COMPOUNDS THAT CAN BE USED FOR PRODUCING AN ORGANIC ELECTRONIC DEVICE

Abstract

The invention relates to compounds that can be used for producing functional layers of electronic devices, in particular for use in electronic devices. The invention further relates to a process for preparing the compounds according to the invention, and to electronic devices comprising same.

Claims

1. An organofunctional compound usable for production of functional layers of electronic devices, wherein the compound comprises at least one structural element of the formula (I) and/or (Ia) ##STR00332## where the dotted bond represents the linkage of this group to another part of the organofunctional compound and in addition: X is the same or different at each instance and is CR or N, with the proviso that not more than three, symbols X are N; R is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar).sub.2, N(R.sup.1).sub.2, C(═O)N(Ar).sub.2, C(═O)N(R.sup.1).sub.2, Si(Ar).sub.3, Si(R.sup.1).sub.3, Ge(Ar).sub.3, Ge(R.sup.1).sub.3, B(Ar).sub.2, B(R.sup.1).sub.2, C(═O)Ar, C(═O)R.sup.1, P(═O)(Ar).sub.2, P(═O)(R.sup.1).sub.2, P(Ar.sup.1).sub.2, P(R.sup.1).sub.2, S(═O)Ar, S(═O)R.sup.1, S(═O).sub.2Ar, S(═O).sub.2R.sup.1, OSO.sub.2Ar, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, Sn(R.sup.1).sub.2, C═O, C═S, C═Se, C═NR.sup.1, —C(═O)O—, —C(═O)NR.sup.1—, NR.sup.1, P(═O)(R.sup.1), —O—, —S—, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two R radicals together may also form a ring system; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, it is possible for two Ar radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.1), C(R.sup.1).sub.2, Si(R.sup.1).sub.2, Ge(R.sup.1).sub.2, C═O, C═NR.sup.1, C═C(R.sup.1).sub.2, O, S, S═O, SO.sub.2, R.sup.1), P(R.sup.1) and P(═O)R.sup.1; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar.sup.1).sub.2, N(R.sup.2).sub.2, C(═O)Ar.sup.1, C(═O)R.sup.2, P(═O)(Ar.sup.1).sub.2, P(Ar.sup.1).sub.2, B(Ar.sup.1).sub.2, B(OR.sup.2).sub.2, Si(Ar.sup.1).sub.3, Si(R.sup.2).sub.3, Ge(Ar.sup.1).sub.3, Ge(R.sup.2).sub.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, Ge(R.sup.2).sub.2, Sn(R.sup.2).sub.2, C═O, C═S, C═Se, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more, R.sup.1 radicals together may form a ring system; at the same time, one or more R.sup.1 radicals with a further part of the organofunctional compound may form a ring system; Ar.sup.1 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more, preferably nonaromatic R.sup.2 radicals; at the same time, it is possible for two Ar.sup.1 radicals bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined to one another via a bridge by a single bond or a bridge selected from B(R.sup.2), C(R.sup.2).sub.2, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, C═C(R.sup.2).sub.2, O, S, S═O, SO.sub.2, N(R.sup.2), P(R.sup.2) and P(═O)R.sup.2; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, B(OR.sup.3).sub.2, NO.sub.2, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, Ge(R.sup.3).sub.3, P(R.sup.3).sub.2, B(R.sup.3).sub.2, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, Ge(R.sup.3).sub.2, Sn(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more, preferably adjacent substituents R.sup.2 together may form a ring system; R.sup.3 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more, substituents R.sup.3 together may form a ring system.

2. The compound as claimed in claim 1, wherein the compound comprises at least one structural element of the formula (II) ##STR00333## where the dotted bond represents the linkage of this group to another part of the organofunctional compound, the R.sup.1 radicals have the definition given in claim 1, the index v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, and the index u is 0, 1, 2, 3, 4, 5, 6, 7 or 8.

3. The compound as claimed in claim 1 wherein the organofunctional compound usable for production of functional layers of electronic devices is selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF (thermally activated delayed fluorescence), host materials, electron transport materials, exciton blocker materials, electron injection materials, hole conductor materials, hole injection materials, n-dopants, p-dopants, wide band gap materials, electron blocker materials and hole blocker materials.

4. The compound of claim 1, wherein the organofunctional compound is selected from the group of the fluorenes, indenofluorenes, spirobifluorenes, carbazoles, indenocarbazoles, indolocarbazoles, spirocarbazoles, pyrimidines, triazines, lactams, triarylamines, dibenzofurans, dibenzothiophenes, dibenzothienes, imidazoles, benzimidazoles, benzoxazoles, benzothiazoles, 5-arylphenanthridin-6-ones, 9,10-dehydrophenanthrenes, fluoranthenes, anthracenes, benzanthracenes, and fluoradenes.

5. The compound of claim 1, wherein the organofunctional compound comprises at least one group conforming to at least one of the formulae (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg) and/or (IIIh) ##STR00334## where the symbols used are as follows: X is the same or different at each instance and is N or CR, preferably CR, or C if an A.sup.a or A.sup.b group is bonded to this atom, with the proviso that not more than two of the X groups in one cycle are N; W is O, S, NR, NA.sup.a, NA.sup.b, BR, BA.sup.a, BA.sup.b, C(R).sub.2, CRA.sup.a, C(A.sup.a).sub.2, CRA.sup.b, C(A.sup.b).sub.2, CA.sup.aA.sup.b, —RC═CR—, —RC═CA.sup.a-, -A.sup.aC═CA.sup.a-, —RC═CA.sup.b-, -A.sup.bC═CA.sup.b-, -A.sup.bC═CA.sup.a-, SO, SO.sub.2, Ge(R).sub.2, Ge(A.sup.a).sub.2, Ge(A.sup.b).sub.2, GeA.sup.aA.sup.b, Si(R).sub.2, Si(A.sup.a).sub.2, Si(A.sup.b).sub.2, SiA.sup.aA.sup.b or C═O; m at each instance is independently 0, 1, 2, 3 or 4, preferably 0, 1 or 2, with the proviso that the sum total of the indices m per ring is not more than 4; o at each instance is independently 0, 1 or 2, preferably 0 or 1, with the proviso that the sum total of the indices o per ring is not more than 2; A.sup.a is a functional structural element, preferably an aromatic or heteroaromatic ring system which has 5 to 40 ring atoms in each case and may be substituted by one or more substituents R; A.sup.b comprises, a structure of formula (I) and/or (Ia) according to claim 1 or a structure of formula (II) and/or (IIa) according to claim 2, where the symbol R has the definition given in claim 1, with the proviso that the structure of formula (IIIa) has at least one A.sup.b group.

6. The compound of claim 1, wherein the organofunctional compound comprises at least one hole transport group.

7. The compound of claim 1, wherein the organofunctional compound comprises at least one electron transport group.

8. The compound of claim 1, wherein the organofunctional compound comprises at least one group that leads to wide bandgap materials.

9. The compound of claim 1, wherein the organofunctional compound comprises at least one group that leads to materials that are used as host material.

10. The compound of claim 1, wherein the organofunctional compound comprises a group selected from the group consisting of phenyl, ortho-, meta- or para-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 9,9′-diarylfluorenyl 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl, pyrenyl, triazinyl, imidazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1-, 2-, 3- or 4-carbazolyl, 1- or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, trans- and cis-indenofluorenyl, indenocarbazolyl, indolocarbazolyl, spirocarbazolyl, 5-aryl-phenanthridin-6-on-yl, 9,10-dehydrophenanthrenyl, fluoranthenyl, tolyl, mesityl, phenoxytolyl, anisolyl, triarylaminyl, bis(triarylaminyl), tris(triarylaminyl), hexamethylindanyl, tetralinyl, monocycloalkyl, biscycloalkyl, tricycloalkyl, alkyl, for example tert-butyl, methyl, propyl, alkoxyl, alkylsulfanyl, alkylaryl, triarylsilyl, trialkylsilyl, xanthenyl, 10-arylphenoxazinyl, phenanthrenyl and triphenylenyl, each of which may be substituted by one or more radicals, where the functional structural element A.sup.a preferably comprises a corresponding group or can be represented by a corresponding group.

11. The compound of claim 1, wherein the compound contains at least one solubilizing structural element or solubilizing group and at least one functional structural element or functional group, the functional structural element or the functional group being selected from hole transport groups, electron transport groups, structural elements or groups which lead to host materials, or structural elements or groups having wide bandgap properties.

12. The compound of claim 1, wherein the compound is a ligand in a metal complex.

13. A metal complex comprising at least one structure of the general Formula (1)
M(L).sub.n(L′).sub.m  Formula (1) where the symbols and indices used are as follows: M is a transition metal; L is the same or different at each instance and is a bidentate ligand; L′ is the same or different at each instance and is a ligand; n is 1, 2 or 3; m is 0, 1, 2, 3 or 4; at the same time, two or more ligands L may be joined to one another or for L to be joined to L′ by a single bond or a bivalent or trivalent bridge, thus forming a tridentate, tetradentate, pentadentate or hexadentate ligand system, wherein the metal complex contains at least one substructure of the formula (2) and/or (2a): ##STR00335## where the dotted bond represents the linkage of this group to a further part of the metal complex of the formula (1), and the symbol X has the definition set out in claim 1.

14. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 1, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

15. A composition comprising at least one compound as claimed in claim 1 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

16. A formulation comprising at least one compound as claimed in claim 1 and at least one solvent.

17. A method comprising utilizing the compound as claimed in claim 1 in an electronic device as emitter, host material, electron transport material, electron injection material, hole conductor material, hole injection material, electron blocker material, hole blocker material and/or wide bandgap material.

18. A process for preparing the compound as claimed in claim 1, wherein, in a coupling reaction, a compound comprising a structure of formula (I) and/or (Ia) is joined to a compound comprising at least one aromatic or heteroaromatic group.

19. An electronic device comprising at least one compound as claimed in claim 1, wherein the electronic device is preferably selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells and organic laser diodes.

Description

EXAMPLES

[0388] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature. In the case of compounds that can display multiple valence-isomeric or tautomeric forms, one valence-isomeric or tautomeric form is shown representatively.

1) Synthesis of the Synthons S

Example S1

[0389] ##STR00276##

[0390] To 100 ml of n-heptane is added 330 mg (0.5 mmol) of bis[(1,2,5,6-η)-1,5-cyclooctadiene]di-μ-methoxydiiridium(I) [12148-71-9], then 268 mg (1 mmol) of 4,4′-di-tert-butyl-[2,2′]bipyridinyl [72914-19-3] and then 508 mg (2 mmol) of bis(pinacolato)diborane, and the mixture is stirred at room temperature for 15 min. Subsequently, 5.08 g (20 mmol) of bis(pinacolato)diborane [73183-34-3] and then 3.61 g (20 mmol) of 1,1a,4,8b-tetrahydro-1,4-ethenobenzo[a]-cyclopropa[c]cycloheptene [50653-71-9] are added, and the mixture is heated to 80° C. for 12 h. After cooling, 50 ml of ethyl acetate is added to the reaction mixture, which is filtered through a silica gel bed, and the filtrate is concentrated completely under reduced pressure. The crude product is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 2.2 g (7 mmol), 35%; purity: about 95% by .sup.1H NMR.

[0391] The following compounds can be prepared analogously:

TABLE-US-00009 Ex. Reactants Product Yield S10 S11 [00277] [00278] 19% 36%

Example S2

[0392] ##STR00279##

[0393] A mixture of 2.37 g (100 mmol) of 2,5-dibromopyridine [624-28-2], 3.06 g (10 mmol) of S1, 2.76 g (20 mmol) of potassium carbonate, 10 g of glass beads (diameter 3 mm), 52.6 mg (0.2 mmol) of triphenylphosphine, 22.5 mg (0.1 mmol) of palladium(II) acetate, 30 ml of acetonitrile and 15 ml of methanol is heated to 60° C. while stirring for 16 h. After cooling, the solvent is largely removed under reduced pressure, and the residue is taken up in 100 ml of ethyl acetate, washed three times with 30 ml each time of 3% by weight aqueous acetylcysteine solution, three times with 30 ml each time of water and once with 30 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness and the solids are recrystallized from acetonitrile. Yield: 2.12 g (6.3 mmol), 63%; purity: about 95% by .sup.1H NMR.

Example S3

[0394] ##STR00280##

[0395] To a mixture of 3.36 g (10 mmol) of S2, 2.80 g (11 mmol) of bis(pinacolato)diborane, 2.94 g (30 mmol) of potassium acetate (anhydrous), 10 g of glass beads (diameter 3 mm) and 50 ml of THF are added, with good stirring, 56.1 mg (0.2 mmol) of tricyclohexylphosphine and then 22.5 mg (0.11 mmol) of palladium(II) acetate, and the mixture is heated under gentle reflux for 16 h. After cooling, the salts and glass beads are removed by suction filtration through a Celite bed in the form of a THF slurry, which is washed through with a little THF, and the filtrate is concentrated to dryness. The residue is taken up in 50 ml of ethyl acetate, washed three times with 30 ml each time of 3% by weight aqueous acetylcysteine solution, three times with 30 ml each time of water and once with 30 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness, the solids are stirred with 20 ml of warm methanol, and the crystallized product is filtered off with suction, washed twice with 5 ml each time of methanol and dried under reduced pressure. Yield: 2.49 g (6.5 mmol), 65%; purity: about 95% by .sup.1H NMR.

Example S4

[0396] ##STR00281##

[0397] To a mixture of 3.83 g (10 mmol) of S3, 2.83 g (10 mmol) of 1-bromo-2-iodobenzene [583-55-1], 3.18 g (30 mmol) of sodium carbonate, 25 ml of toluene, 10 ml of ethanol and 25 ml of water are added, with very good stirring, 78.8 mg (0.3 mmol) of triphenylphosphine and then 22.5 mg (0.1 mmol) of palladium(II) acetate, and the mixture is heated to 75° C. for 48 h. After cooling, the organic phase is separated off, washed three times with 30 ml each time of 3% by weight aqueous acetylcysteine solution, three times with 30 ml each time of water and once with 30 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off and the filtrate is concentrated fully under reduced pressure. The residue is subjected to flash chromatography (CombiFlash Torrent from A. Semrau). Yield: 1.65 g (4 mmol), 40%; purity: about 97% by .sup.1H NMR.

Example S5

[0398] ##STR00282##

[0399] A well-stirred mixture of 2.83 g (10 mmol) of (2-bromo-4-chlorophenyl)phenylamine [2149611-39-0], 3.06 g (10 mmol) of S1, 6.37 g (30 mmol) of tripotassium phosphate, 183 mg (0.6 mmol) of tri-o-tolylphosphine, 22.5 mg (0.1 mmol) of palladium(II) acetate, 40 ml of toluene, 10 ml of dioxane and 40 ml of water is heated under reflux for 16 h. After cooling, the aqueous phase is separated off, washed three times with 30 ml each time of 3% by weight aqueous acetylcysteine solution, three times with 30 ml each time of water and once with 30 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness. The residue is recrystallized from acetonitrile with addition of a little acetone. The secondary amine thus obtained is dissolved in 50 ml of DMAc (dimethylacetamide), 4.54 g (25 mmol) of copper(II) acetate and 22.5 mg (0.1 mmol) of palladium(II) acetate are added, and the mixture is stirred at 140° C. for 4 h. The DMAc is largely removed under reduced pressure, the residue is taken up in 100 ml of DCM, 30 ml of cone, ammonia solution is added, the mixture is stirred at room temperature for 1 h, and the organic phase is separated off and washed three times with 30 ml of cone, ammonia solution, three times with 30 ml each time of 3% by weight aqueous acetylcysteine solution, three times with 30 ml each time of water and once with 30 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The magnesium sulfate is filtered off using a silica gel bed in the form of a DCM slurry, and the filtrate is concentrated to dryness and the residue is subjected to flash chromatography (CombiFlash Torrent from A. Semrau). Yield: 1.25 g (3.3 mmol) 33%. Purity by .sup.1H NMR about 95%.

2) Synthesis of the Ligands L

[0400] The following compounds can be prepared analogously to example S2:

TABLE-US-00010 Ex. Reactants Product Yield L1 [00283] [00284] 47% L2 [00285] [00286] 33% L3 [00287] [00288] 35% L4 [00289] [00290] 38%

Example L5

[0401] ##STR00291##

[0402] To a mixture of 8.15 g (10 mmol) of 3,3′-[5′-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)[1,1′:3′,1″-terphenyl]-2,2″-diyl]bis[4,6-diphenylpyridine [1989597-74-1], 4.12 g (10 mmol) of S4, 6.37 g (30 mmol) of tripotassium phosphate, 30 ml of toluene, 15 ml of dioxane and 30 ml of water are added, with good stirring, 164 mg (0.4 mmol) of SPhos and then 44.9 mg (0.2 mmol) of palladium(II) acetate, and then the mixture is heated under reflux for 24 h. After cooling, the organic phase is separated off, washed three times with 30 ml each time of 3% by weight aqueous acetylcysteine solution, three times with 30 ml each time of water and once with 30 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness under reduced pressure and the glassy crude product is recrystallized at boiling from acetonitrile (˜10 ml) with addition of ethyl acetate (˜2 ml). Yield: 4.77 g (4.6 mmol), 46%; purity: about 95% by .sup.1H NMR.

[0403] The following compounds can be prepared analogously:

TABLE-US-00011 Ex. Reactants Product Yield L6 [00292] [00293] 40% L7 [00294] [00295] 42%

Example L8

[0404] ##STR00296##

[0405] Preparation analogous to L1, except replacing 10 mmol of 2-bromopyridine [109-04-6] with 2.03 g (5 mmol) of 6-bromo-N-(6-bromo-2-pyridinyl)-N-phenyl-2-pyridinamine [894405-86-8], Yield: 1.75 g (2.8 mmol), 56%; purity: about 95% by .sup.1H NMR.

[0406] The following compounds can be prepared analogously:

TABLE-US-00012 Ex. Reactants Product Yield L9  [00297] [00298] 52% L10 [00299] [00300] 50% L11 [00301] [00302] 47% L12 [00303] [00304] 45%

3) Synthesis of the Carbazoles, Amines, Triazines

Example C1

[0407] ##STR00305##

[0408] A well-stirred mixture of 3.80 g (10 mmol) of S5, 3.69 g (10 mmol) of 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole [1126522-69-7], 6.37 g (30 mmol) of tripotassium phosphate, 183 mg (0.6 mmol) of tri-o-tolylphosphine, 22.5 mg (0.1 mmol) of palladium(II) acetate, 40 ml of toluene, 10 ml of dioxane and 40 ml of water is heated under reflux for 16 h. After cooling, the aqueous phase is separated off and the organic phase is concentrated to dryness. The residue is taken up in 50 ml of DCM, washed three times with 30 ml each time of 3% by weight aqueous acetylcysteine solution, three times with 30 ml each time of water and once with 30 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of a DCM slurry, and the filtrate is concentrated to dryness. The residue is extracted by stirring with hot butyl acetateliso-propanol, then extracted three times with hot toluene and purified by heating under reduced pressure (p ˜ 10.sup.−5 mbar, T ˜ 280° C.). Yield: 3.40 g (4.5 mmol) 45%. Purity by HPLC >99.9%.

[0409] The following compounds can be prepared analogously:

TABLE-US-00013 Ex. Reactants Product Yield C2 [00306] [00307] 38% A1 [00308] [00309] 48% T1 [00310] [00311] 44% T2 [00312] [00313] 42% T3 [00314] [00315] 35%

4) Synthesis of the C3-Symmetric Iridium Complexes of Bidentate Ligands L

Example Ir(L1).SUB.3

[0410] ##STR00316##

[0411] Preparation according to WO 2015/104045, Ir(LB.sub.74).sub.3, see page 179. Yield: 41%; purity: >99.9% by HPLC.

[0412] The following compounds can be prepared analogously:

TABLE-US-00014 Ex. Ligand Product Yield Ir(L2).sub.3 L2 [00317] 30% Ir(L3).sub.3 L3 [00318] 35%

5) Synthesis of the C2-Symmetric N,N-Trans-Iridium Complexes of Bidentate Ligands L

Example Ir(L4).SUB.2.(acac)

[0413] ##STR00319##

[0414] Preparation according to WO 2015/104045. First of all, the C1 dimer is prepared analogously to [Ir(L42).sub.2Cl).sub.2, see page 193. This is reacted with acetylacetone analogously to Ir538; see page 218. Yield over two stages: 39%; purity: >99.9% by HPLC.

6) Synthesis of the Tripodal Iridium Complexes

Example IrL5

[0415] ##STR00320##

[0416] Preparation according to WO 2016/124304, Ir(L1) variant A, see page 218. Use of ligand L5. Purification as described therein by chromatography on silica gel, hot extraction three times with DCM/methanol (1:1, w) and three times with DCM/acetonitrile (2:1, w) and heating at T ˜ 200° C. and p ˜10.sup.−6 mbar. Yield: 38%; purity: >99.9% by HPLC.

[0417] The following compounds can be prepared analogously:

TABLE-US-00015 Ex. Ligand Product Yield IrL6 L6 [00321] 33% IrL7 L7 [00322] 34%

7) Synthesis of the Platinum Complexes

Example PtL8

[0418] ##STR00323##

[0419] A mixture of 1.86 g (3.0 mmol) of L5 and 1.14 g (3.5 mmol) of dimethyl-bis-DMSO-platinum(II) [70423-98-2] in 30 ml of DMSO is heated to 70° C. for 24 h. The reaction mixture is allowed to cool, the DMSO is largely removed under reduced pressure, and the black residue is taken up in 50 ml of DCM and chromatographed with DCM on silica gel. The red core fraction is extracted, 50 ml of methanol is added, and DCM is distilled off at 50° C. The crystallized product is filtered off with suction and washed twice with 20 ml each time of MeOH. Further purification is effected by hot extraction, once with DCM/methanol (1:1, vv) and three times with DCM/acetonitrile (2:1, w), and heating at T ˜ 250° C. and p ˜ 10.sup.−6 mbar. Yield: 782 mg (0.96), 32%; purity: >99.9% by HPLC.

[0420] The following compounds can be prepared analogously:

TABLE-US-00016 Ex. Ligand Product Yield PtL9  L9  [00324] 27% PtL10 L10 [00325] 25% PtL11 L11 [00326] 20% PtL12 L12 [00327] 26%

Solution-Processed Devices:

From Soluble Functional Materials of Low Molecular Weight

[0421] The compounds of the invention may also be processed from solution and lead therein to OLEDs which are much simpler in terms of process technology compared to the vacuum-processed OLEDs, but nevertheless have good properties. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in WO 2004/037887). The structure is composed of substrate/ITO/hole injection layer (60 nm)/interlayer (20 nm)/emission layer (60 nm)/hole blocker layer (10 nm)/electron transport layer (40 nm)/cathode. For this purpose, substrates from Technoprint (soda-lime glass) are used, to which the ITO structure (indium tin oxide, a transparent conductive anode) is applied. The substrates are cleaned in a cleanroom with D1 water and a detergent (Deconex 15 PF) and then activated by a UV/ozone plasma treatment. Thereafter, likewise in a cleanroom, a 20 nm hole injection layer (PEDOT:PSS from Clevios™) is applied by spin-coating. The required spin rate depends on the degree of dilution and the specific spin-coater geometry. In order to remove residual water from the layer, the substrates are baked on a hotplate at 200° C. for 30 minutes. The interlayer used serves for hole transport; in this case, HL-X from Merck is used. The interlayer may alternatively also be replaced by one or more layers which merely have to fulfill the condition of not being leached off again by the subsequent processing step of EML deposition from solution. For production of the emission layer, the triplet emitters of the invention are dissolved together with the matrix materials in toluene or chlorobenzene. The typical solids content of such solutions is between 16 and 25 g/l when, as here, the layer thickness of 60 nm which is typical of a device is to be achieved by means of spin-coating. The solution-processed devices contain an emission layer composed of Matrix1:Matrix2:Ir(L) with the percentages specified. The emission layer is spun on in an inert gas atmosphere, argon in the present case, and baked at 160° C. for 10 min. Vapor-deposited atop the latter are the hole blocker layer (10 nm RETM1) and the electron transport layer (40 nm RETM1 (50%)/RETM2 (50%)) (vapor deposition systems from Lesker or the like, typical vapor deposition pressure 5×10.sup.−6 mbar). Finally, a cathode of aluminum (100 nm) (high-purity metal from Aldrich) is applied by vapor deposition. In order to protect the device from air and air humidity, the device is finally encapsulated and then characterized. The OLED examples cited are yet to be optimized; table 1 summarizes the data obtained. The lifetime LT50 is defined as the time after which the luminance in operation drops to 50% of the starting luminance with a starting brightness of 1000 cd/m.sup.2. Table 2 shows the materials used.

TABLE-US-00017 TABLE 1 Results with materials processed from solution Voltage Matrix1 EQE (%) (V) LT50 (h) Matrix2 1000 1000 1000 Ex. Emitter cd/m.sup.2 cd/m.sup.2 CIE x/y cd/m.sup.2 Sol-D1 TMM1 (25%) 21.8 4.6 0.35/0.62 190000 TMM2 (55%) Ir(L1).sub.3 (20%) Sol-D2 TMM1 (25%) 21.0 4.2 0.43/0.55 240000 TMM2 (55%) Ir(L2).sub.3 (20%) Sol-D3 TMM1 (25%) 18.3 4.4 0.68/0.32 190000 TMM2 (55%) Ir(L3).sub.3 (20%) Sol-D4 TMM1 (25%) 20.9 4.2 0.350./61 260000 TMM2 (55%) Ir(L5).sub.3 (20%) Sol-D5 TMM1 (30%) 17.5 4.6 0.69/0.30 200000 TMM2 (55%) Pt(L10).sub.3 (15%) Sol-D6 T1 (30%) 20.4 4.1 0.43/0.55 250000 C1 (10%) TMM2 (40%) Ir(L2).sub.3 (20%) Sol-D7 T3 (30%) 20.8 4.1 0.41/0.56 210000 C2 (10%) TMM2 (40%) Ir(L7).sub.3 (20%) Sol-D8 T3 (40%) 21.2 4.6 0.43/0.52 170000 A1 (10%) TMM2 (40%) Pt(L11).sub.3 (10%)

TABLE-US-00018 TABLE 2 Structural formulae of the materials used [00328] [00329] [00330] [00331]