HETEROAROMATIC COMPOUNDS

Abstract

The present application concerns silafluorene derivatives according to a specific formula. The silafluorene derivatives can be employed in electronic devices. Furthermore, the present application concerns methods for preparation of the silafluorene derivatives, and electronic devices comprising the silafluorene derivatives.

Claims

1. Compound comprising at least one electron transporting group bonded via L.sup.1 to a structure according to formula (A) ##STR00790## wherein L.sup.1 is a single bond or a group selected from aromatic ring systems having 6 to 50 aromatic ring atoms and from heteroaromatic ring systems having 5 to 50 aromatic ring atoms, each of which may be substituted by one or more radicals R.sup.2; X is, identically or differently on each occurrence, selected from CR.sup.1 and N or a C atom if the group L.sup.1 is bound to that carbon atom; R.sup.a is selected, identically or differently at each occurrence, from H, D, F, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 radicals R.sup.a may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.2, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, CNR.sup.2, C(O)O, C(O)NR.sup.2, NR.sup.2, P(O)(R.sup.2), O, S, SO or SO.sub.2; R.sup.1 is selected, identically or differently at each occurrence, from H, D, F, 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 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 radicals R.sup.1 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.2, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, CNR.sup.2, C(O)O, C(O)NR.sup.2, NR.sup.2, P(O)(R.sup.2), O, S, SO or SO.sub.2; R.sup.2 is selected, identically or differently at each occurrence, from H, D, F, C(O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, 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 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 radicals R.sup.2 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.3, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CNR.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; R.sup.3 is selected, identically or differently at each occurrence, from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 C atoms, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R.sup.3 may be connected to each other to form a ring; and where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by F and CN; and the dotted line represents the bond of the group L.sup.1 to the electron transporting group.

2. Compound according to claim 1, wherein the electron transporting goup is selected from pyridines, pyrimidines, pyrazines, pyridazines, triazines, e.g. 1,2,4-triazines, 1,3,5-triazines, benzimidazoles, imidazoles, quinolinates, oxazoles, quinazolines, quinolines, isoquinolines, quinoxalines, lactames, pyrazoles, thiazoles, and benzothiazoles.

3. Compound according to claim 1, wherein the electron transporting goup is a group according to formula (B) ##STR00791## where the following applies to the variable groups: X.sup.1 is, identically or differently on each occurrence, selected from CR.sup.1 and N, with the proviso that at least one of the groups X.sup.1 is N; Ar.sup.1, Ar.sup.2 are selected, identically or differently on each occurrence, from aromatic ring systems having 6 to 40 aromatic ring atoms and from heteroaromatic ring systems having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R.sup.1; wherein dotted line represents the bond to the group according to the structure of formula (A) and R.sup.1 is as defined above in claim 1.

4. Compound of a formula (I) ##STR00792## where the following applies to the variable groups: Ar.sup.1, Ar.sup.2 are selected, identically or differently on each occurrence, from aromatic ring systems having 6 to 40 aromatic ring atoms and from heteroaromatic ring systems having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R.sup.1; Ar.sup.3 is a group according to formula (A) ##STR00793## wherein L.sup.1 is a single bond or a group selected from aromatic ring systems having 6 to 50 aromatic ring atoms and from heteroaromatic ring systems having 5 to 50 aromatic ring atoms, each of which may be substituted by one or more radicals R.sup.2; X is, identically or differently on each occurrence, selected from CR.sup.1 and N or a C atom if the group L.sup.1 is bound to that carbon atom; R.sup.a is selected, identically or differently at each occurrence, from H, D, F, straight-chain alkyl or alkoxy groups having 1 to 20 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 radicals R.sup.a may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.2, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, CNR.sup.2, C(O)O, C(O)NR.sup.2, NR.sup.2, P(O)(R.sup.2), O, S, SO or SO.sub.2; R.sup.1 is selected, identically or differently at each occurrence, from H, D, F, 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 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 radicals R.sup.1 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.2, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, CNR.sup.2, C(O)O, C(O)NR.sup.2, NR.sup.2, P(O)(R.sup.2), O, S, SO or SO.sub.2; R.sup.2 is selected, identically or differently at each occurrence, from H, D, F, C(O)R.sup.3, CN, Si(R.sup.3).sub.3, N(R.sup.3).sub.2, 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 C atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 C atoms, alkenyl or alkynyl groups having 2 to 20 C 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 radicals R.sup.2 may be connected to each other to form a ring; where the said alkyl, alkoxy, alkenyl and alkynyl groups and the said aromatic and heteroaromatic ring systems may in each case be substituted by one or more radicals R.sup.3, and where one or more CH.sub.2 groups in the said alkyl, alkoxy, alkenyl and alkynyl groups may in each case be replaced by R.sup.3CCR.sup.3, CC, Si(R.sup.3).sub.2, CO, CNR.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; R.sup.3 is selected, identically or differently at each occurrence, from H, D, F, CN, alkyl groups having 1 to 20 C atoms, aromatic ring systems having 6 to 40 C atoms, or heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more radicals R.sup.3 may be connected to each other to form a ring; and where the said alkyl groups, aromatic ring systems and heteroaromatic ring systems may be substituted by F and CN; and the dotted line represents the bond of the group L.sup.1 to the triazine group according to formula (I).

5. Compound according to claim 4, wherein the compound of formula (I) includes exactly one group according to formula (A), as defined in claim 1.

6. Compound according to claim 4, wherein the compound of formula (I) includes exactly one triazine group.

7. Compound according to claim 3, wherein the group Ar.sup.1 formula (B) is different to the group Ar.sup.2 in formula (B).

8. Compound according to claim 3, wherein the group Ar.sup.3 in formula (B) is different to the group Ar.sup.1 in formula (B) and to the group Ar.sup.2 in formula (B).

9. Compound according to claim 3, wherein the group Ar.sup.2 in formula (B) comprises more aromatic ring atoms than the group Ar.sup.1 in formula (B).

10. Compound according to claim 3, wherein the group Ar.sup.1 in formula (B) comprises at least two aromatic rings which may be condensed or non-condensed.

11. Compound according to claim 3, wherein the group Ar.sup.2 in formula (B) comprises at least two aromatic rings which may be condensed or non-condensed.

12. Compound according to claim 4, wherein the compound of formula (I) conforms to one of formulae (I-1), (I-2), (I-3) and (I-4) ##STR00794## where the variables occurring are defined as in claim 1.

13. Compound according to claim 4, wherein the compound of formula (I) conforms to one of formulae (I-5), (I-6), (I-7) and (I-8) ##STR00795## where the variables occurring are defined as in claim 1.

14. Compound according to claim 4, wherein the compound of formula (I) conforms to one of formulae (I-5a), (I-6a), (I-7a) and (I-8a) ##STR00796## where the variables occurring are defined as in claim 1.

15. Compound according to claim 4, wherein the compound of formula (I) conforms to one of formulae (I-9), (I-10), (I-11) and (I-12) ##STR00797## where the variables occurring are defined as in claim 1.

16. Process for preparation of a compound according to claim 1, wherein a mono- or dihalogenated silyl derivative is reacted with a halogenated biphenyl group to a silafluorene derivative.

17. Oligomer, polymer or dendrimer, comprising one or more compounds according to claim 1, where the bond(s) to the polymer, oligomer or dendrimer may be localised at any desired positions in formula (A) substituted by R.sup.a, R.sup.1, R.sup.2 or R.sup.3.

18. Formulation, comprising at least one compound according to claim 1 or at least one polymer, oligomer or dendrimer comprising a compound of claim 1 as a substituent, and at least one solvent.

19. Electronic device, comprising at least one compound according to claim 1, or at least one polymer, oligomer or dendrimer comprising a compound of claim 1 as a substituent.

20. Use of a compound according to claim 1, or of a polymer, oligomer or dendrimer comprising a compound of claim 1 as a substituent, in an electronic device.

Description

WORKING EXAMPLES

Scheme 1:

Step 1)

[0190] Main synthetic procedure for the preparation:

##STR00213##

Example 1

Synthesis of 2-Biphenyl-4-yl-4-(9,9-diphenyl-9H-dibenzosilol-4-yl)-6-phenyl-[1,3,5] triazine (1-1) and derivatives (1-2) bis (1-21)

[0191] ##STR00214##

Synthesis of 4-bromo-9,9-diphenyl-9H-9-silafluorene (I-1)

[0192] 10 g (25.58 mmol) of 2,6,2-tribrombiphenyl is suspended in 120 mL of diethyl ether under Ar atmosphere then cool at 3040 C. 22.51 mL of (56.28 mmol/2.5 M in hexane) n-BuLi is added dropwise at 3040 C. and the mixture is stirred for 1 hr at the same temperature. Then, 6.8 g (26.86 mmol) of dichlorodiphenylsilane in diethyl ether (30 mL) dropwise at 3040 C. and the mixture is stirred for 3 hrs at the same temperature then allow to warm up to room temperature. After reaction completion, 200 mL of H.sub.2O and 300 mL of dichloromethane are added in the flask. The organic phase is separated off and dried over magnesium sulfate, filtrated and subsequently evaporated to dryness. The residue is washed with 300 mL of heptane. The yield is 4.2 g (10.16 mmol), corresponding to 40% of theory.

[0193] The following compounds are synthesized analogously:

TABLE-US-00005 Ex Dichlorosilane Tribromo biphenyl Product Yield I-1 [00215] [00216] [00217] 40% I-2 [00218] [00219] [00220] 34% I-3 [00221] [00222] [00223] 37% I-4 [00224] [00225] [00226] 42% I-5 [00227] [00228] [00229] 31% I-6 [00230] [00231] [00232] 38% I-7 [00233] [00234] [00235] 44%

Synthesis of 2-(5,5-diphenylbenzo[b][1] benzosilol-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(II-1)

[0194] 4.0 g (9.68 mmol) of compound (I-1) and 3.0 g (11.61 mmol) of bis(pinacolato)-diboron are suspended in 26 mL of DMF (dimethylformamide) under Ar atmosphere. 2.84 g (29.03 mmol) of potassium acetate is added to the flask and stirred under Ar atmosphere. 0.23 g (0.29 mmol) of Pd(dppf)Cl.sub.2 CH.sub.2Cl.sub.2 is added to the flask and stirred under Ar atmosphere. The reaction mixture is heated at 80 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extract three times with 100 mL of EA (ethyl acetate) and organic phase is washed three times with water, dry over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is purified column chromatography with EA and Heptane. The yield is 4.0 g (8.51 mmol), corresponding to 88% of theory.

[0195] The following compounds are synthesized analogously:

TABLE-US-00006 Ex Bromide Bis(pinacolato)diborane Product Yield II-1 [00236] [00237] [00238] 88% II-2 [00239] [00240] [00241] 68% II-3 [00242] [00243] [00244] 77% II-4 [00245] [00246] [00247] 80% II-5 [00248] [00249] [00250] 65% II-6 [00251] [00252] [00253] 60% II-7 [00254] [00255] [00256] 80%

Synthesis of 2-Chloro-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine(III-1)

[0196] ##STR00257##

[0197] 30 g (150 mmol) of 4-biphenyl boronic acid and 47.9 g (210 mmol) of 2,4-dichloro-6-phenyl-[1,3,5]-triazine are suspended in 420 mL of 1,4-Dioxane, 210 mL of Toluene and 420 mL of H.sub.2O under Ar atmosphere. 17.6 g (166 mmol) of Sodium carbonate is added to the flask and stirred under Ar atmosphere. 1.7 g (0.15 mmol) of tetrakis(triphenyl phosphine) palladium is added to the flask. The reaction mixture is heated at 60 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extracted three times with 200 mL of ethyl acetate. The organic phase is separated off and dried over magnesium sulfate, filtrated and subsequently evaporated to dryness. The residue is washed with EtOH 250 mL. The yield is 41 g (119 mmol), corresponding to 78% of theory.

[0198] The following compounds are synthesized analogously:

TABLE-US-00007 Overall Ex Chloride Boronic acid Product Yield III-1 [00258] [00259] [00260] 78% III-2 [00261] [00262] [00263] 52% III-3 [00264] [00265] [00266] 75% III-4 [00267] [00268] [00269] 88% III-5 [00270] [00271] [00272] 70% III-6 [00273] [00274] [00275] 75% III-7 [00276] [00277] [00278] 46% III-8 [00279] [00280] [00281] 82% III-9 [00282] [00283] [00284] 85% III-10 [00285] [00286] [00287] 88% III-11 [00288] [00289] [00290] 81% III-12 [00291] [00292] [00293] 85% III-13 [00294] [00295] [00296] 87%

Synthesis of 2-(5,5-diphenylbenzo[b][1] benzosilol-1-yl)-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine (1-1)

[0199] 4.0 g (8.69 mmol) of compound (II-1) and 2.98 g (8.69 mmol) of compound (III-1) are suspended in 40 mL of 1,4-Dioxane, 30 mL of Toluene and 40 mL of H.sub.2O under Ar atmosphere. 2.02 g (19.11 mmol) of Sodium carbonate is added to the flask and stirred under Ar atmosphere. 0.3 g (0.26 mmol) of tetrakis(triphenyl-phosphine) palladium is added to the flask. The reaction mixture is heated at 110 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extracted three times with 100 mL of toluene, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is washed with ethyl acetate. The yield is 4.06 g (6.54 mmol), corresponding to 75% of theory.

[0200] The following compounds are synthesized analogously:

TABLE-US-00008 Ex Boronic ester Chloride Product Yield 1-1 [00297] [00298] [00299] 75% 1-2 [00300] [00301] [00302] 63% 1-3 [00303] [00304] [00305] 70% 1-4 [00306] [00307] [00308] 57% 1-5 [00309] [00310] [00311] 72% 1-6 [00312] [00313] [00314] 51% 1-7 [00315] [00316] [00317] 69% 1-8 [00318] [00319] [00320] 79% 1-9 [00321] [00322] [00323] 61% 1-10 [00324] [00325] [00326] 86% 1-11 [00327] [00328] [00329] 82% 1-12 [00330] [00331] [00332] 87% 1-13 [00333] [00334] [00335] 88% 1-14 [00336] [00337] [00338] 70% 1-15 [00339] [00340] [00341] 75% 1-16 [00342] [00343] [00344] 81% 1-17 [00345] [00346] [00347] 66% 1-18 [00348] [00349] [00350] 69% 1-19 [00351] [00352] [00353] 62% 1-20 [00354] [00355] [00356] 55% 1-21 [00357] [00358] [00359] 69%

Example 2

Synthesis of 2-(5,5-diphenylbenzo[b][1] benzosilol-4-yl)-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine (2-1) and derivatives (2-2) bis (2-8)

[0201] ##STR00360##

Synthesis of 1-Chloro-9,9-diphenyl-7H-9-silafluorene (IV-1)

[0202] 8.59 g (32.1 mmol) of 2-bromo-3-chlorobiphenyl in 150 mL of THF under Ar atmosphere then cool at 78 C. 24 mL (38 mmol/1.6 M in hexane) of nBuLi is added dropwise at 78 C. and the mixture is stirred for 30 min at the same temperature. Then, 7.5 ml (38 mmol) of chlorodiphenylsilane in diethyl ether (100 mL) dropwise at 78 C. and the mixture is stirred for 3 hrs at the same temperature then allow to warm up to room temperature. After reaction completion, the mixture is quenched with a saturated aqueous solution of NH.sub.4Cl in water. After extraction with diethyl ether (3100 mL), drying over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is washed with 300 mL of heptane. The yield is 10 g (27 mmol), corresponding to 83% of theory. Tetrabutylammonium iodide (90 mg, 25.1 mmol, 1 mol %) and a solution of tert-butyl hydroperoxide (15 mL/5.5 M in decane, 0.83 mmol, 3.3 eq.) are added to a solution of 8.89 g (25.1 mmol) of 2-(3chloro) biphenyldiphenylsilane in toluene (200 mL).

[0203] After stirring for 5 min at room temperature the mixture is heated to 90 C., stirred for 24 hrs at this temperature and cool to room temperature. After filtration through a short pad of silica eluting with dichloromethane, crude 1H-NMR analysis and concentration in vacuo the residue is purified by fractional column chromatography to afford the desired silafluorenes (IV-1). For analysis, compound is recrystallized from dichloromethane and acetonitrile. The yield is 3.8 g (10.3 mmol), corresponding to 41% of theory.

[0204] The following compounds are synthesized analogously:

TABLE-US-00009 Ex Chlorosilane 2-bromo-3-chlorobiphenyl Product Yield IV-1 [00361] [00362] [00363] 41% IV-2 [00364] [00365] [00366] 25% IV-3 [00367] [00368] [00369] 31% IV-4 [00370] [00371] [00372] 28%

Synthesis of 2-(9,9-Diphenyl-9H-dibenzosilol-1-yl)-4,4,5,5-tetramethyl-[1,3,2] dioxaborolane (V-1)

[0205] 3.8 g (10.30 mmol) of compound (IV-1) and 3.1 g (12.36 mmol) of bis(pinacolato)-diborane are suspended in 26 mL of DMF under Ar atmosphere. 3.1 g (30.90 mmol) of potassium acetate is added to the flask and stirred under Ar atmosphere. 0.25 g (0.31 mmol) of Pd(dpf)Cl.sub.2 CH.sub.2Cl.sub.2 is added to the flask and stirred under Ar atmosphere. The reaction mixture is heated at 80 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extracted three times with 100 mL of EA and organic phase is washed three times with water, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is purified column chromatography with EA and Heptane. The yield is 4.0 g (8.75 mmol), corresponding to 85% of theory.

[0206] The following compounds are synthesized analogously:

TABLE-US-00010 Ex Chloride Bis(pinacolato)diborane Product Yield V-1 [00373] [00374] [00375] 85% V-2 [00376] [00377] [00378] 62% V-3 [00379] [00380] [00381] 68% V-4 [00382] [00383] [00384] 77%

Synthesis of 2-(5,5-diphenylbenzo[b][1] benzosilol-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2-1)

[0207] 4.0 g (8.75 mmol) of compound (V-1) and 3.01 g (8.75 mmol) of compound (III-1) are suspended in 40 mL of 1,4-Dioxane, 30 mL of Toluene and 40 mL of H.sub.2O under Ar atmosphere. 2.04 g (19.25 mmol) of Sodium carbonate is added to the flask and stirred under Ar atmosphere. 0.3 g (0.26 mmol) of tetrakis (triphenyl phosphine) palladium is added to the flask. The reaction mixture is heated at 110 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extracted three times with 100 mL of toluene, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is washed with ethyl acetate. The yield is 4.2 g (6.56 mmol), corresponding to 75% of theory.

[0208] The following compounds are synthesized analogously:

TABLE-US-00011 Ex Boronic ester Chloride Product Yield 2-1 [00385] [00386] [00387] 75% 2-2 [00388] [00389] [00390] 72% 2-3 [00391] [00392] [00393] 62% 2-4 [00394] [00395] [00396] 68% 2-5 [00397] [00398] [00399] 75% 2-6 [00400] [00401] [00402] 77% 2-7 [00403] [00404] [00405] 69% 2-8 [00406] [00407] [00408] 71%

Example 3

Synthesis of 2-[4-(5,5-diphenylbenzo[b][1] benzosilol-1-yl) phenyl]-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine (3-1) and derivatives (3-2) bis (3-10)

[0209] ##STR00409##

Synthesis of 4-(4-chlorophenyl)-9,9-diphenyl-7H-9-silafluorene(VI-1)

[0210] 27.7 g (67 mmol) of compound (I-1), 11.1 g (71 mmol) of 4-chloro-phenyl boronic acid and 14.3 g (135 mmol) of sodium carbonate are suspended in 500 mL of EtOH, 500 mL of H.sub.2O and 200 mL of toluene and stirred under Ar atmosphere. 2.3 g (2 mmol) of tetrakis(triphenyl phosphine)palladium is added to the flask. The reaction mixture is heated at 110 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the reaction mixture is quenched. The organic phase is separated, washed three times with 200 mL of water, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is purified by column chromatography on silica gel using a mixture of DCM/heptane (1:10). The yield is 21.7 g (49 mmol), corresponding to 73% of theory.

[0211] The following compounds are synthesized analogously:

TABLE-US-00012 Ex Bromide Aryl boronic acid Product Yield VI-1 [00410] [00411] [00412] 73% VI-2 [00413] [00414] [00415] 65% VI-3 [00416] [00417] [00418] 67% VI-4 [00419] [00420] [00421] 69% VI-5 [00422] [00423] [00424] 75% VI-6 [00425] [00426] [00427] 77%

Synthesis of 2-[4-(9,9-Diphenyl-9H-dibenzosilol-4-yl)-phenyl]-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane(VII-1)

[0212] 5.0 g (11.23 mmol) of compound (VI-1) and 3.4 g (13.48 mmol) of bis(pinacolato)-diborane are suspended in 30 mL of DMF under Ar atmosphere. 2.62 g (24.7 mmol) of potassium acetate is added to the flask and stir under Ar atmosphere. 0.39 g (0.33 mmol) of Pd(dppf)Cl.sub.2 CH.sub.2Cl.sub.2 is added to the flask and stirred under Ar atmosphere. The reaction mixture is heated at 80 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extracted three times with 100 mL of EA and organic phase is washed three times with water, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is purified column chromatography with EA and Heptane. The yield is 4.9 g (9.2 mmol), corresponding to 82% of theory.

[0213] The following compounds are synthesized analogously:

TABLE-US-00013 Ex Chloride Bis(pinacolato)diborane Product Yield VII-1 [00428] [00429] [00430] 82% VII-2 [00431] [00432] [00433] 65% VII-3 [00434] [00435] [00436] 67% VII-4 [00437] [00438] [00439] 62% VII-5 [00440] [00441] [00442] 76% VII-6 [00443] [00444] [00445] 77%

Synthesis of 2-[4-(5,5-diphenylbenzo[b][1] benzosilol-1-yl) phenyl]-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine (3-1)

[0214] 4.0 g (8.38 mmol) of compound(VII-1) and 2.88 g (8.38 mmol) of compound (III-1) are suspended in 40 mL of 1,4-Dioxane, 30 mL of Toluene and 40 mL of H.sub.2O under Ar atmosphere. 1.95 g (18.43 mmol) of Sodium carbonate is added to the flask and stirred under Ar atmosphere. 0.3 g (0.25 mmol) of tetrakis(triphenylphosphine)palladium is added to the flask. The reaction mixture is heated at 110 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extracted three times with 100 mL of toluene, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is washed with ethyl acetate. The yield is 4.45 g (6.20 mmol), corresponding to 74% of theory

[0215] The following compounds are synthesized analogously:

TABLE-US-00014 Ex Boronic ester Chloride Product Yield 3-1 [00446] [00447] [00448] 74% 3-2 [00449] [00450] [00451] 78% 3-3 [00452] [00453] [00454] 80% 3-4 [00455] [00456] [00457] 79% 3-5 [00458] [00459] [00460] 77% 3-6 [00461] [00462] [00463] 81% 3-7 [00464] [00465] [00466] 83% 3-8 [00467] [00468] [00469] 78% 3-9 [00470] [00471] [00472] 75% 3-10 [00473] [00474] [00475] 80%

Example 4

Synthesis of 2-(5,5-diphenylbenzo[b][1] benzosilol-3-yl)-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine (4-1) and derivatives (4-2) bis (4-17)

[0216] ##STR00476##

[0217] Synthesis of 3,7-dibromo-5,5-diphenyl-benzo[b][1]benzosilole(VIII-1) 26 g (55.34 mmol) of 2,4,2,4-Tetrabromo-biphenyl in 1000 mL of Et.sub.2O under Ar atmosphere then cool at 78 C. 46.4 mL (116 mmol/2.5 M in hexane) of n-BuLi is added dropwise at 78 C. and the mixture is stirred for 1 hr at the same temperature. Then, 14 g (55.34 mmol) dichlorodiphenylsilane in diethyl ether (100 mL) dropwise at 78 C. and the mixture is stirred for 1 hr at the same temperature then allow to warm up to room temperature for 12 hrs. After reaction completion, the mixture is quenched with water. After extraction with EA (3400 mL), drying over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is purified by column chromatography. The yield is 15 g (30.47 mmol), corresponding to 54% of theory.

[0218] The following compounds are synthesized analogously:

TABLE-US-00015 Tetrabrom- Ex Dichlorosilane biphenyl Product Yield VIII- 1 [00477] [00478] [00479] 55% VIII- 2 [00480] [00481] [00482] 48% VIII- 3 [00483] [00484] [00485] 38% VIII- 4 [00486] [00487] [00488] 48% VIII- 5 [00489] [00490] [00491] 31% VIII- 6 [00492] [00493] [00494] 37% VIII- 7 [00495] [00496] [00497] 30%

Synthesis of 3-bromo-5,5-diphenyl-benzo[b][1]benzosilole (IX-1)

[0219] 15 g (30.49 mmol) of compound(VIII-1) in 300 mL of THF under Ar atmosphere then cool at 78 C. 12.2 mL (30.49 mmol/2.5 Min hexane) of n-BuLi is added dropwise at 78 C. and the mixture is stirred for 2 hrs at the same temperature. After reaction completion, the mixture is quenched with water. After extraction with EA (3400 mL), drying over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is purified by column chromatography. The yield is 7 g (16.93 mmol), corresponding to 55% of theory.

[0220] The following compounds are synthesized analogously:

TABLE-US-00016 Ex Dibromo-dibenzosilole Product Yield IX-1 [00498] [00499] 55% IX-2 [00500] [00501] 51% IX-3 [00502] [00503] 47% IX-4 [00504] [00505] 50% IX-5 [00506] [00507] 45% IX-6 [00508] [00509] 42% IX-7 [00510] [00511] 55%

Synthesis of 2-(5,5-diphenylbenzo[b][1] benzosilol-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(X-1)

[0221] 7 g (16.93 mmol) of compound (IX-1) and 5.12 g (20.31 mmol) of bis(pinacolato)-diboron are suspended in 100 mL of DMF under Ar atmosphere. 3.57 g (33.69 mmol) of potassium acetate is added to the flask and stirred under Ar atmosphere. 0.59 g (0.50 mmol) of Pd(dppf)Cl.sub.2 CH.sub.2Cl.sub.2 is added to the flask and stirred under Ar atmosphere. The reaction mixture is heated at 80 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extracted three times with 200 mL of EA and organic phase is washed three times with water, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is purified column chromatography with EA and Heptane.

[0222] The yield is 5.8 g (12.69 mmol), corresponding to 75% of theory.

[0223] The following compounds are synthesized analogously:

TABLE-US-00017 Bromo- Bis(pinacolato) Ex dibenzosilole diborane Product Yield X-1 [00512] [00513] [00514] 75% X-2 [00515] [00516] [00517] 69% X-3 [00518] [00519] [00520] 74% X-4 [00521] [00522] [00523] 68% X-5 [00524] [00525] [00526] 64% X-6 [00527] [00528] [00529] 61% X-7 [00530] [00531] [00532] 72%

Synthesis of 2-(5,5-diphenylbenzo[b][1]benzosilol-3-yl)-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine(4-1)

[0224] 5.8 g (12.69 mmol) of compound (X-1) and 4.36 g (12.69 mmol) of compound (III-1) are suspended in 50 mL of 1,4-Dioxane, 40 mL of Toluene and 50 mL of H.sub.2O under Ar atmosphere. 2.95 g (27.91 mmol) of Sodium carbonate is added to the flask and stirred under Ar atmosphere. 0.43 g (0.38 mmol) of tetrakis(triphenyl-phosphine) palladium is added to the flask. The reaction mixture is heated at 110 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extracted three times with 200 mL of toluene, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is washed with ethyl acetate. The yield is 6.51 g (10.15 mmol), corresponding to 80% of theory.

[0225] The following compounds are synthesized analogously

TABLE-US-00018 Ex Boronic ester Chloride Product Yield 4-1 [00533] [00534] [00535] 74% 4-2 [00536] [00537] [00538] 78% 4-3 [00539] [00540] [00541] 80% 4-4 [00542] [00543] [00544] 79% 4-5 [00545] [00546] [00547] 4-6 [00548] [00549] [00550] 80% 4-7 [00551] [00552] [00553] 81% 4-8 [00554] [00555] [00556] 77% 4-9 [00557] [00558] [00559] 81% 4- 10 [00560] [00561] [00562] 83% 4- 11 [00563] [00564] [00565] 77% 4- 12 [00566] [00567] [00568] 65% 4- 13 [00569] [00570] [00571] 70% 4- 14 [00572] [00573] [00574] 45% 4- 15 [00575] [00576] [00577] 48% 4- 16 [00578] [00579] [00580] 52% 4- 17 [00581] [00582] [00583] 55%

Example 5

Synthesis of 2-[4-(5,5-diphenylbenzo[b][1] benzosilol-3-yl) phenyl]-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine (5-1) and derivatives bis (5-2) and (5-28)

[0226] ##STR00584##

Synthesis of 3-(4-chlorophenyl)-5,5-diphenyl-benzo[b][1] benzosilole (XI-1)

[0227] 27.7 g (67 mmol) of compound (IX-1), 11.1 g (71 mmol) of 4-chloro-phenyl boronic acid and 14.3 g (134 mmol) of sodium carbonate are suspended in 500 mL of EtOH, 500 mL of H.sub.2O and 200 mL of toluene and stirred under Ar atmosphere. 2.3 g (1.3 mmol) of tetrakis(triphenyl phosphine) palladium is added to the flask. The reaction mixture is heated at 110 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the reaction mixture is quenched. The organic phase is separated, washed three times with 200 mL of water, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is purified by column chromatography on silica gel using a mixture of DCM/heptane (1:10). The yield is 24.7 g (55 mmol), corresponding to 83% of theory.

[0228] The following compounds are synthesized analogously:

TABLE-US-00019 Ex Bromide Aryl boronic acid Product Yield XI- 1 [00585] [00586] [00587] 83% XI- 2 [00588] [00589] [00590] 79% XI- 3 [00591] [00592] [00593] 81% XI- 4 [00594] [00595] [00596] 74% XI- 5 [00597] [00598] [00599] 80% XI- 6 [00600] [00601] [00602] 82% XI- 7 [00603] [00604] [00605] 79% XI- 8 [00606] [00607] [00608] 75% XI- 9 [00609] [00610] [00611] 86% XI- 10 [00612] [00613] [00614] 84% XI- 11 [00615] [00616] [00617] 88% XI- 12 [00618] [00619] [00620] 81% XI- 13 [00621] [00622] [00623] 86% XI- 14 [00624] [00625] [00626] 82%

Synthesis of 2-[4-(5,5-diphenylbenzo[b][1] benzosilol-3-yl) phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(XII-1)

[0229] 5.0 g (11.23 mmol) of compound (XI-1) and 3.4 g (13.48 mmol) of bis(pinacolato)-diborane are suspended in 30 mL of DMF under Ar atmosphere. 2.62 g (24.7 mmol) of potassium acetate is added to the flask and stirred under Ar atmosphere. 0.39 g (0.33 mmol) of Pd(dppf)Cl.sub.2 CH.sub.2Cl.sub.2 is added to the flask and stirred under Ar atmosphere. The reaction mixture is heated at 80 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extracted three times with 100 mL of EA and organic phase is washed three times with water, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is purified column chromatography with EA and Heptane. The yield is 4.9 g (9.2 mmol), corresponding to 82% of theory.

[0230] The following compounds are synthesized analogously:

TABLE-US-00020 Bis(pinacolato) Ex Chloride diborane Product Yield XII-1 [00627] [00628] [00629] 82% XII-2 [00630] [00631] [00632] 77% XII-3 [00633] [00634] [00635] 78% XII-4 [00636] [00637] [00638] 75% XII-5 [00639] [00640] [00641] 81% XII-6 [00642] [00643] [00644] 79% XII-7 [00645] [00646] [00647] 81% XII-8 [00648] [00649] [00650] 77% XII-9 [00651] [00652] [00653] 85% XII-10 [00654] [00655] [00656] 81% XII-11 [00657] [00658] [00659] 77% XII-12 [00660] [00661] [00662] 75% XII-13 [00663] [00664] [00665] 79% XII-14 [00666] [00667] [00668] 72%

Synthesis of 2-[4-(5,5-diphenylbenzo[b][1] benzosilol-3-yl) phenyl]-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine (5-1)

[0231] 5.8 g (12.69 mmol) of compound (XII-1) and 4.36 g (12.69 mmol) of compound (III-1) are suspended in 50 mL of 1,4-Dioxane, 40 mL of Toluene and 50 mL of H.sub.2O under Ar atmosphere. 2.95 g (27.91 mmol) of Sodium carbonate is added to the flask and stirred under Ar atmosphere. 0.43 g (0.38 mmol) of tetrakis(triphenyl-phosphine) palladium is added to the flask. The reaction mixture is heated at 110 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extracted three times with 200 mL of toluene, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is washed with ethyl acetate. The yield is 7.56 g (10.53 mmol), corresponding to 83% of theory.

[0232] The following compounds are synthesized analogously:

TABLE-US-00021 Ex Boronic ester Chloride Product Yield 5-1 [00669] [00670] [00671] 85% 5-2 [00672] [00673] [00674] 78% 5-3 [00675] [00676] [00677] 79% 5-4 [00678] [00679] [00680] 80% 5-5 [00681] [00682] [00683] 80% 5-6 [00684] [00685] [00686] 82% 5-7 [00687] [00688] [00689] 79% 5-8 [00690] [00691] [00692] 77% 5-9 [00693] [00694] [00695] 75% 5-10 [00696] [00697] [00698] 78% 5-11 [00699] [00700] [00701] 81% 5-12 [00702] [00703] [00704] 79% 5-13 [00705] [00706] [00707] 83% 5-14 [00708] [00709] [00710] 84% 5-15 [00711] [00712] [00713] 83% 5-16 [00714] [00715] [00716] 72% 5-17 [00717] [00718] [00719] 75% 5-18 [00720] [00721] [00722] 78% 5-19 [00723] [00724] [00725] 69% 5-20 [00726] [00727] [00728] 70% 5-21 [00729] [00730] [00731] 67% 5-22 [00732] [00733] [00734] 69% 5-23 [00735] [00736] [00737] 67% 5-24 [00738] [00739] [00740] 65% 5-25 [00741] [00742] [00743] 79% 5-56 [00744] [00745] [00746] 81% 5-27 [00747] [00748] [00749] 76% 5-28 [00750] [00751] [00752] 78%

Example 6

Synthesis of 2-(5,5-diphenylbenzo[b][1]benzosilol-2-yl)-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine(6-1) and derivatives (6-2) and (6-3)

[0233] ##STR00753##

Synthesis of 2-(5,5-diphenylbenzo[b][1]benzosilol-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(XIII-1)

[0234] 5.0 g (10.86 mmol) of 2-iodo-5,5-diphenyl-benzo[b][1]benzosilole (from WO1610-9386) and 3.3 g (13.03 mmol) of bis(pinacolato)diborane are suspended in 30 mL of DMF under Ar atmosphere. 2.4 g (23.9 mmol) of potassium acetate is added to the flask and stirred under Ar atmosphere. 0.39 g (0.33 mmol) of Pd(dppf)Cl.sub.2 CH.sub.2Cl.sub.2 is added to the flask and stirred under Ar atmosphere. The reaction mixture is heated at 80 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extract three times with 100 mL of EA and organic phase is washed three times with water, dried over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is purified column chromatography with EA and Heptane. The yield is 4.3 g (9.2 mmol), corresponding to 85% of theory.

Synthesis of 2-(5,5-diphenylbenzo[b][1]benzosilol-2-yl)-4-phenyl-6-(4-phenylphenyl)-1,3,5-triazine(6-1)

[0235] 5.8 g (12.69 mmol) of compound (XIII-1) and 4.36 g (12.69 mmol) of compound (III-1) are suspended in 50 mL of 1,4-Dioxane, 40 mL of Toluene and 50 mL of H2O under Ar atmosphere. 2.95 g (27.91 mmol) of sodium carbonate is added to the flask and stirred under Ar atmosphere. 0.43 g (0.38 mmol) of tetrakis (triphenylphosphine) palladium is added to the flask. The reaction mixture is heated at 110 C. and stirred under Ar for 16 hrs. The reaction mixture is cooled to room temperature, the organic phase is quenched with water and extract three times with 200 mL of toluene, dry over magnesium sulfate, filtrated and subsequently evaporate to dryness. The residue is washed with ethyl acetate. The yield is 6.51 g (10.15 mmol), corresponding to 80% of theory.

[0236] The following compounds are synthesized analogously:

TABLE-US-00022 Ex Boronic ester Chloride Product Yield 6-1 [00754] [00755] [00756] 80% 6-2 [00757] [00758] [00759] 83% 6-3 [00760] [00761] [00762] 81%

B) DEVICES EXAMPLES

[0237] OLED devices are prepared according to the following process: The substrates used are glass plates coated with structured ITO (indium tin oxide) in a thickness of 50 nm. The OLEDs have the following layer structure: substrate/hole-injection layer (HIL)/hole-transport layer (HTL)/hole-injection layer (HTL2)/electron-blocking layer (EBL)/emission layer (EML)/electron-transport layer (ETL)/electron-injection layer (EIL) and finally a cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm. The precise structure of the prepared OLEDs is shown in Table 1. The materials required for the production of the OLEDs are shown in Table 3.

[0238] All materials are evaporated by thermal vapor deposition in a vacuum chamber. The emission layer always consists of minimum 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 H1:SEB (5%) denotes that material H1 is present in the layer in a proportion by volume of 95% and SEB is present in the layer in a proportion of 5%. Analogously, other layers may also consist of a mixture of two or more materials.

[0239] The OLEDs are characterized by standard methods. For this purpose, the electroluminescence spectra and the external quantum efficiency (EQE, measured in percent) as a function of the luminous density, calculated from current/voltage/luminous density characteristic lines (IUL characteristic lines) assuming Lambertian emission characteristics, and the lifetime are determined. The expression EQE @ 10 mA/cm.sup.2 denotes the external quantum efficiency at an operating current density of 10 mA/cm.sup.2. LT80 @ 60 mA/cm.sup.2 is the lifetime until the OLED has dropped from its initial luminance of i.e. 5000 cd/m.sup.2 to 80% of the initial intensity, i.e. to 4000 cd/m.sup.2 without using any acceleration factor. The data for the various OLEDs containing inventive and comparative materials are summarized in Table 2.

[0240] Compounds according to the invention are suitable as ETL or matrix material in the EML in OLEDs. They are suitable as a single layer, but also as mixed component as EIL, ETL or within the EML.

[0241] Compared with compounds from prior art (C1 to C4), the samples comprising the compounds according to the invention (E1 to E17) exhibit both higher efficiencies and also improved lifetimes in singlet blue emitting devices.

TABLE-US-00023 TABLE 1 Structure of the OLEDs HIL HTL HTL2 EBL EML ETL EIL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex nm nm nm nm nm nm nm C1 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETMc3:LiQ LiQ NQ(5%) 60 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E1 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM1:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E2 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM2:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E3 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM3:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E4 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM4:LiQ LiQ No(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E5 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM5:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E6 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM6:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E7 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM7:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E8 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM8:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E9 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM9:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E10 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM10:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E11 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM11:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E12 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM12:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E13 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM13:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E14 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM14:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E15 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM15:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E16 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM16:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E17 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM17:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E18 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM18:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E19 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM19:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm E20 HIM:F4TC HIM HTM:F4TC HTM H1:SEB(5%) ETM20:LiQ LiQ NQ(5%) 160 nm NQ(5%) 10 nm 20 nm (50%) 1 nm 20 nm 20 nm 30 nm

TABLE-US-00024 TABLE 2 Data for the OLEDs EQE LT80 Ex. @ 10 mA/cm.sup.2 @ 60 mA/cm.sup.2 C1 7.5 300 E1 7.8 350 E2 8.2 370 E3 8.3 350 E4 7.9 340 E5 8.3 360 E6 7.9 350 E7 8.4 400 E8 8.0 360 E9 8.5 360 E10 8.5 350 E11 8.1 330 E12 8.5 340 E13 8.7 370 E14 8.0 400 E15 7.8 360 E16 8.1 360 E17 7.7 360 E18 7.3 290 E19 7.5 290 E20 7.2 320

TABLE-US-00025 TABLE 3 Structures of the materials used [00763] F4TCNQ [00764] HIM [00765] H1 [00766] SEB [00767] HTM [00768] LiQ [00769] ETMc1 [00770] ETM1 [00771] ETM2 [00772] ETM3 [00773] ETM4 [00774] ETM5 [00775] ETM6 [00776] ETM7 [00777] ETM8 [00778] ETM9 [00779] ETM10 [00780] ETM11 [00781] ETM 12 [00782] ETM 13 [00783] ETM 14 [00784] ETM15 [00785] ETM16 [00786] ETM17 [00787] ETM18 [00788] ETM19 [00789] ETM20

[0242] In the above examples, it is shown, that the external quantum efficiency of the device @ 10 mA/cm.sup.2 with inventive materials ETM1 to ETM17 is higher than the one of the comparative example 1. Even in lifetime the inventive examples E1 to E17 are much better than the reference. The device with ETM7 and ETM14 have a lifetime down to 80% of its initial brightness @60 mA/cm.sup.2 constant driving current density of 400 h. The comparative example achieves 300 h.

[0243] The comparison of inventive materials ETM1 to ETM17 with the inventive materials ETM18 and ETM19 show that an unexpected improvement can be achieved with materials having exactly one triazine group. The inventive examples ETM1 to ETM17 do show higher lifetimes than the Examples ETM 18 and EMT19 with 330 h and twice 400 h.

[0244] Furthermore, the comparison of inventive materials ETM1 to ETM17 with the inventive material EMT20 show that the combination of an aryl linking group with a pyridinyl group as residue Ar.sup.1, a phenyl group as residue Ar.sup.2, two phenyl groups as residue R.sup.a and a 3 position substitution of silafluorene group shows remarkably disadvantages. Although the lifetime of Example E 20 is better than reference Example C1, the results of Example E20 in view of the preferred inventive Examples E1 to E17 are rather low. In particular the comparison of E12 and E20 shows the effect of the position of the substituent.

[0245] In addition thereto, the present examples show that inventive compounds according formula (I) having an Ar.sup.1 or Ar.sup.2 residue comprising an aryl or heteroaryl group having two or more aromatic rings provide astonishing improvements in lifetime and EQE (E4 compared E5 and E6 compared E7) if the residue R.sup.a are alkyl groups or the silafluorene group is substituted at 2-position. In the case that the silafluorene group is substituted at 4-position, astonishing improvements in EQE can be achieved (E8 compared E9).

[0246] Furthermore, the present examples show that inventive compounds according formula (I) having an R.sup.a residue comprising an aryl or heteroaryl group provide astonishing improvements in EQE in view of compounds having only alkyl groups as residue R.sup.a (E1 compared E3 and E6, respectively).

[0247] Moreover, the present examples show that a substitution of the silafluorene group at 2- or 4-position is preferred over a substitution in 3 position (E6 and E8 compared E15).

[0248] Devices for direct comparison, from which the technical effect according to the invention can be seen, are

i) C1 compared to E6 to E9, and E15 to E17
ii) E18 compared to E1 to E5,
iii) E19 compared to E15 to E17, and
iv) E20 compared to E10 to E17.