JP5837051B2 - Formulations and electronic devices - Google Patents

Description

  The present invention relates to a formulation for the manufacture of electronic devices. The invention further relates to an electronic device and a method for its manufacture.

  Electronic devices including organic, organometallic and / or polymer semiconductors are gaining importance. They are used in many products for cost reasons and thanks to their performance. Examples that may be mentioned here are organic materials for photocopiers in copiers (eg triarylamine-based hole transporters), organic or polymer light emitting diodes (OLED or PLED) in display devices, or organic materials in copiers. There is a photoreceptor. Organic solar cell (O-SC), organic field effect transistor (O-FET), organic thin film transistor (O-TFT), organic integrated circuit (O-IC), organic optical amplifier and organic laser diode (O-laser) It is in a much more advanced development stage and can achieve major importance in the future.

Regardless of the specific application, many of these electronic devices have the following general layer structure, which can be adapted to a specific application:
(1) substrate,
(2) Electrodes, often metal or inorganic, but also made from organic or polymeric conductive materials.

(3) Charge injection layer (s) or intermediate layer (s), for example to compensate for electrode non-uniformity ("flattening layer"), often made from conductive doped polymer To be
(4) Organic semiconductor,
(5) optionally further charge transport, charge injection or charge blocking layer,
(6) Reverse electrode, substance (7) sealing as described in (2).

  The above arrangement represents the general structure of an organic electronic device, where various layers can be combined, in the simplest case resulting in an arrangement containing two electrodes, An organic layer is located between them. In this case, the organic layer performs all functions, and in the case of OLED this includes light emission. This type of system is described, for example, in WO 90/13148 A1 based on poly- (p-phenylene).

  However, the problems that arise in this type of “three-layer system” are achieved in a simple way with a multilayer structure, such as the lack of control of charge separation or, for example, in the case of SMOLEDs (“small molecule OLEDs”). There is no way to optimize the properties of individual constituents in different layers.

  Small molecule OLEDs often include one or more organic hole injection layers, hole transport layers, light emitting layers, electron transport layers and / or electron injection layers and anodes and cathodes, and the entire system is typically on a glass substrate. Located in. The advantage of this type of multilayer structure is that the various functions of charge injection, charge transport and light emission can be distributed in different layers and therefore the properties of each layer can be modified separately. This modification can greatly improve the performance of the electronic device.

  A drawback of the electronic devices based on the small molecules described above, ie non-polymeric compounds, is their manufacture. Non-polymeric compounds are usually converted to electronic devices by vapor deposition techniques. This represents a significant cost disadvantage, especially for large area devices. This is because multistage vacuum processes in various chambers are very expensive and must be controlled very accurately. It would be of great advantage here to use less expensive and established coating methods from solution, such as ink jet printing, airbrushing, roll-to-rolling, etc. However, the devices described above that contain small molecules cannot generally be produced by this method due to the low solubility of non-polymeric compounds in common solvents. Although the solubility of these compounds can be improved by modification, the resulting electronic devices exhibit reduced performance and lifetime as compared to devices obtained by vapor deposition.

  Thus, for example, WO2009 / 021107A1 and WO2010 / 006680A1 describe organic compounds suitable for the manufacture of electronic devices, and these compounds can be processed both by vapor deposition and from solution. However, electronic devices obtained by vapor deposition have a more advantageous characteristic profile.

  Known electronic devices have a characteristic profile that is convenient to use. However, there is a continuing need to improve the characteristics of these devices. These characteristics include in particular the lifetime of the electronic device. A further problem is in particular energy efficiency, which allows electronic devices to achieve specific purposes. In the case of organic light-emitting diodes, it can be based on both low-molecular compounds and even polymer materials, but in particular the light yield should be high, which means that the power consumed to achieve a certain luminous flux can be as much as possible. It means you have to be less. Furthermore, the voltage must also be kept as low as possible in order to achieve the previously specified luminous flux density.

  A further object can be regarded as supplying electronic devices with excellent performance as cheaply as possible and with a certain quality.

  Furthermore, electronic devices should be able to be utilized or adapted for many purposes. In particular, the performance of electronic devices should be maintained over a wide temperature range.

  Surprisingly, these and further objects, although not explicitly stated, can be easily derived or inferred from the relevance discussed in the introduction herein, which are all claimed in claim 1 It was found to be achieved by a formulation having the following characteristics: Advantageous modifications of the formulations according to the invention are protected in the claims dependent on claim 1.

The present invention therefore relates to a formulation comprising at least one solvent and at least two functional compounds of different general formula (I)

[here,
A is a functional structural element,
B is a dissolution promoting structural element;
k is an integer in the range of 1-20,
The molecular weight of the functional compound is at least 550 g / mol;
Dissolution-promoting structural element B corresponds to general formula (LI)].

(Where
Ar ¹ and Ar ² are each independently an aryl or heteroaryl group (which may be substituted with one or more radicals R of any desired type);
X is in each case, independently of one another, N or CR ² , preferably CH,
R ¹ and R ² , independently of one another, are hydrogen, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or a branched or A cyclic alkyl, alkoxy or thioalkoxy group or a silyl group or a substituted keto group having 1 to 40 C atoms, an alkoxycarbonyl group having 2 to 40 C atoms, 7 to 40 C An aryloxycarbonyl group having an atom, a cyano group (—CN), a carbamoyl group (—C (═O) NH ₂ ), a haloformyl group (—C (═O) —X, wherein X represents a halogen atom; ), Formyl group (—C (═O) —H), isocyano group, isocyanate group, thiocyanate group or thioisocyanate group, hydroxyl group, nitro group, CF ₃ group , Cl, Br, F, a bridging group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 60 ring atoms, or aryloxy having 5 to 60 ring atoms Or a heteroaryloxy group, or a combination of these systems, wherein one or more of the radicals R ¹ and / or R ² together with the ring to which each and / or the radical R ¹ is attached. May form monocyclic or polycyclic, aliphatic or aromatic ring systems,
l is 0, 1, 2, 3 or 4;
(The bond indicated by the broken line indicates the bond to the functional structural element)
The formulation according to the invention thus represents a mixture of at least two functional compounds of the formula (I) dissolved or dispersed in an organic solvent.

  The formulation according to the invention comprises at least one organic solvent. Suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, diols and / or polyols.

  The solvent preferably comprises at least one aromatic or heteroaromatic compound. The solvent particularly preferably comprises at least one aromatic hydrocarbon and / or halogenated aromatic compound, which particularly preferably has 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. Containing at least one alkyl group and / or cycloalkyl group. These solvents include in particular toluene, dimethylbenzene (xylene), trimethylbenzene, methylnaphthalene, tetralin, cyclopentylbenzene and cyclohexylbenzene.

  According to a further embodiment of the invention, aromatic or heteroaromatic compounds containing heteroatoms in the side groups, in particular esters, ethers, nitriles and / or amides can be used. Preferred compounds of this class include aromatic alkoxy compounds (such as 3-methylanisole, 2-isopropylanisole, 5-methoxyindane, 2-ethoxynaphthalene), and aromatic esters (such as butyl benzoate and ethyl benzoate). Is mentioned. Also suitable are heteroaromatic solvents containing O, N or S atoms in the aromatic ring, such as 2-methylindole and 6-methylquinoline.

  The solvent used may further be a heterocyclic compound such as 1-cyclohexyl-2-pyrrolidinone (N-cyclohexyl-pyrrolidinone).

  Furthermore, alcohol represents a suitable class of solvents. Preferred alcohols are in particular alkylcyclohexanols, in particular methylated alicyclic alcohols (3- or 4-methylcyclohexanol or 2,5-dimethylcyclohexanol), naphthols such as decahydro-2-naphthol or 1,2, Examples include 3,4-tetrahydro-1-naphthol, terpenoids such as α-terpineol, menthol or carveol, nonylphenol, 1-indanol and 2-indanol.

  Further, the solvent utilized may be a cycloalkane such as decalin.

  The solvents can be utilized individually or as a mixture of two, three or more compounds.

  Preferred solvents include, among others, toluene, anisole, xylene, methyl benzoate, dimethylanisole, mesitylene, tetralin, veratrol, tetrahydrofuran and chlorobenzene, and mixtures thereof. The use of aromatic solvents, in particular aromatic hydrocarbons, is particularly preferred. The formulations according to the invention can preferably comprise at least 50% by weight of aromatic solvents, particularly preferably at least 80% by weight and very particularly preferably at least 90% by weight.

In particular, surprising advantages can be achieved with solvents in which the Hansen solubility parameter is preferably in the following range:
H _d (dispersion contribution): in the range of 17.0 to 23.2 MPa ^0.5 , particularly preferably in the range of 18.5 to 21.0 MPa ^0.5 ,
H _p (polarity contribution): in the range of 0.2 to ^12.5 MPa ^0.5 , particularly preferably in the range of 2.0 to 6.0 MPa ^0.5 ,
H _h (contribution to hydrogen bonding): in the range of 0.9 to 14.2 MPa ^0.5 , particularly preferably in the range of 2.0 to 6.0 MPa ^0.5 . The Hansen solubility parameter can be determined using the “Hansen Solubility Parameters in Practice (HSPIP)” computer program (2nd edition) provided by Hansen and Abbott et al.

  Preferred functional compounds of formula (I) can contain 2, 3 or more dissolution-promoting structural elements B. Therefore, the subscript k in formula (I) can be an integer of preferably 2 or more, particularly preferably 3 or more.

  Surprising advantages can be achieved in particular using functional compounds of the general formula (I) having a relatively high molecular weight. Accordingly, preferred functional compounds of the general formula (I) are distinguished by a molecular weight of at least 800 g / mol, particularly preferably at least 900 g / mol and very particularly preferably at least 950 g / mol.

  Furthermore, preferred functional compounds of the formula (I) can have a molecular weight of up to 10,000 g / mol, particularly preferably up to 5000 g / mol and very particularly preferably up to 3000 g / mol.

  Also of particular interest are functional compounds that are distinguished by high glass transition temperatures. In this connection, when determined according to DIN 51005, the general formula (having a glass transition temperature of at least 70 ° C., particularly preferably at least 100 ° C., very particularly preferably at least 125 ° C. and particularly preferably at least 150 ° C. Particular preference is given to functional compounds of I).

  The functional structural element A of the functional compound of formula (I) is not subject to any particular limitation, so the present invention modifies the original electronic properties of known substances by transformation in an unacceptable manner. Instead, it is suitable for converting known substances utilized in electronic devices to achieve functional properties into soluble forms.

These are among others disclosed and widely listed in WO02 / 077060A1 and WO2005 / 014689A2. These are considered part of the present invention by reference. Functional structural element A can be created from the following classes, for example:
Group 1: units capable of producing hole injection and / or hole transport properties;
Group 2: units capable of producing electron injection and / or electron transport properties;
Group 3: units having luminescent properties;
Group 4: Units that can function as host substances or joint host substances,
Group 5: Units that improve the movement from the so-called singlet state to the triplet state.

  Structural elements from group 1 having hole injection and / or hole transport properties include, for example, triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, O-, S- or N-containing heterocycles which are derivatives of dibenzo-para-dioxin, phenoxathiin, carbazole, azulene, thiophene, pyrrole and furan and have a higher HOMO (HOMO = highest occupied molecular orbital) It is.

  As structural elements from group 1 having hole injection and / or hole transport properties, in particular phenylenediamine derivatives (US3615404), arylamine derivatives (US3567450), amino-substituted chalcone derivatives (US3526501), styrylanthracene derivatives (JP- A-56-46234), polycyclic aromatic compound (EP1009041), polyarylalkane derivative (US3615402), fluorenone derivative (JP-A-54-110837), hydrazone derivative (US3717462), acylhydrazone, stilbene derivative (JP) -A-6210363), silazane derivative (US4950950), polysilane (JP-A-2-204996), aniline copolymer (JP-A-2-282263), thiof Oligomers (JP Heisei 1 (1989) 211399), polythiophene, poly (N-vinylcarbazole) (PVK), polypyrrole, polyaniline and other conductive macromolecules, porphyrin compounds (JP-A-63-295965, US 4720432), Aromatic dimethylidene type compounds, carbazole compounds (for example, CDBP, CBP, mCP, aromatic tertiary amine and styrylamine compounds (US4127412), etc.), for example, benzidine type triphenylamine, styrylamine type triphenyl Examples include amine and diamine type triphenylamine. Arylamine dendrimers (JP Heisei 8 (1996) 193191), monomeric triarylamines (US3180730), one or more vinyl radicals, and / or triarylamines containing at least one functional group containing active hydrogen (US3567450) And US Pat. No. 3,658,520) or tetraaryldiamines (two tertiary amine units are linked via an aryl group). Additional triarylamino groups may also be present in the molecule. Also suitable are phthalocyanine derivatives, naphthalocyanine derivatives, butadiene derivatives and quinoline derivatives such as dipyrazino [2,3-f: 2 ', 3'-h] quinoxaline hexacarbonitrile.

Aromatic tertiary amines containing at least two tertiary amine units (US 2008/0102311 A1, US 4720432 and US 5061569), such as NPD (α-NPD = 4,4′-bis [N- (1-naphthyl)- N-phenylamino] biphenyl) (US 5061569), TPD232 (= N, N′-bis- (N, N′-diphenyl-4-aminophenyl) -N, N-diphenyl-4,4′-diamino-1, 1′-biphenyl) or MTDATA (MTDATA or m-MTDATA = 4,4 ′, 4 ″ -tris [3-methylphenyl) phenylamino] -triphenylamine) (JP-A-4-308688), TBDB ( = N, N, N ', N'-tetra (4-biphenyl) diaminobiphenylene), TAPC (= 1,1-bis 4-di-p-tolylaminophenyl) -cyclohexane), TAPPP (= 1,1-bis (4-di-p-tolylaminophenyl) -3-phenylpropane), BDTAPVB (= 1,4-bis [2 -[4- [N, N-di (p-tolyl) amino] phenyl] vinyl] benzene), TTB (= N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl) ), TPD (= 4,4′-bis [N-3-methylphenyl] -N-phenylamino) biphenyl), N, N, N ′, N′-tetraphenyl-4,4 ′ ″-diamino- Tertiary amines which likewise contain carbazole units, such as 1,1 ′, 4 ′, 1 ″, 4 ″, 1 ′ ″-quarterphenyl, such as TCTA (= 4- (9H-carbazole-9 -Yl) -N, N-bis [4- (9H-carbazole-9 Yl) phenyl] - benzenamine) and the like are preferable. Similarly, hexaazatriphenylene compounds and phthalocyanine derivatives (eg H ₂ Pc, CuPc (= copper phthalocyanine), CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂ SiPc according to US2007 / 0092755A1 (HO) AlPc, (HO) GaPc, VOPc, TiOPc, MoOPc, GaPc-O-GaPc) are preferred.

The following triarylamine compounds are particularly preferred, which may also be substituted:

TBDB: EP1162193B1 and EP650955B1

Synth. Metals 1997, 91 (1-3), p.209 and DE196646119A1.

WO2006122630A1 and EP1860097A1

EP1834945A1

JP08053397A and US6251531B1

EP1661888

NPB = 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl

US2005 / 0221124, WO09 / 041635

US7399537B2, US20060061265A1

EP1661888B1

JP08292586A
Furthermore, structural elements that can be used as hole injecting materials are described in EP 0 891 211 A1 and EP 1029909 A1, and in general the injection layer is described in US 2004/0174116 A1.

  These arylamines and heterocycles from group 1, which are commonly utilized as structural elements, preferably result in greater than −5.8 eV (vs. vacuum level), particularly preferably −5. This results in a HOMO of the polymer above 5 eV.

  Structural elements from group 2 having electron injection and / or electron transport properties include, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazine, Ketones, phosphine oxides and phenazine derivatives, but also triarylboranes, and also O-, S- or N-containing heterocycles with low LUMO (LUMO = lowest unoccupied molecular orbital).

Structural elements particularly suitable for electron transport and electron injection layers are metal chelates of 8-hydroxyquinoline (eg LiQ, AlQ ₃ , GaQ ₃ , MgQ ₂ , ZnQ ₂ , InQ ₃ , ZrQ ₄ ), BAlQ, Ga oxinoid complexes 4-azaphenanthrene-5-ol-Be complex (US5529853A),

Butadiene derivatives (US 4356429), heterocyclic optical brighteners (US 4539507), benzimidazole derivatives (US 2007/0273272 A1), such as TPBI (US 5766779),

1,3,5-triazines such as spirobifluorenyltriazine derivatives (for example according to DE 102008064200), pyrenes, anthracene, tetracene, fluorene, spirofluorene, dendrimers, tetracene (eg rubrene derivatives), 1,10-phenanthroline derivatives (JP2003) -115387, JP2004-311184, JP-2001-267080, WO2002 / 043449), silacyclopentadiene derivatives (EP1480280, EP1478032, EP1469533), borane derivatives such as triarylborane derivatives containing Si,

US2007 / 0087219A1
Pyridine derivatives (JP 2004-200162), phenanthrolines, in particular 1,10-phenanthroline derivatives such as BCP and Bphen, and some phenanthrolines linked via biphenyl or other aromatic groups (US-2007-0252517A1) Or phenanthroline (US2007-0122656A1) bound to anthracene.

Likewise suitable are heterocyclic organic compounds such as thiopyran dioxide, oxazole, triazole, imidazole or oxadiazole. For examples of the use of N-containing five-membered rings such as oxazole, thiazole, oxadiazole, thiadiazole, triazole and the like, see inter alia US 2008/010311 A1. Preferred compounds are the following triazoles, for example:

Y. A. Levin, M.M. S. Skorobogatova, Kimimiya Geterosticricheskikh Soedinenii 1967 (Vol. 2), 339-341.

1,3,4-oxadiazole, such as

US2007 / 0273272A1

US2007 / 0273272A1

US2007 / 0273272A1 and the like.

  Organic compounds such as fluorenone, fluorenylidenemethane, perylene tetracarbonate, anthraquinone dimethane, diphenoquinone, anthrone and anthraquinone diethylenediamine derivatives can also be used.

Molecules containing 2,9,10-substituted anthracene (having 1- or 2-naphthyl and 4- or 3-biphenyl) or two anthracene units are preferred (US 2008/0193796 A1). Also very advantageous is the bond between the 9,10-substituted anthracene unit and the benzimidazole derivative.

US6878469B2

US2006147747A

EP15551206A1
The structural elements from group 2 of the compounds of formula (I) utilized according to the invention preferably result in less than −2.5 eV (vs. vacuum level), particularly preferably less than −2.7 eV. Bring LUMO.

  The structural elements from group 3 can emit light. These include, among others, stilbene, stilbeneamine, styrylamine, coumarin, rubrene, rhodamine, thiazole, thiadiazole, cyanine, thiophene, paraphenylene, perylene, phthalalocyanine, porphyrin, ketone, quinoline, imine, anthracene and / or pyrene. The compound containing a structure is mentioned. A compound that is highly efficient from the triplet state and can emit light even at room temperature, that is, a compound that exhibits electrophosphorescence instead of electrofluorescence and often causes an increase in energy efficiency is particularly preferable. Suitable for this purpose are first compounds containing heavy atoms with an atomic number greater than 36. Compounds containing d- or f-transition metals that satisfy the above conditions are preferred. Corresponding structural elements containing elements from groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt) are particularly preferred here. Suitable functional structural elements A for the compounds of the formula (I) are here various complexes as described, for example, in WO 02/068435 A1, WO 02/081488 A1, EP 1239526 A2 and WO 04/026886 A2.

  Preferred structural elements that can function as fluorescent emitters are described using the following examples. Preferred structural elements from group 3 are selected from the classes of monostyrylamine, distyrylamine, tristyrylamine, tetrastyrylamine, styrylphosphine, styryl ether and arylamine.

  Monostyrylamine is intended to mean a compound containing one substituted or unsubstituted styryl group and at least one, preferably aromatic, amine. Distyrylamine is intended to mean a compound containing two substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. A tristyrylamine is intended to mean a compound containing three substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. Tetrastyrylamine is intended to mean a compound containing four substituted or unsubstituted styryl groups and at least one, preferably aromatic, amine. The styryl group is particularly preferably stilbene, which may also be further substituted. Corresponding phosphines and ethers are defined the same as amines. An arylamine or aromatic amine in the sense of the present invention is intended to mean a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly linked to nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a fused ring system, which ring system preferably has at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthracenamine, aromatic anthracene diamine, aromatic pyrene amine, aromatic pyrene diamine, aromatic chrysene amine or aromatic chrysene diamine. By aromatic anthracenamine is meant a compound in which one diarylamino group is directly bonded to the anthracene group, preferably directly bonded to the anthracene group at the 9-position. An aromatic anthracenediamine is intended to mean a compound in which two diarylamino groups are directly bonded to the anthracene group, preferably directly bonded to the anthracene group in the 2,6-position or 9,10-position. Aromatic pyreneamines, pyrenediamines, chrysenamines and chrysenediamines are defined the same way, and these diarylamino groups are preferably attached to pyrene at the 1-position or the 1,6-position.

  Furthermore, preferred structural elements from group 3 are for example indenofluorenamine or indenofluorenamine according to WO 06/122630, for example benzoindenofluorenamine or benzoindenofluramine amine according to WO08 / 006449, and dibenzo according to eg WO07 / 140847. It is selected from indenofluoreneamine or dibenzoindenofluor orangeamine.

  Examples of structural elements from group 3 from the styrylamine class are described in substituted or unsubstituted tristilbeneamines or in WO06 / 000388, WO06 / 058737, WO06 / 000389, WO07 / 0665549 and WO07 / 115610. It is a dopant. Distyrylbenzene and distyrylbiphenyl derivatives are described in US Pat. Furthermore, styrylamine can be found in US2007 / 0122656A1.

Particularly preferred styrylamine structural elements from group 3 are

US7250532B2

DE10 2005 058557A1.

Particularly preferred triarylamine structural elements from group 3 are

CN1588391A

CN1588391A

JP08 / 053397A and US6251531B1, and derivatives of EP1957606A1 and US2008 / 0113101A1.

EP1957606A1

US2006 / 210830A

WO08 / 006449

WO08 / 006449

WO08 / 006449

WO08 / 006449

DE102008035413

DE102008035413

DE102008035413

DE102008035413
Furthermore, preferred structural elements from group 3 are naphthalene, anthracene, tetracene, benzanthracene, benzophenanthrene (DE102009005746), fluorene, fluoranthene, perifrantene, indenoperylene, phenanthrene, perylene (US2007 / 0252517A1), pyrene, chrysene, decacyclene. , Coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, fluorene, spirofluorene, rubrene, coumarin (US4769292, US6020078, US2007 / 0252517A1), pyran, oxazole, benzoxazole, benzothiazole, benzimidazole, pyrazine, cinnamate, Diketopyrrolopyrrole, acridone and quina It is selected from the derivatives of pyrrolidone (US2007 / 0252517A1).

  Among the anthracene compounds, 9,10-substituted anthracene such as 9,10-diphenylanthracene and 9,10-bis (phenylethynyl) anthracene are particularly preferable. 1,4-bis (9'-ethynylanthracenyl) benzene is also a preferred dopant.

  Similarly, derivatives of rubrene, coumarin, rhodamine, quinacridone, such as DMQA (= N, N′-dimethylquinacridone), dicyanomethylenepyran (for example, DCM (= 4- (dicyanoethylene) -6- (4-dimethyl) Aminostyryl-2-methyl) -4H-pyran), thiopyran, polymethine, pyrylium and thiapyrylium salts), perifrantene and indenoperylene are preferred.

  The blue fluorescent emitter is preferably a polycyclic aromatic compound such as 9,10-di (2-naphthylanthracene) and other anthracene derivatives, tetracene, xanthene, perylene derivatives such as 2,5,8, 11-tetra-t-butylperylene, etc., phenylene such as 4,4′-bis (9-ethyl-3-carbazovinylene) -1,1′-biphenyl, fluorene, fluoranthene, arylpyrene (US2006 / 0222886A1), arylene vinylene (US5121029, US5133063), bis (azinyl) imine-boron compound (US2007 / 0092753A1), bis (azinyl) methene compound, carbostyryl compound and the like.

  Further preferred blue fluorescent light emitters include C.I. H. Chen et al., “Recent developments in organic electroluminescent materials” Macromol. Symp. 125, (1997) 1-48 and “Recent progress of molecular organic materials and devices” Mat. Sci. and Eng. R, 39 (2002), pages 143-222.

  Further preferred blue fluorescent emitters are the hydrocarbons disclosed in DE102008035413.

  Preferred structural elements from Group 3 that can function as phosphorescent emitters are represented through the following examples.

  Examples of phosphorescent emitters are clarified by WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP1191612, EP1191614 and WO05 / 033244. In general, all phosphorescent complexes as used according to conventional techniques for phosphorescent OLEDs and known to those skilled in the field of organic electroluminescence are suitable, The trader can use the phosphorescent complex without inventive step.

  The phosphorescent metal complex preferably contains Ir, Ru, Pd, Pt, Os or Re.

  Preferred ligands include 2-phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2- (2-thienyl) pyridine derivatives, 2- (1-naphthyl) pyridine derivatives, 1- (phenylisoquinoline derivatives, 3-phenyl Isoquinoline derivatives or 2-phenylquinoline derivatives, all these compounds are blue and may be substituted, for example with fluoro, cyano and / or trifluoromethyl substituents. Nate or picolinic acid.

Particularly suitable are complexes of Pt or Pd with a tetradentate ligand

(US2007 / 0087219A1, for publication purposes, reference is made to this specification for explanation of substituents and subscripts in the above formula), Pt-porphyrin complexes with expanded ring systems (US2009 / 0061681A1) ) And Ir complexes, such as 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin-Pt (II), tetraphenyl-Pt (II) tetrabenzoporphyrin (US2009 / 0061681A1) , cis-bis ^{(2-phenylpyridinato--N, C 2 ') Pt (} II), cis- bis (2- (2'-thienyl) pyridinato ^{-N, C 3') Pt (} II), cis- bis (2- (2'-thienyl) quinolinato ^{-N, C 5 ') Pt (} II), (2- (4,6- difluorophenyl) pyridine DOO ^{-N, C 2 ') Pt (} II) ( acetylacetonate), or tris ^{(2-phenylpyridinato--N, C 2') Ir (} III) (= Ir (ppy) 3, green), bis ^{(2-phenylpyridinato--N, C 2) Ir (III} ) ( acetylacetonate) (= Ir (ppy) ₂ acetylacetonate, green, US2001 / 0053462A1, Baldo, Thompson et al., Nature, 403, (2000 year), pp. 750-753), bis (1-phenylisoquinolinato--N, C ² ') (2-phenylpyridinato--N, C ^2') iridium (III), bis (2-phenylpyridinato DOO -N, C ² ') (1- phenylisoquinolinato--N, C ^2') iridium (III), bis (2- (2'-benzothienyl) pyridinato -N, C ³ ') iridium (III) (acetylacetonate), bis (2- (4 ', 6'-difluorophenyl) pyridinato -N, C ^2') iridium (III) (Pikkorinato) (FIrpic, blue), bis (2- ( 4 ′, 6′-difluorophenyl) pyridinato-N, C ² ′) Ir (III) (tetrakis (1-pyrazolyl) borate), tris (2- (biphenyl-3-yl) -4-tert-butylpyridine) Iridium (III), (ppz) ₂ Ir (5 phdpym) (US2009 / 0061681A1), (45ooppz) ₂ Ir (5phdpym) (US2009 / 0061681A1), derivatives of 2-phenylpyridine-Ir complexes (eg, PQIr (= iridium (= III) bis (2-phenyl-quinolyl -N, C ² ') acetylacetonate) Tris (2-phenylisoquinolinato--N, C) Ir (III) (red), bis (2- (2'-benzo [4,5-a] thienyl) pyridinato -N, C ³⁾ Ir (acetylacetonate Nate) ([Btp ₂ Ir (acac)], red, Adachi et al., Appl. Phys. Lett. 78 (2001), pages 1622 to 1624).

Also suitable are complexes of trivalent lanthanides, such as Tb ³⁺ and Eu ³⁺ (J. Kido et al., Appl. Phys. Lett. 65 (1994), 2124, Kido et al., Chem. Lett. 657, 1990, US 2007/0252517 A1) or the like, or phosphorescent complexes of Pt (II), Ir (I), Rh (I) with maleonitrile dithiolate (Johnson et al., JACS, 105, 1983). 1795), Re (I) tricarbonyl-diimine complexes (in particular Wrightton, JACS, 96, 1974, 998), Os (II) complexes with cyano ligands and bipyridyl or phenanthroline ligands ( Ma et al., Synth. Metals, 94, 1998, 245).

  Further phosphor emitters with tridentate ligands are described in US6824895 and US10 / 729238. Red emitting phosphorescent complexes are found in US6835469 and US6830828.

Particularly preferred structural elements used as phosphorescent dopants are

US2001 / 0053462A1 and Inorg. Chem. 2001, 40 (7), 1704-1711, JACS, 2001, 123 (18), 4304-4312.

Derivatives are described in US7378162B2, US6835469B2 and JP2003 / 253145A.

  The structural elements from group 4 that are utilized as host materials, particularly with luminescent compounds, include materials from various classes of materials.

Preferred structural elements from group 4, which are used in particular with fluorescent dopants, are oligoarylenes (eg 2,2 ′, 7,7′-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), in particular condensed aromatics. Group containing oligoarylenes such as anthracene, benzanthracene, benzophenanthrene (DE102009005746, WO09 / 069566), phenanthrene, tetracene, coronene, chrysene, fluorene, spirofluorene, perylene, phthaloperylene, naphthaloperylene, decacyclene, rubrene, oligoarylene For example, DPVBi = 4,4′-bis (2,2-diphenylethenyl) -1,1′-biphenyl or spiro-DPVBi according to EP676461 A polypodic metal complex (eg according to WO 04/081017), in particular a metal complex of 8-hydroxyquinoline, such as AlQ ₃ (= aluminum (III) tris (8-hydroxyquinoline)) or bis (2-methyl-8- Quinolinolato) -4- (phenylphenolinolato) aluminum, and those having an imidazole chelate (US2007 / 0092753A1), and quinoline metal complexes, aminoquinoline metal complexes, benzoquinoline metal complexes, hole conducting compounds (eg, WO 04/058911) Electronically conductive compounds, in particular ketones, phosphine oxides, sulfoxides etc. (eg according to WO05 / 084081 and WO05 / 084082), atropisomers (eg according to WO06 / 048268), boronic acid derivatives ( Example, if due to WO06 / 117052) or by benzanthracene (e.g. WO08 / 145239) are selected from classes such as.

  Particularly preferred structural elements from group 4 are selected from the class of oligoarylenes including anthracene, benzanthracene and / or pyrene, or atropisomers of these compounds. In the sense of the present invention, oligoarylene is intended to mean a compound in which at least three aryl or arylene groups are bonded to one another.

Preferred host materials are in particular compounds of the formula (H-1)

Wherein Ar ³ , Ar ⁴ , Ar ⁵ are equal or different each time they appear, and are aryl or heteroaryl groups having 5 to 30 aromatic ring atoms (these are one or more radicals R ¹ R ¹ has the same meaning as described above, p represents an integer in the range of 1 to 5, and when p = 1, Ar ³ , Ar The sum of ⁴ and Ar ⁵ Π electrons is at least 30, at least 36 for p = 2, and at least 42 for p = 3.

In the compound of formula (H-1), the group Ar ⁴ particularly preferably represents anthracene, which may be substituted with one or more radicals R ¹ , and the groups Ar ³ and Ar ⁵ are 9 Bonded at the 10th and 10th positions. Very particularly preferably, at least one of the groups Ar ³ and / or Ar ⁵ is 1- or 2-naphthyl, 2-, 3- or 9-phenanthrenyl or 2-, 3-, 4-, 5-, A fused aryl group selected from 6- or 7-benzanthracenyl, each of which may be substituted with one or more radicals R ¹ . Anthracene-based compounds are described in US 2007/0092753 A1 and US 2007/0252517 A1, for example 2- (4-methylphenyl) -9,10-di- (2-naphthyl) anthracene, 9- (2-naphthyl)- 10- (1,1′-biphenyl) anthracene and 9,10-bis [4- (2,2-diphenylethenyl) phenyl] anthracene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene And 1,4-bis (9′-ethynylanthracenyl) benzene. Compounds containing two anthracene units (US2008 / 0193796A1), for example 10,10′-bis [1,1 ′, 4 ′, 1 ″] terphenyl-2-yl-9,9′-bisanthracenyl Is also preferred.

  Further preferred compounds are arylamine, styrylamine, fluorescein, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, coumarin, oxadiazole, bisbenzoxazoline, oxazole, pyridine, pyrazine, imine , Derivatives of benzothiazole, benzoxazole, benzimidazole (US2007 / 0092753A1), such as 2,2 ′, 2 ″-(1,3,5-phenylene) tris [1-phenyl-1H-benzimidazole], aldazine, Stilbene, styrylarylene derivatives, such as 9,10-bis [4- (2,2-diphenylethenyl) phenyl] anthracene, and distyrylarylene derivatives US5121029), diphenylethylene, vinyl anthracene, diaminocarbazole, pyran, thiopyran, diketopyrrolopyrrole, polymethine, cinnamic acid esters and fluorescent dyes.

Arylamine and styrylamine derivatives such as TNB (= 4,4′-bis [N- (1-naphthyl) -N- (2-naphthyl) amino] biphenyl) are particularly preferred. Metal oxinoid complexes such as LiQ or AlQ ₃ can be used as a joint host.

Preferred compounds as the matrix with oligoarylene are:

In addition, structural elements from group 4 include materials utilized with phosphorous emitters. These structural elements include CBP (N, N-biscarbazolylbiphenyl), carbazole derivatives (eg according to WO05 / 039246, US2005 / 0069729, JP2004 / 288811, EP1205527 or WO08 / 088551), azacarbazole (eg EP16177710, EP1617711). , EP 1731584, JP 2005/347160), ketones (eg according to WO 04/093207 or according to DE 102008033943), phosphine oxides, sulfoxides and sulfones (eg according to WO 05/003253), oligophenylenes, aromatic amines (eg according to US 2005/0069729), Polar matrix material (eg according to WO07 / 137725) Silanes (for example according to WO05 / 111172), 9,9-diarylfluorene derivatives (for example according to DE102008017591), azabolol or boronate esters (for example according to WO06 / 117052), triazine derivatives (for example according to DE102008036982), indolocarbazole derivatives (for example WO07) / 063754 or WO08 / 056746), indenocarbazole derivatives (for example according to DE102009023155 and DE102009031021), diazaphosphole derivatives (for example according to DE102009022858), triazole derivatives, oxazole and oxazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolones Conductor, distyrylpyrazine derivative, thiopyran dioxide derivative, phenylenediamine derivative, tertiary aromatic amine, styrylamine, amino-substituted chalcone derivative, indole, hydrazone derivative, stilbene derivative, silazane derivative, aromatic dimethylidene compound, carbodiimide derivative , Metal complexes of 8-hydroxyquinoline derivatives, such as AlQ ₃ (which may also contain triarylaminophenol ligands) (US2007 / 0134514A1), metal complexes / polysilane compounds, and thiophene, benzothiophene and dibenzothiophene derivatives, etc. Is mentioned.

Examples of preferred carbazole structural elements are mCP (= 1,3-N, N-dicarbazolylbenzene (= 9,9 ′-(1,3-phenylene) bis-9H-carbazole)), CDBP (= 9 , 9 ′-(2,2′-dimethyl [1,1′-biphenyl] -4,4′-diyl) bis-9H-carbazole), 1,3-bis (N, N′-dicarbazolyl) benzene (= 1,3-bis (carbazol-9-yl) benzene), PVK (polyvinylcarbazole), 3,5-di (9H-carbazol-9-yl) biphenyl, and the compounds represented below.

Preferred Si tetraaryl compounds are, for example, (US2004 / 0209115, US2004 / 0209116), H.P. Gilman, E .; A. Zuech, Chemistry & Industry (London, United Kingdom), 1960, 120.

Particularly preferred structural elements from group 4 for the preparation of the matrix for phosphorescent dopants are:

  With respect to functional compounds that can be used according to the invention and can function as host substances, substances having a functional structural element A having at least one nitrogen atom are particularly preferred. These preferably include aromatic amines, triazine derivatives and carbazole derivatives. The carbazole derivatives are therefore particularly surprisingly efficient. Triazine derivatives unexpectedly provide long lifetimes for electronic devices containing such compounds.

  The structural elements from group 5 improve the transition from the singlet state to the triplet state, and when used to assist functional structural elements from group 3, improve the phosphorescent properties of these structural elements. Suitable for this purpose are in particular carbazole and bridged carbazole dimer units, which are described, for example, in WO 04/070772 A2 and WO 04/113468 A1. Ketones, phosphine oxides, sulfoxides, sulfones, silane derivatives and similar compounds are also suitable for this purpose and these are described, for example, in WO 05/040302 A1.

  Publications cited above for the description of functional structural elements are incorporated herein by reference for disclosure purposes.

  The functional structural element A described above can preferably be bound to at least one solubility-promoting structural element B via aromatic and / or heteroaromatic groups. The binding site is generally not important, that is, it is shown above for clarity, although one or more bonds to at least one of the solubility-promoting structural elements B described below are present. Means that it is not represented in the formula. According to a particular embodiment, the functional structural element A described above can be bound to one or more solubility promoting structural elements B via an aromatic or heteroaromatic ring system carbon atom.

In addition to at least one functional structural element A, the compounds according to the invention contain at least one solubility-promoting structural element B of the formula (LI).

(Where
Ar ¹ and Ar ² are each independently an aryl or heteroaryl group (which may be substituted with one or more radicals R of any desired type);
X is in each case, independently of one another, N or CR ² , preferably CH,
R ¹ and R ² are each independently of one another hydrogen, a linear alkyl, alkenyl, alkoxy or thioalkoxy group, each having 1 or 2 to 40 C atoms, or 3 to 40 C atoms. A branched or cyclic alkyl, alkenyl, alkoxy or thioalkoxy group having a silyl group, or a substituted keto group having 1 to 40 C atoms, an alkoxycarbonyl having 2 to 40 C atoms A group, an aryloxycarbonyl group having 7 to 40 C atoms, a cyano group (—CN), a carbamoyl group (—C (═O) NH ₂ ), a haloformyl group (—C (═O) —X, X represents a halogen atom), formyl group (—C (═O) —H), isocyano group, isocyanate group, thiocyanate group or thioisocyanate , Hydroxyl group, nitro group, CF ₃ group, Cl, Br, with a F, crosslinkable groups or 5-60 ring atoms, or an aromatic or heteroaromatic ring system or a substituted or unsubstituted or An aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems, wherein one or more of R ¹ and / or R ² are bonded to each other and / or the group R ¹ Together with the ring in question, may form a monocyclic or polycyclic, aliphatic or aromatic ring system,
l is 0, 1, 2, 3 or 4;
A bond indicated by a broken line indicates a bond to the functional structural element A).

The dissolution-promoting structural element B can preferably conform to the general formula (L-II).

(Where
R ¹ , R ² , R ³ , R ⁴ are each independently of one another hydrogen, a linear alkyl, alkenyl, alkoxy or thioalkoxy group each having 1 or 2 to 40 C atoms, or 3 A branched or cyclic alkyl, alkenyl, alkoxy or thioalkoxy group having ˜40 C atoms, or a silyl group, or a substituted keto group having 1 to 40 C atoms, or 2 to 40 An alkoxycarbonyl group having a C atom, an aryloxycarbonyl group having 7 to 40 C atoms, a formyl group (—C (═O) —H), a CF ₃ group, Cl, Br, F, a crosslinkable group Or an aryloxy if it is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 60 ring atoms, or having 5 to 60 ring atoms Or a heteroaryloxy group, or a combination of these systems, wherein one or more of R ¹ , R ² , R ³ and / or R ⁴ are bonded to each other and / or the ring to which the group R ¹ is bonded Together, they may form monocyclic or polycyclic, aliphatic or aromatic ring systems,
l is 0, 1, 2, 3 or 4;
m is 0, 1, 2 or 3;
n and o are each independently 0, 1, 2, 3, 4 or 5;
Bonds indicated by broken lines indicate bonds to functional structural elements).

The radicals R ¹ , R ² , R ³ , R ⁴ are particularly preferably hydrogen (1, m, n and o = 0), a linear alkyl or alkoxy group having 1 to 20 C atoms, or Represents a branched alkyl or alkoxy group having 3 to 20 C atoms.

Particularly preferred dissolution-promoting structural elements B include, among others, structural elements of the following formula:

(In the formula, a bond indicated by a broken line indicates a bond to the functional structural element A).

The following dissolution promoting structural element B is very particularly preferred:

(Wherein the bond indicated by the dashed line indicates the bond to the functional A structural element).

  Aromatic or heteroaromatic ring systems having 5 to 60 ring atoms, which may in each case also be substituted with any desired radical R and via any desired position May be linked to an aromatic or heteroaromatic ring system), in particular benzene, naphthalene, anthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, Terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, diben Furan, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline Benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridiimidazole, pyrazineimidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthrone Trooxazole, phenanthrooxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine Benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4, 5,9,10-tetraazaperylene, pyrazine, phenazine, fluorine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3 -Oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazide 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, It shall mean a group derived from purine, pteridine, indolizine, benzothiadiazole, benzoanthrene, benzoanthracene, rubicene and triphenylene. For the purposes of the present invention, fluorene, spirobifluorene, indenofluorene, anthracene, phenanthrene, dihydrophenanthrene and carbazole are particularly preferred.

  An aryl group in the sense of the present invention contains 5 to 60 C atoms, and a heteroaryl group in the meaning of the present invention contains 2 to 60 C atoms and at least one heteroatom, provided that The total of C atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Here, an aryl group or heteroaryl group means a simple aromatic ring, such as benzene, or a simple heteroaromatic ring such as pyridine, pyrimidine, thiophene, or a condensed aryl or heteroaryl group such as naphthalene, anthracene, etc. It shall mean any of phenanthrene, quinoline, isoquinoline, benzothiophene, benzofuran and indole.

In the structural units of the general formulas (LI) and (L-II), R ¹ and R ² , and R ¹ , R ² , R ³ and R ⁴ are each independently of each other each occurrence, F, Cl, Br, I, N (Ar) ₂ , N (R ′) ₂ , CN, NO ₂ , Si (R ′) ₃ , B (OR ′) ₂ , C (═O) Ar, C (= O) R ′, P (═O) (Ar) ₂ , P (═O) (R ′) ₂ , S (═O) Ar, S (═O) R ′, S (═O) ₂ Ar, S _{(= O) 2 R ',} - CR' = CR'Ar, OSO 2 R ', 1~40 C atoms, preferably a straight chain having from 1 to 20 C atoms alkyl, alkoxy or thioalkoxy Or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, preferably 3 to 20 C atoms, each of which is 1 Wherein one or more non-adjacent CH ₂ groups are R′C═CR ′, C≡C, Si (R ′) ₂ , Ge (R ′) ₂ , Sn (R ′) ₂ , C═O, C═S, C═Se, C═NR ′, P (═O) (R ′), SO, SO ₂ , NR ′, O, S, or CONR ′ One or more H atoms may be replaced by F, Cl, Br, I, CN or NO ₂ , a bridging group, or an aromatic having 5 to 60 ring atoms Group or heteroaromatic ring systems, which may in each case be substituted by one or more radicals R ′, or aryloxy or heteroaryloxy groups having 5 to 60 ring atoms (these are Which may be substituted with one or more radicals R ′), or a combination of these systems. In which two or more substituents R may be taken together to form a monocyclic or polycyclic, aliphatic or aromatic ring system, wherein R ′ is In each case, independently of each other, is H or is an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms, Ar has 2 to 30 C atoms An aryl or heteroaryl group.

  The structural units of the general formulas (LI) and (L-II) can contain one or more crosslinkable groups as described above. “Crosslinkable group” means a functional group capable of reacting irreversibly. Cross-linked materials are insoluble but are thereby formed. Crosslinking is usually assisted by warming or UV, microwave, x-ray or electron emission. Slight by-product formation now occurs during crosslinking. Furthermore, the crosslinkable groups that may be present in the functional compound crosslink very easily, which means that less energy is required for crosslinking (in the case of thermal crosslinking, for example <200 ° C.).

Examples of crosslinkable groups are double bonds, triple bonds, precursors in which double or triple bonds can be formed in situ, or units containing heterocyclic addition polymerizable radicals. As crosslinkable group, among others, vinyl, alkenyl, preferably ethenyl and propenyl, C 4 _{~ 20} - cycloalkenyl, azide, oxirane, oxetane, di (hydrocarbyl) amino, cyanate ester, hydroxyl, glycidyl ether, C 1 _{~ 10} -Alkyl acrylate, C _1-10 -alkyl methacrylate, alkenyloxy, preferably ethenyloxy, perfluoroalkenyloxy, preferably perfluoroethenyloxy, alkynyl, preferably ethynyl, maleimide, tri (C _{1- 4)} - alkyl siloxy, and tri (C 1 _{~ 4)} - include alkylsilyl. Vinyl and alkenyl are particularly preferred.

In the present invention, an alkyl group having 1 to 40 C atoms (in addition, each H atom or CH ₂ group may be substituted with the above group or radical R) is preferably methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n -Heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl , Heptenyl, cycloheptenyl, octenyl, cyclooct Alkylsulfonyl, ethynyl, propynyl, butynyl, pentynyl, it shall mean the radical hexynyl and octynyl. Alkoxy groups having 1 to 40 C atoms are preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2- It shall mean methylbutoxy.

  According to a particular embodiment of the invention, the weight ratio of structural element A to structural element B in formula (I) is preferably in the range 2: 1 to 1:20, particularly preferably 1: 1 to 1: 3 range.

  The functional compounds of formula (I) present in the formulations according to the invention can be prepared using known methods, in which the starting material containing reactive groups reacts. These reactive starting materials contain the structural units described above, and in each case at least one leaving group such as bromine, iodine, boronic acid or boronic ester.

  Suitable reactions for the formation of C—C linkages are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred coupling reactions all produce C—C linkages and are SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA and HIYAMA coupling reactions.

Particularly preferred functional compounds include compounds of formula (V-Ia), (V-Ib), (V-Ic) and (V-Id).

[Where the following applies to the symbols used:
Each occurrence of DCy is equal or different and contains a cyclic group (which contains at least one donor atom (preferably nitrogen, carbon in the form of a carbene, or phosphorous) via this donor atom. The cyclic group is bonded to a metal, which in turn can carry one or more substituents R ¹⁰ ), the groups DCy and CCy being bonded to each other via a covalent bond;
Each occurrence of CCy is equal or different and includes a cyclic group (which contains a carbon atom, through which the cyclic group is bonded to a metal, and then the metal has one or more Substituent R ¹⁰ can be carried),
Each occurrence of A is equally or differently a monoanionic, bidentate chelating ligand, preferably a diketonate ligand;
R ¹⁰ is equal or different for each occurrence, and H, D, F, Cl, Br, I, CHO, C (═O) Ar ³ , P (═O) (Ar ³ ) ₂ , S (= O) Ar ³ , S (═O) ₂ Ar ³ , CR ¹¹ = CR ¹¹ Ar ³ , CN, NO ₂ , Si (R ¹¹ ) ₃ , B (OR ¹¹ ) ₂ , B (R ¹¹ ) ₂ , B ( N (R ¹¹ ) ₂ ) ₂ , OSO ₂ R ¹¹ , a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or a straight chain alkenyl having 2 to 40 C atoms or An alkynyl group or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which may be substituted with one or more radicals R ¹¹ , one or more non-adjacent CH ₂ ^{group, R 11 C = CR 11,} C _{^{C, Si (R 11) 2}} , Ge (R 11) 2, Sn (R 11) 2, C = O, C = S, C = Se, C = NR 11, P (= O) (R 11), May be replaced by SO, SO ₂ , NR ¹¹ , O, S or CONR ¹¹ , wherein one or more H atoms may be replaced by F, Cl, Br, I, CN or NO ₂ Or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case may be substituted with one or more radicals R ¹¹ , or 5 to 60 An aryloxy or heteroaryloxy group having one aromatic ring atom, which may be substituted with one or more radicals R ¹¹ , or a combination of these systems, wherein two or more adjacent substituents R ¹⁰ may also, together with each other, monocyclic or polycyclic May form an aliphatic or aromatic ring system,
Ar ³ is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each equal or different, that is substituted with one or more radicals R ^11. You can,
R ¹¹ is equal to or different from each occurrence and is H, D, CN, or an aliphatic, aromatic and / or heteroaromatic hydrocarbon radical having 1 to 20 C atoms. In addition, the H atom may be replaced by F, wherein two or more adjacent substituents R ¹¹ are also taken together to form a monocyclic or polycyclic, aliphatic or aromatic May form a ring system,
At least one of said radicals DCy, CCy and / or A contains at least one group of formula (LI) and / or (L-II)].

A bridge may also exist between the groups DCy and CCy by forming a ring system between the radicals R ¹⁰ . Furthermore, a bridge is formed between two or three ligands CCy-DCy or with one or two ligands CCy-DCy by the formation of a ring system between the radicals R ^10. It may also exist between ligands A, resulting in a multidentate or multipodal ligand system, respectively.

According to a further specific embodiment of the invention, a soluble functional compound, in particular a polyacene of the formula (V-II), is utilized.

[Where:
The radicals R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each independently hydrogen, 1 to 40 Straight chain alkyl, alkoxy or thioalkoxy groups having C atoms, or branched or cyclic alkyl, alkoxy or thioalkoxy groups, or silyl groups having 3 to 40 C atoms, or 1 to 40 C A substituted keto group having an atom, an alkoxycarbonyl group having 2 to 40 C atoms, an aryloxycarbonyl group having 7 to 40 C atoms, a cyano group (-CN), a carbamoyl group (-C (= O) NH ₂ ), haloformyl group (—C (═O) —X (wherein X represents a halogen atom), formyl group (—C (═O) —H), isocyano group, isocyanate group, thiocyanate A substituted or unsubstituted aromatic or heteroaromatic group having 5 or 60 ring atoms, or a thioisocyanate group, amino group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, crosslinkable group A ring system of the group or an aryloxy or heteroaryloxy group having 5 to 60 ring atoms, or a combination of these systems, the groups R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and / or R ²³ are combined with each other and / or the ring to which the respective groups are bonded. May form monocyclic or polycyclic, aliphatic or aromatic ring systems, R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁸ and R ¹⁹ , R Each pair of ¹⁹ and R ²⁰ , R ²⁰ and R ²¹ is independently a saturated or unsaturated C ₄ May be formed in some cases a -C ₄₀ ring, they may include one or more oxygen and / or sulfur atom or the formula -N (R ^a) - may be split at a group, R ^a represents a hydrogen atom Or represents an optionally substituted hydrocarbon group, wherein the ring is one or more carbon atoms of the optionally substituted polyacene skeleton is N, P, As, O, S, Se and One or more heteroatoms selected from Te may be optionally substituted, and one or more of the substituents R ^{12 to} R ²³ (located in adjacent ring positions of the polyacene) are taken together May form further saturated or unsaturated rings, which may be interrupted by one or more oxygen and / or sulfur atoms or groups of formula —N (R ^a ) — ^a is a hydrogen atom or A substituted hydrocarbon group or an aromatic ring system bonded to polyacene,
n is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, particularly preferably 0 or 2,
At least one of the radicals R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and / or R ²³ has the formula (L— Including at least one group of I) or (L-II)]
When n in formula (V-II) is equal to 2, this compound is a pentacene compound. When n = 0, the compound can be a “pseudopentacene compound”.

According to a further embodiment, the present invention provides a formulation comprising a functional compound of general formula (V-IIIa) and / or (V-IIIb).

[Where the following applies to symbols and subscripts:
Y ^*, if group X ² is bonded to the group Y, is C, or if any of the groups X ² is not attached to group Y, in each occurrence, equal or different, CR or N And
E is equal or different for each occurrence, and is a single covalent bond or N (R ²⁵ ), B (R ²⁵ ), C (R ²⁵ ) ₂ , O, Si (R ²⁵ ) ₂ , C = A bivalent bridge selected from NR ²⁵ , C═C (R ²⁵ ) ₂ , S, S═O, SO ₂ , P (R ²⁵ ) and P (═O) R ¹ ;
X ¹ is equal or different for each occurrence, and N (R ²⁵ ), B (R ²⁵ ), O, C (R ²⁵ ) ₂ , Si (R ²⁵ ) ₂ , C = NR ²⁵ , C = C A bivalent bridge selected from (R ²⁵ ) ₂ , S, S═O, SO ₂ , P (R ²⁵ ) and P (═O) R ²⁵ ;
X ² is equal or different for each occurrence, and N (R ²⁵ ), B (R ²⁵ ), C (R ²⁵ ) ₂ , Si (R ²⁵ ) ₂ , C═O, C═NR ²⁵ , C = C (R ²⁵ ) ₂ , S, S = O, SO ₂ , CR ²⁵ -CR ²⁵ , P (R ²⁵ ) and P (= O) R ²⁵
X ³ is a bivalent bridge selected from N, B, C (R ¹ ), Si (R ¹ ), P and P (═O), equal or different for each occurrence;
L is a divalent aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted with one or more radicals R ¹ ,
n and m are 0 or 1, provided that n + m = 1 or 2;
q is 1, 2, 3, 4, 5 or 6;
R ²⁴ is the same or different for each occurrence, and H, D, F, Cl, Br, I, N (Ar) ₂ , C (═O) Ar, P (═O) Ar ₂ , S (= O) Ar, S (= O) ₂ Ar, CR ²⁶ = CR ²⁶ Ar, CN, NO ₂ , Si (R ²⁶ ) ₃ , B (OR ²⁶ ) ₂ , OSO ₂ R ²⁶ , 1 to 40 C atoms A straight-chain alkyl, alkoxy or thioalkoxy group having a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is substituted with one or more radicals R ²⁶ Where one or more non-adjacent CH ₂ groups are R ²⁶ C═CR ²⁶ , C≡C, Si (R ²⁶ ) ₂ , Ge (R ²⁶ ) ₂ , Sn (R ²⁶ ) ₂ , C = O, C = S , C = Se, C = NR 26, P (= O) (R 26), SO, SO 2, N ^26, O, may be replaced by S or CONR ^26, 1 or more H atoms, D, F, Cl, Br, I, may be replaced by CN, or NO _2, crosslinkable groups or, Aromatic or heteroaromatic groups having 5 to 40 ring atoms, each of which may be substituted with one or more radicals R ²⁶ , or aromatic having 5 to 40 aromatic ring atoms Or a heteroaromatic ring system, in each case substituted by one or more radicals R ²⁶ , or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms (one or more radicals) R ²⁶ ), or a combination of these systems, wherein two or more substituents R ²⁴ are also taken together to form an atom to which they are attached Together Or together with Ar, if they are attached to Ar, may form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system;
R ²⁵ is equal or different each time it appears, and H, D, F, Cl, Br, I, CN, NO ₂ , CF ₃ , B (OR ²⁶ ) ₂ , Si (R ²⁶ ) ₃ , 1 to A straight chain alkyl, alkoxy or thioalkoxy group having 40 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is one or more One or more non-adjacent CH ₂ groups may be substituted with a radical R ²⁶ where —R ²⁶ C═CR ²⁶ —, —C≡C—, Si (R ²⁶ ) ₂ , Ge (R ²⁶ ) ₂ , Sn (R ²⁶ ) ₂ , C═O, C═S, C═Se, C═NR ²⁶ , —O—, —S—, —COO— or —CONR ²⁶ — may be substituted. One or more H atoms can be placed with D, F, Cl, Br, I, CN or NO ₂ Or arylamine, or substituted or unsubstituted carbazole, each of which may be substituted with one or more radicals R ²⁶ , or aryl having 5 to 40 ring atoms Or a heteroaryl group (optionally substituted with one or more aromatic or heteroaromatic or non-aromatic radicals R ²⁷ ), or aromatic or heteroaromatic having 5 to 40 aromatic ring atoms A ring system (optionally substituted with one or more non-aromatic radicals R ²⁶ ), or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms (one or more non-aromatic radicals R ²⁷ in optionally substituted), or a combination of these systems, where two or more substituents R ²⁵ also together with the atom to which they are attached, a single Expression or polycyclic, aliphatic, it may form together an aromatic or heteroaromatic ring system,
R ²⁶ is an aliphatic or aromatic hydrocarbon radical having H, D or 1 to 20 C atoms, which is equal or different each time it appears;
Ar ⁴ is an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, each equal or different, which may be substituted with one or more radicals R ^25. ,
At least one of the aforementioned radicals comprises a group of formula (LI) and / or (L-II)]
According to a further preferred embodiment of the invention, functional compounds of the general formula (V-IVa) and / or formula (V-IVb) are preferred.

[Where the following applies to symbols and subscripts:
Ar ⁵ is a group of the following formula (V-IVc):

(In the formula, a bond indicated by a broken line indicates a bond with spirobifluorene)
Ar ⁶ is a group of the following formula (V-IVd):

(In the formula, a bond indicated by a broken line indicates a bond with spirobifluorene)
R ²⁸ and R ²⁹ are the same or different each time they appear, and H, D, F, Cl, Br, I, CHO, N (R ³⁰ ) ₂ , N (Ar ⁷ ) ₂ , B (Ar ⁷ ) ₂ , C (═O) Ar ⁷ , P (═O) (Ar ⁷ ) ₂ , S (═O) Ar ⁷ , S (═O) ₂ Ar ⁷ , CR ³⁰ = CR ³⁰ Ar ⁷ , CN, NO ₂ , Si (R ³⁰ ) ₃ , B (OR ³⁰ ) ₂ , B (R ³⁰ ) ₂ , B (N (R ³⁰ ) ₂ ) ₂ , OSO ₂ R ³⁰ , each having 1 or 2 to 40 C atoms A linear alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is one or more may be substituted by radicals R ^30, wherein one or more non-adjacent H ₂ ^{groups, R 30 C = CR 30,} C≡C, Si (R 30) 2, Ge (R 30) 2, Sn (R 30) 2, C = O, C = S, C = Se, C ═NR ³⁰ , P (═O) (R ³⁰ ), SO, SO ₂ , NR ³⁰ , O, S, or CONR ³⁰ , where one or more H atoms are D, F, Cl, Br , I, CN or NO ₂ , a crosslinkable group, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, in each case one or more radicals R may be substituted with ³⁰ or 5 to 60 amino aryloxy or heteroaryloxy group having an aromatic ring atom (optionally substituted by one or more radicals R ^30), or a combination of these systems, , and the wherein the two or more adjacent substituents R ²⁸ also together with each other May form a monocyclic or polycyclic, aliphatic or aromatic ring system,
Ar ⁷ is an aromatic or heteroaromatic ring system (optionally substituted with one or more radicals R ³⁰ ) having 5 to 30 aromatic ring atoms, equal or different each time it appears. Where two radicals Ar ⁷ bonded to the same nitrogen, phosphorus or boron atom are also mutually linked to B (R ³⁰ ), C (R ³⁰ ) ₂ , Si (R ³⁰ ) ₂ , C═O, C = NR ³⁰ , C = C (R ³⁰ ) ₂ , O, S, S═O, SO ₂ , N (R ³⁰ ), P (R ³⁰ ) and P (= O) R ³⁰ They may be linked by a bond or a crosslink,
R ³⁰ is equal to or different from each occurrence H, D, or an aliphatic, aromatic and / or heteroaromatic hydrocarbon radical having 1 to 20 C atoms; The H atom may be replaced by D or F, wherein two or more adjacent substituents R ³⁰ are also taken together to form a monocyclic or polycyclic aliphatic or aromatic ring. A system may be formed,
n is 0 or 1,
m is 0, 1, 2 or 3;
o is 0, 1, 2, 3 or 4 when n = 0 in the same ring, and 0, 1, 2, or 3 when n = 1 in the same ring].

Furthermore, a soluble functional compound of formula (V-V) is preferred.

[Wherein R ¹⁰ has the same meaning as described above for the formulas (V-Ia), (V-Ib), (V-Ic) and (V-Id), Represents the two or three atoms and bonds necessary to create a 5- or 6-membered ring with M, where these atoms may also be substituted with one or more radicals R ¹⁰ , At least one of them comprises a group of formula (LI) and / or (L-II), M represents an alkali metal selected from lithium, sodium, potassium, rubidium and cesium]
Here, the complex of the formula (VV) is in the form of a monomer as shown above, or in the form of an aggregate (for example, two alkali metal ions and two ligands, four alkali metals Ions and four ligands, including six alkali metal ions and six ligands), or other aggregate forms.

Preferred compounds of the formula (V-V) are compounds of the following formulas (V-V1) and (V-V2).

(Wherein the symbols used are those described above for the formulas (V-Ia), (V-Ib), (V-Ic) and (V-Id)) and the formula (V-V ) Has the same meaning as described above, m represents 0, 1, 2 or 3 equal or different for each occurrence, and o equal or different for each occurrence. Represents 0, 1, 2, 3 or 4.

Further preferred organoalkali metal compounds are compounds of the following formula (V-V3):

[Wherein the symbols used are those described above for formulas (V-Ia), (V-Ib), (V-Ic) and (V-Id), and the formula (V-V And at least one of the above-mentioned radicals comprises a group of formula (LI) and / or (L-II)].

  The alkali metal is preferably selected from lithium, sodium and potassium, particularly preferably selected from lithium and sodium, very particularly preferably lithium.

  Particular preference is given to compounds of the formula (V-V1), in particular those with M = lithium. Furthermore, the subscript m is very particularly preferably = 0. The compound is therefore very particularly preferably unsubstituted lithium quinolinate.

According to a preferred embodiment of the present invention, compounds of the general formula (V-VIa) are preferred, particularly preferred is the formula (V-VIb).

(Where the following applies to the symbols used:
R ⁵ is the same or different for each occurrence, hydrogen, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (which may be substituted with one or more radicals R ^6. N (Ar) ₂ , Si (Ar) ₃ , C (═O) Ar, OAr, ArSO, ArSO ₂ , P (Ar) ₂ , P (O) (Ar) ₂ or B ( Ar) ₂ groups,
R ⁶ is the same or different for each occurrence, and H, D, F, Cl, Br, I, CHO, N (Ar) ₂ , C (═O) Ar, P (═O) (Ar) ₂ , S (= O) Ar, S (= O) ₂ Ar, CR ⁷ = CR ⁷ Ar, CN, NO ₂ , Si (R ⁸ ) ₃ , B (OR ⁸ ) ₂ , B (R ⁸ ) ₂ , B (N (R ⁸ ) ₂ ) ₂ , OSO ₂ R ⁸ , a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or branched or cyclic having 3 to 40 C atoms Each of these alkyl, alkoxy or thioalkoxy groups, each optionally substituted by one or more radicals R ⁸ , wherein one or more non-adjacent CH ₂ groups are R ⁸ C═CR ⁸ , C≡ _{^{C, Si (R 8) 2}} , Ge (R 8) 2, Sn (R 8) 2, C = O, C = S, C = Se, C = NR 8 ^{P (= O) (R 8} ), SO, SO 2, NR 8, O, may be replaced by S or CONR ^8, 1 or more H atoms, F, Cl, Br, I , CN or NO ₂ or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms (in each case optionally substituted by one or more radicals R ⁸ ) Or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms (optionally substituted with one or more radicals R ⁸ ), or a combination of these systems,
Each occurrence of R ⁷ is equal or different, H, D, F, or a straight-chain alkyl group having 1 to 20 C atoms, or 3 to 20 C atoms, A branched or cyclic alkyl group, wherein a plurality of radicals R ⁷ may be taken together to form a ring system;
R ⁸ is an aliphatic, aromatic and / or heteroaromatic hydrocarbon radical having H, D, or 1 to 20 C atoms, equal or different each time it appears; The atom may be replaced by F;
Ar is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, each equal or different, that is substituted with one or more non-aromatic radicals R ⁶ . Where two radicals Ar bonded to the same nitrogen, phosphorus or boron atom are also single bonds to each other, or B (R ⁸ ), C (R ⁸ ) ₂ , Si (R ⁸ _{) 2, C = O, C} = NR 8, C = C (R 8) 2, O, S, S = O, SO 2, N (R 8), P (R 8) and P (= O) R ^And may be linked by a bridge selected from ⁸ ).

According to a particularly preferred embodiment, it is possible to utilize compounds of the formula (V-VIc):

[Where the following applies to the symbols used:
Y is C═O or C (R ⁷ ) ₂ ,
X is equal to or different from each occurrence and is CR ⁹ or N;
R ⁵ has the meaning given above in connection with formula (V-VIa)
R ⁷ has the meaning given above in connection with formula (V-VIa),
R ⁹ is equal or different for each occurrence, H, D, F, CN, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or 3 to 40 C atoms Branched or cyclic alkyl, alkoxy or thioalkoxy groups, each of which may be substituted with one or more radicals R ⁷ , wherein one or more non-adjacent CH ₂ groups are R ⁷ C═CR ⁷ , C≡C, O or S may be substituted, and one or more H atoms may be replaced with F].

Particularly preferred functional compounds of formula (I) for use include, among others:

  The formulations according to the invention are distinguished in particular by the presence of a mixture of at least two functional compounds of the formula (I).

  Here, the functional compound may contain different functional structural elements A. With respect to the first preferred embodiment, by way of example, in particular, at least one functional compound in which the functional structural element A of the formula (I) is a unit having luminescent properties, and the functional structural element A of the formula (I) And a mixture containing at least one functional compound which is a unit capable of functioning as a host substance.

  In a second preferred embodiment, the mixture comprises at least one functional compound in which the functional structural element A of the formula (I) is a unit having luminescent properties and the functional structural element A of the formula (I) And at least one functional compound which is a unit capable of functioning as a hole transport material.

  In a third preferred embodiment, the mixture comprises at least one functional compound in which the functional structural element A of the formula (I) is a unit having luminescent properties, and the functional structural element A of the formula (I) And at least one functional compound which is a unit capable of functioning as an electron transport material.

  In this context, it can be explained that the compounds utilized as host materials may also function as electron transport materials or as hole transport materials in some cases.

  In a fourth preferred embodiment, the mixture comprises at least one functional compound in which the functional structural element A of formula (I) is a unit having luminescent properties, and the functional structural element A of formula (I) At least one functional compound which is a unit capable of functioning as a hole transport material, and at least one function wherein the functional structural element A of the formula (I) is a unit capable of functioning as an electron transport material Compound.

  In a fifth preferred embodiment, this mixture comprises at least one functional compound in which the functional structural element A of formula (I) is a unit capable of functioning as a hole transport material, and of formula (I) The functional structural element A includes at least one functional compound that is a unit capable of functioning as an electron transport material.

  In a preferred embodiment, the weight ratio of the functional compound in which the functional structural element A of the formula (I) is a unit having luminescent properties is preferably 2 to 40 with respect to all functional compounds in the formulation. It is in the range of wt%, particularly preferably in the range of 3-30 wt%, in particular in the range of 5-25 wt%. Correspondingly, the weight ratio of at least one functional compound, which is a unit in which the functional structural element A of the formula (I) can function as a host material, is based on all functional compounds in the formulation. The range is preferably 60 to 98% by weight, particularly preferably 70 to 97% by weight, and particularly preferably 75 to 95% by weight.

  However, in a further preferred embodiment, the weight ratio of functional compounds in which the functional structural element A of the formula (I) is a unit having luminescent properties is also preferably with respect to all functional compounds in the formulation , 0.01 to 5% by weight, particularly preferably 0.05 to 3% by weight, and particularly 0.1 to 2% by weight. Correspondingly, in this embodiment, the weight ratio of at least one functional compound, which is a unit in which the functional structural element A of formula (I) can function as a host material, Preferably, it is in the range of 95 to 99.95% by weight, particularly preferably in the range of 97 to 99.9% by weight, particularly in the range of 98 to 99.9% by weight. Good.

  Furthermore, it is also possible to use a mixture whose structural element A exhibits the same functionality. Preferred mixtures of this type include in particular formulations having at least two functional compounds, in which the functional structural element A of the formula (I) is a unit that can function as a host material.

  Here, a mixture comprising at least three functional compounds of the formula (I) is particularly preferred, of which at least two functional compounds exhibit the same functionality and at least one functional compound is the first Includes functionality different from that. In particular, the functional structural element A of the formula (I) is a unit capable of functioning as a host material, and at least two functional compounds, and the functional structural element A of the formula (I) has a luminescent property. Especially preferred are mixtures having at least one functional compound.

  Formulations according to the present invention may also include functional compounds that do not contain dissolution promoting structural elements. However, these formulations often exhibit lower performance profiles than formulations that exclusively contain the functional compound of formula (I) as a functionally active ingredient. Therefore, in particular, the proportion of the functional compound not containing the dissolution promoting structural element B of the general formula (LI) is preferably at most 80% by weight, particularly preferably, based on the total weight of the functional compound, Surprising advantages can be achieved with formulations of up to 50% by weight, very particularly preferably up to 10% by weight. According to a particular embodiment, the formulation according to the invention may be free of functional compounds that do not contain dissolution-promoting structural elements, so that the formulation is essentially a solvent, a functional compound of formula (I) And an additive.

In accordance with certain aspects of the present invention, in particular, formulations containing chemical 222 may be excluded.

In addition, in particular, formulations containing Chemical Formula 223 may be excluded from the present invention.

Furthermore, in accordance with a particularly preferred aspect of the present invention, the formulation comprising 224 may be excluded.

  In addition to the above components, the formulation according to the invention may comprise further additives and processing aids. Among these, surfactants, surfactants, lubricants and greases, additives that increase conductivity, dispersants, hydrophobizing agents, adhesion promoters, flow improvers, antifoaming agents, deaerators , Including diluents (which may be reactive or non-reactive), excipients, auxiliaries, processing aids, dyes, pigments, stabilizers, heat sensitive agents, nanoparticles and inhibitors, etc. It is.

  The compound containing the structural unit according to the invention is preferably an OLED or other electronic device, for example, preferably as a layer for hole transport, hole injection, illuminant, electron transport, electron injection, charge blocking and / or charge generation. Used for the manufacture of.

  The functional layer can be applied, for example, by coating from a solution, preferably by spin coating, or by any desired printing method, such as screen printing, flexographic printing or offset printing, but particularly preferably LITI (light-induced thermal imaging, thermal transfer). Printing) or ink jet printing.

  The invention also relates to the use of functional compounds in organic electronic devices.

  The organic electronic device is preferably an organic electroluminescent device (OLED), a polymer electroluminescent device (PLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT) ), Organic light emitting transistor (O-LET), organic solar cell (O-SC), organic optical detector, organic photoreceptor, organic electric field quenching device (O-FQD), light emitting electrochemical cell (LEC) or organic laser diode (O-laser).

  For the purposes of the present invention, the functional compound according to the present invention is preferably in the form of (or present in) a layer in an electronic device.

  The invention therefore also relates to layers, in particular organic layers comprising one or more compounds as defined above.

  In a further embodiment of the invention, the device comprises a plurality of layers. The compounds according to the invention can preferably be present here in the hole transport, hole injection, electron transport, electron injection and / or luminescent layer. Particular preference is given to the use of the compounds according to the invention in hole transporting and / or light emitting layers.

  The present invention therefore also relates to an electronic device comprising at least three layers, but in a preferred embodiment, all of the layers from the hole injection, hole transport, light emission, electron transport, electron injection, charge blocking and / or charge generation layers. Including said layer, at least one layer contains the compound to be utilized according to the present invention. For example, the thickness of a layer such as a hole transport and / or hole injection layer can preferably be in the range of 1 to 500 nm, particularly preferably in the range of 2 to 200 nm.

  The device may further comprise a layer constructed from a lower molecular weight compound or polymer. They can also be produced by vapor deposition of low molecular compounds in high vacuum.

  Further, the compounds utilized in accordance with the present invention may not be used as pure materials, but instead as a mixture with any desired type of additional polymer, oligomer, dendritic or low molecular material. It may be preferable. They can e.g. improve the electronic properties or emit themselves. The application thus relates to this type of mixture as well.

  In a preferred embodiment of the present invention, the compound according to the present invention is utilized as a host material or matrix material of the light emitting layer. The organic electroluminescent device may here comprise one or more light-emitting layers, at least one light-emitting layer comprising at least one compound according to the invention as defined above. When there are multiple light emitting layers, these preferably have a plurality of light emission of up to 380 nm to 750 nm, producing a white light emission as a whole. That is, various light emitting compounds that can emit fluorescence or phosphorescence are used in the light emitting layer. A three-layer system is very particularly preferred, and the three layers exhibit blue, green and orange or red emission (for basic structure see eg WO05 / 011013). Devices that emit white light are suitable, for example, as backlighting for LCD displays or for general lighting applications.

  Apart from these layers, the organic electroluminescent device also has additional layers, for example in each case one or more hole injection layer, hole transport layer, hole blocking layer, electron transport layer, electron injection layer, exciton blocking. Layer and / or charge generation layer (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer). Similarly, for example, an intermediate layer having an exciton blocking function can be inserted between two light emitting layers. However, it should be pointed out that each of these layers may not necessarily be present. These layers can likewise contain a compound according to the invention as defined above. It is also possible to arrange a plurality of OLEDs above and below, which makes it possible to achieve a further increase in efficiency with respect to light yield. In order to improve the light coupling out, the final organic layer on the light exit side of the OLED can also be, for example, in the form of a nanofoam, resulting in a reduction in the ratio of total reflection.

Further preferred are organic electroluminescent devices wherein one or more layers are applied using a sublimation process, in which case the material is less than 10 ⁻⁵ mbar, preferably less than 10 ⁻⁶ mbar, particularly preferably less than 10 ⁻⁷ mbar. Applied by vapor deposition in a vacuum sublimation unit.

Also preferred are organic electroluminescent devices, characterized in that one or more layers are applied using the OVPD (Organic Vapor Deposition) method or with the aid of carrier gas sublimation, in which case the material is 10 Applied at atmospheric pressure between ^-5 mbar and 1 bar.

  One or more layers may be formed by, for example, spin coating, or any desired printing method such as screen printing, flexographic printing or offset printing, but particularly preferably such as LITI (light-induced thermal imaging, thermal transfer printing) or ink jet printing Further preferred is an organic electroluminescent device, characterized in that it is produced from a solution using

  The device typically includes a cathode and an anode (electrode). In order to ensure highly efficient electron or hole injection, the electrodes (cathode, anode) are for the purposes of the present invention such that their band energies are as close as possible to those of adjacent organic layers. Selected.

The cathode is preferably a metal complex, a metal with a low work function, various metals (eg alkaline earth metals, alkali metals, main group metals or lanthanoids (eg Ca, Ba, Mg, Al, In, Mg, Yb, Sm Etc.) etc.) including metal alloys or multilayer structures. In the case of a multi-layer structure, further metals with a relatively high working function (for example Ag etc.) can also be used in addition to the metals, in which case a combination of metals such as Ca / Ag or Ba / Ag is common Used for. It is also preferred to insert a thin intermediate layer of material having a high dielectric constant between the metal cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal or alkaline earth metal fluorides, but the corresponding oxides (eg LiF, Li ₂ O, BaF ₂ , MgO, NaF, etc.) are also suitable. The layer thickness of this layer is preferably between 1 and 10 nm, particularly preferably between 2 and 8 nm.

The anode preferably comprises a material having a high work function. The anode is preferably vs. Has a potential in excess of 4.5 eV in vacuum. Suitable for this purpose are, on the one hand, metals with a high redox potential, such as Ag, Pt or Au. On the other hand, metal / metal oxide electrodes (eg Al / Ni / NiO _x , Al / PtO _x ) may also be preferred. For some applications, at least one electrode must be transparent to facilitate either organic material (O-SC) irradiation or light coupling out (OLED / PLED, O-laser) . A preferred structure uses a transparent anode. Preferred anode materials here are conductive, mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) is particularly preferred. Even more preferred are conductive, doped organic materials, particularly conductive, doped polymers such as poly (ethylenedioxythiophene) (PEDOT) and polyaniline (PANI).

  The invention likewise relates to a method for the manufacture of an electronic device, wherein the formulation according to the invention is applied to a substrate and dried.

The solvent can be removed preferably at a temperature in the range from −50 ° C. to 300 ° C., particularly preferably in the range from 20 ° C. to 250 ° C. The drying can here be carried out at a pressure in the range from 10 ⁻³ mbar to 1 bar, particularly preferably in the range from 10 ⁻² mbar to 100 mbar.

  The device is correspondingly structured, brought into contact and finally sealed in a manner known per se, depending on the application. This is because the lifetime of such devices is greatly shortened in the presence of moisture and / or air.

  The invention is explained in more detail below with reference to the examples, but without being limited thereby.

[Example]
Example 1
Synthesis of compounds 3 and 4

Synthesis of Compound 3 40.0 g (146 mmol) of 3-borono- [3,1 ′; 5,1 ″] terphenyl 2, 18.8 g (146 mmol) of 1-iodo-3-bromophenyl (1) and 109.3 g (730 mmol) of potassium carbonate is suspended in 1350 ml of toluene and 1150 ml of water. 844 mg (0.73 mmol) tetrakis (triphenylphosphine) palladium (0) is added to the suspension and the reaction mixture is heated to reflux for 16 hours. After cooling, the organic phase is separated, washed 3 times with 200 ml of water, dried using sodium sulphate and subsequently evaporated to dryness. The residue is washed with ethanol, recrystallised from ethyl acetate and finally dried under reduced pressure. The yield is 47.6 g (123 mmol), which corresponds to 84.5% in theory.

Synthesis of Compound 4 40.0 g (104 mmol) of 1-bromo-3-([3,1 ′; 5,1 ″] terfen-1-yl) phenyl 3, 29.0 g (114 mmol) of bispinacolatodi Boron, 29.5 g (301 mmol) of potassium acetate is suspended in 800 ml of dimethyl sulfoxide. 4.24 g (5.2 mmol) of 1,1-bis (diphenylphosphino) ferrocenepalladium (II) dichloride * DCM is added to the suspension and the reaction mixture is heated to reflux for 16 hours. After cooling, 600 ml of ethyl acetate and 400 ml of water are added, the organic phase is separated, washed 3 times with 200 ml of water, dried with sodium sulphate and subsequently evaporated to dryness. The crude product is recrystallized from heptane and finally dried under reduced pressure. The yield is 34.5 g (80 mmol), which corresponds to 46.1% in theory.

Example 2
Synthesis of compound 5

  74.7 g (150 mmol) bis (3,5-dibromophenyl) ketone, 109.7 g (900 mmol) phenylboronic acid, 267.5 g (1162 mmol) tripotassium phosphate monohydrate, 5.5 g (18 mmol) ) Tri-o-tolylphosphine and 673.5 mg (3 mmol) palladium (II) -acetate are suspended in a mixture of 600 ml toluene, 300 ml dioxane and 750 ml water and heated to reflux for 72 hours. After cooling, the organic phase is separated, washed 3 times with water and dried over sodium sulfate. The mixture is subsequently filtered through aluminum oxide, evaporated to approximately 200 ml and 500 ml of ethanol are added, at which point the crude product precipitates. The solid is filtered off with suction, washed with 100 ml of ethanol, then dissolved in boiling toluene and reprecipitated by the addition of hot ethanol. The yield is 44.0 g (90 mmol), which corresponds to 60.2% in theory.

Example 3
Synthesis of compound 6

  The synthesis is carried out in the same way as for compound 5, replacing phenylboronic acid with 1-bromo-3-([3,1 '; 5,1 "]-terphen-1-yl) phenyl3. The yield is 123.2 g (88 mmol), which corresponds to 58.7% in theory.

Example 4
Synthesis of compound 7

  28.0 g (50.0 mmol) spiro-9,9′-bifluorene-2-boronic acid, 14.7 g (55.0 mmol) 2-chloro-4,6-diphenyl-1,3,5-triazine and 44.6 g (210.0 mmol) of tripotassium phosphate are suspended in 500 ml of toluene, 500 ml of dioxane and 500 ml of water. 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium (II) acetate are added to the suspension and the reaction mixture is heated to reflux for 16 hours. After cooling, the organic phase is separated off, filtered through silica gel, washed 3 times with 200 ml of water and subsequently evaporated to dryness. The residue is recrystallised from toluene and finally sublimed in a high vacuum. The yield is 38 g (41.5 mmol), which corresponds to 95.0% in theory.

Example 5
Synthesis of Compound 8

a) Synthesis of 2-chloro-4,6-bis (3-([3,1 ′; 5,1 ″] terfen-1-yl) phen-1-yl) -1,3,5-triazine 80.2 ml of a 2.0 molar solution of n-butyllithium in abs. To a solution cooled to −78 ° C. containing 43.88 g (143 mmol) of 1-bromo-3-([3,1 ′; 5,1 ″] terphen-1-yl) phenyl in 250 ml of tetrahydrofuran is slowly added. Add dropwise and stir the mixture for 15 minutes. The reaction solution was cooled to −78 ° C. and 10.0 g (45 mmol) of cyanuric chloride abs. Slowly add dropwise to a solution in 400 ml of tetrahydrofuran and stop cooling. When it reaches room temperature, the precipitated product is filtered off. The yield is 6.3 g (9.0 mmol), which corresponds to 23.3% in theory.

b) 2- (4,6-bis (3-([3,1 ′; 5,1 ″] terfen-1-yl) phen-1-yl) -1,3,5-triazin-2-yl ) Synthesis of spiro-9,9'-bifluorene Using 4.07 g (11.3 mmol) of spiro-9,9'-bifluorene-2-boronic acid, 2-chloro-4,6-diphenyl-1,3 , 5-triazine, 6.3 g (9.0 mmol) of 2-chloro-4,6-bis- (3-([3,1 ′; 5,1 ″]-terfen-1-yl) phen- 1-yl) -1,3,5-triazine is substituted and the synthesis is carried out in the same manner as compound 7. The yield is 4.9 g (4.8 mmol), corresponding to 56.3% in theory.

Example 6
Synthesis of compound 9

8 g (28.2 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno [2,1-b] fluorene was dissolved in 225 ml of dimethylformamide under a protective gas atmosphere and mineral oil (37 1.5 g) of 60% NaH in 1.5 mmol) is added. After 1 hour at room temperature, a solution of 2-chloro-4,6-diphenyl-1,3,5-triazine (8.5 g, 31.75 mmol) in 75 ml dimethylformamide is added dropwise. The reaction mixture is then stirred at room temperature for 12 hours. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na ₂ SO ₄ and evaporated. The residue is extracted with hot toluene. The yield is 12 g (23 mmol), which corresponds to 83% in theory.

Example 7
Synthesis of compound 10

8.0 g (28 mmol) 12,12-dimethyl-10,12-dihydro-10-azaindeno [2,1-b] fluorene was dissolved in 210 ml dimethylformamide under a protective gas atmosphere and mineral oil (35 mmol) Add 1.4 g of medium 60% NaH. After 1 hour at room temperature, 2-chloro- [4,6-bis-5 ′-(3-bromophenyl)-[1,1 ′; 3 ′, 1 ″] terphenyl-5′-yl] -1 , 3,5-triazine (22.5 g, 31 mmol) in 250 ml dimethylformamide is added dropwise. The reaction mixture is stirred at room temperature for 12 hours. After this time, the reaction mixture is poured onto ice and extracted three times with dichloromethane. The combined organic phases are dried over Na ₂ SO ₄ and evaporated. The residue is recrystallized from heptane / toluene. The yield is 12.2 g (13 mmol), corresponding to 44% in theory.

Example 8
Synthesis of Compound 11

25.0 g (42.1 mmol) of 7-bromo-10- (4,6-diphenyl-1,3,5-triazin-2-yl) -12,12-dimethyl-10,12-dihydro-10-azaindeno 80 ml of [2,1-b] fluorene and 19.9 g of 1-pinacolylboronato-3-([3,1 ′; 5,1 ″] terfen-1-yl) phenyl (46.3 mmol) Dissolve in toluene and degas. 281 ml of degassed 2M K ₂ CO ₃ and 2.4 g (2.1 mmol) of Pd (PPh ₃ ) ₄ are added. The reaction mixture is subsequently stirred for 48 hours at 80 ° C. under a protective gas atmosphere. Toluene is added to the cooled solution and the mixture is washed several times with water, dried and evaporated. The residue is recrystallized from heptane / toluene. The yield is 21.8 g (26.6 mmol), which corresponds to 63.2% in theory.

Example 9
Synthesis of Compound 12

  Compound 12 is prepared as described in WO2008 / 088551A1.

Example 10
Synthesis of Compound 13

  Compound 13 is prepared as described in WO2009 / 124627.

Example 11
Synthesis of Compound 14

  1.7 g (2.0 mmol) of fac-tris [2- (2-pyridinyl-kN) (5-bromophenyl) -kC] -iridium (III), 7.42 g (17 mmol) of 1-pinacolylboronato -3-([3,1 ′; 5,1 ″] terfen-1-yl) benzene, 2.51 g (12 mmol) of potassium phosphate suspended in 100 ml of toluene, 100 ml of dioxane and 111 ml of water. Let 4 mg (0.1 mmol) palladium (II) acetate and 35 mg (0.2 mmol) tri-o-tolylphosphine are added to the suspension and the reaction mixture is heated to reflux for 24 hours. After cooling, the organic phase is separated off, washed 3 times with 200 ml of water, filtered through silica gel, dried with sodium sulphate and subsequently evaporated to dryness. The residue is recrystallized from dioxane / ethanol and finally dried under reduced pressure. The yield is 2.42 g (1.6 mmol), which corresponds to 80.9% in theory.

Example 12
Synthesis of Compound 15

a) Synthesis of 2- (3-pinacolylboronatophenyl) -4,6-diphenyl-1,3,5-triazine (Compound 4a)
The synthesis is carried out in the same manner as the synthesis of compound 4. The yield is 31.9 g (73 mmol), which corresponds to 81.3% in theory.

b) Synthesis of fac-tris [2- (2-pyridinyl-kN) (5- (3-phenyl (4,6-diphenyl-1,3,5-triazine) phenyl) -kC] iridium (III) (compound 15)
The synthesis is carried out in the same way as the synthesis of compound 14. The yield is 1.5 g (0.95 mmol), which corresponds to 55.6% in theory.

Example 13
Synthesis of Compound 16 fac-tris [2- (1-isoquinolinyl-kN) (5- (3-([3,1 ′; 5,1 ″] terphen-1-yl) phenyl) phenyl) -kC] iridium (III)

  The synthesis is carried out in the same way as the synthesis of compound 14. The yield is 6.52 g (3.8 mmol), corresponding to 65.6% in theory.

Example 14
Synthesis of Compound 22

a) Synthesis of Compound 18

  52 ml (130 mmol) n-butyllithium (2.5 M in n-hexane) was stirred vigorously at -78 ° C. with 30.7 g (100 mmol) 4-bromobenz [a] anthracene (17) in 1000 ml Add dropwise to the suspension in THF and stir the mixture for a further 2 hours. 16.7 ml (150 mmol) of trimethyl borate was added in one portion to the red solution with vigorous stirring and the mixture was stirred at −78 ° C. for a further 30 minutes and then allowed to warm to room temperature over 3 hours and 300 ml of water was added. Add and stir the mixture for 30 minutes. The organic phase is separated and evaporated to dryness in vacuo. The solid is taken up in 100 ml n-hexane, filtered off with suction, washed once with 100 ml n-hexane and dried in vacuo. Yield: 23.7 g (87.0 mmol), 87.0%, purity, approximately 90.0% (NMR) amount of boronic acid, boronic anhydride and borinic acid varied. The boronic acid can be used in this form without further purification.

b) Synthesis of compound 20

  25.0 g (97.2 mmol) of 9-bromoanthracene (19), 27.0 g (99.2 mmol) of benz [a] -anthracene-4-boronic acid (18) and 44.5 g (210 mmol) of phosphoric acid Tripotassium is suspended in 500 ml toluene, 600 ml water and 100 ml dioxane. 1.83 g (6.01 mmol) of tri-o-tolylphosphine and then 225 mg (1.00 mmol) of palladium (II) acetate are added to the suspension and the mixture is subsequently heated to reflux for 16 hours. After cooling, the organic phase is separated off, washed 3 times with 500 ml of water, dried with sodium sulphate and subsequently evaporated to dryness. The solid is recrystallized from 300 ml of toluene and finally dried under reduced pressure. The yield is 26.2 g (64.8 mmol), which corresponds to 64.8% in theory.

c) Synthesis of compound 21

  1.30 g (8.02 mmol) of iron (III) chloride, then 13.3 g (74.7 mmol) of N-bromosuccinimide, 26.0 g (64.3 mmol) of compound (20) in 600 ml of chloroform. To a suspension cooled to 0 ° C. and the mixture is stirred at 0 ° C. for 4 hours. After the mixture has been warmed to room temperature, 400 ml of water are added, the organic phase is separated, washed three times with 300 ml of water, dried with sodium sulphate and subsequently evaporated to dryness. The orange solid obtained is recrystallized from toluene and finally dried under reduced pressure. The yield is 23.7 g (49.0 mmol), which corresponds to 76.6% in theory.

d) Synthesis of compound 22

  2.0 g (4.14 mmol) of compound (21), 2.00 g (4.63 mmol) of 1-boronyl-3-([3,1 ′; 5,1 ″] terfen-1-yl) phenyl ( 4) and 1.70 g (16.0 mmol) sodium carbonate are suspended in 30 ml toluene, 7 ml water and 30 ml ethanol. 70 mg (0.061 mmol) of tetrakis (triphenylphosphine) palladium (0) is added to the suspension and the mixture is subsequently heated to reflux for 16 hours. After cooling, the precipitated solid is filtered off with suction and extracted twice with 250 ml of hot toluene, followed by sublimation. The yield is 2.72 g (3.84 mmol), corresponding to 93.8% in theory.

Example 15
Synthesis of Compound 23

  Compound 23 is prepared as described in WO2009 / 100925.

Example 16
Synthesis of Compound 28

a) Synthesis of Compound 24

  40.0 g (156 mmol) 9-bromoanthracene (19), 74.0 g (171 mmol) compound (4) and 58.0 g (547 mmol) sodium carbonate in 900 ml toluene, 900 ml ethanol and 210 ml water. Suspend. 1.80 g (1.56 mmol) of tetrakis (triphenylphosphine) palladium (0) is added to the suspension and the mixture is subsequently heated to reflux for 16 hours. After cooling, the solid is filtered off with suction and taken up in 500 ml of dichloromethane, the organic phase is washed 3 times with 100 ml of water each time, dried with sodium sulphate and subsequently evaporated to dryness. The yield is 70.2 g (145 mmol), which corresponds to 92.9% in theory.

b) Synthesis of compound 25

  2.5 g (15.4 mmol) of iron (III) chloride and then 31.0 g (174 mmol) of N-bromosuccinimide were cooled to 0 ° C., 70.0 g (145 mmol) of compound (24), 1. Add to 4 L of suspension in chloroform and stir the mixture at 0 ° C. for 2 h. After warming to room temperature, 1000 ml of water are added, the organic phase is separated, washed 3 times with 500 ml of water, dried using sodium sulphate and subsequently evaporated to dryness. The solid obtained is recrystallised from a heptane / ethyl acetate mixture and finally dried under reduced pressure. The yield is 56.7 g (101 mmol), which corresponds to 69.7% in theory.

c) Synthesis of Compound 27

35.6 g (138 mmol) of 3-bromophenanthrene (26), 42.0 g (165 mmol) of bispinacolatodiboron and 46.0 g (469 mmol) of potassium acetate are suspended in 500 ml of dimethyl sulfoxide. 3.50 g (4.29 mmol) of 1,1-bis (diphenylphosphino) ferrocenedichloropalladium (II) ^* DCM is added to the suspension and the reaction mixture is stirred at 80 ° C. for 6 hours. After cooling, 1000 ml of ethyl acetate and 1000 ml of water are added, the organic phase is separated, washed three times with 300 ml of water each time, dried with sodium sulphate and subsequently evaporated to dryness. The crude product is passed through silica gel in a column with a heptane / ethyl acetate mixture (10: 1), the corresponding fractions are evaporated and finally dried under reduced pressure. The yield is 38.5 g (127 mmol), which corresponds to 92.0% in theory.

d) Synthesis of compound 28

  13.3 g (23.7 mmol) of compound (25), 7.80 g (25.6 mmol) of compound (27) and 8.80 g (83.0 mmol) of sodium carbonate were added to 140 ml of toluene, 140 ml of ethanol and 35 ml. Suspend in water. 300 mg (260 μmol) of tetrakis (triphenylphosphine) palladium (0) is added to the suspension and the mixture is subsequently heated to reflux for 16 hours. After cooling, the solid is filtered off with suction and extracted with 500 ml of hot toluene. The residue is recrystallized three times from heptane / toluene and sublimed. The yield is 13.1 g (19.9 mmol), corresponding to 84.0% in theory.

Compound 29, Compound 30, Compound 31, and Compound 32 are commercially available and do not include the solubility-promoting structural element of formula (I).

Compound 33 is prepared as described in WO2008 / 006449.

Fabrication and characterization of organic electroluminescent devices The materials utilized according to the present invention are used from solution, which results in simple devices with surprisingly superior properties. The manufacture of such components is based on the manufacture of polymer light emitting diodes (PLEDs), which have already been described many times in the literature (eg WO 2004/037887 A2). In the case of the present invention, the compounds according to the invention are dissolved in toluene or chlorobenzene. The concentrations utilized in the examples shown here are 20% by weight of the phosphor (compounds 14, 15, 16, 19 and 20) and 80% by weight of the matrix material (compounds 5-13, 17 and 18). . As is the case here, if a typical layer thickness of the device of 80 nm is achieved using spin coating, the typical solid content of such a solution is between 16-25 g / l. is there.

  FIG. 1 shows a typical structure of this type of device. The EML includes a matrix material dissolved together and a light emitter in the form of an amorphous layer. Materials for structured ITO substrates and so-called buffer layers (PEDOT, actually PEDOT: PSS) are commercially available (ITO is commercially available from Technoprint and others; PEDOT: PPS C. Starck is commercially available as Clevios P aqueous dispersion). The intermediate layer used (HIL-012, from Merck) functions for hole injection. The light emitting layer is applied by spin coating in an inert gas atmosphere, argon in the present invention, and dried by heating at 160 ° C. or 180 ° C. for 10 minutes. Finally, a cathode containing barium and aluminum is applied by vacuum deposition. The HBL and ETL layers used in the above examples can also be applied by evaporation between the EML and the cathode, and the intermediate layer can also be replaced with one or more layers, but these layers are It only has to satisfy the condition that it is not separated again by EML deposition from the solution, which is a subsequent process step.

  Devices processed from solution are characterized by standard methods, and the examples of OLEDs given are not optimized. Table 1 shows the results.

Table 1:
Results of device configuration according to Figure 1

  As can be seen from the results, the formulations according to the present invention represent a significant improvement in terms of operating voltage, lifetime and efficiency of electronic devices made from them over comparable compositions according to the prior art.

Fabrication and characterization of organic electroluminescent devices comprising compounds 22 and 28 according to the present invention The materials utilized according to the present invention are dissolved in toluene or chlorobenzene as described above. However, the concentration utilized in the example shown here is 5% by weight of the phosphor (cpd.33) and 95% by weight of the matrix material. As is the case here, if a typical layer thickness of the device of 50 nm is achieved using spin coating, the typical solid content of such a solution is between 10-15 g / l. is there,
The device is characterized in a standard way and the example OLED shown is not yet optimized. Table 2 summarizes the data obtained.

Table 2:
Results for materials processed from solution in the device configuration of FIG.

FIG. 1 shows a typical structure of the device.

Claims (14)

A formulation comprising at least one solvent and at least two functional compounds of different general formula (I).

[here,
A is a functional structural element which is a unit having the characteristics of hole injection and / or hole transport, a unit having the characteristics of electron injection and / or electron transport, or a unit having light emission characteristics,
B is a dissolution promoting structural element;
k is an integer in the range of 1-20,
The molecular weight of the functional compound is at least 550 g / mol;
The dissolution-promoting structural element B corresponds to the general formula (L-II )].

(Where
R ¹ , R ² , R ³ and R ⁴ each independently of one another has a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, or 3 to 40 C atoms. A branched or cyclic alkyl, alkoxy or thioalkoxy group, or a silyl group, or a substituted keto group having 1 to 40 C atoms, an alkoxycarbonyl group having 2 to 40 C atoms, 7 to Aryloxycarbonyl group having 40 C atoms, formyl group (—C (═O) —H), CF ₃ group, Cl, Br, F, heating, UV, microwave, X-ray or electron beam If the the crosslinkable group or R ^1, is present, multiple R ¹ is any combination of these systems, when a plurality of R ² are present, the plurality of R ² is, these systems Optional A combination, when a plurality of R ³ are present, a plurality of R ³ is any combination of these systems, when a plurality of R ⁴ are present, the plurality of R ⁴ is, any of these systems A combination,
m is 0, 1, 2 or 3;
n and o are each independently 0, 1, 2, 3, 4 or 5;
l is 0, 1, 2, 3 or 4;
The bond indicated by the broken line indicates the bond to the functional structural element A)   The formulation according to claim 1, characterized in that the functional structural element A in formula (I) contains at least one functional compound which is a unit having phosphorescent properties. Characterized in that it comprises at least one at least one functional compound is a unit comprising a heavy atom functional structural element A in formula (I) having an atomic number of greater than 36, according to claim 1 or 2 Formulation. The formulation according to any one of claims 1 to 3 , characterized in that it comprises at least one functional compound that does not contain the dissolution-promoting structural element B of the general formula ( L-II ). The ratio of the functional compound not containing the dissolution promoting structural element B of the general formula ( L-II ) in the blend is 50% by weight or less based on the total weight of the functional compound. A formulation according to any one of claims 1 to 4 . Aromatic or characterized in that it comprises a solvent at least 80 wt% of the heteroaromatic A formulation according to any one of claims 1 to 5. 7. A formulation according to any one of claims 1 to 6 , characterized in that the subscript k in formula (I) is an integer greater than or equal to 2. The formulation according to any one of claims 1 to 7 , characterized in that the molecular weight of the functional compound in the general formula (I) is at least 800 g / mol. Functional compound in the general formula (I) is characterized by having a glass transition temperature of at least 70 ° C., the formulation according to any one of claims 1 to 8. The weight ratio of structural elements A to structural element B in the formula (I) is 2: 1 to 1: characterized in that it is a range of 20 A formulation according to any one of claims 1 to 9. The electronic device obtained using the formulation as described in any one of Claim 1 to 10 . The at least two functional compounds of the general formula (I) are present in the device as a layer for hole transport, hole injection, emitter, electron transport, electron injection, charge blocking and / or charge generation. The electronic device according to claim 11 , characterized in that: The electronic device is an organic electroluminescence device (OLED), polymer electroluminescence device (PLED), organic integrated circuit (O-IC), organic field effect transistor (O-FET), organic thin film transistor (O-TFT), organic light emission Transistor (O-LET), organic solar cell (O-SC), organic optical detector, organic photoreceptor, organic electric field quenching device (O-FQD), light emitting electrochemical cell (LEC) or organic laser diode (O-laser) 13. The electronic device according to claim 11 or 12 , characterized in that: 14. For the manufacture of an electronic device according to any one of claims 11 to 13 , characterized in that the formulation according to any one of claims 1 to 10 is applied to a substrate and subsequently dried. the method of.

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