CYCLIC COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The invention relates to cyclic compounds which are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices containing said compounds.

Claims

1.-19. (canceled)

20. A compound including at least one structure of the formula (I) ##STR00378## where the symbols and indices used are as follows: Z.sup.1, Z.sup.2 is the same or different at each instance and is N or B; W.sup.1, W.sup.2, W.sup.3, W.sup.4 are the same or different at each instance and are CAr, X, or two adjacent W.sup.1, W.sup.2, W.sup.3, W.sup.4 groups are Ar; Y.sup.1 is the same or different at each instance and is N(Ar), N(R), P(Ar), P(R), P(═O)Ar, P(═O)R, P(═S)Ar, P(═S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2; Y.sup.2 is the same or different at each instance and is a bond, N(Ar), N(R), P(Ar), P(R), P(═O)Ar, P(═O)R, P(═S)Ar, P(═S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr, C═C(R).sub.2, O, S, Se, S═O, or SO.sub.2; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R radicals; the Ar group here may form a ring system with at least one Ar group, an R group or a further group; X is the same or different at each instance and is N or CR, with the proviso that not more than two of the X, X.sup.3 groups in one cycle are N; X.sup.1 is the same or different at each instance and is N, CR.sup.a or CAr, with the proviso that not more than two of the X.sup.1, X.sup.2, X.sup.3 groups in one cycle are N; X.sup.2 is the same or different at each instance and is N, CR.sup.b or CAr, with the proviso that not more than two of the X.sup.1, X.sup.2, X.sup.3 groups in one cycle are N; X.sup.3 is the same or different at each instance and is N, CR.sup.c, CAr or C if p is 1, with the proviso that not more than two of the X, X.sup.1, X.sup.2, X.sup.3 groups in one cycle are N; p is the same or different and is 0 or 1, where p=1 if W.sup.3, W.sup.4 are not Ar; R, R.sup.a, R.sup.b, R.sup.c is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar′).sub.2, N(R.sup.1).sub.2, C(═O)OAr′, C(═O)OR.sup.1, C(═O)N(Ar′).sub.2, C(═O)N(R.sup.1).sub.2, C(Ar′).sub.3, C(R′).sub.3, Si(Ar′).sub.3, Si(R.sup.1).sub.3, B(Ar′).sub.2, B(R.sup.1).sub.2, C(═O)Ar′, C(═O)R.sup.1, P(═O)(Ar′).sub.2, P(═O)(R.sup.1).sub.2, P(Ar′).sub.2, P(R.sup.1).sub.2, S(═O)Ar′, S(═O)R.sup.1, S(═O).sub.2Ar′, S(═O).sub.2R.sup.1, OSO.sub.2Ar′, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C═CR.sup.1, C≡C, Si(R.sup.1).sub.2, C═O, C═S, C═Se, C═NR.sup.1, —C(═O)O—, —C(═O)NR.sup.1—, NR.sup.1, P(═O)(R.sup.1), —O—, —S—, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two R, R.sup.a, R.sup.b, R.sup.c radicals may also form a ring system together or with a further group; Ar′ is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, it is possible for two Ar′ radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.1), C(R.sup.1).sub.2, Si(R.sup.1).sub.2, C═O, C═NR.sup.1, C═C(R.sup.1).sub.2, O, S, S═O, SO.sub.2, N(R.sup.1), P(R.sup.1) and P(═O)R.sup.1; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar″).sub.2, N(R.sup.2).sub.2, C(═O)OAr″, C(═O)OR.sup.2, C(═O)Ar″, C(═O)R.sup.2, P(═O)(Ar″).sub.2, P(Ar″).sub.2, B(Ar″).sub.2, B(R.sup.2).sub.2, C(Ar″).sub.3, C(R.sup.2).sub.3, Si(Ar″).sub.3, Si(R.sup.2).sub.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 or an alkenyl group having 2 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═Se, 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 60 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 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 R.sup.1 radicals together may form a ring system; at the same time, one or more R.sup.1 radicals may form a ring system with a further part of the compound; Ar″ is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, it is possible for two Ar″ radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.2), C(R.sup.2).sub.2, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, C═C(R.sup.2).sub.2, O, S, S═O, SO.sub.2, N(R.sup.2), P(R.sup.2) and P(═O)R.sup.2; R.sup.2 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more substituents R.sup.2 together may form a ring system.

21. The compound as claimed in claim 20, comprising at least one structure of the formulae (IIa) to (IIk) ##STR00379## ##STR00380## ##STR00381## where W.sup.1, W.sup.2, Y.sup.1, Y.sup.2, Z.sup.1, Z.sup.2, X.sup.1, X.sup.2 and X.sup.3 have the definitions given in claim 20 and the further symbols and indices are as follows: X is the same or different at each instance and is N, CR or C if p is 1, with the proviso that not more than two X groups in one cycle are N; Y.sup.3 is the same or different at each instance and is O, S, N(Ar′), N(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, B(Ar′) or B(R); p is 0 or 1.

22. The compound claim 20, comprising at least one structure of the formulae (IIIa) to (IIIk) ##STR00382## ##STR00383## ##STR00384## where Y.sup.1, Y.sup.2, Z.sup.1, Z.sup.2, X.sup.1, X.sup.2 and V.sup.3 have the definitions given in claim 20, and X is the same or different at each instance and is N, CR or C if p is 1, with the proviso that not more than two X groups in one cycle are N; Y.sup.3 is the same or different at each instance and is O, S, N(Ar′), N(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, B(Ar′) or B(R); p is 0 or 1.

23. The compound as claimed in claim 20, comprising at least one structure of the formulae (IV-1) to (IV-20): ##STR00385## ##STR00386## ##STR00387## ##STR00388## ##STR00389## where Y.sup.1, Y.sup.2, Z.sup.1, Z.sup.2, R, R.sup.a, R.sup.b and R.sup.c have the definitions given in claim 20, Y.sup.3 is the same or different at each instance and is O, S, N(Ar′), N(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, B(Ar′) or B(R); the index 1 is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, the index n is 0, 1, 2 or 3, the index j is 0, 1 or 2, and the index k is 0 or 1.

24. The compound as claimed in claim 20, wherein at least one of the Z.sup.1 and Z.sup.2 groups is N and at least one of the Y.sup.1 and Y.sup.2 groups is B(Ar), B(R), P(═O)Ar, P(═O)R, Al(Ar), Al(R), Ga(Ar), Ga(R), C═O, S═O or SO.sub.2.

25. The compound as claimed in claim 20, wherein at least one of the Z.sup.1 and Z.sup.2 groups is N and at least one of the Y.sup.1 and Y.sup.2 groups is N(Ar), N(R), P(Ar), P(R), O, S or Se.

26. The compound as claimed in claim 20, wherein at least one of the Z.sup.1 and Z.sup.2 groups is B and at least one of the Y.sup.1 and Y.sup.2 groups is N(Ar), N(R), P(Ar), P(R), O, S or Se.

27. The compound as claimed in claim 20, wherein at least one of the Z.sup.1 and Z.sup.2 groups is B and at least one of the Y.sup.1 and Y.sup.2 groups is B(Ar), B(R), P(═O)Ar, P(═O)R, Al(Ar), Al(R), Ga(Ar), Ga(R), C═O, S═O or SO.sub.2.

28. The compound as claimed in claim 20, comprising at least one structure of the formula (V-1) to (V-40): ##STR00390## ##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395## ##STR00396## ##STR00397## ##STR00398## where Z.sup.1, Z.sup.2, X, X.sup.1 and X.sup.2 have the definitions given in claim 20; Y.sup.3 is the same or different at each instance and is O, S, N(Ar′), N(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, B(Ar′) or B(R); and Z.sup.3, Z.sup.4 is the same or different at each instance and is N, B, P(═O) or Si(R).

29. The compound as claimed in claim 20, including at least one structure of the formula (VI-1) to (VI-40): ##STR00399## ##STR00400## ##STR00401## ##STR00402## ##STR00403## ##STR00404## ##STR00405## ##STR00406## ##STR00407## ##STR00408## where the symbols Z.sup.1, Z.sup.2, R, R.sup.a and R.sup.b have the definitions given in claim 20; Y.sup.3 is the same or different at each instance and is O, S, N(Ar′), N(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, B(Ar) or B(R); Z.sup.3, Z.sup.4 is the same or different at each instance and is N, B, P(═O) or Si(R), the index 1 is 0, 1, 2, 3, 4 or 5; the index m is 0, 1, 2, 3 or 4; and the index j is 0, 1 or 2.

30. The compound as claimed in claim 20, wherein at least two R, R, R.sup.b, R.sup.c radicals together with the further groups to which the two R, R, R.sup.b, R.sup.c radicals bind form a fused ring, where the two R, R, R.sup.b, R.sup.c radicals form at least one structure of the formulae (RA-1) to (RA-12): ##STR00409## ##STR00410## where R.sup.1 has the definition set out above, the dotted bonds represent the sites of attachment to the atoms of the groups to which the two R, R.sup.a, R.sup.b, R.sup.c radicals bind, and the further symbols are defined as follows: Y.sup.4 is the same or different at each instance and is C(R.sup.1).sub.2, (R.sup.1).sub.2C—C(R.sup.1).sub.2, (R′)C═C(R′), NR.sup.1, NAr′, O or S; R.sup.d is the same or different at each instance and is F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case 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═Se, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═O)(R.sup.1), —O—, —S—, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 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 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, two R.sup.d radicals together or one R.sup.d radical together with an R.sup.1 radical or with a further group may also form a ring system; s is 0, 1, 2, 3, 4, 5 or 6; t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

31. The compound as claimed in claim 20, that at least two R, R.sup.a, R.sup.b, R.sup.c radicals together with the further groups to which the two R, R.sup.a, R.sup.b, R.sup.c radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b, R.sup.c radicals form structures of the formula (RB): ##STR00411## where R.sup.1 has the definition set out in claim 20, the dotted bonds represent the sites of attachment to which the two R, RV, R.sup.b, R.sup.c radicals bind, the index m is 0, 1, 2, 3 or 4 and Y.sup.5 is C(R.sup.1).sub.2, NR.sup.1, NAr′, BR.sup.1, BAr′, O or S.

32. The compound as claimed in claim 20, comprising at least one structure of the formulae (VII-1) to (VII-50), where the compounds have at least one fused ring, ##STR00412## ##STR00413## ##STR00414## ##STR00415## ##STR00416## ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421## where Y.sup.1, Y.sup.2, Z.sup.1, Z.sup.2, R, R.sup.a, R.sup.b and R.sup.c have the definitions given in claim 20; Y.sup.3 is the same or different at each instance and is O, S, N(Ar′), N(R), C═O, C(R).sub.2, Si(R).sub.2, C═NR, C═NAr′, C═C(R).sub.2, B(Ar′) or B(R); the symbol o represents the attachment sites, and the further symbols are defined as follows: l is 0, 1, 2, 3, 4 or 5; m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3; j is 0, 1 or 2; and k is 0 or 1.

33. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 20, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

34. A formulation comprising at least one compound as claimed in claim 20 and at least one further compound.

35. A composition comprising at least one compound as claimed in claim 20 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF, host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

36. A process for preparing a compound as claimed in claim 20, comprising preparing a base skeleton having a Z.sup.1 group or a Z.sup.2 group or a precursor of one of the Z.sup.1, Z.sup.2 groups, and introducing at least one of the Y.sup.1, Y.sup.2 groups by means of a nucleophilic aromatic substitution reaction or a coupling reaction.

37. A method comprising providing the compound as claimed in claim 20 and incorporating the compound in an electronic device.

38. An electronic device comprising at least one compound as claimed in claim 20.

Description

EXAMPLES

[0196] 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. In the case of compounds that can have multiple enantiomeric, diastereomeric or tautomeric forms, one form is shown in a representative manner.

Synthesis of Synthons S

Example S1

[0197] ##STR00239##

[0198] Procedure analogous to Chung-Chieh Lee et al., Synthesis 2008, 9, 1359. Complete procedure including workup under protective gas.

[0199] A mixture of 34.0 g (120 mmol) of 1-bromo-2-iodobenzene [583-55-1], 8.5 g (50 mmol) of 2,3-dihydro-1H-perimidine [69098-80-2], 20.7 g (150 mmol) of potassium carbonate, 1.9 g (10 mmol) of copper iodide [7681-65-4], 2.9 g (20 mmol) of 1R,2R—N,N-dimethylcyclohexane-1,2-diamine [67579-81-8], 50 g of glass beads and 200 ml of o-xylene is stirred at 130° C. for 24 h. After cooling, 300 ml of ethyl acetate and 500 ml of water are added to the reaction mixture, and the organic phase is removed, washed once with 500 ml of water and twice with 300 ml each time of saturated sodium chloride solution, and dried over magnesium sulfate. The mixture is filtered through a silica gel bed in the form of an ethyl acetate slurry, the filtrate is concentrated to dryness, the residue is boiled with 150 ml of ethanol, the solids are filtered off with suction, and these are washed twice with 30 ml of ethanol, dried under reduced pressure and recrystallized from acetonitrile/DCM (dichloromethane). Further purification can be effected by flash chromatography on an automated column system (Torrent, from A. Semrau). Yield: 15.8 g (33 mmol) 65%; purity about 95% by .sup.1H NMR.

[0200] The following compounds can be prepared analogously:

TABLE-US-00002 Ex.. Reactants Product Yield S2 [00240] [00241] 81% 69098-82-4 S3 [00242]   96843-22-0 [00243] 61% S4 [00244]   [00245] 65% 900806-53-3 S5 [00246]   1846603-15-3 [00247] 59% S6 [00248]   676267-05-3 [00249] 52% S7 [00250]   90948-03-1 [00251] 55% S8 [00252]   93188-73-9 [00253] 63% S9 [00254]   916747-51-8 [00255] 67% S10 [00256]   1541101-10-3 [00257] 50% S11 [00258]   184885-74-3 [00259] 54% S12 [00260]   1776056-64-4 [00261] 50% S13 [00262]   1801624-64-5 [00263] 52% S14 [00264]   1801624-66-7 [00265] 56% S15 [00266]   52776-05-3 [00267] 49% S16 [00268]   103698-58-4 [00269] 53% S17 [00270]   192865-46-6 [00271] 46% S18 [00272]   1548470-73-0 [00273] 50% S19 [00274]   2226847-79-4 [00275] 56% S20 [00276]   1548471-03-9 [00277] 55% S21 [00278]   140898-76-6 [00279] 52% S22 [00280]   2086712-49-2 [00281] 55% S23 [00282]   2222443-14-1 [00283] 58% S24 [00284]   2222442-94-4 [00285] 48% S25 [00286]   1549979-42-1 [00287] 50% S26 [00288]   2173184-34-2 [00289] 56% S27 [00290]   1549979-37-4 [00291] 54% S28 [00292]   2186703-50-2 [00293] 43%

Example, Dopant D1

[0201] Steps 1 to 3 of the sequence that follows are conducted as a three-stage one-pot reaction. The workup in step 3 is effected under protective gas.

[0202] Step 1: Lithiation of S1:

##STR00294##

[0203] A baked-out, argon-inertized four-neck flask with magnetic stirrer bar, dropping funnel, water separator, reflux condenser and argon blanketing is charged with 24.0 g (50 mmol) of 51 in 1700 ml of tert-butylbenzene. The reaction mixture is cooled down to −40° C., and then 110.5 ml (210 mmol) of tert-butyllithium, 1.9 M in n-pentane, is added dropwise. The mixture is stirred at −40° C. for a further 30 min, allowed to warm up to room temperature, then heated 70° C., in the course of which the n-pentane is distilled off via the water separator over about 1 h.

Step 2: Transmetalation and Cyclization

[0204] ##STR00295##

[0205] The reaction mixture is cooled back down to −40° C. 10.4 ml (110 mmol) of boron tribromide is added dropwise over a period of about 10 min. On completion of addition, the reaction mixture is stirred at RT for 1 h. Then the reaction mixture is cooled down to 0° C., and 19.2 ml (110 mmol) of di-iso-propylethylamine is added dropwise over a period of about 30 min. Then the reaction mixture is stirred at 160° C. for 16 h. After cooling, di-iso-propylethylammmonium hydrobromide is filtered off using a double-ended frit, and the filtrate is cooled down to −78° C.

[0206] Step 3: Arylation

##STR00296##

[0207] A second baked-out, argon-inertized Schlenk flask with magnetic stirrer bar is charged with 27.8 g (150 mmol) of 2-bromo-1,3-dimethylbenzene [576-22-7] in 1000 ml of diethyl ether and cooled down to −78° C. Then 60.0 ml (150 mmol) of n-butyllithium, 2.5 M in n-hexane, is added dropwise thereto and the mixture is stirred for a further 30 min. The reaction mixture is allowed to warm up to RT and stirred for a further 1 h, and the solvent is removed completely under reduced pressure. The lithium organyl is suspended in 300 ml of toluene and transferred into the cryogenic reaction mixture from step 2. The mixture is stirred for a further 1 h, and the reaction mixture is left to warm up to RT overnight. 15 ml of acetone is added cautiously to the reaction mixture, which is concentrated to dryness. The oily residue is absorbed with DCM onto ISOLUTE® and hot-filtered through a silica gel bed with a pentane-DCM mixture (10:1). The filtrate is concentrated to dryness. The residue is subjected to flash chromatography twice, silica gel, n-heptane/ethyl acetate, Torrent automated column system from A. Semrau.

[0208] Step 4: Oxidation to D1

##STR00297##

[0209] Procedure analogous to R. Doringer et al., Monatshefte für Chemie, 2006, 137, 185. The product from step 3 is taken up in 150 ml of chlorobenzene, 20 g of activated 3 A molecular sieve is added, and the mixture is stirred in the dark under air at 60° C. until oxidation is complete (about 5 h). The molecular sieve is filtered off and rinsed with a little chlorobenzene, and the mixture is concentrated to dryness under reduced pressure. The residue is subjected to flash chromatography twice, silica gel, n-heptane/ethyl acetate, Torrent automated column system from A. Semrau. Further purification is effected by repeated hot extraction crystallization with DCM/acetonitrile and final fractional sublimation or heat treatment under reduced pressure. Yield: 12.43 g (22 mmol) 44%; purity about 99.9% by .sup.1H NMR.

[0210] The following compounds can be prepared analogously:

TABLE-US-00003 Ex. Reactant Products Yield D2 S2   [00298]   3972-65-4 [00299] 56% D3 S3   [00300]   [00301] 40% 126866-29-3 D4 S4   [00302]   576-83-0 [00303] 45% D5 S5   [00304]   10368-73-7 [00305] 23% D6 S6   [00306]   90-11-9 [00307] 38% D7 S7   [00308]   7412-67-1 Use in step 3 as ethereal standard solution [00309] 17% D8 S8   [00310]   23674-20-6 [00311] 29% D9 S9   [00312]   576-83-0 [00313] 46% D10 S10   [00314]   576-83-0 [00315] 50% D11 S11   [00316]   23674-20-6 [00317] 22% D12 S12   [00318]   23674-20-6 [00319] 48% D13 S13   [00320]   576-83-0 [00321] 42% D14 S14   [00322]   57190-17-7 [00323] 26% D15 S15   [00324]   10368-73-7 [00325] 24% D16 S16   [00326]   10368-73-7 [00327] 22% D17 S17   [00328]   576-83-0 [00329] 40% D18 S18   [00330]   576-83-0 [00331] 23% D19 S19   [00332]   50548-45-3 [00333] 21% D20 S19   [00334] [00335] 19% 50548-45-3 D21 S21   [00336]   942615-32-9 [00337] 26% D22 S22   [00338]   576-83-0 [00339] 41% D23 S23   [00340]   64248-56-2 [00341] 16% S24 S24   [00342]   1562418-80-7 [00343] 13% D25 S25   [00344]   2052-07-5 [00345] 37% D26 S25   [00346]   1801624-97-4 [00347] 42% D27 S27   [00348]   758673-19-5 [00349] 36% D28 S27   [00350]   3972-65-4 [00351] 17% D100 Steps 1, 2 & 4   [00352]   75-44-5 1 M in toluene [00353] 30% D200 Steps 1, 2 & 4   [00354]   [00355] 21% 824-72-6 Racemate D300 Steps 1, 2 & 4   [00356]   10545-99-0 [00357] 28% D400 Steps 1, 2 & 4   [00358]   7791-25-5 [00359] 31% D500 Steps 1, 2 & 4   [00360] [00361] 17% 103-33-3 D600 Steps 1, 2 & 4   [00362]   18395-90-9 [00363] 34% D601 Steps 1, 2 & 4   [00364]   80-10-4 [00365] 38%

Example, Dopants D6PA, D6PB and D6PC

[0211] ##STR00366##

[0212] Preparation from D6 by flash vacuum pyrolysis, carrier gas: argon, reduced pressure about 10.sup.−2 torr, pyrolysis zone temperature 550° C., catalyst: 1% PdO on alumina. Chromatography separation, DCM/n-heptane, silica gel. Yields: D100A 9%; D100B 15%, D100C 8%.

[0213] Production of OLED Components

[0214] 1) Vacuum-Processed Components:

[0215] OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 2004/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).

[0216] In the examples which follow, the results for various OLEDs are presented. Cleaned glass plates (cleaning in Miele laboratory glass washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm are pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and, within 30 min, for improved processing, coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180° C. for 10 min. These coated glass plates form the substrates to which the OLEDs are applied.

[0217] The OLEDs basically have the following layer structure: Substrate/hole injection layer 1 (HIL1) consisting of Ref-HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 1 (HTL1) composed of: 150 nm HTM1 for UV & blue OLEDs; 50 nm for green and yellow OLEDs; 110 nm for red OLEDs/hole transport layer 2 (HTL2) composed of: 10 nm for blue OLEDs; 20 nm for green & yellow OLEDs; 10 nm for red OLEDs/emission layer (EML): 25 nm for blue OLEDs; 40 nm for green & yellow OLEDs; 35 nm for red OLEDs/hole blocker layer (HBL) 10 nm/electron transport layer (ETL) 30 nm/electron injection layer (EIL) composed of 1 nm ETM2/and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm.

[0218] First of all, vacuum-processed OLEDs are described. For this purpose, all the materials are applied by thermal vapor 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 SMB1:D1 (95:5%) mean here that the material SEB1 is present in the layer in a proportion by volume of 95% and D1 in a proportion of 5%. Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in table 1. The materials used for production of the OLEDs are shown in table 3.

[0219] 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 Im/W) and the external quantum efficiency (EQE, measured in percent) are, as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics. The electroluminescent spectra are recorded at a luminance of 1000 cd/m.sup.2, and these are used to infer the emission color and the EL-FWHM values (ELectroluminescence-Full Width Half Maximum—width of the EL emission spectra at half the peak height in eV; for better comparability over the entire spectral range).

[0220] Use of compounds of the invention as materials in OLEDs: One use of the compounds of the invention can be as dopant in the emission layer and as transport or blocker materials (HBL) in OLEDs. The compounds D-Ref.1 according to table 3 are used as a comparison according to the prior art. The results for the OLEDs are collated in table 2.

TABLE-US-00004 TABLE 1 Structure of the OLEDs Ex. EML HBL ETL Blue OLEDs (400-499 nm) D-Ref.1 SMB1:D-Ref.1 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D1 SMB1:D1 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D2 SMB4:D2 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D3 SMB1:D3 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D4 SMB1:D4 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D7 SMB1:D7 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D9 SMB1:D9 ETM1 ETM1:ETM2 (92%:8%) (50%:50%) D-D10 SMB1:D10 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D12 SMB1:D12 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D13 SMB1:D13 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D14 SMB1:D14 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D17 SMB1:D17 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D18 SMB1:D18 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D19 SMB1:D19 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D22 SMB1:D22 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D23 SMB1:D23 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D24 SMB1:D24 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D25 SMB3:D25 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D26 SMB2:D26 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D100 SMB4:D100 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D200 SMB1:D1 D200 ETM1:ETM2 (95%:5%) (50%:50%) Green & yellow OLEDs (500-590 nm) D-D300 SMB1:D300 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D6PA SMB1:D6PA ETM1 ETM1:ETM2 (97%:3%) (50%:50%) D-D6PB SMB1:D6PB ETM1 ETM1:ETM2 (97%:3%) (50%:50%) D-D6PC SMB1:D6PC ETM1 ETM1:ETM2 (97%:3%) (50%:50%)

TABLE-US-00005 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) EL-FWHM Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 Color [eV] Blue OLEDs (430-475 nm) Sky blue OLEDs (476-504) Ref.1 6.1 4.6 blue 0.17 D-D1 6.3 4.5 blue 0.14 D-D2 6.5 4.4 blue 0.16 D-D3 6.2 4.3 blue 0.16 D-D4 6.5 4.4 blue 0.16 D-D7 6.6 4.4 blue 0.17 D-D9 6.4 4.5 blue 0.15 D-D10 6.5 4.6 blue 0.14 D-D12 7.0 4.4 blue 0.16 D-D13 6.9 4.5 blue 0.15 D-D14 6.4 4.4 blue 0.15 D-D17 7.3 4.3 blue 0.16 D-D18 6.5 4.4 blue 0.17 D-D19 7.2 4.3 sky blue 0.17 D-D22 5.9 4.4 blue 0.14 D-D23 6.6 4.3 sky blue 0.16 D-D24 6.6 4.4 sky blue 0.17 D-D25 6.4 4.4 blue 0.14 D-D26 6.8 4.3 sky blue 0.15 D-D100 6.1 4.3 blue 0.21 D-D200 6.4 4.5 blue 0.15 Green OLEDs (505-549 nm) Yellow OLEDs (550-600 nm) D-D300 6.9 4.2 green 0.22 D-D6PA 6.6 4.3 yellow 0.21 D-D6PB 7.1 4.2 yellow 0.17 D-D6PC 6.8 4.4 yellow 0.14

[0221] 2) Solution-Processed Components:

[0222] The production of solution-based OLEDs is fundamentally described in the literature, for example in WO 2004/037887 and WO 2010/097155. The examples that follow combined the two production processes (application from the gas phase and solution processing), such that layers up to and including emission layer were processed from solution and the subsequent layers (hole blocker layer/electron transport layer) were applied by vapor deposition under reduced pressure. For this purpose, the previously described general methods are matched to the circumstances described here (layer thickness variation, materials) and combined as follows.

[0223] The construction used is thus as follows: [0224] substrate, [0225] ITO (50 nm), [0226] PEDOT (20 nm), [0227] hole transport layer (HIL2) (20 nm), [0228] emission layer (92% host, 8% dopant) (60 nm), [0229] electron transport layer (ETM1 50%+ETM2 50%) (20 nm), [0230] cathode (Al).

[0231] Substrates used are glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm. For better processing, these are coated with the buffer (PEDOT) Clevios P VP AI 4083 (Heraeus Clevios GmbH, Leverkusen); PEDOT is at the top. Spin-coating is effected under air from water. The layer is subsequently baked at 180° C. for 10 minutes. The hole transport layer and the emission layer are applied to the glass plates thus coated. The hole transport layer is the polymer of the structure shown in table 3, which was synthesized according to WO 2010/097155. The polymer is dissolved in toluene, such that the solution typically has a solids content of about 5 g/l when, as is the case here, the layer thickness of 20 nm typical of a device is to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 180° C. for 60 min.

[0232] The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). Details given in such a form as H1 (92%):D (8%) mean here that the material H1 is present in the emission layer in a proportion by weight of 92% and the dopant D in a proportion by weight of 8%. The mixture for the emission layer is dissolved in toluene or chlorobenzene. The typical solids content of such solutions is about 18 g/l when, as here, the layer thickness of 60 nm which is typical of a device is to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 140 to 160° C. for 10 minutes. The materials used are shown in table 3.

[0233] The materials for the electron transport layer and for the cathode are applied by thermal vapor deposition in a vacuum chamber. The electron transport layer, for example, may consist of more than one material, the materials being added to one another by co-evaporation in a particular proportion by volume. Details given in such a form as ETM1:ETM2 (50%:50%) mean here that the ETM1 and ETM2 materials are present in the layer in a proportion by volume of 50% each. The materials used in the present case are shown in table 3.

TABLE-US-00006 TABLE 2 Results for the solution-processed OLEDs at 1000 cd/m.sup.2 EQE Voltage EL-FWHM Ex. Dopant (%) (V) Color [eV] Blue OLEDs (430-475 nm) Ref.-Sol. Ref.-D1 4.4 4.9 blue 0.19 Sol.-D5 D5 5.3 4.7 blue 0.19 Sol.-D6 D6 5.0 4.5 blue 0.24 Sol.-D11 D11 5.1 4.7 blue 0.18 Sol.-D15 D15 5.2 4.6 blue 0.17 Sol.-D16 D16 5.2 4.7 blue 0.17 Sol.-D20 D20 3.7 4.7 blue 0.19 Sol.-D21 D21 4.8 4.6 blue 0.21 Sol.-D27 D27 4.9 4.6 blue 0.15 Sol.-D28 D28 5.1 4.7 blue 0.19

TABLE-US-00007 TABLE 3 Structural formulae of the materials used [00367] HTM1 [136463-07-5] [00368] HTM2 [1450933-44-4] [00369] SMB1 [1087346-88-0] [00370] SMB2 [667940-34-3] [00371] SMB3 [1627916-48-6] [00372] H1 [1818872-85-3] [00373] SMB4 [342638-54-4] [00374] [1805802-42-9] Ref.-D1 [00375] ETM1 [1233200-52-6] [00376] ETM2 [25387-93-3] [00377] HIL2

[0234] By comparison with the references, some of the compounds of the invention show narrower or comparably narrow electroluminescence spectra, recognizable by the smaller or equal EL-FWHM values (ELectroluminescence-Full Width Half Maximum—width of the EL emission spectra in eV at half the peak height). Narrower electroluminescence spectra lead to a distinct improvement in color purity (lower CIE y values). Moreover, EQE values (External Quantum Efficiencies) are distinctly greater and operating voltages are lower compared to the reference, which leads to a distinct improvement in power efficiencies of the device and hence to lower power consumption.