CN112771024A - Process for preparing sterically hindered nitrogen-containing heteroaromatics - Google Patents

Process for preparing sterically hindered nitrogen-containing heteroaromatics Download PDF

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CN112771024A
CN112771024A CN201980063487.9A CN201980063487A CN112771024A CN 112771024 A CN112771024 A CN 112771024A CN 201980063487 A CN201980063487 A CN 201980063487A CN 112771024 A CN112771024 A CN 112771024A
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菲利普·施特塞尔
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Merck Patent GmbH
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Abstract

The present invention relates to a process for preparing sterically hindered nitrogen-containing heteroaromatic compounds, in particular for use in electronic devices. The invention also relates to compounds obtainable by this process and to electronic devices comprising these compounds.

Description

Process for preparing sterically hindered nitrogen-containing heteroaromatics
The invention relates to a method for producing sterically hindered heteroaromatic nitrogen compounds. The invention also relates to compounds obtainable by said process and to electronic devices comprising these compounds.
The structure of organic electroluminescent devices (OLEDs) in which organic semiconductors are used as functional materials is described, for example, in US 4539507, US 5151629, EP 0676461 and WO 98/27136. The luminescent materials used are often organometallic complexes which exhibit phosphorescence. For quantum mechanical reasons, up to four times the energy and power efficiency can be achieved with organometallic compounds relative to fluorescent emitters. In general, there is still a need for improvements in OLEDs, in particular also in OLEDs which exhibit phosphorescence, for example with regard to efficiency, operating voltage and lifetime. Organic electroluminescent devices comprising fluorescent emitters or emitters exhibiting TADF (thermally activated delayed fluorescence) are also known.
The properties of the organic electroluminescent device are not only determined by the luminophor used. In particular, the other materials used, such as host/matrix materials, hole-blocking materials, electron-transport materials, hole-transport materials, and electron-or exciton-blocking materials, are also of particular interest here. Improvements in these materials can lead to significant improvements in electroluminescent devices.
According to the prior art, compounds having a bicyclic or tricyclic ring system are used, inter alia, for preparing metal complexes which exhibit phosphorescence. These compounds act in particular as ligands in the corresponding complexes. This prior art includes, inter alia, documents WO 2014/094960 a1, WO 2014/094961 a1, WO 2015/104045 a1, WO 2015/117718 a1 and WO 2016/124304. These documents do not list a host material, an electron transport material, a hole transport material, a fluorescent emitter, or an emitter exhibiting TADF (thermally activated delayed fluorescence).
Furthermore, document WO 2015/036078 discloses heterocyclic compounds which are particularly useful as matrix materials, electron-transporting materials or hole-transporting materials. Most of these compounds comprise a bicyclic ring system fused to a pyridine or pyridazine structure, to which an aromatic or heteroaromatic ring system is in turn fused.
The compounds detailed above are relatively complex in their preparation and produce a relatively high proportion of by-products. The preparation of the compounds detailed above also requires relatively expensive and sensitive starting materials.
Furthermore, in the case of the use of these materials as, for example, matrix materials, hole conductor materials or electron transport materials, there is still a general need for improvement, in particular with regard to the lifetime of the devices, and also with regard to the efficiency and operating voltage. Furthermore, the compounds should have a high color purity.
It is a further object of the present invention to provide compounds which are suitable for use as fluorescent emitters or emitters exhibiting TADF (thermally activated delayed fluorescence) in organic electronic devices, in particular in organic electroluminescent devices, and which lead to good device properties when used in such devices, and to corresponding electronic devices.
It is therefore an object of the present invention to provide a particularly simple and inexpensive process for the preparation of these compounds. More particularly, the process will result in high yields and will result in a minimum proportion of by-products. In addition, the reaction conditions will be very mild. Furthermore, the compounds detailed above will be able to be prepared using relatively cheap, readily available and insensitive starting materials.
It is a further object of the present invention to provide compounds which are suitable for use in organic electronic devices, in particular in organic electroluminescent devices, and which lead to good device properties when used in such devices, and to provide corresponding electronic devices.
It is a particular object of the present invention to provide compounds which result in a high lifetime, good efficiency and low operating voltage. In particular the properties of the matrix material, the hole conductor material or the electron transport material also have a significant influence on the lifetime and efficiency of the organic electroluminescent device.
Another problem solved by the present invention may be considered to be to provide compounds suitable for use in phosphorescent or fluorescent OLEDs, in particular for use as matrix materials. More particularly, the problem addressed by the present invention is to provide a matrix material suitable for red-, yellow-and green-phosphorescent OLEDs.
In addition, the compounds, especially when they are used as matrix materials, as hole conductor materials or as electron transport materials in organic electroluminescent devices, should lead to devices having excellent color purity.
Furthermore, the compounds should be processable in a very simple manner and should in particular exhibit good solubility and film-forming properties. For example, the compounds should exhibit increased oxidative stability and improved glass transition temperatures.
Another object may be considered to be to provide electronic devices with excellent performance very inexpensively and at constant quality.
Furthermore, it should be possible to use or adapt the electronic device for a variety of uses. More particularly, the performance of the electronic device should be maintained over a wide temperature range.
It has been unexpectedly found that the specific processes and compounds described in detail hereinafter achieve these objects and eliminate the disadvantages of the prior art. The use of said compounds leads to very good properties of organic electronic devices, in particular organic electroluminescent devices, in particular with respect to lifetime, efficiency and operating voltage. The invention therefore provides electronic devices, in particular organic electroluminescent devices, comprising such compounds, and corresponding preferred embodiments.
Accordingly, the present invention provides a process for preparing a sterically hindered heteroaromatic nitrogen compound, which comprises the steps of:
A) providing 1,2, 4-triazine;
B) providing an activated olefin having a non-aromatic or non-heteroaromatic polycyclic ring system, and
C) reacting the compounds provided in steps A) and B) to obtain a sterically hindered heteroaromatic nitrogen compound,
it is characterized in that
At least one of the compounds provided in steps A) and/or B) comprises an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and which may be substituted.
The following may be preferred: the activated double bond of the olefin provided in step B) is part of a bicyclic, tricyclic or oligomeric ring.
In a preferred embodiment, the alkene provided in step B) is preferably a cyclic enolate and/or an enamine.
The following may also be the case: the olefin provided in step B) is derived from a bicyclic, tricyclic or oligomeric cyclic ketone.
In a preferred configuration, the 1,2, 4-triazine may be represented by formula (I)
Figure BDA0002994034760000041
The symbols used therein are as follows:
Ra，Rb，Rcthe same or different and is: h, D, F, Cl, Br, I, N (R)1)2，CN，NO2，OH，COOH，C(＝O)N(R1)2，Si(R1)3，B(OR1)2，C(＝O)R1，P(＝O)(R1)2，S(＝O)R1，S(＝O)2R1，OSO2R1A linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein each of said alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl groups may be substituted with one or more R1Radical substitution of one or more non-adjacent CH2The group can be represented by R1C＝CR1、C≡C、Si(R1)2、C＝O、NR1O, S or CONR1Instead of, or with 5 to 40 aromatic ring atoms and may in each case be substituted by one or more R1Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 40 aromatic ring atoms and which may be substituted by one or more R1A group-substituted aryloxy or heteroaryloxy group; at the same time, two Ra、RbAnd/or RcThe radicals together may also form a mono-or polycyclic, aliphatic or aromatic ring system;
R1the same or different at each occurrence and is: h, D, F, Cl, Br, I, N (R)2)2，CN，NO2，Si(R2)3，B(OR2)2，C(＝O)R2，P(＝O)(R2)2，S(＝O)R2，S(＝O)2R2，OSO2R2Straight-chain alkyl, alkoxy or thioalkoxy groups having 1 to 20 carbon atoms or alkenyl or alkynyl groups having 2 to 20 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 20 carbon atoms, wherein each alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted by one or more R2Radical substitution of one or more non-adjacent CH2The group can be represented by R2C＝CR2、C≡C、Si(R2)2、C＝O、NR2O, S or CONR2Instead of, or with 5 to 40 aromatic ring atoms and may in each case be substituted by one or more R2Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 40 aromatic ring atoms and which may be substituted by one or more R2Aryloxy or heteroaryloxy radicals substituted by radicals, or having 5 to 40 aromatic ring atoms and which may be substituted by one or more R2Aralkyl or heteroaralkyl groups substituted by radicals, or having 10 to 40 aromatic ring atoms and which may be substituted by one or more R2A group-substituted diarylamino group, diheteroarylamino group, or arylheteroarylamino group; simultaneously, two or more preferably adjacent R1The radicals together may form a mono-or polycyclic, aliphatic or aromatic ring system;
R2the same or different at each occurrence and is: h, D, F, or aliphatic, aromatic and/or heteroaromatic organic radicals having from 1 to 20 carbon atoms, in particular hydrocarbon radicals, in which one or more hydrogen atoms may also be replaced by F, while two or more, preferably adjacent, R2The substituents together may also form a mono-or polycyclic, aliphatic or aromatic ring system.
The following may be preferred: ra、Rb、RcAt least one of the radicals is an aromatic ring having from 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R1Radical-substituted aromatic or heteroaromatic ring systems, where R is preferablyaAnd/or RbAt least one of the radicals being an aromatic or heteroaromatic ring system having from 5 to 40 aromatic ring atoms, and RbThe radicals are more preferably aromatic or heteroaromatic ring systems having from 5 to 40 aromatic ring atoms.
Adjacent carbon atoms in the sense of the present invention are carbon atoms which are directly bonded to one another. In addition, "adjacent groups" in the definition of groups means that these groups are bonded to the same carbon atom or to adjacent carbon atoms. These definitions apply in particular correspondingly to the terms "adjacent group" and "adjacent substituent".
Within the scope of the present description, the expression that two or more radicals together may form a ring should be understood to mean in particular that the two radicals are linked to one another in a chemical bond as formally eliminating two hydrogen atoms. This is illustrated by the following scheme:
Figure BDA0002994034760000061
however, in addition, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group is bonded to the position to which the hydrogen atom is bonded, thereby forming a ring. This should be illustrated by the following scheme:
Figure BDA0002994034760000062
a fused aryl group, a fused aromatic ring system or a fused heteroaromatic ring system in the sense of the present invention is a group in which two or more aromatic groups are fused to one another along a common side, i.e. a ring is added, so that for example two carbon atoms belong to at least two aromatic or heteroaromatic rings, as in, for example, naphthalene. In contrast, for example, fluorene is not a fused aryl group in the sense of the present invention, since the two aromatic groups in fluorene do not have a common edge. The corresponding definitions apply to heteroaryl groups and fused ring systems which may, but need not, also contain heteroatoms.
If two or more are preferably adjacent R, R1And/or R2The radicals together form a ring system, the result may then be a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system.
Aryl groups in the sense of the present invention contain 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms; heteroaryl groups in the sense of the present invention contain 2 to 60 carbon atoms, preferably 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and/or S. Aryl or heteroaryl groups are understood here to mean simple aromatic rings, i.e. benzene, or simple heteroaromatic rings, such as pyridine, pyrimidine, thiophene, etc., or fused aryl or heteroaryl groups, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.
An aromatic ring system in the sense of the present invention contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms in the ring system. A heteroaromatic ring system in the sense of the present invention contains 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms and at least one heteroatom in the ring system, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and/or S. An aromatic or heteroaromatic ring system in the sense of the present invention is understood to mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of atoms other than H), for example carbon, nitrogen or oxygen atoms or carbonyl groups. Thus, for example, systems such as 9, 9' -spirobifluorene, 9-diarylfluorene, triarylamines, diaryl ethers, stilbenes, etc., should also be regarded as aromatic ring systems in the sense of the present invention, and also systems in which two or more aryl groups are interrupted by, for example, linear or cyclic alkyl groups or by silyl groups. In addition, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, such as biphenyl, terphenyl, quaterphenyl or bipyridine, are likewise to be regarded as aromatic or heteroaromatic ring systems.
Cyclic alkyl, alkoxy or thioalkoxy groups in the sense of the present invention are understood to mean monocyclic, bicyclic or polycyclic groups.
Within the scope of the invention, wherein the individual hydrogen atoms or CH2C whose radicals may also be replaced by the above-mentioned radicals1-to C20Alkyl groups are understood to mean, for example: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo [ 2.2.2.2 ] n-bicyclo]Octyl, 2-bicyclo [2.2.2]Octyl, 2- (2, 6-dimethyl) octyl, 3- (3, 7-dimethyl) octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, 1-dimethyl-n-hexyl-1-yl, 1-dimethyl-n-hept-1-yl, 1-dimethyl-n-oct-1-yl, 1-dimethyl-n-decan-1-yl, 1-dimethyl-n-dodecane-1-yl, 1-dimethyl-n-tetradec-1-yl, 1-dimethyl-n-hexadecan-1-yl, 1-dimethyl-n-octadecan-1-yl, 1-diethyl-n-hex-1-yl, 1, 1-diethyl-n-hept-1-yl, 1-diethyl-n-oct-1-yl, 1-diethyl-n-dec-1-yl, 1-diethyl-n-dodec-1-yl, 1-diethyl-n-tetradec-1-yl, 1-diethyl-n-hexadecan-1-yl, 1-diethyl-n-octadecan-1-yl, 1- (n-propyl) cyclohex-1-yl, 1- (n-butyl) cyclohex-1-yl, 1- (n-hexyl) cyclohex-1-yl, 1- (n-octyl) cyclohex-1-yl and 1- (n-decyl) cyclohex-1-yl groups. Alkenyl groups are understood as meaning, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. Alkynyl groups are understood as meaning, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. C1-to C40-alkoxy radicalA radical is understood as meaning, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy.
Aromatic or heteroaromatic ring systems which have from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, aromatic ring atoms and can also be substituted in each case by the abovementioned radicals and can be attached to the aromatic or heteroaromatic system via any desired position are understood as meaning, for example, radicals which originate from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, triphenylene, pyrene, chicory, perylene, fluoranthene, benzofluoranthene, tetracene, pentacene, benzopyrene, biphenyl, dibenzylidene, terphenyl, bistyryl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-monobenzindenofluorene, cis-or trans-dibenzindenofluorene, truxene, isotridecylindene, spirotricondene, spiroisotridecylindene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, thiophene.
Figure BDA0002994034760000092
Oxazines, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthoimidazoles, phenanthroimidazoles, pyridoimidazoles, pyrazinoimidazoles, quinoxaloimidazoles,
Figure BDA0002994034760000093
Azole, benzo
Figure BDA0002994034760000094
Azoles, naphtho
Figure BDA0002994034760000095
Azoles, anthracenes
Figure BDA0002994034760000096
Azole, phenanthro
Figure BDA0002994034760000097
Oxazole, iso
Figure BDA0002994034760000098
Oxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diaza anthracene, 2, 7-diaza pyrene, 2, 3-diaza pyrene, 1, 6-diaza pyrene, 1, 8-diaza pyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, thiophene
Figure BDA0002994034760000099
Oxazines, phenothiazines, fluoranthenes, naphthyridines, azacarbazoles, benzocarbazoles, phenanthrolines, 1,2, 3-triazoles, 1,2, 4-triazoles, benzotriazoles, 1,2,3-
Figure BDA00029940347600000910
Oxadiazole, 1,2,4-
Figure BDA00029940347600000911
Oxadiazole, 1,2,5-
Figure BDA00029940347600000912
Oxadiazole, 1,3,4-
Figure BDA00029940347600000913
Oxadiazoles, 1,2, 3-thiadiazoles, 1,2, 4-thiadiazoles, 1,2, 5-thiadiazoles, 1,3, 4-thiadiazoles, 1,3, 5-triazines, 1,2, 4-triazines, 1,2, 3-triazines, tetrazoles, 1,2,4, 5-tetrazines, 1,2,3, 4-tetrazines, 1,2,3, 5-tetrazines, purines, pteridines, indolizines and benzothiadiazoles.
The activated olefin may preferably be represented by formula (II):
Figure BDA0002994034760000091
the symbols used therein are as follows:
x is OH, ORdOr NRd 2；
RdIs H, D, a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 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 can be substituted in each case by one or more R1Substituted by groups; at the same time, two RdThe radicals together may also form a mono-or polycyclic aliphatic or aromatic ring system in which R1As defined above especially for formula (I);
wherein the bicyclic/polycyclic ring may have one or more substituents R, and
r is the same or different at each occurrence and is: h, D, F, Cl, Br, I, N (R)1)2，CN，NO2，OH，COOH，C(＝O)N(R1)2，Si(R1)3，B(OR1)2，C(＝O)R1，P(＝O)(R1)2，S(＝O)R1，S(＝O)2R1，OSO2R1A linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein each of said alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl groups may be substituted with one or more R1Radical substitution of one or more non-adjacent CH2The group can be represented by R1C＝CR1、C≡C、Si(R1)2、C＝O、NR1O, S or CONR1Instead of, or with 5 to 40 aromatic ring atoms and may in each case be substituted by one or more R1Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 40 aromatic ring atoms and which may be substituted by one or more R1A group-substituted aryloxy or heteroaryloxy group; also, two R groups together may also form a mono-or polycyclic aliphatic or aromatic ring system, where R1As above especially forThe definition given for formula (I).
In a preferred embodiment, the following may be the case: the olefin provided in step B) originates from a ketone of the formulae (IIa) to (IIo)
Figure BDA0002994034760000101
Figure BDA0002994034760000111
Figure BDA0002994034760000121
Wherein the structures of formulae (IIa) to (IIo) shown may be substituted by one or more R1Is substituted by radicals in which R1As defined above especially for formula (I).
In one embodiment, the following may be the case: the activated olefin provided in step B) is a chiral compound and is used in enantiomeric excess.
In another embodiment, the following may be the case: the activated olefin provided in step B) is a chiral compound and is used in racemic form.
As already set forth above, the activated alkene provided in step B) can be obtained from the ketone via a suitable reaction. The corresponding ketones, in particular the ketones of the formulae (IIa) to (IIo), are in many cases commercially available, which applies both to the racemic and to the enantiomeric excess of the composition. An overview of the corresponding CAS numbers of the compounds is given below:
Figure BDA0002994034760000122
Figure BDA0002994034760000131
preferred bicyclic, tricyclic and oligomeric cyclic ketones as detailed above can be used, for example, in the form of enolates or in the form of enamine derivatives.
For example, preferred enamines may be prepared using secondary amines, preferred amines being especially cyclic secondary amines, such as pyrrolidine [123-75-1], piperidine [110-89-4] and morpholine [110-91-8 ]. The reaction may be carried out in a suitable solvent, preferably a hydrocarbon solvent such as heptane, cyclohexane and the like. In addition, the reaction may be accelerated by a catalyst such as titanium tetrachloride.
The preparation of enolates or enamines from bicyclic, tricyclic or oligomeric cyclic ketones is in principle known from the literature of similar compounds and can be readily adapted by the person skilled in the art to prepare the compounds of the invention. More information may be found in the embodiments.
The following may also be the case: step C) is carried out at a temperature of less than 200 ℃ and preferably less than 160 ℃.
In addition, the following may be the case: step C) is carried out in a solvent. Preferably, a high boiling point inert solvent can be used. Typical solvents include dichlorobenzene, benzonitrile, nitrobenzene, DMSO, DMAC, NMP, oligo/polyethers such as diglyme, triglyme, tetraglyme, and the like. Other suitable solvents are boiling points<Those at 150 ℃ in which case the reaction is preferably carried out in a stirred autoclave. Boiling point<Typical solvents at 50 ℃ are, for example, heptane, cyclohexane, toluene, methyl tert-butyl ether, THF, bis
Figure BDA0002994034760000141
Alkanes, acetone, ethyl acetate, butyl acetate, acetonitrile, and the like. The solvents mentioned may be used individually or as mixtures.
The following may also be the case: the molar ratio of 1,2, 4-triazine to activated alkene, preferably enamine or enolate, is preferably in the range of 2.0:1.0 to 0.5:2.0, more preferably in the range of 1.0:1.0 to 1.0: 1.2.
The principles of the preparation methods detailed above are in principle known from the literature for similar compounds and can be readily adapted by the person skilled in the art to prepare the compounds of the invention. For example, the following references describe the reaction of 1,2, 4-triazines with activated olefins: boger, Dale l.; zhang, Minsheng, & E-EROS Organic Synthesis Reagents (e-EROS Encyclopedia of Reagents for Organic Synthesis) (2001); boger, Dale l. and Panek, James s, Journal of Organic Chemistry (Journal of Organic Chemistry), 46(10), 2179-82; 1981. however, these documents do not contain any indication of compounds that can be used as active components in electronic devices. More particularly, the 1,2, 4-triazines used in the prior art do not react with the polycyclic compounds. More information may be found in the embodiments.
The 1,2, 4-triazine is preferably obtained by the reaction of 1, 2-dicarbonyl with formamidrazone (formamidrazone). In one embodiment, the formamidinehydrazone is preferably obtained in situ by reacting an amidine compound with hydrazine.
The combination of steps A), B) and C) of the invention with the preparation of 1,2, 4-triazine by reaction of 1, 2-dicarbonyl with formamidrazone can bring unexpected advantages in terms of cost, purity and yield. Thus, the combination may achieve a synergistic effect.
In a preferred embodiment, the following may be the case: the 1, 2-dicarbonyl group may be represented by formula (III)
Figure BDA0002994034760000151
Wherein the symbol RbAnd RcHaving the definitions given above, in particular for formula (I).
The formamidrazones may preferably be represented by formula (IV)
Figure BDA0002994034760000152
Wherein the symbol RaHaving the definitions given above, in particular for formula (I).
The principle of the process detailed above for the preparation of 1,2, 4-triazines by reaction of 1, 2-dicarbonyl with formamidrazone is in principle known from the literature of similar compounds and can be easily adapted by the person skilled in the art to prepare the compounds of the invention. More information may be found in the embodiments.
In addition, the following may be the case: the formamidrazone preparation and/or the reaction thereof with the 1, 2-dicarbonyl compound is carried out in a solvent. Typical solvents are, for example, alcohols, methanol, ethanol and corresponding polar solvents and the like. The solvents mentioned may be used individually or as mixtures. The 1,2, 4-triazine thus obtained may be purified in a known manner, for example by crystallization from a suitable solvent or solvent mixture (typical solvents are, for example, heptane, cyclohexane, toluene, methyl tert-butyl ether, THF, bis
Figure BDA0002994034760000153
Alkane, acetone, ethyl acetate, butyl acetate, acetonitrile, isopropanol, ethanol, methanol, etc.), or by chromatography/flash chromatography on silica gel or alumina.
The principles of the preparation methods detailed above are in principle known from the literature for similar compounds and can be readily adapted by the person skilled in the art to prepare the compounds of the invention. The preparation of formamidrazone is described, for example, in Patrick J.G.Saris and Mark E.Thompson, organic chemistry Command (org.Lett.)2016, 18, 3960-. More information may be found in the embodiments.
In another configuration of the present invention, the following may be the case: 1,2, 4-triazine is obtained by reacting a nitroaromatic or nitroheteroaromatic compound with an amidine compound.
The principle of the process for preparing 1,2, 4-triazines by reaction of nitroaromatics or nitroheteroaromatics with amidine compounds detailed above is known in principle from the literature of similar compounds and can be readily adapted by the person skilled in the art to prepare the compounds of the invention. For example, Suzuki, Hitomi and Kawakami, Takehiko detail such reactions in Journal of Organic Chemistry (Journal of Organic Chemistry, JOC), 1999, 64, 3361(DOI:10.1021/jo982139 m). More information may be found in the embodiments.
The compounds obtainable by steps a) to C) can be reacted with other compounds comprising at least one aromatic or heteroaromatic group by known coupling reactions, the requirements for this purpose being known to the person skilled in the art and the detailed description in the examples helping the person skilled in the art to carry out these reactions.
Particularly suitable and preferred coupling reactions which all lead to the formation of C-C bonds and/or C-N bonds are those according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONGASHIRA and HIYAMA. These reactions are well known and the examples will provide further guidance to those skilled in the art.
The principles of the preparation methods detailed above are in principle known from the literature for similar compounds and can be readily adapted by the person skilled in the art to prepare the compounds of the invention. More information may be found in the embodiments.
By these methods, if necessary followed by purification, e.g. recrystallization or sublimation, high purity, preferably greater than 99%, can be obtained (by1H NMR and/or HPLC) of a compound obtainable according to the invention.
In another configuration, the following may be the case: the compounds obtainable by the process of the present invention comprise fused aromatic or heteroaromatic ring systems having at least 2, preferably 3, fused rings which may optionally be substituted.
In another embodiment, the following may be the case: at least one of the compounds provided in steps A) and/or B) comprises a hole-transporting group, or the product obtained in step C) is reacted with a compound comprising a hole-transporting group, in which case R, R in the structures of formulae (I) to (IV)a、RbOr RcThe groups comprise and preferably constitute hole transport groups. Hole transporting groups are known in the art and they preferably comprise triarylamine or carbazole groups.
The following may be preferred: the hole-transporting group comprises a group selected from the group consisting of formulas (H-1) to (H-3), and is preferably a group selected from the group consisting of formulas (H-1) to (H-3)
Figure BDA0002994034760000171
Figure BDA0002994034760000181
Wherein the dotted lines denote the connection positions, an
Ar2，Ar3，Ar4Each independently is an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which may be substituted by one or more R1Substituted by groups;
p is 0 or 1, and
z is a bond or C (R)1)2、Si(R1)2、C＝O、N-R1、N-Ar1、BR1、PR1、PO(R1)、SO、SO2Se, O or S, preferably a bond or C (R)1)2、N-R1O or S, where the symbol R1Having the definitions given above, especially for formula (I), and Ar1Is an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms, each of which may be substituted by one or more R1And (4) substituting the group. In addition, the presence of N-N bonds is preferably excluded.
Further, the following may be the case: the hole-transporting group comprises a group selected from the group consisting of formulae (H-4) to (H-26) and is preferably a group selected from the group consisting of formulae (H-4) to (H-26)
Figure BDA0002994034760000182
Figure BDA0002994034760000191
Figure BDA0002994034760000201
Wherein Y is1Is O, S, C (R)1)2、NR1Or NAr1The dotted bonds denote the connecting positions, e is 0, 1 or 2, j is 0, 1,2 or 3, h is identical or different on each occurrence and is 0, 1,2,3 or 4, p is 0 or 1, R1Having the definitions given above, especially for formula (I), and Ar1And Ar2Having the definitions given above, especially for formula (H-1) or (H-2). Also, the presence of N-N bonds is preferably excluded.
From the above wording it is clear that if the label is p ═ 0, then the corresponding Ar2The groups are absent and form bonds.
Preferably, Ar2The group may react with Ar of the formulae (H-1) to (H-26)2The groups may form complete conjugation with the aromatic or heteroaromatic groups or nitrogen atoms to which they are bonded.
In another preferred embodiment of the present invention, Ar2Is an aromatic or heteroaromatic ring system having from 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having from 6 to 12 carbon atoms, and the ring system may be interrupted by one or more R1Substituted, but preferably unsubstituted, by radicals in which R is1May have the definitions given above, especially for formula (I). More preferably, Ar2Is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, which may each be substituted by one or more R1Substituted, but preferably unsubstituted, by radicals in which R is1May have the definitions given above, especially for formula (I).
Also preferably, symbol Ar shown in formulae (H-1) to (H-26)2In particular aryl or heteroaryl groups having from 5 to 24 ring atoms, preferably from 6 to 13 ring atoms, more preferably from 6 to 10 ring atoms, such that the aromatic or heteroaromatic groups of the aromatic or heteroaromatic ring system are bonded directly to the corresponding atoms of the other groups, i.e. via atoms of said aromatic or heteroaromatic groups.
The following may also be the case: ar shown in formulas (H-1) to (H-26)2The group comprises an aromatic ring system having no more than two fused aromatic and/or heteroaromatic 6-membered rings; preferably it does not comprise any fused aromatic or heteroaromatic ring system with fused 6-membered rings. Thus, the naphthyl structure is preferred over the anthracene structure. In addition, fluorenyl, spirobifluorenyl, dibenzofuranyl, and/or dibenzothiophenyl structures are preferred over naphthyl structures. Particularly preferred are structures without condensed rings, such as phenyl, biphenyl, terphenyl and/or quaterphenyl structures.
The following may also be the case: ar shown in formulas (H-1) to (H-26)2The radicals have in particular not more than 1 nitrogen atom, preferably not more than 2 heteroatoms, particularly preferably not more than 1 heteroatom, particularly preferably no heteroatoms.
In another preferred embodiment of the present invention, Ar3And/or Ar4Identical or different on each occurrence and is an aromatic or heteroaromatic ring system having from 6 to 24 aromatic ring atoms, preferably from 6 to 18 aromatic ring atoms, and more preferably is an aromatic ring system having from 6 to 12 aromatic ring atoms or a heteroaromatic ring system having from 6 to 13 aromatic ring atoms, which ring systems may each be substituted by one or more R1Substituted, but preferably unsubstituted, by radicals in which R is1May have the definitions given above, especially in formula (I).
In another preferred embodiment, the following may be the case: at least one of the compounds provided in step A) and/or step B) comprises a group comprising an electron-transporting group, or the product obtained in step C) is reacted with a compound comprising a group comprising an electron-transporting group, in which case in the structures of formulae (I) to (IV), R, Ra、RbOr RcThe group preferably comprises and preferably constitutes an electron transport group-containing group. Electron transport groups are well known in the art and facilitate the ability of a compound to transport and/or conduct electrons.
In addition, the compounds obtainable by the present process, which compounds comprise at least one structure selected from pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinazoline, quinoxaline, quinoline, isoquinoline, imidazole and/or benzimidazole, particularly preferably pyrimidine, triazine and quinazoline, show surprising advantages. These structures generally facilitate the ability of the compound to transport and/or conduct electrons.
In one preferred configuration of the present invention, the following may be the case: the group containing an electron-transporting group includes and is preferably a group which can be represented by the formula (QL)
Figure BDA0002994034760000221
Wherein L is1Represents a bond or has 5 to 40, preferably 5 to 30, aromatic ring atoms and may be substituted by one or more R1A group-substituted aromatic or heteroaromatic ring system, Q is an electron-transporting group, wherein R is1Having the definitions given above, in particular for formula (I), and the key marks the connection location.
Preferably, L1The group may be substituted with a Q group and L of formula (QL)1The atoms, preferably carbon or nitrogen atoms, to which the groups are bonded form a complete conjugation. Once a direct bond is formed between adjacent aromatic or heteroaromatic rings, complete conjugation of the aromatic or heteroaromatic system is formed. Other bonds between the aforementioned conjugated groups, such as other bonds via sulfur, nitrogen or oxygen atoms or carbonyl groups, are not detrimental to conjugation. In the case of fluorene systems, the two aromatic rings are directly bonded, with sp in the 9 position3Hybridization of the carbon atom does prevent the fusion of the rings, but due to the sp in position 93The hybrid carbon atom is not necessarily located between the electron-transporting Q group and the atom via which the group of formula (QL) is bonded to the other structural units of the compounds of the invention, so conjugation is possible. In contrast, in the case of the second spirobifluorene structure, if the Q group is bonded to L of formula (QL)1Complete conjugation can be formed if the bonds between the aromatic or heteroaromatic groups to which the groups are bonded are via the same phenyl group in the spirobifluorene structure or via phenyl groups in the spirobifluorene structure that are directly bonded to one another and in one plane. If the Q group is bonded to L of the formula (QL)1The bond between the aromatic or heteroaromatic groups to which the groups are bonded is via sp through the 9-position3The conjugation is interrupted if there is a different phenyl group in the second spirobifluorene structure to which the hybridized carbon atom is bonded.
In another preferred embodiment of the present invention, L1Is a bond or an aromatic or heteroaromatic ring system having 5 to 14 aromatic or heteroaromatic ring atoms, preferably an aromatic ring system having 6 to 12 carbon atoms, and which may be substituted by one or more R1Substituted, but preferably unsubstituted, by radicals in which R is1May have the definitions given above, especially for formula (I). More preferably, L1Is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, which may each be substituted by one or more R1Substituted, but preferably unsubstituted, by radicals in which R is1May have the definitions given above, especially for formula (I).
Also preferably, symbol L shown in formula (QL)1In particular an aryl or heteroaryl group which is identical or different on each occurrence and is a bond or has from 5 to 24 ring atoms, preferably from 6 to 13 ring atoms, more preferably from 6 to 10 ring atoms, such that the aromatic or heteroaromatic groups of the aromatic or heteroaromatic ring system are bonded directly to the corresponding atoms of the other groups, i.e. via atoms of said aromatic or heteroaromatic groups.
Further, the following may be the case: l shown in formula (QL)1The groups comprise aromatic ring systems having no more than two fused aromatic and/or heteroaromatic 6-membered rings, preferably without any fused aromatic or heteroaromatic ring systems. Thus, the naphthyl structure is preferred over the anthracene structure. In addition, fluorenyl, spirobifluorenyl, dibenzofuranyl, and/or dibenzothiophenyl structures are preferred over naphthyl structures.
Particularly preferred are structures without condensed rings, such as phenyl, biphenyl, terphenyl and/or quaterphenyl structures.
Suitable aromatic or heteroaromatic ring systems L1Examples of (b) are selected from: ortho-, meta-or para-phenylenes, ortho-, meta-or para-biphenylenes, terphenylenes, especially branched terphenylenes, quaterphenylenes,In particular branched-chain tetrabiphenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothiophenylene and carbazolylene; each of which may be substituted by one or more R1The radicals are substituted, but preferably unsubstituted.
The following may also be the case: l shown in formula (QL)1The radical in particular has not more than 1 nitrogen atom, preferably not more than 2 heteroatoms, particularly preferably not more than 1 heteroatom and more preferably no heteroatoms.
Preferably, especially the Q group, or electron transport group, shown in formula (QL) may be selected from the structures of formula (Q-1), (Q-2), (Q-4), (Q-5), (Q-6), (Q-7), (Q-8), (Q-9) and/or (Q-10)
Figure BDA0002994034760000241
Figure BDA0002994034760000251
Wherein the dotted line key marks the connection position,
q' is the same or different at each occurrence and is CR1Or N, and
q' is NR1O or S;
wherein at least one Q' is N, and
R1as defined above especially in formula (I).
In addition, especially the Q group, or electron transport group, shown in formula (QL) can be selected from the structures of formula (Q-11), (Q-12), (Q-13), (Q-14) and/or (Q-15)
Figure BDA0002994034760000261
Wherein the symbol R1Having the definitions given above, especially for formula (I), X' is N or CR1And the dashed bonds indicate the attachment position, wherein X' is preferably a nitrogen atom.
In another embodiment, especially the Q group, or electron transport group, shown in formula (QL), can be selected from the structures of formula (Q-16), (Q-17), (Q-18), (Q-19), (Q-20), (Q-21) and/or (Q-22)
Figure BDA0002994034760000271
Wherein the symbol R1With the definitions detailed above, especially for formula (I), the dashed bonds denote the connecting positions and m is 0, 1,2,3 or 4, preferably 0, 1 or 2, n is 0, 1,2 or 3, preferably 0, 1 or 2, and o is 0, 1 or 2, preferably 1 or 2. Preferred herein are structures of the formulae (Q-16), (Q-17), (Q-18) and (Q-19).
In another embodiment, especially the Q group, or electron transport group, shown in formula (QL), can be selected from the structures of formula (Q-23), (Q-24) and/or (Q-25)
Figure BDA0002994034760000281
Wherein the symbol R1Have the definitions set out above, in particular for formula (I), and the dashed bonds denote the connection positions.
In another embodiment, especially the Q group, or electron transport group, shown in formula (QL), can be selected from the structures of formula (Q-26), (Q-27), (Q-28), (Q-29), and/or (Q-30)
Figure BDA0002994034760000282
Figure BDA0002994034760000291
Wherein symbol Ar1And R1Having the definitions given above, especially for formula (I), X' is N or CR1And the dashed bonds mark the connection locations. Preferably, in the structures of the formulae (Q-26), (Q-27) and (Q-28), it is exactlyOne X' is a nitrogen atom.
Preferably, especially the Q group, or electron transport group, shown in formula (QL) may be selected from the structures of formula (Q-31), (Q-32), (Q-33), (Q-34), (Q-35), (Q-36), (Q-37), (Q-38), (Q-39), (Q-40), (Q-41), (Q-42), (Q-43) and/or (Q-44)
Figure BDA0002994034760000301
Figure BDA0002994034760000311
Figure BDA0002994034760000321
Wherein symbol Ar1And R1With the definitions set forth above, especially for formula (I) or (H-1), the dashed bonds denote the connecting positions and m is 0, 1,2,3 or 4, preferably 0, 1 or 2, n is 0, 1,2 or 3, preferably 0 or 1, n is 0, 1,2 or 3, preferably 0, 1 or 2, and l is 1,2,3,4 or 5, preferably 0, 1 or 2.
In another preferred embodiment of the present invention, Ar1Identical or different on each occurrence and is an aromatic or heteroaromatic ring system, preferably an aryl or heteroaryl group having 5 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, and more preferably an aromatic ring system, preferably an aryl group having 6 to 12 aromatic ring atoms, or a heteroaromatic ring system, preferably a heteroaryl group having 5 to 13 aromatic ring atoms, which ring systems may each be substituted by one or more R1Substituted, but preferably unsubstituted, by radicals in which R is1May have the definitions detailed above, especially in formula (I).
Preferably, the symbol Ar1Is an aryl or heteroaryl group, such that an aromatic or heteroaromatic group of an aromatic or heteroaromatic ring system is directly bonded to the corresponding atom of another group, i.e. via an atom of the aromatic or heteroaromatic group with anotherThe corresponding atoms of the groups, such as the carbon or nitrogen atoms of the (H-1) to (H-26) or (Q-26) to (Q-44) groups shown above, are directly bonded.
Advantageously, Ar in formulae (H-1) to (H-26) or (Q-26) to (Q-44)1Is a compound having 6 to 12 aromatic ring atoms and may be substituted by one or more R1Substituted, but preferably unsubstituted, aromatic ring systems, in which R is1May have the definitions detailed above, especially for formula (I).
Preferably, R in the formulae (H-1) to (H-26) or (Q-1) to (Q-44)1Or R2The group not being different from the R1Or R2Aryl or heteroaryl group Ar to which the group is bonded1、Ar2、Ar3And/or Ar4Form a fused ring system. This includes bonding to R1Possible substituents R of the radicals2Forming a fused ring system.
When X is CR, CRa、CRbOr CRcWhen, or when the aromatic and/or heteroaromatic groups are substituted with substituents R, these substituents R are preferably selected from: h, D, F, CN, N (Ar)2，C(＝O)Ar，P(＝O)(Ar)2A linear alkyl or alkoxy group having 1 to 10 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, each of which may be substituted by one or more R1Radical substitution of one or more non-adjacent CH2The radicals being substitutable for O and in which one or more hydrogen atoms are substitutable for D or F, having 5 to 24 aromatic ring atoms and being substitutable in each case by one or more R1An aromatic or heteroaromatic ring system which is substituted but preferably unsubstituted, or has 5 to 25 aromatic ring atoms and may be substituted by one or more R1A group-substituted aralkyl or heteroaralkyl group; here, the two substituents R bonded to adjacent carbon atoms may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more R1Substituted by radicals in which the Ar radicals are identical or different on each occurrence and are of 5 to 40 aromatic ring atoms and may be substituted by one or moreR1A group-substituted aromatic or heteroaromatic ring system; here, the two Ar groups bonded to the same silicon atom, nitrogen atom, phosphorus atom or boron atom may be bonded through a single bond or selected from B (R)1)、C(R1)2、Si(R1)2、C＝O、C＝NR1、C＝C(R1)2、O、S、S＝O、SO2、N(R1)、P(R1) And P (═ O) R1Are bridged to each other.
More preferably, these substituents R are selected from: h, D, F, CN, N (Ar)2A straight-chain alkyl group having from 1 to 8 carbon atoms, preferably having 1,2,3 or 4 carbon atoms, or a branched or cyclic alkyl group having from 3 to 8 carbon atoms, preferably having 3 or 4 carbon atoms, or an alkenyl group having from 2 to 8 carbon atoms, preferably having 2,3 or 4 carbon atoms, each of which may be substituted by one or more R1Are unsubstituted, or have 5 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, and may in each case be substituted by one or more non-aromatic R1An aromatic or heteroaromatic ring system which is substituted, but preferably unsubstituted; at the same time, two substituents R bonded to adjacent carbon atoms are preferred1Optionally can form a mono-or polycyclic aliphatic ring system which may be substituted by one or more R2The radicals are substituted, but are preferably unsubstituted, wherein Ar may have the definitions set out above.
Most preferably, the substituent R, Ra、RbOr RcSelected from H and a compound having from 6 to 18 aromatic ring atoms, preferably from 6 to 13 aromatic ring atoms, and which may be substituted in each case by one or more nonaromatic R1The radicals substituted, but preferably unsubstituted, aromatic or heteroaromatic ring systems. Examples of suitable substituents R are selected from: phenyl, o-, m-or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3-or 4-fluorenyl, 1-, 2-, 3-or 4-spirobifluorenyl, pyridyl, pyrimidyl, 1-, 2-, 3-or 4-dibenzofuranyl, 1-, 2-, 3-or 4-dibenzothienyl, 1-, 2-, 3-or 4-carbazolyl and indenocarbazoleEach of which may be substituted by one or more R1The radicals are substituted, but preferably unsubstituted.
In addition, the following may be the case: a substituent R, R of a ring system of formula (I) or (II)a、RbOr RcThe ring atoms of the ring systems not bound to these radicals either not being able to lie between one another, i.e. in particular the substituents RbAnd RcForm a fused aromatic or heteroaromatic ring system with one another, preferably without forming any fused ring system. This includes the key R, Ra、RbOr RcPossible substituents R of the radicals1、R2Forming a fused ring system.
The following may be the case: ar, Ar1、Ar2、Ar3And/or Ar4The group is selected from: phenyl, o-, m-or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3-or 4-fluorenyl, 1-, 2-, 3-or 4-spirobifluorenyl, pyridyl, pyrimidyl, 1-, 2-, 3-or 4-dibenzofuranyl, 1-, 2-, 3-or 4-dibenzothienyl, pyrenyl, triazinyl, imidazolyl, benzimidazolyl, benzofuranyl
Figure BDA0002994034760000341
Azolyl, benzothiazolyl, 1-, 2-, 3-or 4-carbazolyl, indenocarbazolyl, 1-or 2-naphthyl, anthracenyl, preferably 9-anthracenyl, phenanthrenyl and/or terphenylidene, each of which may be substituted by one or more R1And/or R2The radicals substituted, but preferably unsubstituted, are particularly preferably phenyl, spirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene, phenanthrene, terphenylene radicals.
In another preferred embodiment, the following may be the case: the compounds obtainable according to the present invention comprise at least two, preferably at least three, non-aromatic or non-heteroaromatic polycyclic ring systems having at least 2, preferably at least 3 rings.
When X' is CR1Or when the aromatic and/or heteroaromatic radical is substituted by a substituent R1When substituted, these substituents R1Preferably selected from: h, D, F, CN, N: (Ar1)2，C(＝O)Ar1，P(＝O)(Ar1)2A linear alkyl or alkoxy group having 1 to 10 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, each of which may be substituted by one or more R2Radical substitution of one or more non-adjacent CH2The radicals being substitutable for O and in which one or more hydrogen atoms are substitutable for D or F, having 5 to 24 aromatic ring atoms and being substitutable in each case by one or more R2An aromatic or heteroaromatic ring system which is substituted but preferably unsubstituted, or has 5 to 25 aromatic ring atoms and may be substituted by one or more R2A group-substituted aralkyl or heteroaralkyl group; at the same time, two substituents R bonded to adjacent carbon atoms are preferred1Optionally aliphatic, aromatic or heteroaromatic ring systems which may form a single ring or multiple rings, which may be substituted by one or more R1Substituted by groups; wherein Ar is1The radicals have the definitions given above, in particular for the formulae (H-1) to (H-3).
More preferably, these substituents R1Selected from: h, D, F, CN, N (Ar)1)2A straight-chain alkyl group having from 1 to 8 carbon atoms, preferably having 1,2,3 or 4 carbon atoms, or a branched or cyclic alkyl group having from 3 to 8 carbon atoms, preferably having 3 or 4 carbon atoms, or an alkenyl group having from 2 to 8 carbon atoms, preferably having 2,3 or 4 carbon atoms, each of which may be substituted by one or more R2Are unsubstituted, or have 5 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms, and may in each case be substituted by one or more non-aromatic R1An aromatic or heteroaromatic ring system which is substituted, but preferably unsubstituted; at the same time, two substituents R bonded to adjacent carbon atoms are preferred1Optionally can form a mono-or polycyclic aliphatic ring system which may be substituted by one or more R2The radicals substituted, but preferably unsubstituted, wherein Ar1May have the definitions set out above.
Most preferably, the substituent R1Selected from H or having 6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms and in each case optionally substituted by one or more non-aromatic R2The radicals substituted, but preferably unsubstituted, aromatic or heteroaromatic ring systems. Suitable substituents R1Examples of (b) are selected from: phenyl, o-, m-or p-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-, 2-, 3-or 4-fluorenyl, 1-, 2-, 3-or 4-spirobifluorenyl, pyridyl, pyrimidyl, 1-, 2-, 3-or 4-dibenzofuranyl, 1-, 2-, 3-or 4-dibenzothienyl, 1-, 2-, 3-or 4-carbazolyl and indenocarbazolyl, each of which may be substituted by one or more R2The radicals are substituted, but preferably unsubstituted.
The following may also be the case: substituent R of heteroaromatic ring systems of the formulae (I) to (IV)1Do not form a fused aromatic or heteroaromatic ring system with the ring atoms of said aromatic or heteroaromatic ring system, preferably do not form any fused ring systems. This includes bonding to R1Possible substituents R of the radicals2Forming a fused ring system.
The following may also be the case: in the structures of formulae (I), (II), (III) and/or (IV), at least one R1The radicals are selected from the formula (R)1-1) to (R)1-92), or in the structures of formulae (H-1) to (H-26) and/or (Q-1) to (Q-44), at least one Ar1Or R1The radicals are selected from the formula (R)1-1) to (R)1Group of-92)
Figure BDA0002994034760000361
Figure BDA0002994034760000371
Figure BDA0002994034760000381
Figure BDA0002994034760000391
Figure BDA0002994034760000401
Figure BDA0002994034760000411
Figure BDA0002994034760000421
Figure BDA0002994034760000431
The symbols used therein are as follows:
Y1is O, S or NR2Preferably O or S;
k is independently at each occurrence 0 or 1;
i is independently at each occurrence 0, 1 or 2;
j is independently at each occurrence 0, 1,2, or 3;
h is independently at each occurrence 0, 1,2,3, or 4;
g is independently at each occurrence 0, 1,2,3,4 or 5;
R2may have the definitions given above, especially for formula (I), and
the dotted bond marks the connection location.
Preference is given here to the formula R1-1 to R1A group of-54, particularly preferably R1-1、R1-3、R1-5、R1-6、R1-15、R1-29、R1-30、R1-31、R1-32、R1-33、R1-38、R1-39、R1-40、R1-41、R1-42、R1-43、R1-44 and/or R1-45 groups.
The following may be preferred: formula (R)1-1) to (R)1The sum of the indices k, i, j, h and g in the structure of-92) is in each case not more than 3, preferably not more than 2, more preferably not more than 1.
Preferably, formula (R)1-1) to (R)1R in-92)2The group not being different from the R2The ring atoms of the aryl or heteroaryl group to which the group is bonded form a fused aromatic or heteroaromatic ring system, preferably not any fused ring system.
Preferred are compounds comprising at least one structure of formulae (H-1) to (H-26), wherein Ar2The group is selected from the formula (L)1-1) to (L)1-108), and/or a compound comprising a structure of formula (QL), wherein L1The radicals are bonds or are selected from the formula (L)1-1) to (L)1Group of-108)
Figure BDA0002994034760000441
Figure BDA0002994034760000451
Figure BDA0002994034760000461
Figure BDA0002994034760000471
Figure BDA0002994034760000481
Figure BDA0002994034760000491
Figure BDA0002994034760000501
Figure BDA0002994034760000511
Figure BDA0002994034760000521
Wherein the dashed bonds in each case denote a connecting position, the index k is 0 or 1, the index l is 0, 1 or 2, the index j is independently in each occurrence 0, 1,2 or 3; the index h is independently at each occurrence 0, 1,2,3 or 4, the index g is 0, 1,2,3,4 or 5; symbol Y1Is O, S or NR1Preferably O or S; and the symbol R1Having the definitions given above, in particular for formula (I).
The following may be preferred: formula (L)1-1) to (L)1The sum of the indices k, l, g, h and j in the structure of-108) is in each case at most 3, preferably at most 2 and more preferably at most 1.
Preferred compounds of the present invention having a group of the formulae (H-1) to (H-26) comprise a compound selected from the group consisting of the formulae (L)1-1) to (L)1-78) and/or (L)1-92) to (L)1One of-108), preferably of formula (L)1-1) to (L)1-54) and/or (L)1-92) to (L)1One of the formulae (L) to (108) and particularly preferably of the formula (L)1-1) to (L)1-29) and/or (L)1-92) to (L)1Ar of one of the groups-103)2A group. Advantageously, of the formula (L)1-1) to (L)1-78) and/or (L)1-92) to (L)1-108), preferably of formula (L)1-1) to (L)1-54) and/or (L)1-92) to (L)1-108), particularly preferably of formula (L)1-1) to (L)1-29) and/or (L)1-92) to (L)1The sum of the indices k, l, g, h and j in the structure of-103), in each caseMay be no greater than 3, preferably no greater than 2, more preferably no greater than 1.
Preferred compounds of the invention having a group of formula (QL) comprise L1Group, said L1The group represents a bond or is selected from the formula (L)1-1) to (L)1-78) and/or (L)1-92) to (L)1-108), preferably of formula (L)1-1) to (L)1-54) and/or (L)1-92) to (L)1One of the formulae (L) to (108), particularly preferably of the formula (L)1-1) to (L)1-29) and/or (L)1-92) to (L)1-103). Advantageously, of the formula (L)1-1) to (L)1-78) and/or (L)1-92) to (L)1-108), preferably of formula (L)1-1) to (L)1-54) and/or (L)1-92) to (L)1-108), particularly preferably of formula (L)1-1) to (L)1-29) and/or (L)1-92) to (L)1The sum of the indices k, l, g, h and j in the structure of-103) may in each case be not more than 3, preferably not more than 2, more preferably not more than 1.
Preferably, formula (L)1-1) to (L)1R in-108)1The group not being different from the R1The ring atoms of the aryl or heteroaryl group to which the group is bonded form a fused aromatic or heteroaromatic ring system, and preferably do not form any fused ring systems. This includes bonding to R2Possible substituents R of the radicals2Forming a fused ring system.
When the compounds of the invention are substituted by aromatic or heteroaromatic R1Or R2When substituted, preferably they do not have any aryl or heteroaryl groups having more than two aromatic six-membered rings directly fused to one another. More preferably, the substituents are completely free of any aryl or heteroaryl groups having six-membered rings directly fused to each other. The reason for this preference is the low triplet energy of such structures. Fused aryl radicals which have more than two aromatic six-membered rings directly fused to one another but which are still suitable according to the invention are phenanthrene and terphenylene since they also have high triplet energy levels.
The compounds obtainable according to the invention are used as fluorescent emitters or as blue emittersIn the case of the construction of OLED materials, preferred compounds can contain corresponding groups, for example fluorene, anthracene and/or pyrene groups, which groups can be substituted by R1Or R2Substituted by a group, or the group is passed through (R)1-1) to (R)1-95) group, preferably (R)1-33) to (R)1-57) and (R)1-76) to (R)1-86), or (L)1-1) to (L)1-109), preferably (L)1-30) to (L)1-60) and (L)1-71) to (L)1-91) substituted R2Formed by corresponding substitution.
In another preferred embodiment of the invention, R2For example in the structures of formulae (I) to (IV) and preferred embodiments of the structures or structures relating to these formulae, the same or different at each occurrence and are selected from: h, D, an aliphatic hydrocarbon radical having from 1 to 10 carbon atoms, preferably having from 1,2,3 or 4 carbon atoms, or an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, preferably from 5 to 24 aromatic ring atoms, more preferably from 5 to 13 aromatic ring atoms, which may be substituted by one or more alkyl groups each having from 1 to 4 carbon atoms, but is preferably unsubstituted.
Preferably, R2The group not being different from the R2The ring atoms of the aryl or heteroaryl group to which the group is bonded form a fused aromatic or heteroaromatic ring system, and preferably do not form any fused ring systems.
Preferred embodiments of the compounds of the present invention are specifically enumerated in the examples, and these compounds may be used alone or in combination with other compounds for all purposes of the present invention.
The above-described preferred embodiments may be combined with each other as needed as long as the conditions specified in claim 1 are satisfied. In a particularly preferred embodiment of the invention, the above-described preferred embodiments apply at the same time.
The compounds obtainable by the process of the invention are novel. Thus, the present invention further provides a compound obtainable by a process.
Preferred compounds comprise a structure that can be represented by formula (V)
Figure BDA0002994034760000541
Wherein the symbol Ra、RbAnd RcHaving the definitions given above, especially for formula (I), the bicyclic/polycyclic ring may have one or more substituents R, and R has the definitions given above, especially for formula (II). The bicyclic/polycyclic ring shown in formula (V) is derived from the activated olefin and thus the detailed description set forth in this connection is also applicable to the compounds of formula (V). The same applies to Ra、RbAnd RcA group.
Preferably, the bicyclic/polycyclic ring shown in formula (II) or (V) is a non-aromatic or non-heteroaromatic polycyclic ring system having at least 2, preferably at least 3 rings. In particular, the bicyclic/polycyclic rings shown in formula (II) or (V) form substructures of formulae (N-1) to (N-14)
Figure BDA0002994034760000551
Figure BDA0002994034760000561
Wherein the dotted line represents the linkage of the bicyclic/polycyclic ring to the piperidine structure shown in formula (V) to which the bicyclic/polycyclic ring is fused. The substructures of the formulae (N-1) to (N-14) shown may be substituted by one or more R groups, wherein R is as defined above especially for formula (I).
In a preferred embodiment, the following may be the case: the pyridine structure shown in formula (V) to which the bicyclic/polycyclic ring is fused is not fused with other ring systems. Thus, RbAnd RcThe radicals preferably do not form any ring system. This includes bonding to RbOr RcPossible substituents R of the radicals1、R2Forming a fused ring system.
The following may also be the case: the compound has at least two compounds shown in formula (V)And (5) structure. In a preferred embodiment, these compounds may be represented as Ra、RbAnd RcOne of the groups forms a bond or a linking group, wherein the linking group is preferably L having the definition given above, especially for formula (QL)1A group. These compounds, which preferably have two structures shown in formula (V), are preferably symmetrical, which symmetry preferably results from a linking group or bond linking at least two structures shown in formula (V).
In a preferred configuration, the compounds obtainable according to the invention, preferably compounds having the structure of formula (V), are selected from the group consisting of phenyl-containing compounds, halophenyl compounds, biphenyl, terphenyl, quaterphenyl, fluorene, indenofluorene, spirobifluorene, carbazole, indenocarbazole, indolocarbazole, spirocarbazole, pyrimidine, triazine, lactam, triarylamine, dibenzofuran, dibenzothiophene, imidazole, benzimidazole, benzol
Figure BDA0002994034760000572
Oxazole, benzothiazole, 5-arylphenanthridin-6-one, 9, 10-dehydrophenanthrene, fluoranthene, anthracene, pyrene, perylene, borane, triarylborane, heteroarylborane, triazaneborane, benzanthracene, indeno [1,2,3-jk ]]Fluorene.
In a preferred configuration, the compound obtainable according to the invention, preferably the compound having the structure of formula (V), may be represented by the structure of formula (V). Preferably, the compounds obtainable according to the invention, preferably the compounds having the structure of formula (V), have a molecular weight of not more than 5000g/mol, preferably not more than 4000g/mol, particularly preferably not more than 3000g/mol, particularly preferably not more than 2000g/mol, most preferably not more than 1200 g/mol.
In addition, preferred compounds of the invention are characterized in that they are sublimable. The molar mass of these compounds is generally less than about 1200 g/mol.
In a preferred embodiment, preferred compounds include those comprising a structure of formula (V) and exactly one structure of formula (V) having the following characteristics:
Figure BDA0002994034760000571
Figure BDA0002994034760000581
Figure BDA0002994034760000591
Figure BDA0002994034760000601
Figure BDA0002994034760000611
Figure BDA0002994034760000621
in the compounds detailed above, "RaThe expression comprising means R in the structure (V)aThe radicals containing radicals of the corresponding formula, e.g. of the formula (R)1-1) to (R)1-92), (H-1) to (H-26) and/or (Q-1) to (Q-44), wherein this group can be bonded to structure (V) directly or via a linking group, wherein the linking group is preferably L having the definition given above, in particular for formula (QL)1A group. This is for formula (R)1-1) to (R)1The groups of (A) -92) and/or (Q-1) to (Q-44) are especially so. More preferably, formula (R)1-1) to (R)1-92), (H-1) to (H-26) and/or (Q-1) to (Q-44) via a bond or a group of formula (L)1-1) to (L)1-108), more preferably (L)1-1) to (L)1-5) and/or (L)1-92) to (L)1The group of-103) is bonded to the pyridine structure shown in the formula (V). The same applies to "RbComprising "and" RcThe expression comprising.
In a preferred embodiment, preferred compounds include those comprising a structure of formula (V) and exactly two structures of formula (V) having the following characteristics:
Figure BDA0002994034760000622
Figure BDA0002994034760000631
Figure BDA0002994034760000641
Figure BDA0002994034760000651
Figure BDA0002994034760000661
Figure BDA0002994034760000671
Figure BDA0002994034760000681
Figure BDA0002994034760000691
Figure BDA0002994034760000701
Figure BDA0002994034760000711
Figure BDA0002994034760000721
Figure BDA0002994034760000731
Figure BDA0002994034760000741
Figure BDA0002994034760000751
Figure BDA0002994034760000761
Figure BDA0002994034760000771
Figure BDA0002994034760000781
Figure BDA0002994034760000791
Figure BDA0002994034760000801
Figure BDA0002994034760000811
in the compounds detailed above, "RaThe expression comprising means R in the structure (V)aRadical (I)Containing radicals of the corresponding formula, e.g. of the formula (R)1-1) to (R)1-92), (H-1) to (H-26) and/or (Q-1) to (Q-44), wherein this group can be bonded to structure (V) directly or via a linking group, wherein the linking group is preferably L having the definition given above, in particular for formula (QL)1A group. This is for formula (R)1-1) to (R)1The groups of (A) -92) and/or (Q-1) to (Q-44) are especially so. More preferably, formula (R)1-1) to (R)1-92), (H-1) to (H-26) and/or (Q-1) to (Q-44) via a bond or a group of formula (L)1-1) to (L)1-108), more preferably (L)1-1) to (L)1-5) and/or (L)1-92) to (L)1The group of-103) is bonded to the pyridine structure shown in the formula (V). The same applies to "RbComprising "and" RcThe expression comprising. "(L)1-1) to (L)1-108), preferably (L)1-1) to (L)1-5) and/or (L)1-92) to (L)1The expression "103" means the corresponding Ra、RbOr RcThe group comprises the formula (L)1-1) to (L)1-108), two structures of formula (V) and said formula (L)1-1) to (L)1-108) or via said formula (L)1-1) to (L)1-108) are bonded such that the compound comprising two structures of formula (V) comprises exactly one R via which the rest of the substructure is connecteda、RbOr RcA group. "(R)1-1) to (R)1-92), preferably (R)1-1) to (R)1-4), in each case via a bond; the expression "means the corresponding Ra、RbOr RcThe radicals in each case comprising the formula (R)1-1) to (R)1-92), wherein these radicals of formula (R)1-1) to (R)1The radicals of-92) are bonded via a bond in each case, thereby connecting the two structures of the formula (V). In this case, the compound comprising two structures of formula (V) has exactly two R via which the remaining substructures are bondeda、RbOr RcA group. Similar expressions have corresponding meanings. The expression "bond" means the corresponding Ra、RbOr RcEach of the groups represents a bond via which two structures of formula (V) are linked such that a compound comprising two structures of formula (V) comprises exactly one R representing a bonda、RbOr RcA group via which the remaining substructure is linked.
The compounds obtainable according to the invention, preferably compounds having the structure of formula (V), may also have suitable substituents, for example by relatively long alkyl groups (about 4 to 20 carbon atoms), especially branched alkyl groups, or optionally substituted aryl groups, for example xylyl, trimethylphenyl or branched terphenyl or quaterphenyl groups, which give solubility in standard organic solvents, so that the compounds are soluble at room temperature in toluene or xylene, for example in sufficient concentration to enable processing of the compounds from solution. These soluble compounds have particularly good suitability for processing from solution, for example by printing processes. In addition, it should be emphasized that the compounds obtainable according to the invention, preferably the compounds having the structure of formula (V), have enhanced solubility in these solvents.
The compounds obtainable according to the invention can also be mixed with polymers. These compounds may also be covalently incorporated into polymers. This may be particularly true of compounds substituted with a reactive leaving group such as bromo, iodo, chloro, boronic acid or boronic ester, or with a reactive polymerizable group such as alkene or oxetane. These can be used as monomers for the manufacture of corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably effected via halogen functionality or boronic acid functionality or via polymerizable groups. The polymers may additionally be crosslinked via such groups. The compounds and polymers of the invention may be used in the form of crosslinked or uncrosslinked layers.
The present invention therefore further provides oligomers, polymers or dendrimers containing one or more structures of formula (V) as detailed above or compounds obtainable according to the present invention, wherein a compound of the present invention or a structure of formula (V) is present in association with one or more bonds of the polymer, oligomer or dendrimer. According to the structure of formula (V) or the linkages of said compounds, they thus form side chains or linkages in the main chain of the oligomer or polymer. The polymer, oligomer or dendrimer may be conjugated, partially conjugated or non-conjugated. The oligomer or polymer may be linear, branched or dendritic. The same preferences as above apply with respect to the oligomers, dendrimers and repeating units of the compounds of the invention in the polymers.
To prepare the oligomers or polymers, the monomers of the invention are homopolymerized or copolymerized with other monomers. Preference is given to copolymers in which the units of the formula (V) or the units of the preferred embodiments listed above and below are present to the extent of from 0.01 to 99.9 mol%, preferably from 5 to 90 mol%, more preferably from 20 to 80 mol%. Suitable and preferred comonomers forming the basic skeleton of the polymer are selected 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 a plurality of these units. The polymers, oligomers and dendrimers may also contain other units, such as hole transport units, especially those based on triarylamines, and/or electron transport units.
Of particular interest are also the compounds of the invention which are characterized by a high glass transition temperature. In this connection, particular preference is given to compounds obtainable according to the invention having a glass transition temperature of at least 70 ℃, more preferably at least 110 ℃, even more preferably at least 125 ℃ and particularly preferably at least 150 ℃ as determined according to DIN 51005 (version 2005-08), preferably compounds comprising the structure of the formula (V) or the preferred embodiments listed above and below.
For processing the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, the compounds of the invention are requiredThe formulation of (1). These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents can preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, diclorobenzene
Figure BDA0002994034760000841
Alkanes, phenoxytoluenes, especially 3-phenoxytoluene, (-) -fenchone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 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, methyl benzoate, NMP, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl ether, triethylene glycol butyl 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, hexamethylindane, or a mixture of these solvents.
Thus, the present invention further provides a formulation comprising a compound of the invention and at least one other compound. The further compound may be, for example, a solvent, especially one of the above-mentioned solvents or a mixture of these solvents. Alternatively, the further compound may be at least one organic or inorganic compound which is also used in the electronic device, for example a luminescent compound, such as a fluorescent dopant, a phosphorescent dopant or a compound exhibiting TADF (thermally activated delayed fluorescence), especially a phosphorescent dopant, and/or another host material. The other compounds may also be polymeric.
Accordingly, the present invention further provides compositions comprising a compound of the present invention and at least one other organic functional material. The functional material is typically an organic or inorganic material introduced between the anode and the cathode. Preferably, the organic functional material is selected from fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocking materials, hole blocking materials, wide band gap materials and n-type dopants.
The present invention therefore also relates to a composition comprising at least one compound obtainable according to the invention, preferably a compound comprising the structure of formula (V) or the preferred embodiments listed above and below, and at least one further matrix material. According to a particular aspect of the invention, the further host material has hole transporting properties.
The present invention further provides a composition comprising at least one compound obtainable according to the present invention, preferably a compound comprising the structure of formula (V) or the preferred embodiments listed above and below, and at least one wide bandgap material, a wide bandgap material being understood to mean a material in the sense of the disclosure of US7,294,849. These systems exhibit particularly advantageous performance data in electroluminescent devices.
Preferably, the further compound may have a band gap of 2.5eV or more, preferably 3.0eV or more, very preferably 3.5eV or more. One way to calculate the bandgap is through the energy levels of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO).
Molecular orbitals, in particular the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), their energy levels and the lowest triplet state T of the material1Energy of and lowest excited singlet state S1The energy of (c) is determined by quantum chemical calculations. To calculate the organic material without metal, first a geometry optimization was performed by the "ground state/semi-empirical/default spin/AM 1/charge 0/spin singlet" method. Subsequently, energy calculations are performed on the basis of the optimized geometry. This was done using the "TD-SFC/DFT/default spin/B3 PW 91" method and the "6-31G (d)" basis set (charge 0, spin singlet). For metal-containing compounds by "ground stateHartree-Fock/default spin/LanL 2 MB/Charge 0/spin singlet "method, geometry optimization. The energy calculation was performed similarly to the above method for organic substances, except that the "LanL 2 DZ" basis set was used for the metal atoms and the "6-31G (d)" basis set was used for the ligands. The HOMO energy level HEh or LUMO energy level LEh is obtained from the energy calculation in hartree (hartree). It was used to determine the HOMO and LUMO energy levels in electron volts as follows, calibrated by cyclic voltammetry measurements:
HOMO(eV)＝((HEh*27.212)-0.9899)/1.1206
LUMO(eV)＝((LEh*27.212)-2.0041)/1.385
in the sense of the present application, these values will be considered as HOMO and LUMO energy levels of the material.
Lowest triplet state T1The energy, defined as the triplet state with the lowest energy, is evident from the quantum chemistry calculations described.
Lowest excited singlet S1The energy defined as the excited singlet state with the lowest energy, which is evident from the quantum chemistry calculations described.
The methods described herein are independent of the software package used and give the same results throughout. Examples of programs often used for this purpose are "Gaussian09W" (Gaussian) and Q-Chem 4.1 (Q-Chem).
The invention also relates to a composition comprising at least one compound obtainable according to the invention, preferably a compound comprising formula (V) or the structures of the preferred embodiments listed above and below, and at least one phosphorescent emitter, the term "phosphorescent emitter" also being understood to mean a phosphorescent dopant.
The dopant in the system comprising the host material and the dopant is understood to mean the component in the mixture in smaller proportions. Correspondingly, the host material in a system comprising a host material and a dopant is understood to mean the component in the mixture in greater proportion.
Preferred phosphorescent dopants for use in the matrix system, preferably the mixed matrix system, are the preferred phosphorescent dopants specified hereinafter.
The term "phosphorescent dopant" generally includes compounds in which light emission is achieved by spin-forbidden transitions, e.g., from an excited triplet state or a state with a higher spin quantum number, e.g., a quintet state transition.
Suitable phosphorescent compounds (═ triplet emitters) are in particular those in which: which, when suitably excited, emits light, preferably in the visible region, and also contains at least one atom having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80, in particular a metal having this atomic number. Phosphorescent emitters which are preferably used are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular iridium-or platinum-containing compounds. In the sense of the present invention, all luminescent compounds containing the above-mentioned metals are considered as phosphorescent compounds.
Examples of such emitters can be found in the following 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 2016124304, WO 2017032439, WO 2018019687, WO 2018019688, WO 2018041769, WO 2018054798, WO 2018069196, WO 2018069197, WO 2018069273.
In general, all phosphorescent complexes used for phosphorescent OLEDs according to the prior art and known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art will be able to use other phosphorescent complexes without inventive effort.
The above-mentioned compounds obtainable according to the present invention, preferably compounds comprising the structure of formula (V) or the preferred embodiments listed above and below, may preferably be used as active components in electronic devices. Electronic device is understood to mean any device comprising an anode, a cathode and at least one layer between the anode and the cathode, said layer comprising at least one organic or organometallic compound. The electronic device of the invention thus comprises an anode, a cathode and at least one intermediate layer comprising at least one compound comprising the structure of formula (I). Preferred electronic devices are herein selected from: organic electroluminescent devices (OLED, PLED), organic integrated circuits (O-IC), organic field effect transistors (O-FET), organic thin film transistors (O-TFT), organic light emitting transistors (O-LET), organic solar cells (O-SC), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQD), organic electric sensors, light emitting electrochemical cells (LEC), organic laser diodes (O-laser) and organic plasma light emitting devices (d.m. koller et al, Nature Photonics (Nature Photonics)2008, 1-4), preferably organic electroluminescent devices (OLED, PLED), especially phosphorescent OLEDs, said electronic devices containing in at least one layer at least one compound comprising a structure of formula (I). Particularly preferred are organic electroluminescent devices. The active component is typically an organic or inorganic material introduced between the anode and the cathode, such as charge injection, charge transport or charge blocking materials, but especially light emitting materials and host materials.
One preferred embodiment of the present invention is an organic electroluminescent device. The organic electroluminescent device comprises a cathode, an anode and at least one light-emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers and/or organic or inorganic p/n junctions. Also, one or more of the hole transport layers may be p-type doped, for example with a metal oxide such as MoO3Or WO3Or doped with a (per) fluorinated electron-poor aromatic system, and/or one or more of the electron transport layers may be n-type doped. It is also possible to introduce intermediate layers between the two light-emitting layers, which intermediate layers have, for example, an exciton blocking function and/or control the charge balance in the electroluminescent device. However, it is not limited toIt should be noted that each of these layers need not necessarily be present.
In this case, the organic electroluminescent device may have one light-emitting layer, or it may have a plurality of light-emitting layers. If a plurality of light-emitting layers are present, these light-emitting layers preferably have several emission peaks overall between 380nm and 750nm, so that the overall result is white emission; in other words, a plurality of light-emitting compounds which can emit fluorescence or phosphorescence are used in the light-emitting layer. Especially preferred are three-layer systems in which the three layers exhibit blue, green and orange or red luminescence (see for example WO 2005/011013 for basic structures); or a system with more than three light-emitting layers. In addition, tandem OLEDs are also preferred. The system may also be a mixed system in which one or more layers fluoresce and one or more other layers phosphoresce.
In a preferred embodiment of the present invention, the organic electroluminescent device contains a compound according to the invention, preferably a compound comprising the structure of formula (V) or the preferred embodiments detailed above, as a matrix material in the light-emitting layer or layers, preferably as an electron-conducting matrix material, preferably in combination with other matrix materials, preferably hole-conducting matrix materials. In another preferred embodiment of the invention, the further matrix material is an electron transport compound. In yet another preferred embodiment, the further matrix material is a compound with a large band gap, which does not participate to a significant extent even if it participates in hole and electron transport in the layer. The light-emitting layer comprises at least one light-emitting compound.
In a further particularly preferred embodiment of the present invention, the organic electroluminescent device of the invention comprises in the hole conductor layer or in the electron conductor layer a compound obtainable according to the invention, preferably a compound comprising formula (V) or the structure of the preferred embodiments detailed above.
Suitable matrix materials which can be used in combination with the compounds obtainable according to the invention, preferably compounds comprising a structure of formula (V) or a preferred embodiment, 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, especially monoamines, for example according to WO 2014/015935, carbazole derivatives, for example CBP (N, N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851, indolocarbazole derivatives, for example according to WO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, for example according to WO 2010/136109 and WO 2011/000455, azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, ambipolar matrix materials, for example according to WO 2007/137725, silanes, for example according to WO 2005/111172, borazacyclopentasilanes or boronates, for example according to WO 2006/117052, triazine derivatives, for example according to WO 2010/015306, WO 2007/063754 or WO 2008/056746, zinc complexes, for example according to EP 652273 or WO 2009/062578, sildiazacyclorac or siltetraazacyclopentasilane derivatives, for example according to WO 2010/054729, phosphodiazacyclorac derivatives, for example according to WO 2010/054730, bridged carbazole derivatives, for example according to US 2009/0136779, WO 2010/050778, WO 2011/042107, WO 2011/088877 or WO 2012/143080, bitriphenylidene derivatives, for example according to WO 2012/048781, lactams, for example according to WO 2011/116865, WO 2011/137951 or WO 2013/064206, 4-spirocarbazole derivatives, for example according to WO 2014/094963 or WO 2015/192939, or dibenzofuran derivatives, for example according to WO 2015/169412, WO 2016/015810, WO 2016/023608 or the unpublished applications EP16158460.2 and EP 16159829.7. Other phosphorescent emitters which emit at shorter wavelengths than the actual emitter may also be present as co-hosts in the mixture.
Preferred co-host materials are triarylamine derivatives, especially monoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives, lactams, and carbazole derivatives.
It may also be preferred to use a plurality of different matrix materials as a mixture, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material. It is also preferred to use a mixture of a charge transport matrix material and an electrically inert matrix material which does not participate to a significant level even if it participates in charge transport, as described for example in WO 2010/108579.
It is also preferred to use mixtures of two or more triplet emitters together with a matrix. In this case, the triplet emitter having a shorter-wave emission spectrum serves as a co-host for the triplet emitter having a longer-wave emission spectrum.
More preferably, in a preferred embodiment, the compounds obtainable according to the present invention, preferably the compounds comprising the structure of formula (V), can be used as matrix material in the light emitting layer of an organic electronic device, especially an organic electroluminescent device, such as an OLED or OLEC. In this case, the host material containing the compound obtainable according to the invention, preferably a compound comprising the structure of formula (V) or the preferred embodiments listed above and below, is present in the electronic device in combination with one or more dopants, preferably phosphorescent dopants.
The proportion of matrix material in the luminescent layer in this case is between 50.0% and 99.9% by volume for the fluorescent luminescent layer, preferably between 80.0% and 99.5% by volume, more preferably between 92.0% and 99.5% by volume, and between 85.0% and 97.0% by volume for the phosphorescent luminescent layer.
Accordingly, the proportion of the dopant is between 0.1 vol% and 50.0 vol%, preferably between 0.5 vol% and 20.0 vol%, more preferably between 0.5 vol% and 8.0 vol% for the fluorescent light-emitting layer and between 3.0 vol% and 15.0 vol% for the phosphorescent light-emitting layer.
The light-emitting layer of the organic electroluminescent device may also comprise a system comprising a plurality of host materials (mixed host system) and/or a plurality of dopants. Also in this case, the dopants are generally those materials which are in a smaller proportion in the system and the host materials are those materials which are in a larger proportion in the system. However, in individual cases, the proportion of a single matrix material in the system may be less than the proportion of a single dopant.
In another preferred embodiment of the present invention, the compounds obtainable according to the present invention, preferably the compounds comprising the structure of formula (V) or the preferred embodiments listed above and below, are used as components of a mixed matrix system. The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material having a hole transporting property, and the other material is a material having an electron transporting property. However, the desired electron transporting and hole transporting properties of the mixed matrix component may also be combined primarily or entirely in a single mixed matrix component, in which case the other mixed matrix component or components perform other functions. The two different matrix materials may be present here in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, most preferably 1:4 to 1: 1. Preferably, mixed matrix systems are used in phosphorescent organic electroluminescent devices. One source of more detailed information on mixed matrix systems is application WO 2010/108579.
The present invention further provides an electronic device, preferably an organic electroluminescent device, comprising one or more compounds of the invention and/or at least one oligomer, polymer or dendrimer of the invention as electron-conducting compound in one or more electron-conducting layers.
Preferred cathodes are metals with a low work function, metal alloys or multilayer structures composed of various metals, such as alkaline earth metals, alkali metals, main group metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Furthermore, suitable are alloys of alkali metals or alkaline earth metals with silver, for example alloys of magnesium and silver. In the case of a multilayer structure, in addition to the mentioned metals, other metals having a relatively high work function, such as Ag, can also be used, in which case combinations of the metals, such as Mg/Ag, Ca/Ag or Ba/Ag, are generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are fluorides of alkali metals or alkaline earth metals, and the corresponding oxides or carbonates (e.g. LiF, Li)2O、BaF2、MgO、NaF、CsF、Cs2CO3Etc.). Also useful for this purpose are organic alkali metal complexes such as Liq (lithium quinolinate). The layer thickness of this layer is preferably between 0.5nm and 5 nm.
The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5eV relative to vacuum. Suitable for this purpose are, firstly, metals having a high redox potential, such as Ag, Pt or Au. Second, metal/metal oxide electrodes (e.g., Al/Ni/NiO) may also be preferredx、Al/PtOx). For some applications, at least one of the electrodes must be transparent or partially transparent in order to be able to achieve illumination of the organic material (O-SC) or emission of light (OLED/PLED, O-laser). Preferred anode materials herein are conductive mixed metal oxides. Particularly preferred is Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO). Also preferred are conductively doped organic materials, especially conductively doped polymers, such as PEDOT, PANI or derivatives of these polymers. It is also preferred that a p-type doped hole transport material is applied to the anode as a hole injection layer, in which case a suitable p-type dopant is a metal oxide, such as MoO3Or WO3Or (per) fluorinated electron poor aromatic systems. Other suitable p-type dopants are HAT-CN (hexacyanohexanazaterphenyl) or the compound NPD9 from Novaled. Such a layer simplifies hole injection in materials with a low HOMO, i.e. a HOMO that is large in magnitude.
In other layers, generally any material as used in the prior art for said layers can be used, and the person skilled in the art is able to combine any of these materials with the material of the invention in an electronic device without inventive effort.
Since the lifetime of such a device is severely shortened in the presence of water and/or air, the device is structured accordingly (depending on the application), provided with contact connections and finally hermetically sealed.
Also preferred are electronic devices, in particular organic electroluminescent devices, which are characterized in that one or more layers are applied by a sublimation process. In this case, it is preferable that the air conditioner,in vacuum sublimation systems at temperatures typically less than 10 deg.f-5Mbar, preferably less than 10-6The material is applied by vapour deposition at an initial pressure of mbar. The initial pressure may also be even lower or even higher, e.g. less than 10-7Millibar.
Also preferred are electronic devices, in particular organic electroluminescent devices, which are characterized in that one or more layers are applied by the OVPD (organic vapor deposition) method or by sublimation with the aid of a carrier gas. In this case, 10-5The material is applied at a pressure between mbar and 1 bar. One special case of this method is the OVJP (organic vapor jet printing) method, in which the material is applied directly through a nozzle and is thus structured (for example m.s. arnold et al, applied physical flash (appl. phys. lett.)2008, 92, 053301).
Also preferred are electronic devices, especially organic electroluminescent devices, characterized in that one or more layers are produced from solution, for example by spin coating, or by any printing method, such as screen printing, flexographic printing, offset printing or nozzle printing, but more preferably LITI (photo induced thermal imaging, thermal transfer) or inkjet printing. For this purpose, soluble compounds are required, which are obtained, for example, by appropriate substitution.
Electronic devices, in particular organic electroluminescent devices, can also be produced as mixed systems by applying one or more layers from solution and one or more further layers by vapor deposition. For example, it is possible to apply the light-emitting layer containing the compound obtainable according to the invention, preferably a compound comprising a structure of formula (V), and a matrix material from a solution and to apply thereto a hole-blocking layer and/or an electron-transporting layer by vapor deposition under reduced pressure.
These methods are generally known to the person skilled in the art and can be applied without difficulty to electronic devices, in particular organic electroluminescent devices, containing compounds obtainable according to the invention, preferably compounds comprising the structure of formula (V) or the preferred embodiments detailed above.
It is noteworthy that the electronic devices of the invention, in particular the organic electroluminescent devices, are superior to the prior art in one or more of the following surprising advantages:
1. the compounds, oligomers, polymers or dendrimers containing the compounds, oligomers, polymers or dendrimers obtainable according to the invention, preferably comprising the structure of formula (V) or the preferred embodiments listed above and below, have very good lifetimes, especially as electron-conducting and/or hole-conductor materials or as matrix materials for electronic devices, especially organic electroluminescent devices.
2. Electronic devices, in particular organic electroluminescent devices, containing compounds, oligomers, polymers or dendrimers obtainable according to the invention, preferably comprising a structure of formula (V) or the preferred embodiments listed above and below, in particular as electron transport materials, hole conductor materials and/or as host materials, have excellent efficiency. More particularly, the efficiency is significantly higher compared to a similar compound not containing any non-aromatic or non-heteroaromatic polycyclic ring system having at least 2 rings. In this case, the compounds, oligomers, polymers or dendrimers obtainable according to the present invention, preferably comprising the structure of formula (V) or the preferred embodiments listed above and below, when used in electronic devices, give rise to low operating voltages. In this case, these compounds give, in particular, a low roll-off, i.e. the power efficiency of the device drops less at high luminance.
3. Electronic devices, in particular organic electroluminescent devices, which contain compounds, oligomers, polymers or dendrimers obtainable according to the invention, preferably compounds, oligomers, polymers or dendrimers comprising the structure of formula (V) or the preferred embodiments listed above and below, as electron transport materials, hole conductor materials and/or as host materials, have excellent color purity.
4. The compounds, oligomers, polymers or dendrimers obtainable according to the present invention, preferably comprising the structure of formula (V) or the preferred embodiments listed above and below, exhibit very high thermal and photochemical stability and lead to compounds having a very long lifetime.
5. The formation of light-loss channels in electronic devices, in particular organic electroluminescent devices, can be avoided with the compounds, oligomers, polymers or dendrimers obtainable according to the present invention, preferably compounds, oligomers, polymers or dendrimers comprising the structure of formula (V) or the preferred embodiments listed above and below. As a result, these devices are characterized by high PL efficiency and hence high EL efficiency of the emitter, and excellent energy transfer from the host to the dopant.
6. The compounds, oligomers, polymers or dendrimers obtainable according to the present invention, preferably compounds, oligomers, polymers or dendrimers comprising the structure of formula (V) or the preferred embodiments listed above and below, have excellent glass film formability.
7. The compounds, oligomers, polymers or dendrimers obtainable according to the present invention, preferably compounds, oligomers, polymers or dendrimers comprising the structure of formula (V) or the preferred embodiments listed above and below, form very good films from solution.
These above-mentioned advantages are not accompanied by deterioration of other electronic properties.
The compounds and mixtures of the invention are suitable for use in electronic devices. An electronic device is understood here to mean a device which comprises at least one layer which contains at least one organic compound. However, the component may also comprise inorganic materials or layers formed entirely of inorganic materials.
The present invention therefore further provides for the use of the compounds or mixtures according to the invention in electronic devices, in particular in organic electroluminescent devices.
The present invention further provides for the use of a compound of the invention and/or an oligomer, polymer or dendrimer of the invention as fluorescent emitter, emitter exhibiting TADF (thermally activated delayed fluorescence), host material, electron transport material, electron injection material, hole conducting material, hole injection material, electron blocking material, hole blocking material and/or wide band gap material in an electronic device, preferably as fluorescent emitter (singlet emitter), host material, hole conducting material and/or electron transport material.
The present invention still further provides electronic devices comprising at least one compound or mixture of the invention as detailed above. In this case, the preferences detailed above for the compounds also apply to the electronic device. More preferably, the electronic device is selected from: organic electroluminescent devices (OLED, PLED), organic integrated circuits (O-IC), organic field effect transistors (O-FET), organic thin film transistors (O-TFT), organic light emitting transistors (O-LET), organic solar cells (O-SC), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQD), organic electric sensors, light emitting electrochemical cells (LEC), organic laser diodes (O-laser) and organic plasma light emitting devices (d.m. koller et al, Nature Photonics (Nature Photonics)2008, 1-4), preferably organic electroluminescent devices (OLED, PLED), especially phosphorescent OLEDs.
In another embodiment of the present invention, the organic electroluminescent device of the present invention does not contain any separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, which means that the light-emitting layer directly adjoins the hole injection layer or the anode and/or the light-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 the same or similar metal complexes as the metal complexes in the light-emitting layer as the hole-transporting or hole-injecting material directly adjacent to the light-emitting layer, as described, for example, in WO 2009/030981.
In the other layers of the organic electroluminescent device of the present invention, any material may be used as generally used in the art. The person skilled in the art is thus able, without inventive effort, to use any material known for use in organic electroluminescent devices in combination with the compounds, oligomers, polymers or dendrimers obtainable according to the present invention, preferably compounds, oligomers, polymers or dendrimers comprising the structure of formula (V) or according to a preferred embodiment.
The compounds according to the invention generally have very good properties when used in organic electroluminescent devices. Especially in the case of using the compounds according to the invention in organic electroluminescent devices, the lifetimes are significantly better compared with analogous compounds of the prior art. At the same time, other properties of the organic electroluminescent device, in particular efficiency and voltage, are equally better or at least comparable.
It should be noted that variations of the embodiments described in the present invention are covered by the scope of the present invention. Any feature disclosed in this application may be replaced by an alternative feature serving the same purpose, or an equivalent or similar purpose, unless expressly excluded. Thus, unless otherwise indicated, any feature disclosed in this specification should be considered as an example of a generic series or as an equivalent or similar feature.
All features of the invention may be combined with each other in any manner, unless the specific features and/or steps are mutually exclusive. This is particularly true for the preferred features of the present invention. Also, features that are not necessarily combined may be used separately (rather than in combination).
It should also be noted that many of the features, especially those of the preferred embodiments of the invention, are to be considered inventive in their own right and not just as some embodiments of the invention. Independent protection may be sought for these features in addition to or instead of any presently claimed invention.
The technical teaching of the present disclosure may be extracted and combined with other examples.
The following examples illustrate the invention in more detail without any intention to limit it thereby.
Those skilled in the art will be able to utilize the detailed information presented to fabricate other electronic devices of the invention and thereby practice the invention within the full scope of the claims without the exercise of inventive faculty.
Examples
Unless otherwise stated, the following syntheses are carried out in dry solvents under a protective gas atmosphere. The metal complexes are additionally treated protected from light or under yellow light. Solvents and reagents may be purchased, for example, from Sigma-ALDRICH or ABCR. For individual compounds, the corresponding numbers in brackets or the cited numbers relate to the CAS number of the compound known from the literature. In the case of a compound that can exhibit multiple tautomeric forms, one tautomeric form is typically exhibited.
General procedure for enamine synthesis:
to a well stirred mixture of 6.0eq of secondary amine in n-heptane (0.3ml/mmol) cooled to 0 ℃ was added dropwise 1.2eq of titanium (IV) chloride in n-heptane (2 ml/mmol). Suitable secondary amines are, in particular, cyclic secondary amines, such as pyrrolidine [123-75-1], piperidine [110-89-4] and morpholine [110-91-8 ]. The mixture was mixed with 1.0eq of ketone and then heated at reflux for 24 hours. After cooling, the titanium dioxide was filtered off and washed three times with n-heptane. N-heptane was distilled off and the enamine was purified by kugelrohr distillation under reduced pressure.
Example E1:
Figure BDA0002994034760000981
to 50.2ml (600mmol) of pyrrolidine [123-75-1]]13.2ml (120mmol) of titanium (IV) chloride in 240ml of n-heptane are added dropwise to the well-stirred mixture cooled to 0 ℃ in 200ml of n-heptane. The mixture was mixed with 16.4g (100mmol) homoadamantanone [24669-56-5]Mixed and then heated under reflux for 24 hours. After cooling, the titanium dioxide was filtered off and washed three times with 100ml of n-heptane. N-heptane was distilled off and the enamine was purified by kugelrohr distillation under reduced pressure. Yield: 16.7g (77mmol), 77%. Purity: by passing1H NMR was determined to be about 97%.
The following compounds can be prepared analogously:
Figure BDA0002994034760000991
general procedure for pyridine synthesis:
Figure BDA0002994034760001001
step 1 and step 2:
step 1 and step 2 are performed sequentially, preferably strictly following the time in formamidine hydrazone formation.
To a solution of 1.0eq formamidine acetate [3473-63-0]To a well-stirred solution (3.5ml/mmol) in methanol was added 1.0eq of hydrazine hydrate [7803-57-8]The mixture was stirred at room temperature for 5 minutes. This solution is poured into a 1.0eq solution or suspension (7ml/mmol) of glyoxal or glyoxal hydrate in methanol, followed immediately by the addition of 1.0eq of triethylamine. The reaction mixture was stirred at room temperature for 60 hours. Methanol was removed under reduced pressure at 30 ℃, the residue was dissolved in 5N aqueous hydrochloric acid (2ml/eq) and the aqueous phase of the hydrochloric acid was extracted 3 times with methyl tert-butyl ether (1 ml/eq). While cooling with ice, the aqueous phase in hydrochloric acid is adjusted to pH with ice-cold 1N sodium hydroxide solution>10 and extracted 3 times with Dichloromethane (DCM) (2 ml/eq). The combined organic phases were dried over magnesium sulfate. The desiccant was filtered off as a slurry in dichloromethane using a bed of alumina (alumina, basic, activity level 1 (from Woelm)), and the filtrate was concentrated to dryness under reduced pressure. By crystallization from a suitable solvent or solvent mixture (typical solvents are e.g. heptane, cyclohexane, toluene, methyl tert-butyl ether, THF, di
Figure BDA0002994034760001011
Alkane, acetone, ethyl acetate, butyl acetate, acetonitrile, isopropanol, ethanol, methanol, etc.), or by chromatography/flash chromatography on silica gel.
And step 3:
1,2, 4-triazine and enamine are first charged under an argon atmosphere in a ratio of 1.0:1.0 to typically 1.0:1.2 into a four-necked flask with a distillation system, internal thermometer and precision glass stirrer. The mixture is heated to 150 ℃ to 200 ℃, typically 160 ℃ to 180 ℃ while stirring,with nitrogen bleed for about 30 to 60 minutes. The secondary amine formed is distilled off by means of a distillation system. If solid or high-melting reactants are reacted, high-boiling inert solvents (typical solvents are, for example, chlorobenzene, benzonitrile, nitrobenzene, DMSO, DMAC, NMP, oligoethers/polyethers, such as di-, tri-, tetraglyme, etc.) may be added. In addition, boiling point may also be used<Solvent/solvent mixture at 150 deg.C (typical solvents are e.g. heptane, cyclohexane, toluene, methyl tert-butyl ether, THF, di
Figure BDA0002994034760001012
Alkane, acetone, ethyl acetate, butyl acetate, acetonitrile). In this case, the reaction was carried out in a stirred autoclave. The progress of the reaction can in this case be monitored by the pressure increase.
After the nitrogen evolution has ended or the pressure has ceased to rise, stirring is continued for a further 30 to 60 minutes. The conversion rate of the reaction can be, for example, by1H NMR spectroscopy. After cooling, the crude product is crystallized from a suitable solvent or solvent mixture (typical solvents are e.g.heptane, cyclohexane, toluene, methyl tert-butyl ether, THF, di-tert-butyl ether)
Figure BDA0002994034760001013
Alkane, acetone, ethyl acetate, butyl acetate, acetonitrile, isopropanol, ethanol, methanol, etc.), or by chromatography/flash chromatography on silica gel, or by repeated thermal extraction and/or distillation/kugelrohr distillation/sublimation at standard or reduced pressure. Synthon S for further conversion into OLED material1Typical purity by H NMR>95 percent. Typical purities of the OLED materials HTM (hole transport material), TMM (triplet matrix material), ETM (electron transport material), SMB (singlet matrix blue) determined by HPLC>99.9% and is at least sublimed once or heat treated under high vacuum.
Example S1:
Figure BDA0002994034760001021
example S1 a: steps 1 and 2
Figure BDA0002994034760001022
To 10.4g (100mmol) of formamidine acetate [347363-0]To a well stirred solution in 350ml methanol was added 5.0g (100mmol) hydrazine hydrate [ 7803-57-8%]And the mixture was stirred at room temperature for 5 minutes. The solution was poured into 18.7g (100mmol) of (p-chlorophenyl) glyoxal [4998-15-6 ]]A solution in 700ml of methanol was added immediately after which 10.2g (100mmol) of triethylamine were added. The reaction mixture was stirred at room temperature for 60 hours. Methanol was removed under reduced pressure at 30 ℃, the residue was dissolved in 200ml of 5N aqueous hydrochloric acid, and the aqueous phase in the hydrochloric acid was extracted 3 times with 100ml of methyl tert-butyl ether. While cooling with ice, the aqueous phase in hydrochloric acid is adjusted to pH with ice-cold 1N sodium hydroxide solution>10 and extracted 3 times with 200ml of DCM. The combined organic phases were dried over magnesium sulfate. The desiccant was filtered off as a slurry of DCM through a bed of alumina (100g of alumina, basic, activity level 1 (from Woelm)). Further purification was performed by crystallization from cyclohexane with addition of small amounts of ethyl acetate. Yield: 10.0g (mmol), 52%. Purity: by passing1H NMR was determined to be about 95%.
Example S1 b: step 3
Figure BDA0002994034760001023
A mixture of 19.2g (100mmol) of 1,2, 4-triazine S1a and 21.7g (105mmol) of enamine E1 was initially charged under an argon atmosphere to a four-necked flask with distillation system, internal thermometer and precision glass stirrer. While stirring, the mixture was heated to 160 ℃. After 30 minutes, the nitrogen bleed was complete. Stirring was continued for another 30 minutes and then the mixture was allowed to cool. The distilled pyrrolidine was discarded. The crude product was chromatographed on silica gel (10g Merck silica gel 60/1g crude product, n-heptane/ethyl acetate 20: 1). Yield: 24.3g (78mmol), 78%. Purity: by passing1H NMR was determined to be about 97%, see fig. 1.
The following compounds can be prepared analogously:
Figure BDA0002994034760001031
Figure BDA0002994034760001041
Figure BDA0002994034760001051
Figure BDA0002994034760001061
synthesis of tripodal ligand TL:
a: synthesis of a tripodal ligand with three identical bidentate sub-ligands
Example TL 1:
Figure BDA0002994034760001062
prepared according to WO 2016/124304. First, a boronic ester was prepared in analogy to example 21, variant B, using S1; see page 116. Thereafter, the boronic ester is reacted with 1,3, 5-tris (2-bromophenyl) benzene [380626-56-2 ] in analogy to example L1 (see page 160)]And (4) reacting. Yield over two stages: 56 percent; purity: by passing1H NMR determined about 97%.
The following compounds can be prepared analogously:
Figure BDA0002994034760001063
Figure BDA0002994034760001071
b: synthesis of tripodal ligands with different bidentate sub-ligands
Example TL 4:
Figure BDA0002994034760001072
prepared according to WO 2016/124304. First, a boronic ester was prepared in analogy to example 21, variant B, using S1; see page 116. Thereafter, analogously to example L1201 (see page 374), the boronic ester is reacted with 2,2 ' - [5 "- (2-bromophenyl) [1,1 ': 2 ', 1": 3 ", 1" ': 2 "', 1" "-pentabiphenyl]-4, 4' -diyl]Bipyridine [1989605-04-0]And (4) reacting. Yield over two stages: 67%; purity: by passing1H NMR determined about 97%.
The following compounds can be prepared analogously:
Figure BDA0002994034760001081
synthesis of C3-and C1-symmetric tripodal iridium complexes:
example Ir (TL1):
Figure BDA0002994034760001091
preparation was carried out according to WO 2016/124304, Ir (L1) variant a, see page 218. Purify by silica gel chromatography as described therein, heat extract 3 times with DCM/MeOH (1:1, vv) and 3 times with DCM/acetonitrile (2:1, vv) and about 10 at p-6Sublimation/heat treatment in mbar. Yield: 77%; purity: determination by HPLC>99.9％。
The following compounds can be prepared analogously:
Figure BDA0002994034760001092
Figure BDA0002994034760001101
Figure BDA0002994034760001111
synthesis of C3-symmetric iridium complex of bidentate ligand L:
example Ir (L1)3:
Figure BDA0002994034760001112
According to WO 2015/104045, Ir (LB74)3See page 179 for preparation. Yield: 57 percent; purity: determination by HPLC>99.9％。
C2 synthesis of symmetric N, N-trans iridium complex of bidentate ligand L:
example Ir (L2)2(acac):
Figure BDA0002994034760001113
Prepared according to WO 2015/104045. First, similar to [ Ir (L42)2Cl)2The Cl dimer was prepared, see page 193. Analogously to Ir538, it is reacted with acetylacetone; see page 218. Yield over two stages: 53 percent; purity: determination by HPLC>99.9％。
The following compounds can be prepared analogously:
Figure BDA0002994034760001121
vacuum processed devices:
the OLEDs of the invention and of the prior art are manufactured by the general method according to WO 2004/058911, modified to the environment described here (variation of layer thickness, materials used).
In the following examples, the results of various OLEDs are presented. Clean glass plates coated with structured ITO (indium tin oxide) with a thickness of 50nm (cleaned in a Miele laboratory glass washer, Merck Extran cleaner) were pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and, for improved processing, 20nm of PEDOT: PSS (poly (3, 4-ethylenedioxythiophene) poly (styrene sulfonate) as CLEVOS) was applied within 30 minutesTMP VP AI 4083 was purchased from Heraeus preciouss Metals GmbH, germany, spin coated from aqueous solution) and then baked at 180 ℃ for 10 minutes. These coated glass plates form the substrate to which the OLED is applied.
OLEDs have essentially the following layer structure: substrate/hole injection layer 1(HIL1) consisting of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 1(HTL 1)/hole transport layer 2(HTL 2)/emissive layer (EML)/Hole Blocking Layer (HBL)/Electron Transport Layer (ETL)/optional Electron Injection Layer (EIL) and finally a cathode. The cathode is formed of an aluminum layer having a thickness of 100 nm.
First, a vacuum processed OLED is described. For this purpose, all materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the light-emitting layer always consists of at least one host material (host material) and a light-emitting dopant (emitter) which is added to the host material(s) by co-evaporation in a specific volume proportion. The detailed information given in the form RTMM1: RTMM2: Ir (L1) (55%: 35%: 10%) here means that the material RTMM1 is present in the layer in a proportion of 55% by volume, RTMM2 in a proportion of 35% and Ir (L1) in a proportion of 10%. Similarly, the electron transport layer may also be composed of a mixture of two materials. The exact structure of the OLED can be found in table 1. The materials used to make the OLEDs are shown in table 4.
OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd/a), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in%) are determined, which are calculated as a function of the luminance from a current-voltage-luminance characteristic (IUL characteristic) exhibiting lambertian luminous characteristics, and the lifetime is also determined. Electroluminescent spectrum is 1000cd/m2Is determined under the brightnessAnd the CIE 1931x and y color coordinates are calculated therefrom. Lifetime LD90 is defined as being in 10000 cd/m2The elapsed time when the luminance in operation drops to 90% of the initial luminance.
OLEDs may also initially operate at different starting luminances. The lifetime value can then be converted to a value at other starting luminances by means of conversion equations known to those skilled in the art.
Use of the compounds of the invention as materials in phosphorescent OLEDs
The compounds according to the invention can be used, in particular, as HTM (hole-transport material), TMM (triplet matrix material), ETM (electron-transport material) in OLEDs and as phosphorescent emitter material in the light-emitting layer. Iridium compounds according to table 4 were used as comparison according to the prior art. The results of the OLED are summarized in Table 2.
Table 1: structure of OLED
Figure BDA0002994034760001141
Figure BDA0002994034760001151
Table 2: results of vacuum processed OLEDs
Figure BDA0002994034760001161
Solution processed devices:
a: from low molecular weight soluble functional materials
The iridium complexes can also be processed from solution, in which case the result is that the OLEDs are considerably simpler in terms of processing technology than vacuum-processed OLEDs, but nevertheless have good properties. The manufacture of such assemblies is based on the manufacture of Polymer Light Emitting Diodes (PLED), which have been described in the literature several times (for example in WO 2004/037887). The structure consists of a substrate/ITO/hole-injection layer (60 nm)/intermediate layer (20nm) in a manner such that the substrate/ITO/hole-injection layer/intermediate layer (60nm) can be used for acting on a substrate or aA light-emitting layer (60 nm)/a hole blocking layer (10 nm)/an electron transport layer (40 nm)/a cathode. For this purpose, a substrate from Technoprint (soda lime glass) is used, to which an ITO structure (indium tin oxide, transparent conductive anode) is applied. The substrate was cleaned in a clean room with deionized water and a cleaner (Deconex 15PF) and then activated by UV/ozone plasma treatment. After that, also in a clean room, a hole injection layer of 20nm was applied by spin coating. The required spin rate depends on the dilution and the particular spin coater geometry. To remove residual water from the layer, the substrate was baked on a hot plate at 200 ℃ for 30 minutes. The interlayer used serves for hole transport; in this case, HL-X from Merck was used. Alternatively, the intermediate layer may be replaced by one or more layers that need only satisfy conditions that do not re-leach as a result of subsequent processing steps to deposit the EML from solution. For the production of the light-emitting layer, the triplet emitters according to the invention are dissolved together with the matrix material in toluene or chlorobenzene. Typical solids contents of such solutions are between 16 and 25g/l, when the concentration is such that a typical layer thickness of 60nm of the device will be obtained by means of spin coating. The solution processed devices contained a light emitting layer composed of RTMM3: RTMM4: Ir (TL) (20%: 58%: 22%). The light-emitting layer was spin-coated in an inert gas atmosphere, in this case argon, and baked at 160 ℃ for 10 minutes. Over the latter was vapor deposited a hole blocking layer (10nm ETM1) and an electron transport layer (40nm RETM1 (50%)/RETM 2 (50%)) (vapor deposition system from Lesker et al, typical vapor deposition pressure was 5X 10-6Millibar). Finally, a cathode of aluminum (100nm) (high purity metal ex Aldrich) was applied by vapor deposition. To protect the device from air and air humidity, the device is finally packaged and then characterized. The cited OLED examples remain to be optimized; table 3 summarizes the data obtained. Lifetime LD50 is defined as being at 1000cd/m2The elapsed time when the luminance in operation decreases to 50% of the initial luminance.
Table 3: results with materials processed from solution
Figure BDA0002994034760001171
Table 4: structural formula of material used
Figure BDA0002994034760001181
Figure BDA0002994034760001191

Claims (17)

1. A process for preparing a sterically hindered heteroaromatic nitrogen compound, comprising the steps of:
A) providing 1,2, 4-triazine;
B) providing an activated olefin having a non-aromatic or non-heteroaromatic polycyclic ring system, and
C) reacting the compounds provided in steps A) and B) to obtain a sterically hindered heteroaromatic nitrogen compound,
it is characterized in that
At least one of the compounds provided in steps A) and/or B) comprises an aromatic or heteroaromatic ring system having 5 to 60 ring atoms and which may be substituted.
2. The process according to claim 1, characterized in that the activated double bond of the olefin provided in step B) is part of a bicyclic, tricyclic or oligomeric ring.
3. Process according to claim 1 or 2, characterized in that the olefin provided in step B) is a cyclic enolate and/or an enamine, preferably derived from a bicyclic, tricyclic or oligomeric cyclic ketone.
4. The process according to one or more of claims 1 to 3, characterized in that the 1,2, 4-triazine is obtained by reaction of a1, 2-dicarbonyl with formamidinehydrazone.
5. The process according to one or more of claims 1 to 3, characterized in that the 1,2, 4-triazine is obtained by reacting a nitroaromatic or nitroheteroaromatic compound with an amidine compound.
6. Process according to one or more of claims 1 to 5, characterized in that the 1,2, 4-triazine may be represented by formula (I)
Figure FDA0002994034750000021
The symbols used therein are as follows:
Ra，Rb，Rcthe same or different and is: h, D, F, Cl, Br, I, N (R)1)2，CN，NO2，OH，COOH，C(＝O)N(R1)2，Si(R1)3，B(OR1)2，C(＝O)R1，P(＝O)(R1)2，S(＝O)R1，S(＝O)2R1，OSO2R1A linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein each of said alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl groups may be substituted with one or more R1Radical substitution of one or more non-adjacent CH2The group can be represented by R1C＝CR1、C≡C、Si(R1)2、C＝O、NR1O, S or CONR1Instead of, or with 5 to 40 aromatic ring atoms and may in each case be substituted by one or more R1Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 40 aromatic ring atoms and which may be substituted by one or more R1A group-substituted aryloxy or heteroaryloxy group; at the same time, two Ra、RbAnd/or RcThe radicals together also being able to form a mono-or polycyclic aliphatic radicalAn aromatic ring system;
R1the same or different at each occurrence and is: h, D, F, Cl, Br, I, N (R)2)2，CN，NO2，Si(R2)3，B(OR2)2，C(＝O)R2，P(＝O)(R2)2，S(＝O)R2，S(＝O)2R2，OSO2R2Straight-chain alkyl, alkoxy or thioalkoxy groups having 1 to 20 carbon atoms or alkenyl or alkynyl groups having 2 to 20 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 20 carbon atoms, wherein each alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted by one or more R2Radical substitution of one or more non-adjacent CH2The group can be represented by R2C＝CR2、C≡C、Si(R2)2、C＝O、NR2O, S or CONR2Instead of, or with 5 to 40 aromatic ring atoms and may in each case be substituted by one or more R2Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 40 aromatic ring atoms and which may be substituted by one or more R2Aryloxy or heteroaryloxy radicals substituted by radicals, or having 5 to 40 aromatic ring atoms and which may be substituted by one or more R2Aralkyl or heteroaralkyl groups substituted by radicals, or having 10 to 40 aromatic ring atoms and which may be substituted by one or more R2A group-substituted diarylamino group, diheteroarylamino group, or arylheteroarylamino group; simultaneously, two or more R1The radicals together may form a mono-or polycyclic, aliphatic or aromatic ring system;
R2the same or different at each occurrence and is: h, D, F, or aliphatic, aromatic and/or heteroaromatic organic radicals having from 1 to 20 carbon atoms, in particular hydrocarbon radicals, in which one or more hydrogen atoms may also be replaced by F, and, at the same time, two or more R2The substituents together may also form a mono-or polycyclic, aliphatic or aromatic ring system.
7. The process according to one or more of claims 1 to 6, characterized in that the activated olefin can be represented by formula (II):
Figure FDA0002994034750000031
the symbols used therein are as follows:
x is OH, ORdOr NRd 2；
RdIs H, D, a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 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 can be substituted in each case by one or more R1Substituted by groups; also, two R groups together may form a ring system, where R1According to the definition in claim 8;
wherein the bicyclic/polycyclic rings may have one or more substituents R, and
r is the same or different at each occurrence and is: h, D, F, Cl, Br, I, N (R)1)2，CN，NO2，OH，COOH，C(＝O)N(R1)2，Si(R1)3，B(OR1)2，C(＝O)R1，P(＝O)(R1)2，S(＝O)R1，S(＝O)2R1，OSO2R1A linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein each of said alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl groups may be substituted with one or more R1Radical substitution of one or more non-adjacent CH2The group can be represented by R1C＝CR1、C≡C、Si(R1)2、C＝O、NR1O, S or CONR1Instead of the formerOr having 5 to 40 aromatic ring atoms and may in each case be substituted by one or more R1Aromatic or heteroaromatic ring systems substituted by radicals, or having 5 to 40 aromatic ring atoms and which may be substituted by one or more R1A group-substituted aryloxy or heteroaryloxy group; also, two R groups together may also form a mono-or polycyclic aliphatic or aromatic ring system, where R1As defined in claim 8.
8. The process according to one or more of claims 1 to 7, characterized in that the olefin provided in step B) originates from a ketone of formula (IIa) to (IIo)
Figure FDA0002994034750000041
Figure FDA0002994034750000051
Wherein the structures of formulae (IIa) to (IIo) shown may be substituted by one or more R1Is substituted by radicals in which R1As defined in claim 8.
9. The process according to one or more of claims 4 to 8, characterized in that the 1, 2-dicarbonyl can be represented by formula (III)
Figure FDA0002994034750000061
Wherein the symbol RbAnd RcHaving the definition set forth in claim 8.
10. Method according to one or more of claims 4 to 9, characterized in that the formamidrazone can be represented by formula (IV)
Figure FDA0002994034750000062
Wherein the symbol RaHaving the definition set forth in claim 8.
11. A compound obtainable by the process according to claims 1 to 9.
12. A compound according to claim 11, characterised in that no other ring system is fused to the ring via which the fusion takes place via the bicyclic/polycyclic, preferably non-aromatic or non-heteroaromatic, polycyclic ring system shown in ring (II) or (V), preferably having at least 2, preferably at least 3 rings.
13. An oligomer, polymer or dendrimer containing one or more compounds according to claim 11 or 12, wherein one or more bonds of the compounds to the polymer, oligomer or dendrimer are present in place of a hydrogen atom or substituent.
14. A composition comprising at least one compound according to claim 11 or 12 or an oligomer, polymer or dendrimer according to claim 13 and at least one further compound selected from: fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF (thermally activated delayed fluorescence), host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocking materials, and hole blocking materials.
15. A formulation comprising at least one compound according to claim 11 or 12 or an oligomer, polymer or dendrimer according to claim 13 or a composition according to claim 14 and at least one solvent.
16. Use of a compound according to claim 11 or 12 or an oligomer, polymer or dendrimer according to claim 13 or a composition according to claim 14 as fluorescent emitter, emitter exhibiting TADF (thermally activated delayed fluorescence), host material, electron transport material, electron injection material, hole transport material, hole injection material, electron blocking material, hole blocking material and/or wide band gap material in an electronic device, preferably as fluorescent emitter (singlet emitter), host material, hole transport material and/or electron transport material.
17. An electronic device comprising at least one compound according to claim 11 or 12 or an oligomer, polymer or dendrimer according to claim 13 or a composition according to claim 14, wherein the electronic device is preferably selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells or organic laser diodes.
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