POLYCYCLIC COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to polycyclic compounds suitable for use in electronic devices, and to electronic devices, especially organic electroluminescent devices, comprising these compounds.

Claims

1.-20. (canceled)

21. A compound comprising at least one structure of the formula (I) ##STR00294## where the symbols and indices used are as follows: Z is the same or different at each instance and is N or B; Q is the same or different at each instance and is C═O, C(═O)—C(═O), (R.sup.d).sub.2C—C(R.sup.d).sub.2, (R.sup.d).sub.2C═C(R.sup.d) or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and binds to the Y.sup.1 and Y.sup.2 groups via two adjacent and mutually bonded carbon atoms and may be substituted in each case by one or more R.sup.d radicals; Y.sup.1, Y.sup.2 is the same or different at each instance and is N(Ar), N(R), B(Ar), B(R), Al(Ar) or Al(R); Y.sup.3, Y.sup.4 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; 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 an Ar or R radical or a further group; X.sup.1 is the same or different at each instance and is N, CR.sup.a, CAr, or C if a ring system is formed by a bond to an Ar or R radical or a further group, with the proviso that not more than two of the X.sup.1, X.sup.2 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 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 a ring system is formed by a bond to an Ar or R radical or a further group; R, R.sup.a, R.sup.b, R.sup.c, R.sup.d 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.sup.1).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—, —Se—, —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, R.sup.d 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.sub.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.

22. The compound as claimed in claim 21, comprising at least one structure of the formula (II) ##STR00295## where Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Z, Q, R.sup.a, R.sup.b and R.sup.c have the definitions given in claim 21 and the index j is 0, 1 or 2.

23. The compound claim 21, comprising at least one structure of the formulae (IIIa) to (IIIk): ##STR00296## ##STR00297## ##STR00298## where Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, X.sup.1, X.sup.2, X.sup.3, R.sup.d and Z have the definitions given in claim 21, X.sup.4 is the same or different at each instance and is N, CR.sup.d, or C if a ring system is formed by a bond to an Ar or R radical or a further group, and Y.sup.5 is C(R).sub.2, NR, NAr′, BR, BAr′, O or S, where R and Ar′ have the definitions given in claim 21.

24. The compound as claimed in claim 21, comprising at least one structure of the formula (IVa) to (IVn): ##STR00299## ##STR00300## ##STR00301## ##STR00302## where Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Z, R.sup.a, R.sup.b, R.sup.c and R.sup.d have the definitions given in claim 21, the index j is 0, 1 or 2, the index m is 0, 1, 2, 3 or 4, and Y.sup.5 is C(R).sub.2, NR, NAr′, BR, BAr′, O or S, where R and Ar′ have the definitions given in claim 21.

25. The compound as claimed in claim 21, wherein Z is N and at least one of the Y.sup.1, Y.sup.2 groups is B(Ar), B(R), Al(Ar), or Al(R).

26. The compound as claimed in claim 21, wherein Z is N and at least one of the Y.sup.1, Y.sup.2 groups is N(Ar) or N(R).

27. The compound as claimed in claim 21, wherein at least one of the Y.sup.1, Y.sup.2 groups represent(s) N(Ar) or N(R) and at least one of the Y.sup.3, Y.sup.4 groups is B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), P(═O)Ar, P(═O)R, C═O, S═O or SO.sub.2.

28. The compound as claimed in claim 21, wherein Z is B and at least one of the Y.sup.1, Y.sup.2 groups is N(Ar) or N(R).

29. The compound as claimed in claim 21, wherein Z is B and at least one of the Y.sup.1, Y.sup.2 groups is B(Ar), B(R), Al(Ar), or Al(R).

30. The compound as claimed in claim 21, wherein at least one of the Y.sup.1, Y.sup.2 groups represents B(Ar), B(R), Al(Ar) or Al(R) and at least one of the Y.sup.3, Y.sup.4 groups is N(Ar), N(R), P(Ar), P(R), O, S or Se.

31. The compound as claimed in claim 21, comprising at least one structure of the formulae (Va) to (Vk): ##STR00303## ##STR00304## ##STR00305## where Y.sup.3, Y.sup.4, X.sup.1, X.sup.2, X.sup.3 and Z have the definitions given in claim 21, X.sup.4 is the same or different at each instance and is N, CR.sup.d, or C if a ring system is formed by a bond to an Ar or R radical or a further group, Y.sup.5 is C(R).sub.2, NR, NAr′, BR, BAr′, O or S, where R and Ar have the definitions given in claim 21: Z.sup.1, Z.sup.2 is the same or different at each instance and is N, B or Al; X is the same or different at each instance and is N, CR, or C if a ring system is formed by a bond to an X.sup.3 radical or a further group, with the proviso that not more than two of the X groups in one cycle are N, where R is as defined in claim 21; Y.sup.6, Y.sup.7 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, where R and Ae have the definitions given in claim 21; p, q is the same or different at each instance and is 0 or 1, where 0 means that the corresponding group is absent.

32. The compound as claimed in claim 21, comprising at least one structure of the formulae (VI-1) to (VI-39): ##STR00306## ##STR00307## ##STR00308## ##STR00309## ##STR00310## ##STR00311## ##STR00312## ##STR00313## ##STR00314## ##STR00315## ##STR00316## where Y.sup.3, Y.sup.4, Z, R, R.sup.a, R.sup.b, R.sup.c and R.sup.d have the definitions given in claim 21, and the further symbols have the following definition: Z.sup.1, Z.sup.2 is the same or different at each instance and is N, B or Al; l is 0, 1, 2, 3, 4 or 5; m is 0, 1, 2, 3 or 4; j is 0, 1 or 2; k is 0 or 1; and Y.sup.5 is C(R).sub.2, NR, NAr′, BR, BAr′, O or S, where R and Ar′ have the definitions given in claim 21.

33. The compound as claimed in claim 21, comprising at least one structure of the formulae ##STR00317## ##STR00318## ##STR00319## ##STR00320## ##STR00321## where Z, R, R.sup.a, R.sup.b, R.sup.c and R.sup.d have the definitions given in claim 21, and the further symbols have the following definition: Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.4 is the same or different at each instance and is N, B or Al; l is 0, 1, 2, 3, 4 or 5; m is 0, 1, 2, 3 or 4; j is 0, 1 or 2; k is 0 or 1.

34. The compound as claimed in claim 21, wherein at least two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d radicals together with the further groups to which the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d radicals form at least one structure of the formulae (RA-1) to (RA-12): ##STR00322## ##STR00323## where R.sup.1 has the definition set out above, the dotted bonds represent the sites of attachment via which the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d radicals bind, and the further symbols have the following definition: Y.sup.8 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.sup.1)C═C(R.sup.1), NR.sup.1, NAr′, O or S; R.sup.e 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, 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; at the same time, two R.sup.e radicals, or one R.sup.e radical with an R.sup.1 radical or with a further group, may also form a ring system, where R.sup.1 and R.sup.2 have the definitions given in claim 21; 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.

35. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 21, wherein, in place of a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

36. A formulation comprising at least one compound as claimed in claim 21 and at least one further compound.

37. A composition comprising at least one compound as claimed in claim 21 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.

38. A process for preparing a compound as claimed in claim 21, comprising synthesizing a base skeleton having a Z group or a precursor of the Z group, and introducing at least one of the Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4 groups by means of a nucleophilic aromatic substitution reaction or a coupling reaction.

39. A method comprising providing at least one compound as claimed in claim 21 and including the compound in an electronic device.

40. An electronic device comprising at least one compound as claimed in claim 21.

Description

EXAMPLES

[0246] 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

[0247] ##STR00190##

[0248] Complete procedure including workup under protective gas and exclusion of light. To a well-stirred solution, cooled to 0° C., of 36.6 g (100 mmol) of N,N-bis-(1-methyl-2-indolyl)-4-methylaniline [415975-13-2] in 300 ml of dichloromethane is added, in portions of the course of 60 min, 35.6 g (200 mmol) of N-bromosuccinimide, and the mixture is then stirred at 0° C. for 5 h. The precipitated succinimide is filtered off, and the organic phase is washed three times with 200 g of ice-water and once with saturated sodium chloride solution, and dried over magnesium sulfate.

[0249] The desiccant is filtered off, the filtrate is concentrated to dryness and the residue is subjected to extraction by stirring with 150 ml of methanol. Yield: 35.2 g (67 mmol) 67%; purity about 95% by .sup.1H NMR.

[0250] The following compounds can be prepared analogously

TABLE-US-00002 Ex.. Reactants Product Yield S2 [00191] [00192] 64% S3 [00193] [00194] 55%

Example S100

Step 1: Lithiation of S1

[0251] ##STR00195## [0252] Intermediat, nicht isoliert

[0253] A baked-out, argon-inertized four-neck flask with magnetic stirrer bar, dropping funnel, water separator, reflux condenser and argon blanketing is charged with 26.2 g (50 mmol) of S1 in 1300 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

[0254] ##STR00196## [0255] Intermediat, nicht isoliert

[0256] 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 12 h. After cooling, di-iso-propylethylammmonium hydrobromide is filtered off using a double-ended frit, and the filtrate is cooled down to −78° C.

Step 3: Arylatlon

[0257] ##STR00197##

[0258] Intermediat, nicht isoliert 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 ECM onto ISOLUTE® and hot-filtered through a silica gel bed with an n-pentane-DCM mixture (10:1).

[0259] The filtrate is concentrated to dryness.

Step 4: Demethylaton to S100

[0260] ##STR00198##

[0261] Procedure as per the process described by T. Rosenau et al., Org. Lett., 2006, 6(4), 541. The product from step 3 is divided into 4 portions and converted, residence time in the reactive zone 10 min., the combined eluates are finally extracted by stirring from ethanol. Yield over 4 stages: 5.1 g (9 mmol), 18%: Purity: about 95% by .sup.1H NMR.

[0262] The following compounds can be prepared analogously:

TABLE-US-00003 Ex. Reactant Products Yield S101 [00199] [00200] 22% S102 [00201] [00202] 23% S103 [00203] [00204] 26% S104 [00205] [00206] 20% S105 [00207] [00208] 27% S106 [00209] [00210] 25% S107 [00211] [00212] 21% S108 [00213] [00214] 20% S109 [00215] [00216] 22% S110 [00217] [00218] 30% S111 [00219] [00220] 25% S112 [00221] [00222] 17% S113 [00223] [00224] 24% S114 [00225] [00226]  8% S115 [00227] [00228] 25% S116 [00229] [00230] 27%

Example D100

[0263] ##STR00231##

[0264] To a solution of 5.65 g (10.0 mmol) of S100 in 200 ml of THF is added in portions, with good stirring and ice cooling, 4.8 g (20.0 mmol) of sodium hydride, and then the mixture is stirred for 1 h. 10.0 ml (10.0 mmol) of a phosgene solution (1 M in toluene) is added dropwise, the mixture is stirred for 1 h, and then the solvent is removed under reduced pressure. The residue is subjected to sublimation under high vacuum (p about 10.sup.−4 mbar, T 250-300° C.), with sublimation of the product to leave the salts. The sublimate is fractionally sublimed again. Yield: 1.66 g (2.8 mmol) 28%; purity about 99.9% by .sup.1H NMR.

[0265] The following compounds can be prepared analogously:

TABLE-US-00004 Ex.. Reactants Product Yield D101 [00232] [00233] 46%

Example D200

[0266] ##STR00234##

[0267] A mixture of 5.65 g (10.0 mmol) of D100, 2.83 g (12.0 mmol) of 1,2-dibromobenzene [583-53-9], 2.88 g (30.0 mmol) of sodium tert-butoxide, 48.6 mg (0.24 mmol) of tri-tert tributylphosphine, 44.9 mg (0.20 mmol) of palladium(II) acetate and 70 ml of o-xylene is stirred under reflux for 16 h. The mixture is left to cool to 50° C., 100 ml of water and 200 ml of ethyl acetate are added, and the organic phase is separated off and washed three times with 100 ml each time of water and twice with 100 ml of saturated sodium chloride solution and dried over magnesium sulfate. The desiccant is filtered off using a Celite bed in the form of an ethyl acetate slurry, the filtrate is concentrated to dryness and the residue is subjected to hot extraction with ethanol. Further purification is effected by flash chromatography (Torrent automated column system from A. Semrau, ethyl acetate/n-heptane gradient), by repeated hot extraction crystallization (dichloromethane/acetonitrile (1:2 vv)) and final fractional sublimation or heat treatment under high vacuum. Yield: 2.83 g (4.4 mmol) 44%; purity about 99.9% by .sup.1H NMR.

[0268] The following compounds can be prepared analogously:

TABLE-US-00005 Ex.. Reactants Product Yield D201 [00235] [00236] 55% D202 [00237] [00238] 51% D203 [00239] [00240] 32% D204 [00241] [00242] 36% D205 [00243] [00244] 30% D206 [00245] [00246] 38% D207 [00247] [00248] 40% D208 [00249] [00250] 45% D209 [00251] [00252] 43% D210 [00253] [00254] 40% D211 [00255] [00256] 37% D212 [00257] [00258] 39% D213 [00259] [00260] 33% D214 [00261] [00262] 40% D215 [00263] [00264] 38% D216 [00265] [00266] 40% D217 [00267] [00268] 40% D218 [00269] [00270] 30% D219 [00271] [00272] 37% D220 [00273] [00274] 42% D221 [00275] [00276] 19% S222 [00277] [00278] 42% D223 [00279] [00280] 36%

Example, Dopant D203P

[0269] ##STR00281##

[0270] Preparation from D203 by flash vacuum pyrolysis, carrier gas: argon, reduced pressure about 10.sup.−2 torr, pyrolysis zone temperature 550° C., catalyst: 5% PdO on alumina. Chromatography separation, DCM/n-heptane, silica gel. Yield: 22%.

[0271] In an analogous manner, it is possible to prepare D204P from D204; yield: 16%.

##STR00282##

[0272] Production of OLED Components

[0273] 1) Vacuum-Processed Components

[0274] 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).

[0275] 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 Germany, 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.

[0276] 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: 160 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.

[0277] 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 4.

[0278] 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) are, as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics. The electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2.

[0279] Use of compounds of the invention as materials in OLEDs: One use of the compounds of the invention is as dopant in the emission layer and as transport or blocker materials (HBL) in OLEDs. The compounds D-Ref.1 according to table 4 are used as a comparison according to the prior art. The results for the OLEDs are collated in table 2.

[0280] Table 1: Structure of the OLEDs

TABLE-US-00006 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-D100 SMB1:D100 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D101 SMB1:D101 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D200 SMB1:D200 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D201 SMB1:D201 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D203 SMB1:D203 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D204 SMB1:D204 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D205 SMB1:D205 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D206 SMB1:D206 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D209 SMB3:D209 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D211 SMB1:D211 ETM1 ETM1:ETM2 (97%:3%) (50%:50%) D-D216 SMB1:D216 ETM1 ETM1:ETM2 (92%:8%) (50%:50%) Green OLEDs (500-549 nm) Yellow OLEDs (550-600 nm) D-D202 SMB2:D202 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) D-D217 SMB1:D217 ETM1 ETM1:ETM2 (95%:5%) (50%:50%)

TABLE-US-00007 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 Color Blue OLEDs (430-499 nm) Ref. 1 6.0 4.7 blue D-D100 6.4 4.3 blue D-D101 6.0 4.3 blue D-D200 6.5 4.3 blue D-D201 6.4 4.2 blue D-D203 6.7 4.4 blue D-D204 6.5 4.4 blue D-D205 6.4 4.5 blue D-D206 6.8 4.3 blue D-D209 6.6 4.3 blue D-D211 6.5 4.2 blue D-D216 6.5 4.4 blue Green OLEDs (500-549 nm) Yellow OLEDs (550-600 nm) D-D217 6.7 3.6 green D-D202 6.8 3.4 yellow

[0281] 2) Solution-Processed Components:

[0282] 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.

[0283] The construction used is thus as follows: [0284] substrate, [0285] ITO (50 nm), [0286] PEDOT (20 nm), [0287] hole transport layer (HIL2) (20 nm), [0288] emission layer (92% host H1, 8% dopant) (60 nm), [0289] electron transport layer (ETM1 50%+ETM2 50%) (20 nm), [0290] cathode (Al).

[0291] Substrates used are glass plates 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 4, 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.

[0292] 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 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 4.

[0293] 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 4.

TABLE-US-00008 TABLE 3 Results for the solution-processed OLEDs at 1000 cd/m.sup.2 EQE Voltage Ex. Dopant (%) (V) Color Blue OLEDs (430-499 nm) Ref.-Sol. Ref.-D1 4.4 4.9 blue Sol.-D207 D207 4.9 4.5 blue Sol.-D208 D208 5.0 4.4 blue Sol.-D212 D212 5.2 4.5 blue Sol.-D213 D213 5.3 4.6 blue Sol.-D215 D215 4.9 4.4 blue Green OLEDs (500-549 nm) Yellow OLEDs (550-600 nm) Sol.-D210 D210 6.7 4.0 yellow Sol. D219 D219 6.3 4.2 green

TABLE-US-00009 TABLE 4 Structural formulae of the materials used [00283] [00284] [00285] [00286] [00287] [00288] [00289] [00290] [00291] [00292] [00293]

[0294] The compounds of the invention show higher EQE values (External Quantum Efficiencies) at reduced operating voltages compared to the reference, which leads to a distinct improvement in power efficiencies of the device and hence to lower power consumption.