DE102004003008A1 - Organic semiconductor, for use in organic LEDs and solar cells and laser diodes, contains a polymer and structural units which emit light from the triplet state and a triplet emitter - Google Patents

Abstract

Organic semiconductor contains at least one polymer, structural units which emit light from the triplet state, and at least one triplet emitter. The mixture has two polymers where one has a triplet emitter in a covalent bond, and the other is a copolymer.

Description

The The present invention describes new materials and material blends for the Use in organic electronic components, such as electroluminescent elements, and their use in displays based thereon.

For about 12 years, a wide-ranging research on the commercialization of display and lighting elements based on polymeric (organic) light-emitting diodes (PLEDs). This development was triggered by the fundamental developments that took place in EP 423 283 (WO 90/13148) are disclosed. Recently, a first product in the form of a smaller display (in a shaver from PHILIPS NV) is also available on the market. However, significant improvements are still needed to make these displays a real competitor to, or outstrip, the currently dominant liquid crystal displays (LCDs).

A Development, which for some years mainly in the field the "Small molecule "displays appear, is the use of materials that emit light from the triplet state can and thus show phosphorescence instead of fluorescence (M.A. Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). For theoretical reasons is up to four times using such triplet emitters Energy and power efficiency possible. Whether this development however, it will prevail strongly depends on whether appropriate device compositions are found can, which can also implement these advantages in OLEDs. As essential conditions for the Practical applicability here is in particular an efficient transfer of energy to the triplet emitter (and associated efficient light emission), a long operating life and low operating and operating voltage to call.

To achieve this, apart from the properties of the triplet emitter, the properties of the matrix material are of outstanding importance. While for a long time especially carbazole compounds have been considered and have shown first good results, recently new matrix materials based on keto and imine compounds (application not disclosed DE 10317556.3 ) or on phosphine oxides, sulfones and sulfoxides (application not disclosed DE 10330761.3 ), gives excellent results both in terms of efficiency and device lifetime.

In Recently, there are increasing efforts to become the above Benefits of evaporable triplet emitter also for polymer applications to use close. Thus, so-called hybrid device structures are considered the benefits of the "small-molecule" OLEDs with those connect the polymer OLEDs (= PLEDs) and by mixing the triplet emitter arise in the polymer. On the other hand, the triplet emitter also be covalently bound to the polymer. Both methods have the advantage that the compounds can be processed from solution and that no more expensive and elaborate Vapor deposition process as for Devices based on low molecular weight compounds is required. The application from solution (eg with the help of high-resolution Printing process) will have significant long-term advantages over the today common vacuum evaporation process have, v. a. in terms of scalability, structurability, Coating efficiency and economy. Again, a suitable matrix material is necessary, the one allows efficient energy transfer to the triplet emitter and That in conjunction with this good life at low operating voltages having.

In the not-disclosed application DE 10304819.7 Blends and co-polymers of triplet emitters are described with certain carbazole-containing conjugated polymers resulting in efficient emission and reduced operating voltage. Further improvement has been achieved by the introduction of certain bridged carbazole units, as disclosed in the unpublished application DE 10328627.6 are described.

• (1) Die Effizienz der Elektrolumineszenzelemente ist deutlich höher als in Devices gemäß Stand der Technik.
• (2) Die Lebensdauer der Elektrolumineszenzelemente ist deutlich höher als in Devices gemäß Stand der Technik.
• (3) Die Löslichkeit der Polymere und Blends mit den oben beschriebenen überbrückten Carbazol-Einheiten, die den nächst liegenden Stand der Technik darstellen, ist noch nicht immer zufriedenstellend. So ist es beispielsweise nicht möglich, einen hohen Anteil der dort beschriebenen überbrückten Carbazol- Einheiten einzupolymerisieren, da dies zu unlöslichen Polymeren führt. Für die Anwendung sind jedoch lösliche Polymere nötig.
• (4) Die oben beschriebenen Carbazol-Einheiten zeigen zwar in der Anwendung schon recht gute Ergebnisse. Ein weiterer Nachteil dieser Einheiten, außer der eingeschränkten Löslichkeit, ist jedoch der teilweise sehr aufwändige chemische Zugang zu diesen Verbindungen. Hier wäre es wünschenswert, Verbindungen und Monomere zur Verfügung zu haben, deren Device-Eigenschaften vergleichbar oder besser sind, die aber leichter chemisch zugänglich sind.
• (5) Die Polymere und Mischungen gemäß Stand der Technik zeigen eine hohe Sauerstoffempfindlichkeit. So lassen sie sich nur unter sorgfältigem Ausschluss von Sauerstoff verarbeiten. Hier wären weniger empfindliche Substanzen deutlich von Vorteil.

However, despite the advances cited in the above-mentioned publications and application notes, there is still considerable potential for improvement for corresponding materials in the field of solution-processable triplet emitters. U. a. There is still a clear need for improvement in the following fields:

• (1) The efficiency of the electroluminescent elements is significantly higher than in devices according to the prior art.
• (2) The lifetime of the electroluminescent elements is significantly higher than in devices according to the prior art.
• (3) The solubility of the polymers and blends with the above-described bridged carbazole units, which are the closest prior art, is still not always satisfactory. Thus, for example, it is not possible to copolymerize a high proportion of the bridged carbazole units described therein, since this leads to insoluble polymers. For the application, however, soluble polymers are needed.
• (4) Although the above-described carbazole units show quite good results in the application. Another disadvantage of these units, apart from the limited solubility, however, is the sometimes very complicated chemical access to these compounds. Here it would be desirable to have available compounds and monomers whose device properties are comparable or better, but which are more readily chemically accessible.
• (5) The prior art polymers and blends exhibit high oxygen sensitivity. So they can be processed only with careful exclusion of oxygen. Here, less sensitive substances would be clearly beneficial.

It It is therefore obvious that there is still a great need for improvement here.

Surprised was found that - so far unknown - polymers and mixtures containing certain structural units in combination with triplet emitters Here are significant improvements compared to mixtures or polymers as per stand of technology. The device properties remain comparable good or better. These polymers and blends are through Standard reactions readily chemically available or even partially commercially available and lead generally to well soluble polymers. Furthermore show a lower sensitivity to oxygen, what their production and processing significantly easier. They are therefore subject of the present application.

WO 03/046108 describes polymers which comprise 9-oxo-9-phosphafluorene building blocks in combination with arylene building blocks. In the undisclosed application EP 03018832.0 describes oligomers and polymers containing triarylphosphine oxide. However, these polymers are used as fluorescent compounds and not in combination with a triplet emitter.

In WO 03-099901 there is a random Disclosure of a per se copolymer of a polymer backbone, the Ester groups (or carbonyl, sulfone, sulfoxide or phosphine oxide groups) contains and polymerized iridium and platinum complexes. The combination such polymer backbones with triplet emitters are therefore excluded from the invention.

In US 03/022908 there is a random Disclosure of a per se inventive blend of a polymer, the covalently bound triplet emitter contains and a charge transport polymer wherein two of the disclosed charge transport polymers (based on triarylamines) additionally keto or sulfone groups wear. Special advantages of this combination are not listed. These Blends are excluded from the invention.

• (A) mindestens ein Polymer,
• (B) mindestens eine Struktureinheit L=X, wobei für die verwendeten Symbole gilt: L ist bei jedem Auftreten gleich oder verschieden (R¹)(R²)C, (R¹)P, (R¹)As, (R¹)Sb, (R¹)Bi, (R¹)(R²)(R³)P, (R¹)(R²)(R³)As, (R¹)(R²)(R³)Sb, (R¹)(R²)(R³)Bi, (R¹)(R²)S, (R¹)(R²)Se, (R¹)(R²)Te, (R1)(R²)S(=O), (R1)(R²)Se(=O) oder (R¹)(R²)Te(=O); X ist bei jedem Auftreten gleich oder verschieden O, S, Se oder N-R⁴, mit der Maßgabe, dass X nicht S oder Se ist, wenn L für S, Se oder Te steht; R¹, R², R³ ist bei jedem Auftreten gleich oder verschieden H, F, CN, N(R⁴)₂, eine geradkettige, verzweigte oder cyclische Alkyl-, Alkoxy- oder Thioalkoxygruppe mit 1 bis 40 C-Atomen, die mit R⁵ substituiert oder auch unsubstituiert sein kann, wobei ein oder mehrere nicht benachbarte CH₂-Gruppen durch -R⁶C=CR⁶-, -C ≡C-, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C=O, C=S, C=Se, C=NR⁶, -O-, -S-, -NR⁶- oder -CONR⁶- ersetzt sein können und wobei ein oder mehrere H-Atome durch F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder eine Aryl-, Aryloxy- oder Heteroarylgruppe mit 1 bis 40 C-Atomen, die durch ein oder mehrere Reste R⁵ substituiert sein können, wobei zwei oder mehrere Substituenten R¹, R² und/oder R³ miteinander ein mono- oder polycyclisches, aliphatisches oder aromatisches Ringsystem bilden können; dabei dürfen nicht alle Substituenten R¹ bis R³ an einer Struktureinheit H oder F sein; R⁴ ist bei jedem Auftreten gleich oder verschieden eine geradkettige, verzweigte oder cyclische Alkyl- oder Alkoxykette mit 1 bis 22 C-Atomen, in der auch ein oder mehrere nicht benachbarte C-Atome durch -R⁶C=CR⁶-, -C≡C-, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, -NR⁶-, -O-, -S-, -CO-O-, -O-CO-O- ersetzt sein können, wobei auch ein oder mehrere H-Atome durch Fluor ersetzt sein können, eine Aryl-, Heteroaryl- oder Aryloxygruppe mit 1 bis 40 C-Atomen, welche auch durch ein oder mehrere Reste R⁶ substituiert sein können, oder OH oder N(R⁵)₂; R⁵ ist bei jedem Auftreten gleich oder verschieden R⁴ oder CN, B(R⁶)₂ oder Si(R⁶)³. R⁶ ist bei jedem Auftreten gleich oder verschieden H oder ein aliphatischer oder aromatischer Kohlenwasserstoffrest mit 1 bis 20 C-Atomen; und
• (C) mindestens einen Triplett-Emitter;

mit der Maßgabe, dass Mischungen aus zwei Polymeren ausgenommen sind, in denen das eine Polymer kovalent gebundene Triplett-Emitter enthält und das andere ein Copolymer ist aus Tetraphenyldiaminobiphenyl-Einheiten und Diphenylsulfonether- bzw. Diphenylketonether-Einheiten.The invention relates to mixtures (blends) containing

• (A) at least one polymer,
• (B) at least one structural unit L = X, wherein for the symbols used: L is the same or different at each occurrence (R ¹ ) (R ² ) C, (R ¹ ) P, (R ¹ ) As, (R ¹ ) Sb, (R ¹ ) Bi, (R ¹ ) (R ² ) (R ³ ) P, (R ¹ ) (R ² ) (R ³ ) As, (R ¹ ) (R ² ) (R ³ ) Sb , (R ¹ ) (R ² ) (R ³ ) Bi, (R ¹ ) (R ² ) S, (R ¹ ) (R ² ) Se, (R ¹ ) (R ² ) Te, (R ¹ ) (R ² ) S (= O), (R1) (R ² ) Se (= O) or (R ¹ ) (R ² ) Te (= O); X is the same or different at each occurrence as O, S, Se or NR ⁴ , with the proviso that X is not S or Se when L is S, Se or Te; R ¹ , R ² , R ³ are each the same or different at each occurrence, H, F, CN, N (R ⁴ ) ₂ , a straight, branched or cyclic alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, which may be substituted with R ⁵ or else unsubstituted, where one or more non-adjacent CH ₂ groups is replaced by -R ⁶ C =CR ⁶ -, -C≡C-, Si (R ⁶ ) ₂ , Ge (R ⁶ ) ₂ , Sn (R ⁶ ) ₂ , C = O, C = S, C = Se, C = NR ⁶ , -O-, -S-, -NR ⁶ - or -CONR ⁶ - may be replaced and wherein one or more H Atoms can be replaced by F, Cl, Br, I, CN or NO ₂ , or an aryl, aryloxy or heteroaryl group having 1 to 40 C atoms, which may be substituted by one or more R ⁵ radicals, where two or a plurality of substituents R ¹ , R ² and / or R ^{3 may} together form a mono- or polycyclic, aliphatic or aromatic ring system; not all substituents R ¹ to R ³ on a structural unit may be H or F; R ⁴ is the same or different at each instance of a straight-chain, branched or cyclic alkyl or Alkoxy chain having 1 to 22 carbon atoms, in which also one or more non-adjacent C atoms by -R ⁶ C = CR ⁶ -, -C≡C-, Si (R ⁶ ) ₂ , Ge (R ⁶ ) ₂ , Sn (R ⁶ ) ₂ , -NR ⁶ -, -O-, -S-, -CO-O-, -O-CO-O- may be replaced, wherein one or more H atoms may be replaced by fluorine an aryl, heteroaryl or aryloxy group having 1 to 40 carbon atoms, which may also be substituted by one or more radicals R ⁶ , or OH or N (R ⁵ ) ₂ ; R ⁵ is the same or different at each occurrence as R ⁴ or CN, B (R ⁶ ) ₂ or Si (R ⁶ ) ³ . R ⁶ is the same or different at each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms; and
• (C) at least one triplet emitter;

with the proviso that mixtures of two polymers are excluded, in which one polymer contains a covalently bound triplet emitter and the other is a copolymer of Tetraphenyldiaminobiphenyl units and Diphenylsulfonether- or Diphenylketonether units.

The The symbol "=" used above and below denotes a double bond in the sense the Lewis notation of two-electron two-center bonds.

wobei die verwendeten Symbole folgende Bedeutung haben:
X ist bei jedem Auftreten gleich oder verschieden O, S, Se oder N-R⁴, mit der Maßgabe, dass X für Formel (4) und (5) nicht S oder Se sein darf;
Y ist bei jedem Auftreten gleich oder verschieden P, As, Sb oder Bi;
Z ist bei jedem Auftreten gleich oder verschieden S, Se oder Te;
R¹ bis R⁶ haben dieselbe Bedeutung, wie oben beschrieben.Preferred structural units L = X, as described above, are thus selected from the formulas (1) to (5),

where the symbols used have the following meaning:
X is the same or different at each occurrence as O, S, Se or NR ⁴ , with the proviso that X for formula (4) and (5) may not be S or Se;
Y is the same or different P, As, Sb or Bi at each occurrence;
Z is the same or different at each occurrence, S, Se or Te;
R ¹ to R ⁶ have the same meaning as described above.

The mixtures according to the invention are preferably present as amorphous mixtures.

Under a triplet emitter in the context of the invention is intended to be a compound which emits light from the triplet state, So in electroluminescence phosphorescence instead of fluorescence shows, preferably an organometallic triplet emitter. This connection can in principle be low molecular weight, oligomeric, dendritic or polymeric. these are especially compounds which are heavy atoms, d. H. Atoms from the periodic table of elements with an atomic number greater than 36. Particularly suitable for this purpose Compounds which are d and f transition metals contain the o. g. Fulfill condition. Especially suitable here are corresponding structural units, which elements of the group 8 to 10 (i.e., Ru, Os, Rh, Ir, Pd, Pt). Without one To be bound to special theory, in the sense of this application all emitting compounds containing these elements of group 8 to contain 10, as a triplet emitter designated.

at the mixtures according to the invention there are different embodiments, in which the units L = X, or units according to formula (1) to (5) and / or the triplet emitter either mixed or covalently attached to the polymer are bound.

• (A) 5–99,5 Gew.% mindestens eines Polymers POLY1; POLY1 enthält 1–100 mol%, bevorzugt 5–80 mol%, besonders bevorzugt 10–50 mol% einer oder mehrerer Wiederholeinheiten MONO1, wobei MONO1 mindestens eine Struktureinheit L=X, bzw. eine Struktureinheit gemäß Formel (1) bis (5), enthält, und außerdem
• (B) 0,5–95 Gew.%, bevorzugt 0,5–80 Gew.%, besonders bevorzugt 1–50 Gew.%, insbesondere 2–25 Gew.% eines oder mehrerer Triplett-Emitter (TRIP1).

One embodiment of the invention are blends BLEND1 containing

• (A) 5-99.5% by weight of at least one polymer POLY1; POLY1 contains 1-100 mol%, preferably 5-80 mol%, particularly preferably 10-50 mol% of one or more repeat units MONO1, where MONO1 contains at least one structural unit L = X, or a structural unit according to formula (1) to (5) , contains, and besides
• (B) 0.5-95% by weight, preferably 0.5-80% by weight, particularly preferably 1-50% by weight, in particular 2-25% by weight of one or more triplet emitters (TRIP1).

Although this is apparent from the description, it should be noted that the Repeat unit MONO1, the structural units L = X, or contains the structural units according to formula (1) to (5) may also contain more than one such unit.

In the embodiment BLEND1, the triplet emitter (TRIP1) is non-covalently mixed with the polymer POLY1. The repeat units MONO1, containing structural elements L = X, or units according to formulas (1) to (5), are covalently bonded to the polymer. The bond can in principle take place at any desired position, ie these units can be incorporated via one or more positions on R ¹ to R ³ or optionally via R ⁴ , R ⁵ and / or R ⁶ in formula (1) to (5) become. Depending on the linkage, these structural units are then incorporated into the main or side chain of the polymer.

• (A) 0,5–99 Gew.% mindestens eines Polymers POLY2; POLY2 enthält 0,5–100 mol% eines oder mehrerer Triplett-Emitter (TRIP2) kovalent gebunden, und außerdem
• (B) 1–99,5 Gew.% mindestens einer Verbindung VERB1, die mindestens eine Struktureinheit L=X, bzw. mindestens eine Struktureinheit gemäß Formel (1) bis (5) enthält und die in der Lage ist, bei Raumtemperatur glasartige Schichten zu bilden, bevorzugt mit einer Glasübergangstemperatur größer 70 °C.

Another embodiment of the invention are blends BLEND2 containing

• (A) 0.5-99% by weight of at least one polymer POLY2; POLY2 contains 0.5-100 mol% of one or more triplet emitters (TRIP2) covalently bound, as well as
• (B) 1-99.5% by weight of at least one compound VERB1 which contains at least one structural unit L = X, or at least one structural unit according to formula (1) to (5) and which is capable of room-temperature glassy layers to form, preferably with a glass transition temperature greater than 70 ° C.

Also if that's from the description for BLEND2, it should be noted that that the compound VERB1, the structural units L = X, or structural units according to formula (1) to (5) contains can also contain more than one of these units.

Of the Triplet Emitter TRIP2 can be in the main and / or in the Side chain of the polymer POLY2 be incorporated.

• (A) 0,5–98,5 Gew.% mindestens eines Polymers POLY3;
• (B) 1–99 Gew.% mindestens einer Verbindung VERB1, die mindestens eine Struktureinheit L=X, bzw. mindestens eine Struktureinheit der Formel (1) bis (5) enthält und in der Lage ist, bei Raumtemperatur glasartige Schichten zu bilden, bevorzugt mit einer Glasübergangstemperatur größer 70 °C; und außerdem
• (C) 0,5–95 Gew.%, bevorzugt 0,5–80 Gew.%, besonders bevorzugt 1–50 Gew.%, insbesondere 2–25 Gew.% eines oder mehrerer Triplett-Emitter (TRIP1).

Another aspect of this invention are blends containing BLEND3

• (A) 0.5-98.5% by weight of at least one polymer POLY3;
• (B) 1-99% by weight of at least one compound VERB1 which contains at least one structural unit L = X or at least one structural unit of the formula (1) to (5) and is capable of forming vitreous layers at room temperature, preferably with a glass transition temperature greater than 70 ° C; and also
• (C) 0.5-95% by weight, preferably 0.5-80% by weight, more preferably 1-50% by weight, in particular 2-25% by weight, of one or more triplet emitters (TRIP1).

• (A) 0,5–98,5 Gew.% mindestens eines Polymers POLY3; und außerdem
• (B) 1,5–99,5 Gew.% einer Verbindung TRIP3; TRIP3 enthält mindestens eine Struktureinheit L=X, bzw. Einheiten der Formel (1) bis (5) kovalent an einen oder mehrere Triplett-Emitter gebunden enthält, wobei mindestens eine Gruppe X frei, d. h. nicht an ein Metallatom koordiniert, vorliegt; dies schließt nicht aus, dass weitere Struktureinheiten L=X, bzw. Struktureinheiten der Formel (1) bis (5) vorhanden sein können, deren Atom X an ein Metallatom koordiniert ist (beispielsweise Acetylacetonat-Liganden, etc.).

Another aspect of this invention are blends containing BLEND4

• (A) 0.5-98.5% by weight of at least one polymer POLY3; and also
• (B) 1.5-99.5% by weight of a compound TRIP3; TRIP3 contains at least one structural unit L = X, or units of the formula (1) to (5) covalently bonded to one or more triplet emitters, wherein at least one group X is free, that is not coordinated to a metal atom; this does not exclude that further structural units L = X, or structural units of the formula (1) to (5) may be present, whose atom X is coordinated to a metal atom (for example, acetylacetonate ligands, etc.).

The Polymers POLY1 to POLY3 can conjugated, partially conjugated, crossed-conjugated or non-conjugated be.

Conjugated polymers in the context of this invention are polymers which contain mainly sp ² -hybridized (or sp-hybridized) carbon atoms in the main chain, which may also be replaced by corresponding heteroatoms and whose units are in conjugation with one another. In the simplest case this means alternating presence of double and single bonds in the main chain. Mainly, of course, that of course (without further action) occurring defects that lead to conjugation interruptions, do not devalue the term "conjugated polymer". Furthermore, in this application text is also referred to as conjugated when in the main chain Arylamineinheiten, Arylphosphineinheiten and / or certain heterocycles (ie conjugation of N, O, S or P atoms) and / or organometallic complexes, such as units according to TRIP2 (conjugation via the metal atom). Partially conjugated polymers for the purposes of this invention are polymers which either contain longer conjugated portions in the main chain which are interrupted by non-conjugated portions or which contain longer conjugated portions in the side chains of a polymer which is not conjugated in the main chain. Cross-conjugated polymers in the sense of this invention are polymers in which two conjugated sections do not conjugate with each other, but each of these sections is conjugated to a third unit. This is the case, for example, when two conjugated segments are linked directly via a keto group, a sulfoxide group, a sulfone group or a phosphine oxide group, but also for example when geminally linking two conjugated segments via a substituted or unsubstituted alkene group or when linking Fung two conjugated sections on, for example, a meta-phenylene group. By contrast, units such as simple alkylene chains, (thio) ether bridges, ester, amide, or imide linkages are clearly defined as non-conjugated segments.

The Polymers POLY1, POLY2 and POLY3 can be used in addition to the units MONO1 (in POLY1) and the triplet emitter TRIP2 (in POLY2) various other structural elements contain. these can For example, be structural units that form the polymer backbone can, or structural units having the charge injection or charge transport properties influence.

Such units are for example in WO 03/020790 and in the application not disclosed DE 10337346.2 described in detail. The statements made there are via quotation part of the present application.

A suitable class of connection for Cross-conjugated polymers POLY1 are aromatic polyketones and aromatic polysulfones, each for better solubility still be substituted. An overview of this Link classes give P.A. Staniland in "Comprehensive Polymer Science," Ed 5, chapters 29, 483-497 and F. Parodi, ibid., Chapter 33, 561-591. Likewise come aromatic polyphosphine oxides in question.

If the polymers POLY1, POLY2 or POLY3 are non-conjugated Polymers come, come for this In principle, any classes of compounds in question, provided that the polymers a sufficient solubility in a solvent or a solvent mixture in which the other blend components are soluble, so that all components can be processed together from solution.

Examples for non-conjugated Polymers POLY1, the units L = X, or units according to formula (1) to (5) covalently bound are polycarboxylic acid derivatives in the broadest sense, such as main chain polyester, side chain polyester, Poly (glycolic acids), Poly (lactic acids), Poly (ε-caprolacone), polyarylates, Poly (hydroxybenzoic acids), Poly (alkylene terephthalates), polycarboxylic acid anhydrides, polyamides, poly (ε-caprolactams), Polypeptides, polyaramides, polybenzamides, polyimides, poly (amide-imides), Poly (esterimides), poly (etherimides), etc., but also polymers, such as for example, polycarbonates, poly (ester-co-carbonate), poly (isocyanurates), Polyurethanes or polyester polyurethanes. Preference is given here to polymers, which directly to the carbonyl group at least one aromatic group have tied. As examples of Main chain polyester would be here z. As poly (terephthalate) to call. As examples of side chain polyesters would be z. Poly (acrylates), especially poly (phenyl acrylates), poly (cyanoacrylates), Poly (vinyl ester) or poly (vinyl acetates) to call. Other non-conjugated Polymers containing covalently bound units L = X are, for example Side chain polyphosphine oxides, polyether ketones (PEK), polyethersulfones, Polysulfonamides, polysulfone, etc. Furthermore, for example substituted or unsubstituted poly (vinyl ketones) in question, preferably aromatic polyvinyl ketones, or substituted or unsubstituted Poly (vinylbenzophenones) or other polystyrene-analogous ketones, such as Poly (4-benzoyl-α-methylstyrene). Also, polycarbazenes, such as poly-nitriles or poly-isonitriles come in question.

When examples for non-conjugated POLY3 polymers containing neither L = X nor triplet emitter contain covalently bound, for example, polymers come into question, which derive in the broadest sense of polyethylene or polystyrene, but also electronically active, non-conjugated polymers such as PVK (Polyvinylcarbazole) or derivatives thereof.

The Polymers POLY1, POLY2 and POLY3 are either homopolymers, i. H. they then contain only a single monomer structure, or they are Copolymers. The copolymers can have statistical, alternating or block-like structures or alternatively have several of these structures alternately. As well can the polymers are both linear and branched or dendritic be. By using several different structural elements can Properties such as Solubility, Solid phase morphology, etc., can be set.

Polymers POLY1, POLY2 and POLY3 are made by polymerizing one or more monomers. In particular, for the synthesis of conjugated or crossed-conjugated polymers, some types have been found to lead to C [BOND] C linkages (SUZUKI coupling, YAMAMOTO coupling, STILLE coupling) or CN linking (HARTWIG-BUCHWALD coupling). How the polymerization can be carried out by these methods and how the polymers can then be separated and purified from the reaction medium is described in detail, for example, in the unpublished application DE 10249723.0 ,

To These methods may also include the synthesis of partially conjugated or nonconjugated Polymers performed be used by using appropriate monomers that are not continuously are conjugated. For however, partially conjugated or non-conjugated polymers also come Other synthetic methods in question, such as those commonly used in polymer chemistry common are such as polycondensations, the z. To ester or amide linkages to lead, or cationic, anionic or radical polymerizations, the for example about the reaction of alkenes expire and become polyethylene derivatives in the lead to the broadest sense, containing the chromophores bound in the side chains.

For preferred structural units according to formulas (1) to (5), the following applies:
X is O, S or NR ⁴ ;
Y stands for P or As;
Z stands for S or Se;
R ¹ to R ⁶ are as defined above, wherein at each structural unit according to formula (1) to (5) at least one of the substituents R ¹ to R ^{3 represents} an aryl or heteroaryl group having 1 to 40 carbon atoms, with one or a plurality of substituents R ^{4 may be} substituted or unsubstituted.

For particularly preferred structures according to formulas (1) to (5), the following applies:
X is O or NR ⁴ ;
Y stands for P;
Z stands for S;
R ¹ to R ⁶ are as defined above, wherein on each structural unit of the formula (1) to (5) at least two of the substituents R ¹ to R ^{3 represent} an aryl or heteroaryl group having 1 to 40 carbon atoms, with one or a plurality of substituents R ^{4 may be} substituted or unsubstituted.

Examples of particularly preferred repeat units MONO1 or compounds VERB1 which contain structural units according to the formulas (1) to (5) are substituted or unsubstituted structures according to the depicted formulas (6) to (148), where the dashed single bonds represent a possible linkage in the Polymer (MONO1) or molecular extension linkages (VERB1); Ph is a substituted or unsubstituted phenyl group and alkyl is a straight, branched or cyclic alkyl chain which may be substituted or unsubstituted and in which one or more H atoms may be replaced by fluorine. These structural elements according to the formulas (6) to (148) are also preferably constituents of the compounds TRIP3, which represent a combination of triplet emitters and units of the formula (1) to (5). Potential substituents are usually not shown because of the better clarity:

Although this is evident from the description, it should again be explicitly stated here that the structural units according to the formulas (6) to (148) can also be unsymmetrically substituted, ie that different substituents R ⁴ can be present on one unit, or these can also be tied to different positions.

The Repeat units MONO1 are a covalent constituent of POLY1. It has been found that a proportion in the range of 5-100 mol% of these repeat units (referring to all repeat units in Polymer) achieved good results here. Preferred is for POLY1 a share of 5-100 mol% repetition units MONO1. Particularly preferred is a proportion from 10-80 mol% repeat units MONO1, very particularly preferred is a Share of 10-50 mol% repetition units MONO1.

links VERB1 are blend component of BLEND2 and BLEND3. It has shown that a proportion in the range of 5-99 wt.% Of these compounds in the mix achieved good results here. Preferred is for BLEND2 and BLEND3 that is a proportion of 5-99% by weight of compounds VERB1. Particularly preferred is a proportion of 10-80 wt.% VERB1, especially a proportion of 10-50 is preferred Weight% VERB1.

A further preferred embodiment is the blend BLEND5, which by mixing compounds VERB1 in BLEND1 arises, so that here structural units L = X, or units according to formula (1) to (5) both covalently bound to the polymer and mixed available. Here it has been shown that a total proportion of 5-99 mol% Structural units according to this Formulas achieved good results, regardless of whether these units are covalently bound to the polymer or are mixed. Prefers So here is a total amount of 5 -99 mol% structural units L = X, or units according to formulas (1) to (5). Particularly preferred is a total proportion of 10-80 mol% Structural units L = X, or units according to formulas (1) to (5), completely Particularly preferred is a total proportion of 10-50 mol% of structural units according to formulas (1) to (5).

A further preferred embodiment is the mixture APERT, which is formed by blending compounds VERB1 in BLEND4, so that here structural units L = X, or units according to formula (1) to (5) both covalently bound to the triplet emitter as well as mixed available. Again, it has been found that a total content of 5-99 mol% of these structural units gives good results, regardless of whether these units are covalently bound to the triplet emitter or are mixed. Preference is thus here a total amount of 5-99 mol% structural units L = X, or units according to formulas (1) to (5). Particularly preferred is a total proportion of 10-80 mol% structural units L = X, or units according to formulas (1) to (5), very particularly preferably a total proportion of 10-50 mol% structural units L = X, or Units according to formulas (1) to (5).

The triplet emitters TRIP1, blended in BLEND1 and BLEND3, respectively the triplet emitter TRIP2 copolymerized in POLY2 (= BLEND2), or the TRIP3 triplet emitters mixed in BLEND4 can turn off any organic, organometallic or inorganic substance classes selected which emit light at room temperature from the triplet state can, So phosphorescence instead of fluorescence show: These are first all compounds which are heavy atoms, d. H. Atoms from the periodic table of elements with an atomic number greater than 36. Particularly suitable for this are compounds, which d and f transition metals contain the o. g. Fulfill condition. Very particularly preferred here are corresponding structural units, which elements of the group 8 to 10 (i.e., Ru, Os, Rh, Ir, Pd, Pt).

The triplet emitters TRIP1 or TRIP3 can be low molecular weight, oligomeric, dendritic or polymeric compounds. Since these are processed as a mixture component (BLEND1, BLEND3 or BLEND4), sufficient solubility in suitable solvents (eg toluene, xylene, anisole, THF, methylanisole, methylnaphthalene or mixtures of these solvents) must be present to prevent processing Solution is possible. As low molecular structural units come here z. B. various complexes in question, which, for example, in the application WO 02/068435, WO 02/081488, EP 1239526 and the undisclosed logon letter DE 10238903.9 are described. In particular, the halogenated complexes described in WO 02/068435 are also suitable as starting compounds for TRIP3, since the halogen functionality allows easy derivatization of the complexes having structural units of the formula (1) to (5). Suitable dendrimer structures for TRIP1 or TRIP3 complexes are those which are described, for example, in the application documents WO 99/21935, WO 01/059030 and WO 02/066552. The corresponding descriptions are considered as part of the registration via quotation.

The triplet emitter TRIP2 is covalently incorporated into the polymer chain of POLY2 (BLEND2). To enable the incorporation of TRIP2 into POLY2, functional polymerizable groups must be present on TRIP2. Examples of corresponding brominated complexes that can be used as monomers in polymerization reactions are described in WO 02/068435 and in the application not disclosed DE 10350606.3 , The corresponding descriptions are considered as part of the registration via quotation.

The inventive mixture BLEND1 is obtained by giving the polymer POLY1 a triplet emitter TRIP1 be mixed.

The inventive mixture BLEND2 is obtained by adding to the polymer POLY2 compound VERB1, containing structural units L = X, or structural units according to formula (1) to (5) is mixed.

The inventive mixture BLEND3 is obtained by adding to the polymer POLY3 compound VERB1, containing structural units L = X, or structural units according to formula (1) to (5), and a triplet emitter TRIP1 be mixed.

The inventive mixture BLEND4 is obtained by adding POLY3 units TRIP3 to the polymer become.

It can also be preferred, in BLEND1 to BLEND4 any further conjugated, partially conjugated, crossed-conjugated or non-conjugated polymers, Oligomers, dendrimers or any other low molecular weight compounds interfere. The addition of additional components may prove appropriate for some applications prove useful: For example, by adding a electronically active substance the hole or electron injection, the hole or electron transport or the charge balance in appropriate blend are regulated. The additional component can also facilitate the singlet-triplet transfer. But also the Adding electronically inert compounds may be helpful for example, the viscosity a solution or to control the morphology of the formed film. The Blends thus obtained are also the subject of the invention.

• (A) 1–99,5 mol%, bevorzugt 5–80 mol%, besonders bevorzugt 10–50 mol% einer oder mehrerer Wiederholeinheiten MONO1 mit mindestens einer Struktureinheit L=X, wobei für Symbole L, X, R¹, R², R³, R⁴, R⁵ und R⁶ dieselbe Bedeutung besitzen, wie oben beschrieben; und
• (B) 0,5–95 mol%, bevorzugt 1–50 mol%, besonders bevorzugt 2–25 mol% eines oder mehrerer Triplett-Emitter TRIP2;

mit der Maßgabe, dass Polymere, die einerseits kovalent gebundene Triplett-Emitter und andererseits Einheiten gemäß Formel (a) enthalten, von der Erfindung ausgenommen sind:

worin Ar¹ und Ar² jeweils unabhängig eine tetravalente aromatische Kohlenwasserstoffgruppe oder eine tetravalente heterocyclische Gruppe bedeuten;
eine der Einheiten X¹ und X² bedeutet C(=O) oder C(R¹)(R²) und die andere bedeutet O, S, C(=O), S(=O), SO₂, Si(R³)(R⁴), N(R⁵), B(R⁶), P(R⁷) oder P(=O)(R⁸);
wobei in der Formel (a) die Reste R¹, R², R³, R⁴, R⁵, R⁶, R⁷ und R⁸ jeweils unabhängig ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Alkoxygruppe, eine Alkylthiogruppe, eine Alkylaminogruppe, eine Arylgruppe, eine Aryloxygruppe, eine Arylthiogruppe, eine Arylaminogruppe, eine Arylalkylgruppe, eine Arylalkoxygruppe, eine Arylalkylthiogruppe, eine Arylalkylaminogruppe, eine Acylgruppe, eine Acyloxygruppe, eine Amidgruppe, eine Imingruppe, eine substituierte Silylgruppe, eine substituierte Silyloxygruppe, eine substituierte Silylthiogruppe, eine substituierte Silylaminogruppe, eine monovalente heterocyclische Gruppe, eine Arylalkenylgruppe, eine Arylethinylgruppe oder eine Cyanogruppe) bedeuten,
M bedeutet eine Gruppe, die durch Formel (b), Formel (c) oder Formel (d) dargestellt wird. -Y¹-Y²- Formel (b)worin Y¹ und Y² jeweils unabhängig O, S, C(=O), S(=O), SO₂, C(R⁹)(R¹⁰), Si(R¹¹)(R^{1 2}), N(R^{1 3}), B(R¹⁴), P(R¹⁵) oder P(=O)(R¹⁶) bedeuten,
wobei in der Formel (b) die Reste R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ und R¹⁶ jeweils unabhängig ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Alkoxygruppe, eine Alkylthiogruppe, eine Alkylaminogruppe, eine Arylgruppe, eine Aryloxygruppe, eine Arylthiogruppe, eine Arylaminogruppe, eine Arylalkylgruppe, eine Arylalkoxygruppe, eine Arylalkylthiogruppe, eine Arylalkylaminogruppe, eine Acylgruppe, eine Acyloxygruppe, eine Amidgruppe, eine Imingruppe, eine substituierte Silylgruppe, eine substituierte Silyloxygruppe, eine substituierte Silylthiogruppe, eine substituierte Silylaminogruppe, eine monovalente heterocyclische Gruppe, eine Arylalkenylgruppe, eine Arylethinylgruppe oder eine Cyanogruppe) bedeuten,
wobei Y¹ und Y² nicht identisch sind, wenn Y¹ nicht C(R⁹)(R1¹⁰) oder Si(R¹¹)(R¹²) ist.] -Y³=Y⁴- Formel (c)worin Y³ und Y⁴ jeweils unabhängig N, B, P, C(R¹⁷) oder Si(R¹⁸) bedeuten; in der Formel (c) die Reste R¹⁷ und R¹⁸ jeweils unabhängig ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Alkoxygruppe, eine Alkylthiogruppe, eine Alkylaminogruppe, eine Arylgruppe, eine Aryloxygruppe, eine Arylthiogruppe, eine Arylaminogruppe, eine Arylalkylgruppe, eine Arylalkoxygruppe, eine Arylalkylthiogruppe, eine Arylalkylaminogruppe, eine Acylgruppe, eine Acyloxygruppe, eine Amidgruppe, eine Imingruppe, eine substituierte Silylgruppe, eine substituierte Silyloxygruppe, eine substituierte Silylthiogruppe, eine substituierte Silylaminogruppe, eine monovalente heterocyclische Gruppe, eine Arylalkenylgruppe, eine Arylethinylgruppe oder eine Cyanogruppe bedeuten; -Y⁵- Formel (d) worin Y⁵ O, S, C(=O), S(=O), SO₂, C(R¹⁹)(R²⁰), Si(R²¹)(R²²), N(R²³), B(R²⁴), P(R²⁵) oder P(=O)(R²⁶) bedeutet;
wobei in de Formel (d) die Reste R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵ und R²⁶ jeweils unabhängig ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Alkoxygruppe, eine Alkylthiogruppe, eine Alkylaminogruppe, eine Arylgruppe, eine Aryloxygruppe, eine Arylthiogruppe, eine Arylaminogruppe, eine Arylalkylgruppe, eine Arylalkoxygruppe, eine Arylalkylthiogruppe, eine Arylalkylaminogruppe, eine Acylgruppe, eine Acyloxygruppe, eine Amidgruppe, eine Imingruppe, eine substituierte Silylgruppe, eine substituierte Silyloxygruppe, eine substituierte Silylthiogruppe, eine substituierte Silylaminogruppe, eine monovalente heterocyclische Gruppe, eine Arylalkenylgruppe, eine Arylethinylgruppe oder eine Cyanogruppe) bedeuten;
Z₁ bedeutet-CR³⁶=CR³⁷- oder-C≡C-; R³⁶ und R³⁷ bedeuten jeweils unabhängig ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine monovalente heterocyclische Gruppe oder eine Cyanogruppe; d bedeutet 0 oder 1.Another object of the invention are polymers POLY4 containing

• (A) 1-99.5 mol%, preferably 5-80 mol%, particularly preferably 10-50 mol% of one or more repeat units MONO1 having at least one structural unit L = X, where for symbols L, X, R ¹ , R ² R ³ , R ⁴ , R ⁵ and R ^{6 have the} same meaning as described above; and
• (B) 0.5-95 mol%, preferably 1-50 mol%, particularly preferably 2-25 mol% of one or more tri plate emitter TRIP2;

with the proviso that polymers which contain, on the one hand, covalently bound triplet emitters and, on the other hand, units of the formula (a) are excluded from the invention:

wherein Ar ¹ and Ar ² each independently represent a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group;
one of the units X ¹ and X ² is C (= O) or C (R ¹ ) (R ² ) and the other is O, S, C (= O), S (= O), SO ₂ , Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (= O) (R ⁸ );
wherein in the formula (a), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a Alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkylamino group, an acyl group, an acyloxy group, an amide group, an imine group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group),
M represents a group represented by formula (b), formula (c) or formula (d). -Y ¹ -Y ² - formula (b) wherein Y ¹ and Y ² are each independently O, S, C (= O), S (= O), SO _2, C (R ⁹⁾ (R ¹⁰⁾ Si (R ¹¹⁾ (R ^{1 2),} N ( R ^{1 3} ), B (R ¹⁴ ), P (R ¹⁵ ) or P (= O) (R ¹⁶ ),
wherein in the formula (b), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a Alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkylamino group, an acyl group, an acyloxy group, an amide group, an imine group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group),
where Y ¹ and Y ^{2 are} not identical if Y ^{1 is} not C (R ⁹ ) (R ^{1 10} ) or Si (R ¹¹ ) (R ¹² ).] -Y ³ = Y ⁴ - formula (c) wherein Y ³ and Y ^{4 are} each independently N, B, P, C (R ¹⁷ ) or Si (R ¹⁸ ); in the formula (c), the radicals R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group an arylalkylthio group, an arylalkylamino group, an acyl group, an acyloxy group, an amide group, an imine group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group; -Y ⁵ - formula (d) wherein Y ^{5 is} O, S, C (OO), S (OO), SO ₂ , C (R ¹⁹ ) (R ²⁰ ), Si (R ²¹ ) (R ²² ), N (R ²³ ), B ( R ²⁴ ), P (R ²⁵ ) or P (= O) (R ²⁶ );
wherein in formula (d) the radicals R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a Alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkylamino group, an acyl group, an acyloxy group, an amide group, an imine group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group);
Z _{1 represents} -CR ³⁶ = CR ³⁷ - or -C≡C-; R ³⁶ and R ³⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group; d means 0 or 1.

wobei die Symbole X, Y, Z und R¹–R⁶ dieselbe Bedeutung besitzen, wie oben beschrieben.Preferred structural units L = X are units of the formulas (1) to (5)

where the symbols X, Y, Z and R ¹ -R ^{6 have the} same meaning as described above.

there the incorporation of repeat units MONO1, as for the polymer POLY1, in the main and / or side chain of POLY4. Likewise, the installation of the triplet emitter TRIP2, as for POLY2 described in the main and / or side chain of POLY4.

The Polymer POLY4 can be conjugated, partially conjugated, cross-conjugated or nonconjugated.

POLY4 may contain further structural elements as described for POLY1 to POLY3. Likewise, it can be statistically, alternately or block-like, may be linear, branched or dendritic. The synthesis of POLY4 takes place as for POLY1 to POLY3 described. Particularly preferred repeat units MONO1 Here are structures according to formula (6) to (148).

Of Furthermore, it may be preferable to have any further conjugated in POLY4, partially conjugated, crossed-conjugated or non-conjugated polymers, Oligomers, dendrimers or any other low molecular weight compounds to intervene, so that here too a mixture arises. Here can it prefers extra Intermix compounds VERB1, giving the total share of structures L = X, or structures according to formula (1) to (5) increased becomes. Likewise, the additional Mixing in of further triplet emitters TRIP1 may be preferred. But The addition of other components may also be useful for some applications prove. For example, by adding an electronic active substance the Lochbzw. Electron injection, the hole or Electron transport or the charge balance of the resulting blend be regulated. The additional component can also be the singlet-triplet transfer facilitate. However, the addition of electronically inert compounds can be helpful, for example, the viscosity of a solution or to control the morphology of the formed film. The way out POLY4 obtained mixtures are also the subject of the invention.

The Representation from BLEND1 to BLEND6 (and possibly blends off POLY4 and other components) is done as follows: The Individual components of the blend are combined in a suitable mixing ratio and in a suitable solvent solved. Suitable solvents are for example, toluene, anisole, xylenes, methylanisole, methylnaphthalene, Chlorobenzene, cyclic ethers (eg, dioxane, THF, methyldioxane), Amides (eg NMP, DMF) or mixtures of these solvents. Alternatively, the Components of the blend can also be solved individually. The solution of Blends receives one in this case by assembling the individual solutions in the suitable mixing ratio. The dissolving process is preferred in an inert atmosphere and optionally at elevated Temperature instead. The blend is usually not as a solid (by repeated failures) isolated but directly from solution further processed; however, blends that have been precipitated once again are Subject of the invention.

One suitable ratio of the individual components is for example a mixture that total 1-99.5 mol%, preferably 5-99 mol%, more preferably 10-80 mol%, especially 10-50 mol% units L = X, or units according to formulas (1) to (5) (MONO1 in POLY1 or VERB1) and 0.5-95 mol%, preferably 0.5-80 mol%, more preferably 1-50 mol%, especially 2 -25 contains mol% TRIP1, TRIP2 and TRIP3, where the information on the total existing units (Blendbestandteile or repeating units in the polymer). This is independent of whether the components are covalently bound to a polymer or mixed are.

• • Die Löslichkeit in organischen Lösemitteln ist im Allgemeinen besser als die Löslichkeit der Polymere und Mischungen gemäß Stand der Technik. Die bessere Löslichkeit bietet einen Vorteil beispielsweise gegenüber überbrückten Carbazol-Einheiten, die als nächst liegender Stand der Technik angeführt werden, da dort häufig der maximale Carbazolanteil durch die schlechte Löslichkeit festgelegt wird, jedoch in manchen Fällen ein höherer Carbazolanteil für die weitere Verbesserung der Device-Eigenschaften wünschenswert wäre.
• • Die chemische Zugänglichkeit der Einheiten gemäß Formel (1) bis (5), sowohl als Blendbestandteil wie auch als Monomer, ist unproblematisch. Teilweise sind diese Blendbestandteile und Monomere auch kommerziell erhältlich. Dies ist ein entscheidender Vorteil gegenüber beispielsweise den überbrückten Carbazol-Einheiten ( DE 10328627.6 ), deren Synthese und Aufreinigung deutlich aufwändiger ist.
• • Die erfindungsgemäßen Mischungen und Polymere zeigen eine höhere Sauerstoffstabilität als Mischungen und Polymere gemäß Stand der Technik. Dadurch vereinfacht sich die Herstellung dieser Verbindungen und Mischungen und auch deren Verarbeitung, was einen erheblichen praktischen Vorteil darstellt.
• • Die Effizienz der Lichtemission des Triplett-Emitters ist in erfindungsgemäßen Mischungen BLEND1 bis BLEND6 bzw. Polymeren POLY4 vergleichbar oder besser im Vergleich zu Polymeren und Mischungen gemäß Stand der Technik.

The mixtures according to the invention BLEND1 to BLEND6 and polymers POLY4 have the following surprising advantages over the above-mentioned prior art, inter alia:

• Solubility in organic solvents is generally better than the solubility of the polymers and blends of the prior art. The better solubility offers an advantage, for example, over bridged carbazole units, which are listed as the closest prior art, since the maximum carbazole content is often determined by the poor solubility, but in some cases If a higher carbazole content would be desirable for the further improvement of the device properties.
• • The chemical accessibility of the units according to formula (1) to (5), both as a blend component as well as a monomer, is not a problem. In part, these blend components and monomers are also commercially available. This is a decisive advantage over, for example, the bridged carbazole units ( DE 10328627.6 ), whose synthesis and purification is significantly more expensive.
• The mixtures and polymers according to the invention show a higher oxygen stability than mixtures and polymers according to the prior art. This simplifies the preparation of these compounds and mixtures and also their processing, which represents a significant practical advantage.
• The efficiency of the light emission of the triplet emitter is comparable or better in mixtures according to the invention BLEND1 to BLEND6 or polymers POLY4 compared to polymers and mixtures according to the prior art.

The blends BLEND1 to BLEND6 or the polymers POLY4 can be used in PLEDs, in particular as electroluminescent materials (emitting materials). For the construction of PLEDs, a general method is usually used, which must be adapted accordingly for the individual case. Such a method has been used, for example, in DE 10249723.0 described in detail.

object The invention therefore also relates to the use of a blend BLEND1 according to the invention to BLEND6 or a polymer according to the invention POLY4 in one PLED as electroluminescent material.

object The invention is therefore also a PLED with one or more Layers, wherein at least one of these layers one or more inventive mixtures BLEND1 to BLEND6 or polymers according to the invention POLY4 contains.

in the present application text and in the following examples is on the use of mixtures according to the invention BLEND1 to BLEND6 or inventive polymers POLY4 in relation aimed at PLEDs and the corresponding displays. Despite this restriction the description is for the skilled person without further inventive step possible, the polymers of the invention or blends too for further uses in other electronic devices (devices) to use, for. For example organic solar cells (O-SCs), non-linear optics or organic ones Laser diodes (O-lasers), to name only a few applications. Also these are the subject of the present invention.

The Invention is illustrated by the following examples, without thereby restricting them want.

Examples

Example 1: Synthesis of Co-monomers for the polymers

The synthesis of the co-monomers used for conjugated polymers is described in WO 02/077060 and the references cited therein, as well as in the application not disclosed DE 10337346.2 described in detail. The monomers M1 to M5 and M8 used in the following are reproduced here for the sake of clarity:

Example 2: 4,4'-Dibromobenaophenone (Monomer M6 according to formula (1))

4,4'-dibromobenzophenone was obtained by Fluka in a purity of 98% and by more Recrystallization from ethanol to a purity of 99.7% (according to HPLC) purified.

Example 3: Synthesis of Bis (4-bromophenyl) -phenylphosphine oxide (monomer M7 according to formula (3))

a) Synthesis of bis (4-bromophenyl) phenylphosphine

In a dry 1000 mL four-necked flask with internal thermometer, stirrer, argon overlay and 2 dropping funnels, 33.9 g (144 mmol) of dibromobenzene were dissolved in 300 mL of dry THF and cooled to -70 ° C. Within 30 min. were added dropwise 90 mL (144 mmol) of n-butyllithium (1.6M in hexane) and stirred for 1 h at this temperature. Then, at this temperature, 12.9 g (9.75 ml, 72 mmol) of dichlorophenyl Phosphane in 60 mL dry THF was added dropwise. Overnight allowed to come to room temperature. 20 mL of methanol was added and the reaction was evaporated to dryness. The residue was taken up in dichloromethane, filtered and the solvent removed in vacuo. The compound was used without further purification for the following reaction. b) Synthesis of bis (4-bromophenyl) phenylphosphine oxide

In a 500 ml four-necked flask with internal thermometer, mechanical stirrer, reflux condenser and dropping funnel, 10.05 g (24 mmol) of bis (4-bromophenyl) phenylphosphine were dissolved in 200 ml of ethyl acetate and cooled to 5 ° C. internal temperature. This was within 30 min. a solution of 2.25 mL (26.4 mmol) of N ₂ O ₂ (35%) in 17.5 mL of water was added dropwise and stirred for a further 12 h at room temperature. Subsequently, 25 mL of saturated sodium sulfite solution were added, the organic phase separated, washed twice with saturated sodium sulfite solution and dried over sodium sulfate. The solvent was removed in vacuo. The purification was carried out first by column chromatography on silica with a solvent mixture of initially hexane: ethyl acetate 2: 1 to hexane: ethyl acetate 1: 1. Further purification was carried out by recrystallization from heptane / toluene. There were obtained 6.5 g of product in a purity of 99.7% (according to HPLC). ¹ H-NMR (500 MHz, _CDCl3): [ppm] 7.46 to 7.66 (m). ³¹ P-NMR _(CDCl3): [ppm] 28,40.

Example 4: Blend components V1 (VERB1 according to formula (1))

As the blend component V1, the following ketone was used by way of example, the synthesis of which was already described in DE 10317556.3 is described:

As the blend component V2, the following phosphine oxide was used by way of example, whose synthesis in DE 10330761.3 is described:

Example 5: Structural units TRIP1 for use in blends

The compounds TRIP1 used by way of example here are derivatives of tris (phenylpyridyl) iridium (III). The synthesis of these compounds has already been described in the application WO 02/081488 and in the unpublished patent application DE 10238903.9 , For a review, the iridium complexes used by way of example here are reproduced below:

Example 6: Synthesis of conjugated Polymers POLY3

The synthesis of conjugated polymers POLY3 which contain no units according to formulas (1) to (5) and no compounds TRIP2 has already been described, for example, in the patent applications WO 02/077060, DE 10143353.0 . DE 10249723.0 and DE 10304819.7 described. These are via quote part of the present application.

Example 7: Synthesis of Polymer P1

The synthesis was carried out according to the method described in WO 03/048224. The following were used: 1.6013 g (2 mmol) of monomer M1, 0.8118 g (1.2 mmol) of monomer M2, 0.3035 g (0.4 mmol) of monomer M5, 0.1744 g (0.4 mmol ) Monomer M7 and 2.03 g (2.2 equivalents) of potassium phosphate hydrate in 19 mL dioxane, 6 mL toluene and 12 mL H ₂ O. The catalyst used was: 0.45 mg Pd (OAc) ₂ and 3.65 mg P (o-tolyl) ₃ . After working up, 1.57 g of polymer were obtained which had a molecular weight M _n 58,000 and M _w 185,000 (GPC in THF with polystyrene standard).

Example 8: Synthesis of Polymer P2:

The synthesis was carried out according to the method described in WO 03/048224. The following were used: 1.2889 g (2 mmol) of monomer M3, 0.7951 g (1.2 mmol) of monomer M4, 0.3035 g (0.4 mmol) of monomer M5, 0.1360 g (0.4 mmol ) Monomer M6 and 2.03 g (2.2 equivalents) of potassium phosphate hydrate in 19 mL dioxane, 6 mL toluene, and 12 mL H ₂ O. The catalyst used was: 0.45 mg Pd (OAc) ₂ and 3.65 mg P (o-tolyl) ₃ . After work-up, 1.72 g of polymer were obtained which had a molecular weight M _n 87,000 and M _w 219,000 (GPC in THF with polystyrene standard).

Example 10: Production the blends

The Preparation of the mixtures was carried out by dissolving the blend components in desired relationship and in the desired Concentration in a suitable solvent. As a solvent toluene was used here. The dissolution process was in an inert the atmosphere at 60 ° C carried out. The solution was without isolation of the mixture (repeated precipitation of the Solids) directly processed.

Example 11: Preparation polymeric light-emitting diodes (PLEDs)

How PLEDs can be represented is in DE 10249723.0 and the literature cited therein. It has been found that the polymers and blends according to the invention form more homogeneous films than the polymers and blends according to the prior art. Without wishing to be bound by any particular theory, we suspect that this may be due to the better solubility of these compounds.

Example 12: 2,7-Dibromo-9-keto-10- (2-ethylhexyl) -10-methoxy-dihydrophenanthrene (Monomer M9 according to formula (1))

a) Synthesis of 2,7-dibromo-9-keto-10- (2-ethylhexyl) -10-hydroxy-dihydrophenanthrene

In a 500 mL four-necked flask with reflux condenser, mechanical stirrer, internal thermometer, Argonüberlagerung and dropping funnel 4.6 g (185 mmol) of magnesium were submitted. The apparatus was baked, a granule of iodine was added, then 37.6 mL (185 mmol) of ethylhexyl bromide in 175 mL of absolute THF was added dropwise. It was heated to reflux until all the magnesium was consumed. After cooling to room temperature, the Grignard solution was transferred to a dropping funnel. In a 1000 ml four-necked flask with mechanical stirrer, internal thermometer, reflux condenser, dropping funnel and argon superposition, 45 g (123 mmol) of dibromophenanthrenequinone were suspended at 0 ° C. in 300 ml of THF. For this purpose, the Grignard solution was added dropwise so that the internal temperature did not exceed 25 ° C. It was then stirred overnight at room temperature. 200 ml of sat. NH ₄ Cl solution was added. Ethyl acetate was added, washed twice with sat. NaCl, dried over Na ₂ SO ₄ and the solvent removed. The residue was boiled in 250 mL hexane, filtered from green solid and crystallized. The yield was 39.3 g (67% of theory). ¹ H-NMR _(CDCl3): [ppm] = 8:03 (m, 1 H), 7.91 (m, 1 H), 7.78 (m, 2 H), 7.62 (m, 1 H), 7:52 (m, 1 H), 3.91 (s, interchangeable with D ₂ O, 1 H), 1.72 (m, 2 H), 1.33 (m, 1 H), 1.10 (m, 8 H), 0.81 (m, 3 H), 0.65 (m, 3H).

b) Synthesis of 2,7-dibromo-9-keto-10- (2-ethylhexyl) -10-methoxy-dihydrophenanthrene

3.3 g (81.5 mmol) of NaH (60% dispersion in mineral oil) in 30 ml of DMSO were placed in a heated 500 ml four-necked flask with mechanical stirrer, condenser, thermometer and dropping funnel. To this was added dropwise 21.6 g (54.3 mmol) of 2,7-dibromo-9-keto-10- (2-ethylhexyl) -10-hydroxy-dihydrophenanthren in 60 mL of DMSO slowly, and it was 30 min. stirred at room temperature. Then 5.1 mL (81.5 mmol) of methyl iodide were added dropwise over 1 h with ice-cooling. It was stirred for 2 days at room temperature, then was cooled to 5 ° C, 90 mL semiconc. NH ₄ OH added dropwise, 100 mL MeOH was added dropwise, stirred for 30 min in an ice bath, filtered off, washed with MeON and dried in a vacuum oven at 60 ° C. The crude product was recrystallized several times from methanol. The yield was 11.0 g (41% of theory) with a purity of> 99.8%.
Yield: 17.3g (64.5%). ¹ H-NMR (CDCl ₃ ): [ppm] = 8.16 (d, ⁴ J _HH = 2.3 Hz, 1 H), 7.78 (m, 4 H), 7.56 (dd, ³ J _HH = 8.7 Hz, ⁴ J _HH = 2.3Hz, 2H), 3.17 (s, 3H), 1.71 (m, 2H), 1.26 (m, 1H), 1.06 (m, 8H), 0.77 (m, 3H), 0.59 ( m, 3 H).

Example 13: Synthesis of 2,7-dibromo-9-keto-10,10-bis (4-tert-butylphenyl) dihydrophenanthrene (M10 monomer of formula (1))

200 ml of para-toluenesulfonic acid and 10 g (15.8 mmol) of 2,7-dibromo-9,10-bis (4-tert-butylphenyl) -9,10- in a 250 mL round bottom flask equipped with magnetic stirrer and condenser with condenser were used. dihydro-dihydrophenanthren suspended in 80 mL of toluene and boiled for 3 h on a water. The precipitate was filtered off, washed with methanol, recrystallized twice from toluene and dried under vacuum. The yield was 6.3 g (65% of theory) with a purity of> 99.9%. ¹ H-NMR (CDCl ₃ ): [ppm] = 8.06 (d, ⁴ J _HH = 2.0 Hz, 1 H), 7.80 (d, ³ J _HH = 8.7 Hz, 1 H), 7.73 (d, ³ J _HH = 8.7 Hz, 1 H), 7.68 (dd, ³ J _HH = 8.4 Hz, ⁴ J _HH = 2.0 Hz, 1 H), 7.55 (dd, ³ J _HH = 8.3 Hz, ⁴ J _HH = 2.0 Hz, 1 H ), 7.26 (m, 4 H), 6.91 (d, ⁴ J _HH = 2.0 Hz, 1 H), 6.83 (m, 4 H), 1.26 (s, 18 H).

Example 14: Non-conjugated Polymers (POLY1) P6 and P7

polystyrene P6 of melt index 7.5 was commercially obtained from Aldrich. The synthesis of poly (vinylbenzophenone) P7 was carried out according to Helv. Chim. Acta 1999, 82, 338-346.

Example 15: Further blend components

Other blending components used were the spiro-triarylamine derivative AMIN1 and the spiro-oxadiazole derivative OX1, the structures of which are shown below:

Example 16: Overview of the synthesized and used polymers

table 1 gives an overview of the Composition of some of the synthesized and used in the devices Polymers.

Tabelle 1: Übersicht über die Zusammensetzung einiger Polymere

Table 1: Overview of the composition of some polymers

Example 17: Device examples

Table 2 gives an overview of various blends of polymers and triplet emitters, optionally with further components.

Claims (28)

Mixtures (blends) containing (A) at least one polymer, (B) at least one structural unit L = X, where for the symbols used: L is identical or different at each occurrence (R ¹ ) (R ² ) C, (R ¹ ) P, (R ¹ ) As, (R ¹ ) Sb, (R ¹ ) Bi, (R ¹ ) (R ² ) (R ³ ) P, (R ¹ ) (R ² ) (R ³ ) As, (R ¹ ) (R ² ) (R ³ ) Sb, (R ¹ ) (R ² ) (R ³ ) Bi, (R ¹ ) (R ² ) S, (R ¹ ) (R ² ) Se, (R ¹ ) (R ² ) Te, (R ¹ ) (R ² ) S (= O), (R ¹ ) (R ² ) Se (= O) or (R ¹ ) (R ² ) Te (= O); X is the same or different at each occurrence as O, S, Se or NR ⁴ , with the proviso that X is not S or Se when L is S, Se or Te; R ¹ , R ² , R ³ are each, identically or differently H, F, CN, N (R ⁴ ) ₂ , a straight-chained, branched or cyclic alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, which are represented by R 1 ^{5 may be} substituted or unsubstituted, wherein one or more non-adjacent CH ₂ groups by -R ⁶ C = CR ⁶ -, -C≡C-, Si (R ⁶ ) ₂ , Ge (R ⁶ ) ₂ , Sn ( R ⁶ ) ₂ , C = O, C = S, C = Se, C = NR ⁶ , -O-, -S-, -NR ⁶ - or -CONR ⁶ - may be replaced and wherein one or more H atoms be replaced by F, Cl, Br, I, CN or NO ₂ , or an aryl, aryloxy or heteroaryl group having 1 to 40 carbon atoms, which may be substituted by one or more radicals R ⁵ , wherein two or more Substituents R ¹ , R ² and / or R ^{3 may} together form a mono- or polycyclic, aliphatic or aromatic ring system; not all substituents R ¹ to R ³ on a structural unit may be H or F; R ⁴ is the same or different at each occurrence as a straight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22 C atoms, in which also one or more non-adjacent C atoms is replaced by -R ⁶ C = CR ⁶ -, -C ≡C-, Si (R ⁶ ) ₂ , Ge (R ⁶ ) ₂ , Sn (R ⁶ ) ₂ , -NR ⁶ -, -O-, -S-, -CO-O-, -O-CO-O - Can be replaced, wherein one or more H atoms may be replaced by fluorine, an aryl, heteroaryl or aryloxy group having 1 to 40 carbon atoms, which may also be substituted by one or more radicals R ⁶ , or OH or N (R ⁵ ) ₂ ; R ⁵ is the same or different at each occurrence as R ⁴ or CN, B (R ⁶ ) ₂ or Si (R ⁶ ) ₃ . R ⁶ is the same or different at each occurrence, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms; and (C) at least one triplet emitter; with the proviso that mixtures of two polymers are excluded, in which the polymer contains a covalently bound triplet emitter and the other is a copolymer of TPD units and Diphenylsulfonether- or Diphenylketonether units. Mixtures (blends) according to claim 1, characterized in that the structural units L = X are selected from the formulas (1) to (5),

wherein the symbols used have the following meaning: X is the same or different at each occurrence O, S, Se or NR ⁴ , with the proviso that X for formula (4) and (5) may not be S or Se; Y is the same or different P, As, Sb or Bi at each occurrence; Z is the same or different at each occurrence, S, Se or Te; R ¹ to R ⁶ have the same meaning as described in claim 1. Mixtures according to claim 1 and / or 2, characterized in that these at least 0.5 wt.% at least one polymer, at least 1% by weight of at least one Structural unit L = X, or a structural unit according to the formulas (1) to (5) and at least 0.5 wt.% Of at least one triplet emitter. Mixtures (BLEND1) according to one or more of claims 1 to 3, containing (A) 5-99.5 % By weight of at least one polymer (POLY1) containing 1-100 mol% of one or more Repeating units (MONO1) containing at least one structural unit L = X, or at least one structural unit according to formula (1) to (5), contains, and (B) 0.5-95 % By weight of one or more triplet emitters (TRIP1). Mixtures (BLEND2) according to one or more of claims 1 to 3, containing (A) 0.5-99 % By weight of at least one polymer (POLY2) containing 0.5-99.5 mol% of one or more Contains triplet emitter (TRIP2) covalently bound, and (B) 1-99.5% by weight at least one compound (VERB1) containing at least one structural unit L = X, or at least one structural unit according to formula (1) to (5) contains and in is able to form glassy layers at room temperature. Mixtures (BLEND3) according to one or more of claims 1 to 3, containing (A) 0.5-98.5 % By weight of any polymer (POLY3), and (B) 1-99% by weight at least one compound (VERB1) containing at least one structural unit L = X, or at least one structural unit according to formula (1) to (5) contains and in is able to form vitreous layers at room temperature, and (C) 0.5-95 % By weight of one or more triplet emitters (TRIP1). Mixtures (BLEND4) according to one or more of claims 1 to 3, containing (A) 0.5-98.5 % By weight of at least one polymer (POLY3); and (B) 1.5 to 99.5 % By weight of a compound (TRIP3) containing at least one structural unit L = X, or at least one structural unit of the formula (1) to (5) covalently bound to one or more triplet emitters, wherein the Binding between the triplet emitter and the structural unit L = X can be done at any position of the two units with the restriction, in (TRIP3) at least one group X is free and not a metal atom must be coordinated. Mixtures according to one or more of the claims 1 to 7, characterized in that the polymers (POLY1 to POLY3) conjugated, partially conjugated, crossed-conjugated or non-conjugated are. Mixtures according to one or more of the claims 1 to 8, characterized in that the polymers POLY1 to POLY3 contain further structural elements. Mixtures according to one or more of claims 1 to 9, characterized in that for the symbols of the formulas (1) to (5) the following applies: X is O, S or NR ⁴ ; Y stands for P or As; Z stands for S or Se; R ¹ -R ⁶ are defined according to claim 1 and 2, wherein at each structural unit according to formula (1) to (5) at least one of the substituents R ¹ to R ^{3 represents} an aryl or heteroaryl group having 1 to 40 carbon atoms, which may be substituted or unsubstituted with one or more substituents R ⁴ . Mixtures according to one or more of claims 1 to 10, characterized in that for the symbols of the formulas (1) to (5): X is O or NR ⁴ ; Y stands for P; Z stands for S; R ¹ -R ⁶ are defined according to claim 1 and 2, wherein at each structural unit according to formula (1) to (5) at least two of the substituents R ¹ to R ³ aryl or heteroaryl groups having 1 to 40 carbon atoms, with one or more substituents R ^{4 may be} substituted or unsubstituted. Mixtures according to one or more of the claims 1 to 11, characterized in that the repeat units (MONO1), the structural elements L = X, or structural elements according to formula (1) to (5) are selected from the formulas (6) to (148), which may be substituted or unsubstituted. Mixtures according to one or more of claims 1 to 11, characterized in that the polymers are selected from the classes of aromatic polyketones, aromatic polyphosphine oxides or aromatic polysulfones, which may be substituted for better solubility, the polycarboxylic acid derivatives, backbone polyester, side chains Polyesters, poly (glycolic acids), poly (lactic acids), poly (ε-caprolactones), polyarylates, poly (hydroxybenzoic acids), poly (alkylene terephthalates), polycarboxylic acid anhydrides, polyamides, poly (ε-caprolactams), polypeptides, polyaramides, polybenzamides, polyimides , Polyamide-imides), poly (ester-imides), poly (ether-imides), polycarbonates, poly (ester-co-carbonates), poly (isocyanurates), polyurethanes, polyester-polyurethanes, poly (terephthalates), poly (acrylates), poly (phenylacrylates) , Poly (cyanoacrylates), poly (vinyl esters), poly (vinyl acetates), side chain polyphosphine oxides, polyether ketones (PEK), polyether sulfones, polysulfonamides, polysulfone imides, Po ly (vinyl ketones), aromatic polyvinyl ketones, substituted or unsubstituted poly (vinylbenzophenones), polystyrene-analogous ketones, polycarbazenes, poly-nitriles, poly-isonitriles, polystyrene, PVK (polyvinylcarbazole) or derivatives thereof. Mixtures according to one or more of the claims 1 to 11, characterized in that the compound (VERB1), the Structural elements L = X, or structural elements according to formulas (1) to (5) contains, from the Formulas (6) to (148) selected which may be substituted or unsubstituted. Mixtures according to one or more of the claims 1 to 11, characterized in that the compound (TRIP3) structural elements contains which are selected from the formulas (6) to (148) which substitutes or unsubstituted. Mixtures according to one or more of the claims 1 to 15, characterized in that the triplet emitter atoms from the periodic table of the elements with an ordinal number of more as 36 included. Mixtures according to claim 16, characterized in that the triplet emitters contain d or f transition metals. Mixtures according to claim 17, characterized in that the triplet emitter metals of group 8 to 10 contain. Mixtures according to one or more of the claims 1 to 18, characterized in that the mixtures still further molecules be mixed, the low molecular weight, oligomeric, dendritic or can be polymeric. Mixtures according to one or more of the claims 1 to 19, characterized in that the mixture additionally compounds, the structural units L = X, or structural units according to formula (1) to (5), to be mixed. Mixtures according to one or more of the claims 1 to 20, characterized in that the total proportion of structural units according to formula (1) to (5) 10-50 mol%. Polymers POLY4 containing (A) 1-99.5 mol% of one or more repeating units MONO1 having at least one structural unit L = X, where for symbols L, X, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have the} same meaning as described in claim 1; (B) 0.5-95 mol% of one or more triplet emitters TRIP2; with the proviso that polymers which contain, on the one hand, covalently bound triplet emitters and, on the other hand, units of the formula (a) are excluded from the invention:

wherein Ar ¹ and Ar ² each independently represent a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group; one of the units X ¹ and X ² is C (= O) or C (R ¹ ) (R ² ) and the other is O, S, C (= O), S (= O), So ₂ , Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (= O) (R ⁸ ); wherein in the formula (a), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a Alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkylamino group, an acyl group, an acyloxy group, an amide group, an imine group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group), M represents a group represented by formula (b), formula (c) or formula (d). -Y ¹ -Y ² - formula (b) wherein Y ¹ and Y ^{2 are} each independently O, S, C (= O), S (= O), So ₂ , C (R ⁹ ) (R ¹⁰ ), Si (R ¹¹ ) (R ¹² ), N (R ¹³ ), B (R ¹⁴ ), P (R ¹⁵ ) or P (= O) (R ¹⁶ ), where in the formula (b) the radicals R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, a Arylalkylamino group, an acyl group, an acyloxy group, an amide group, an imine group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group), wherein Y is ¹ and Y ^{2 are} not identical if Y ^{1 is} not C (R ⁹ ) (R ¹⁰ ) or Si (R ¹¹ ) (R ¹² ).] -Y ³ = Y ⁴ - formula (c) wherein Y ³ and Y ^{4 are} each independently N, B, P, C (R ¹⁷ ) or Si (R ¹⁸ ); in the formula (c), the radicals R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group an arylalkylthio group, an arylalkylamino group, an acyl group, an acyloxy group, an amide group, an imine group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group; -Y ⁵ - formula (d) wherein Y ^{5 is} O, S, C (OO), S (OO), SO ₂ , C (R ¹⁹ ) (R ²⁰ ), Si (R ²¹ ) (R ²² ), N (R ²³ ), B ( R ²⁴ ), P (R ²⁵ ) or P (= O) (R ²⁶ ); wherein in formula (d) the radicals R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a Alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkylamino group, an acyl group, an acyloxy group, an amide group, an imine group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group); Z ^{1 represents} -CR ³⁶ = CR ³⁷ - or -C≡C-; R ³⁶ and R ³⁷ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group; d means 0 or 1. Polymers POLY4 according to claim 22, characterized in that the structural units L = X are selected from the formulas (1) to (5),

where the symbols X, Y, Z and R ¹ -R ^{6 have the} same meaning as described in claims 1 and 2. Polymers according to claim 22 and / or 23, characterized in that they except structural elements L = X and the triplet emitter contain further structural elements. Mixtures of at least one polymer according to one or more of the claims 22 to 24, characterized in that the polymer (POLY4) still other molecules, which may be low molecular weight, oligomeric, dendrimeric or polymeric become. Use of a mixture or a polymer according to one or more of the claims 1 to 25 in organic light-emitting diodes (PLED), organic solar cells (O-SCs), organic laser diodes (O-lasers) or in the non-linear Look. Electronic component, which has one or more active layers, wherein at least one of these active layers one or more mixtures or polymers according to one or more of claims 1 to 25 contains. Electronic component according to claim 27, characterized that it is an organic light emitting diode, an organic solar cell or an organic laser diode.