Organic metal complexes

Abstract

The present invention relates inter alia to novel organic metal complexes comprising, e.g., platinum and specific side groups, their preparation and their use in electronic devices.

Claims

1. A compound according to Formula (9), ##STR00124## wherein Z is phenyl, M is a transition metal or metal ion; z4 is 1, R.sup.1 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(═O)R.sup.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups is optionally 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, P(═O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, 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 R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a combination of two or more of these groups; two or more radicals R.sup.1 here may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.2 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, N(R.sup.3).sub.2, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, C(═O)R.sup.3, P(═O)(R.sup.3).sub.2, S(═O)R.sup.3, S(═O).sub.2R.sup.3, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.3, where one or more non-adjacent CH.sub.2 groups is optionally 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═Se, C═NR.sup.3, P(═O)(R.sup.3), SO, SO.sub.2, NR.sup.3, O, S or CONR.sup.3 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, 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 R.sup.3, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or a combination of two or more of these groups; two or more adjacent radicals R.sup.2 here may form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.3 is, identically or differently on each occurrence, 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 is optionally replaced by F; two or more substituents R.sup.3 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; W is, identically or differently on each occurrence, selected from a compound of the following Formula (2) ##STR00125## where the rings B′ and F′ can be substituted with one or more R1 selected from substituted or unsubstituted aliphatic, aromatic or heteroaromatic ring having 5 to 60 atoms or a substituted or unsubstituted polycyclic ring system, which is optionally condensed with the adjacent rings, X is CR.sup.1; T is selected identically or differently on each occurrence and is —C(R.sup.1).sub.2, —Si(R.sup.1).sub.2, —N, —NR.sup.1, —O, —S, —C(═O), —S(═O), —SO.sub.2, —CF.sub.2, —SF.sub.4, —P, —P(═O)R.sup.1, —PF.sub.2, —P(═S)R.sup.1, —As, —As(═O), —As(═S), —Sb, —Sb(═O) or —Sb(═S); U is —N—; V is selected independently on each occurrence and is C(R.sup.1).sub.2, NR.sup.1, O or S; K is R.sup.1; M′ is a phenyl which is either unsubstituted or substituted by one or more R.sup.1; N is R.sup.1; k is 0 thus M′ and ring C′ are not bonded via K to each other; m is 0; n is 0; r is 1 or 2; s is 0 or 1; t is 1; and v is 0 and ring D′ is a 5 membered ring.

2. The compound according to claim 1, wherein M is Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, or Pt.

3. The compound according to claim 1, wherein W is, identically or differently on each occurrence, selected from a compound of the following Formulae (72) to (77) ##STR00126## ##STR00127## wherein R.sup.1 is defined as in claim 1 and ## denotes the position of binding between W and Z or the metal M-bearing core.

4. The compound according to claim 1, wherein R.sup.1 is, identically or differently on each occurrence, selected from the following Formulae (84) to (242) ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## wherein the R.sup.1 having the Formulae (84) to (242) can be, identically or differently on each occurrence, substituted with one or more R.sup.2 and wherein the lines indicate the position of binding.

5. A composition comprising at least one compound according to claim 1 and at least one organic functional material selected from hole transport material (HTM), hole injection material (HIM), electron transport material (ETM), electron injection material (EIM), hole blocking material (HBM), exciton blocking material (ExBM), host or matrix material, fluorescent emitter, and phosphorescent emitter.

6. The composition according to claim 5, wherein the at least one organic functional material is a matrix material selected from ketones, phosphinoxides, sulfoxides, sulfones, triarylamines, carbazoles, indolocarbazoles, indenocarbazoles, aza-carbazoles, bipolar matrix materials, silanes, azaborolenes, boronesters, triazines, zinc complexes, diaza- or tetraazasiloles or diazaphospholes or mixtures thereof.

7. An electronic device which comprises the composition according to claim 6 wherein the device is an organic electroluminescent device, an organic light emitting diode, polymer light emitting diode, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell, or an organic laser diode and the composition is in one or more light emitting layers.

8. A formulation comprising at least one compound according to claim 1 and at least one solvent.

9. An electronic device which comprises the compound according to claim 1.

10. The electronic device according to claim 9, wherein the device is an organic electroluminescent device, an organic light emitting diode, polymer light emitting diode, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell, or an organic laser diode.

11. An electroluminescent device comprising at least one compound according to claim 1.

12. A process for phototherapy in medicine which comprises irradiating or treating humans or animals with the electroluminescent device according to claim 11.

13. A cosmetic which comprises the electroluminescent device according to claim 11.

14. A method for the treatment of the skin with phototherapy which comprises treating the skin by employing a light emitting device comprising a compound according to claim 1.

15. A compound according to Formula (9), ##STR00150## wherein Z is phenyl, M is a transition metal or metal ion; z4 is 0, R.sup.1 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, N(R.sup.2).sub.2, CN, NO.sub.2, Si(R.sup.2).sub.3, B(OR.sup.2).sub.2, C(═O)R.sup.2, P(═O)(R.sup.2).sub.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, OSO.sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.2, where one or more non-adjacent CH.sub.2 groups is optionally 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, P(═O)(R.sup.2), SO, SO.sub.2, NR.sup.2, O, S or CONR.sup.2 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, 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 R.sup.2, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a combination of two or more of these groups; two or more radicals R.sup.1 here may also form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one another; R.sup.2 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, N(R.sup.3).sub.2, CN, NO.sub.2, Si(R.sup.3).sub.3, B(OR.sup.3).sub.2, C(═O)R.sup.3, P(═O)(R.sup.3).sub.2, S(═O)R.sup.3, S(═O).sub.2R.sup.3, OSO.sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sup.3, where one or more non-adjacent CH.sub.2 groups is optionally 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═Se, C═NR.sup.3, P(═O)(R.sup.3), SO, SO.sub.2, NR.sup.3, O, S or CONR.sup.3 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO.sub.2, 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 R.sup.3, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.3, or a combination of two or more of these groups; two or more adjacent radicals R.sup.2 here may form a mono- or polycyclic, aliphatic or aromatic ring system with one another; R.sup.3 is, identically or differently on each occurrence, 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 is optionally replaced by F; two or more substituents R.sup.3 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another; W is, identically or differently on each occurrence, selected from a compound of the following Formula (2) ##STR00151## where the rings B′ and F′ can be substituted with one or more R1 selected from substituted or unsubstituted aliphatic, aromatic or heteroaromatic ring having 5 to 60 atoms or a substituted or unsubstituted polycyclic ring system, which is optionally condensed with the adjacent rings, X is CR.sup.1; T is selected identically or differently on each occurrence and is —C(R.sup.1).sub.2, —Si(R.sup.1).sub.2, —N, —NR.sup.1, —O, —S, —C(═O), —S(═O), —SO.sub.2, —CF.sub.2, —SF.sub.4, —P, —P(═O)R.sup.1, —PF.sub.2, —P(═S)R.sup.1, —As, —As(═O), —As(═S), —Sb, —Sb(═O) or —Sb(═S); U is —N—; V is selected independently on each occurrence and is C(R.sup.1).sub.2, NR.sup.1, O or S; K is, if m =1, C(R.sup.1).sub.2 or a single bond between M′ and ring C′; M′ is a phenyl which is either unsubstituted or substituted by one or more R.sup.1; N is, if m =1, C(R.sup.1).sub.2 or a single bond between M′ and ring E′; k is 0 thus M′ and ring C′ are not bonded via K to each other; m is 1; n is 0 and M′ and ring E′ are not bonded via N to each other; r is 1 or 2; s is 0 or 1; t is 1; and v is 0 and ring D′ is a 5 membered ring.

16. The compound according to claim 15, wherein M is Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, or Pt.

17. The compound according to claim 15, wherein W is, identically or differently on each occurrence, selected from a compound of the following Formulae (72) to (77) ##STR00152## ##STR00153## wherein R.sup.1 is defined as in claim 15 and ## denotes the position of binding between W and Z or the metal M-bearing core.

18. The compound according to claim 15, wherein R.sup.1 is, identically or differently on each occurrence, selected from the following Formulae (84) to (242) ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## wherein the R.sup.1 having the Formulae (84) to (242) can be, identically or differently on each occurrence, substituted with one or more R.sup.2 and wherein the lines indicate the position of binding.

19. A composition comprising at least one compound according to claim 15 and at least one organic functional material selected from the group consisting of hole transport material (HTM), hole injection material (HIM), electron transport material (ETM), electron injection material (EIIVI), hole blocking material (HBM), exciton blocking material (ExBM), host or matrix material, fluorescent emitter and phosphorescent emitter.

20. The composition according to claim 19, wherein the at least one organic functional material is a matrix material selected from ketones, phosphinoxides, sulfoxides, sulfones, triarylamines, carbazoles, indolocarbazoles, indenocarbazoles, azacarbazoles, bipolar matrix materials, silanes, azaborolenes, boronesters, triazines, zinc complexes, diaza- or tetraaza-siloles or diazaphospholes or mixtures thereof.

21. An electronic device which comprises the composition according to claim 19 wherein the device is an organic electroluminescent device , an organic light emitting diode, polymer light emitting diode, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell, or an organic laser diode and the composition is in one or more light emitting layers.

22. A formulation comprising at least one compound according to claim 15 and at least one solvent.

23. An electronic device which comprises the compound according to claim 15.

24. The electronic device according to claim 23, wherein the device is an organic electroluminescent device , an organic light emitting diode, polymer light emitting diode, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell, or an organic laser diode.

25. An electroluminescent device comprising at least one compound according to claim 15.

26. A process for phototherapy in medicine which comprises irradiating or treating humans or animals with the electroluminescent device according to claim 25.

27. A cosmetic which comprises the electroluminescent device according to claim 25.

28. A method for the treatment of the skin with phototherapy which comprises treating the skin by employing a light emitting device comprising a compound according to claim 15.

Description

WORKING EXAMPLES

Examples

(1) The following syntheses are, unless indicated otherwise, carried out under a protective-gas atmosphere in dried solvents. Compounds (I) and (V) can be prepared in accordance with WO 2005/042444. Compounds (II), (VIII) and (XIII) can be prepared in accordance with WO2010/136109. Compound (X) can be prepared in accordance with Synthetic Communications, 40(1), 58-63, 2010. Compound (XVI) can be prepared according to Journal of Heterocyclic Chemistry, 29(5), 1237-1239; 1992. Compound (XVII) is commercial product from Aldrich. Compound (XXI) can be prepared in accordance with WO 2010/050778.

Example 1

Preparation of Compound (IV)

(2) Synthetic procedure for the preparation of compound (IV):

(3) ##STR00108## ##STR00109##

Preparation of Compound (III)

(4) 13.8 g (28.8 mmol) of compound (I), 7.4 g (26.2 mmol) of compound (II) and 3.0 g (31.4 mmol) of sodium t-butoxide are suspended in 200 mL of toluene. 176 mg (0.78 mmol) of Pd(OAc).sub.2 and 1.3 mL of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 24 h. After cooling, the organic phase is separated off, washed three times with 200 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using a mixture of ethylacetate/heptane (1:2). The yield is 13.2 g (19.4 mmol), corresponding to 74% of theory.

Preparation of Compound (IV)

(5) 13.0 g (19.1 mmol) of compound (III) and 7.9 g (19.1 mmol) of potassium platinum(II) chloride are heated under reflux for 72 h in 100 mL of acetic acid. After cooling, the mixture is evaporated to dryness, and 100 mL of dichloromethane (dcm) and 200 mL of water are added to the crude product. The organic phase is separated off, washed three times with 300 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using dcm as eluting solvent. The yield is 7.2 g (8.2 mmol), corresponding to 43% of theory.

Example 2

Preparation of Compound (VII)

(6) Synthetic procedure for the preparation of compound (VII):

(7) ##STR00110##

Preparation of Compound (VI)

(8) 14.5 g (30.3 mmol) of compound (V), 7.8 g (27.5 mmol) of compound (II) and 3.2 g (33.0 mmol) of sodium t-butoxide are suspended in 200 mL of toluene. 185 mg (0.82 mmol) of Pd(OAc).sub.2 and 1.3 mL of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 27 h. After cooling, the organic phase is separated off, washed three times with 300 mL of water and subsequently evaporated to dryness. The residue is purified by column chromatography using a mixture of ethylacetate/heptane (1:2). The yield is 13.3 g (19.5 mmol), corresponding to 71% of theory.

Preparation of Compound (VII)

(9) 13.1 g (19.2 mmol) of compound (VI) and 8.0 g (19.2 mmol) of potassium platinum(II) chloride are heated under reflux for 72 h in 100 mL of acetic acid. After cooling, the mixture is evaporated to dryness, and 100 mL of dcm and 300 mL of water are added to the crude product. The organic phase is separated off, washed three times with 300 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using dcm as eluting solvent. The yield is 7.0 g (8.0 mmol), corresponding to 42% of theory.

Example 3

Preparation of Compound (XII)

(10) Synthetic procedure for the preparation of compound (XII):

(11) ##STR00111## ##STR00112##

Preparation of Compound (IX)

(12) 22.4 g (51.1 mmol) of compound (VIII), 9.7 g (51.1 mmol) of copper iodide, 6.6 g (102.2 mmol) of sodium azide, 5.4 g (61.3 mmol) of N,N-dimethylethane-1,2-diamine are heated under reflux for 10 h in 300 mL of dimethylsulfoxide (DMSO). After cooling, 200 mL of ethylacetate and 100 mL of a solution of saturated NH.sub.4Cl are added to the reaction mixture. The organic phase is separated off, washed three times with 300 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is recrystallised from toluene and finally dried under reduced pressure. The yield is 11.3 g (30.2 mmol), corresponding to 59% of theory.

Preparation of Compound (XI)

(13) 11.1 g (29.6 mmol) of compound (IX), 13.9 g (62.2 mmol) of compound (X) and 6.8 g (71.0 mmol) of sodium t-butoxide are suspended in 250 mL of toluene. 332 mg (1.5 mmol) of Pd(OAc).sub.2 and 2.4 mL of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 28 h. After cooling, the organic phase is separated off, washed three times with 300 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using a mixture of ethylacetate/heptane (1:2). The yield is 12.8 g (18.8 mmol), corresponding to 64% of theory.

Preparation of Compound (XII)

(14) 12.5 g (18.4 mmol) of compound (XI) and 7.6 g (18.4 mmol) of potassium platinum(II) chloride are heated under reflux for 72 h in 100 mL of acetic acid. After cooling, the mixture is evaporated to dryness, and 100 mL of dcm and 300 mL of water are added to the crude product. The organic phase is separated off, washed three times with 300 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using dcm as eluting solvent. The yield is 6.9 g (7.9 mmol), corresponding to 43% of theory.

Example 4

Preparation of Compound (XV)

(15) Synthetic procedure for the preparation of compound (XV):

(16) ##STR00113## ##STR00114##

Preparation of Compound (XIV)

(17) 12.1 g (25.4 mmol) of compound (V), 18.1 g (30.4 mmol) of compound (XIII) and 4.2 g (30.4 mmol) of potassium carbonate are suspended in 300 mL of toluene and 100 mL of water. 290 mg (0.25 mmol) of tetrakis(triphenyl-phosphine)palladium(0) are added to this suspension, and the reaction mixture is heated under reflux for 48 h. After cooling, the organic phase is separated off, washed three times with 300 mL of water, dried over sodium sulfate and subsequently evaporated to dryness. The residue is purified by column chromatography using a mixture of ethylacetate/heptane (1:2). The yield is 15.2 g (16.7 mmol), corresponding to 66% of theory.

Preparation of Compound (XV)

(18) 15.0 g (16.5 mmol) of compound (XIV) and 6.8 g (16.5 mmol) of potassium platinum(II) chloride are heated under reflux for 72 h in 100 mL of acetic acid. After cooling, the mixture is evaporated to dryness, and 100 mL of dcm and 300 mL of water are added to the crude product. The organic phase is separated off, washed three times with 300 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using dcm as eluting solvent. The yield is 7.8 g (7.1 mmol), corresponding to 43% of theory.

Example 5

Preparation of Compound (XX)

(19) Synthetic procedure for the preparation of compound (XX):

(20) ##STR00115## ##STR00116##

Preparation of Compound (XVIII)

(21) 15.0 g (58.5 mmol) of compound (XVI), 10.1 g (64.4 mmol) of compound (XVII) and 6.7 g (70.2 mmol) of sodium t-butoxide are suspended in 250 mL of toluene. 390 mg (1.8 mmol) of Pd(OAc).sub.2 and 2.9 mL of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 24 h. After cooling, the organic phase is separated off, washed three times with 200 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using a mixture of ethylacetate/heptane (1:4). The yield is 13.3 g (40.0 mmol), corresponding to 68% of theory.

Preparation of Compound (XIX)

(22) 13.0 g (39.2 mmol) of compound (XVIII), 17.0 g (35.6 mmol) of compound (I) and 4.1 g (42.7 mmol) of sodium t-butoxide are suspended in 250 mL of toluene. 240 mg (1.1 mmol) of Pd(OAc).sub.2 and 1.8 mL of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 21 h. After cooling, the organic phase is separated off, washed three times with 200 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using a mixture of ethylacetate/heptane (1:2). The yield is 16.8 g (23.0 mmol), corresponding to 65% of theory.

Preparation of Compound (XX)

(23) 16.6 g (22.8 mmol) of compound (XIX) and 9.5 g (22.8 mmol) of potassium platinum(II) chloride are heated under reflux for 72 h in 100 mL of acetic acid. After cooling, the mixture is evaporated to dryness, and 100 mL of dcm and 300 mL of water are added to the crude product. The organic phase is separated off, washed three times with 300 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using dcm as eluting solvent. The yield is 8.4 g (9.1 mmol), corresponding to 40% of theory.

Example 6

Preparation of Compound (XXIV)

(24) Synthetic procedure for the preparation of compound (XXIV)

(25) ##STR00117## ##STR00118##

Preparation of Compound (XXII)

(26) 18.5 g (51.1 mmol) of compound (XXI), 9.7 g (51.1 mmol) of copper iodide, 6.6 g (102.2 mmol) of sodium azide and 5.4 g (61.3 mmol) of N,N-dimethylethane-1,2-diamine are heated under reflux for 10 h in 300 mL of dmso. After cooling, 200 mL of ethylacetate and 100 mL of a solution of saturated NH.sub.4Cl are added to the reaction mixture. The organic phase is separated off, washed three times with 300 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is recrystallised from a mixture of toluene/ethanol and finally dried under reduced pressure. The yield is 8.8 g (29.5 mmol), corresponding to 58% of theory.

Preparation of Compound (XXIII)

(27) 8.5 g (28.5 mmol) of compound (XXII), 14.1 g (60.1 mmol) of compound (X) and 6.6 g (68.6 mmol) of sodium t-butoxide are suspended in 250 mL of toluene. 320 mg (1.4 mmol) of Pd(OAc).sub.2 and 2.2 mL of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 27 h. After cooling, the organic phase is separated off, washed three times with 200 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using a mixture of ethylacetate/heptane (1:2). The yield is 11.3 g (18.7 mmol), corresponding to 66% of theory.

Preparation of Compound (XXIV)

(28) 11.1 g (18.4 mmol) of compound (XXIII) and 7.6 g (18.4 mmol) of potassium platinum(II) chloride are heated under reflux for 72 h in 100 mL of acetic acid. After cooling, the mixture is evaporated to dryness, and 100 mL of dcm and 300 mL of water are added to the crude product. The organic phase is separated off, washed three times with 300 mL of water, dried over magnesium sulfate, filtered and subsequently evaporated to dryness. The residue is purified by column chromatography on silica gel using dcm as eluting solvent. The yield is 6.1 g (7.7 mmol), corresponding to 42% of theory.

Examples 7 to 13

Production and Characterization of Organic Electroluminescent Devices

(29) The structures of compounds TE-1 to TE-6 according to the invention, TMM-1 (synthesized in accordance with DE 102008036982—WO 2010/015306) and TMM-2 (synthesized in accordance with DE 102008017591—WO 2009/124627) are depicted below for clarity.

(30) Structures of the emitters related to this invention

(31) ##STR00119## ##STR00120## ##STR00121##

(32) Structure of the emitter related to the comparative example (synthesized according to WO 2005/042444)

(33) ##STR00122##

(34) Structures of the matrices

(35) ##STR00123##

(36) Materials according to the invention can be used from solution, where they result in simple devices having good properties. The production of such components 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). In the present case, compounds TE-1 to TE-6 according to the invention are dissolved in toluene. The typical solids content of such solutions is between 16 and 25 g/l if, as here, the typical layer thickness of 80 nm for a device is to be achieved by means of spin coating. Structured ITO substrates and the material for the so-called buffer layer (PEDOT, actually PEDOT:PSS) are commercially available (ITO from Technoprint and others, PEDOT:PSS as Clevios Baytron P aqueous dispersion from H.C. Starck). The interlayer used serves for hole injection; in this case, HIL-012 from Merck is used. The emission layer is applied by spin coating in an inert-gas atmosphere, in the present case argon, and dried by heating at 160° C. for 10 min. Finally, a cathode comprising barium and aluminium is applied by vacuum vapor deposition. A hole-blocking layer and/or an electron-transport layer can also be applied between the emitting layer and the cathode by vapor deposition, and the interlayer may also be replaced by one or more layers which merely have to satisfy the condition of not being detached again by the subsequent processing step of deposition of the emitting layer from solution. The devices are characterized by standard methods, and the OLED examples given have not yet been optimized. Table 1 summarizes the data obtained. In the case of the processed devices, it is evident here that the materials according to the invention have superior efficiency and/or lifetime to those available previously (comparative example). The OLED here exhibits the following layer structure: I) cathode (Ba/Al: 3 nm/150 nm), II) emitting layer (80 nm; 47.5% by weight of TMM-1+47.5% by weight of TMM-2+5% by weight of TE), III) interlayer (20 nm), IV) buffer layer (80 nm; PEDOT) and V) anode.

(37) TABLE-US-00002 TABLE 1 Results with materials processed from solution in the device configuration indicated Max. Voltage [V] Lifetime [h], initial EML eff. at 100 CIE luminance Ex. 80 nm [cd/A] cd/m.sup.2 (x, y) 1000 cd/m.sup.2  7 (comp) TMM-1:TMM-2:TE-C 8.5 5.3 0.64/0.36 10500  8 TMM-1:TMM-2:TE-1 12.8 4.8 0.64/0.36 28500  9 TMM-1:TMM-2:TE-2 12.4 5.0 0.64/0.37 25000 10 TMM-1:TMM-2:TE-3 11.1 4.9 0.66/0.36 30500 11 TMM-1:TMM-2:TE-4 11.8 5.0 0.67/0.35 26000 12 TMM-1:TMM-2:TE-5 11.4 4.9 0.68/0.36 23500 13 TMM-1:TMM-2:TE-6 13 4.8 0.64/0.35 22000