HETEROCYCLIC COMPOUNDS FOR USE IN ELECTRONIC DEVICES

Abstract

The present invention relates to heterocyclic compounds and to electronic devices, especially organic electroluminescent devices, comprising these compounds.

Claims

1.-23. (canceled)

24. A compound comprising structures of the formula (I) ##STR00418## wherein: X is the same or different at each instance and is N or CR.sup.1, preferably CR.sup.1, with the proviso that not more than two of the X groups in one cycle are N; Z is a bond, C(R.sup.1)2, O or S; L.sup.1 is a bond, an aromatic ring system having 6 to 60 carbon atoms or a heteroaromatic ring system having 3 to 60 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals; Ar.sup.1, Ar.sup.2, Ar.sup.3 is an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, B(OR.sup.2).sub.2, CHO, C(═O)R.sup.2, CR.sup.2═C(R.sup.2).sub.2, CN, C(═O)OR.sup.2, C(═O)N(R.sup.2).sub.2, Si(R.sup.2).sub.3, N(R.sup.2).sub.2, NO.sub.2, P(═O)(R.sup.2).sub.2, OSO.sub.2R.sup.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.1 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.2 is the same or different at each instance and is H, D, F, Cl, Br, I, B(OR.sup.3).sub.2, CHO, C(═O)R.sup.3, CR.sup.3═C(R.sup.3).sub.2, CN, C(═O)OR.sup.3, C(═O)N(R.sup.3).sub.2, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, NO.sub.2, P(═O)(R.sup.3).sub.2, OSO.sub.2R.sup.3, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.3 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.3C═CR.sup.3—, —C≡C—, Si(R.sup.3).sub.2, C═O, C═S, C═NR.sup.3, —C(═O)O—, —C(═O)NR.sup.3—, NR.sup.3, P(═O)(R.sup.3), —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R.sup.3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R.sup.3 radicals, or a combination of these systems; at the same time, two or more adjacent R.sup.2 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.3 is the same or different at each instance and is H, D, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, in which hydrogen atoms may also be replaced by F; at the same time, two or more adjacent R.sup.3 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system; with the proviso that at least one of the Ar.sup.2 and/or Ar.sup.3 radicals is a group of the formula (IIa) or (IIb) ##STR00419## in which X is the same or different at each instance and is N or CR.sup.1, preferably CR.sup.1, with the proviso that not more than two of the X groups in one cycle are N; L.sup.2 is a bond, an aromatic ring system having 6 to 60 carbon atoms or a heteroaromatic ring system having 3 to 60 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals; R.sup.1 is as defined above and the dotted line represents the bonding site, such that L.sup.2 binds to the same nitrogen atom as L.sup.1.

25. The compound according to claim 24, wherein a structure of formula (Ia) is formed ##STR00420## in which h independently at each instance is 0, 1, 2, 3 or 4, preferably 0, 1 or 2 and more preferably 0 or 1; Ar.sup.4 is an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.1 radicals, and the symbols Ar.sup.1, Ar.sup.2, Ar.sup.3, L.sup.1 and Z are as defined in claim 24.

26. The compound according to claim 24, wherein the Z group is a bond, such that a structure of the formula (Ib) or (Ic) is formed ##STR00421## in which the symbols are as defined in claim 24.

27. The compound according to claim 24, wherein the two R.sup.1 radicals bonded to the carbon atom in position 9 in the fluorene structure of formula (IIa) or (IIb) are each an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, where the two ring systems are joined to one another.

28. The compound according to claim 27, wherein at least one of the Ar.sup.2 and/or Ar.sup.3 radicals comprises a group of the formula (IIc) or (IId) ##STR00422## in which the symbols are as defined in claim 24.

29. The compound according to claim 24, wherein the two R.sup.1 radicals bonded to the carbon atom in position 9 in the fluorene structure of formula (IIa) or (IIb) are each an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals, where the two ring systems are not joined to one another, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═S, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.2), —O—, —S—, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2.

30. The compound according to claim 24, wherein at least one of the Ar.sup.2 and/or Ar.sup.3 radicals comprises a group of the formula (IIe) or (IIf) ##STR00423## in which the symbols X and L.sup.2 are as defined in claim 24 and R.sup.4 is H, an aromatic ring system having 6 to 30 aromatic ring atoms, preferably an aryl group having 6 to 20 carbon atoms, more preferably phenyl, biphenyl or naphthyl, or an alkyl group having 1 to 20 carbon atoms, preferably methyl, ethyl, propyl or butyl, more preferably methyl.

31. The compound according to claim 24, wherein, in formulae (I), (Ib), (IIa), (IIb), (IIc), (IId), (IIe) and formula (IIf), not more than two and preferably not more than one X group is N, and preferably all X are CR.sup.1, where preferably at most 4, more preferably at most 3 and especially preferably at most 2 of the CR.sup.1 groups that X represents are not the CH group.

32. The compound according to claim 24, wherein, in the structures of formulae (I), (Ib), (IIa), (IIb), (IIc), (IId), (IIe) or formula (IIf), at least one R.sup.1, Ar.sup.2, Ar.sup.3 or Ar.sup.4 radical is a group selected from the formulae (R.sup.1-1) to (R.sup.1-72) ##STR00424## ##STR00425## ##STR00426## ##STR00427## ##STR00428## ##STR00429## ##STR00430## ##STR00431## ##STR00432## ##STR00433## ##STR00434## ##STR00435## ##STR00436## where the symbols used are as follows: Y is O, S or NR.sup.2, preferably O or S; j independently at each instance is 0, 1, 2 or 3; h independently at each instance is 0, 1, 2, 3 or 4; g independently at each instance is 0, 1, 2, 3, 4 or 5; the dotted bond marks the attachment position; and R.sup.2 is as defined in claim 24.

33. The compound according to claim 32, wherein the sum total of the indices g, h and j in the structures of the formula (R.sup.1-1) to (R.sup.1-72) is at most 3 in each case, preferably at most 2 and more preferably at most 1.

34. The compound according to claim 24, wherein, in the structure of formulae (I), (IIa) and (IIb), at least one L.sup.1 and/or L.sup.2 group is a group selected from the formulae (L-1) to (L-78) ##STR00437## ##STR00438## ##STR00439## ##STR00440## ##STR00441## ##STR00442## ##STR00443## ##STR00444## ##STR00445## ##STR00446## ##STR00447## ##STR00448## ##STR00449## ##STR00450## where the dotted bonds in each case mark the attachment positions, the index 1 is 0, 1 or 2, the index g is 0, 1, 2, 3, 4 or 5, j independently at each instance is 0, 1, 2 or 3; h independently at each instance is 0, 1, 2, 3 or 4; Y is O, S or NR.sup.2, preferably O or S; and R.sup.2 is as defined in claim 24.

35. The compound according to claim 34, wherein the sum total of the indices 1, g, h and j in the structures of the formula (L-1) to (L-78) is at most 3 in each case, preferably at most 2 and more preferably at most 1.

36. The compound according to claim 34, wherein, in the structure of formula (I), the L.sup.1 group is a bond and, in formula (IIa) and/or (IIb), the L.sup.2 group is a group selected from the formulae (L-1) to (L-78), preferably from the formulae (L-1) to (L-5), as described in claim 34.

37. The compound according to claim 34, wherein, in the structure of formula (IIa) and/or (IIb), the L.sup.2 group is a bond and, in formula (I), the L.sup.1 group is a group selected from the formulae (L-1) to (L-78), preferably from the formulae (L-1) to (L-5), as described in claim 34.

38. The compound according to claim 24, wherein, in the structure of formula (I), (IIa) and/or (IIb), the L.sup.1 and L.sup.2 groups are a bond.

39. The compound according to claim 24, wherein, in the structure of formula (I), (IIa) and/or (IIb), the L.sup.1 and L.sup.2 groups are a group selected from the formulae (L-1) to (L-78), preferably from the formulae (L-1) to (L-5), as described in claim 34.

40. The compound according to claim 24, wherein Ar.sup.1 and Ar.sup.3 are an aromatic ring system which has 6 to 12 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals.

41. An oligomer, polymer or dendrimer containing one or more compounds according to claim 24, wherein one or more bonds of the compounds to the polymer, oligomer or dendrimer are present.

42. A composition comprising at least one compound according to claim 24 or an oligomer, polymer or dendrimer according to claim 41 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

43. A formulation comprising at least one compound according to claim 24, an oligomer, polymer or dendrimer according to claim 41, or at least one composition according to claim 42 and at least one solvent.

44. a process for preparing a compound as claimed in claim 24 or an oligomer, polymer or dendrimer according to claim 41, comprising joining, in a coupling reaction, a group comprising at least one carbazole radical to a group comprising at least one fluorene radical.

45. A method comprising utilizing the compound according to claim 24, or the oligomer, polymer or dendrimer according to claim 41, or the composition according to claim 42 in an electronic device as matrix material, electron blocker material, hole injection material and/or a hole transport material, preferably as matrix material.

46. An electronic device comprising at least one compound according to claim 24, or the oligomer, polymer or dendrimer according to claim 41, or the composition according to claim 42, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells and organic laser diodes.

Description

EXAMPLES

[0168] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature.

[0169] Preparation examples:

##STR00253##

Preparation of 4-bromo-9-phenyl-9H-carbazole 3a

[0170] A 500 ml four-neck flask is initially charged with 15.0 g (61.0 mmol, 1.0 eq) of 4-bromo-9H-carbazole 1a (CAS 3652-89-9) together with 13.6 ml (122 mmol, 2.0 eq) of iodobenzene 2a and 16.8 g (122 mmol, 2.0 eq) of potassium carbonate, which are dissolved in 180 ml of dried DMF. After degassing by means of a nitrogen stream for 30 minutes, 1.38 g (6.10 mmol, 0.10 eq) of 1,3-di(2-pyridyl)-1,3-propanedione and 1.16 g (6.10 mmol, 0.10 eq) of copper(I) iodide are added. The mixture is stirred at 110° C. overnight and, after the reaction has ended, the solvent is removed on a rotary evaporator. The residue is taken up in 250 ml of DCM, conc. ammonium chloride solution is added and the mixture is filtered through Celite. Subsequently, the phases are separated, the aqueous phase is extracted twice with 100 ml each time of DCM and the combined organic phases are finally washed with water. After drying over sodium sulphate and removing the solvent under reduced pressure, the oily residue together with heptane is filtered through silica gel and the solvent is again removed on a rotary evaporator. 19.0 g (59.0 mmol, 97%) of a colourless oil 3a are obtained.

[0171] The following are prepared analogously:

TABLE-US-00002 Com- Yield pound Reactant 1 Reactant 2 Product 3 [%] 3b [00254] [00255] [00256] 92 3c [00257] [00258] [00259] 89 3d [00260] [00261] [00262] 96 3e [00263] [00264] [00265] 84

Preparation of 4-(4-chlorophenyl)-9-phenyl-9H-carbazole 5a

[0172] In a 500 ml four-neck flask, 18.9 g (58.7 mmol, 1.0 eq) of 4-bromo-9-phenyl-9H-carbazole 3, 9.17 g (58.7 mmol, 1.0 eq) of 4-chlorophenyl-boronic acid (CAS 1679-18-1) and 6.22 g (58.7 mmol, 1.0 eq) of sodium carbonate are dissolved in 150 ml of toluene, 36 ml of ethanol and 77 ml of water. After degassing by means of a nitrogen stream for 30 minutes, 678 mg (0.587 mmol, 0.01 eq) of tetrakis(triphenylphosphine)-palladium are added and the mixture is heated at reflux overnight. After the reaction has ended, the phases are separated, the aqueous phase is extracted three times with toluene and the combined organic phases are then washed with water. The organic phases are dried over sodium sulphate and the solution is concentrated on a rotary evaporator. The residue is introduced into 250 ml of ethanol and the solid formed is filtered off with suction. 19.9 g (56.4 mmol, 96%) of the desired product 5a are obtained.

[0173] The following are prepared analogously:

TABLE-US-00003 Com- Yield pound Reactant 3 Reactant 4 Product 5 [%] 5b [00266] [00267] [00268] 91 5c [00269] [00270] [00271] 87 5d [00272] [00273] [00274] 93 5e [00275] [00276] [00277] 72 5f [00278] [00279] [00280] 88 5g [00281] [00282] [00283] 91 5h [00284] [00285] [00286] 97 5i [00287] [00288] [00289] 87

Preparation of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-4-yl)amine 8a (Variant A)

[0174] A 1 l four-neck flask is initially charged with 14.0 g (51.4 mmol, 1.0 eq) of 4-bromo-9,9-dimethylfluorene 7a, and also 10.5 g (60.8 mmol, 1.2 eq) of biphenyl-4-amine 6a and 12.9 g (134 mmol, 2.6 eq) of sodium tert-butoxide, which are dissolved in 300 ml of dry p-xylene. Subsequently, the mixture is degassed for 45 minutes and 346 mg (154 mmol, 0.03 eq) of palladium(II) acetate and 1.71 g (3.09 mmol, 0.06 eq) of 1,1′-bis(diphenylphosphino)ferrocene are added and the mixture is stirred at 140° C. overnight. After the reaction has ended, the solvent is removed under reduced pressure, the residue is taken up in dichloromethane and heptane is added. The precipitated solid is filtered off with suction and dried in a vacuum drying cabinet. 11.0 g (30.5 mmol, 59%) of the desired product 8a are obtained.

[0175] The following are prepared analogously:

TABLE-US-00004 Com- pound Reactant 6 Reactant 7 8b [00290] [00291] 8c [00292] [00293] 8d [00294] [00295] 8e [00296] [00297] 8f [00298] [00299] 8g [00300] [00301] 8h [00302] [00303] 8i [00304] [00305] 8j [00306] [00307] 8k [00308] [00309] 8l [00310] [00311] 8m [00312] [00313] 8n [00314] [00315] 8o [00316] [00317] Compound Product 8 Yield [%] 8b [00318] 73 8c [00319] 85 8d [00320] 69 8e [00321] 37 8f [00322] 88 8g [00323] 81 8h [00324] 77 8i [00325] 89 8j [00326] 93 8k [00327] 21 8l [00328] 67 8m [00329] 84 8n [00330] 91 8o [00331] 74

Preparation of biphenyl-4-yl(9,9-dimethyl-9H-fluoren-4-yl)[4-(9-phenyl-9H-carbazol-4-yl)phenyl]amine 9a (Variant A)

[0176] 11.0 g (30.5 mmol, 1.0 eq) of the secondary amine 8a, and also 11.9 g (33.6 mmol, 1.1 eq) of 4-(4-chlorophenyl)-9-phenyl-9H-carbazole 5a, are dissolved in 250 ml of dry toluene and saturated with argon for about 30 minutes. Subsequently, 279 mg (0.305 mmol, 0.1 eq) of tris(dibenzylideneacetone)dipalladium and 250 mg (0.610 mmol, 0.02 eq) of 2-dicyclohexylphosphino-2′,6′-methoxybiphenyl are added and the mixture is heated to reflux. After the reaction has ended, the mixture is transferred into a separating funnel and extracted twice with 300 ml of water. The aqueous phase is again extracted by shaking with toluene and the combined organic phases are dried over sodium sulphate. After the solvent has been removed on a rotary evaporator, a resinous solid is obtained, which is taken up in a little dichloromethane and introduced into ethanol. The solid obtained is purified by means of hot extraction and triple recrystallization from toluene/heptane and finally sublimed. 7.04 g (10.4 mmol, 34%) of the final stage 9a are obtained with an HPLC purity of >99.9%.

[0177] The following are prepared analogously:

TABLE-US-00005 Com- pound Reactant 6 Reactant 7 9b [00332] [00333] 9c [00334] [00335] 9d [00336] [00337] 9e [00338] [00339] 9f [00340] [00341] 9g [00342] [00343] 9h [00344] [00345] 9i [00346] [00347] 9j [00348] [00349] 9k [00350] [00351] 9l [00352] [00353] 9m [00354] [00355] 9n [00356] [00357] 9o [00358] [00359] 9p [00360] [00361] 9q [00362] [00363] 9r [00364] [00365] 9s [00366] [00367] 9t [00368] [00369] 9u [00370] [00371] Compound Product 8 Yield [%] 9b [00372] 45 9c [00373] 51 9d [00374] 47 9e [00375] 21 9f [00376] 63 9g [00377] 44 9h [00378] 41 9i [00379] 37 9j [00380] 52 9k [00381] 28 9l [00382] 46 9m [00383] 41 9n [00384] 39 9o [00385] 36 9p [00386] 22 9q [00387] 63 9r [00388] 58 9s [00389] 45 9t [00390] 44 9u [00391] 17

[0178] Production of the OLEDs

[0179] In Examples C1 to I14 which follow (see Tables 1 and 2), the data of various OLEDs are presented.

[0180] 30

[0181] Pretreatment for Examples C1-I14: Glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm, for improved processing, are coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulphonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution). These coated glass plaques form the substrates to which the OLEDs are applied.

[0182] The OLEDs basically have the following layer structure: substrate/hole transport layer (HTL)/optional interlayer (IL)/electron blocker layer (EBL)/emission layer (EML)/optional hole blocker layer (HBL) electron transport layer (ETL)/optional electron injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer of thickness 100 nm. The exact structure of the OLEDs can be found in Table 1. The materials required for production of the OLEDs are shown in Table 3.

[0183] All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as IC1:PA:TEG1 (55%:35%:10%) mean here that the material IC1 is present in the layer in a proportion by volume of 55%, PA in a proportion of 35% and TEG1 in a proportion of 10%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0184] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics, and also the lifetime are determined. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and the CIE 1931 x and y colour coordinates are calculated therefrom. The parameter U1000 in Table 2 refers to the voltage which is required for a luminance of 1000 cd/m.sup.2. CE1000 and PE1000 respectively refer to the current and power efficiencies which are achieved at 1000 cd/m.sup.2. Finally, EQE1000 refers to the external quantum efficiency at an operating luminance of 1000 cd/m.sup.2. The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion L.sub.1 in the course of operation with constant current. A figure of L.sub.0;j.sub.0=4000 cd/m.sup.2 and L.sub.1=70% in Table 2 means that the lifetime reported in the LT column corresponds to the time after which the starting luminance falls from 4000 cd/m.sup.2 to 2800 cd/m.sup.2. Analogously, L.sub.0;j.sub.0=20 mA/cm.sup.2, L.sub.1=80% means that the luminance in the course of operation at 20 mA/cm.sup.2falls to 80% of its starting value after the time LT.

[0185] The data for the various OLEDs are collated in Table 2. Example C1 is a comparative example according to the prior art; Examples I1-I14 show data of OLEDs of the invention.

[0186] Some of the examples are elucidated in detail hereinafter, in order to illustrate the advantages of the OLEDs of the invention.

[0187] Use of Compounds of the Invention as Hole-Transporting Matrix Material of Phosphorescent OLEDs

[0188] The materials of the invention, when used as hole-transporting matrix material in combination with an electron-conducting compound (for example compound IC1 in the examples adduced below) in the emission layer (EML) in phosphorescent OLEDs, result in significant improvements over the prior art, particularly in relation to the lifetime of the OLEDs. Through use of compounds 9a and 9h of the invention, it is possible to observe an improvement in lifetime of more than 50% compared to the compound from the prior art PA (Examples C1, I1 and I2 or C2 and I15).

TABLE-US-00006 TABLE 1 Structure of the OLEDs HIL IL HTL EBL EML HBL ETL EIL Ex. thickness thickness thickness thickness thickness thickness thickness thickness C1 SpA1 HATCN SpMA1 — IC1:PA:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 70 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm C2 SpA1 HATCN SpMA1 — IC1:PA2:TEG1 IC1 ST2:LiQ 70 nm 5 nm 70 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm I1 SpA1 HATCN SpMA1 — IC1:9a:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 70 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm I2 SpA1 HATCN SpMA1 — IC1:9h:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 70 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm I3 SpA1 HATCN SpMA1 9b IC1:IC3:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 80 nm 10 nm (65%:30%:5%) 10 nm (50%:50%) 30 nm 30 nm I4 SpA1 HATCN SpMA1 9c IC1:IC3:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 80 nm 10 nm (65%:30%:5%) 10 nm (50%:50%) 30 nm 30 nm I5 SpA1 HATCN SpMA1 — IC1:9f:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 90 nm (65%:30%:5%) 10 nm (50%:50%) 30 nm 30 nm I6 SpA1 HATCN SpMA1 9g IC1:TER1 — ST2:LiQ — 90 nm 5 nm 110 nm 20 nm (92%:8%) 40 nm (50%:50%) 40 nm I7 SpA1 HATCN SpMA1 — IC1:9i:TEG1 — ST2:LiQ — 90 nm 5 nm 130 nm (87%:5%:8%) (50%:50%) 40 nm 40 nm I8 SpA1 HATCN SpMA1 9j IC1:9j:TER1 — ST2:LiQ — 90 nm 5 nm 110 nm 20 nm (82%:10%:8%) (50%:50%) 40 nm 40 nm I9 SpA1 HATCN SpMA1 — IC1:9k:TEG1 — ST2:LiQ — 90 nm 5 nm 130 nm (87%:5%:8%) (50%:50%) 40 nm 40 nm I10 SpA1 HATCN SpMA1 — IC1:9n:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 70 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm I11 SpA1 HATCN SpMA1 — IC1:9p:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm I12 SpA1 HATCN SpMA1 — IC1:9q:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 70 nm (60%:30%:10%) 10 nm (50%:50%) 30 nm 30 nm I13 SpA1 HATCN SpMA1 9r IC1:IC3:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 80 nm 10 nm (55%:35%:10%) 10 nm (50%:50%) 30 nm 30 nm I14 SpA1 HATCN SpMA1 9u IC1:IC3:TEG1 IC1 ST2:LiQ — 70 nm 5 nm 80 nm 10 nm (55%:35%:10%) 10 nm (50%:50%) 30 nm 30 nm I15 SpA1 HATCN SpMA1 — IC1:9h:TEG1 IC1 ST2:LiQ 70 nm 5 nm 70 nm (45%:45%:10%) 10 nm (50%:50%) 30 nm 30 nm

TABLE-US-00007 TABLE 2 Data of the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at LT Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 L.sub.0; j.sub.0 L.sub.1 % (h) C1 3.3 60 57 16.7% 0.32/0.63 20 mA/cm.sup.2 80 120 C1 3.4 59 55 16.4% 0.32/0.63 20 mA/cm.sup.2 80 145 I1 3.5 58 52 16.4% 0.33/0.62 20 mA/cm.sup.2 80 220 I2 3.4 60 55 16.5% 0.33/0.63 20 mA/cm.sup.2 80 180 I3 3.6 62 54 16.8% 0.32/0.63 20 mA/cm.sup.2 80 200 I4 3.4 59 55 16.6% 0.32/0.63 20 mA/cm.sup.2 80 220 I5 3.3 58 55 16.4% 0.33/0.62 20 mA/cm.sup.2 80 130 I6 4.4 12 9 13.1% 0.67/0.33 4000 cd/m.sup.2 80 310 I7 4.5 13 9 13.2% 0.67/0.33 4000 cd/m.sup.2 80 510 I8 4.6 13 9 13.0% 0.66/0.34 4000 cd/m.sup.2 80 530 I9 4.4 12 9 12.9% 0.67/0.33 4000 cd/m.sup.2 80 490 I10 3.5 58 52 16.3% 0.34/0.62 20 mA/cm.sup.2 80 230 I11 3.6 60 52 16.4% 0.32/0.63 20 mA/cm.sup.2 80 190 I12 3.6 61 53 16.5% 0.34/0.62 20 mA/cm.sup.2 80 200 I13 3.5 63 57 16.9% 0.32/0.64 20 mA/cm.sup.2 80 170 I14 3.4 58 54 16.2% 0.33/0.63 20 mA/cm.sup.2 80 210 I15 3.4 60 55 16.5% 0.33/0.63 20 mA/cm.sup.2 80 180

TABLE-US-00008 TABLE 3 Structural formulae of the materials for the OLEDs [00392] HATCN [00393] SpA1 [00394] SpMA1 [00395] LiQ [00396] SpMA2 [00397] TEG1 [00398] TER1 [00399] ST2 [00400] IC1 [00401] IC3 [00402] PA [00403] 9a [00404] 9h [00405] 9b [00406] 9c [00407] 9f [00408] 9g [00409] 9i [00410] 9j [00411] 9k [00412] 9n [00413] 9p [00414] 9q [00415] 9r [00416] 9u [00417] PA2