " ), SO 2 , SiR 10 R 11 , CO, CO-O, O-CO and (CR 12 R 13 ) X , wherein one or more nonadjacent groups (CR 12 R 13 ) may be substituted by arylene, heteroarylene, alkynylene, alkenylene wherein the groups may be substituted or unsubstituted, NR 5 , PR 6 , BR 7 , BRV, CR 9 (O " ), O, S, SO, SO 2 , SiR 10 R 11 , CO, CO-O, O-CO, preferably CH 2 , CH CH, 1, 2-phenylene, CH (amino), CH (O " ), BR 8 2 " ,
• x is 2 to 10, preferably 2 to 5, preferably 2 or 3;
• Alkenyl which groups may be substituted or unsubstituted, or groups having donor or acceptor activity, e.g. Amino or alkoxy, preferred
• the groups form Y 1 and Y 2 in the above-mentioned bridged carbene a bridge having at least two atoms, preferably having a total of two to four, more preferably two to three atoms, form, of which one or more atoms, preferably one or two atoms, Heteroatoms, preferably N, and the remaining atoms are carbon atoms, so that the group NCDo together with this bridge preferably forms a 5- to 7-membered, more preferably 5- to 6-membered ring, optionally 2 - or in the case of 6- or 7-membered ring - may have three double bonds, and optionally with alkyl or aryl groups, which groups may be substituted or unsubstituted, and / or groups may be substituted with donor or acceptor and optionally heteroatoms, preferably N wherein a 5-membered or 6-membered aromatic ring containing alkyl or aryl groups, wherein the groups substituie may be unsubstituted
• Preferred bridged carbene ligands thus have the following general formulas:
• R 2 , r, Do, X 1 , X 2 , X 3 , X 4 and Do ' have the meanings given above, and the curved line represents the bridge formed jointly of Y 1 and Y 2 , which is as defined above is.
• Particularly preferred bridges formed by Y 1 and Y 2 are the bridges illustrated in structures IIa, Mab, Mac and Mad.
• carbene ligands of the formula II are selected from
• R 18 in the groups A, A ', A “, A'” or R 19 in the groups B, B ', B “, B'” may each have the same or different meanings;
• a and B, A 'and B', A "and B" or A '"and B'" each independently form together a radical of the following formula:
• transition metal carbene complexes of the formula I preferably have carbene ligands of the formula II in which the groups A, A ', A "and A'” and the groups B, B ', B “and B'” or A and B, A 'and B ', A “and B” or A' “and B '” each have the same meanings.
• transition metal carbene complexes of formula I Both bridged and unbridged carbene ligands may coexist in the transition metal carbene complexes of formula I, but it is also possible that the transition metal carbene complex of formula I carries only one or more unbridged or only one or more bridged carbene ligands.
• preferred transition metal carbene complexes are shown:
• the symbols M 1 , K, L, m and o in the transition metal carbene complexes of the general formula I mean
• M 1 Pt, Os, Ru, Ir most preferably Pt (II), Pt (IV), Ir (I), Ir (III), Os (II), Ru (II);
• n is 0 to 5, preferably 0 to 3, particularly preferably 0 to 2;
• p is 0, 1, 2 or 3, preferably 0, 1 or 2;
• R 1 , R 2 are each independently substituted or unsubstituted alkyl, preferably methyl, i-propyl, n-butyl, substituted or unsubstituted cycloalkenyl, kyl, preferably cyclohexyl, or substituted or unsubstituted aralkyl, preferably benzyl;
• R 18 in the groups A, A ', A “, A'” and R 19 in the groups B, B ', B “, B'” in each case independently of one another denote hydrogen or groups with donor or acceptor action;
• a and B, A 'and B', A "and B" or A '"and B'" independently form together a remainder of the following
• Z ' are independently CR 21 or N; preferably 0 to 3 groups Z 'N, more preferably 0 to 2, most preferably 0 or 1, wherein the remaining groups Z' is CR 21 ;
• R 21 is hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl, alkynyl, alkenyl, where the groups may be substituted or unsubstituted, or a moiety with donor or acceptor action or in each case two radicals R 21 together form a fused ring which optionally contain at least one heteroatom;
• R 8 is hydrogen, alkyl, cycloalkyl or aryl, which groups may be substituted or unsubstituted, preferably hydrogen or alkyl.
• Tetracarbene complexes e.g.
• R 8 is hydrogen, alkyl, cycloalkyl or aryl, which groups may be substituted or unsubstituted, preferably hydrogen or alkyl, for example methyl, ethyl, iPropyl means;
• R 1 , R 2 are independently substituted or unsubstituted alkyl, for example methyl, ipropyl, n-butyl, substituted or unsubstituted cycloalkyl, eg cyclohexyl, substituted or unsubstituted aryl, eg 2,4,6-methylphenyl, substituted or unsubstituted aralkyl, eg benzyl;
• Tetracarbene complexes e.g.
• R 8 is hydrogen, alkyl, cycloalkyl or aryl, which groups may be substituted or unsubstituted, preferably hydrogen or alkyl, for example methyl, ethyl, iPropyl means;
• Halide eg Br “ , I "
• Pseudohalide eg CN “ , or OAc “ .
• Tetracarbene complexes e.g.
• R 1 , R 2 are independently substituted or unsubstituted alkyl, for example methyl, ipropyl, n-butyl, substituted or unsubstituted cycloalkyl, eg cyclohexyl, substituted or unsubstituted aryl, eg 2,4,6-methylphenyl, substituted or unsubstituted aralkyl, eg benzyl;
• Halide eg Br “ , I "
• Pseudohalide eg CN “ , or OAc “ .
• R 1 , R 2 are independently substituted or unsubstituted alkyl, for example methyl, ipropyl, n-butyl, substituted or unsubstituted cycloalkyl, for example
• Cyclohexyl substituted or unsubstituted aryl, e.g. 2,4,6-methylphenyl, substituted or unsubstituted aralkyl, e.g. benzyl;
• R ' is C 1 -C 6 -alkyl or donor / acceptor substituents, preferably methyl, ethyl-i-propyl, tert-butyl;
• x ' is 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, most preferably 0.
• transition metal carbene complexes of the formula I used according to the invention can in principle be prepared according to processes known to the person skilled in the art or analogously to processes known to the person skilled in the art. Suitable general methods for the preparation of carbene complexes are, for. For example, in the review articles WA Hermann et al., Advances in Organometallic Chemistry, 2001, Vol. 48, 1 to 69, WA Hermann et al., Angew. Chem. 1997, 109, 2256-2282 and G. Bertrand et al., Chem. Rev. 2000, 100, 39 to 91 and the literature cited therein. Other manufacturing processes are z. In Ch. -M.
• transition metal carbene complexes of the formula I are prepared from precursors corresponding to the carbene ligands and suitable metal complexes containing the desired metal.
• Suitable ligand precursors of the carbene ligands are known to the person skilled in the art. Preference is given to cationic precursors of the general formula III
• Q ' is a monoanionic counterion, preferably halide, pseudohalide, BF 4 " , BPh 4 “ , PF 6 “ , AsF 6 “ or SbF 6 " ,
• Suitable ligand precursors are thus z. Imidazolium salts, bisimidazolium salts, tetraimidazolium salts and derivatives thereof.
• the ligand precursors of the general formula III can be prepared according to methods known to the person skilled in the art. Suitable processes for preparing the ligand precursors are mentioned in the abovementioned literature cited therein. Some of the suitable ligand precursors are commercially available.
• the preparation of the transition metal-carbene complexes of the formula I preferably takes place by reacting at least one ligand precursor of the general formula III with a metal complex containing at least one metal M 1 , wherein M 1 has the meanings given above.
• the molar ratio between the ligand precursors of the formula III and the metal complex containing at least one metal M 1 depends on the structure of the desired transition metal carbene complex of the formula I and on the type of carbene ligand, ie whether it is one or more unbridged monocarboxylic ligands or one or more bridged bis-, tri- or tetracarbene ligands.
• n in the transition metal carbene complexes of the formula I is> 1, it is possible that these transition metal carbene complexes are obtained by reacting the metal complex containing at least one metal M 1 with identical carbene ligands or by reacting with different carbene ligands.
• homo- and heteroleptic transition metal carbene complexes of the formula I can be prepared. Suitable processes and reaction sequences for the preparation of the various transition metal carbene complexes of the formula I are known to the person skilled in the art.
• the metal complex containing at least one metal M 1 is a metal complex containing at least one metal atom selected from the group IIB, HIB, IVB, VB, VIB, VIIB, VIII of the Periodic Table of the Elements (CAS) transition metals. Version) and Cu, preferably selected from the group consisting of Ir, Co, Rh, Ni, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, Mn, Tc, Re and Cu, particularly preferably Ir, Os, Ru, Rh, Pd, Co and Pt, most preferably Ir, Pt, Rh, Pd, Ru and Os in any suitable oxidation state possible for the corresponding metal.
• Suitable metal complexes are known to the person skilled in the art. Examples of suitable metal complexes are: Pd (OAc) 2, Pt (cod) Cl 2, Pt (cod) Me 2, Pt (acac) 2, Pt (PPh 3) 2 Cl 2, PtCl 2, [Rh (COD) Cl ] 2 , Rh (acac) CO (PPh 3 ), Rh (acac) (CO) 2 , Rh (cod) 2 BF 4 , RhCl (PPh 3 ) 3 , RhCl 3 x nH 2 O, Rh (acac) 3 , [Os (CO) 3 l 2 ] 2 , [Os 3 (CO) i2 ], OsH 4 (PPh 3 ) 3 Cp 2 0s, Cp * 2 Os, H 2 OsCl 6 x 6H 2 O, OsCl 3 x H 2 O, Ru (acac) 3 , RuCl 2 (cod), Ru (2-methylallyl)
• the tetracarbene complexes containing two biscarbene ligands can be prepared either by reacting the corresponding metal complex containing at least one transition metal atom M 1 with about twice the stoichiometric amount of one or two different carbene ligands or by first reacting a corresponding biscarbene complex by reacting the metal complex containing at least one transition metal atom M 1 is reacted with approximately stoichiometric amounts of a biscarbene ligand and the obtained Biscarbenkomplex is then reacted with an approximately stoichiometric amount of another - same or different - Biscarbenkomplexes.
• the resulting transition metal carbene complex of the formula I is worked up by methods known to the person skilled in the art and optionally purified. Usually, work-up and purification by extraction, column chromatography and / or recrystallization are carried out according to methods known to the person skilled in the art.
• the transition metal carbene complexes of the formula I are used in organic light-emitting diodes (OLEDs). They are suitable as emitter substances because they have an emission (electroluminescence) in the visible range of the electromagnetic spectrum. With the help of the transition metal carbene complexes used according to the invention of the formula I as emitter substances, it is possible to provide compounds which show electroluminescence in the red, green and in the blue region of the electromagnetic spectrum with good efficiency. The quantum yield is high and the stability of the transition metal carbene complexes of the formula I used according to the invention in the device is high.
• transition metal carbene complexes of the formula I used according to the invention are suitable as electron, exciton or hole blockers or hole conductors, electron conductors, hole injection layer or matrix material in OLEDs, depending on the ligands used and the central metal used.
• OLEDs Organic light-emitting diodes
• the OLED does not have all of the layers mentioned, for example an OLED with the layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) is also suitable. wherein the functions of the layers (2) (hole-transporting layer) and (4) (electron-transporting layer) are taken over by the adjacent layers. OLEDs comprising layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are also suitable.
• the transition metal carbene complexes of the formula I can be used in various layers of an OLED.
• a further subject of the present invention is therefore an OLED containing at least one transition metal carbene complex of the formula I.
• the transition metal carbene complexes of the formula I are preferably used in the light-emitting layer, particularly preferably as emitter molecules.
• Another object of the present invention is therefore a light-emitting layer containing at least one transition metal carbene complex of the formula I, preferably as an emitter molecule.
• Preferred transition metal carbene complexes of the formula I are mentioned above.
• transition metal carbene complexes of the formula I used according to the invention can be present in bulk-without further additives-in the light-emitting layer or another layer of the OLED, preferably in the light-emitting layer.
• further compounds are present in the layers, preferably in the light-emitting layer.
• a fluorescent dye may be present in the light-emitting layer in order to change the emission color of the transition metal carbene complex of the formula I used as emitter molecule.
• a diluent material can be used.
• CDP CBP
• the individual of the abovementioned layers of the OLED can in turn be composed of 2 or more layers.
• the hole-transporting layer may be composed of a layer into which holes are injected from the electrode and a layer that transports the holes away from the hole-injecting layer into the light-emitting layer.
• the electron-transporting layer may also consist of several layers, for example a layer in which electrons are injected through the electrode and a layer which receives electrons from the electron-injection layer and transports them into the light-emitting layer. These layers are selected in each case according to factors such as energy level, temperature resistance and charge carrier mobility, as well as the energy difference of said layers with the organic layers or the metal electrodes.
• the person skilled in the art is able to select the structure of the OLEDs in such a way that it is optimally adapted to the transition metal carbene complexes of the formula I used according to the invention, preferably as emitter substances.
• the HOMO (highest occupied molecular orbital) of the hole-transporting layer should be aligned with the work function of the anode and the LUMO (lowest unoccupied molecular orbital) of the electron-transporting layer should be aligned with the work function of the cathode.
• a further subject of the present application is an OLED containing at least one light-emitting layer according to the invention.
• the further layers in the OLED may be constructed of any material commonly employed in such layers and known to those skilled in the art.
• the anode (1) is an electrode that provides positive charge carriers.
• it may be constructed of materials including a metal, a mixture of various metals, a metal alloy, a metal oxide, or a mixture of various metal oxides.
• the anode may be a conductive polymer. Suitable metals include the metals of Groups 11, 4, 5 and 6 of the Periodic Table of Elements and the transition metals of Groups 8 to 10.
• ITO indium tin oxide
• the anode (1) contains an organic material, for example polyaniline, as described for example in Nature, Vol. 357, pages 477 to 479 (June 11, 1992). At least either the anode or the cathode should be at least partially transparent in order to be able to decouple the light formed.
• Suitable hole transport materials for the layer (2) of the OLED according to the invention are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996. Both hole transporting molecules and polymers can be used as hole transport material.
• Commonly used hole transporting molecules are selected from the group consisting of 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), N, N'-diphenyl-N , N'-Bis (3-methylphenyl) - [1,1'-biphenyl] -4,4'-diamine (TPD), 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC) , N, N'-bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl) - [1, 1 '- (3,3'-dimethyl) biphenyl] -4,4'-diamine (ETPD ), Tetrakis (3-methylphenyl) -N, N, N ', N'-2,5-phenylenediamine (PDA), ⁇ -phenyl-4-N,
• hole-transporting polymers are selected from the group consisting of polyvinylcarbazoles, (phenylmethyl) polysilanes, PEDOT (poly (3,4-ethylenedioxythiophene), preferably PEDOT doped with PSS (polystyrene sulfonate), and polyanilines. It is also possible to obtain hole transporting polymers by doping hole transporting molecules into polymers such as polystyrene and polycarbonate. Suitable hole-transporting molecules are the molecules already mentioned above.
• Suitable electron transport materials for layer (4) of the OLEDs according to the invention comprise chelated metals with oxinoid compounds, such as tris (8-hydroxyquinolato) aluminum (Alq 3 ), phenanthroline-based compounds, such as 2,9-dimethyl, 4,7-diphenyl-1, 10.
• oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq 3 )
• phenanthroline-based compounds such as 2,9-dimethyl, 4,7-diphenyl-1, 10.
• the layer (4) can serve both to facilitate the electron transport and as a buffer layer or as a barrier layer in order to avoid quenching of the exciton at the interfaces of the layers of the OLED.
• the layer (4) improves the mobility of the electrons and reduces quenching of the exciton.
• hole transporting materials and electron transporting materials some may fulfill several functions.
• some of the electron-conducting materials are at the same time hole-blocking materials if they have a deep HOMO.
• the charge transport layers can also be electronically doped in order to improve the transport properties of the materials used, on the one hand to make the layer thicknesses more generous (avoidance of pinholes / short circuits) and on the other hand to minimize the operating voltage of the device.
• the hole transport materials can be doped with electron acceptors, for example phthalocyanines or arylamines such as TPD or TDTA can be doped with tetrafluorotetracyanoquinodimethane (F4-TCNQ).
• the electron transport materials can be doped, for example, with alkali metals, for example Alq 3 with lithium.
• the electronic doping is known to the person skilled in the art and described, for example, in W. Gao, A. Kahn, J. Appl.
• the cathode (5) is an electrode which serves to introduce electrons or negative charge carriers.
• the cathode may be any metal or non-metal that has a lower work function than the anode.
• Suitable materials for the cathodes are selected from the group consisting of Group 1 alkali metals, for example Li, Cs, Group 2 alkaline earth metals, Group 12 metals of the Periodic Table of the Elements comprising the rare earth metals and the lanthanides and actinides. Furthermore, metals such as aluminum, indium, calcium, barium, samarium and magnesium and combinations thereof can be used. Furthermore, lithium-containing organometallic compounds or LiF can be applied between the organic layer and the cathode in order to reduce the operating voltage (operating voltage).
• Group 1 alkali metals for example Li, Cs, Group 2 alkaline earth metals, Group 12 metals of the Periodic Table of the Elements comprising the rare earth metals and the lanthanides and actinides.
• metals such as aluminum, indium, calcium, barium, samarium and magnesium and combinations thereof can be used.
• lithium-containing organometallic compounds or LiF can be applied between the organic layer and the cathode in order
• the OLED according to the present invention may additionally contain further layers which are known to the person skilled in the art.
• a layer can be applied between the layer (2) and the light-emitting layer (3), which facilitates the transport of the positive charge and / or adapts the band gap of the layers to one another.
• this further layer can serve as a protective layer.
• additional layers may be present between the light-emitting layer (3) and the layer (4) to facilitate the transport of the negative charge and / or to match the band gap between the layers.
• this layer can serve as a protective layer.
• the OLED according to the invention contains at least one of the further layers mentioned below: a hole injection layer between the anode (1) and the hole-transporting layer (2); a blocking layer for electrons and / or excitons between the hole-transporting layer (2) and the light-emitting layer (3); a blocking layer for holes and / or excitons between the light-emitting layer (3) and the electron-transporting layer (4); an electron injection layer between the electron-transporting layer (4) and the cathode (5).
• the OLED does not have all of the mentioned layers (1) to (5), for example an OLED with the Layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) are also suitable, the functions of the layers (2) (hole-transporting layer) and (4) (electron-transporting layer ) are taken over by the adjacent layers.
• OLEDs comprising layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are also suitable.
• Suitable materials for the individual layers and suitable OLED structures are known in the art and z. As disclosed in WO2005 / 1 13704.
• each of the mentioned layers of the OLED according to the invention can be composed of two or more layers. Further, it is possible that some or all of the layers (1), (2), (3), (4) and (5) are surface treated to increase the efficiency of charge carrier transport. The selection of materials for each of said layers is preferably determined by obtaining an OLED having a high efficiency.
• the preparation of the OLEDs according to the invention can be carried out by methods known to the person skilled in the art.
• the OLED is fabricated by sequential vapor deposition of the individual layers onto a suitable substrate.
• Suitable substrates are, for example, glass or polymer films.
• conventional techniques can be used such as thermal evaporation, chemical vapor deposition and others.
• the organic layers may be coated from solutions or dispersions in suitable solvents, using coating techniques known to those skilled in the art.
• Compositions which, in addition to the at least one transition metal carbene complex of the formula I, comprise a polymeric material in one of the layers of the OLED, preferably in the light-emitting layer, are generally applied as a layer by means of solution-processing methods.
• the various layers have the following thicknesses: anode (1) 500 to 5000 ⁇ , preferably 1000 to 2000 ⁇ ; Hole-transporting layer (2) 50 to 1000 ⁇ , preferably 200 to 800 ⁇ , light-emitting layer (3) 10 to 1000 ⁇ , preferably 100 to 800 ⁇ , Electron-transporting layer (4) 50 to 1000 ⁇ , preferably 200 to 800 ⁇ , cathode (5) 200 to 10,000 ⁇ , preferably 300 to 5000 ⁇ .
• the location of Recombination zone of holes and electrons in the inventive OLED and thus the emission spectrum of the OLED can be influenced by the relative thickness of each layer.
• the thickness of the electron transport layer should preferably be selected so that the electron / holes recombination zone is in the light-emitting layer.
• the ratio of the layer thicknesses of the individual layers in the OLED depends on the materials used.
• the layer thicknesses of optionally used additional layers are known to the person skilled in the art.
• OLEDs By using the transition metal carbene complexes of the formula I in at least one layer of the OLED according to the invention, preferably as emitter molecule in the light-emitting layer of the inventive OLEDs, OLEDs can be obtained with high efficiency.
• the efficiency of the OLEDs according to the invention can be further improved by optimizing the other layers.
• highly efficient cathodes such as Ca, Ba or LiF can be used.
• Shaped substrates and new hole-transporting materials that bring about a reduction in the operating voltage or an increase in quantum efficiency are also usable in the OLEDs according to the invention.
• additional layers may be present in the OLEDs to adjust the energy levels of the various layers and to facilitate electroluminescence.
• the OLEDs according to the invention can be used in all devices in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile screens. Stationary screens are e.g. Screens of computers, televisions, screens in printers, kitchen appliances and billboards, lights and signboards. Mobile screens are e.g. Screens in mobile phones, laptops, cameras, in particular digital cameras, vehicles and destination displays on buses and trains.
• Stationary screens are e.g. Screens of computers, televisions, screens in printers, kitchen appliances and billboards, lights and signboards.
• Mobile screens are e.g. Screens in mobile phones, laptops, cameras, in particular digital cameras, vehicles and destination displays on buses and trains.
• transition metal carbene complexes of the formula I can be used in OLEDs having an internal structure.
• the transition metal carbene complexes of the general formula I used according to the invention are preferably used in these inverse OLEDs in turn in the light-emitting layer.
• the construction of inverse OLEDs and the materials usually used therein are known to the person skilled in the art.
• the following examples further illustrate the invention: Examples
• 0.5 mmol of platinum (II) acetylacetonate (0.197 g) are introduced into 3 ml of dimethyl sulfoxide and heated to 100 ° C.
• a solution of 0.5 mmol of 1,1-dimethyl-3,3'-methylene-diimidazolium dibromide 3 (0.169 g) in 20 ml dimethyl sulfoxide is added over 13 hours using a syringe pump.
• the entire reaction mixture is stirred for a further 2 hours at 100.degree. Thereafter, the solvent is removed at 70 ° C in vacuo and the resulting solid washed twice with a little water and twice with a little tetrahydrofuran.
• the white solid 2 is still to dry.
• a corresponding PMMA (polymethyl methacrylate) film containing 2% by weight of the transition metal complex is prepared in PVP.
• PMMA film 2 mg transition metal carbene complex 5 are dissolved in 1 ml 10% (mass percent) PMMA solution (PMMA in dichloromethane) and a film is spread onto a microscope slide (quartz glass) with a 60 ⁇ m doctor blade. The film is then dried. The photoluminescence data of the transition metal carbene complex are determined on the resulting film.

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