Electroluminescent Polymers and the Use Thereof

• US 20070205714A1
• Filed: 04/26/2005
• Published: 09/06/2007
• Est. Priority Date: 04/26/2004
• Status: Active Grant

• Current Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Original Assignee: Merck Patent GmbH (Merck & Co., Inc.)
• Inventors: Heun, Susanne, Leske, Corinna, Busing, Arne, Turk, Silke
• Granted Patent: US 7,947,382 B2
• Time in Patent Office: Days
• US Class Current: 313/504
• CPC Class Codes: C07C 211/61 with at least one of the condensed ring systems formed by three or more rings
• CPC Class Codes: C07C 25/22 with condensed rings
• CPC Class Codes: C07C 25/24 Halogenated aromatic hydrocarbons with unsaturated side chains
• CPC Class Codes: C07C 2603/26 Phenanthrenes; Hydrogenated phenanthrenes
• CPC Class Codes: C08G 61/12 Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• CPC Class Codes: C08G 61/121 derived from organic halides
• CPC Class Codes: C08G 73/02 Polyamines
• CPC Class Codes: C09B 69/101 containing an anthracene dye
• CPC Class Codes: C09B 69/105 containing a methine or polymethine dye
• CPC Class Codes: C09B 69/109 containing other specific dyes
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: C09K 2211/1416 Condensed systems
• CPC Class Codes: C09K 2211/1458 containing sulfur as the only heteroatom
• CPC Class Codes: C09K 2211/1466 containing nitrogen as the only heteroatom
• CPC Class Codes: H05B 33/14 characterised by the chemical or physical composition or the arrangement of the electroluminescent material , or by the simultaneous addition of the electroluminescent material in or onto the light source
• CPC Class Codes: H10K 50/11 characterised by the electroluminescent [EL] layers
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: H10K 85/151 Copolymers
• CPC Class Codes: H10K 85/615 Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
• CPC Class Codes: H10K 85/631 Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
• CPC Class Codes: Y02E 10/549 : Organic PV cells
• CPC Class Codes: Y10T 428/12556 : Organic component

Abstract

The present invention relates to polymers which contain novel structural units of the formula (I). The materials according to the invention exhibit improved efficiency and a longer lifetime on use in a polymeric organic light-emitting diode.

Claims

1. Polymers containing at least 5 mol % of units of the formula (1)

2. Polymers according to claim 1, wherein the polymers are conjugated or partially conjugated polymers.

3. Polymers according to claim 1, which additionally comprise further structural elements besides the units of the formula (1).

4. Polymers according to claim 3, wherein the further structural elements which increase the hole-injection and/or -transport properties are triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-p-dioxin, phenoxathiyne, carbazole, azulene, thiophene, pyrrole, furan derivatives or O—

, S—

or N-containing heterocycles having a high HOMO.

5. Polymers according to claim 3, wherein the further structural elements which increase the electron-injection and/or -transport properties are pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, benzothiadiazole, phenazine derivatives, triarylboranes or O—

, S—

or N-containing heterocycles having a low LUMO.

6. Polymers according to claim 4, wherein the further structural elements have combinations of individual units selected from the group consisting of triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine. phenoxazine, dihydrophenazine. thianthrene, dibenzo-p-dioxin, phenoxathivne, carbazole, azulene, thiophene, pyrrole, furan derivatives, O—

, S—

or N-containing heterocvcles having a high HOMO, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, benzothiadiazole, phenazine derivatives, triarylboranes or O—

, S— and

N-containing heterocycles having a low LUMO.

7. Polymers according to claim 3, wherein the further structural elements change the emission characteristics to such an extent that electrophosphorescence can be obtained instead of electrofluorescence.

8. Polymers according to claim 3, wherein the further structural elements improve the transition from the singlet state to the triplet state, selected from the classes of the carbazole and bridged carbazole dimer units, ketones, phosphine oxides, sulfoxides, sulfones and silane derivatives.

9. Polymers according to claim 3, wherein the further structural elements are 1,4-phenylene, 1,4-naphthylene, 1,4- or 9,10-anthrylene, 1,6- or 2,7- or 4,9-pyrenylene, 3,9- or 3,10-perylenylene, 4,4′

-biphenylylene, 4,4″

-terphenylylene, 4,4′

-bi-1,1′

-naphthylylene, 4,4′

-tolanylene, 4,4′

-stilbenylene or 4,4″

-bisstyrylarylene derivatives.

10. Polymers according to claim 3, wherein the further structural elements are used as backbone, selected from the classes of the 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, 9,9′

-spirobifluorene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydrodibenzoxepine derivatives and cis- and trans-indenofluorene derivatives.

11. Polymers according to claim 3, wherein the proportion of the units of the formula (1) is at least 10 mol %.

12. Polymers according to claim 1, wherein in addition to units of the formula (1), the polymers contain at least two structural units from selected from the group consisting of triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-p-dioxin, phenoxathiyne, carbazole, azulene, thiophene, pyrrole, furan derivatives, O—

, S—

or N-containing hetero cycles having a high HOMO, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, benzothiadiazole, phenazine derivatives, triarylboranes, O—

, S—

or N-containing heterocycles having a low LUMO, carbazole and bridged carbazole dimer units, ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives, 1,4-phenylene, 1,4-naphthylene, 1,4- or 9,10-anthrylene, 1,6- or 2,7- or 4,9-pyrenylene, 3,9- or 3,10- perylenylene, 4,4′

-biphenylylene, 4,4″

-terphenylylene, 4,4′

-bi-1,1′

-naphthylylene, 4,4′

-tolanylene, 4,4′

-stilbenylene or 4,4″

-bisstyrylarylene derivatives 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, fluorene derivatives, 9,9′

-spirobifluorene derivatives, 9,10-dihydrophenanthrene derivatives, 5,7-dihydrodibenzoxepine derivatives and cis- and trans-indenofluorene derivatives.

13. Polymers according to claim 12, characterized in that one of these structural units is selected from the group of the hole-conducting units and the other group is an emitting unit.

14. Polymers according to claim 1, wherein the symbol R, identically or differently on each occurrence, stands for a straight-chain, branched or cyclic alkyl chain having 2 to 15 C atoms, in which, in addition, one or more non-adjacent C atoms may be replaced by N—

R¹, O, S, O—

CO—

O, CO—

O, —

CH═

CH—

or —

C≡

C—

, with the proviso that the heteroatoms are not bonded directly to the phenanthrene unit, and in which, in addition, one or more H atoms may be replaced by F or CN, or an aromatic or heteroaromatic group having 4 to 20 C atoms, which may also be substituted by one or more non-aromatic radicals R¹, or a combination of a plurality of these systems;

the two radicals R here may together also form a further mono- or polycyclic, aromatic or aliphatic ring system.

15. Polymers according to claim 1, wherein the symbol X, identically or differently on each occurrence, stands for —

CH═

Ch—

, —

C≡

C—

or N—

Ar.

16. Polymers according to claim 1, wherein the symbol Y, identically or differently on each occurrence, stands for a divalent aromatic or heteroaromatic ring system having 4 to 25 C atoms, which may be substituted by one or more radicals R¹.

17. Polymers according to claim 1, wherein the symbol Ar, identically or differently on each occurrence, stands for a monovalent aromatic or heteroaromatic ring system having 4 to 25 C atoms, which may be substituted by R¹ or unsubstituted.

18. Polymers according to claim 1, wherein the index m, identically or differently on each occurrence, stands for 0 or 1.

19. Polymers according to claim 1, wherein the polymer contains units of the formula (1) as backbone, and and

n is on each occurrence equal to 0.

20. Polymers according to claim 1, wherein the polymer contains units of the formula (1) as hole-transporting units, and

n is on each occurrence, identically or differently, 0 or 1, where at least one n=1;

m is on each occurrence, identically or differently, 0, 1 or 2, where m is not equal to 0 if the corresponding n=1; and

X is on each occurrence N—

Ar.

21. Polymers according to claim 1, wherein the polymer contains units of the formula (1) as emitters, and

n is on each occurrence, identically or differently, 0 or 1, where at least one n=1;

m is on each occurrence, identically or differently, 0, 1 or 2, where m is not equal to 0 if the corresponding n=1; and

X is on each occurrence, identically or differently, —

CR¹═

CR¹—

, —

C≡

C—

or N—

Ar, where at least one X is equal to —

CR¹═

CR¹—

or —

C≡

C—

.

22. Polymers according to claim 1, wherein the units of the formula (1) are symmetrically substituted in the 9,10-positions of the phenanthrene units.

23. Polymers according to claim 1, wherein the polymer is prepared by SUZUKI polymerisation, YAMAMOTO polymerisation, STILLE polymerisation or HARTWIG-BUCHWALD polymerisation.

28. Solutions and formulations of one or more polymers or blends according to claim 1 in one or more solvents.

30. Organic electronic component having one or more active layers, characterized in that at least one of these active layers comprises one or more polymers or blends according to claim 1.

31. Organic electronic component according to claim 30, characterized in that it is polymeric light-emitting diodes (PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic solar cells (O-SCs), organic field-quench devices (O-FQDs) or organic laser diodes (O-lasers).

32. Organic electronic component according to claim 31, characterized in that it is a polymeric light-emitting diode.

24. Bifunctional monomeric compounds of the formula (2)

25. Bifunctional monomeric compounds according to claim 24, characterized in that A is selected from Cl, Br, I, O-tosylate, O-triflate, O—

SO₂R², B(OR²)₂ and Sn(R²)₃, where R² has the same meaning as described in claim 24, and where two or more radicals R² may also optionally form a ring system with one another.

26. Bifunctional monomeric compounds according to claim 24 wherein the C—

C linking reactions are selected from the groups of the SUZUKI coupling, the YAMAMOTO coupling or the STILLE coupling or in that the C—

N linking reaction is a HARTWIG-BUCHWALD coupling.

27. Mixtures (blends) of one or more polymers according to with further polymeric, oligomeric, dendritic or low-molecular-weight substances.

29. canceled