Materials for organic electroluminescent devices

Abstract

Fluorene derivatives that are connected in one or more of the 1-, 1′-, 4-, or 4′-positions in any combination to a carbon atom of a diaryl substituted triazinyl or pyrimidinyl derivative. The fluorene derivatives are not spirobifluorene derivatives. The compounds are suitable for use in electronic devices, in particular organic electroluminescent devices, comprising these compounds. In some embodiments, the compounds are used as matrix materials for phosphorescent or fluorescent emitters as well as a hole-blocking or an electron-transport layer.

Claims

1. A compound of formula (IV) or (V): ##STR00310## wherein: Z.sub.1 and Z.sub.2 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar.sub.1).sub.2, C(═O)Ar.sub.1, P(═O)(Ar.sub.1).sub.2, S(═O)Ar.sub.1, S(═O).sub.2Ar.sub.1, CR.sub.2═CR.sub.2Ar.sub.1, CN, NO.sub.2, Si(R.sub.1).sub.3, B(OR.sub.1).sub.2, B(R.sub.1).sub.2, B(N(R.sub.1).sub.2).sub.2, OSO.sub.2R.sub.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sub.1, wherein one or more CH.sub.2 groups are optionally replaced by (R.sub.1)C═C(R.sub.1), C≡C, Si(R.sub.1).sub.2, Ge(R.sub.1).sub.2, Sn(R.sub.1).sub.2, C═O, C═S, C═Se, C═N(R.sub.1), P(═O)(R.sub.1), SO, SO.sub.2, N(R.sub.1).sub.2, O, S, or CON(R.sub.1).sub.2, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sub.1, and wherein Z.sub.1 and Z.sub.2 do not form a bis-spirobifluorene; Y.sub.1 and Y.sub.2 are on each occurrence, identically or differently, D, F, Cl, Br, I, CHO, N(Ar.sub.1).sub.2, C(═O)Ar.sub.1, P(═O)(Ar.sub.1).sub.2, S(═O)Ar.sub.1, S(═O).sub.2Ar.sub.1, (R.sub.1)C═C(R.sub.1)Ar.sub.1, CN, NO.sub.2, Si(R.sub.1).sub.3, B(OR.sub.1).sub.2, B(R.sub.1).sub.2, B(N(R.sub.1).sub.2).sub.2, OSO.sub.2R.sub.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sub.1, wherein one or more CH.sub.2 groups are optionally replaced by (R.sub.1)C═C(R.sub.1), C≡C, Si(R.sub.1).sub.2, Ge(R.sub.1).sub.2, Sn(R.sub.1).sub.2, C═O, C═S, C═Se, C═N(R.sub.1).sub.2, P(═O(R.sub.1).sub.2, SO, SO.sub.2, N(R.sub.1).sub.2, O, S, or CON(R.sub.1).sub.2 and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sub.1, or a combination of these systems; and wherein two or more adjacent substituents Y.sub.1 or Y.sub.2 optionally define an annulated mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another; Ar.sub.1 and Ar.sub.2 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 23 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, with the proviso that a heteroaromatic ring system is connected via a carbon-carbon bond; R.sub.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, Si(R.sub.2).sub.3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkyl with 3-40 C-atoms which is optionally substituted by one or more radicals R.sub.2, wherein each one or more non-adjacent CH.sub.2 groups are optionally replaced by C(R.sub.2)═C(R.sub.2), Si(R.sub.2).sub.2, C═NR.sub.2, P(═O)(R.sub.2), SO, SO.sub.2, NR.sub.2, O, S, or CONR.sub.2 and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, or I, an aromatic or heteroaromatic ring system having 6 to 40 carbon atoms which are optionally substituted by one or more radicals R.sub.2, an aryloxy group having 5 to 60 aromatic ring atoms which are optionally substituted by one or more radicals R.sub.2, or an aralkyl group having 5 to 60 aromatic ring atoms which are optionally substituted by one or more radicals R.sub.2, wherein two or more adjacent substituents R.sub.1 optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one another, which is optionally substituted with one or more radicals R.sub.2; wherein R.sub.2 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, wherein two or more adjacent substituents R.sub.2 optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one another; X is on each occurrence, identically or differently, CR.sub.1 or N, with the proviso that at least one X is N; L is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R.sub.1; c and d are each, identically or differently, 0 or 1 with the proviso one of c or d is 1; e and f are each, identically or differently, 0, 1, 2, or 3; and n is on each occurrence, identically or differently, 0 or 1.

2. The compound of claim 1, where Z.sub.1 and Z.sub.2 are identical and are not connected to each other at any point other than at the 9-position of the fluorene nucleus.

3. The compound of claim 1, wherein e or f are both 0 according to formula (III): ##STR00311##

4. The compound of claim 1, wherein e and f are both 0.

5. The compound according to claim 1, wherein the compound is a compound of formula (VI) or (VII) ##STR00312##

6. A compound of formula (I): ##STR00313## wherein: Z.sub.1 and Z.sub.2 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar.sub.1).sub.2, C(═O)Ar.sub.1, P(═O)(Ar.sub.1).sub.2, S(═O)Ar.sub.1, S(═O).sub.2Ar.sub.1, CR.sub.2═CR.sub.2Ar.sub.1, CN, NO.sub.2, Si(R.sub.1).sub.3, B(OR.sub.1).sub.2, B(R.sub.1).sub.2, B(N(R.sub.1).sub.2).sub.2, OSO.sub.2R.sub.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sub.1, wherein one or more CH.sub.2 groups are optionally replaced by (R.sub.1)C═C(R.sub.1), C≡C, Si(R.sub.1).sub.2, Ge(R.sub.1).sub.2, Sn(R.sub.1).sub.2, C═O, C═S, C═Se, C═N(R.sub.1), P(═O)(R.sub.1), SO, SO.sub.2, N(R.sub.1).sub.2, O, S, or CON(R.sub.1).sub.2, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sub.1, and wherein Z.sub.1 and Z.sub.2 do not form a bis-spirobifluorene; Y.sub.1 and Y.sub.2 are on each occurrence, identically or differently, D, F, Cl, Br, I, CHO, N(Ar.sub.1).sub.2, C(═O)Ar.sub.1, P(═O)(Ar.sub.1).sub.2, S(═O)Ar.sub.1, S(═O).sub.2Ar.sub.1, (R.sub.1)C═C(R.sub.1)Ar.sub.1, CN, NO.sub.2, Si(R.sub.1).sub.3, B(OR.sub.1).sub.2, B(R.sub.1).sub.2, B(N(R.sub.1).sub.2).sub.2, OSO.sub.2R.sub.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sub.1, wherein one or more CH.sub.2 groups are optionally replaced by (R.sub.1)C═C(R.sub.1), C≡C, Si(R.sub.1).sub.2, Ge(R.sub.1).sub.2, Sn(R.sub.1).sub.2, C═O, C═S, C═Se, C═N(R.sub.1).sub.2, P(═O(R.sub.1).sub.2, SO, SO.sub.2, N(R.sub.1).sub.2, O, S, or CON(R.sub.1).sub.2 and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sub.1, or a combination of these systems; and wherein two or more adjacent substituents Y.sub.1 or Y.sub.2 optionally define an annulated mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another; Ar.sub.1 and Ar.sub.2 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 23 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, with the proviso that a heteroaromatic ring system is connected via a carbon-carbon bond; R.sub.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, Si(R.sub.2).sub.3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkyl with 3-40 C-atoms which is optionally substituted by one or more radicals R.sub.2, wherein each one or more non-adjacent CH.sub.2 groups are optionally replaced by C(R.sub.2)═C(R.sub.2), Si(R.sub.2).sub.2, C═NR.sub.2, P(═O)(R.sub.2), SO, SO.sub.2, NR.sub.2, O, S, or CONR.sub.2 and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, or I, an aromatic or heteroaromatic ring system having 6 to 40 carbon atoms which are optionally substituted by one or more radicals R.sub.2, an aryloxy group having 5 to 60 aromatic ring atoms which are optionally substituted by one or more radicals R.sub.2, or an aralkyl group having 5 to 60 aromatic ring atoms which are optionally substituted by one or more radicals R.sub.2, wherein two or more adjacent substituents R.sub.1 optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one another, which is optionally substituted with one or more radicals R.sub.2; wherein R.sub.2 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, wherein two or more adjacent substituents R.sub.2 optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one another; X is on each occurrence, identically or differently, CR.sub.1 or N, with the proviso that at least one X is N; L is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R.sub.1; a, b, c, and d are each, identically or differently, 0 or 1 with the proviso that at least one of a, b, c, or d is 1; e and f are each, identically or differently, 0, 1, 2, or 3; and n is on each occurrence, identically or differently, 0 or 1, wherein whenever a, b, c, or d is not 0, one X is nitrogen and the other is CR.sub.I.

7. The compound of claim 6, wherein b is 1 while a, c, and d are 0 according to formula (VIIIa) or wherein a is 1 while b, c, and d are 0 according to formula (VIIIb): ##STR00314## and wherein in each formula one X is N and the other is CR.sub.1.

8. The compound of claim 7, wherein the compound is a compound of formulae IX through XVII: ##STR00315## ##STR00316## wherein, in each formula one X is N and the other is CR.sub.1.

9. A compound of formula (I): ##STR00317## wherein: Z.sub.1 and Z.sub.2 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar.sub.1).sub.2, C(═O)Ar.sub.1, P(═O)(Ar.sub.1).sub.2, S(═O)Ar.sub.1, S(═O).sub.2Ar.sub.1, CR.sub.2═CR.sub.2Ar.sub.1, CN, NO.sub.2, Si(R.sub.1).sub.3, B(OR.sub.1).sub.2, B(R.sub.1).sub.2, B(N(R.sub.1).sub.2).sub.2, OSO.sub.2R.sub.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sub.1, wherein one or more CH.sub.2 groups are optionally replaced by (R.sub.1)C═C(R.sub.1), C≡C, Si(R.sub.1).sub.2, Ge(R.sub.1).sub.2, Sn(R.sub.1).sub.2, C═O, C═S, C═Se, C═N(R.sub.1), P(═O)(R.sub.1), SO, SO.sub.2, N(R.sub.1).sub.2, O, S, or CON(R.sub.1).sub.2, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sub.1, and wherein Z.sub.1 and Z.sub.2 do not form a bis-spirobifluorene; Y.sub.1 and Y.sub.2 are on each occurrence, identically or differently, D, F, Cl, Br, I, CHO, N(Ar.sub.1).sub.2, C(═O)Ar.sub.1, P(═O)(Ar.sub.1).sub.2, S(═O)Ar.sub.1, S(═O).sub.2Ar.sub.1, (R.sub.1)C═C(R.sub.1)Ar.sub.1, CN, NO.sub.2, Si(R.sub.1).sub.3, B(OR.sub.1).sub.2, B(R.sub.1).sub.2, B(N(R.sub.1).sub.2).sub.2, OSO.sub.2R.sub.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sub.1, wherein one or more CH.sub.2 groups are optionally replaced by (R.sub.1)C═C(R.sub.1), C≡C, Si(R.sub.1).sub.2, Ge(R.sub.1).sub.2, Sn(R.sub.1).sub.2, C═O, C═S, C═Se, C═N(R.sub.1).sub.2, P(═O(R.sub.1).sub.2, SO, SO.sub.2, N(R.sub.1).sub.2, O, S, or CON(R.sub.1).sub.2 and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sub.1, or a combination of these systems; and wherein two or more adjacent substituents Y.sub.1 or Y.sub.2 optionally define an annulated mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another; Ar.sub.1 and Ar.sub.2 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 23 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, with the proviso that a heteroaromatic ring system is connected via a carbon-carbon bond; R.sub.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, Si(R.sub.2).sub.3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkyl with 3-40 C-atoms which is optionally substituted by one or more radicals R.sub.2, wherein each one or more non-adjacent CH.sub.2 groups are optionally replaced by C(R.sub.2)═C(R.sub.2), Si(R.sub.2).sub.2, C═NR.sub.2, P(═O)(R.sub.2), SO, SO.sub.2, NR.sub.2, O, S, or CONR.sub.2 and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, or I, an aromatic or heteroaromatic ring system having 6 to 40 carbon atoms which are optionally substituted by one or more radicals R.sub.2, an aryloxy group having 5 to 60 aromatic ring atoms which are optionally substituted by one or more radicals R.sub.2, or an aralkyl group having 5 to 60 aromatic ring atoms which are optionally substituted by one or more radicals R.sub.2, wherein two or more adjacent substituents R.sub.1 optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one another, which is optionally substituted with one or more radicals R.sub.2; wherein R.sub.2 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, wherein two or more adjacent substituents R.sub.2 optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one another; X is on each occurrence, identically or differently, CR.sub.1 or N, with the proviso that at least one X is N; L is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R.sub.1; a, b, c, and d are each, identically or differently, 0 or 1 with the proviso that at least one of a, b, c, or d is 1; e and f are each, identically or differently, 0, 1, 2, or 3; and n is on each occurrence, identically or differently, 0 or 1, wherein Ar.sub.1 is selected from the group consisting of N-phenylcarbazole, dibenzofuran, and dibenzothiophene, and wherein Ar.sub.2 is selected from the group consisting of benzene, ortho-biphenyl, meta-biphenyl, para-biphenyl, ortho-terphenyl, meta-terphenyl, para-terphenyl, branched terphenyl, naphthyl, triphenylene, 9,9-dialkylfluorenyl, N-phenylcarbazole, dibenzofuran, and bidenzothiophene.

10. A process for preparing a compound of claim 5, comprising the steps of (1) synthesizing a skeleton of compound (VI) or (VII) which contains no triazinyl or pyrimidinyl group and (2) reacting the skeleton in a C—C coupling or a C—N coupling.

11. An oligomer, polymer, or dendrimer containing one or more compounds of formula (I): ##STR00318## wherein: Z.sub.1 and Z.sub.2 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar.sub.1).sub.2, C(═O)Ar.sub.1, P(═O)(Ar.sub.1).sub.2, S(═O)Ar.sub.1, S(═O).sub.2Ar.sub.1, CR.sub.2═CR.sub.2Ar.sub.1, CN, NO.sub.2, Si(R.sub.1).sub.3, B(OR.sub.1).sub.2, B(R.sub.1).sub.2, B(N(R.sub.1).sub.2).sub.2, OSO.sub.2R.sub.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sub.1, wherein one or more CH.sub.2 groups are optionally replaced by (R.sub.1)C═C(R.sub.1), C≡C, Si(R.sub.1).sub.2, Ge(R.sub.1).sub.2, Sn(R.sub.1).sub.2, C═O, C═S, C═Se, C═N(R.sub.1), P(═O)(R.sub.1), SO, SO.sub.2, N(R.sub.1).sub.2, O, S, or CON(R.sub.1).sub.2, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sub.1, and wherein Z.sub.1 and Z.sub.2 do not form a bis-spirobifluorene; Y.sub.1 and Y.sub.2 are on each occurrence, identically or differently, D, F, Cl, Br, I, CHO, N(Ar.sub.1).sub.2, C(═O)Ar.sub.1, P(═O)(Ar.sub.1).sub.2, S(═O)Ar.sub.1, S(═O).sub.2Ar.sub.1, (R.sub.1)C═C(R.sub.1)Ar.sub.1, CN, NO.sub.2, Si(R.sub.1).sub.3, B(OR.sub.1).sub.2, B(R.sub.1).sub.2, B(N(R.sub.1).sub.2).sub.2, OSO.sub.2R.sub.1, a straight-chain alkyl, alkoxy, or thioalkoxy group having 1 to 40 C atoms, a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms, or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy, or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R.sub.1, wherein one or more CH.sub.2 groups are optionally replaced by (R.sub.1)C═C(R.sub.1), C≡C, Si(R.sub.1).sub.2, Ge(R.sub.1).sub.2, Sn(R.sub.1).sub.2, C═O, C═S, C═Se, C═N(R.sub.1).sub.2, P(═O(R.sub.1).sub.2, SO, SO.sub.2, N(R.sub.1).sub.2, O, S, or CON(R.sub.1).sub.2 and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, or NO.sub.2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R.sub.1, or a combination of these systems; and wherein two or more adjacent substituents Y.sub.1 or Y.sub.2 optionally define an annulated mono- or polycyclic, aliphatic or aromatic or heteroaromatic ring system with one another; Ar.sub.1 and Ar.sub.2 are on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 23 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R.sub.1, with the proviso that a heteroaromatic ring system is connected via a carbon-carbon bond; R.sub.1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, Si(R.sub.2).sub.3, a straight-chain alkyl, alkoxy, or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy, or thioalkyl with 3-40 C-atoms which is optionally substituted by one or more radicals R.sub.2, wherein each one or more non-adjacent CH.sub.2 groups are optionally replaced by C(R.sub.2)═C(R.sub.2), Si(R.sub.2).sub.2, C═NR.sub.2, P(═O)(R.sub.2), SO, SO.sub.2, NR.sub.2, O, S, or CONR.sub.2 and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, or I, an aromatic or heteroaromatic ring system having 6 to 40 carbon atoms which are optionally substituted by one or more radicals R.sub.2, an aryloxy group having 5 to 60 aromatic ring atoms which are optionally substituted by one or more radicals R.sub.2, or an aralkyl group having 5 to 60 aromatic ring atoms which are optionally substituted by one or more radicals R.sub.2, wherein two or more adjacent substituents R.sub.1 optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one another, which is optionally substituted with one or more radicals R.sub.2; wherein R.sub.2 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, wherein two or more adjacent substituents R.sub.2 optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system with one another; X is on each occurrence, identically or differently, CR.sub.1 or N, with the proviso that at least one X is N; L is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R.sub.1; a, b, c, and d are each, identically or differently, 0 or 1 with the proviso that at least one of a, b, c, or d is 1; e and f are each, identically or differently, 0, 1, 2, or 3; and n is on each occurrence, identically or differently, 0 or 1, wherein one or more bonds from the compound to the polymer, oligomer, or dendrimer are present instead of substituents at one or more positions.

12. A formulation comprising at least one compound of claim 5 and at least one solvent.

13. A formulation comprising an oligomer, polymer, or dendrimer of claim 11 and at least one solvent.

14. An electronic device comprising at least one compound of claim 5.

15. The electronic device of claim 14, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes, and organic plasmon emitting devices.

16. An electronic device comprising the oligomer, polymer, or dendrimer of claim 11.

17. The electronic device of claim 16, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes, and organic plasmon emitting devices.

18. An organic electroluminescent device comprising a matrix material for a phosphorescent or fluorescent emitter, an electron-blocking or exciton-blocking layer, a charge generation layer, a hole-blocking layer, and/or an electron-transport layer comprising a matrix material comprising a compound of claim 1.

19. An organic electroluminescent device comprising a matrix material for a phosphorescent or fluorescent emitter, an electron-blocking or exciton-blocking layer, a charge generation layer, a hole-blocking layer, and/or an electron-transport layer comprising a matrix material comprising an oligomer, polymer, or dendrimer of claim 11.

20. A formulation comprising at least one compound of claim 1 and at least one solvent.

21. A formulation comprising at least one compound of claim 6 and at least one solvent.

22. A formulation comprising at least one compound of claim 9 and at least one solvent.

23. An electronic device comprising at least one compound of claim 1.

24. An electronic device comprising at least one compound of claim 6.

25. An electronic device comprising at least one compound of claim 9.

26. The electronic device according to claim 25, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes, and organic plasmon emitting devices.

27. A process for preparing a compound of claim 1, comprising the steps of (1) synthesizing a skeleton of compound (IV) or (V) which contains no triazinyl or pyrimidinyl group and (2) reacting the skeleton in a C—C coupling or a C—N coupling.

28. A process for preparing a compound of claim 6, comprising the steps of (1) synthesizing a skeleton of compound (I) which contains no triazinyl or pyrimidinyl group and (2) reacting the skeleton in a C—C coupling or a C—N coupling.

29. A process for preparing a compound of claim 9, comprising the steps of (1) synthesizing a skeleton of compound (I) which contains no triazinyl or pyrimidinyl group and (2) reacting the skeleton in a C—C coupling or a C—N coupling.

30. The electronic device according to claim 23, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes, and organic plasmon emitting devices.

31. The electronic device according to claim 24, wherein the electronic device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes, and organic plasmon emitting devices.

32. An organic electroluminescent device comprising a matrix material for a phosphorescent or fluorescent emitter, an electron-blocking or exciton-blocking layer, a charge generation layer, a hole-blocking layer, and/or an electron-transport layer comprising a matrix material comprising an oligomer, polymer, or dendrimer of claim 6.

33. An organic electroluminescent device comprising a matrix material for a phosphorescent or fluorescent emitter, an electron-blocking or exciton-blocking layer, a charge generation layer, a hole-blocking layer, and/or an electron-transport layer comprising a matrix material comprising an oligomer, polymer, or dendrimer of claim 9.

Description

EXAMPLES

Synthesis Examples

(1) The following syntheses are carried out, unless indicated otherwise, under a protective-gas atmosphere in dried solvents. The solvents and reagents can be purchased from ALDRICH or ABCR. The numbers indicated in the case of the starting materials which are commercially available are the corresponding CAS numbers.

(2) The materials of the invention can generally be prepared according to the following synthetic scheme 1 (Note: In Scheme 1, two or three X will be N and for when there are two nitrogens, the other X will be CR.sub.1 and R.sub.3 is preferably, but is not limited to, the fluorene skeleton; in some embodiments, the fluorene skeleton may be added in step 1 or 2a/b):

(3) ##STR00117##
Step 1:

(4) 295 g (1.6 mol, 1.0 eq) of 2,4,6-trichloro-1,3,5-triazine [108-77-0] 1 are solved in 800 ml dried THF in a four-necked flask under an inert atmosphere. The solution is cooled with an ice bath to about 0° C. and 800 ml (1.6 mol, 1.0 eq) of a 2 mol/l phenylmagnesiumchloride solution are added slowly to maintain the temperature below 10° C. Then, the mixture is stirred at room temperature overnight and after the reaction had finished, 800 ml of toluene and 1.2 L of HCl 2% are added. The organic phase is separated, extracted three times with water and dried over sodium sulfate. The solvent is evaporated under reduced pressure until the product precipitates. After washing the solid with ethanol, 242 g (1.1 mol, 67%) of the desired product 3a are obtained.

(5) Other examples are obtained analogously:

(6) TABLE-US-00001 Yield Cmpd. Reactant 1 Reactant 2 Product 3 [%] 3a 0 67 3b 74 3c 89 3d 62 3e 0 45 3f 86 3g 81 3h 0 65
Step 2a:

(7) 1.5 g (61 mmol, 1.12 eq) of magnesium turnings are heated in a four-necked flask for a few minutes. Then, a few ml of 19 g (60 mmol, 1.10 eq) of 1-Bromo-3,5-diphenylbenzene [103068-20-8] in 100 ml dried THF were added until the Grignard reaction starts. Then, the solution was added slowly to maintain the Grignard reaction at reflux. After the addition is complete, the mixture was cooled to about 0° C. with an ice bath. In a second apparatus, 12.3 g (54 mmol, 1.0 eq) 2,4-dichloro-6-phenyl-[1,3,5]-triazine 3a are solved in 60 ml dried THF and cooled with an ice bath. The Grignard reagent was transferred into a dropping funnel and slowly added to the solution of 3a. After stirring over night at room temperature, the mixture was diluted with 100 ml THF and 50 ml of a 1 M HCl are added. The formed precipitate is washed with water, ethanol and heptane. After purification by hot extraction from toluene 16 g (39 mmol, 72%) of the desired product 5a are obtained.

(8) Other examples are obtained analogously

(9) TABLE-US-00002 Yield Cmpd. Reactant 3 Reactant 4 Product 5 [%] 5a 71 5b 65 5c 0 62 5d 83
Step 2b:

(10) 35 g (150 mmol, 1.0 eq) 2,4-Dichloro-6-phenyl-[1,3,5]triazine, 35 g (150 mmol, 1.0 eq) dibenzothiophene-4-boronic acid [108847-20-7] and 18 g (170 mmol, 1.10 eq) sodium carbonate are dissolved in 300 ml 1,4-dioxane, 300 ml water and 120 ml toluene under an inert atmosphere. Then, 1.8 g (1.5 mmol, 0.01 eq) tetrakis(triphenylphosphine)palladium is added and the mixture refluxed over night at 110° C. After the reaction is completed, 100 ml water are added and the precipitated (48 g) solid is filtered. The organic layer is separated, washed with water and dried over sodium sulfate. After evaporation of the solvent, another 13 g of the crude product are obtained. The combined solids are recrystallized twice from toluene to give 32 g (86 mmol, 56%) of the desired product 7a.

(11) Other examples are obtained analogously

(12) TABLE-US-00003 Yield Cmpd. Reactant 3 Reactant 6 Product 7 [%] 7a 65 7b 76 7c 0 45 7d 62 7e 71 7f 0 39 7g 46 7h 68 7i 0 77 7j 62
Step 3b:

(13) 30 g (80 mmol, 1.0 eq) of 7a, 21 g (88 mmol, 1.1 eq) 9,9-Dimethyl-9H-fluoren-4-yl-boronic acid [1246022-50-3] and 17 g (160 mmol, 2.0 eq) sodium carbonate are dissolved in 400 ml toluene, 250 ml water and 170 ml ethanol under an inert atmosphere. Then, 0.93 g (0.80 mmol, 0.01 eq) tetrakis(triphenylphosphine)palladium is added and the mixture refluxed over night at 110° C. After the reaction is completed, 300 ml water were added and the precipitated (36 g) solid is filtered. The organic layer is separated, washed with water and dried over sodium sulfate. After evaporation of the solvent, another 5.1 g of the crude product are obtained. The combined solids are purified by hot extraction from toluene/heptane, recrystallized twice from toluene/heptane and sublimed to give 20 g (38 mmol, 47%) of the desired product 9a.

(14) Other examples are obtained analogously:

(15) TABLE-US-00004 Yield Cmpd. Reactant 5 or 7 Reactant 8 Product 9 [%] 9a 45 9b 33 9c 0 56 9d 31 9e 28 9f 00 01 55 9g 02 03 04 67 9h 05 06 07 53 9i 08 09 0 41 9j 76 9k 64 9l 37 9m 0 21 9n 49 9p 37 9q 0 52 9r 56 9s 48 9t 0 69 9x 58 9z 64 9u 68 9v 0 63 9w 59 9y 58 9aa 0 63 9ab 66 9ac 57 9ad 0 60

(16) The present invention furthermore relates to a process for the preparation of a compound of the formula (I), comprising the reaction steps of: synthesis of the skeleton of compound (I) which as yet contains no triazinyl or pyrimidinyl group; and reaction of the skeleton (preferably in the first step) in a C—C coupling, such as Suzuki, Negishi, Yamamoto, GrignardCross or Stille coupling, etc., or C—N coupling, such as Buchwald or Ullmann coupling.

Fabrication of OLEDs

(17) The following examples V1-V7 and E1-E22 (see Table 1 and 2) show data from various OLEDs.

Substrate Pre-Treatment of Examples V1-V7 and E1-E22

(18) Glass plates with structured ITO (50 nm, indium tin oxide) are coated with 20 nm PEDOT:PSS (Poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate), CLEVIOS™ PVP AI 4083 from Heraeus Precious Metals GmbH Germany, spin-coated from a water-based solution) and form the substrates on which the OLEDs are processed.

(19) The OLEDs have in principle the following layer structure: substrate/hole-transport layer (HTL)/optional interlayer (IL)/electron-blocking layer (EBL)/emission layer (EML)/optional hole-blocking layer (HBL)/electron-transport layer (ETL)/optional electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminium layer with a thickness of 100 nm. The exact layer structure is denoted in Table 1. The materials used for the OLED fabrication are presented in Table 3.

(20) All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer here always consists of at least one matrix material (host material) and an emitting dopant (emitter), which is admixed with the matrix material or matrix materials in a certain proportion by volume by co-evaporation. An expression such as IC1:M1:TEG1 (55%:35%:10%) here means that material IC1 is present in the layer in a proportion by volume of 55%, M1 is present in the layer in a proportion of 35% and TEG1 is present in the layer in a proportion of 10%. Analogously, the electron-transport layer may also consist of a mixture of two materials.

(21) The OLEDs are characterised by standard methods. For this purpose, the electroluminescence spectra, the current efficiency (CE1000, measured in cd/A at 1000 cd/m.sup.2), the luminous efficacy (LE1000, measured in lm/W at 1000 cd/m.sup.2), the external quantum efficiency (EQE1000, measured in % at 1000 cd/m.sup.2) and the voltage (U1000, measured at 1000 cd/m.sup.2 in V) are determined from current/voltage/luminance characteristic lines (IUL characteristic lines) assuming a Lambertian emission profile. The electroluminescence (EL) spectra are recorded at a luminous density of 1000 cd/m.sup.2 and the CIE 1931 x,y coordinates are then calculated from the EL spectrum.

(22) For selected experiments, the lifetime is determined. The lifetime is defined as the time after which the luminous density has dropped to a certain proportion from a certain initial luminous density L.sub.1 when the OLED is driven at a constant current. The starting condition L.sub.0;j.sub.0=4000 cd/m.sup.2 and L.sub.1=70% in Table 2 indicates that the in column LT denoted lifetime corresponds to the time in hours (h) needed to fade the OLED from a starting luminous density of 4000 cd/m.sup.2 to 2800 cd/m.sup.2. Accordingly, the lifetime of the starting condition L.sub.0;j.sub.0=20 mA/cm.sup.2, L.sub.1=80% is the time needed to fade the OLED operated at the constant current of 20 mA/cm.sup.2 to 80% of the initial luminous density.

(23) The device data of various OLEDs is summarized in Table 2. The examples V1-V7 are comparison examples according to the state-of-the-art. The examples E1-E22 show data of inventive OLEDs.

(24) In the following section several examples are described in more detail to show the advantages of the inventive OLEDs.

(25) Use of Inventive Compounds as Electron Transport Layer and Host Material in Phosphorescent OLEDs

(26) The use of the inventive compounds as electron transport layer and as host material results in significantly improved OLED device data compared to state-of-the-art materials, especially with respect to device lifetime.

(27) The use of the inventive materials (1) and (187) in an ETL mixed with LiQ results in improved LT compared to devices with the materials CE1 and CE2 (comparison of example V1 and V2 with E1 and E3, respectively). Furthermore, in comparison to material CE3 (which is a 3-(9,9-dimethylfluorenyl)triazine material), an inventive compound (186) which is identical to CE3 except it is a 4-(9,9-dimethylfluorenyl)triazine results in a significant improvement in LT efficacy when tested as a host in triplet green OLEDs (see V3 vs E2). It should also be noted that CE6 (sample V6), which is a 4-(9,9-dimethylfluorene)triazine with a 9,9′-spirobifluorene substituent on the triazine hardly gives any improvement compared to CE1 (sample V1) which is like CE6 but where a phenyl replaces the 4-(9,9-dimethylfluorene) group on the triazine.

(28) TABLE-US-00005 TABLE 1 OLED Layer Structure and Thickness Ex. IL HTL EBL EML HBL ETL EIL V1  SpA1 HATCN SpMA1 M2:SEB — CE1:LiQ — 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm V2  SpA1 HATCN SpMA1 M2:SEB — CE2:LiQ — 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm V3  SpA1 HATCN SpMA1 IC1:TEG1 IC1 CE3:LiQ —  70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm V4  SpA1 HATCN SpMA1 M2:SEB — CE4:LiQ — 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm V5  SpA1 HATCN SpMA1 CE5:TEG1 ST2:LiQ —  70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 40 nm V6  SpA1 HATCN SpMA1 M2:SEB — CE6:LiQ — 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm V7  SpA1 HATCN SpMA1 (CE7):TEG1 ST2:LiQ —  70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 40 nm E1  SpA1 HATCN SpMA1 M2:SEB — (1):LiQ — 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm E2  SpA1 HATCN SpMA1 IC1:TEG1 IC1 (186):LiQ —  70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E3  SpA1 HATCN SpMA1 M2:SEB — (187):LiQ — 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm E4  SpA1 HATCN SpMA1 (188):TEG1 ST2 ST2:LiQ —  70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E5  SpA1 HATCN SpMA1 (38):TEG1 ST2 ST2:LiQ —  70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E6  SpA1 HATCN SpMA1 (45):TEG1 ST2 ST2:LiQ —  70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E7  SpA1 HATCN SpMA1 (88):TEG1 ST2 ST2:LiQ —  70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E8  SpA1 HATCN SpMA1 IC1:TEG1 — (41):LiQ —  70 nm 5 nm 90 nm (90%:10%) (50%:50%) 30 nm 40 nm E9  SpA1 HATCN SpMA1 IC1:TEG1 IC1 (189):LiQ —  70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E10 SpA1 HATCN SpMA1 M2:SEB — (1):LiQ — 140 nm 5 nm 20 nm (95%:5%) (50%:50%) 20 nm 30 nm E11 SpA1 HATCN SpMA1 (88):TEG1 ST2 ST2:LiQ —  70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E12 SpA1 HATCN SpMA1 IC1:TEG1 (33) ST2:LiQ —  70 nm 5 nm 90 nm (90%:10%) 10 nm (50%:50%) 30 nm 30 nm E13 SpA1 HATCN SpMA1 M2:SEB — 9x:LiQ — 140 nm 5 nm 20 nm (95%:5%) (45%:55%) 20 nm 30 nm E14 SpA1 HATCN SpMA1 M2:SEB — 9z:LiQ — 140 nm 5 nm 20 nm (95%:5%) (45%:55%) 20 nm 30 nm E15 SpA1 HATCN SpMA1 M2:SEB 9u 9u:LiQ — 140 nm 5 nm 20 nm (95%:5%)  5 nm (45%:55%) 20 nm 25 nm E16 SpA1 HATCN SpMA1 M2:SEB — 9v:LiQ — 140 nm 5 nm 20 nm (95%:5%) (45%:55%) 20 nm 30 nm E17 SpA1 HATCN SpMA1 M2:SEB — 9w:LiQ — 140 nm 5 nm 20 nm (95%:5%) (45%:55%) 20 nm 30 nm E18 SpA1 HATCN SpMA1 IC1:IC3:TEG1 9y 9y:LiQ —  70 nm 5 nm 90 nm (65%:30%:5%) 10 nm (50%:50%) 30 nm 30 nm E19 SpA1 HATCN SpMA1 IC1:IC3:TEG1 — 9aa:LiQ —  70 nm 5 nm 90 nm (65%:30%:5%) (50%:50%) 30 nm 40 nm E20 SpA1 HATCN SpMA1 IC1:IC3:TEG1 9ab 9ab:LiQ —  70 nm 5 nm 90 nm (65%:30%:5%) 10 nm (50%:50%) 30 nm 30 nm E21 SpA1 HATCN SpMA1 IC1:IC3:TEG1 — 9ac:LiQ —  70 nm 5 nm 90 nm (65%:30%:5%) (50%:50%) 30 nm 40 nm E22 SpA1 HATCN SpMA1 IC1:IC3:TEG1 — 9ad:LiQ —  70 nm 5 nm 90 nm (65%:30%:5%) (50%:50%) 30 nm 40 nm

(29) TABLE-US-00006 TABLE 2 OLED Device Data U1000 CE1000 LE1000 EQE CIE x/y at Ex. (V) (cd/A) (lm/W) 1000 1000 cd/m.sup.2 L.sub.0; j.sub.0 L.sub.1 % LT (h) V1  4.5 8 6  7.1% 0.14/0.14 6000 cd/m.sup.2 80 35 V2  4.8 8 5  7.2% 0.13/0.14 6000 cd/m.sup.2 80 32 V3  3.4 62 57 17.3% 0.31/0.64 20 mA/m.sup.2 80 115 V4  4.9 7 4  6.8% 0.14/0.13 6000 cd/m.sup.2 80 47 V5  3.2 57 56 15.4% 0.34/0.63 20 mA/m.sup.2 80 195 V6  4.8 8 5  7.0% 0.14/0.13 6000 cd/m.sup.2 80 45 V7  3.4 54 50 15.0% 0.31/0.64 20 mA/m.sup.2 80 240 E1  5.0 8 5  6.9% 0.13/0.14 6000 cd/m.sup.2 80 42 E2  3.6 64 56 17.1% 0.31/0.64 20 mA/m.sup.2 80 140 E3  4.5 8 6  7.3% 0.14/0.13 6000 cd/m.sup.2 80 48 E4  4.3 56 41 15.8% 0.32/0.63 20 mA/m.sup.2 80 50 E5  4.0 53 42 14.0% 0.33/0.63 20 mA/m.sup.2 80 40 E6  4.1 57 44 15.2% 0.33/0.63 20 mA/m.sup.2 80 55 E7  3.8 63 52 16.9% 0.31/0.65 20 mA/m.sup.2 80 85 E8  3.4 64 59 17.2% 0.34/0.62 20 mA/m.sup.2 80 125 E9  3.6 64 56 17.4% 0.32/0.64 20 mA/m.sup.2 80 120 E10 4.8 8 5  7.4% 0.14/0.14 6000 cd/m.sup.2 80 40 E11 3.9 62 50 16.8% 0.33/0.63 20 mA/m.sup.2 80 90 E12 3.4 65 60 17.3% 0.35/0.62 20 mA/m.sup.2 80 110 E13 4.8 8.1 5.3  7.2% 0.14/0.13 6000 cd/m.sup.2 80 35 E14 5.0 8.0 5.0  7.1% 0.14/0.13 6000 cd/m.sup.2 80 43 E15 4.8 8.4 5.5  7.1% 0.14/0.15 6000 cd/m.sup.2 80 41 E16 5.1 7.6 4.7  6.7% 0.14/0.14 6000 cd/m.sup.2 80 48 E17 5.0 7.5 4.7  6.8% 0.14/0.13 6000 cd/m.sup.2 80 46 E18 3.4 63 58 16.9% 0.34/0.62 20 mA/m.sup.2 80 205 E19 3.5 60 54 16.7% 0.32/0.63 20 mA/m.sup.2 80 200 E20 3.5 59 53 16.6% 0.32/0.63 20 mA/m.sup.2 80 220 E21 3.3 60 57 16.4% 0.33/0.63 20 mA/m.sup.2 80 215 E22 3.6 62 54 17.1% 0.32/0.63 20 mA/m.sup.2 80 170

(30) TABLE-US-00007 TABLE 3 Chemical structures of the OLED materials used in examples 0 0 00 01 02 03 04 05 06 07 08 09