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EP-4263544-B1 - INDOLO[3.2.1-JK]CARBAZOLE-6-CARBONITRILE DERIVATIVES AS BLUE EMITTERS IN OLEDS

EP4263544B1EP 4263544 B1EP4263544 B1EP 4263544B1EP-4263544-B1

Inventors

  • STOESSEL, PHILIPP

Dates

Publication Date
20260513
Application Date
20211215

Claims (20)

  1. A compound according to formula (I), wherein the symbols and indices used are as follows: X is the same or different at each instance and is N, C-CN, C-Y-R y , or CR b , preferably N, C-CN, or C-Y-R y , particularly preferably C-CN; Y is the same or different at each instance and is CO, P(=O)R a , SO, SO 2 , C(O)O, C(S)O, C(O)S, C(=O)NR a , C(=O)NAr, preferably CO, P(=O)R a , SO, SO 2 , particularly preferably CO; R is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO 2 , N(Ar) 2 , N(R e ) 2 , C(=O)N(Ar) 2 , C(=O)N(R e ) 2 , C(Ar) 3 , C(R e ) 3 , Si(Ar) 3 , Si(R e ) 3 , B(Ar) 2 , B(R e ) 2 , C(=O)Ar, C(=O)R e , P(=O)(Ar) 2 , P(=O)(R e ) 2 , P(Ar) 2 , P(R e ) 2 , S(=O)Ar, S(=O)R e , S(=O) 2 Ar, S(=O) 2 R e , OSO 2 Ar, OSO 2 R e , a straight-chain alkyl or alkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, wherein the alkyl or alkoxy group may each be substituted with one or more R e radicals, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R e radicals, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R e radicals, or an arylthio or heteroarylthio group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R e radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R e radicals, or an arylalkyl or heteroarylalkyl group having 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl radical, and which may be substituted by one or more radicals R e ; wherein any R radical may form a ring system with a further group, preferably R d ; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, which may be substituted with one or more R e radicals, wherein two Ar radicals bonded to the same C atom, Si atom, N atom, P atom, or B atom may also be joined by a single bond or a bridge selected from B(R e ), C(R e ) 2 , Si(R e ) 2 , C=O, C=NR e , C=C(R e ) 2 , O, S, S=O, SO 2 , N(R e ), P(R e ) and P(=O)R e ; R a , R b , R c , R d , R e is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO 2 , N(Ar') 2 , N(R e ) 2 , C(=O)N(Ar') 2 , C(=O)N(R 1 ) 2 , C(Ar') 3 , C(R 1 ) 3 , Si(Ar') 3 , Si(R 1 ) 3 , B(Ar') 2 , B(R 1 ) 2 , C(=O)Ar', C(=O)R 1 , P(=O)(Ar') 2 , P(=O)(R 1 ) 2 , P(Ar') 2 , P(R 1 ) 2 , S(=O)Ar', S(=O)R 1 , S(=O) 2 Ar', S(=O) 2 R 1 , OSO 2 Ar', OSO 2 R 1 , a straight-chain alkyl or alkoxy group with 1 to 40 C atoms or a branched or cyclic alkyl or alkoxy group with 3 to 20 carbon atoms, wherein the alkyl or alkoxy group may each be substituted with one or more R 1 radicals, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may each be substituted by one or more R 1 radicals, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R 1 radicals; wherein two radicals R a , R b , R c , R d , R e may also form a ring system together or with a further group, preferably R or R y ; R y is the same or different at each instance and is C(Ar') 3 , C(R 1 ) 3 , Si(Ar') 3 , Si(R 1 ) 3 , N(Ar') 2 , N(R e ) 2 , a straight-chain alkyl or alkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, wherein the alkyl or alkoxy group may be substituted in each case by one or more R 1 radicals, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms and which may be substituted by one or more R 1 radicals; wherein two R y radicals may also form a ring system with one another, or one R y radical may form a ring system with one radical R a , R b , R c , R d , R e , preferably a R a radical; Ar' is the same or different at each instance and is an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms and which may be substituted by one or more R 1 radicals, wherein two radicals Ar', which are bonded to the same C atom, Si atom, N atom, P atom, or B atom, may also be joined together by a single bond or a bridge selected from B(R 1 ), C(R 1 ) 2 , Si(R 1 ) 2 , C=O, C=NR 1 , C=C(R 1 ) 2 , O, S, S=O, SO 2 , N(R 1 ), P(R 1 ) and P(=O)R 1 ; R 1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO 2 , N(Ar") 2 , N(R 2 ) 2 , C(=O)Ar", C(=O)R 2 , P(=O)(Ar") 2 , P(Ar") 2 , B(Ar") 2 , B(R 2 ) 2 , C(Ar") 3 , C(R 2 ) 3 , Si(Ar") 3 , Si(R 2 ) 3 , a straight-chain alkyl or alkoxy group with 1 to 40 C atoms or a branched or cyclic alkyl or alkoxy group with 3 to 40 C atoms, which each may be substituted by one or more R 2 radicals, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which each may be substituted by one or more R 2 radicals, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and which may be substituted by one or more radicals R 2 , or an aralkyl or heteroaralkyl group with 5 to 60 aromatic ring atoms and which may be substituted by one or more R 2 radicals, or a combination of these systems; wherein two or more, preferably adjacent, R 1 radicals may form a ring system with one another, wherein one or more R 1 radicals may form a ring system with a further part of the compound; Ar" is the same or different at each instance and is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and may be substituted with one or more R 2 radicals, wherein two Ar" radicals bonded to the same C atom, Si atom, N atom, P atom, or B atom may also be joined together by a single bond or a bridge selected from B(R 2 ), C(R 2 ) 2 , Si(R 2 ) 2 , C=O, C=NR 2 , C=C(R 2 ) 2 ,O, S, S=O, SO 2 , N(R 2 ), P(R 2 ) and P(=O)R 2 ; R 2 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and in which one or more H atoms may be replaced by D, F, Cl, Br, I, or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms, wherein two or more, preferably adjacent substituents R 2 together may form a ring system; characterized in that two radicals R a together with the further groups to which the two radicals R a bind form a fused ring.
  2. The compound according to claim 1, characterized in that at least one, preferably at least two, of the R, R a , R b , R c , R d , R e radicals are not H, preferably are not H, D, OH, NO 2 , F, Cl, Br, I.
  3. The compound according to claim 1 or 2, characterized in that at least one, preferably at least two, of the R a , R c radicals are a straight-chain alkyl or alkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, wherein the alkyl or alkoxy group may be substituted in each case by one or more radicals R 1 .
  4. The compound according to one or more of claims 1 to 3, characterized in that the R radical is an aromatic or heteroaromatic ring system having 5 to 13 aromatic ring atoms and which may be substituted with one or more radicals R e .
  5. The compound according to one or more of claims 1 to 4, characterized in that two R a radicals together with the further groups to which the two R a radicals bind form an aliphatic or heteroaliphatic ring having 3 to 20 or an aromatic or heteroaromatic ring having 5 to 13 ring atoms.
  6. The compound according to one or more of claims 1 to 5, characterized in that two R c radicals together with the further groups to which the two R c radicals bind form a fused ring, preferably an aliphatic or heteroaliphatic ring having 3 to 20, preferably 5 to 18 ring atoms, or an aromatic or heteroaromatic ring having 5 to 13 ring atoms, particularly preferably an aliphatic or heteroaliphatic ring having 3 to 20, preferably 5 to 18 ring atoms.
  7. The compound according to one or more of claims 1 to 6, which is a compound according to one of formulae (1-1) to (1-83), wherein the symbols R a , R b , R c , R d , R e and R y have the meanings given in claim 1 and the further symbols and indices used are as follows: X 1 is the same or different at each instance and is N or CR e , preferably CR e , with the proviso that not more than two of the X 1 groups in one cycle are N; Y 1 is the same or different at each instance and is C(R e ) 2 , (R e )2-C(R e ) 2 , (R e )C=C(R e ), NR e , NAr', O, S, SO, SO 2 , Se, P(O)R e , BR e or Si(R e ) 2 , preferably C(R e ) 2 , (R e ) 2 -C(R e ) 2 , (R e )C=C(R e ), O or S, particularly preferably C(R e ) 2 ; T 1 is the same or different at each instance and is a condensed ring, preferably an aliphatic or heteroaliphatic ring having 3 to 20, preferably 5 to 18 ring atoms, or an aromatic or heteroaromatic ring having 5 to 13 ring atoms, particularly preferably for an aliphatic or heteroaliphatic ring having 3 to 20, preferably 5 to 18 ring atoms, which may be substituted by one or more R 1 , wherein R 1 has the meaning given in claim 1; n is 0, 1, 2, or 3, preferably 0, 1, or 2; m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2.
  8. The compound according to one or more of claims 1 to 7, characterized in that at least two R, R a , R b , R c , R d , R e , R y radicals together with the further groups to which the two R, R a , R b , R c , R d , R e , R y radicals bind, form a condensed ring, wherein the two R, R a , R b , R c , R d , R e , R y radicals form at least one structure of the following formulae (Cy-1) to (Cy-10), wherein R 1 and R 2 have the meanings given in claim 1, the dashed bonds represent the sites of attachment to the atoms of the groups to which the two R, R a , R b , R c , R d , R e , R y radicals bind, and furthermore: Z 1 , Z 3 is the same or different at each instance and is C(R 3 ) 2 , O, S, NR 3 or C(=O); Z 2 is C(R 1 ) 2 , O, S, NR 1 , or C(=O), wherein two adjacent groups Z 2 represent -CR 1 =CR 1 - or an ortho-bonded arylene or heteroarylene group having 5 to 14 aromatic ring atoms which may be substituted by one or more R 1 radicals; G is an alkylene group having 1, 2, or 3 C atoms and which may be substituted by one or more R 1 radicals, -CR 1 =CR 1 - or an ortho-bonded arylene or heteroarylene group having 5 to 14 aromatic ring atoms which may be substituted by one or more R 1 radicals; R 3 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO 2 , N(Ar") 2 , N(R 2 ) 2 , C(=O)Ar", C(=O)R 2 , P(=O)(Ar") 2 , P(Ar") 2 , B(Ar") 2 , B(R 2 ) 2 , C(Ar") 3 , C(R 2 ) 3 , Si(Ar") 3 , Si(R 2 ) 3 , a straight-chain alkyl or alkoxy group with 1 to 40 C atoms or a branched or cyclic alkyl or alkoxy group with 3 to 40 C atoms, each of which may be substituted by one or more R 2 radicals, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and each of which may be substituted by one or more R 2 radicals, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R 2 radicals, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R 2 radicals, or a combination of these systems; wherein two R 3 radicals bonded to the same carbon atom may be joined together to form an aliphatic or aromatic ring system, thus forming a spiro system; furthermore, R 3 may form a ring system with a R, R a , R c , R d , R e , or R 1 radical; with the proviso that no two heteroatoms in these groups are bonded directly to one another and no two C=O groups are bonded directly to one another.
  9. The compound according to one or more of claims 1 to 8, characterized in that at least two R, R a , R b , R c , R d , R e , R y radicals form a fused ring together with the further groups to which the two R, R a , R b , R c , R d , R e , R y radicals bind, wherein the two R, R a , R b , R c , R d , R e , R y radicals form at least one structure of the formulae (RA-1) to (RA-13): wherein R 1 has the meaning given above, the dashed lines represent the sites of attachment to the atoms of the groups to which the two R, R a , R b , R c , R d , R e , R y radicals bind, and the further symbols used are as follows: Y 2 is the same or different at each instance and is C(R 1 ) 2 , (R 1 ) 2 C-C(R 1 ) 2 , (R 1 )C=C(R 1 ), NR 1 , NAr', O, or S, preferably C(R 1 ) 2 , (R 1 ) 2 C-C(R 1 ) 2 , (R 1 )C=C(R 1 ), O, or S; R f is the same or different at each instance and is F, a straight-chain alkyl or alkoxy group with 1 to 40 C atoms or a branched or cyclic alkyl or alkoxy group with 3 to 20 carbon atoms, wherein the alkyl or alkoxy group may be substituted in each case with one or more R 2 radicals, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms and which may be substituted in each case by one or more R 2 radicals, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which may be substituted by one or more R 2 radicals; wherein two R f radicals may also form a ring system with one another, or one R f radical may form a ring system with one R f radical or with a further group; r is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, particularly preferably 0 or 1; s is 0, 1, 2, 3, 4, 5, or 6, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1, or 2; t is 0, 1, 2, 3, 4, 5, 6, 7, or 8, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1, or 2; v is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9, preferably 0, 1, 2, 3, or 4, particularly preferably 0, 1, or 2, wherein structures of the formulae RA-1, RA-3, RA-4, and RA-5 are preferred and structures of the formulae RA-4 and RA-5 are particularly preferred.
  10. The compound according to one or more of claims 1 to 9, wherein at least two R, R a , R b , R c , R d , R e , R y radicals form a fused ring together with the further groups to which the two R, R a , R b , R c , R d , R e , R y radicals bind, wherein the two R, R a , R b , R c , R d , R e , R y radicals form structures of formula (RB): wherein R 1 has the meaning set forth in claim 1, the dashed bonds represent the sites of attachment via which the two R, R a , R b , R c , R d , R e , R y radicals bind, the index m is 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and Y 3 is C(R 1 ) 2 ,NR 1 , NAr', BR 1 , BAr', O or S, preferably C(R 1 ) 2 , NAr' or O.
  11. The compound according to one or more of claims 1 to 10, characterized in that R or Ar is the same or different at each instance and is selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, or triphenylene, and each of which may be substituted with one or more R e radicals.
  12. The compound according to at least one of the preceding claims, characterized in that the compound is symmetrical with respect to the R a and R c radicals.
  13. The compound according to at least one of the preceding claims, characterized in that the R e and/or R d radical comprises at least one group selected from C(Ar') 3 , C(R 1 ) 3 , Si(Ar') 3 , Si(R 1 ) 3 , B(R 1 ) 2 , preferably selected from C(Ar') 3 , C(R 1 ) 3 , Si(Ar') 3 , Si(R 1 ) 3 , preferably a fluorene group that is substituted with one or more R 1 radicals or that forms a fluorene group with a R d or R e radical, respectively.
  14. The compound according to at least one of the preceding claims, characterized in that the compound comprises exactly two or exactly three structures according to formula (I) and/or (I-1) to (I-81).
  15. An oligomer, polymer, or dendrimer containing one or more compounds according to any one of claims 1 to 14, wherein one or more bonds of the compounds to the polymer, oligomer, or dendrimer are present instead of a hydrogen atom or a substituent.
  16. A formulation comprising at least one compound according to one or more of claims 1 to 14 or an oligomer, polymer, or dendrimer according to claim 15, and at least one further compound, wherein the further compound is preferably selected from one or more solvents.
  17. A composition comprising at least one compound according to one or more of claims 1 to 14 or an oligomer, polymer or dendrimer according to claim 15, and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF, host materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials, and hole blocking materials, preferably host materials.
  18. The composition according to claim 17, characterized in that the composition comprises at least one further compound which is a TADF host material and/or at least one further compound which is a phosphorescent emitter (triplet emitter), wherein the further compounds together with a compound according to one or more of claims 1 to 14 or an oligomer, polymer or dendrimer according to claim 15, preferably form a hyperfluorescence and/or hyperphosphorescence system.
  19. A method for producing a compound according to one or more of claims 1 to 14, characterized in that a basic structure having an aromatic amino group is synthesized and at least one aromatic or heteroaromatic residue is introduced, preferably by means of a nucleophilic aromatic substitution reaction or a coupling reaction.
  20. A use of a compound according to one or more of claims 1 to 14 or an oligomer, polymer, or dendrimer according to claim 15 in an electronic device, preferably as a blue emitter.

Description

The present invention relates to aromatic compounds for use in electronic devices, in particular in organic electroluminescent devices, and to electronic devices, in particular organic electroluminescent devices, containing these aromatic compounds. In organic electroluminescence devices, phosphorescent organometallic complexes or fluorescent compounds are frequently used as emitting materials. Generally, there is still room for improvement in electroluminescence devices. Out of US 2010/0051928 , WO 2010/104047 A1 , US 2014/319507 A1 , WO 2017/175690 , US 2019/0393439 , CN 110452226 A , WO 2019/132506 A1 and WO 2020/064666 A1 Polycyclic compounds are known that can be used in organic electroluminescence devices. From WO 2019/194617 A and WO 2019/111971 A1 Indolo[3.2.1-jk]carbazole-6-carbonitrile derivatives are known as emitters for use in OLEDs. John B. Henry et al. ( Henry, John B. et al., The Journal of Physical Chemistry A, Vol. 115, No. 21, pages 5435-5442 (2011 )) describes Indolo[3.2.1-jk]carbazole-5-carbonitrile as an emitter for use in OLEDs. In general, there is still room for improvement with these heterocyclic compounds, for example for use as emitters, especially as fluorescent emitters, particularly with regard to lifetime, color purity, but also with regard to the efficiency and operating voltage of the device. The object of the present invention is therefore to provide compounds that are suitable for use in an organic electronic device, in particular in an organic electroluminescence device, and which, when used in This device will lead to good device characteristics, as well as the provision of the corresponding electronic device. In particular, the object of the present invention is to provide connections that lead to a long service life, good efficiency and low operating voltage. Furthermore, the compounds should exhibit excellent processability, and in particular, good solubility. A further object of the present invention can be seen as providing compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, in particular as emitters. In particular, it is an object of the present invention to provide emitters suitable for red, green, or blue electroluminescent devices, preferably for blue electroluminescent devices. Furthermore, the compounds, especially when used as emitters in organic electroluminescent devices, should lead to devices that exhibit excellent color purity. Another task can be seen as providing electronic devices with excellent performance as cost-effectively and with consistent quality as possible. Furthermore, the electronic devices should be usable or adaptable for many purposes. In particular, the performance of the electronic devices should be maintained over a wide temperature range. Surprisingly, it was found that certain compounds, described in more detail below, solve this problem, are very well suited for use in electroluminescent devices, and lead to organic electroluminescent devices that are particularly advantageous with regard to These compounds exhibit very good properties in terms of lifespan, color purity, efficiency, and operating voltage. These compounds, as well as electronic devices, in particular organic electroluminescent devices containing such compounds, are therefore the subject of the present invention. The subject of the present invention is a compound according to formula (I), where the following applies to the symbols used: X In each instance, the represents N, C-CN, CYR y or CR b , preferably N, C-CN, or CYR y , and particularly preferably C-CN; Y is the same or different in each occurrence CO, P(=O)R a , SO, SO 2 , C(O)O, C(S)O, C(O)S, C(=O)NR a , C(=O)NAr, preferably CO, P(=O)R a , SO, SO 2 , particularly preferably CO; R is the same or different in each occurrence H, D, OH, F, Cl, Br, I, CN, NO 2 , N(Ar) 2 , N(R e ) 2 , C(=O)N(Ar) 2 , C(=O)N(R e ) 2 , C(Ar) 3 , C(R e ) 3 , Si(Ar)3, Si(R e ) 3 , B(Ar) 2 , B(R e ) 2 , C(=O)Ar, C(=O)R e , P(=O)(Ar) 2 , P(=O)( R e ) 2 , P(Ar) 2 , P(R e ) 2 , S(=O)Ar, S(=O)R e , S(=O) 2 Ar, S(=O) 2 R e , OSO 2 Ar, OSO 2 R e , a straight-chain alkyl or alkoxy group with 1 to 40 carbon atoms or a branched or cyclic alkyl or alkoxy group with 3 to 20 carbon atoms, wherein the an alkyl or alkoxy group, each of which may be substituted with one or more R e groups, or an aromatic or heteroaromatic ring system with 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R e groups, or an aryloxy or heteroaryloxy group with 5 to 60 aromatic ring atoms, which may be substituted by one or more R e groups, or an arylthio or heteroarylthio group with 5 to 60 aromatic ring atoms, which may be substituted by one or more R e groups, or a diarylamino, arylheteroarylamino, diheteroarylamino group with 5 to 60 aromatic ring atoms, which may be substituted by one or more R e groups, or an arylalkyl or heteroarylalkyl group with 5 to 60 aromatic ring atoms and 1 to 10 carbon atom