Compounds and organic electronic devices
The present invention relates to certain fluorenes, to the use of the compounds in an electronic device, and to an electronic device comprising at least one of these compounds. Furthermore, the present invention relates to a process for the preparation of the compounds and to a formulation and composition comprising one or more of the compounds.
1. A compound of the formula (1)
where the following applies to the symbols and indices used:
R 1 is on each occurrence, identically or differently, preferably identically, H, D, F, Cl, Br, I, C(═O)R 4 , CN, Si(R 4 ) 3 , NO 2 , P(═O)(R 4 ) 2 , S(═O)R 4 , S(═O) 2 R 4 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R 4 and where one or more CH 2 groups in the above-mentioned groups is optionally replaced by —R 4 C═CR 4 —, —C≡C—, Si(R 4 ) 2 , C═O, C═S, C═NR 4 , —C(═O)O—, —C(═O)NR 4 —, P(═O)(R 4 ), —O—, —S—, SO or SO 2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 4 , or an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 4 , or an aralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 4 , where the two radicals R 1 is optionally linked to one another and may form a ring, so that a spiro compound forms in position 9 of the fluorene, where spirobifluorenes are excluded;
R 2 and R 3 are on each occurrence, identically or differently, preferably identically, H, D, F, Cl, Br, I, C(═O)R 4 , CN, Si(R 4 ) 3 , NO 2 , P(═O)(R 4 ) 2 , S(═O)R 4 , S(═O) 2 R 4 , N(R 4 ) 2 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R 4 and where one or more CH 2 groups in the above-mentioned groups is optionally replaced by —R 4 C═CR 4 —, —C≡C—, Si(R 4 ) 2 , C═O, C═S, C═NR 4 , —C(═O)O—, —C(═O)NR 4 —, P(═O)(R 4 ), —O—, —S—, SO or SO 2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 4 , or an aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 4 , or an aralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 4 , where two or more radicals R 2 or two or more radicals R 3 is optionally linked to one another and may form a ring;
R 4 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R 5 , CN, Si(R 5 ) 3 , NO 2 , P(═O)(R 5 ) 2 , S(═O)R 5 , S(═O) 2 R 5 , N(R 5 ) 2 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R 5 and where one or more CH 2 groups in the above-mentioned groups is optionally replaced by —R 5 C═CR 5 —, —C≡C—, Si(R 5 ) 2 , C═O, C═S, C═NR 5 , —C(═O)O—, —C(═O)NR 5 —, P(═O)(R 5 ), —O—, —S—, SO or SO 2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 , or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R 5 ;
R 5 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, in which one or more H atoms is optionally replaced by D or F, where two or more adjacent substituents R 5 may form a mono- or polycyclic, aliphatic ring system with one another;
p and r are each 0;
q is 1;
Z a p , and Z c r are, identically or differently on each occurrence, equal to R 3 ;
Z b q is equal to
B′ is a phenylene, biphenylene, terphenylene, naphthylene, dibenzofuranylene or dibenzo-thiophenylene group, which is optionally substituted by one or more radicals R 4 ;
Ar 1 and Ar 2 are on each occurrence, identically or differently, an aromatic group having 6 to 60 ring atoms or a heteroaromatic group having 5 to 60 ring atoms, each of which is optionally substituted by one or more radicals R 6 , which are identical to or different from one another, where at least one of the two groups Ar 1 and Ar 2 must contain a fluorene group;
wherein Ar 1 and Ar 2 contain no carbazoles;
R 6 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R 5 , CN, Si(R 5 ) 3 , NO 2 , P(═O)(R 5 ) 2 , S(═O)R 5 , S(═O) 2 R 5 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R 5 and where one or more CH 2 groups in the above-mentioned groups is optionally replaced by —R 5 C═CR 5 —, —C≡C—, Si(R 5 )2, C═O, C═S, C═NR 5 , —C(═O)O—, —C(═O)NR 5 —, P(═O)(R 5 ), —O—, —S—, SO or SO 2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 , or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R 5 .
2. The compound according to claim 1 , wherein the compound has the general formula (2)
where the definitions from claim 1 apply to the symbols used.
3. The compound according to claim 1 , wherein the compound has the general formula (7)
where the definitions from claim 1 apply to the symbols used.
4. The compound according to claim 1 , wherein the compound has the general formula (10)
where the definitions from claim 1 apply to the symbols used.
5. The compound according to claim 1 , wherein both R 1 are identical.
6. The compound according to claim 1 , wherein both groups Ar 1 and Ar 2 contain at least two aromatic or heteroaromatic rings.
7. Process for the preparation of a compound according to claim 1 by means of one-step Buchwald coupling by reaction of a fluorene derivative containing a leaving group with Ar 2 —NH—Ar 1 .
8. A process for the preparation of the compound according to claim 1 by means of two-step Buchwald coupling by stepwise reaction of a fluorene derivative containing a leaving group with (1) Ar 2 —NH 2 and (2) NH 2 —Ar 1 .
9. A process for the preparation of the compound according to claim 1 , wherein the compound is prepared from a benzochromen-6-one.
10. A formulation comprising at least one compound according to claim 1 and at least one solvent.
11. An oligomer, polymer or dendrimer comprising one or more compounds according to claim 1 , where the bond(s) to the polymer, oligomer or dendrimer is optionally localized at any position in formula (1) that are substituted by R 1 to R 6 .
12. A composition comprising one or more compounds according to claim 1 and at least one further material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron-transport materials, electron-injection materials, hole-conductor materials, hole-injection materials, electron-blocking materials, hole-blocking materials and p-dopants.
13. The process according to claim 10 comprising the following steps:
a) adding an organometallic compound onto a benzochromen-6-one and subsequent
b) acid-catalysed cyclisation to give a 4-hydroxyfluorene derivative and subsequent
c) converting the hydroxyl group in position 4 of the fluorene into a leaving group and subsequent, and
d) converting the fluorene into the desired product.
14. An electronic device comprising at least one compound according to claim 1 .