Patent Application
20250185505
The present invention relates to nitrogen-containing heterocycles for use in electronic devices, especially in organic electroluminescent devices, and to electronic devices, especially organic electroluminescent devices comprising these heterocyclic compounds.
Emitting materials used in organic electroluminescent devices are frequently phosphorescent organometallic complexes or fluorescent compounds. There is generally still a need for improvement in electroluminescent devices.
US 2010/0051928, WO 2010/104047 A1, WO 2017/175690, WO 2019/132506 A1, WO 2019/111971 A1 and WO 2020/064666 A1 disclose polycyclic compounds that can be used in organic electroluminescent devices. There is no disclosure of compounds according to the present invention.
Compounds described as preferred in WO 2019/111971 A1 are in particular those substituted by a diarylamino group at positions R5 and R14 in formulae (3-11) and having no further substituents on the particular aromatic group to which the diarylamino group binds (cf. WO 2019/111971 A1, formula (3-13)).
Moreover, document CN 109761981 discloses compounds having anthracene groups that can be used as matrix material. No use of this compound as emitter is described, nor is it appropriate. Similar compounds are additionally described in John B. Henry et al., J. Phys. Chem. A 2011, 115, 5435-5442.
In general terms, there is still a need for improvement in these heterocyclic compounds, for example for use as emitters, especially as fluorescent emitters, particularly in relation to lifetime and color purity, but also in relation to the efficiency and operating voltage of the device.
It is therefore an object of the present invention to provide compounds which are suitable for use in an organic electronic device, especially in an organic electroluminescent device, and which lead to good device properties when used in this device, and to provide the corresponding electronic device.
More particularly, the object addressed by the present invention is that of providing compounds which lead to a high lifetime, good efficiency and low operating voltage.
In addition, the compounds should have excellent processability, and the compounds should especially show good solubility.
A further object of the present invention can be considered that of providing compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, especially as emitter. A particular problem addressed by the present invention is that of providing emitters suitable for red, green or blue electroluminescent devices, preferably for blue electroluminescent devices.
In addition, the compounds, especially when they are used as emitters in organic electroluminescent devices, should lead to devices having excellent color purity.
A further object can be considered that of providing electronic devices having excellent performance very inexpensively and in constant quality.
Furthermore, it should be possible to use or adapt the electronic devices for many purposes. More particularly, the performance of the electronic devices should be maintained over a broad temperature range.
It has been found that, surprisingly, this object is achieved by particular compounds described in detail below that are of very good suitability for use in preferably electroluminescent devices and lead to organic electroluminescent devices that show very good properties, especially in relation to lifetime, color purity, efficiency and operating voltage. The present invention therefore provides these compounds and electronic devices, especially organic electroluminescent devices, comprising such compounds.
The present invention provides a compound comprising at least one structure of the formula (I), preferably a compound of the formula (I):
where A is the same or different at each instance and is a substructure of the formula (A1) or (A2), preferably of the formula (A1):
to which two substructures B are fused, and the symbols o and * represent the two fusion sites of the respective substructure B, where one substructure B is fused to A via the positions labeled o and one substructure B is fused to A via the positions labeled *, and B is the same or different at each instance and is a substructure of the formula (B)
where the dotted bonds represent the fusion sites of the substructure B to A,
the ring Cb is the same or different at each instance and is a fused aliphatic or heteroaliphatic ring which has 5 to 60 ring atoms and may be substituted by one or more R radicals, preferably an aliphatic or heteroaliphatic ring which has 5 to 20, more preferably 5 to 18, most preferably 5 to 12, ring atoms and may be substituted by one or more R radicals,
and the further symbols are as follows:
In a preferred configuration, the compounds of the invention may comprise a structure of the formulae (1-1) and/or (I-2); more preferably, the compounds of the invention may be selected from the compounds of the formulae (1-1) and/or (1-2):
where the symbols Cb, W1, W2, Z, X, Xa, Xb and Xc have the definitions given above, especially for formula (I), where preference is given to structures of the formula (1-1).
It may preferably be the case that at least one, preferably at least two, of the R, Ra, Rb, Rc, Rd radicals are not H, preferably not H, D, OH, NO2, F, CI, Br, I. Accordingly, the R radical, which is preferably adjacent to an Xb or Rb group, is preferably selected from CN, N(Ar)2, N(Rd)2, C(═O)N(Ar)2, C(═O)N(Rd)2, C(Ar)3, C(Rd)3, Si(Ar)3, Si(Rd)3, B(Ar)2, B(Rd)2, C(═O)Ar, C(═O)Rd, P(═O)(Ar)2, P(═O)(Rd)2, P(Ar)2, P(Rd)2, S(═O)Ar, S(═O)Rd, S(═O)2Ar, S(═O)2Rd, OSO2Ar, OSO2Rd, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted in each case by one or more Rd radicals, where one or more nonadjacent CH2 groups may be replaced by RdC═CRd, C═C, Si(Rd)2, C═O, C═S, C═Se, C═NRd, —C(═O)O—, —C(═O)NRd—, NRd, P(═O)(Rd), —O—, —S—, SO or SO2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more Rd radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more Rd radicals, or an arylthio or heteroarylthio group which has 5 to 60 aromatic ring atoms and may be substituted by one or more Rd radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group which has 5 to 60 aromatic ring atoms and may be substituted by one or more Rd radicals, or an arylalkyl or heteroarylalkyl group which has 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl radical and may be substituted by one or more Rd radicals; at the same time, an R radical may form a ring system with a further group, preferably R or Rb; and/or at least one of the Ra, Rb, Rc, Rd radicals is preferably the same or different at each instance and is selected from CN, N(Ar′)2, N(R1)2, C(═O)N(Ar′)2, C(═O)N(R1)2, C(Ar′)3, C(R1)3, Si(Ar′)3, Si(R1)3, B(Ar′)2, B(R1)2, C(═O)Ar′, C(═O)R1, P(═O)(Ar′)2, P(═O)(R1)2, P(Ar′)2, P(R1)2, S(═O)Ar′, S(═O)R1, S(═O)2Ar′, S(═O)2R1, OSO2Ar′, OSO2R1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted in each case by one or more R1 radicals, where one or more nonadjacent CH2 groups may be replaced by R1C═CR1, C═C, Si(R1)2, C═O, C═S, C═Se, C═NR1, —C(═O)O—, —C(═O)NR1—, NR1, P(═O)(R1), —O—, —S—, SO or SO2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R1 radicals; at the same time, two Ra, Rb, Rc, Rd radicals may also form a ring system together or with a further group. In this context, N(Ar)2 and N(Rd)2 radicals are less preferred compared to the other groups mentioned.
An aryl group in the context of this invention contains 6 to 40 carbon atoms; a heteroaryl group in the context of this invention contains 2 to 40 carbon atoms and at least one heteroatom, with the proviso that the sum total of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aryl group or heteroaryl group is understood here to mean either a simple aromatic cycle, i.e. benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a fused (annelated) aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatics joined to one another by a single bond, for example biphenyl, by contrast, are not referred to as an aryl or heteroaryl group but as an aromatic ring system.
An electron-deficient heteroaryl group in the context of the present invention is a heteroaryl group having at least one heteroaromatic six-membered ring having at least one nitrogen atom. Further aromatic or heteroaromatic five-membered or six-membered rings may be fused onto this six-membered ring. Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline or quinoxaline.
An aromatic ring system in the context of this invention contains 6 to 60 carbon atoms in the ring system, preferably 6 to 40 carbon atoms in the ring system. A heteroaromatic ring system in the context of this invention contains 2 to 60 carbon atoms, preferably 3 to 40 carbon atoms, and at least one heteroatom in the ring system, with the proviso that the sum total of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the context of this invention shall be understood to mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which it is also possible for two or more aryl or heteroaryl groups to be joined by a non-aromatic unit, for example a carbon, nitrogen or oxygen atom. For example, systems such as fluorene, 9,9′-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers, stilbene, etc. shall also be regarded as aromatic ring systems in the context of this invention, and likewise systems in which two or more aryl groups are joined, for example, by a short alkyl group. Preferably, the aromatic ring system is selected from fluorene, 9,9′-spirobifluorene, 9,9-diarylamine or groups in which two or more aryl and/or heteroaryl groups are joined to one another by single bonds.
In the context of the present invention, an aliphatic hydrocarbyl radical or an alkyl group or an alkenyl or alkynyl group which may contain 1 to 20 carbon atoms and in which individual hydrogen atoms or CH2 groups may also be substituted by the abovementioned groups is preferably understood to mean the methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl radicals. An alkoxy group having 1 to 40 carbon atoms is preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. A thioalkyl group having 1 to 40 carbon atoms is understood to mean especially methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, alkyl, alkoxy or thioalkyl groups according to the present invention may be straight-chain, branched or cyclic, where one or more nonadjacent CH2 groups may be replaced by the abovementioned groups; in addition, it is also possible for one or more hydrogen atoms to be replaced by D, F, Cl, Br, I, CN or NO2, preferably F, CI or CN, further preferably F or CN, especially preferably CN.
An aromatic or heteroaromatic ring system which has 5-60 or 5-40 aromatic ring atoms and may also be substituted in each case by the abovementioned radicals and which may be joined to the aromatic or heteroaromatic system via any desired positions is understood to mean especially groups derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, truxene, isotruxene, spirotruxene, spiroisotruxene, 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, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubine, 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, or groups derived from combinations of these systems.
The wording that two or more radicals together may form a ring, in the context of the present description, should be understood to mean, inter alia, that the two radicals are joined to one another by a chemical bond with formal elimination of two hydrogen atoms. This is illustrated by the following scheme:
In addition, however, the abovementioned wording shall also be understood to mean that, if one of the two radicals is hydrogen, the second radical binds to the position to which the hydrogen atom was bonded, forming a ring. This will be illustrated by the following scheme:
It may preferably the case that at least one of the R, Rd radicals is/are not H; preferably, at least one of the R, Rd radicals is/are not H, D, F, Cl, Br, I.
It may preferably be the case that at least one of the Re radicals, preferably both Rc radicals, is/are H or D.
In a preferred configuration, it may be the case that one R radical, preferably the R radical adjacent to an Xb group or an Rb radical, is an aromatic or heteroaromatic ring system which has 5 to 13 aromatic ring atoms and may be substituted by one or more Rd radicals.
In a further-preferred configuration, it may be the case that a compound of the invention comprises at least one substructure of the formulae (B1-1) to (B1-30):
where the symbols Cb, W1, W2, Z, R, Rb, Rc and Rd have the definitions given above, especially for formula (I), the dotted bonds represent the fusion sites of the substructure to A, and the further symbols and indices used are as follows:
Preference is given here to structures of the formulae (B1-1) to (B1-18), particular preference to structures of the formulae (B1-1) and (B1-3), and special preference to structures of the formulae (B1-2) and (B1-3).
In a preferred configuration, the compounds of the invention may comprise a structure of the formulae (II-1) to (II-15); more preferably, the compounds of the invention may be selected from the compounds of the formulae (II-1) to (II-15):
where the symbols Cb, W1, W2, Z, R, Ra, Rb, Rc and Rd have the definitions given above, especially for formula (I), the symbol Y1 has the definition given above, especially for formulae (B1-1) to (B1-30), and the further indices used are as follows:
Preference is given here to structures/compounds of the formulae (II-1) and (II-2), and particular preference to structures/compounds of the formula (II-1).
It may further be the case that the fused ring Cb is selected from a structure of the formulae (BCY-1) to (BCY-10):
where R has the definition given above, especially for formula (I), the dotted bonds represent the bonding sites of the fused ring to the further groups, and in addition:
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.
In a preferred embodiment of the invention, R3 is not H and/or D.
When adjacent radicals in the structures of the invention form an aliphatic ring system, it is preferable when the latter does not have any acidic benzylic protons. Benzylic protons are understood to mean protons which bind to an alkyl carbon atom bonded directly to an aryl or heteroaryl group. This can be achieved in that the carbon atoms in the aliphatic ring system which bind directly to an aryl or heteroaryl group are fully substituted and do not contain any bonded hydrogen atoms. Thus, the absence of acidic benzylic protons in the formulae (BCy-1) to (BCy-3) is achieved in that Z1 and Z3, when they are C(R3)2, are defined such that R3 is not hydrogen. This can additionally also be achieved in that the carbon atoms in the aliphatic ring system which bind directly to an aryl or heteroaryl group are the bridgeheads in a bi- or polycyclic structure. The protons bonded to bridgehead carbon atoms, because of the spatial structure of the bi- or polycycle, are significantly less acidic than benzylic protons on carbon atoms which are not bonded within a bi- or polycyclic structure, and are regarded as non-acidic protons in the context of the present invention. Thus, the absence of acidic benzylic protons in formulae (BCy-4) to (BCy-10) is achieved in that this is a bicyclic structure, as a result of which R1, when it is H, is much less acidic than benzylic protons since the corresponding anion of the bicyclic structure is not mesomerically stabilized. Even when R1 in formulae (BCy-4) to (BCy-10) is H, this is therefore a non-acidic proton in the context of the present application.
It may preferably be the case that, especially in formulae (BCy-1) to (BCy-3):
It may preferably be the case that, especially in formulae (BCy-1) to (BCy-3):
In a preferred embodiment of the structure of the formulae (BCy-1) to (BCy-10), not more than one of the Z1, Z2 and Z3 groups is a heteroatom, especially O or NR, and the other groups are C(R3)2 or C(R)2, or Z1 and Z3 are the same or different at each instance and are O and Z2 is C(R)2. In a particularly preferred embodiment of the invention, Z1 and Z3 are the same or different at each instance and are C(R3)2, and Z2 is C(R)2 and more preferably C(R3)2 or CH2.
In a preferred embodiment of the invention, the R radical bonded to the bridgehead atom, preferably to the bridgehead atom in formulae (BCy-4) to (BCy-10), is the same or different at each instance and is selected from the group consisting of H, D, F, a straight-chain alkyl group which has 1 to 10 carbon atoms and may be substituted by one or more R1 radicals, but is preferably unsubstituted, a branched or cyclic alkyl group which has 3 to 10 carbon atoms and may be substituted by one or more R1 radicals, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system which has 5 to 12 aromatic ring atoms and may be substituted in each case by one or more R1 radicals. More preferably, the R radical bonded to the bridgehead atom in formula (BCy-4) is the same or different at each instance and is selected from the group consisting of H, F, a straight-chain alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 or 4 carbon atoms and a phenyl group which may be substituted by an alkyl group having 1 to 4 carbon atoms, but is preferably unsubstituted. Most preferably, the R radical is the same or different at each instance and is selected from the group consisting of H, methyl and tert-butyl.
In a preferred configuration of the present invention, it may be the case that the fused ring Cb is selected from a structure of the formulae (BRA-1) to (BRA-12):
where R has the definition given above, especially for formula (I), the dotted bonds represent the sites of attachment of the fused ring to the further groups and the further symbols and indices are defined as follows:
Preference is given here to structures of the formulae BRA-1 to RBA-4, and particular preference to structures of the formulae BRA-3 and BRA-4.
It may more preferably be the case that the fused ring Cb is selected from a structure of the formulae (BRA-1a) to (BRA-3f):
where the dotted bonds represent the sites of attachment of the fused ring to the further groups, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the symbols R, Rd, Rf and the indices s, t and v have the definitions set out above, especially for formula (I) and/or formulae (BRA-1) to (BRA-12).
Preference is given here to structures of the formula BRA-3f.
In a preferred configuration, it may be the case that the ring Cb detailed above and hereinafter is substituted by substituents Rd rather than R. In this preferred configuration, for example, the substituents R and Rd of the W1, W2, Z1 to Z3, G, Y2, R3 and Rf groups detailed above and hereinafter should be replaced by Rd and R1 respectively. This is especially true of the formulae (BCy-1) to (BCy-10), (BRA-1) to (BRA-12) and (BRA-1a) to (BRA-3f), in which, for example, the substituents R and Rd should be replaced by Rd and R1 respectively.
In a further-preferred embodiment, it may be the case that the ring Cb detailed above and hereinafter is substituted by substituents R1 rather than R. In this preferred configuration, for example, the substituents R and Rd of the W1, W2, Z1 to Z3, G, Y2, R3 and Rf groups detailed above and hereinafter should be replaced by R1 and R2 respectively, where these definitions are detailed by way of example for the Z5 to Z7, G1, Y4 and Rg groups detailed hereinafter and are correspondingly applicable. This is especially true of the formulae (BCy-1) to (BCy-10), (BRA-1) to (BRA-12) and (BRA-1a) to (BRA-3f), in which, for example, the substituents R and Rd should be replaced by R1 and R2 respectively.
The ring Cb comprises W1, W2 groups, where the effect of these groups is that aromatic or heteroaromatic substituents R that may originate from these groups cannot form through-conjugation with the base skeleton of the substructure B, especially with the ring having the Z or Xc group.
In a preferred configuration of the present invention, it may be the case that at least two R, Ra, Rb, Rc, Rd radicals together with the further groups to which the two R, Ra, Rb, Rc, Rd radicals bind form a fused ring, where the two R, Ra, Rb, Rc, Rd radicals form at least one structure of the following formulae (Cy-1) to (Cy-10):
where R1 has the definition given above, especially for formula (I), the dotted bonds represent the sites of attachment to the atoms of the groups to which the two R, Ra, Rb, Rc, Rd radicals bind, and in addition:
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.
In a preferred embodiment of the invention, R4 is not H and/or D.
The absence of acidic benzylic protons in the formulae (Cy-1) to (Cy-3) is preferably achieved in that Z5 and Z7, when they are C(R4)2, are defined such that R4 is not hydrogen. This can additionally also be achieved in that the carbon atoms in the aliphatic ring system which bind directly to an aryl or heteroaryl group are the bridgeheads in a bi- or polycyclic structure. The protons bonded to bridgehead carbon atoms, because of the spatial structure of the bi- or polycycle, are significantly less acidic than benzylic protons on carbon atoms which are not bonded within a bi- or polycyclic structure, and are regarded as non-acidic protons in the context of the present invention. Thus, the absence of acidic benzylic protons in formulae (Cy-4) to (Cy-10) is preferably achieved in that this is a bicyclic structure, as a result of which R1, when it is H, is much less acidic than benzylic protons since the corresponding anion of the bicyclic structure is not mesomerically stabilized. Even when R1 in formulae (Cy-4) to (Cy-10) is H, this is therefore a non-acidic proton in the context of the present application.
It may preferably be the case that, especially in formulae (Cy-1) to (Cy-3):
It may preferably be the case that, especially in formulae (Cy-1) to (Cy-3):
In a preferred embodiment of the structure of the formulae (Cy-1) to (Cy-10), not more than one of the Z5, Z6 and Z7 groups is a heteroatom, especially O or NR4, or O or NR1, and the other groups are C(R4)2 or C(R1)2, or Z5 and Z7 are the same or different at each instance and are O or NR4, and Z6 is C(R1)2. In a particularly preferred embodiment of the invention, Z5 and Z7 are the same or different at each instance and are C(R4)2, and Z6 is C(R1)2 and more preferably C(R4)2 or CH2.
In a preferred embodiment of the invention, the R1 radical bonded to the bridgehead atom, preferably to the bridgehead atom in formulae (Cy-4) to (Cy-10), is the same or different at each instance and is selected from the group consisting of H, D, F, a straight-chain alkyl group which has 1 to 10 carbon atoms and may be substituted by one or more R2 radicals, but is preferably unsubstituted, a branched or cyclic alkyl group which has 3 to 10 carbon atoms and may be substituted by one or more R2 radicals, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system which has 5 to 12 aromatic ring atoms and may be substituted in each case by one or more R2 radicals. More preferably, the R1 radical bonded to the bridgehead atom in formula (CY-4) is the same or different at each instance and is selected from the group consisting of H, F, a straight-chain alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 or 4 carbon atoms and a phenyl group which may be substituted by an alkyl group having 1 to 4 carbon atoms, but is preferably unsubstituted. Most preferably, the R1 radical is the same or different at each instance and is selected from the group consisting of H, methyl and tert-butyl.
In a preferred development of the present invention, it may be the case that at least two R, Ra, Rb, Rc, Rd radicals together with the further groups to which the two R, Ra, Rb, Rc, Rd radicals bind form a fused ring, where the two R, Ra, Rb, Rc, Rd radicals form at least one structure of the formulae (RA-1) to (RA-13):
where R1 has the definition set out above, the dotted bonds represent the sites of attachment to the atoms of the groups to which the two R, Ra, Rb, Rc, Rd radicals bind, and the further symbols have the following definition:
Preference is given here to structures of the formulae RA-1, RA-3, RA-4 and RA-5, and particular preference to structures of the formulae RA-4 and RA-5.
In a preferred embodiment of the invention, at least two R, Ra, Rb, Rc, Rd radicals together with the further groups to which the two R, Ra, Rb, Rc, Rd radicals bind form a fused ring, where the two R, Ra, Rb, Rc, Rd radicals form structures of the formulae (RA-1a) to (RA-4f):
where the dotted bonds represent the sites of attachment via which the two R, R°, RO, R°, Rd radicals bind, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the symbols R1, R2, R° and indices s and t have the definition given above, especially for formula (I) and/or formulae (RA-1) to (RA-13).
Preference is given here to structures of the formula RA-4f.
It may further be the case that one Ra radical and one Rd radical form structures of the formulae (Cy-1) to (Cy-10), (RA-1) to (RA-13) and/or (RA-1a) to (RA-4f) and form a fused ring, where the Rb radical and the Rd radical are preferably adjacent.
It may additionally be the case that two Rd radicals form the structures of the formulae (Cy-1) to (Cy-10), (RA-1) to (RA-13) and/or (RA-1a) to (RA-4f) and form a fused ring, where the Rd radicals are preferably adjacent. In addition, the two Rd radicals may also come from different rings.
In a further configuration, one Rb radical together with one R or Rd radical form the structures of the formulae (Cy-1) to (Cy-10), (RA-1) to (RA-13) and/or (RA-1a) to (RA-4f) and form a fused ring.
In a further-preferred configuration, at least two R, Ra, Rb, Rc, Rd radicals, preferably at least two R, Rb, Rd radicals, together with the further groups to which the two R, Ra, Rb, Rc, Rd radicals or the two R, Rb, Rd radicals bind form a fused ring, where the two R, Ra, Rb, Rc, Rd radicals, preferably the two R, Rb, Rd radicals, form structures of the formula (RB):
where R1 has the definition given above, especially for formula (I), the dotted bonds represent the bonding sites via which the two R, Ra, Rb, Rc, Rd radicals or the two R, Rb, Rd radicals bind, the index m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y5 is C(R1)2, NR1, NAr′, BR1, BAr′, O or S, preferably C(R1)2, NAr′ or O, more preferably C(R1)2 or O, where Ar′ has the definition given above, especially for formula (I).
It may be the case here that one Rb radical together with one R or Rd radical form the structures of the formula (RB) and form a fused ring. It may further be the case that two Rd radicals form the structures of the formula (RB) and form a fused ring, where the Rd radicals are preferably adjacent. It may further be the case that one Rb radical and one Rd radical form the structures of the formula (RB) and form a fused ring, where the Rb radicals and Rd radical are preferably adjacent.
More particularly, it may be the case that, in preferred structures/compounds, the sum total of the indices r, s, t, v, m and n is preferably 0, 1, 2 or 3, more preferably 1 or 2.
More preferably, the compounds include at least one structure of the formulae (III-1) to (III-8); more preferably, the compounds are selected from compounds of the formulae (III-1) to (III-8), where the compounds have at least one fused ring:
where the symbols Cb, W1, W2, Z, Ra, Rb, Re and Rd have the definitions given above, especially for formula (I), the symbol o represents the fusion sites of the at least one fused ring, and the further indices are defined as follows:
It may preferably be the case that the compounds have at least two fused rings, where at least one fused ring is formed by structures of the formulae (RA-1) to (RA-13) and/or (RA-1a) to (RA-4f) and a further ring by structures of the formulae (RA-1) to (RA-13), (RA-1a) to (RA-4f) or (RB).
More preferably, the compounds include at least one structure of the formulae (IV-1) to (IV-3); more preferably, the compounds are selected from compounds of the formulae (IV-1) to (IV-3), where the compounds have at least two fused rings:
where the symbols Cb, W1, W2, Z, Ra, Rb and Rc have the definitions given above, especially for formula (I), the symbol o represents the fusion sites of the at least two fused rings.
Preferably, at least one of the fused rings, more preferably both fused rings, especially in formulae (IV-1) to (IV-3), is/are formed by at least two R, Ra, Rb, Rc, Rd radicals and the further groups to which the two R, Ra, Rb, Rc, Rd radicals bind, where the at least two R, Ra, Rb, Rc, Rd radicals form structures of the formulae (RA-1) to (RA-12) and/or of the formula (RB), preferably structures of the formulae (RA-1) to (RA-12).
It may additionally be the case that the substituents R, Ra, Rb, Rc, Rd, Rf, R9, R1, R2, R3 and R4 according to the above formulae do not form a fused aromatic or heteroaromatic ring system with the ring atoms of the ring system to which the substituents R, Ra, Rb, Rc, Rd, Rf, Rf, R1, R2, R3 and R4 bind. This includes the formation of a fused aromatic or heteroaromatic ring system with possible substituents Rd, R1 and R2 that may be bonded to the substituents R, Ra, Rb, Rc, Rd, Rf, Rf, R1, R3 and R4.
When the compound of the invention is substituted by aromatic or heteroaromatic R, Ra, Rb, Rc, Rd, Rf, R9, R1, R2, R3 or R4 groups, it is preferable when these do not have any aryl or heteroaryl groups having more than two aromatic six-membered rings fused directly to one another. More preferably, the substituents do not have any aryl or heteroaryl groups having six-membered rings fused directly to one another at all. The reason for this preference is the low triplet energy of such structures. Fused aryl groups which have more than two aromatic six-membered rings fused directly to one another but are nevertheless also suitable in accordance with the invention are phenanthrene and triphenylene, since these also have a high triplet level.
It may therefore preferably be the case that the R radical does not have any through-conjugated anthracene group; preferably, none of the R, Ra, Rb, Rc, Rd, Rf, Rf, R1, R2, R3 and R4 radicals comprises a through-conjugated anthracene group.
Through-conjugation of the anthracene group is formed if direct bonds are formed between the anthracene group, the base skeleton of the invention shown in formula (I), and an optional aromatic or heteroaromatic connecting group. A further bond between the aforementioned conjugated groups, for example via a sulfur, nitrogen or oxygen atom or a carbonyl group, is not detrimental to conjugation. In the case of a fluorene system, the two aromatic rings are bonded directly, where the sp3-hybridized carbon atom in position 9 does prevent fusion of these rings, but conjugation is possible, since this sp3-hybridized carbon atom in position 9 does not necessarily lie between the groups connected via a connecting group. In contrast, in the case of a spirobifluorene structure, through-conjugation can be formed if the bond between the groups connected via the spirobifluorene group is via the same phenyl group in the spirobifluorene structure or via phenyl groups in the spirobifluorene structure that are bonded directly to one another and are in one plane. If the bond between the groups connected via a spirobifluorene group is via different phenyl groups in the second spirobifluorene structure bonded via the sp3-hybridized carbon atom in position 9, the conjugation is interrupted.
It may also more preferably be the case that the R radical does not comprise any anthracene group; preferably, none of the R, Ra, Rb, Rc and Rd radicals, more preferably none of the R, Ra, Rb, Rc, Rd, Rf, Rf, R1, R2, R3 and R4 radicals, comprises an anthracene group.
Very especially preferably, it may further be the case that the R radical does not comprise any aromatic or heteroaromatic ring system having three aromatic 6-membered rings fused in a linear manner, where preferably none of the R, Ra, Rb, Re and Rd radicals, more preferably none of the R, Ra, Rb, Rc, Rd, Rf, R9, R1, R2, R3 and R4 radicals, comprises an aromatic or heteroaromatic ring system having three aromatic 6-membered rings fused in a linear manner.
It may also be the case that none of the R, Ra, Rb, Re and Rd radicals, more preferably none of the R, Ra, Rb, Rc, Rd, Rf, R9, R1, R2, R3 and R4 radicals, comprises or forms a fluorenone group. This includes substituents that bind to the R, Ra, Rb, Rc, Rd radicals, etc. A fluorenone comprises a 5-membered ring with a CO group to which two aromatic 6-membered rings are fused.
When two radicals that may especially be selected from R, Ra, Rb, Rc, Rd, Rf, R9, R1, R2, R3 and R4 form a ring system with one another, this ring system may be mono- or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. In this case, the radicals which together form a ring system may be adjacent, meaning that these radicals are bonded to the same carbon atom or to carbon atoms directly bonded to one another, or they may be further removed from one another. In addition, the ring systems endowed with the substituents R, Ra, Rb, Rc, Rd, Rf, R9, R1, R2, R3 and/or R4 may also be joined to one another via a bond, such that this can bring about a ring closure. In this case, each of the corresponding bonding sites has preferably been endowed with a substituent R, Ra, Rb, Rc, Rd, Rf, Rg, R1, R2, R3 and/or R4.
It may preferably be the case that the structure/compound is symmetric in relation to the substructures B.
What is meant more particularly by “symmetric in relation to the substructures B” is that the corresponding R, Ra, Rb, Rc, Rd, Rf, Rf, R1, R2, R3 and R4 radicals are the same and do not differ.
Structures/compounds in which the substructures B are symmetric are notable for surprisingly high color purity which is reflected particularly in a narrow emission spectrum.
In a further configuration, the structure/compound may be asymmetric in relation to the compound in relation to the substructures B.
In addition, it may be the case that an R radical, preferably the R radical adjacent to an Xb group or an Rb radical, is at least one group selected from C(Ar)3, C(Rd)3, Si(Ar)3, Si(Rd)3, B(Rd)2, preferably selected from C(Ar)3, C(Rd)3, Si(Ar)3, Si(Rd)3, and more preferably represents, or forms together with an Rb radical, a fluorene group that may be substituted by one or more Rd radicals.
It may also be the case that the Rb and/or Rd radical comprises, represents, or forms together with an Rb or Rd radical, at least one group selected from C(Ar′)3, C(R1)3, Si(Ar′)3, Si(R1)3, B(R1)2, preferably selected from C(Ar′)3, C(R1)3, Si(Ar′)3, Si(R1)3, preferably a fluorene group that may be substituted by one or more R1 radicals.
Structures/compounds having one of the aforementioned groups selected from C(Ar)3, C(Rd)3, Si(Ar)3, Si(Rd)3, B(Rd)2 or C(Ar′)3, C(R1)3, Si(Ar′)3, Si(R1)3, B(R1)2, more preferably a fluorene group, are notable for surprisingly high efficiency.
In a preferred configuration, a compound of the invention can be represented by at least one of the structures of formulae (I), (I-1) and/or (I-2). Preferably, compounds of the invention, preferably comprising structures of formulae (I), (1-1) and/or (1-2), have a molecular weight of not more than 5000 g/mol, preferably not more than 4000 g/mol, particularly preferably not more than 3000 g/mol, especially preferably not more than 2000 g/mol and most preferably not more than 1200 g/mol.
In addition, it is a feature of preferred compounds of the invention that they are sublimable. These compounds generally have a molar mass of less than about 1200 g/mol.
Preferred aromatic or heteroaromatic ring systems Ar, R, Ra, Rb, Rc, Rd, Rf, R9, R3, R4 and/or Ar′ are selected from phenyl, biphenyl, especially ortho-, meta- or para-biphenyl, terphenyl, especially ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, especially ortho-, meta- or para-quaterphenyl or branched quaterphenyl, fluorene which may be joined via the 1, 2, 3 or 4 position, spirobifluorene which may be joined via the 1, 2, 3 or 4 position, naphthalene, especially 1- or 2-bonded naphthalene, indole, benzofuran, benzothiophene, carbazole which may be joined via the 1, 2, 3, 4 or 9 position, dibenzofuran which may be joined via the 1, 2, 3 or 4 position, dibenzothiophene which may be joined via the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which may be substituted by one or more Rd, R1 or R2 radicals.
It may preferably the case that at least one substituent R, Ra, Rb, Rc, Rd is the same or different at each instance and is selected from the group consisting of H, D, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms or an aromatic or heteroaromatic ring system selected from the groups of the following formulae Ar-1 to Ar-75; preferably, the substituents R, Ra, Rb, Rc, Rd either form a fused ring, preferably according to the structures of the formulae (RA-1) to (RA-13) or (RB), or the substituent R, Ra, Rb, Rc, Rd is the same or different at each instance and is selected from the group consisting of H, D or an aromatic or heteroaromatic ring system selected from the groups of the following formulae Ar-1 to Ar-75, and/or the Ar′ group is the same or different at each instance and is selected from the groups of the following formulae Ar-1 to Ar-75:
where R1 has the definitions given above, the dotted bond represents the site of attachment to the corresponding group and in addition:
In this case, preference is given to the structures of the formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (Ar-45), (Ar-46), (Ar-69), (Ar-70), (Ar-75), and particular preference to structures of the formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16).
When the abovementioned groups for Ar have two or more A groups, possible options for these include all combinations from the definition of A. Preferred embodiments in that case are those in which one A group is NR1 and the other A group is C(R1)2 or in which both A groups are NR1 or in which both A groups are O.
When A is NR1, the substituent R1 bonded to the nitrogen atom is preferably an aromatic or heteroaromatic ring system which has 5 to 24 aromatic ring atoms and may also be substituted by one or more R2 radicals. In a particularly preferred embodiment, this R1 substituent is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 24 aromatic ring atoms, especially 6 to 18 aromatic ring atoms, which does not have any fused aryl groups and which does not have any fused heteroaryl groups in which two or more aromatic or heteroaromatic 6-membered ring groups are fused directly to one another, and which may also be substituted in each case by one or more R2 radicals. Preference is given to phenyl, biphenyl, terphenyl and quaterphenyl having bonding patterns as listed above for Ar-1 to Ar-11, where these structures, rather than by R1, may be substituted by one or more R2 radicals, but are preferably unsubstituted. Preference is further given to triazine, pyrimidine and quinazoline as listed above for Ar-47 to Ar-50, Ar-57 and Ar-58, where these structures, rather than by R1, may be substituted by one or more R2 radicals.
There follows a description of preferred substituents R, Ra, Rb, Rc, Rd, Rf and Rg.
In a preferred embodiment of the invention, R, Ra, Rb, Rc, Rd are the same or different at each instance and are selected from the group consisting of H, D, F, CN, NO2, Si(R1)3, B(OR1)2, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group may be substituted in each case by one or more R1 radicals, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and may be substituted in each case by one or more R1 radicals.
In a further-preferred embodiment of the invention, substituent R, Ra, Rb, Rc, Rd is the same or different at each instance and is selected from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group may be substituted in each case by one or more R1 radicals, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and may be substituted in each case by one or more R1 radicals.
It may further be the case that at least one substituent R, Ra, Rb, Rc, Rd is the same or different at each instance and is selected from the group consisting of H, D, an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more R1 radicals. In a further-preferred embodiment of the invention, the substituents R, Ra, Rb, Rc, Rd either form a ring according to the structures of the formulae (RA-1) to (RA-13), (RA-1a) to (RA-4f) or (RB), or R, Ra, Rb, Rc, Rd is the same or different at each instance and is selected from the group consisting of H, D, an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more R1 radicals. More preferably, substituent R, Ra, Rb, Rc, Rd is the same or different at each instance and is selected from the group consisting of H or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, more preferably having 6 to 13 aromatic ring atoms, each of which may be substituted by one or more R1 radicals.
In a preferred embodiment of the invention, Rf or R° is the same or different at each instance and is selected from the group consisting of a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, where the alkyl group may be substituted in each case by one or more Rd or R2 radicals, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, and may be substituted in each case by one or more Rd or R2 radicals.
In a further-preferred embodiment of the invention, Rf or Rg is the same or different at each instance and are selected from the group consisting of a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the alkyl group may be substituted in each case by one or more Rd or R2 radicals, an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and may be substituted by one or more Rd or R2 radicals.
More preferably, the R radical, which is preferably adjacent to an Xb or Rb group, or Rd, is the same or different at each instance and is selected from the group consisting of a straight-chain alkyl group having 1 to 5 carbon atoms or a branched or cyclic alkyl group having 3 to 5 carbon atoms, where the alkyl group may be substituted in each case by one or more Rd or R1 radicals, or an aromatic or heteroaromatic ring system which has 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, and may be substituted in each case by one or more Rd or R1 radicals.
In a preferred embodiment of the invention, Rf or Rg is the same or different at each instance and is selected from the group consisting of a straight-chain alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms, where the alkyl group may be substituted in each case by one or more Rd or R2 radicals, or an aromatic or heteroaromatic ring system which has 6 to 24 aromatic ring atoms and may be substituted in each case by one or more Rd or R2 radicals; at the same time, two Rf or Rg radicals together may also form a ring system. More preferably, Rf or Rg is the same or different at each instance and is selected from the group consisting of a straight-chain alkyl group having 1, 2, 3 or 4 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms, where the alkyl group may be substituted in each case by one or more Rd or R2 radicals, but is preferably unsubstituted, or an aromatic ring system which has 6 to 12 aromatic ring atoms, especially 6 aromatic ring atoms, and may be substituted in each case by one or more, preferably nonaromatic Rd or R2 radicals, but is preferably unsubstituted; at the same time, two Rf or Rg radicals together may form a ring system. Most preferably, Rf or Ro is the same or different at each instance and is selected from the group consisting of a straight-chain alkyl group having 1, 2, 3 or 4 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms. Most preferably, Rf or Ro is a methyl group or is a phenyl group, where two phenyl groups together may form a ring system, preference being given to a methyl group over a phenyl group.
Preferred aromatic or heteroaromatic ring systems represented by the substituents R, R3, Ra, Rb, Rc, Rd, Rf, Rg or Ar, Ar′ or Ar″ are selected from phenyl, biphenyl, especially ortho-, meta- or para-biphenyl, terphenyl, especially ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, especially ortho-, meta- or para-quaterphenyl or branched quaterphenyl, fluorene which may be joined via the 1, 2, 3 or 4 position, spirobifluorene which may be joined via the 1, 2, 3 or 4 position, naphthalene, especially 1- or 2-bonded naphthalene, indole, benzofuran, benzothiophene, carbazole which may be joined via the 1, 2, 3 or 4 position, dibenzofuran which may be joined via the 1, 2, 3 or 4 position, dibenzothiophene which may be joined via the 1, 2, 3 or 4 position, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which may be substituted by one or more Rd, R1 or R2 radicals. Particular preference is given to the structures Ar-1 to Ar-75 shown above, preference being given to structures of the formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (Ar-45), (Ar-46), (Ar-69), (Ar-70), (Ar-75), and particular preference to structures of the formulae (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16). With regard to the structures Ar-1 to Ar-75, it should be stated that these are shown with a substituent R1. In the case of the ring system R, R3, Rf or Ar, these substituents R1 should be replaced by Rd, and in the case of Ar″, Rg, these substituents R1 should be replaced by R2.
Further suitable R, Ra, Rb, Rc, Rd groups are groups of the formula —Ar4—N(Ar2)(Ar3) where Ar2, Ar3 and Art are the same or different at each instance and are an aromatic or heteroaromatic ring system which has 5 to 24 aromatic ring atoms and may be substituted in each case by one or more R1 radicals. The total number of aromatic ring atoms in Ar2, Ar3 and Ar4 here is not more than 60 and preferably not more than 40. However, these groups of the formula —Ar4—N(Ar2)(Ar3) are not preferred.
Ar4 and Ar2 here may also be bonded to one another and/or Ar2 and Ar3 to one another by a group selected from C(R1)2, NR1, O and S. Preferably, Ar4 and Ar2 are joined to one another and Ar2 and Ar3 to one another in the respective ortho position to the bond to the nitrogen atom. In a further embodiment of the invention, none of the Ar2, Ar3 and Art groups are bonded to one another.
Preferably, Ar4 is an aromatic or heteroaromatic ring system which has 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, and may be substituted in each case by one or more R1 radicals. More preferably, Ar4 is selected from the group consisting of ortho-, meta- or para-phenylene or ortho-, meta- or para-biphenyl, each of which may be substituted by one or more R1 radicals, but are preferably unsubstituted. Most preferably, Ar4 is an unsubstituted phenylene group.
Preferably, Ar2 and Ar3 are the same or different at each instance and are an aromatic or heteroaromatic ring system which has 6 to 24 aromatic ring atoms and may be substituted in each case by one or more R1 radicals. Particularly preferred Ar2 and Ar3 groups are the same or different at each instance and are selected from the group consisting of benzene, ortho-, meta- or para-biphenyl, ortho-, meta- or para-terphenyl or branched terphenyl, ortho-, meta- or para-quaterphenyl or branched quaterphenyl, 1-2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, indole, benzofuran, benzothiophene, 1-, 2-, 3- or 4-carbazole, 1-, 2-, 3- or 4-dibenzofuran, 1-, 2-, 3- or 4-dibenzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-, 4- or 5-pyrimidine, pyrazine, pyridazine, triazine, phenanthrene or triphenylene, each of which may be substituted by one or more R1 radicals. Most preferably, Ar2 and Ar3 are the same or different at each instance and are selected from the group consisting of benzene, biphenyl, especially ortho-, meta- or para-biphenyl, terphenyl, especially ortho-, meta- or para-terphenyl or branched terphenyl, quaterphenyl, especially ortho-, meta- or para-quaterphenyl or branched quaterphenyl, fluorene, especially 1-, 2-, 3- or 4-fluorene, or spirobifluorene, especially 1-, 2-, 3- or 4-spirobifluorene.
In a further preferred embodiment of the invention, R1 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the alkyl group may be substituted in each case by one or more R2 radicals, or an aromatic or heteroaromatic ring system which has 6 to 24 aromatic ring atoms and may be substituted in each case by one or more R2 radicals. In a particularly preferred embodiment of the invention, R1 is the same or different at each instance and is selected from the group consisting of H, a straight-chain alkyl group having 1 to 6 carbon atoms, especially having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, where the alkyl group may be substituted by one or more R2 radicals, but is preferably unsubstituted, or an aromatic or heteroaromatic ring system which has 6 to 13 aromatic ring atoms and may be substituted in each case by one or more R2 radicals, but is preferably unsubstituted.
In a further preferred embodiment of the invention, R2 is the same or different at each instance and is H, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be substituted by an alkyl group having 1 to 4 carbon atoms, but is preferably unsubstituted.
At the same time, in compounds of the invention that are processed by vacuum evaporation, the alkyl groups preferably have not more than five carbon atoms, more preferably not more than 4 carbon atoms, most preferably not more than 1 carbon atom. For compounds that are processed from solution, suitable compounds are also those substituted by alkyl groups, especially branched alkyl groups, having up to 10 carbon atoms or those substituted by oligoarylene groups, for example ortho-, meta- or para-terphenyl or branched terphenyl or quaterphenyl groups.
Furthermore, it may be the case that the compound comprises exactly two or exactly three structures of formula (I), (I-1), (1-2) and/or (II-1) to (II-15), where preferably one of the aromatic or heteroaromatic ring systems that can be represented by at least one of the R, Rb, Rd groups or to which the R, Rb, Rd groups bind is shared by the two structures.
In a preferred configuration, the compounds are selected from compounds of the formula (D-1), (D-2) and (D-3)
where the L1 group is a connecting group, preferably a bond or an aromatic or heteroaromatic ring system which has 5 to 40, preferably 5 to 30, aromatic ring atoms and may be substituted by one or more R radicals, and the further symbols used have the definitions given above, especially for formula (I).
In a further preferred embodiment of the invention, L1 is a bond or an aromatic or heteroaromatic ring system which has 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system which has 6 to 12 carbon atoms, and which may be substituted by one or more R radicals, but is preferably unsubstituted, where R may have the definition given above, especially for formula (I). More preferably, L1 is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be substituted by one or more R1 radicals, but is preferably unsubstituted, where R1 may have the definition given above, especially for formula (I).
Further preferably, the symbol L1 shown in formula (D3) inter alia is the same or different at each instance and is a bond or an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, such that an aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is bonded to the respective atom of the further group directly, i.e. via an atom of the aromatic or heteroaromatic group.
It may additionally be the case that the L1 group shown in formula (D3) comprises an aromatic ring system having not more than two fused aromatic and/or heteroaromatic 6-membered rings, preferably does not comprise any fused aromatic or heteroaromatic ring system. Accordingly, naphthyl structures are preferred over anthracene structures. In addition, fluorenyl, spirobifluorenyl, dibenzofuranyl and/or dibenzothienyl structures are preferred over naphthyl structures.
Particular preference is given to structures having no fusion, for example phenyl, biphenyl, terphenyl and/or quaterphenyl structures.
Examples of suitable aromatic or heteroaromatic ring systems L1 are selected from the group consisting of ortho-, meta- or para-phenylene, ortho-, meta- or para-biphenylene, terphenylene, especially branched terphenylene, quaterphenylene, especially branched quaterphenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothienylene and carbazolylene, each of which may be substituted by one or more R1 radicals, but are preferably unsubstituted.
The abovementioned preferred embodiments may be combined with one another as desired within the restrictions defined in claim 1. In a particularly preferred embodiment of the invention, the abovementioned preferences occur simultaneously.
In a further configuration of the present invention, preference is given to compounds comprising a structure of formula (I), preferably compounds of formula (l) in which at least one ring Cb has the following properties'
In a further configuration of the present invention, preference is given to compounds comprising a structure of formula (I), preferably compounds of formula (I), in which at least one ring Cb has the following properties:
In a further configuration of the present invention, preference is given to compounds comprising a structure of formula (II-1), preferably compounds of formula (II-1), in which the ring Cb and the radicals Ra, Rb, Rc and Rd are the same or different at each instance and have the following definitions:
In a further configuration of the present invention, preference is given to compounds comprising a structure of formula (II-2), preferably compounds of formula (II-2), where the index l is preferably in each case not more than 3, more preferably in each case 0, 1 or 2 and especially preferably in each case 0 or 1, and in which the ring Cb and the radicals Ra, Rb, Re and Rd are the same or different at each instance and have the following definitions:
In the above tables, the radicals specified in the column under the Rd group are the substituents on the phenyl ring of the base skeleton which is likewise substituted by the Rb radical mentioned (see, for example, formula (II-1)), or are the substituents on the phenyl ring that binds to the phenyl ring of the base skeleton which is likewise substituted by the Rb radical mentioned (see, for example, formula (II-2)). Most preferably, Rd is a methyl group or a phenyl group. In this case, the Rd radicals together may also form a ring system, which leads to a spiro system.
The expression “alkyl” in the above tables especially encompasses straight-chain alkyl groups or branched or cyclic alkyl groups according to the definition set out above for the respective group.
The expression “aryl, heteroaryl” in the above tables especially encompasses aryl or heteroaryl groups having 5 to 40 aromatic ring atoms according to the definition set out above for the respective group, where the aryl groups preferably have 6 to 12 and more preferably 6 ring atoms and the heteroaryl groups preferably have 5 to 13 and more preferably 5 ring atoms. More preferably, heteroaryl groups comprise one or two heteroatoms, preferably N, O or S.
The designations “BRA-1”, “BRA-2”, “BRA-3”, “BRA-3f”, “BRA-4”, “BRA-5”, “Ar-1”, “Ar-75” relate to the structural formulae shown above and hereinafter.
What is meant by ring formation with a group is that the two groups together form a phenyl ring that may in each case be substituted by R1 radicals according to the definition set out above for the respective group. Typically, this results in formation of a naphthyl group with the phenyl group which is bonded to the nitrogen atom and is substituted by the Rb and R or Rd radicals. The same applies to the further definitions of ring formation.
What is meant by the word “and”, particularly in the description of preferred Rb groups, is that the two radicals are different, where one of the Rb radicals conforms to a first definition and the second Rb radical to a second definition. What is meant by the expression “aryl, heteroaryl, and phenyl ring formation with Rd” is that one of the Rb radicals is an aryl or heteroaryl group and the second Rb radical forms a phenyl ring with Rd. If a field does not include an “and” expression, all radicals represent a corresponding group. The expression “Ar-1 to Ar-75” for the Rd group means that both Rb radicals are an aryl or heteroaryl radical according to the formulae Ar-1 to Ar-75 above or hereinafter.
The same applies to the further use of the word “and” in the above tables.
The preferences with regard to the ring Cb and the various substituents Ra, Rb, Rc and Rd that are set out in the formulae (II-1) and (II-2) are of course also correspondingly applicable to the other formulae (II-3) to (II-15) set out above.
Examples of preferred compounds according to the embodiments detailed above are the compounds shown in the following table:
Preferred embodiments of compounds of the invention are recited in detail in the examples, these compounds being usable alone or in combination with further compounds for all purposes of the invention.
Provided that the conditions specified in claim 1 are met, the abovementioned preferred embodiments can be combined with one another as desired. In a particularly preferred embodiment of the invention, the abovementioned preferred embodiments apply simultaneously.
The compounds of the invention are preparable in principle by various processes. However, the processes described hereinafter have been found to be particularly suitable.
Therefore, the present invention further provides a process for preparing the compounds of the invention, in which a base skeleton having an aromatic amino group is synthesized and at least one aromatic or heteroaromatic radical is introduced, preferably by means of a nucleophilic aromatic substitution reaction or a coupling reaction.
Suitable compounds comprising a base skeleton having an aromatic amino group are in many cases commercially available, and the starting compounds detailed in the examples are obtainable by known processes, and so reference is made thereto.
These compounds can be reacted with further compounds by known coupling reactions, the necessary conditions for this purpose being known to the person skilled in the art, and detailed specifications in the examples giving support to the person skilled in the art in conducting these reactions.
Particularly suitable and preferred coupling reactions which all lead to C—C bond formations and/or C—N bond formations are those according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA and HIYAMA. These reactions are widely known, and the examples will provide the person skilled in the art with further pointers.
The compounds of the invention can be synthesized by methods including those according to schemes 1, 2 and/or 3 below.
For example, a synthesis can be conducted in three steps, as shown in scheme 1. First of all, the bis-halogen-functionalized (Br, I) or bis-triflate-functionalized starting materials BS may be used to prepare a secondary o-chloroarylamine in a palladium/phosphine-catalyzed C—N coupling of the Hartwig-Buchwald type by reaction with a primary arylamine (stage 1). Illustrative starting materials BS are cited in the examples, to which reference is made here in a general manner. The product of the first stage can be cyclized in stage 2 in a palladium/phosphine-catalyzed C—C coupling to give the carbazole. The carbazoles thus obtained can then be reacted in an SN2Ar reaction with 1,4-dichloro-2,5-difluoroaromatics (see stage 3, scheme 1), and the coupling product can be cyclized in situ, by addition of a Pd source and a phosphine, in a palladium/phosphine-catalyzed C—C coupling to give the compounds of the invention (see stage 3, step 2). If two different carbazoles—as a mixture or by sequential addition—are used in stage 3, it is possible to obtain functionalized compounds of the invention having mixed functionalization.
Alternatively, the compounds of the invention can be prepared proceeding from the carbazoles having a substituent R′ in the o position to Z (for synthesis see Experimental) in four steps (see scheme 2).
First of all, carbazoles having a substituent R′ in the o position to N(for synthesis see Experimental) can be subjected to regioselective NBS bromination in the o position to the carbazole nitrogen atom (stage 1). The bromine function can be reacted in a palladium/phosphine-catalyzed borylation with B2Pin2 to give the B-Pin ester (stage 2). Subsequently, in a palladium/phosphine-catalyzed C—C coupling of the Suzuki type, the central ring unit is coupled (stage 3). Finally, cyclization is effected in a palladium/phosphine-catalyzed C—C coupling to give the compounds of the invention (stage 4).
Alternatively, the compounds of the invention can be prepared proceeding from the starting materials BS in three steps (see scheme 3).
First of all, the iodo- or amino-functionalized starting materials BS (for synthesis see Experimental) may be used to prepare a secondary o-bischloroarylamine in a palladium/phosphine-catalyzed C—N coupling of the Hartwig-Buchwald type by reaction with a primary o-chloroarylamine or o-chlorobromo/iodoaromatic (stage 1a or 1b). The latter can be cyclized in stage 2 in a palladium/phosphine-catalyzed C—C coupling to give the o-chlorocarbazole. The carbazole can then be cyclized in a palladium/phosphine-catalyzed C—N coupling and a subsequent C—C coupling to give the compounds of the invention (see stage 3) The C—N or C—C couplings may be conducted sequentially or in a one-pot reaction. If two different carbazoles—as a mixture or by sequential addition—are used in stage 3, it is possible to obtain functionalized compounds of the invention having mixed functionalization.
This procedure has the advantage that it is regioselective with respect to the carbazole in terms of the coupling and the cyclization on the central unit in stage 3.
The definition of the symbols used in schemes 1, 2 and 3 corresponds essentially to that which was defined for formula (I), or preferred embodiments of these structures, dispensing with numbering and complete representation of all symbols for reasons of clarity. In addition, for reasons of clarity, the use of symbols for representation of possible nitrogen atoms in the heteroaromatic rings has been dispensed with in many cases, as shown in particular in formulae (1-1) and (1-2) by the symbols X, Xa, Xb and Xc. These details should therefore be understood by way of illustration; the person skilled in the art is capable of applying the syntheses set out above and hereinafter, especially in the examples, to compounds in which one or more of the symbols X, Xa, Xb and Xc are nitrogen.
The principles of the preparation processes detailed above are known in principle from the literature for similar compounds and can be adapted easily by the person skilled in the art for the preparation of the compounds of the invention. Further information can be found in the examples.
It is possible by these methods, if necessary followed by purification, for example recrystallization or sublimation, to obtain the compounds of the invention in high purity, preferably more than 99% (determined by means of 1H NMR and/or HPLC).
The compounds of the invention may also be mixed with a polymer. It is likewise possible to incorporate these compounds covalently into a polymer. This is especially possible with compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic ester, or by reactive polymerizable groups such as olefins or oxetanes. These may find use as monomers for production of corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably effected via the halogen functionality or the boronic acid functionality or via the polymerizable group. It is additionally possible to crosslink the polymers via groups of this kind. The compounds and polymers of the invention may be used in the form of a crosslinked or uncrosslinked layer.
The invention therefore further provides oligomers, polymers or dendrimers containing one or more of the above-detailed structures of the formula (I) and preferred embodiments of this formula or compounds of the invention, wherein one or more bonds of the compounds of the invention or of the structures of the formula (I) and preferred embodiments of that formula to the polymer, oligomer or dendrimer are present. According to the linkage of the structures of the formula (I) and preferred embodiments of this formula or of the compounds, these therefore form a side chain of the oligomer or polymer or are bonded within the main chain. The polymers, oligomers or dendrimers may be conjugated, partly conjugated or nonconjugated. The oligomers or polymers may be linear, branched or dendritic. For the repeat units of the compounds of the invention in oligomers, dendrimers and polymers, the same preferences apply as described above.
For preparation of the oligomers or polymers, the monomers of the invention are homopolymerized or copolymerized with further monomers. Preference is given to copolymers wherein the units of formula (1) or the preferred embodiments recited above and hereinafter are present to an extent of 0.01 to 99.9 mol %, preferably 5 to 90 mol %, more preferably 20 to 80 mol %. Suitable and preferred comonomers which form the polymer base skeleton are chosen from fluorenes (for example according to EP 842208 or WO 2000/022026), spirobifluorenes (for example according to EP 707020, EP 894107 or WO 2006/061181), paraphenylenes (for example according to WO 92/18552), carbazoles (for example according to WO 2004/070772 or WO 2004/113468), thiophenes (for example according to EP 1028136), dihydrophenanthrenes (for example according to WO 2005/014689), cis- and trans-indenofluorenes (for example according to WO 2004/041901 or WO 2004/113412), ketones (for example according to WO 2005/040302), phenanthrenes (for example according to WO 2005/104264 or WO 2007/017066) or else a plurality of these units. The polymers, oligomers and dendrimers may contain still further units, for example hole transport units, especially those based on triarylamines, and/or electron transport units.
Additionally of particular interest are compounds of the invention which feature a high glass transition temperature. In this connection, preference is given especially to compounds of the invention comprising structures of the formula (I) or the preferred embodiments recited above and hereinafter which have a glass transition temperature of at least 70° C., more preferably of at least 110° C., even more preferably of at least 125° C. and especially preferably of at least 150° C., determined in accordance with DIN 51005 (2005-08 version).
For the processing of the compounds of the invention from a liquid phase, for example by spin-coating or by printing methods, formulations of the compounds of the invention are required. These formulations may, for example, be solutions, dispersions or emulsions. For this purpose, it may be preferable to use mixtures of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl) ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate or mixtures of these solvents.
The present invention therefore further provides a formulation or a composition comprising at least one compound of the invention and at least one further compound. The further compound may, for example, be a solvent, especially one of the abovementioned solvents or a mixture of these solvents. If the further compound comprises a solvent, this mixture is referred to herein as formulation. The further compound may alternatively be at least one further organic or inorganic compound which is likewise used in the electronic device, for example an emitter and/or a matrix material, where these compounds differ from the compounds of the invention. Suitable emitters and matrix materials are listed at the back in connection with the organic electroluminescent device. The further compound may also be polymeric.
The present invention therefore still further provides a composition comprising a compound of the invention and at least one further organofunctional material. Functional materials are generally the organic or inorganic materials introduced between the anode and cathode. Preferably, the organically functional material is selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials, hole blocker materials, wide bandgap materials and n-dopants, preferably host materials.
The present invention further provides for the use of a compound of the invention in an electronic device, especially in an organic electroluminescent device, preferably as emitter, more preferably as green, red or blue emitter, especially preferably as blue emitter. In this case, compounds of the invention preferably exhibit fluorescent properties and thus provide preferentially fluorescent emitters.
The present invention still further provides an electronic device comprising at least one compound of the invention. An electronic device in the context of the present invention is a device comprising at least one layer comprising at least one organic compound. This component may also comprise inorganic materials or else layers formed entirely from inorganic materials.
The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLEDs, SOLED, PLEDs, LECs, etc.), preferably organic light-emitting diodes (OLEDs), organic light-emitting diodes based on small molecules (sOLEDs), organic light-emitting diodes based on polymers (PLEDs), light-emitting mechanical cells (LECs), organic laser diodes (O-laser), organic plasmon-emitting devices (D. M. Koller et al., Nature Photonics 2008, 1-4), organic integrated circuits (O—ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O—SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs) and organic electrical sensors, preferably organic electroluminescent devices ( ) more preferably organic light-emitting diodes (OLEDs), organic light-emitting diodes based on small molecules (sOLEDs), organic light-emitting diodes based on polymers (PLEDs), especially phosphorescent OLEDs.
The organic electroluminescent device comprises cathode, anode and at least one emitting layer. Apart from these layers, it may also comprise further layers, for example in each case one or more hole injection layers, hole transport layers, hole blocker layers, electron transport layers, electron injection layers, exciton blocker layers, electron blocker layers and/or charge generation layers. It is likewise possible for interlayers having an exciton-blocking function, for example, to be introduced between two emitting layers. However, it should be pointed out that not necessarily every one of these layers need be present. In this case, it is possible for the organic electroluminescent device to contain an emitting layer, or for it to contain a plurality of emitting layers. If a plurality of emission layers are present, these preferably have several emission maxima between 380 nm and 750 nm overall, such that the overall result is white emission; in other words, various emitting compounds which may fluoresce or phosphoresce are used in the emitting layers. Especially preferred are systems having three emitting layers, where the three layers show blue, green and orange or red emission. The organic electroluminescent device of the invention may also be a tandem electroluminescent device, especially for white-emitting OLEDs.
The compound of the invention may be used in different layers, according to the exact structure. Preference is given to an organic electroluminescent device comprising a compound of formula (I) or the above-detailed preferred embodiments in an emitting layer as emitter, preferably red, green or blue emitter, more preferably as blue emitter.
When the compound of the invention is used as emitter in an emitting layer, preference is given to using a suitable matrix material which is known as such.
A preferred mixture of the compound of the invention and a matrix material contains between 99% and 1% by volume, preferably between 98% and 10% by volume, more preferably between 97% and 60% by volume and especially between 95% and 80% by volume of matrix material, based on the overall mixture of emitter and matrix material. Correspondingly, the mixture contains between 1% and 99% by volume, preferably between 2% and 90% by volume, more preferably between 3% and 40% by volume and especially between 5% and 20% by volume of the emitter, based on the overall mixture of emitter and matrix material.
Suitable matrix materials which can be used in combination with the inventive compounds are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, e.g. CBP(N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527, WO 2008/086851 or WO 2013/041176, indolocarbazole derivatives, for example according to WO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, for example according to WO 2010/136109, WO 2011/000455, WO 2013/041176 or WO 2013/056776, azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrix materials, for example according to WO 2007/137725, silanes, for example according to WO 2005/111172, azaboroles or boronic esters, for example according to WO 2006/117052, triazine derivatives, for example according to WO 2007/063754, WO 2008/056746, WO 2010/015306, WO 2011/057706, WO 2011/060859 or WO 2011/060877, zinc complexes, for example according to EP 652273 or WO 2009/062578, diazasilole or tetraazasilole derivatives, for example according to WO 2010/054729, diazaphosphole derivatives, for example according to WO 2010/054730, bridged carbazole derivatives, for example according to WO 2011/042107, WO 2011/060867, WO 2011/088877 and WO 2012/143080, triphenylene derivatives, for example according to WO 2012/048781, dibenzofuran derivatives, for example according to WO 2015/169412, WO 2016/015810, WO 2016/023608, WO 2017/148564 or WO 2017/148565, or biscarbazoles, for example according to JP 3139321 B2.
In addition, the co-host used may be a compound that does not take part in charge transport to a significant degree, if at all, as described, for example, in WO 2010/108579. Especially suitable in combination with the compound of the invention as co-matrix material are compounds which have a large bandgap and themselves take part at least not to a significant degree, if any at all, in the charge transport of the emitting layer. Such materials are preferably pure hydrocarbons. Examples of such materials can be found, for example, in WO 2009/124627 or in WO 2010/006680.
In a preferred configuration, a compound of the invention which is used as emitter is preferably used in combination with one or more phosphorescent materials (triplet emitters) and/or a compound which is a TADF (thermally activated delayed fluorescence) host material. Preference is given here to forming a hyperfluorescence and/or hyperphosphorescence system.
WO 2015/091716 A1 and WO 2016/193243 A1 disclose OLEDs containing both a phosphorescent compound and a fluorescent emitter in the emission layer, where the energy is transferred from the phosphorescent compound to the fluorescent emitter (hyperphosphorescence). In this context, the phosphorescent compound accordingly behaves as a host material. As the person skilled in the art knows, host materials have higher singlet and triplet energies as compared to the emitters in order that the energy from the host material will also be transferred to the emitter with maximum efficiency. The systems disclosed in the prior art have exactly such an energy relation.
Phosphorescence in the context of this invention is understood to mean luminescence from an excited state having higher spin multiplicity, i.e. a spin state >1, especially from an excited triplet state. In the context of this application, all luminescent complexes with transition metals or lanthanides, especially all iridium, platinum and copper complexes, shall be regarded as phosphorescent compounds.
Suitable phosphorescent compounds (=triplet emitters) are especially compounds which, when suitably excited, emit light, preferably in the visible region, and also contain at least one atom of atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, especially a metal having this atomic number. Preferred phosphorescence emitters used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium or platinum.
Examples of the emitters described above can be found in applications WO 00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373, US 2005/0258742, WO 2009/146770, WO 2010/015307, WO 2010/031485, WO 2010/054731, WO 2010/054728, WO 2010/086089, WO 2010/099852, WO 2010/102709, WO 2011/032626, WO 2011/066898, WO 2011/157339, WO 2012/007086, WO 2014/008982, WO 2014/023377, WO 2014/094961, WO 2014/094960, WO 2015/036074, WO 2015/104045, WO 2015/117718, WO 2016/015815, WO 2016/124304, WO 2017/032439, WO 2018/011186, WO 2018/001990, WO 2018/019687, WO 2018/019688, WO 2018/041769, WO 2018/054798, WO 2018/069196, WO 2018/069197, WO 2018/069273, WO 2018/178001, WO 2018/177981, WO 2019/020538, WO 2019/115423, WO 2019/158453 and WO 2019/179909. In general, all phosphorescent complexes as used for phosphorescent electroluminescent devices according to the prior art and as known to those skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art will be able to use further phosphorescent complexes without exercising inventive skill.
A compound of the invention may preferably be used in combination with a TADF host material and/or a TADF emitter, as set out above.
The process referred to as thermally activated delayed fluorescence (TADF) is described, for example, by B. H. Uoyama et al., Nature 2012, Vol. 492, 234. In order to enable this process, a comparatively small singlet-triplet separation ΔE(S1-T1) of less than about 2000 cm−1, for example, is needed in the emitter. In order to open up the T1→S1 transition which is spin-forbidden in principle, as well as the emitter, it is possible to provide a further compound in the matrix that has strong spin-orbit coupling, such that intersystem crossing is enabled via the spatial proximity and the interaction which is thus possible between the molecules, or the spin-orbit coupling is generated by means of a metal atom present in the emitter.
Sources of further valuable information relating to hyperfluorescence systems include WO2012/133188 (Idemitsu), WO2015/022974 (Kyushu Univ.), WO2015/098975 (Idemitsu), WO2020/053150 (Merck) and DE202019005189 (Merck).
Sources of further valuable information relating to hyperphosphorescence systems include WO2015/091716 A1, WO2016/193243 A1 (BASF), WO01/08230 A1 (Princeton Univ. (Mark Thompson)), US2005/0214575A1 (Fuji), WO2012/079673 (Merck), WO2020/053314 (Merck) and WO2020/053315 (Merck).
In a further embodiment of the invention, the organic electroluminescent device of the invention does not contain any separate hole injection layer and/or hole transport layer and/or hole blocker layer and/or electron transport layer, meaning that the emitting layer directly adjoins the hole injection layer or the anode, and/or the emitting layer directly adjoins the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005/053051. It is additionally possible to use a metal complex identical or similar to the metal complex in the emitting layer as hole transport or hole injection material directly adjoining the emitting layer, as described, for example, in WO 2009/030981.
In the further layers of the organic electroluminescent device of the invention, it is possible to use any materials as typically used according to the prior art. The person skilled in the art will therefore be able, without exercising inventive skill, to use any materials known for organic electroluminescent devices in combination with the inventive compounds of formula (I) or the above-recited preferred embodiments.
Additionally preferred is an organic electroluminescent device, characterized in that one or more layers are coated by a sublimation process. In this case, the materials are applied by vapor deposition in vacuum sublimation systems at an initial pressure of less than 10−5 mbar, preferably less than 10−6 mbar. However, it is also possible that the initial pressure is even lower, for example less than 10−7 mbar.
Preference is likewise given to an organic electroluminescent device, characterized in that one or more layers are coated by the OVPD (organic vapor phase deposition) method or with the aid of a carrier gas sublimation. In this case, the materials are applied at a pressure between 10−5 mbar and 1 bar. A special case of this method is the OVJP(organic vapor jet printing) method, in which the materials are applied directly by a nozzle and thus structured.
Preference is additionally given to an organic electroluminescent device, characterized in that one or more layers are produced from solution, for example by spin-coating, or by any printing method, for example screen printing, flexographic printing, offset printing, LITI (light-induced thermal imaging, thermal transfer printing), inkjet printing or nozzle printing. For this purpose, soluble compounds are needed, which are obtained, for example, through suitable substitution.
Formulations for applying a compound of formula (I) or the preferred embodiments thereof detailed above are novel. The present invention therefore further provides formulations containing at least one solvent and a compound according to formula (I) or the preferred embodiments thereof detailed above.
In addition, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
Those skilled in the art are generally aware of these methods and are able to apply them without exercising inventive skill to organic electroluminescent devices comprising the compounds of the invention.
The compounds of the invention and the organic electroluminescent devices of the invention have the particular feature of an improved lifetime and higher color purity with respect to the prior art. At the same time, the further electronic properties of the electroluminescent devices, such as efficiency or operating voltage, remain at least equally good. In a further variant, the compounds of the invention and the organic electroluminescent devices of the invention especially feature improved efficiency and/or operating voltage and higher lifetime compared to the prior art.
The electronic devices of the invention, especially organic electroluminescent devices, are notable for one or more of the following surprising advantages over the prior art:
These abovementioned advantages are not accompanied by an inordinately high deterioration in the further electronic properties.
It should be pointed out that variations of the embodiments described in the present invention are covered by the scope of this invention. Any feature disclosed in the present invention may, unless this is explicitly ruled out, be exchanged for alternative features which serve the same purpose or an equivalent or similar purpose. Thus, any feature disclosed in the present invention, unless stated otherwise, should be considered as an example of a generic series or as an equivalent or similar feature.
All features of the present invention may be combined with one another in any manner, unless particular features and/or steps are mutually exclusive. This is especially true of preferred features of the present invention.
Equally, features of non-essential combinations may be used separately (and not in combination).
It should also be pointed out that many of the features, and especially those of the preferred embodiments of the present invention, should themselves be regarded as inventive and not merely as some of the embodiments of the present invention. For these features, independent protection may be sought in addition to or as an alternative to any currently claimed invention.
The technical teaching disclosed with the present invention may be abstracted and combined with other examples.
The invention is illustrated in detail by the examples which follow, without any intention of restricting it thereby. The person skilled in the art will be able to use the information given to execute the invention over the entire scope disclosed and to prepare further compounds of the invention without exercising inventive skill and to use them in electronic devices or to employ the process of the invention.
The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature. In the case of compounds that can show multiple configurational isomers, enantiomers, diastereomers or tautomeric forms, one form is shown in a representative manner. The following abbreviations for solvents and reagents are used: DCM-dichloromethane, EA-ethyl acetate, THF-tetrahydrofuran, EtOH-ethanol, NCS—N-chlorosuccinimide, NBS—N-bromosuccinimide, NIS, N-iodosuccinimide.
S1 can be prepared in 69% yield by the above route, according to the following literature:
Stages 1 and 2: W. S. Tan et al., J. Chin. Chem. Soc., 2012, 59, 399. Stage 3: J. M. Herbert et al., J. Label. Compd. Radiopharm., 2007, 50, 440.
Purification is effected by flash chromatography using an automated column system (Combi-Flash Torrent, from Axel Semrau).
The following synthons can be prepared analogously:
Alternatively, S1 to S 4 can be prepared in improved yield by the following route:
Stages 1 and 3: Analogously to W. S. Tan et al., J. Chin. Chem. Soc., 2012, 59, 399. Stage 1 yield ˜95%; stage 3 yield quantitative. Stage 2: lodination with N-iodosuccinimide in trifluoroethanol (TFE) or hexafluoroisopropanol analogously to R.-J. Tang et al. J. Org. Chem., 2018, 83, 930. Yield 93%.
Analogously, the corresponding bromo triflates can be obtained by using N-bromosuccinimide. Yield over 3 stages 87%.
Analogously, the corresponding chloro triflates can be obtained by using N-chlorosuccinimide. Yield over 3 stages 69%.
Procedure analogous to W. S. Tan et al., J. Chin. Chem. Soc., 2012, 59, 399. Rather than DMF, dimethylacetamide (DMAC) is used, which leads to improved yields. Yield 66%.
Analogously to S1 (alternative mode of preparation) and S10, it is possible to prepare the following synthons:
Alternatively, S10 can be prepared as follows:
Stage 1: Analogously to M. A. Zolfigol et al., Molecules 2001, 6, 614. Yield: 93%.
Stage 2: G. Ralf et al. Journal fuer Praktische Chemie 1987, 329 (6), 945. Yield 89%.
Stage 3: Analogously to S. Chandrappa et al., Synlett 2010, 3019. Yield: 87%.
Stage 4: E. A. Krasnokutskaya, Synthesis 2007, (1), 81. Yield 70%
To a solution, cooled to 0° C., of 29.5 g (100 mmol) of 1-cyano-4-hydroxytriptycene is added dropwise a mixture of 19.0 g of 65% by weight nitric acid and 20.0 g of 96% by weight nitric acid over the course of 1 h. The mixture is stirred for a further 30 min and then poured cautiously (foaming!) with very good stirring to a mixture of 37.8 g (450 mmol) of sodium hydrogencarbonate and 3 I of ice-water. The organic phase is separated off, the aqueous phase is extracted three times with 200 ml each time of DCM, and the combined organic phases are dried with saturated sodium chloride solution and over magnesium sulfate. The desiccant is filtered off, the DCM is removed under reduced pressure and the residue is chromatographed (silica gel, n-heptane/EA 5:1). Yield: 31.5 g (93 mmol), 93%; purity: about 98% by 1H NMR.
To a well-stirred mixture of 34.0 g (100 mmol) of 1-cyano-3-nitro-4-hydroxytriptycene and 93.5 ml (1 mol) of phosphoryl chloride is added 21.0 ml (120 mmol) of diisopropylethylamine (DIPEA), and the mixture is stirred under reflux for 4 h. The reaction mixture is poured gradually (exothermic, induction period!) onto 2 I of ice-water with very good stirring and stirred for a further 30 min. The aqueous phase is extracted five times with 200 ml each time of DCM, and the combined organic phases are dried with saturated sodium chloride solution and over magnesium sulfate. The desiccant is filtered off, the DCM is removed under reduced pressure and the residue is chromatographed (silica gel, n-heptane/EA 5:1). Yield: 40.1 g (89 mmol), 89%; purity: about 97% by 1H NMR.
To a well-stirred suspension of 35.9 g (100 mmol) of 1-cyano-3-nitro-4-chlorotriptycene and 25.1 g (450 mmol) of iron powder in 700 ml EtOH is added dropwise, under reflux over 30 minutes, 75.0 ml of 37% by weight aqueous hydrochloric acid (caution: evolution of hydrogen!). The mixture is stirred at reflux for another 3 h, diluted with 2 I of water and 2 1 of DCM, and alkalized with cautious addition (foaming!) of solid sodium carbonate (PH˜9). The mixture is filtered with suction through Celite, the organic phase of the filtrate is separated off, the aqueous phase is extracted five times with 100 ml each time of DCM, and the combined organic phases are dried by washing twice with 300 ml each time of saturated sodium chloride solution and over magnesium sulfate. The desiccant is filtered off, the DCM is removed under reduced pressure, and the crude product is applied to Isolute and chromatographed (silica gel, n-heptane/DCM 1:1 >1:2). Another chromatography step is performed if necessary until the product is obtained in white to pale beige form. Yield: 28.5 g (87 mmol), 87%; purity: about 98% by 1H NMR.
To a solution of 32.9 g (100 mmol) of 1-cyano-3-amino-4-chlorotriptycene in 500 ml of acetonitrile (4 I four-neck flask, internal thermometer, dropping funnel, precision glass stirrer, argon blanketing) is added 57.1 g (300 mmol) of p-toluenesulfonic acid monohydrate [6192-52-5] in portions, and then the mixture is cooled to 10° C. in an ice bath. To the suspension is added dropwise, with good stirring and ice cooling, a solution of 13.9 g (200 mmol) of sodium nitrite and 37.5 g (250 mmol) of potassium iodide in 60 ml of water, and the mixture is stirred at 10° C. for 15 min (caution: evolution of nitrogen-foaming). The mixture is then allowed to warm up to room temperature and stirred for a further 70 min. Then the mixture is diluted with 1500 ml of water, adjusted to pH 9.5 by adding saturated sodium hydrogen carbonate solution and admixed with 200 ml of 2M sodium bisulfite solution. The precipitated crude product is filtered off with suction, washed twice with 50 ml each time of water and briefly dried by suction. The crude product is dissolved in 500 ml of DCM, the solution is dried over sodium sulfate, the desiccant is filtered off and the crude product is applied to Isolute. Purification is effected by flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 31.1 g (70 mmol), 70%; purity: about 97% by 1H NMR.
Compounds S11-S15 can be prepared analogously:
Stages 1 to 5 are conducted analogously to syntheses known from the literature:
The enamines can be prepared by the process detailed in WO 2020/064662, page 108, from the ketones shown and morpholine in yields of about 60-80%, or are known from the literature.
A mixture of 23.3 g (100 mmol) of S100 (analogously for the other 6- and 7-membered enamines), 22.6 g (120 mmol) of 4-(aminomethylene)-2-phenyl-5 (4H)-oxazolone [3674-51-9], 47.3 ml (500 mmol) of acetic anhydride [108-24-7] and 150 ml of toluene is stirred at 100° C. for 4 h (5-membered enamines are converted in o-xylene at 130° C./4 h in an autoclave). The mixture is concentrated completely under reduced pressure, 70 ml of methanol is added to the oil, the mixture is stirred for a further 3 h, and the crystallized product is filtered off with suction, washed once with 25 ml of ice-cold methanol and dried under reduced pressure. The crude product thus obtained is converted further without purification. Yield: 26.2 g (78 mmol), 78% E,Z isomer mixture; purity: about 95% by 1H NMR.
A mixture of 33.4 g (100 mmol) S200a and 200 ml of 1-methyl-2-pyrrolidinone (NMP) is stirred at 200-205° C. for 1.5 h. The mixture is allowed to cool to about 100° C., the NMP is largely removed and reduced pressure, the glassy, viscous residue is taken up in 100 ml of warm acetonitrile, stirred at room temperature for a further 12 h, and the crystallite product is filtered off and dried under reduced pressure. Yield: 25.1 g (75 mmol), 75%; purity: about 95% by 1H NMR.
To a suspension of 33.4 g (100 mmol) of S200b in a mixture of 150 ml of N,N-dimethylformamide (DMF), under ice-salt cooling (about −10° C.), is added dropwise 14.0 ml (150 mmol) of phosphoryl chloride in 50 ml of DMF, and then the mixture is stirred at room temperature for a further 16 h. The reaction mixture is poured cautiously on to 1000 ml of ice-water and stirred for a further 10 min, 200 ml of dichloromethane (DCM) is added, the mixture is stirred for a further 10 min, and the organic phase is removed. The aqueous phase is basified (pH 8-9) with cautious addition of conc. ammonia solution, the aqueous phase is extracted three times with 200 ml each time of ethyl acetate, and the combined ethyl acetate extracts are washed twice with 200 ml each time of ice-water, once with 200 ml of saturated sodium hydrogencarbonate solution and twice with 100 ml each time of saturated sodium chloride solution. The mixture is dried over a mixture of magnesium sulfate and sodium carbonate, the desiccant is filtered off, the organic phase is concentrated under reduced pressure and the residue is recrystallized once from acetonitrile with addition of ethyl acetate (EA). Yield: 24.7 g (81 mmol), 81%; purity: about 95% by 1H NMR.
A mixture of 30.4 g (100 mmol) of S200c, 100 ml of 3 N sulfuric acid and 200 ml of dioxane is stirred at 100° C. for 1.5 h. After cooling, the reaction mixture is diluted with 1000 ml of ice-water and then adjusted to PH˜7.5 with 3 N NaOH while cooling with ice. The aqueous phase is extracted three times with 200 ml each time of DCM, and the combined organic phases are washed twice with 200 ml of water and once with 200 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness and the solids are recrystallized from methanol. Yield: 23.1 g (93 mmol), 93%; purity: about 95% by 1H NMR.
24.9 g (100 mmol) of S200d is introduced with good stirring into 500 ml of concentrated hydrochloric acid cooled to 3-5° C. To the suspension is added dropwise, with good stirring over the course of 15 min, a cooled solution of 10.4 g (150 mmol) of sodium nitrite in 50 ml of water, and then the mixture is stirred at 5° C. for about a further 20 min. The diazonium solution thus obtained is poured into a well-stirred solution, cooled to 5° C., of 90.0 g (600 mmol) of potassium iodide in 5000 ml of water to which 1000 ml of DCM has been added (caution: foaming!). After evolution of nitrogen has ended (about 25 min), sodium bisulfite solution is added until decolorization, and the pH is adjusted cautiously to ˜0.5 with 5 N NaOH under very good cooling. The mixture is diluted with a further 1500 ml of DCM, the organic phase is removed, the aqueous phase is re-extracted twice with 500 ml each time of DCM, and the combined organic phases are washed twice with 500 ml each time of water and twice with 500 ml each time of saturated sodium chloride solution and then dried over magnesium sulfate. After the DCM has been removed under reduced pressure, the residue is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 22.9 g (63 mmol), 63%; purity: about 97% by 1H NMR.
To a solution of 24.9 g (100 mmol) of S200d in 500 ml of acetonitrile is added 57.1 g (300 mmol) of p-toluenesulfonic acid monohydrate [6192-52-5] in portions, and then the mixture is cooled to 10° C. in an ice bath. To the suspension is added in portions, with good stirring and ice cooling, a solution of 13.9 g (200 mmol) of sodium nitrite and 37.5 g (250 mmol) of potassium iodide in 60 ml of water, and the mixture is stirred at 10° C. for 15 min. The mixture is then allowed to warm up to room temperature and stirred for a further 70 min. Then the mixture is diluted with 1500 ml of water, adjusted to pH 9.5 by adding saturated sodium hydrogen carbonate solution and admixed with 200 ml of 2M sodium bisulfite solution. The precipitated crude product is filtered off with suction, washed twice with 50 ml each time of water and briefly dried by suction. The crude product is dissolved in 500 ml of DCM, the solution is dried over sodium sulfate, the desiccant is filtered off and the crude product is applied to Isolute. Purification is effected by flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 25.0 g (72 mmol), 72%; purity: about 97% by 1H NMR.
The following pyridines can be obtained analogously to stages 1 to 5. Yield over five stages (stages 1-5):
Stage 1: Analogously to M. A. Zolfigol et al., Molecules 2001, 6, 614. Yield: 96%.
Stage 2: G. Ralf et al. Journal fuer Praktische Chemie 1987, 329 (6), 945. Yield 91%.
Stage 3: Analogously to S. Chandrappa et al., Synlett 2010, 3019. Yield: 90%.
Stage 4: E. A. Krasnokutskaya, Synthesis 2007, (1), 81. Yield: 78%.
The following compounds can be prepared analogously; yield over four stages:
Suzuki coupling: Starting mixture: 21.7 g (50 mmol) of 1,4-chloro-2,5-difluoro-3,6-diiodobenzene [2410043-16-0], 13.4 g (110 mmol) of phenylboronic acid, 31.8 g (300 mmol) of sodium carbonate, 702 mg (1 mmol) of bis(triphenylphosphino) palladium (II) chloride, 250 ml of acetonitrile, 250 ml of methanol, 60° C., 12 h. Workup: filter off salts, concentrate filtrate, work up residue by extraction with DCM: water. Purification by flash chromatography. Yield: 12.9 g (38 mmol), 76%; purity: about 97% by 1H NMR.
The following compounds can be prepared analogously
A well-stirred mixture of 44.0 g (100 mmol) of S10, 9.8 g (105 mmol) of aniline, 28.8 g (300 mmol) of sodium tert-butoxide, 1.11 g (2 mmol) of dppf, 225 mg (1 mmol) of palladium (II) acetate in 500 ml of toluene is heated under reflux for 1 h. The mixture is allowed to cool to 70° C., 500 ml of water is added, the mixture is stirred for a further 10 min, and the organic phase is separated off and washed twice with 300 ml each time of water and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a Celite bed in the form of a toluene slurry, the filtrate is concentrated under reduced pressure, the residue is dissolved in 300 ml of DCM, and the latter is removed under reduced pressure, with replacement of the DCM distilled off by simultaneous addition of EtOH. The crystallized product is filtered off with suction, washed three times with 50 ml each time of EtOH and dried under reduced pressure. Yield: 36.7 g (91 mmol), 91%; purity: about 98% by 1H NMR. When triflates are used, the triflate is metered in gradually; see J. Louie et al., Journal of Organic Chemistry 1997, 62 (5), 1268.
A well-stirred mixture of 40.5 g (100 mmol) of the amine from stage 1, 69.1 g (500 mmol) of potassium carbonate, 3.1 g (30 mmol) of pivalic acid, 1.16 g (4 mmol) of tri-tert-butylphosphonium tetrafluoroborate, 449 mg (2 mmol) of palladium (II) acetate, 100 g of glass beads (diameter 3 mm) and 1000 ml of dimethylacetamide (DMAC) is stirred at 150° C. for 1 h. The mixture is filtered while still hot through a Celite bed in the form of a DMAC slurry, the filtrate is concentrated to dryness, the residue is dissolved in 500 ml of DCM, and the latter is removed under reduced pressure, with replacement of the DCM distilled off by simultaneous addition of 300 ml of EtOH. The crystallized product is filtered off with suction, washed three times with 50 ml each time of EtOH and dried under reduced pressure. Yield: 29.5 g (80 mmol), 80%; purity: about 98% by 1H NMR.
The following compounds can be prepared analogously; yield over two stages:
769-92-6
1459-48-9
91-59-8
92-67-1
118951-68-1
37521-64-5
37521-66-7
1882060-04-9
22948-06-7
1801716-11-9
1884138-08-2
31997-11-2
4106-66-5
1268519-74-9
1093882-02-0
667919-05-3
53897-95-3
1644466-73-8
1346517-64-3
Preparation according to
1287739-22-3
1287739-22-3
769-92-6
769-92-6
769-92-6
769-92-6
42265-67-8
1931588-39-4
42265-67-8
85911-33-7
To a well-stirred solution of 42.5 g (100 mmol) of C2 in 1000 ml DCM is added 19.8 g (100 mmol) of N-bromosuccinimide (NBS) in portions, and then the mixture is stirred at RT for 5 h. The DCM is removed under reduced pressure, with replacement of the DCM distilled off by simultaneous addition of MeOH; final volume about 300 ml. The crystallized product is filtered off with suction, washed twice with 50 ml each time of MeOH and dried under reduced pressure. Yield: 48.0 g (95 mmol), 95%; purity: about 98% by 1H NMR.
A well-stirred mixture of 44.7 g (100 mmol) of the Br-carbazole from stage 1, 7.0 ml (50 mmol) of trimethylboroxine [823-96-1], 41.5 g (300 mmol) of potassium carbonate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 449 mg (2 mmol) of palladium (II) acetate, 100 g of glass beads (diameter 3 mm) and 800 ml of dimethylacetamide (DMAC) is stirred at 120° C. for 12 h. The mixture is filtered while still hot through a Celite bed in the form of a DMAC slurry, the filtrate is concentrated to dryness, the residue is dissolved in 500 ml of DCM, and the latter is removed under reduced pressure, with replacement of the DCM distilled off by simultaneous addition of 300 ml of EtOH. The crystallized product is filtered off with suction, washed three times with 50 ml each time of EtOH and dried under reduced pressure. Yield: 31.7 g (83 mmol), 83%; purity: about 98% by 1H-NMR.
The following compounds can be prepared analogously; yield over two stages:
701261-35-0
98-80-6
1332481-37-4
63076-51-7
701261-35-0
800041-89-0
123324-71-0
5980-97-2
A well-stirred mixture of 36.8 g (100 mmol) of carbazole C1, 9.1 g (50 mmol) of 1,4-dichloro-2,5-difluorobenzene [400-05-5], 69.1 g (500 mmol) of potassium carbonate, 100 g of glass beads (diameter 3 mm) and 1000 ml of dimethylacetamide (DMAC) is stirred at 150° C. for 3 h. The mixture is left to cool to 80° C., 3.1 g (30 mmol) of pivalic acid, 1.16 g (4 mmol) of tri-tert-butylphosphonium tetrafluoroborate and 449 mg (2 mmol) of palladium (II) acetate are added, and the mixture is stirred at 150° C. for a further 2 h. The mixture is left to cool down to 80° C., 2000 ml of water is added dropwise, and the precipitated crude product is filtered off with suction, washed three times with 200 ml each time of water and three times with 200 ml each time of ethanol, and dried under reduced pressure. The crude product is dissolved in 500-1000 ml of DCM (in the case of pyridines, 10% by weight of ethyl acetate is added), the mixture is filtered through a silica gel bed in the form of a DCM slurry and the DCM is removed under reduced pressure, with replacement of the DCM distilled off by simultaneous addition of 300 ml of EtOH toward the end. The crystallized product is filtered off with suction, washed three times with 50 ml each time of EtOH and dried under reduced pressure. Further purification is effected by continuous hot extraction (standard organic solvents or a combination thereof, preferably DCM or acetonitrile/DCM 3:1 to 1:3) or by flash chromatography (CombiFlash Torrent automated column system from A. Semrau, silica gel, RP silica gels, aluminum oxide, eluent: toluene/n-heptane/triethylamine, acetonitrile/THF or DCM) and final fractional sublimation or heat treatment under high vacuum (typically T about 200-400° C., p about 10−5 to 10−6 mbar). Yield: 30.0 g (26 mmol), 52%; purity: about 99.9% by HPLC.
If two different carbazoles C are used—as a mixture or preferably by sequential addition, i.e. first 50 mmol of the first carbazole, then, after a reaction time of about 2 h, 50 mmol of the second carbazole—compounds of the invention with mixed functionalization can be obtained after chromatographic separation of the possible coupling and cyclization products.
The following compounds can be prepared analogously:
400-05-5
1198-62-5
Isomer mixture
60341-41-5
syn & anti
syn & anti
2253-30-7
2249721-44-4
132992-30-4
2634722-73-7
27023-66-1
2253-30-7
36556-54-4
25566-69-2
36556-54-4
Stage 1: Double Buchwald-Hartwig coupling, procedure analogous to EP3723149A1, Examples 2-5, Intermediate 12. The bis(chlorocarbazole) is isolated. Yield: 63%
Stage 2: Double cyclization, procedure analogous to example C1, stage 2, yield 57%. Rather than H—P(t-Bu3)BF4, H—P(t-Cy3)BF4 can be used; an addition of 30 mol % of pivalic acid typically has a yield-enhancing effect. Alternatively, cyclization can be effected with NHC—Pd complexes, for example allyl-[1,3-bis(2,6-diisopropylphenyl) imidazol-2-ylidene]chloropalladium (II); for example analogously to T. Kader et al.,
Chem. Europ. J., 2019, 25 (17), 4412 or analogously to U.S. Pat. No. 9,000,421 B1; typical yields 30-80%.
The following compounds can be prepared analogously:
1124-08-9
249898-94-0
2710372-69-1
96843-21-9
1074-24-4
Stage 1: Pd-catalyzed borylation, procedure analogous to EP3723149A1, Examples 2-4, Intermediate 10. Yield: 80%
Stage 2: Double Suzuki coupling, procedure analogous to EP3723149A1, Examples 2-4, Intermediate 11. Yield: 78%
Stage 3: Double Ullmann reaction with cyclization, procedure analogous to EP3723149A1, Examples 2-4, BD-6. Yield: 48%.
The following compounds can be prepared analogously:
2129135-58-4
201160-24-9
Stages 1 & 2: Procedure analogous to Taisei Taniguchi et al., Chem. Lett. 2019, 48, 1160. Yield: 21% D800; 8% F100.
The following compounds can be prepared analogously:
FIG. 1 shows the PL spectrum of the inventive compounds D2, measured with a Hitachi F-4500 PL PL spectrometer, in about 10−5 molar, degassed toluene solution at room temperature (about 25° C.).
The spectrum shown in FIG. 1 has the following data: PLmax: 453 nm, FWHM: 16.3 nm, 0.098 eV
The PL spectra have very narrow emission bands with low FWHM values (typically <0.15 eV) and lead to particularly pure-color emission. Moreover, in the long-wave emission flank, they show a shoulder or a secondary maximum having less than 30% of the intensity of the main maximum. In top emission OLED components, this leads to a favorably small viewing angle dependence of color impression compared to narrowband boron-containing emitters according to the prior art, which often do not have any such shoulders or secondary maxima and show greater viewing angle dependence of color impression.
One use of the compounds of the invention is as dopant in the emission layer in fluorescence and hyperfluorescence OLED components.
OLEDs (organic light emitting diodes) of the invention and OLEDs according to the prior art are produced by a general method according to WO 2004/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).
In the examples which follow, the results for various OLEDs are presented. Cleaned glass plates (cleaning in Miele laboratory glass washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm are pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and, within 30 min, for improved processing, coated with 20 nm of PEDOT: PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS™ P VP AI 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180° C. for 10 min. These coated glass plates form the substrates to which the OLEDs are applied. After the production, the OLEDs are encapsulated for protection against oxygen and water vapor. The exact layer structure of the electroluminescent OLEDs can be found in the examples. The materials required for production of the OLEDs are shown in table 8.
The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in Im/W) and the external quantum efficiency (EQE, measured in percent) are, as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics. The electroluminescent spectra are recorded at a luminance of 100 or 1000 cd/m2, and these are used to infer the emission color and the EL-FWHM values (ELectroluminescence—Full Width Half Maximum—width of the EL emission spectra at half the peak height in eV; for better comparability over the entire spectral range).
All materials are applied by thermal vapor deposition in a vacuum chamber. The emission layer (EML) always consists of at least one matrix material (host material) SMB and an emitting dopant (emitter) ES or EAS which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as SMB: ES or EAS (97: 3%) mean here that the material SMB is present in the layer in a proportion by volume of 97% and the dopant ES or EAS in a proportion of 3%. Analogously, the electron transport layer may also consist of a mixture of two materials, for example here of ETM1 (50%) and ETM2 (50%); see table 1. The materials used for production of the OLEDs are shown in table 8. A comparison used is compound Ref.-D1; see table 8.
The OLEDs basically have the following layer structure:
Substrate
All materials are applied by thermal vapor deposition in a vacuum chamber. The emission layer(s)(EML) always consist(s) of at least one matrix material (host material) TMM, a (phosphorescent) sensitizer PS and a fluorescent emitter ES or EAS. The matrix material (host material) TMM may consist of two components that are evaporated as a mixture (premixed host, e.g. TMM2), and the composition is likewise shown in table 8. Sensitizers and fluorescent emitter ES or EAS are added to the host material TMM in a particular proportion by volume by coevaporation. Details given in such a form as TMM: PS (5%): ES or EAS (3%) mean here that the material TMM is present in the layer in a proportion by volume of 92%, PS in a proportion of 5% and ES or EAS in a proportion of 3%.
The OLEDs basically have the following layer structure:
The OLEDs basically have the following layer structure:
The production of solution-based OLEDs is fundamentally described in the literature, for example in WO 2004/037887 and WO 2010/097155. The examples that follow combined the two production processes (application from the gas phase and solution processing), such that layers up to and including emission layer were processed from solution and the subsequent layers (hole blocker layer/electron transport layer) were applied by vapor deposition under reduced pressure. For this purpose, the previously described general methods are matched to the circumstances described here (layer thickness variation, materials) and combined as follows.
The construction used is thus as follows:
Substrates used are glass plates coated with structured ITO (indium tin oxide) of thickness 50 nm. For better processing, these are coated with the buffer (PEDOT)Clevios P VP AI 4083 (Heraeus Clevios GmbH, Leverkusen); PEDOT is at the top. Spin-coating is effected under air from water. The layer is subsequently baked at 180° C. for 10 minutes. The hole transport layer and the emission layer are applied to the glass plates thus coated. The hole transport layer is the polymer HTM-Sol of the structure shown in table 8, which was synthesized according to WO 2010/097155. The polymer is dissolved in toluene, such that the solution typically has a solids content of about 5 g/l when, as is the case here, the layer thickness of 20 nm typical of a device is to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 180° C. for 60 min.
The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). Details given in such a form as SMB4 (97%) and ES or EAS (3%) mean here that the material SMB4 is present in the emission layer in a proportion by weight of 97% and the dopant ES or EAS in a proportion by weight of 3%. The mixture for the emission layer is dissolved in toluene or chlorobenzene. The typical solids content of such solutions is about 18 g/l when, as here, the layer thickness of 50 nm which is typical of a device is to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 140 to 160° C. for 10 minutes. The materials used are shown in table 8.
The materials for the electron transport layer and for the cathode are applied by thermal vapor deposition in a vacuum chamber. The electron transport layer, for example, may consist of more than one material, the materials being added to one another by co-evaporation in a particular proportion by volume. Details given in such a form as ETM1 (50%) and ETM2 (50%) mean here that the ETM1 and ETM2 materials are present in the layer in a proportion by volume of 50% each. The materials used in the present case are shown in table 8.
[1365840-52-3]
[1450933-44-4]
[1401068-29-8]
[1087346-88-0]
[667940-34-3]
[1627916-48-6]
[1818872-85-3]
[1201800-83-0]
[1643476-29-2] (40%)
[1822310-86-0] (60%)
2286203-95-8
[1615218-73-9]
[1233200-52-6]
[25387-93-3]
The abbreviations of the inventive compounds that are used in the tables set out above in relation to the OLED components relate to the abbreviations provided in the above synthesis examples.
By comparison with the reference, the inventive compounds shown narrower electroluminescence spectra, recognizable by the smaller or equal EL-FWHM values (ELectroluminescence—Full Width Half Maximum—width of the EL emission spectra in eV at half the peak height). Narrower electroluminescence spectra lead to a distinct improvement in color purity (lower CIE y values). Moreover, EQE values (External Quantum Efficiencies) are distinctly greater and operating voltages are lower compared to the reference, which leads to a distinct improvement in power efficiencies of the device and hence to lower power consumption.
The compounds of the invention can be used for color conversion. For this purpose, compounds are incorporated into a composition which is then processed by known methods (pin-coating, slit-coating, screenprinting, nozzle printing, inkjet printing, etc.) to give pixels or two-dimensional layers. The compositions typically consist of crosslinkable components (monomers, oligomers, polymers), for example based on acrylates, acrylamide, polyesters, silicones etc., and one or more thermally or photochemically activatable starter components. It is additionally possible to introduce further components such as organic auxiliaries (antioxidants, stabilizers, levelling aids, viscosity moderators, etc.) or inorganic fillers (SiO2, TiO2, Al2O3, etc.).
0.5 g of the inventive compound ES or EAS, 0.2 g of titanium dioxide (TiO2 ToyoColor, from Toyo Ink Group) and 10 g of OE-6550 Optical Encapsulant (from Dow Corning) are homogenized at 40° C. with very good stirring (magnetic stirrer) under the action of ultrasound (ultrasound bath). Layers of layer thickness about 15 μm are produced by knife-coating and then cured by baking under a nitrogen atmosphere (150° C., 1 hour).
Fluorescence spectra and EQE values (external quantum efficiency, EQE =photons emitted/photons absorbed) of the layers are ascertained in a fluorescence spectrometer (C9920, Hamamatsu photonics) with an Ulbricht sphere and fiber optics (excitation wavelength CWL: 420-440 nm for blue, 450 nm for green emitters, reference measurement under air at room temperature).
Table 9 summarizes the results:
| Number | Date | Country | Kind |
|---|---|---|---|
| 22158139.0 | Feb 2022 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2023/054130 | 2/20/2023 | WO |
