Materials for electronic devices
The invention relates to phenanthrene compounds comprising one or more arylamino groups. Said compounds can be used in electronic devices, in particular OLED's.
1. A compound containing a phenanthrene group of the formulae (I-1) or (I-2):
where the symbols that occur are as follows:
R 1 is the same or different at each instance and is selected from H, D, F, C(═O)R 6 , CN, Si(R 6 ) 3 , P(═O)(R 6 ) 2 , OR 6 , S(═O)R 6 , S(═O) 2 R 6 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems which have 6 to 40 aromatic ring atoms and may be substituted by one or more R 6 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and may be substituted by one or more R 6 radicals,
where the alkyl, alkoxy, alkenyl and alkynyl groups may each be substituted by one or more R 6 radicals and
where one or more CH 2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups may be replaced by —R 6 C═CR 6 —, —C≡C—, Si(R 6 ) 2 , C═O, C═NR 6 , —C(═O)O—, —C(═O)NR 6 —, NR 6 , P(═O)(R 6 ), —O—, —S—, SO or SO 2 ,
R 2 , R 3 are the same or different at each instance and are selected from H, D, F, C(═O)R 6 , CN, Si(R 6 ) 3 , P(═O)(R 6 ) 2 , OR 6 , S(═O)R 6 , S(═O) 2 R 6 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems which have 6 to 40 aromatic ring atoms and is optionally substituted by one or more R 6 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 6 radicals,
where the alkyl, alkoxy, alkenyl and alkynyl groups may each be substituted by one or more R 6 radicals, and
where one or more CH 2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups is optionally replaced by
—R 6 C═CR 6 —, —C≡C—, Si(R 6 ) 2 , C═O, C═NR 6 , —C(═O)O—,
—C(═O)NR 6 —, NR 6 , P(═O)(R 6 ), —O—, —S—, SO or SO 2 ,
R 6 is the same or different at each instance and is selected from H, D, F, C(═O)R 7 , CN, Si(R 7 ) 3 , P(═O)(R 7 ) 2 , OR 7 , S(═O)R 7 , S(═O) 2 R 7 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems which have 6 to 40 aromatic ring atoms and is optionally substituted by one or more R 7 radicals, and heteroaromatic ring systems which have 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 7 radicals,
where the alkyl, alkoxy, alkenyl and alkynyl groups may each be substituted by one or more R 7 radicals,
where one or more CH 2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups is optionally replaced by
—R 7 C═CR 7 —, —C≡C—, Si(R 7 ) 2 , C═O, C═NR 7 , —C(═O)O—,
—C(═O)NR 7 —, NR 7 , P(═O)(R 7 ), —O—, —S—, SO or SO 2 ;
R 7 is the same or different at each instance and is selected from H, D, F, CN and aliphatic, aromatic or heteroaromatic organic radicals having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by D, F or CN;
Ar 1 is selected, identically or differently, from benzene, naphthalene, fluoranthene, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzimidazole, pyrimidine, pyrazine and triazine, each optionally substituted by one or more R4 radicals;
R 4 are the same or different at each instance and are selected from H, D, F, CN, Si(R 6 ) 3 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, where the alkyl and alkoxy groups mentioned may each be substituted by one or more R 6 radicals and where one or more CH 2 groups in the alkyl and alkoxy groups mentioned may be replaced by —C≡C—, —R 6 C═CR 6 —, Si(R 6 ) 2 , C═O, C═NR 6 , —NR 6 —, —O—, —S—, —C(═O)O— or —C(═O)NR 6 —; or benzene, naphthalene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole, each of which may be substituted by one or more R 6 radicals.
2. The compound as claimed in claim 1 , wherein two Ar 1 groups bonded to the same nitrogen atom are not the same.
3. The compound as claimed in claim 1 , wherein R 6 is the same or different at each instance and is selected from H, D, F, CN, Si(R 7 ) 3 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems which have 6 to 24 aromatic ring atoms and is optionally substituted by one or more R 7 radicals, and heteroaromatic ring systems which have 5 to 24 aromatic ring atoms and is optionally substituted by one or more R 7 radicals,
where the alkyl and alkoxy groups may each be substituted by one or more R 7 radicals and where one or more CH 2 groups in the alkyl and alkoxy groups is optionally replaced by —C≡C—, —R 7 C═CR 7 —, Si(R 7 ) 2 , C═O, C═NR 7 , —NR 7 —, —O—, —S—, —C(═O)O— or —C(═O)NR 7 —.
4. A process for preparing the compound as claimed in claim 1 , which comprises reacting a phenanthrene compound substituted by a leaving group in the 1 and/or 4 position in a coupling reaction with a diarylamino compound or with a triarylamino compound substituted by a leaving group.
5. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 1 , wherein the bond(s) to the polymer, oligomer or dendrimer is optionally localized at any positions substituted by R 1 , R 2 , R 3 , R 4 , R 6 or R 7 in formula (I).
6. A formulation comprising at least one compound as claimed in claim 1 and at least one solvent.
7. An electronic device selected from organic integrated circuits (OICs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting transistors (OLETs), organic solar cells (OSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs), comprising at least one compound as claimed in claim 1 .
8. An organic electroluminescent device comprising cathode, anode and at least one organic layer comprising at least one compound as claimed in claim 1 .
9. An organic electroluminescent device which comprises the compound as claimed in claim 1 as hole transport material in a hole transport layer, an electron blocker layer or a hole injection layer, or as emitting compound in an emitting layer, or as matrix compound together with one or more emitting compounds in an emitting layer.
10. The compound as claimed in claim 1 , wherein Ar 1 is selected, identically or differently on each occurrence, from formulae (Ar 1 -1) to (Ar 1 -59)
where the bond marked with * in each case represents the bond to the nitrogen atom, and where the formulae may bear R4 radicals at their unoccupied positions.
11. The compound as claimed in claim 1 , wherein the compound contains, aside from the phenanthrene group depicted in formulae (I-1) or (I-2), no further fused aryl group having more than 10 aromatic ring atoms.
12. The compound as claimed in claim 1 , wherein
R 1 is the same or different at each instance and is selected from H, D, F, CN, Si(R 6 ) 3 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems which have 6 to 24 aromatic ring atoms and may be substituted by one or more R 6 radicals, heteroaromatic ring systems which have 5 to 24 aromatic ring atoms and may be substituted by one or more R 6 radicals, groups of the formula (A), as defined above, and groups of the formula (B), where the alkyl and alkoxy groups may each be substituted by one or more R 6 radicals and where one or more CH 2 groups in the alkyl and alkoxy groups may be replaced by —C≡C—, —R 6 C═CR 6 —, Si(R 6 ) 2 , C═O, C═NR 6 , —NR 6 —, —O—, —S—, —C(═O)O— or —C(═O)NR 6 —;
and R 2 , R 3 are the same or different at each instance and are selected from H, D, F, CN, Si(R 6 ) 3 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems which have 6 to 24 aromatic ring atoms and may be substituted by one or more R 6 radicals, and heteroaromatic ring systems which have 5 to 24 aromatic ring atoms and may be substituted by one or more R 6 radicals, where the alkyl and alkoxy groups may each be substituted by one or more R 6 radicals and where one or more CH 2 groups in the alkyl and alkoxy groups may be replaced by —C≡C—, —R 6 C═CR 6 —, Si(R 6 ) 2 , C═O, C═NR 6 , —NR 6 —, —O—, —S—, —C(═O)O— or —C(═O)NR 6 —.
13. The compound as claimed in claim 1 , wherein Ar 1 is selected, identically or differently on each occurrence, from formulae (Ar 1 -1) to (Ar 1 -59)
where the bond marked with * in each case represents the bond to the nitrogen atom, and where the formulae may bear R4 radicals at their unoccupied positions;
wherein the compound contains, aside from the phenanthrene group depicted in formulae (I-1) or (I-2), no further fused aryl group having more than 10 aromatic ring atoms;
wherein
R 1 is the same or different at each instance and is selected from H, D, F, CN, Si(R 6 ) 3 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems which have 6 to 24 aromatic ring atoms and may be substituted by one or more R 6 radicals, heteroaromatic ring systems which have 5 to 24 aromatic ring atoms and may be substituted by one or more R 6 radicals, groups of the formula (A), as defined above, and groups of the formula (B), where the alkyl and alkoxy groups may each be substituted by one or more R 6 radicals and where one or more CH 2 groups in the alkyl and alkoxy groups may be replaced by —C≡C—, —R 6 C═CR 6 —, Si(R 6 ) 2 , C═O, C═NR 6 , —NR 6 —, —O—, —S—, —C(═O)O— or —C(═O)NR 6 —;
and R 2 , R 3 are the same or different at each instance and are selected from H, D, F, CN, Si(R 6 ) 3 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems which have 6 to 24 aromatic ring atoms and may be substituted by one or more R 6 radicals, and heteroaromatic ring systems which have 5 to 24 aromatic ring atoms and may be substituted by one or more R 6 radicals, where the alkyl and alkoxy groups may each be substituted by one or more R 6 radicals and where one or more CH 2 groups in the alkyl and alkoxy groups may be replaced by —C≡C—, —R 6 C═CR 6 —, Si(R 6 ) 2 , C═O, C═NR 6 , —NR 6 —, —O—, —S—, —C(═O)O— or —C(═O)NR 6 —,
wherein R 4 are the same or different at each instance and are selected from H, D, F, CN, Si(R 6 ) 3 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, where the alkyl and alkoxy groups mentioned may each be substituted by one or more R 6 radicals and where one or more CH 2 groups in the alkyl and alkoxy groups mentioned may be replaced by —C≡C—, —R 6 C═CR 6 —, Si(R 6 ) 2 , C═O, C═NR 6 , —NR 6 —, —O—, —S—, —C(═O)O— or —C(═O)NR 6 —; or benzene, naphthalene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole, each of which may be substituted by one or more R 6 radicals;
and
wherein R 6 is the same or different at each instance and is selected from H, D, F, CN, Si(R 7 ) 3 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, aromatic ring systems which have 6 to 24 aromatic ring atoms and is optionally substituted by one or more R 7 radicals, and heteroaromatic ring systems which have 5 to 24 aromatic ring atoms and is optionally substituted by one or more R 7 radicals, where the alkyl and alkoxy groups may each be substituted by one or more R 7 radicals and where one or more CH 2 groups in the alkyl and alkoxy groups is optionally replaced by —C≡C—, —R 7 C═CR 7 —, Si(R 7 ) 2 , C═O, C═NR 7 , —NR 7 —, —O—, —S—, —C(═O)O— or —C(═O)NR 7 —.