Materials for organic electroluminescence devices

Abstract

The present invention relates to copolymers containing indenocarbazole derivatives having electron- and hole-transporting properties, in particular for use in the interlayer, emission layer and/or charge-transport layer of electroluminescent devices. The invention furthermore relates to a process for the preparation of the compounds according to the invention and to electronic devices comprising these compounds.

Claims

1. A copolymer containing one or more structural units of the general formula (2), (3), and/or (5) ##STR00038## where the following applies to the symbols and indices: A and B are selected, identically or differently on each occurrence, from the group consisting of —C(R.sup.1).sub.2, —Si(R.sup.1).sub.2, —NR.sup.1, —O, —S, —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) and —Sb(═S), with the proviso that A and B are not simultaneously either —C(R.sup.1).sub.2 or —NR.sup.1; Y is C if a group Ar.sup.1, Ar.sup.2 or Ar.sup.3 is bonded to the group Y or is, identically or differently on each occurrence, CR.sup.1 or N; R.sup.1 is, identically or differently on each occurrence, —H, —X, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)N(R.sup.2).sub.2, —C(═O)X, —C(═O)R.sup.1, —NH.sub.2, —N(R.sup.2).sub.2, —SH, —SR.sup.2, —SO.sub.3H, —SO.sub.2R.sup.2, —OH, —NO.sub.2, —CF.sub.3, —SF.sub.5, substituted or unsubstituted silyl, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, 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 group having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aromatic or heteroaromatic ring system having 5 to 40 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 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; two or more substituents R.sup.1 here may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, together with the atoms to which they are bonded, where two groups R.sup.1 may also form a spiro group together with the fluorene unit to which they are bonded; X is halogen; R.sup.2 is on each occurrence, identically or differently, H, D or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms; Ar.sup.1, Ar.sup.2 and Ar.sup.3 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is optionally substituted by one or more radicals R′, where the ring system may also be condensed onto positions 7,8 or 8,9 of the basic compound; a, b and c are each, independently of one another, 0 or 1; and n is greater than or equal to 1; where the copolymer contains at least one structural unit which is different from the structural unit of the formula (2), (3) and/or (5).

2. The copolymer according to claim 1, wherein the structural units of the formulae (2), (3) or (5) correspond to the structural units of the formulae (2a), (3a) or (5a) ##STR00039## wherein the symbols and indices have the meanings indicated in claim 1.

3. The copolymer according to claim 1, wherein the structural units of the formulae (2), (3) or (5) correspond to the structural units of the formulae (2b), (3b) or (5b) ##STR00040## wherein the symbols and indices have the meanings indicated in claim 1.

4. The copolymer according to claim 1, wherein the structural units of the formulae (2), (3) or (5) correspond to the structural units of the formulae (2c), (3c) or (5c) ##STR00041## wherein the symbols and indices have the meanings indicated in claim 1.

5. The copolymer according to claim 1, wherein A and B are selected, identically or differently on each occurrence, from C(R.sup.1).sub.2, NR.sup.1, O, S or C(═O).

6. The copolymer according to claim 1, wherein the at least one further structural unit is an emitter unit.

7. The copolymer according to claim 1, wherein the at least one further structural unit is a triplet emitter unit.

8. A process for the preparation of the copolymer according to claim 1, which comprises preparing the copolymer by SUZUKI, YAMAMOTO, STILLE or HARTWIG-BUCHWALD polymerization.

9. A mixture of a copolymer according to claim 1 with further polymeric, oligomeric, dendritic and/or a low-molecular-weight substance.

10. The mixture according to claim 9, wherein the low-molecular-weight substance is a triplet emitter.

11. A solution which comprises the copolymer according to claim 1 in one or more solvents.

12. An organic electroluminescent device which comprises a copolymer containing one or more structural units of the general formula (2), (3) and/or (5) ##STR00042## where the following applies to the symbols and indices: A and B are selected, identically or differently on each occurrence, from the group consisting of —C(R.sup.1).sub.2, —Si(R.sup.1).sub.2, —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) and —Sb(═S), with the proviso that A and B are not simultaneously either —C(R.sup.1).sub.2; Y is C if a group Ar.sup.1, Ar.sup.2 or Ar.sup.3 is bonded to the group Y or is, identically or differently on each occurrence, CR.sup.1 or N; R.sup.1 is, identically or differently on each occurrence, —H, —X, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)N(R.sup.2).sub.2, —C(═O)X, —C(═O)R.sup.1, —NH.sub.2, —N(R.sup.2).sub.2, —SH, —SR.sup.2, —SO.sub.3H, —SO.sub.2R.sup.2, —OH, —NO.sub.2, —CF.sub.3, —SF.sub.5, substituted or unsubstituted silyl, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, 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 group having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aromatic or heteroaromatic ring system having 5 to 40 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 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; two or more substituents R.sup.1 here may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, together with the atoms to which they are bonded, where two groups R.sup.1 may also form a spiro group together with the fluorene unit to which they are bonded; X is halogen; R.sup.2 is on each occurrence, identically or differently, H, D or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms; Ar.sup.1, Ar.sup.e and Ar.sup.a are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is optionally substituted by one or more radicals R.sup.1, where the ring system may also be condensed onto positions 7,8 or 8,9 of the basic compound; a, b and c are each, independently of one another, 0 or 1; and n is greater than or equal to 1; where the copolymer contains at least one structural unit which is different from the structural unit of the formula (2), (3) and/or (5).

13. A triplet matrix material in an emitter layer or in the form of an interlayer which comprises the copolymer according to claim 1.

14. An organic electronic device which comprises one or more active layers, wherein at least one of said active layers comprises one or more copolymers according to claim 1.

15. An organic electronic device comprising in at least one active layer a polymer containing one or more structural units of the general formula (2), (3) and/or (5) ##STR00043## where the following applies to the symbols and indices: A and B are selected, identically or differently on each occurrence, from the group consisting of —C(R.sup.1).sub.2, —Si(R.sup.1).sub.2, —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′, —As, —As(═O), —As(═S), —Sb, —Sb(═O) and —Sb(═S), with the proviso that A and B are not simultaneously either —C(R.sup.1).sub.2; Y is C if a group Ar.sup.1, Ar.sup.2 or Ar.sup.3 is bonded to the group Y or is, identically or differently on each occurrence, CR.sup.1 or N; R.sup.1 is, identically or differently on each occurrence, —H, —X, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)N(R.sup.2).sub.2, —C(═O)X, —C(═O)R.sup.1, —NH.sub.2, —N(R.sup.2).sub.2, —SH, —SR.sup.2, —SO.sub.3H, —SO.sub.2R.sup.2, —OH, —NO.sub.2, —CF.sub.3, —SF.sub.5, substituted or unsubstituted silyl, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, 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 group having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aromatic or heteroaromatic ring system having 5 to 40 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 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; two or more substituents R.sup.1 here may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, together with the atoms to which they are bonded, where two groups R.sup.1 may also form a spiro group together with the fluorene unit to which they are bonded; X is halogen; R.sup.2 is on each occurrence, identically or differently, H, D or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms; Ar.sup.1, Ar.sup.2 and Ar.sup.3 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is optionally substituted by one or more radicals R.sup.1, where the ring system may also be condensed onto positions 7,8 or 8,9 of the basic compound; a, b and c are each, independently of one another, 0 or 1; and n is greater than or equal to 1.

16. The organic electronic device according to claim 15, wherein A and B are selected, identically or differently on each occurrence, from C(R.sup.1).sub.2, NR.sup.1, O, S or C(═O).

17. The organic electronic device according to claim 14, wherein the device is an organic or polymeric organic electroluminescent device.

18. The organic electronic device according to claim 14, wherein the active layer is an emitter layer or an interlayer.

19. The organic electronic device according to claim 14, wherein the device is selected from the group consisting of an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic solar cell, a dye-sensitized organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, an organic laser diode and an organic plasmon emitting device.

20. A copolymer comprising one or more structural units of the general formula (1), ##STR00044## where the following applies to the symbols and indices: A and B are selected, identically or differently on each occurrence, from the group consisting of —C(R.sup.1).sub.2, —Si(R.sup.1).sub.2, —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) and —Sb(═S), wherein only one of A or B can be —NR.sup.1; Y is C if a group Ar.sup.1, Ar.sup.2 or Ar.sup.3 is bonded to the group Y or is, identically or differently on each occurrence, CR.sup.1 or N; R.sup.1 is, identically or differently on each occurrence, —H, —X, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)N(R.sup.2).sub.2, —C(═O)X, —C(═O)R′, —NH.sub.2, —N(R.sup.2).sub.2, —SH, —SR.sup.2, —SO.sub.3H, —SO.sub.2R.sup.2, —OH, —NO.sub.2, —CF.sub.3, —SF.sub.5, substituted or unsubstituted silyl, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, 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 group having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aromatic or heteroaromatic ring system having 5 to 40 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 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; two or more substituents R.sup.1 here may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, together with the atoms to which they are bonded, where two groups R.sup.1 may also form a spiro group together with the fluorene unit to which they are bonded; X is halogen; R.sup.2 is on each occurrence, identically or differently, H, D or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms; Ar.sup.1, Ar.sup.2 and Ar.sup.3 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is optionally substituted by one or more radicals R.sup.1, where the ring system may also be condensed onto positions 7,8 or 8,9 of the basic compound; a, b and c are each, independently of one another, 0 or 1; and n is greater than or equal to 1; where the copolymer contains at least one structural unit which is different from the structural unit of the formula (1).

21. A mixture of a copolymer containing one or more structural units of the general formula (2), (3), and/or (5) with a low-molecular-weight substance, ##STR00045## where the following applies to the symbols and indices: A and B are selected, identically or differently on each occurrence, from the group consisting of —C(R.sup.1).sub.2, —Si(R.sup.1).sub.2, —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) and —Sb(═S), with the proviso that A and B are not simultaneously —NR.sup.1; Y is C if a group Ar.sup.1, Ar.sup.2 or Ar.sup.3 is bonded to the group Y or is, identically or differently on each occurrence, CR.sup.1 or N; R.sup.1 is, identically or differently on each occurrence, —H, —X, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)N(R.sup.2).sub.2, —C(═O)X, —C(═O)R.sup.1, —NH.sub.2, —N(R.sup.2).sub.2, —SH, —SR.sup.2, —SO.sub.3H, —SO.sub.2R.sup.2, —OH, —NO.sub.2, —CF.sub.3, —SF.sub.5, substituted or unsubstituted silyl, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, 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 group having 5 to 40 ring atoms, which may in each case be substituted by one or more radicals R.sup.2, or an aromatic or heteroaromatic ring system having 5 to 40 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 40 aromatic ring atoms, which is optionally substituted by one or more radicals R.sup.2, or a combination of these systems; two or more substituents R.sup.1 here may also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another, together with the atoms to which they are bonded, where two groups R.sup.1 may also form a spiro group together with the fluorene unit to which they are bonded; X is halogen; R.sup.2 is on each occurrence, identically or differently, H, D or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms; Ar.sup.1, Ar.sup.2 and Ar.sup.3 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, which is optionally substituted by one or more radicals R.sup.1, where the ring system may also be condensed onto positions 7,8 or 8,9 of the basic compound; a, b and c are each, independently of one another, 0 or 1; and n is greater than or equal to 1; where the copolymer contains at least one structural unit which is different from the structural unit of the formula (2), (3) and/or (5), wherein the low-molecular-weight substance is a triplet emitter.

Description

WORKING EXAMPLES

Example 1

(1) Preparation of Compound 4 (M2)

(2) Compound 4 is prepared as follows:

(3) ##STR00009##
1.1 Compound 2

(4) ##STR00010##

(5) 7.6 g (1 molar equivalent, 29.7 mmol) of indolocarbazole, 15.1 g (2.1 molar equivalents, 62.3 mmol) and 8.8 g of Na tert-butoxide are initially introduced in 100 ml of o-xylene and carefully degassed. The reaction solution is warmed to 130° C., and 133 mg of palladium acetate and 1.8 ml of 10% tributylphosphine solution in toluene (1 mol/l) are added, and the mixture is warmed under reflux for 2 hours. The reaction solution is cooled to room temperature. 50 ml of water are added to the batch. The phases are separated. The aqueous phase is extracted with toluene. The combined organic phases are washed with water, dried over MgSO.sub.4, filtered, and the solvent is stripped off in vacuo.

(6) The solid obtained is recrystallised from isopropanol.

(7) .sup.1H NMR (CDCl.sub.3, δ (ppm), J (Hz)): 1.04 (t, 6H, J=7.2 Hz), 1.32 (m, 20H), 3.51 (t, 4H, J=7.5 Hz), 7.23 (s, 1H), 7.29 (dt, 2H, J=7.3 Hz, J=2.8 Hz), 7.34 (t, 2H, J=8 Hz), 7.37 (d, 4H, J=7.55), 7.47 (d, 4H, J=7.55), 8.23 (d, 2H, 7.75 Hz), 7.42 (d, 4H, J=8.6), 8.82 (s, 1H).

(8) 1.2 Compound 3 (M1)

(9) ##STR00011##

(10) 10 g (1 molar equivalent, 17.2 mmol) of compound 2 are suspended in 150 ml of glacial acetic acid. 8.6 g (2.2 molar equivalents, 37.8 mmol) of N-iodosuccinimide are added with exclusion of light. The reaction solution is stirred at room temperature for 2.5 hours. The deposited precipitate is filtered off with suction and washed with water and methanol.

(11) The product is obtained as beige solid by recrystallisation from n-butanol.

(12) .sup.1H NMR (CDCl.sub.3, δ (ppm), J (Hz)): 1.02 (t, 6H, J=7.2 Hz), 1.32 (m, 20H), 3.58 (t, 4H, J=7.5 Hz), 6.98 (s, 1H), 7.12 (d, 2H, J=7.3 Hz), 7.42 (d, 4H, J=7.55), 7.47 (d, 4H, J=7.55), 8.62 (s, 2H), 9.18 (s, 1H).

(13) 1.3 Compound 4 (M2)

(14) ##STR00012##

(15) 50 ml of dioxane, 4.88 g (2 molar equivalents, 19.2 mmol) of bis(pinacolato)diborane and 3.66 g (2.9 molar equivalents, 27.8 mmol) of potassium acetate are added to 8 g (1 molar equivalent, 9.6 mmol) of compound 3. 0.41 g (0.5 mmol) of 1,1-bis(diphenylphosphine)ferrocene-palladium(II) chloride (complex with dichloromethane (1:1), Pd: 13%) are subsequently added. The batch is heated to 110° C. After a TLC check, the batch is cooled to room temperature, and 50 ml of water are added. 50 ml of water is subsequently added again for phase separation. The mixture is extracted with ethyl acetate, the combined organic phases are then dried over magnesium sulfate, filtered, and the solvent is stripped off in vacuo.

(16) The product is obtained as white solid by recrystallisation from acetonitrile.

(17) .sup.1H NMR (CDCl.sub.3, δ (ppm), J (Hz)): 0.99 (t, 6H, J=7.2 Hz), 1.28 (m, 20H), 1.41 (s, 24H), 3.48 (t, 4H, J=7.5 Hz), 7.02 (s, 1H), 7.19 (d, 2H, J=7.3 Hz), 7.42 (d, 4H, J=7.55), 7.47 (d, 4H, J=7.55), 8.22 (s, 2H), 9.18 (s, 1H)

Example 2

(18) ##STR00013##

Example 3

(19) ##STR00014##

Example 4

(20) ##STR00015##

Example 5

(21) ##STR00016##

Example 6

(22) ##STR00017##

(23) Compound 10 is prepared as follows:

(24) ##STR00018## ##STR00019##

(25) Compound 7 is prepared as described in DE 102009023155.

(26) Compound 8

(27) ##STR00020##

(28) 12 g (1 molar equivalent, 42.3 mmol) of indenocarbazole 7, 9.9 g (1.1 molar equivalents, 46.5 mmol) of p-bromo-tert-butylbenzene and 6.1 g of Na tert-butoxide are initially introduced in 100 ml of o-xylene and carefully degassed. The reaction solution is warmed to 130° C., and 133 mg of palladium acetate and 1.8 ml of 10% tributylphosphine solution in toluene (1 mol/l) are added, and the mixture is warmed under reflux for 2 hours. The reaction solution is cooled to room temperature. 50 ml of water are added to the batch. The phases are separated. The aqueous phase is extracted with toluene. The combined organic phases are washed with water, dried over MgSO.sub.4, filtered, and the solvent is stripped off in vacuo. The solid obtained is recrystallised from isopropanol.

(29) Compound 9 (M7)

(30) ##STR00021##

(31) 8 g (1 molar equivalent, 19 mmol) of compound 8 are suspended in 150 ml of glacial acetic acid. 5.3 g (2.2 molar equivalents, 41.8 mmol) of N-iodosuccinimide are added with exclusion of light. The reaction solution is stirred at room temperature for 2.5 hours. The deposited precipitate is filtered off with suction and washed with water and methanol. The product is obtained as beige solid by recrystallisation from n-butanol.

(32) Compound 10 (M8)

(33) ##STR00022##

(34) 50 ml of dioxane, 4.7 g (2 molar equivalents, 18.4 mmol) of bis(pinacolato)diborane and 3.51 g (2.9 molar equivalents, 26.7 mmol) of potassium acetate are added to 8 g (1 molar equivalent, 9.2 mmol) of compound 9. 0.41 g (0.5 mmol) of 1,1-bis(diphenylphosphine)ferrocene-palladium(II) chloride (complex with dichloromethane (1:1), Pd: 13%) are subsequently added. The batch is heated to 110° C. After a TLC check, the batch is cooled to room temperature, and 50 ml of water are added. 50 ml of water is subsequently again added for phase separation. The mixture is extracted with ethyl acetate, the combined organic phases are then dried over magnesium sulfate, filtered, and the solvent is stripped off in vacuo.

Example 7: (Comparative Backbone Monomer M9)

(35) ##STR00023##

Examples 8 to 17: Preparation of the Polymers

(36) Copolymers P1 to P8 according to the invention and comparative polymers V1 and V2 are synthesised by SUZUKI coupling in accordance with WO 03/048225 A2 using the following monomers (percent data=mol %).

Example 8: (Polymer P1)

(37) ##STR00024##

Example 9: (Polymer P2)

(38) ##STR00025##

Example 10: (Polymer P3)

(39) ##STR00026##

Example 11: (Polymer P4)

(40) ##STR00027##

Example 12: (Polymer P5)

(41) ##STR00028##

Example 13: (Polymer P6)

(42) ##STR00029##

Example 14: (Polymer P7)

(43) ##STR00030##

Example 15: (Polymer P8)

(44) ##STR00031##

Example 16: (Comparative Polymer V1—Interlayer)

(45) ##STR00032##

Example 17: (Comparative Polymer V2—Polymer Matrix)

(46) ##STR00033##

(47) Further materials used:

(48) Structure of triplet emitter TEG1, which is used as emitter in the emission layer (EML). Photoluminescence spectrum of TEG1 in toluene was recorded and exhibits a minimum at 491.65 nm (2.52 eV) and a maximum at 512.4 nm (2.42 eV).

(49) ##STR00034##

(50) Structure of the soluble SM matrix material TMM1 which serves as reference matrix material.

(51) ##STR00035##

Example 18: (Quantum-Chemical Simulation of the Energy Levels of the Materials Used)

(52) In order to develop a suitable material for use in OLEDs, predictions of the energy levels, in particular the HOMO and LUMO levels of excited triplet states of the various materials are essential.

(53) The quantum-chemical simulation of the energy levels can be carried out by means of the Gaussian 03W software (Gaussian Inc.). Firstly, the molecular geometry is optimised via an AM1 method. An energy calculation is subsequently preferably carried out by the TD-DFT (time-dependent density function theory) method with the B3PW9 correction function and the 6-31G(d) base set, where this method includes calculation of the HOMO/LUMO levels and the energy levels for the triplet and singlet state. The respective first singlet and triplet states, which are referred to below as S1 and T1 levels, are the most important here.

(54) The HOMO and LUMO levels are corrected as follows using cyclic voltammetry: a material set is measured by means of CV and calculated using, for example, the above-mentioned method with Gaussian 03W. The calculated values are then calibrated with reference to the measured values. The calibration factor is then used for further calculations. For simplification, trimers of the polymers are calculated. For example, M2-M3-M2 denotes a structure building block as follows, where the polymerisable groups have been removed:

(55) ##STR00036##
Detailed Description of the Quantum-Chemical Calculation:

(56) The HOMO and LUMO positions and the triplet/singlet level of the organic functional materials are determined via quantum-chemical calculations. To this end, the “Gaussian03W” program package (Gaussian Inc.) is used. In order to calculate organic substances without metals, firstly a geometry optimisation is carried out using a “Ground State/Semi-empirical/Default spin/AM1” semi-empirical method (charge 0/spin singlet). This is followed by an energy calculation on the basis of the optimised geometry. The “TD-SCF/DFT/Default Spin/B3PW91” method with the “6-31G(d)” base set is used here (charge 0/spin singlet). For organometallic compounds, the geometry calculation is optimised via the “Ground State/Hartree-Fock/Default Spin/LanL2MB” method (charge 0/spin singlet). The energy calculation is carried out analogously to the organic substances as described above, with the difference that the “LanL2DZ” base set (pseudo=LanL2) is used for the metal atom and the “6-31G(d)” base set is used for the ligands. The most important results are HOMO/LUMO levels and energies for the triplet and singlet excited states. The first singlet and excited singlet/triplet states are the most important and are known as S1 and T1 levels. The energy calculation gives the HOMO HEh or LUMO LEh in hartree units. The HOMO and LUMO values in electron-volts are determined therefrom as follows, where these relationships arise from the calibration with reference to cyclic voltammetry measurements:
HOMO (eV)=((HEh*27.212)−0.9899)/1.1206
LUMO (eV)=((LEh*27.212)−2.0041)/1.385

(57) These values are to be regarded in the sense of the present application as energetic position of the HOMO level or LUMO level of the materials. As example, an HOMO of −0.20435 hartrees and an LUMO of −0.06350 hartrees are obtained for compound TMM1 (see also Table 1) from the calculation, which corresponds to a calibrated HOMO of −5.85 eV and a calibrated LUMO of −2.70 eV.

(58) The T1 level is corrected by measurement as follows: for organic compounds which contain no metal, in general, for example, triplet matrix materials, hole-transport materials and electron-transport materials, the T1 level is measured by time-resolved spectroscopy at low temperatures as follows: 100 nm organic films are coated onto quartz and then excited by a YAG laser (@ 355 nm) or an N.sub.2 laser (@ 337 nm) at helium temperature (10K). The delayed photoluminescence after 10 μs is recorded. The T1 level is determined from the beginning of the delayed photoluminescence. For emissive metal complexes, the T1 level is determined simply by employing the photoluminescence at room temperature.

(59) For polymers, in particular conjugated polymers, a trimer of the polymer is calculated. For example for a polymer which is polymerised from monomer M1 and M2, trimers M2-M3-M2 and/or M3-M2-M3 have been used in the calculation, where the polymerisable groups are removed and relatively long alkyl chains have been reduced to a methyl chain. For agreement between the CV measurements and the simulations of polymers, reference can be made to the disclosure in WO 2008/011953 A1.

(60) ##STR00037##

(61) For P6 to P8, there are three different configurations of trimers, since monomer M8 has two non-equivalent polymerisable ends, which are labelled “a” and “b”. For P6, configurations “aM8b-M5-bM8a”, “bM8a-M5-bM8a” and “aM8b-M5-aM8b”, for example, exist. For simplicity, only trimer M1-M8-M1 is calculated for P8.

(62) The simulated energy levels are summarised in Table 1. P1, P2, P4, P5, P6 and P8 are used as polymer matrix or co-matrix for triplet emitter TEG1. TMM1 is a reference material for the matrix, which functions well with TEG1. If the novel matrix has materials having the same or a higher T1 level than TMM1, the novel matrix materials should also function with TEG1. This is the case, for example, for polymers P1, P2, P4, P5, P6 and P8. According to the PL spectrum of TEG1, the minimum requirement of the matrix material for TEG1 is a T1 level which is higher than 2.42 eV, preferably higher than 2.52 eV. Polymer V2 is a further reference polymer matrix, which has a very low T1 level of 2.42 eV.

(63) P3, P4, P5, P7 and P8 are employed as interlayer in comparison with a standard interlayer in polymer V1. The interlayer should have a hole-transport and electron-blocking function. Thus, the novel interlayer polymer should have a similar HOMO level, but a higher LUMO level than V1 in order to have a better electron-blocking action. Furthermore, it is also very desirable for the interlayer to have an exciton-blocking function, for example a high T1 level in the case of the triplet EML, in order to prevent diffusion of excitons from the EML to the anode. The polymers in accordance with the present invention all have much higher T1 levels and LUMO levels than V1.

(64) TABLE-US-00001 TABLE 1 Summary of the energy levels of P1 to P8, V1 and V2 and TMM1 Lumo Triplet Singlet Homo corr. corr. T1 S1 Material Simulated unit [eV] [eV] [eV] [eV] P1 M2-M3-M2 −5.52 −2.68 2.64 2.81 P2 M2-M5-M2 −5.48 −2.59 2.74 2.90 P3 M2-M4-M2 −5.00 −2.14 2.63 2.85 P4 M1-M2-M1 −5.20 −2.12 2.72 2.96 P5 M2-M6-M2 −5.23 −2.12 2.76 3.00 P6 bM8a-M5-aM8b −5.57 −2.62 2.77 2.91 P6 aM8b-M5-aM8b −5.55 −2.66 2.59 3.05 P6 aM8b-M5-bM8a −5.54 −2.69 2.59 3.12 P7 bM8a-M4-aM8b −5.05 −2.12 2.64 2.85 P7 aM8b-M4-aM8b −5.06 −2.24 2.51 2.94 P7 aM8b-M4-bM8a −5.08 −2.29 2.48 3.06 P8 M1-M8-M1 −5.24 −2.17 2.63 2.96 V1 M9-M4-M9 −5.14 −2.47 2.37 2.90 V2 M9-M3-M9 −5.75 −2.85 2.42 3.12 TMM1 TMM1 −5.85 −2.70 2.65 3.35

Example 19: Production of a Device (OLED)

(65) OLED1 to OLED4 having a structure in accordance with the prior art, ITO/PEDOT/interlayer/EML/cathode, are produced in accordance with the following procedure using the corresponding solutions as summarised in Table 2:

(66) 1) PEDOT (Baytron P AI 4083) is deposited as buffer layer having a thickness of 80 nm on an ITO-coated glass substrate by spin coating and then heated at 180° C. for 10 minutes;

(67) 2) a 20 nm interlayer (IL) is deposited thereon by means of spin coating from a toluene solution having a concentration of 0.5% by weight in a glove box;

(68) 3) the interlayer is heated at 180° C. for 1 hour in a glove box;

(69) 4) an emission layer (EML) is deposited by spin coating from solution in toluene having a suitable concentration in order to produce a layer having a thickness of 80 nm;

(70) 5) the device obtained is heated in a glove box in order to remove solvent residues;

(71) 6) a Ba/Al cathode is deposited by vapour deposition on the emission layer having a thickness of 3 nm/150 nm;

(72) 7) the device is encapsulated.

(73) The OLEDs produced in this way are listed in Table 2. Of them, OLED 1 to OLED 6 is, in order to check the uses of P1, P2, P4, P5, P6 and P8 as matrix polymer for green triplet emitters, with V1 as interlayer and Ref1 and Ref2 as reference; in OLED7-11, P3, P4, P5, P7 and P8 are tested, as interlayer with the same standard EML and Ref1 as reference.

(74) TABLE-US-00002 TABLE 2 Summary of the OLED devices EML Conc. in Interlayer Material toluene Ref. 1 V1 80% TMM1:20% TEG1 25 mg/ml Ref. 2 V1 80% V2:20% TEG1 10 mg/ml OLED 1 V1 80% P1:20% TEG1 10 mg/ml OLED 2 V1 80% P2:20% TEG1 10 mg/ml OLED 3 V1 20% P4:60% TMM1:20% TEG1 15 mg/ml OLED 4 V1 20% P5:60% TMM1:20% TEG1 15 mg/ml OLED 5 V1 80% P6:20% TEG1 10 mg/ml OLED 6 V1 20% P8:60% TMM1:20% TEG1 15 mg/ml OLED 7 P3 80% TMM1:20% TEG1 25 mg/ml OLED 8 P4 80% TMM1:20% TEG1 25 mg/ml OLED 9 P5 80% TMM1:20% TEG1 25 mg/ml OLED 10 P7 80% TMM1:20% TEG1 25 mg/ml OLED 11 P8 80% TMM1:20% TEG1 25 mg/ml

Example 20: Results of the Polymers on Use as Triplet Matrix

(75) The OLEDs obtained in this way, OLED 1 to OLED 6, Ref. 1 and Ref. 2, are characterised by standard methods. The following properties are measured here: VIL characteristics, electroluminescence spectrum, colour coordinates, efficiency, operating voltage and lifetime.

(76) Comparison with Ref. 1 and Ref. 2 as reference is summarised in Table 3, where U.sub.on stands for the use voltage, U(100) stands for the voltage at 100 cd/m.sup.2 and U(1000) stands for the voltage at 1000 cd/m.sup.2. The external quantum efficiency is abbreviated to EQE. Lifetime is measured in DC mode. LT DC is defined as the time by which the luminous density of the OLED drops by 50% of the original luminous density at constant current.

(77) TABLE-US-00003 TABLE 3 Performance comparison of OLED 1 to OLED 6 and Ref. 1 and Ref. 2 Max. CIE @ EQE @ eff. Uon U(100) 1000 max. LT DC [cd/A] [V] [V] cd/m.sup.2 eff. [hrs @ nits] Ref. 1 22.0 2.8 4.4 0.34/0.62 6.2%  95 6000 Ref. 2 2.1 5.5 10.1 0.33/0.61 0.6% — — OLED 1 27.8 2.9 4.6 0.34/0.62 7.7% 140 6000 OLED 2 29.5 3.0 4.7 0.33/0.62 8.2% 151 6000 OLED 3 32.5 2.9 4.5 0.34/0.62 9.0% 221 6000 OLED 4 31.2 2.8 4.3 0.33/0.63 8.4% 212 6000 OLED 5 30.5 3.0 4.5 0.33/0.62 8.5% 183 6000 OLED 6 33.2 2.9 4.4 0.33/0.63 8.9% 231 6000

(78) All OLEDs exhibit a similar colour at 1000 cd/m.sup.2.

(79) Ref. 2 gives a very low efficiency, which is attributable to the quenching effect owing to the low T1 level. In other words, most of the triplet excitons on TEG1 have been transferred into the non-emitting matrix V2. A lifetime test is not possible for Ref. 2.

(80) OLED 1, OLED 2 and OLED 5, in which P1, P2 and P6 are used as single-component polymer matrix, give a better efficiency and longer lifetime compared with Ref. 1.

(81) A further improvement is achieved in OLED 3, OLED 4 and OLED 6, where bipolar matrices are used. In particular, the lifetime can be increased considerably. P4, P5 and P8 are said to be good hole-transport materials and are intended to be used in combination with other electron-transport matrix materials in the EML. A further optimisation can be expected, for example using an additional hole-blocking layer on the upper side of the EML and an optimisation of the composition of the EML.

(82) A further advantage of the polymer matrices in accordance with the present invention compared with the SM matrix material lies in the fact that the polymer matrix can be processed more easily from a solution and also has a better film-formation property after application to the substrate, for example by ink-jet printing.

Example 21: Results of the Polymers on Use as Interlayer

(83) The OLEDs obtained in this way, OLED 7 to OLED 11 and Ref. 1, are characterised by standard methods. The following properties are measured here: VIL characteristics, electroluminescence spectrum, colour coordinates, efficiency, operating voltage and lifetime.

(84) Comparison with Ref. 1 as reference is summarised in Table 4. Compared with Ref. 1, OLED 7 to OLED 11, in which the novel interlayer polymers in accordance with the present invention are used, exhibit excellent performance with respect to efficiency and lifetime. An improvement of this type can be attributed to the better electron blocking and/or better exciton blocking through the use of the novel interlayer polymers. Of them, OLED 7 and OLED 11, which use P3 and P8 as interlayer polymer, give the longest lifetime.

(85) TABLE-US-00004 TABLE 4 Comparison of the performance of OLED 7 to OLED 11 and Ref. 1 Max. CIE @ EQE @ eff. Uon U(100) 1000 max. LT DC [cd/A] [V] [V] cd/m.sup.2 eff. [hrs @ nits] Ref. 1 22.0 2.8 4.4 0.34/0.62 6.2% 95 6000 OLED 7 29.5 3.0 4.2 0.34/0.62 8.2% 281 6000 OLED 8 34.6 2.8 4.1 0.33/0.63 9.5% 250 6000 OLED 9 23.0 2.8 4.5 0.33/0.63 6.2% 111 6000 OLED 10 36.6 2.7 4.0 0.34/0.63 10.3% 273 6000 OLED 11 35.2 2.7 4.1 0.33/0.63 9.7% 291 6000