COMPOUNDS FOR ELECTRONIC DEVICES

Abstract

The present application relates to a compound of a formula (I), to the use thereof in electronic devices, to processes for preparing the compound, and electronic devices comprising the compound.

Claims

1.-29. (canceled)

30. Compound of formula (I) ##STR01011## where: Y is the same or different at each instance and is selected from O, S, NAr.sup.0 and CAr.sup.1, where there must be at least one Y present which is selected from O, S and NAr.sup.0; Z is the same or different at each instance and is selected from N and CR.sup.1; Ar.sup.0 is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.2 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.2 radicals; Ar.sup.1 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.2, CN, Si(R.sup.2).sub.3, P(═O)(R.sup.2).sub.2, OR.sup.2, S(═O)R.sup.2, S(═O).sub.2R.sup.2, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.2 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.2C═CR.sup.2—, —C≡C—, Si(R.sup.2).sub.2, C═O, C═NR.sup.2, —C(═O)O—, —C(═O)NR.sup.2—, NR.sup.2, P(═P)(R.sup.2), —O—, —S—, SO or SO.sub.2, with exclusion of joining of two AO groups to one another to form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.0 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.1, CN, Si(R.sup.1).sub.3, N(R.sup.1).sub.2, P(═O)(R.sup.1).sub.2, OR.sup.1, S(═O)R.sup.1, S(═O).sub.2R.sup.1, straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, heteroaromatic ring systems having 5 to 40 aromatic ring atoms, aryloxy or heteroaryloxy groups having 5 to 40 aromatic ring atoms, and aralkyl groups having 5 to 40 aromatic ring atoms; where the two R.sup.0 radicals may be joined to one another and may form an aliphatic or heteroaliphatic ring, so as to form a spiro compound in position 8 of the fluorene derivative, especially a spirobifluorene derivative; where the alkyl, alkoxy, thioalkyl, alkenyl, alkynyl, aryloxy, heteroaryloxy and aralkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.1 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, thioalkyl, alkenyl, alkynyl, aryloxy, heteroaryloxy and aralkyl groups mentioned may be replaced by —R.sup.1C═CR.sup.1—, —C≡C—, Si(R.sup.1).sub.2, C═O, C═NR.sup.1, —C(═O)O—, —C(═O)NR.sup.1—, P(═O)(R.sup.1), —O—, —S—, SO or SO.sub.2; R.sup.1 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.1 radicals may be joined to one another and may form an aliphatic or heteroaliphatic ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.2 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.2 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2; R.sup.5 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.6, CN, Si(R.sup.6).sub.3, N(R.sup.6).sub.2, P(═O)(R.sup.6).sub.2, OR.sup.6, S(═O)R.sup.6, S(═O).sub.2R.sup.6, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.5 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.6 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.6C═CR.sup.6—, —C≡C—, Si(R.sup.6).sub.2, C═O, C═NR.sup.6, —C(═O)O—, —C(═O)NR.sup.6—, NR.sup.6, P(═O)(R.sup.6), —O—, —S—, SO or SO.sub.2; R.sup.6 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, CN, alkyl or alkoxy groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.6 radicals may be joined to one another and may form a ring; and where the alkyl, alkoxy, alkenyl and alkynyl groups, aromatic ring systems and heteroaromatic ring systems mentioned may be substituted by one or more radicals selected from F and CN; and in the formula (I), at least one R.sup.1 radical, one Ar.sup.0 group or one Ar.sup.1 group is substituted by an A group conforming to a formula (A): ##STR01012## where: * denotes the bond to the structure of the formula (I); Ar.sup.L is the same or different at each instance and is selected from aromatic ring systems which have 6 to 40 aromatic ring atoms and are substituted by R.sup.2 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and are substituted by R.sup.2 radicals; ET is the same or different at each instance and is an electron-transporting group selected from electron-deficient heteroaromatic groups to which one or more Ar.sup.2 groups are bonded; Ar.sup.2 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.3, CN, Si(R.sup.3).sub.3, P(═O)(R.sup.3).sub.2, OR.sup.3, S(═O)R.sup.3, S(═O).sub.2R.sup.3, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.3 radicals; where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.3C═CR.sup.3—, Si(R.sup.3).sub.2, C═O, 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 two or more adjacent Ar.sup.2 groups together may form a mono- or polycyclic, aliphatic or aromatic ring system; R.sup.3 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.5, CN, Si(R.sup.5).sub.3, N(R.sup.5).sub.2, P(═O)(R.sup.5).sub.2, OR.sup.5, S(═O)R.sup.5, S(═O).sub.2R.sup.5, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R.sup.3 radicals may be joined to one another and may form a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned may be replaced by —R.sup.5C═CR.sup.5—, —C≡C—, Si(R.sup.5).sub.2, C═O, C═NR.sup.5, —C(═O)O—, —C(═O)NR.sup.5—, NR.sup.5, P(═O)(R.sup.5), —O—, —S—, SO or SO.sub.2, and n is 0 or 1.

31. Compound according to claim 30, characterized in that exactly one Y is selected from O, S and NAr.sup.0, and two Y are CAr.sup.1.

32. Compound according to claim 30, characterized in that exactly one Y is selected from O and S, and two Y are CAr.sup.1.

33. Compound according to claim 30, characterized in that the Z groups are CR.sup.1.

34. Compound according to claim 30, characterized in that Ar.sup.1 is the same or different at each instance and is selected from phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, fluorenyl, especially 9,9′-dimethylfluorenyl and 9,9′-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, indenofluorenyl, indenocarbazolyl, dibenzofuranyl, dibenzothiophenyl, benzofuranyl, benzothiophenyl, benzofused dibenzofuranyl, benzofused dibenzothiophenyl, naphthyl-substituted phenyl, fluorenyl-substituted phenyl, spirobifluorenyl-substituted phenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, carbazolyl-substituted phenyl, pyridyl-substituted phenyl, pyrimidyl-substituted phenyl, triazinyl-substituted phenyl, where the groups mentioned are each substituted by R.sup.2 radicals, and H.

35. Compound according to claim 30, characterized in that R.sup.1 is the same or different at each instance and is selected from H, D, Si(R.sup.5).sub.3, straight-chain alkyl groups which have 1 to 20 carbon atoms and may be deuterated, branched or cyclic alkyl groups which have 3 to 20 carbon atoms and may be deuterated, aromatic ring systems which have 6 to 40 aromatic ring atoms and may be deuterated, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be deuterated, where the alkyl groups mentioned, the aromatic ring systems mentioned and the heteroaromatic ring systems mentioned are each substituted by R.sup.5 radicals.

36. Compound according to claim 30, characterized in that Ar.sup.L is the same or different at each instance and is selected from divalent groups derived from benzene, biphenyl, terphenyl, naphthalene, fluorene, indenofluorene, indenocarbazole, spirobifluorene, dibenzofuran and dibenzothiophene, each of which are substituted by R.sup.2 radicals.

37. Compound according to claim 30, characterized in that the ET group is the same or different at each instance and is selected from heteroaryl groups which have 5 to 40 aromatic ring atoms and are substituted by Ar.sup.2 groups.

38. Compound according to claim 30, characterized in that the ET group is the same or different at each instance and is selected from the groups of the formulae (ET-1) to (11C): ##STR01013## ##STR01014## where Q′ is the same or different at each instance and is selected from CAr.sup.2 or N; Q″ is the same or different at each instance and is selected from NR.sup.2, O or S; the dotted line in each case marks the attachment position to the rest of the formula (I), and R.sup.2 and Ar.sup.2 are as defined in claim 30; and where at least one Q′ is N.

39. Compound according to claim 30, characterized in that the ET group is the same or different at each instance and is selected from the groups of the formulae (ET-12) to (ET-35) ##STR01015## ##STR01016## ##STR01017## ##STR01018## where the dotted lines represent the bonds to the rest of the formula (I), and Ar.sup.2 is as defined in claim 30.

40. Compound according to claim 30, characterized in that Ar.sup.2 is the same or different at each instance and is selected from H, straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to aromatic ring atoms, where the alkyl groups, alkoxy groups, aromatic ring systems and heteroaromatic ring systems may each be substituted by one or more R.sup.3 radicals, and where two or more adjacent Ar.sup.2 groups together may form a mono- or polycyclic, aliphatic or aromatic ring system.

41. Compound according to claim 30, characterized in that it conforms to the following formula (I-A): ##STR01019## where the variables are as defined in claim 30 and at least one A group is present per formula; and R.sup.4 is the same or different at each instance and is selected from H, D, F, Cl, Br, I, C(═O)R.sup.1, CN, Si(R.sup.1).sub.3, N(R.sup.1).sub.2, P(═O)(R.sup.1).sub.2, OR.sup.1, S(═O)R.sup.1, S(═O).sub.2R.sup.1, straight-chain alkyl, alkoxy or thioalkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, heteroaromatic ring systems having 5 to 40 aromatic ring atoms, aryloxy or heteroaryloxy groups having 5 to 40 aromatic ring atoms, and aralkyl groups having 5 to 40 aromatic ring atoms; with exclusion of joining of the two R.sup.4 radicals to one another to form an aliphatic or heteroaliphatic ring; where the alkyl, alkoxy, thioalkyl, alkenyl, alkynyl, aryloxy, heteroaryloxy and aralkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.1 radicals; and where one or more CH.sub.2 groups in the alkyl, alkoxy, thioalkyl, alkenyl, alkynyl, aryloxy, heteroaryloxy and aralkyl groups mentioned may be replaced by —R.sup.1C═CR.sup.1—, —C≡C, Si(R.sup.1).sub.2, C═O, 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.

42. Compound according to claim 30, characterized in that it corresponds to one of the following formulae (II-A), (III-A) and (IV-A): ##STR01020## where the variables are as defined in claim 30 and at least one A group is present per formula; and R.sup.4 is the same or different at each instance and is selected from F, CN, Si(R.sup.1).sub.3, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where the alkyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned are each substituted by R.sup.1 radicals, and with exclusion of bonding of the two R.sup.4 radicals to one another to form an aliphatic or heteroaliphatic ring.

43. Compound according to claim 30, characterized in that it conforms to one of the following formulae: ##STR01021## ##STR01022## ##STR01023## ##STR01024## ##STR01025## ##STR01026## where the variables are as defined in claim 30.

44. Compound according to claim 30, characterized in that it conforms to the following formula (I-B): ##STR01027## where W is the same or different at each instance and is selected from N and CR.sup.1; U is selected from O and S; k is 0 or 1, where, in the case that k=0, the relevant heteroatom U is absent and U is instead a single bond that connects the corresponding two aromatic six-membered rings; and at least one A group is present in the formula (I-B), where the variables Z, Y and R.sup.1 and the at least one A group are as defined in claim 30.

45. Compound according to claim 44, characterized in that the W groups are CR.sup.1.

46. Compound according to claim 44, characterized in that it conforms to one of the following formulae (II-B) to (IV-B) and (II-C) to (IV-C): ##STR01028## where the variables are as defined in claim 44, and the unoccupied positions on the benzene rings are each substituted by R.sup.1 radicals, and where at least one A group is present per formula.

47. Compound according to claim 44, characterized in that k=0.

48. Compound according to claim 44, characterized in that it conforms to one of the following formulae: ##STR01029## ##STR01030## ##STR01031## ##STR01032## ##STR01033## ##STR01034## ##STR01035##

49. Process for preparing a compound according to claim 30, characterized in that in a first step a Suzuki coupling is conducted, in which a heteroaromatic five-membered ring is coupled to a benzene ring, where the heteroaromatic five-membered ring or the benzene ring bears a carboxylic acid group; in a second step the carboxylic acid group is cyclized by ring closure reaction under acidic conditions to form a bridging carbonyl group between the heteroaromatic five-membered ring and the benzene ring; in a third step the carbonyl group is reduced and, with addition of an organohalogen compound or an organometallic reagent, a substituted methylene bridge is obtained between the heteroaromatic five-membered ring and the benzene ring; and in a fourth step a Suzuki coupling with a heteroaryl compound is conducted; or in a third step an ortho-halogenated or ortho-metallated bisaryl is added on and a further ring closure reaction is conducted; and in a fourth step a Suzuki coupling with a heteroaryl compound is conducted to obtain a compound of the formula (I).

50. Oligomer, polymer or dendrimer containing one or more compounds according to claim 30, wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R.sup.0, R.sup.1, R.sup.2 or R.sup.3 in formula (I).

51. Formulation comprising at least one compound according to claim 30, and at least one solvent.

52. Composition comprising at least one compound according to claim 30 and at least one further compound selected from hole injection materials, hole transport materials, hole blocker materials, wide bandgap materials, fluorescent emitters, phosphorescent emitters, delayed fluorescent materials, host materials, matrix materials, electron blocker materials, electron transport materials and electron injection materials, n-dopants and p-dopants.

53. Electronic device comprising at least one compound according to claim 30.

54. Electronic device according to claim 53, characterized in that it is an organic electroluminescent device and contains anode, cathode and at least one emitting layer, and in that the compound is present in an electron-transporting layer or in an emitting layer of the device.

55. Electronic device according to claim 54, characterized in that the compound is present as electron-transporting material in the electron transport layer together with one or more further electron-transporting compounds.

56. Electronic device according to claim 54, characterized in that the compound is present as electron-transporting material in the electron transport layer and one or more further electron-transporting compounds are present in the electron injection layer.

57. Electronic device according to claim 54, characterized in that the compound is present as electron-transporting material in the emitting layer together with a hole-transporting material.

Description

EXAMPLES

A) Synthesis Examples

[0274] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The reactants can be purchased from ALDRICH (potassium fluoride (spray-dried), tri-tert-butylphosphine, palladium(II) acetate). 3-Chloro-5,6-diphenyl-1,2,4-triazine can be prepared analogously to EP 577559. 2′,7′-Di-tert-butyl-spiro-9,9″-bifluorene-2,7-bisboronic acid glycol ester can be prepared according to WO 02/077060, and 2-chloro-4,6-diphenyl-1,3,5-triazine according to U.S. Pat. No. 5,438,138. Spiro-9,9′-bifluorene-2,7-bis(boronic acid glycol ester) can be prepared analogously to WO 02/077060.

a) 6-chloroindeno[1,2-c]thiophen-4-one 1a

[0275] ##STR00785##

[0276] 10 g (41.9 mmol) of 4-(4-chlorophenyl)thiophene-3-carboxylic acid is suspended in 73 ml of trifluoromethanesulfonic acid and heated at 90° C. for 2 hours. After cooling, the residue is poured onto ice and extracted with ethyl acetate. After a phase separation, the solvent is removed under reduced pressure and the residue is separated by chromatography (heptane/ethyl acetate, 1:1).

[0277] The yield is 2.9 g (13.4 mmol), corresponding to 32% of theory.

b) 6-chloro-4H-indeno[1,2-c]thiophene 1b

[0278] ##STR00786##

[0279] To a well-stirred suspension, boiling under reflux, of 6-chloroindeno[1,2-c]thiophen-4-one in a mixture of 1000 ml of toluene and 2000 ml of ethanol are added 49 ml (1000 mmol) of hydrazine hydrate and then 3 g of freshly prepared Raney nickel. After 2 h under reflux, the mixture is allowed to cool, the solvent is removed under reduced pressure, the residue is taken up in 1000 ml of warm chloroform, the solution is filtered through silica gel, the clear solution is concentrated to 100 ml, and 300 ml of ethanol is added. After the mixture had been left to stand for 12 h, the colourless crystals were filtered off with suction and then recrystallized twice from chloroform/ethanol.

[0280] Yield: 49 g (238 mmol), 96% of theory; purity: 94% by .sup.1H NMR.

[0281] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00013 Reactant 1 Product Yield 2b [00787]   [1407534-82-0] [00788] 89% 3b [00789]   2d [00790] 875 4b [00791]   3d [00792] 90% 5b [00793]   [6263-90-7] [00794] 89%

c) 6-chloro-4,4-dimethylindeno[1,2-c]thiophene 1c

[0282] ##STR00795##

[0283] 31 g (152 mmol) of 6-chloro-4H-indeno[1,2-c]thiophene is dissolved in 600 ml of dried DMSO in a baked-out flask. 43.9 g (457 mmol) of NaOtBu is added at room temperature. The now blue suspension is brought to an internal temperature of 80° C. At this temperature, 64.8 g (457 mmol) of iodomethane is added dropwise to the now violet solution at such a rate that the internal temperature does not exceed 90° C. (duration: 30 min). The mixture is stirred at internal temperature 80-90° C. for a further 30 min.

[0284] Yield: 30.5 g (132 mmol), 88% of theory; purity: 96% by .sup.1H NMR

[0285] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00014 Reactant 1 Product Yield 2c [00796] [00797] 66% 3c [00798] [00799] 67% 4c [00800] [00801] 58% 5c [00802] [00803] 60%

d) 6-chloro-1,3-diphenylindeno[1,2-c]thiophen-4-one 1d

[0286] ##STR00804##

[0287] An initial charge of 4 A molecular sieve is baked out, then initially charged under protective gas with 30 g (136 mmol) of 6-chloroindeno[1,2-c]thiophen-4-one, 72 g (220 mmol) of caesium carbonate, 46 g (294 mmol) of bromobenzene, 2.2 g (7.3 mmol) of {[1,1′-biphenyl]-2-yl}di-tert-butyl)phosphine and 0.83 g (3.6 mmol) of palladium(II) acetate in 325 ml of dry DMF, and the mixture is stirred at 150° C. overnight. Thereafter, the mixture is hot-filtered through Celite, washed through with ethyl acetate and concentrated, and recrystallized in toluene/heptane.

[0288] The yield is 30.4 g (82 mmol), corresponding to 60% of theory.

[0289] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00015 Reactant Reactant 1 2 Product Yield 2d [00805] [00806] [00807] 67% 3d [00808] [00809] [00810] 57% [1367747-08-7] 4d [00811] [00812] [00813] 61% [1511966-22-5] 5d [00814] [00815]   [864377-31-1] [00816] 60%

e) 4-bromo-1,3′-diphenyl-spiro[fluorene-9,4′-indeno[1,2-c]thiophene] 1e

[0290] ##STR00817##

[0291] A 1 l four-neck flask is initially charged with 40 g (112.2 mmol) of 2,2′-dibromobiphenyl in 350 ml of THF and cooled to −78° C. By means of a dropping funnel, 49 ml (123.5 mmol) of n-butyllithium (2.5 M in n-hexane) is added dropwise at this temperature and the mixture is stirred for 1 h. Subsequently, 38 g (112 mmol) of 1,3-diphenyl-8H-indeno[1,2-c]thiophen-8-one, dissolved in 300 ml of THF, is added via a dropping funnel, and the mixture is allowed to come to room temperature overnight. Thereafter, THF is removed by rotary evaporation, then hydrolysis is effected with 500 ml of water/200 ml of ethyl acetate, followed by extractive shaking and drying. The solids are dissolved in 440 ml of toluene and boiled under reflux with 2.1 g (11.198 mmol) of toluene-4-sulfonic acid monohydrate overnight. This is followed by addition of water and ethyl acetate, separation of the phases and removal of the organic solvent on a rotary evaporator. The solids are subjected to hot extraction with n-heptane/toluene (1:1) over alumina and recrystallization in heptane/toluene.

[0292] The yield is 58.8 g (106 mmol), corresponding to 90% of theory.

[0293] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00016 Reactant 1 Reactant 2 Product Yield 2e [00818] [00819] [00820] 93% [5706-22-9] 3e [00821] [00822] [00823] 89% [6072-53-3] 4e [00824] [00825] [00826] 90% [1924664-17-4] 5e [00827]   [1346266-91-8] [00828] [00829] 87% 6e [00830]   [1407534-82-0] [00831] [00832] 84% 7e [00833] [00834] [00835] 91% 8e [00836] [00837] [00838] 92%

f) 2-bromospiro[4a,8a-dihydroindeno[1,2-b]furan-4,9′-fluorene] 1f

[0294] ##STR00839##

[0295] To a solution of 46.2 g (150 mmol) of spiro[4a,8a-dihydroindeno[1,2-b]furan-4,9′-fluorene]

[0296] in chloroform (900 ml) is added in portions, at 0° C. in the dark, N-bromosuccinimide (26.6 g, 150 mmol), and the mixture is stirred at this temperature for 2 h. The reaction is ended by addition of sodium sulfite solution and the mixture is stirred at room temperature for a further 30 min. After phase separation, the organic phase is washed with water and the aqueous phase is extracted with dichloromethane. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is dissolved in toluene and filtered through silica gel. Subsequently, the crude product is recrystallized from toluene/heptane.

[0297] Yield: 44 g (115 mmol), 77% of theory, colourless solid.

g) (1′,3′-diphenylspiro[fluorene-9,4′-indeno[1,2-c]thiophene]-4-yl)boronic acid 1g

[0298] ##STR00840##

[0299] To a solution, cooled to −78° C., of 144 g (270 mmol) of 4-bromo-1′,3′-diphenyl-spiro[fluorene-9,4′-indeno[1,2-c]thiophene] in 1500 ml of diethyl ether are added dropwise 110 ml (276 mmol) of n-butyllithium (2.5 M in hexane). The reaction mixture is stirred at −78° C. for 30 min. The mixture is allowed to come to room temperature and cooled again to −78° C., and then a mixture of 40 ml (351 mmol) of trimethyl borate in 50 ml of diethyl ether is added rapidly. After warming to −10° C., hydrolysis is effected with 135 ml of 2 N hydrochloric acid. The organic phase is removed, washed with water, dried over sodium sulfate and concentrated to dryness. The residue is taken up in 300 ml of n-heptane, and the colourless solid is filtered off with suction, washed with n-heptane and dried under reduced pressure.

[0300] Yield: 135 g (262 mmol), 97% of theory; purity: 96% by HPLC.

[0301] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00017 Reactant 1 Product Yield 2g [00841]   [91155-62-7] [00842] 87% 3g [00843] [00844] 84% [2291155-93-4] 4g [00845] [00846] 71% [899793-65-8] 5g [00847] [00848] 87% [885484-69-5 6g [00849] [00850] 76% 7g [00851] [00852] 91% 8g [00853] [00854] 77% [2291155-80-9 9g [00855] [00856] 67% [1644610-91-2 10g [00857] [00858] 65% [2291155-62-7] 11g [00859] [00860] 52% [2165343-88-2 12g [00861]   [2104697-12-10] [00862] 86% 13g [00863] [00864] 66% [1346266-93-0] 14g [00865] [00866] 62% [911649-11-1] 15g [00867]   1643688-07-6] [00868] 87% 16g [00869] [00870] 67% 17g [00871] [00872] 59%

h) 2-(1′,3′-diphenylspiro[fluorene-9,4′-indeno[1,2-c]thiophen]-4-yl)-4,6-diphenyl-1,3,5-triazine 1h

[0302] ##STR00873##

[0303] 57 g (110 mmol) of (1′,3′-diphenylspiro[fluorene-9,4′-indeno[1,2-c]thiophen]-4-yl)boronic acid, 30 g (110.0 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 45 g (210.0 mmol) of tripotassium phosphate are suspended in 500 ml of toluene, 500 ml of dioxane and 500 ml of water. Added to this suspension are 913 mg (3.0 mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) of palladium(II) acetate, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is removed, filtered through silica gel, washed three times with 200 ml of water and then concentrated to dryness. The residue is recrystallized from toluene and from dichloromethane/iso-propanol and finally sublimed under high vacuum (p=5×10.sup.−5 mbar, T=377° C.). The yield is 63.6 g (90 mmol), corresponding to 82% of theory.

[0304] In an analogous manner, it is possible to obtain the following compounds:

TABLE-US-00018 Reactant 1 Reactant 2 Product Yield 2h [00874] [00875]   40734-4-5 [00876] 84% 3h [00877] [00878]   [2142681-84-1] [00879] 88% 4h [00880] [00881]   [2142681-84-1] [00882] 67% 5h [00883] [00884]   [2251105-15-2] [00885] 71% 6h [00886] [00887]   [864377-31-1] [00888] 75% 7h [00889] [00890]   [864377-31-1] [00891] 79% 8h [00892] [00893]   [2251105-15-2] [00894] 85% 9h [00895] [00896]   [864377-31-1] [00897] 78% 10h [00898] [00899]   [1373265-66-7] [00900] 80% 11h [00901] [00902]   [3842-55-5] [00903] 81% 12h [00904] [00905]   [3842-55-5] [00906] 82% 13h [00907] [00908]   [2915-16-4] [00909] 79% 14h [00910] [00911]   [3842-55-5] [00912] 78% 15h [00913] [00914]   [1205748-51-1] [00915] 87% 16h [00916] [00917]   [3842-55-5] [00918] 72% 17h [00919] [00920]   [40734-4-5] [00921] 61% 18h [00922] [00923]   [3842-55-5] [00924] 79% 19h [00925] [00926]   [3842-55-5] [00927] 75% 20h [00928] [00929]   [2915-16-4] [00930] 67% 21h [00931] [00932]   [864377-31-1] [00933] 82% 22h [00934] [00935]   [864377-31-1] [00936] 76% 23h [00937] [00938]   [2251105-15-2] [00939] 71% 24h [00940] [00941]   [1205748-51-1] [00942] 73% 25h [00943] [00944]   [1616231-59-4] [00945] 70% 26h [00946] [00947]   [1387596-01-1] [00948] 67% 27h [00949] [00950]   [1403252-58-3] [00951] 81% 28h [00952] [00953]   [1342819-12-8] [00954] 76% 29h [00955] [00956]   [1616231-59-4] [00957] 74% 30h [00958] [00959]   [864377-31-1] [00960] 75% 31h [00961]   [2165343-79-1] [00962]   [1612243-82-9] [00963] 72% 32h [00964] [00965]   [1518823-39-6] [00966] 70% 33h [00967] [00968]   [1252825-65-6] [00969] 69% 34h [00970] [00971]   [1252825-65-6] [00972] 81% 35h [00973] [00974]   [1612243-82-9] [00975] 76% 36h [00976] [00977]   [1612243-82-9] [00978] 66% 37h [00979]   [1072830-32-0] [00980]   [1612243-82-9] [00981] 64% 36h [00982]   [1072830-32-0] [00983]   [1252825-65-6] [00984] 67% 37h [00985] [00986]   [1252825-65-6] [00987] 65% 38h [00988] [00989]   [1883265-32-4] [00990] 83%

B) Device Examples

1) General Production Process for the OLEDs and Characterization of the OLEDs

[0305] Glass plaques which have been coated with structured ITO (indium tin oxide) in a thickness of 50 nm form the substrates to which the OLEDs are applied.

[0306] The OLEDs basically have the following layer structure: substrate/optional interlayer (IL)/hole injection layer (HIL)/hole transport layer (HTL)/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 the tables which follow. The structure of the OLEDs produced and the materials used for production of the OLEDs are shown in tables 2 and 3 below.

[0307] All materials are applied by thermal vapour deposition in a vacuum chamber. In this case, the emission layer consists of at least one matrix material (host material) and an emitting dopant which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as EG1:TER5

[0308] (97%:3%) mean here that the material EG1 is present in the layer in a proportion by volume of 97% and TER5 in a proportion of 3%. Analogously, the electron transport layer may also consist of a mixture of two materials.

[0309] The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (CE, measured in cd/A) and the external quantum efficiency (EQE, measured in %) are determined as a function of luminance, calculated from current-voltage-luminance characteristics assuming Lambertian emission characteristics, as is the lifetime. 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 4 refers to the voltage which is required fora luminance of 1000 cd/m.sup.2. CE1000 and EQE1000 respectively denote the current efficiency and external quantum efficiency that are attained at 1000 cd/m.sup.2.

[0310] The lifetime LT is defined as the time after which the luminance drops from the starting luminance to a certain proportion L1 in the course of operation with constant current density j.sub.0. A figure of L1=95% in table 4 means that the lifetime reported in the LT column corresponds to the time after which the luminance falls to 95% of its starting value.

2) Use and Benefit of the Inventive Compounds of the Formula (I) in OLEDs

[0311] A mixture of two host materials is typically used in the emission layer of OLEDs in order to achieve optimal charge balance and hence very good performance data of the OLED. With regard to simplified production of OLEDs, a reduction in the materials to be used is desirable. The use of just one host material in the emission layer is thus advantageous.

2a) Use of Compounds of the Invention in the Emission Layer of Phosphorescent Red OLEDs

[0312] By the use of the inventive compounds EG1 to EG2 in examples E1 and E2, and E5 and E6, as matrix material in the emission layer of phosphorescent red OLEDs, it is possible to show that use as a single material (E1 and E5) and particularly in a mixture with a second host material IC2 (E2 and E6) gives improved performance data of the OLEDs compared to the prior art, particularly with regard to lifetime and efficiency.

2b) Use of Compounds of the Invention in the Emission Layer of Phosphorescent Green OLEDs

[0313] By the use of the inventive compounds EG3 to EG6 having higher triplet energy in examples E9 to E12 as matrix material in the emission layer of phosphorescent green OLEDs, it is possible to show that use in a mixture with a second host material IC2 gives a good lifetime.

[0314] Table 4 collates the results for the performance data of the OLEDs from examples E1 to E12.

2c) Use of Compounds of the Invention as Electron Transport Material in the Electron Transport Layer of OLEDs

[0315] When the inventive compounds EG3 to EG6 are used as electron transport material, significantly lower voltage and better efficiency and lifetime (examples E15 to E18) are achieved than with the substance SdT1 and SdT2 according to the prior art (examples E13 to E14).

[0316] Table 5 collates the results for the performance data of the OLEDs from examples E13 to E18.

TABLE-US-00019 TABLE 2 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. IL thickness thickness thickness thickness thickness thickness thickness E1 HATCN SpMA1 SpMA3 EG1:TER5 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm E2 HATCN SpMA1 SpMA3 IV1:IC2:TER5 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm E3 HATCN SpMA1 SpMA3 SdT1:TER5 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm E4 HATCN SpMA1 SpMA3 SdT1:IC2:TER5 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm E5 HATCN SpMA1 SpMA3 EG2:TER5 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm E6 HATCN SpMA1 SpMA3 EG2:IC2:TER5 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm E7 HATCN SpMA1 SpMA3 SdT2:TER5 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (97%:3%) 35 nm 10 nm (50%:50%) 30 nm E8 HATCN SpMA1 SpMA3 SdT2:IC2:TER5 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm E9 HATCN SpMA1 SpMA3 EG3:IC2:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm E10 HATCN SpMA1 SpMA3 EG4:IC2:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm E11 HATCN SpMA1 SpMA3 EG5:IC2:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm E12 HATCN SpMA1 SpMA3 EG6:IC2:TEG1 ST2 ST2:LiQ LiQ 1 nm 5 nm 125 nm 10 nm (44%:44%:12%) 10 nm (50%:50%) 30 nm 30 nm E13 SpA1 HATCN SpMA1 M2:SEB — SdT1:LiQ — 140 nm  5 nm 20 nm (95%:5%) 20 nm (50%:50%) 30 nm E14 SpA1 HATCN SpMA1 IC1:TEG1 IC1 SdT2:LiQ —  70 nm  5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm E15 SpA1 HATCN SpMA1 M2:SEB — EG4:LiQ — 140 nm  5 nm 20 nm (95%:5%) 20 nm (50%:50%) 30 nm E16 SpA1 HATCN SpMA1 IC1:TEG1 IC1 EG4:LiQ —  70 nm  5 nm 90 nm (90%:10%) 30 nm 10 nm (50%:50%) 30 nm E17 SpA1 HATCN SpMA1 M2:SEB — EG5:LiQ — 140 nm  5 nm 20 nm (95%:5%) 20 nm (50%:50%) 30 nm E18 SpA1 HATCN SpMA1 IC1:TEG1 — EG6:LiQ —  70 nm  5 nm 90 nm (90%:10%) 30 nm (50%:50%) 40 nm

TABLE-US-00020 TABLE 3 Structural formulae of the materials for the OLEDs [00991] HATCN [00992] SpMA1 [00993] SpMA3 [00994] TER5 [00995] IC2 [00996] TEG1 [00997] LiQ [00998] ST2 [00999] SpA1 [01000] IC1 [01001] SEB [01002] M2 [01003] EG1 (36 h) [01004] SdT1 [01005] EG2 (37 h) [01006] SdT2 [01007] EG3 (11 h) [01008] EG4 (1 h) [01009] EG5 (5 d) [01010] EG6 (6 h)

TABLE-US-00021 TABLE 4 Data of the OLEDs U1000 SE1000 EQE 1000 CIE x/y at j.sub.0 L1 LT Ex. (V) (cd/A) (%) 1000 cd/m.sup.2 (mA/cm.sup.2) (%) (h) E1 4.3 23 15 0.67/0.33 20 95 500 E2 3.3 23 20 0.66/0.34 20 95 1110 E3 3.9 23 14 0.66/0.33 20 95 410 E4 3.4 24 15 0.67/0.34 20 95 840 E5 3.9 23 20 0.66/0.33 20 95 830 E6 3.4 23 21 0.66/0.34 20 95 1000 E7 3.8 23 15 0.67/0.33 20 95 540 E8 3.8 24 18 0.67/0.33 20 95 760 E9 3.5 70 17.5 0.32/0.64 20 80 700 E10 3.2 67 19.1 0.33/0.63 20 80 820 E11 3.1 69 18.8 0.32/0.64 20 80 790 E12 3.2 74 18.5 0.32/0.63 20 80 766

TABLE-US-00022 TABLE 5 Data of the OLEDs CIE x/y U1000 CE1000 LE1000 EQE at 1000 L.sub.1 LT Ex. (V) (cd/A) (lm/W) 1000 cd/m.sup.2 L.sub.0; j.sub.0 % (h) E13 6 8 5  7.0% 0.13/ 6000 80 30 0.14 cd/m.sup.2 E14 5.0 62 53   13% 0.31/ 20 mA/ 80 50 0.64 cm.sup.2 E15 4.1 8 5  7.0% 0.13/ 6000 80 45 0.14 cd/m.sup.2 E16 3.6 62 53 17.4% 0.31/ 20 mA/ 80 142 0.64 cm.sup.2 E17 3.5 8 6  7.3% 0.14/ 6000 80 47 0.13 cd/m.sup.2 E18 3.2 62 51 16.1% 0.34/ 20 mA/ 80 124 0.62 cm.sup.2