Heterocyclic compounds for optoelectronic devices

Abstract

The present invention relates to: heterocyclic compounds suitable for use in electronic devices; and electronic devices, in particular optoelectronic devices, containing these compounds.

Description

[0001] The present invention relates to heterocyclic compounds for use in electronic devices, especially organic optoelectronic devices, and to electronic devices, especially organic optoelectronic devices, comprising these heterocyclic compounds.

[0002] Photosensitizers used in organic photodetectors are generally heterocyclic compounds. CN 110964007 A, EP 3026722A1, EP 3243822 A1, EP 3473622 A1, EP 3757108 A1, EP 3770163 A1, US 2019 / 131541 A1 and EP 3848374 A1 disclose heterocyclic compounds that can be used in photodetectors. Compounds according to the present invention are not disclosed.

[0003] In general, in the case of these heterocyclic compounds used, for example, as photosensitizers, there is still a need for improvement, in particular with regard to the lifetime, but also with regard to the efficiency and operating voltage of the devices.

[0004] It was therefore an object of the present invention to provide compounds which are suitable for use in organic electronic devices, in particular in organic photodetectors, and to provide corresponding electronic devices, which compounds when used in such devices lead to good device properties.

[0005] More particularly, the problem addressed by the present invention is that of providing compounds which lead to a long lifetime, good efficiency and low operating voltage.

[0006] Furthermore, the compounds should have excellent processing properties and in particular the compounds should show good solubility.

[0007] Another object of the present invention may be considered to be to provide compounds suitable for use in organic photodetectors, especially as photosensitizers. A particular object of the present invention is to provide photosensitizers suitable for use in infrared, red, green or blue photodetectors, preferably green photodetectors.

[0008] Another object that can be considered is to provide very cheap and stable electronic devices with excellent performance.

[0009] Furthermore, it should be possible to use or modify the electronic device for many purposes. More particularly, the performance of the electronic device should be maintained over a wide temperature range.

[0010] It has been found that, surprisingly, this object is achieved by specific compounds, which are described in detail below, which are very suitable for use in electronic devices and lead to organic photodetectors that exhibit very good properties, especially with regard to lifetime, efficiency and operating voltage. The present invention therefore provides these compounds and electronic devices, especially organic photodetectors, comprising such compounds.

[0011] The present invention provides a compound comprising at least one structure of formula (I), preferably a compound of formula (I),

[0012]

[0013] The symbols used are as follows:

[0014] Ar a are identical or different in each case and are aromatic rings having 5 to 60 atoms and may be replaced by one or more Ar or R a group-substituted aromatic or heteroaromatic ring systems;

[0015] Ar b are identical or different in each case and are aromatic rings having 5 to 60 atoms and may be replaced by one or more Ar or R b group-substituted aromatic or heteroaromatic ring systems;

[0016] Z is identical or different in each case and is a moiety having 5 to 60 aromatic ring atoms and can be replaced by one or more R d Aromatic or heteroaromatic ring system substituted with a group, and the aromatic or heteroaromatic ring system may be combined with other groups such as R c The groups form a ring system, characterized in that the Z group has a strong electron-withdrawing effect;

[0017] Y 1 are in each case identical or different and are O, S, Se, Te, NAr, NR, C(R)2, Ge(R)2, Si(R)2, preferably O, S, Se, Te, NAr, more preferably S or Se;

[0018] Y 2 are in each case identical or different and are a bond, O, S, Se, Te, NAr, NR e ,BAr,BR e , C(R e )2、Ge(R e )2、Si(R e 2. -CR e =CR e -、C=NR e , S=O, SO2, preferably a bond, C(R e )2, O, S, NAr, more preferably C(R e )2;

[0019] L is identical or different in each case and is a linking group, preferably a bond, C(R)2, O, S, NR, NAr, C(=O), BAr, B(R), Si(R)2, C=NR, C=C(R)2, S=O, SO2, P(R), P(=O)R, -CR=CR- or an aromatic or heteroaromatic ring system having 5 to 40, preferably 5 to 30, aromatic ring atoms and which may be substituted by one or more R groups, more preferably a bond, C(R)2, O, S, NAr, NR, -CR=CR- or an ortho-linked aryl or heteroaryl group having 5 to 14 aromatic ring atoms, most preferably a bond, C(R)2, O, S, NAr or NR;

[0020] Ar is in each case identical or different and is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups; the Ar groups may be substituted with at least one Ar, R, R a , R b , R c , R d , R e Groups or other groups form a ring system;

[0021] R, R a , R b , R c , R d , R e are in each case identical or different and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)N(Ar')2,C(=O)N(R 1 )2,C(Ar')3,C(R 1 )3,Si(Ar')3,Si(R 1 )3,B(Ar')2,B(R 1 )2,C(=O)Ar',C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2,P(Ar')2,P(R 1 )2,S(=O)Ar',S(=O)R 1 ,S(=O)2Ar',S(=O)2R 1 , OSO2Ar', OSO2R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R1 group, wherein one or more non-adjacent CH2 groups may be replaced by R 1 C=CR 1 、C≡C、Si(R 1 )2. C=O, C=S, C=Se, C=NR 1 、C(=O)O、C(=O)NR 1 NR 1 、P(=O)(R 1 )、Se、Te、NAr'、BR 1 , Ge(R 1 )2, O, S, SO or SO2, or has 5 to 60 aromatic ring atoms and can be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 substituted aryloxy or heteroaryloxy groups, or having 5 to 60 aromatic ring atoms and may be replaced by one or more R 1 substituted arylthio or heteroarylthio groups, or having 5 to 60 aromatic ring atoms and may be replaced by one or more R 1 A diarylamino, arylheteroarylamino, diheteroarylamino group substituted with a group, or a diarylamino group having 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl group and being substituted with one or more R 1 an aralkyl or heteroaralkyl group substituted with a group; two R, R a , R b , R c , R d , R e The groups together or with other groups here can also form a ring system;

[0022] Ar' is identical or different in each case and is a ring having 5 to 60 aromatic ring atoms and may be replaced by one or more R 1 At the same time, two Ar' groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom may also be bridged to each other by a single bond or a bridging group selected from the following groups: B(R 1 )、C(R 1 )2、Si(R 1 )2. C=O, C=NR 1 、C=C(R 1 )2, O, S, S=O, SO2, N(R 1 )、P(R 1 ) and P(=O)R 1 ;

[0023] R 1are in each case identical or different and are H, D, F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R 2 )2,C(=O)Ar'',C(=O)R 2 ,P(=O)(Ar'')2,P(Ar'')2,B(Ar'')2,B(R 2 )2,C(Ar'')3,C(R 2 )3,Si(Ar'')3,Si(R 2 )3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2. C=O, C=S, C=Se, C=NR 2 、C(=O)O、C(=O)NR 2 NR 2 、P(=O)(R 2 ), O, S, SO or SO2, and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or having 5 to 60 aromatic ring atoms and in each case by one or more R 2 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 substituted aryloxy or heteroaryloxy groups, or having 5 to 60 aromatic ring atoms and may be replaced by one or more R 2 substituted aralkyl or heteroaralkyl groups, or combinations of these systems; at the same time, two or more preferably adjacent R 1 The groups can form a ring system with each other; at the same time, one or more R 1 The group and the other parts of the compound can form a ring system;

[0024] Ar'' is identical or different in each case and is a cyclic aromatic ring having 5 to 30 atoms and may be replaced by one or more R 2 At the same time, two Ar'' groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom may also be bridged to each other by a single bond or a bridging group selected from the following groups: B(R 2 )、C(R 2 )2、Si(R 2)2. C=O, C=NR 2 、C=C(R 2 )2, O, S, S=O, SO2, N(R 2 )、P(R 2 ) and P(=O)R 2 ;

[0025] R 2 are in each case identical or different and are selected from H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and which may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms; at the same time, two or more preferably adjacent substituents R 2 Together they can form a ring system.

[0026] In a preferred configuration of the present invention, the Z group is known for its strong -M effect, so the strong electron-withdrawing effect is particularly caused by electron-withdrawing isomerism. Therefore, the preferred Z group exhibits a strong -M effect. Groups that cause a strong -M effect and are therefore preferably present in the Z group are known in the professional field. These groups include cyano groups, nitro groups, carbonyl groups and triarylborane groups.

[0027] Furthermore, particularly preferred Z groups have LEeV values ​​of less than -0.20 eV, preferably less than -0.40 eV, more preferably less than -1.00 eV, and most preferably less than -1.40 eV.

[0028] The LEeV value herein refers to the LUMO energy level, and LEh in Hartree units is converted to electron volts (eV).

[0029] The molecular orbital of Z group, especially the lowest unoccupied molecular orbital (LUMO) is determined via quantum chemical calculation. For the calculation of organic substances, it is preferred to first optimize the geometry by the "ground state / semi-empirical / default spin / AM1 / charge 0 / spin singlet" method. Subsequently, energy calculations are performed based on the optimized geometry. This is done using the "TD-SCF / DFT / default spin / B3PW91" method and the "6-31G (d)" basis set (charge 0, spin singlet).

[0030] The energy calculation gives the LUMO energy level LEh in Hartree units, which gives the LUMO energy level LEeV in electron volts.

[0031] In the context of the present application, the LEeV value rounded to two decimal places should be regarded as the LUMO level of the electron-withdrawing group Z.

[0032] Thus, the electron withdrawing properties of Z can be determined by quantum chemical calculations, wherein preferred Z groups are characterized by the LEeV values ​​detailed above.

[0033] The method described herein is independent of the software package used and always gives the same results. Examples of frequently used programs for this purpose are "Gaussian09W" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

[0034] Preferably, the LEeV value of the Z group is determined using the structure of the formula HZ, wherein Z has the meaning given above, in particular for formula (I), and wherein H is hydrogen.

[0035] The Z group preferably does not comprise any metal. If the Z group should contain metal, then optimize the geometry via the "ground state / Hartree-Fock / default spin / LanL2MB / charge 0 / spin singlet" method. Energy calculations are carried out similarly to the above-mentioned method for organic substances, except that the "LanL2DZ" basis set is used for metal atoms, and the "6-31G (d)" basis set is used for ligands.

[0036] It is also possible that the Z group has at least one selected from CN, NO2, C(=O)R d , B(R d )2, preferably at least one CN group, more preferably at least two CN groups.

[0037] Furthermore, it is possible that the Z group has at least one nitrogen-containing heteroaryl group.

[0038] It is also possible that the Z radical has at least one NO2 group.

[0039] In another preferred configuration of the invention, it is possible for the Z group to have no CO group.

[0040] Also particularly preferred are structures / compounds of formula (I) in which at least one of the Z groups is selected from the group consisting of CN, NO2, C(=O)R d , B(R d )2, preferably at least one CN group, more preferably at least two CN groups and containing Y 1 The 5-membered ring of the group is completely conjugated.

[0041] The term "conjugated" or "conjugated" is well known in the art and is therefore referred to herein. At least one of the Z groups is selected from CN, NO2, C(=O)R d , B(R d)2, preferably at least one CN group, more preferably at least two CN groups, for example, complete conjugation is formed by at least one selected from CN, NO2, C(=O)R d , B(R d )2, preferably at least one CN group, more preferably at least two CN groups are directly combined with an aryl or heteroaryl group, at least one of which is selected from CN, NO2, C(=O)R d , B(R d )2, preferably at least one CN group, more preferably at least two CN groups combined with the aryl or heteroaryl group and the group containing Y 1 The 5-membered ring of the group is completely conjugated. Additional bonds between the above-mentioned conjugated groups, for example via sulfur, nitrogen or oxygen atoms or carbonyl groups, do not impair the conjugation.

[0042] In addition, as long as at least one of the Z groups is selected from CN, NO2, C(=O)R d , B(R d )2, preferably at least one CN group, more preferably at least two CN groups and containing Y 1 The 5-membered rings of the group form alternating double bonds and single bonds, and at least one of the Z groups is selected from CN, NO2, C(=O)R d , B(R d )2 groups, preferably at least one CN group, more preferably at least two CN groups are fully conjugated.

[0043] Ar a ,Ar b , R c , R d , Y 1 , Y 2 Preferred embodiments of the radicals A and L derive in particular from structures or compounds described in the prior art.

[0044] In this example, Ar a ,Ar b , R c , R d , Y 1 , Y 2 Structures or compounds similar to the L group come in particular from European patent application EP 3848374A1 with application number EP 21151295.9 filed on January 13, 2021 in the European Patent Office, which publication is hereby incorporated by reference for the purpose of disclosure.

[0045] One of the distinguishing features of the structure of the compound of formula (I) described in detail in EP 3848374 A1 from the compound of the present invention is the Z group, which is not disclosed in EP 3848374 A1.

[0046]

[0047] The present invention example is similar to the example in which Ar a ,Ar b , R c , R d , Y 1 , Y 2 Preferred structures or compounds are similar to those of the L group.

[0048] Under the above mentioned conditions, that is, the following and described in detail in EP 3848374 A1 containing Ar 3 and R 1The substructure of the group is replaced by the Z group, and the following structures, in particular the structures described in detail in EP 3848374 A1, are incorporated into the present application by reference for the purpose of disclosure: the structure of formula (1) (see EP 3848374 A1, page 3, paragraph

[0009] , the structure of formula (2A) (see EP 3848374 A1, page 4, paragraph

[0011] , the structure of formula (2A-1) (see EP 3848374 A1, page 5, paragraph

[0013] , the structure of formula (2A-2) (see EP 3848374 A1, page 5, paragraph

[0014] , the structure of formula (2B) (see EP 3848374 A1, page 6, paragraph

[0016] , the structure of formula (2B-1) (see EP 3848374 A1, page 6, paragraph

[0016] A1, page 6, paragraph

[0019] , structure of formula (2B-2) (see EP 3848374 A1, page 7, paragraph

[0020] , structure of formula (2C) (see EP 3848374 A1, page 7, paragraph

[0022] , structure of formula (2C-1) (see EP 3848374 A1, page 8, paragraph

[0026] , structure of formula (2C-2) (see EP 3848374 A1, page 9, paragraph

[0027] , structure of formula (2D) (see EP 3848374 A1, page 9, paragraph

[0029] , structure of formula (2D-1) (see EP 3848374 A1, page 10, paragraph

[0032] , structure of formula (2D-2) (see EP 3848374 A1, page 10, paragraph

[0034] , structure of formula (2E) (see EP 3848374 A1, page 11, paragraph

[0035] , structure of formula (2E-1) (see EP 3848374 A1, page 12, paragraph

[0038] , structure of formula (2E-2) (see EP 3848374 A1, page 12, paragraph

[0039] .

[0049] Particularly preferred structures will be described in detail later. These structures are superior to the above-mentioned structures.

[0050] It is also possible that the Z group is a substructure of formula (Z-1), or contains a substructure of formula (Z-1), preferably a substructure of formula (Z-1),

[0051]

[0052] Where X 1 , X 2 , X 3 are the same or different in each case and are N, CZ 2 or CR d , where Z 2is an electron-withdrawing substituent, preferably CN, NO2, C(=O)R d , B(R d )2, more preferably CN, wherein R d has the definitions given above, in particular for formula (I), and the dotted bond indicates the attachment site, wherein X 1 , X 2 , X 3 At least one, preferably at least two, of the groups are N or CZ 2 , wherein, more preferably, X 1 , X 2 , X 3 At least one of the groups is CZ 2 Preferably, the substructure of formula (Z-1) and the substructure containing Y 1 The 5-membered ring of the group is completely conjugated.

[0053] The structure / compound of formula (I) may contain one, two, three, four or more substructures of formula (Z-1).

[0054] It is also possible that, especially for the structure of formula (Z-1), X 1 , X 2 , X 3 Exactly one of the groups, preferably X 3 The group is CZ 2 And Z 2 = NO2, where the other X 1 , X 2 , X 3 Groups, especially X 1 , X 2 Group, preferably CR d .

[0055] It is preferred that, especially for the structure of formula (Z-1), X 1 , X 2 , X 3 At least one of the groups, preferably X 3 The group is CZ 2 And Z 2 =CN, where X 1 , X 2 , X 3 Preferably at least two of the groups, preferably X 3 Group and X 2 One of the groups is CZ 2 And Z 2 In each case, CN, where the other X 1 , X 2 , X 3 Groups, especially X2 One of the groups and X 1 Group, preferably CR d .

[0056] In addition, it is preferable that, especially for the structure of formula (Z-1), X 1 , X 2 , X 3 At least one of the groups, preferably X 3 The group is CZ 2 And Z 2 =CN, and X 1 , X 2 , X 3 At least one of the groups, preferably X 1 One of the groups is N.

[0057] It is preferred here that the Z group contains at least one CN group.

[0058] More preferably, the Z group is a substructure of formula (Z-1a) to (Z-1n), or contains a substructure of formula (Z-1a) to (Z-1n), preferably a substructure of formula (Z-1a) to (Z-1n),

[0059]

[0060]

[0061] Where R d has the definitions given above, in particular for formula (I), the dashed bond indicates the attachment site, and the other symbols have the following definitions:

[0062] n is 0, 1, 2 or 3, preferably 0, 1 or 2,

[0063] o is 0, 1 or 2, preferably 0 or 1.

[0064] Preference is given here to groups of the formulae (Z-1a), (Z-1b), (Z-1h), (Z-1i) and (Z-1m), particular preference to groups of the formulae (Z-1a) and (Z-1h).

[0065] In a preferred configuration, it is possible that the compound of the present invention comprises a structure of formula (II), wherein the compound of the present invention may be more preferably selected from compounds of formula (II),

[0066] Formula (II)

[0067] The symbol Ar a ,Ar b , Rc , Y 1 , Y 2 and L have the meanings given above, in particular for formula (I), the symbol X 1 , X 2 and X 3 has the definitions given above, especially for formula (Z-1), L 1 is a bond or an aromatic or heteroaromatic ring system having 6 to 40, preferably 6 to 30, aromatic ring atoms and which may be substituted by one or more R groups.

[0068] Preferred aromatic or heteroaromatic ring systems L 1 is selected from the group consisting of a phenylene group; a biphenyl group, in particular an o-, m- or p-biphenyl group; a terphenyl group, in particular an o-, m-, p- or branched terphenyl group; a quaterphenyl group, in particular an o-, m-, p- or branched quaterphenyl group; a fluorene group which may be attached via the 1-, 2-, 3- or 4-position; a spirobifluorene group which may be attached via the 1-, 2-, 3- or 4-position; a naphthalene group, in particular a naphthalene group attached via the 1- or 2-position; an indolyl group; a benzofuranyl group; a benzene group a 1-thiophene subunit; a carbazole subunit which may be attached via the 1-, 2-, 3-, 4- or 9-position; a dibenzofuran subunit which may be attached via the 1-, 2-, 3- or 4-position; a benzothiophene subunit which may be attached via the 1-, 2-, 3- or 4-position; an indenocarbazole subunit; an indolecarbazole subunit; a pyridine subunit; a pyrimidine subunit; a pyrazine subunit; a pyridazine subunit; a triazine subunit; a quinoline subunit; an isoquinoline subunit; a quinazoline subunit; a quinoxaline subunit; a phenanthren subunit or a terphenylidene subunit, each of which may be substituted with one or more R groups.

[0069] It is preferably possible that, especially in formula (II), L 1 The group represents a bond or is identical or different in each case and is selected from the structures of the formulae (Ar-1) to (Ar-9),

[0070]

[0071] The symbols and notations used are as follows:

[0072] i is 0, 1 or 2, preferably 0 or 1;

[0073] j is independently 0, 1, 2 or 3 in each case;

[0074] h is independently at each occurrence 0, 1, 2, 3 or 4;

[0075] R has the meaning given above, in particular for formula (I), and the dashed bond marks the point of attachment.

[0076] In this case, L 1 The group is preferably a bond or a structure selected from the formula (Ar-1) to (Ar-4), wherein L 1 More preferably, the group is a bond.

[0077] Aryl groups in the context of the present invention contain 6 to 40 carbon atoms; heteroaryl groups in the context of the present invention contain 2 to 40 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Here, aryl groups or heteroaryl groups are understood to mean: simple aromatic rings, i.e. benzene; or simple heteroaromatic rings, such as pyridine, pyrimidine, thiophene, etc.; or fused (annulated) aryl or heteroaryl groups, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic compounds which are linked to one another by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0078] The electron-deficient heteroaryl group in the context of the present invention is a heteroaryl group with at least one heteroaromatic six-membered ring, and the heteroaromatic six-membered ring has at least one nitrogen-atom. Other aromatic or heteroaromatic five-membered rings or six-membered rings can be fused to the six-membered ring. The example of the electron-deficient heteroaryl group is pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline or quinoxaline.

[0079] The aromatic ring system in the context of the present invention contains 6 to 60 carbon atoms in the ring system, preferably 6 to 40 carbon atoms in the ring system. The heteroaromatic ring system in the context of the present invention contains 2 to 60 carbon atoms, preferably 3 to 40 carbon atoms and at least one heteroatom in the ring system, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. The aromatic or heteroaromatic ring system in the context of the present invention is understood to refer to the following system: it does not necessarily contain only aryl or heteroaryl groups, but two or more aryl or heteroaryl groups in which can also be connected by non-aromatic units such as carbon, nitrogen or oxygen atoms. For example, in the context of the present invention, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. should also be regarded as aromatic ring systems, and the same is true for systems in which two or more aryl groups are connected, for example, by short alkyl groups. Preferably, the aromatic ring system is selected from fluorene, 9,9′-spirobifluorene, 9,9-diarylamine or a group in which two or more aryl and / or heteroaryl groups are linked to each other via a single bond.

[0080] In the context of the present invention, an aliphatic hydrocarbyl radical or an alkyl radical or an alkenyl or alkynyl radical which may contain 1 to 20 carbon atoms and in which individual hydrogen atoms or CH2 groups may also be replaced by the abovementioned radicals is preferably understood as meaning a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl radical. Alkoxy groups having 1 to 40 carbon atoms are preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Thioalkyl radicals having 1 to 40 carbon atoms are understood to mean in particular methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. Generally, the alkyl, alkoxy or thioalkyl group according to the present invention can be linear, branched or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the above groups; in addition, one or more hydrogen atoms can also be replaced by D, F, Cl, Br, I, CN or NO2, preferably by F, Cl or CN, further preferably by F or CN, and particularly preferably by CN.

[0081] Aromatic or heteroaromatic ring systems having 5 to 60 or 5 to 40 aromatic ring atoms which in each case may also be substituted by the abovementioned radicals and which can be linked to the aromatic or heteroaromatic system via any desired position are understood to mean in particular radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, lettuce, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylylidene, terphenyl, biphenylylidene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indole Carbazole, trimerized indene, isotrimerized indene, spirotrimerized indene, spiroisotrimerized indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthymidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthylimidazole oxazole, anthraquinone oxazole, phenanthroquinone oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazaterphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorescein ring, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4 -triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole, or radicals derived from combinations of these systems.

[0082] In the context of this specification, the expression that two or more groups together can form a ring is understood to mean in particular that the two groups are connected to each other by a chemical bond under the conditions of formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0083] .

[0084] 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 bound to the position where the hydrogen atom is bonded, thereby forming a ring. This will be illustrated by the following scheme:

[0085] .

[0086] In a preferred configuration, it is possible that the compound of the present invention comprises a structure of formula (III), wherein the compound of the present invention may be more preferably selected from compounds of formula (III),

[0087]

[0088] The symbol R c , Y 1 , Y 2 and L have the meanings given above, in particular for formula (I), the symbol X 1 , X 2 and X 3 Having the definitions given above, especially for formula (Z-1), the symbol L 1 have the definitions given above, especially for formula (II), and the other symbols have the following definitions:

[0089] X a are the same or different in each case and are N or CR a , preferably CR a , provided that there are no more than two X in a ring a The group is N, where R a have the meanings detailed above, especially those detailed for formula (I); or two adjacent X a Together they are a group of the formula:

[0090]

[0091] wherein dashed bonds represent the connection of the groups within the structure;

[0092] X b are the same or different and are N or CR in each case b , preferably CR b , provided that there are no more than two X in a ring b The group is N, where R b have the meanings detailed above, especially those detailed for formula (I); or two adjacent X b Together they are a group of the formula:

[0093]

[0094] The dashed bonds represent the connection of the groups within the structure.

[0095] It is preferred that in formula (III), there are not more than three, preferably not more than two Xa and X b More preferably, all X a and X b The group is CR a or CR b , or a fused benzo group as described in detail above.

[0096] In a particularly preferred configuration, it is possible that the compound of the present invention comprises a structure of formula (IV) or (IVa) to (IVf), wherein the compound of the present invention may more preferably be selected from compounds of formula (IV) or (IVa) to (IVf),

[0097]

[0098]

[0099] The compounds may also be partially or fully deuterated, symbol R a , R b , R c , Y 1 , Y 2 and L have the meanings given above, in particular for formula (I), the symbol X 1 , X 2 and X 3 Having the definitions given above, especially for formula (Z-1), the symbol L 1 have the definitions given above, especially for formula (II), and the other symbols have the following definitions:

[0100] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0101] n is 0, 1, 2 or 3, preferably 0, 1 or 2.

[0102] It is also possible that, in particular in formula (I), (II), (III) and / or (IV), the L group is a bond, C(R)2, O, S, NAr or NR, Y 2 The group is C(R e )2, and Y 1 The group is O, S, Se, Te, NR or NAr, preferably S or Se. In the compounds of formula (IVa) to (IVf), Y 2 The group is preferably C(R e )2 and Y 1 The group is O, S, Se, Te, NR, NAr, preferably S or Se.

[0103] Furthermore, it is preferably possible that, in particular in formulae (I), (II), (III) and / or (IV) or (IVa) to (IVf), Y 2 The group is NR e , BR e , C(R e )2、Ge(R e )2、Si(R e 2. -CR e =CR e -、C=NR e , preferably C(R e )2, and Y 2 R e The radicals are straight-chain alkyl radicals having 1 to 10 carbon atoms, branched or cyclic alkyl radicals having 3 to 12 carbon atoms, wherein the alkyl radicals may in each case be replaced by one or more R 1 A phenyl group is substituted with one or more R 1 Group substitution, where Y 2 The two R's of the group e The groups may together form a ring having 5 to 10 atoms and may be ringed by one or more R 1 In a particularly preferred embodiment, Y 2 The group is C(R e )2 and Y 2 The two R's of the group e The groups together form a ring having 5 to 10 atoms and may be replaced by one or more R 1 This preferably results in a spirocyclic system in which the two R e The ring formed by the group is preferably a 5-membered ring, a 6-membered ring, a 7-membered ring, or an 8-membered ring that can be bridged. e The ring formed by the group is a monocyclic cyclopentyl, cyclohexyl or cycloheptyl ring, preferably a monocyclic cyclopentyl or cyclohexyl, or a tricyclic adamantyl ring. 2 C(R e )2, R e Preferably, F, methyl, ethyl, neopentyl or phenyl, wherein each of these radicals may also be partially or fully deuterated, and wherein both R e The groups may also form a ring together, or two R e The groups together with the carbon atom to which they are attached form a cyclopentyl, cyclohexyl or adamantyl group, which may also be partially or fully deuterated. More preferably, R e is a methyl group, which may also be partially or fully deuterated.

[0104] Another possible situation is that R c The radical is H, a straight-chain alkyl radical having 1 to 10 carbon atoms, a branched or cyclic alkyl radical having 3 to 12 carbon atoms, wherein the alkyl radical may in each case be replaced by one or more R 1 or an aryl or heteroaryl group having 5 to 12 aromatic ring atoms, preferably a phenyl group, which may in each case be substituted by one or more R 1 Group substitution, where R c Group and R d The groups together may form a ring having 5 to 10 atoms and may be replaced by one or more R 1 The ring is substituted with a group.

[0105] Another possible situation is that at least one R d The radical is H, a straight-chain alkyl radical having 1 to 10 carbon atoms, a branched or cyclic alkyl radical having 3 to 12 carbon atoms, wherein the alkyl radical may in each case be replaced by one or more R 1 or an aryl or heteroaryl group having 5 to 12 aromatic ring atoms, preferably a phenyl group, which may in each case be substituted by one or more R 1 group-substituted, wherein at least one R d Group and R c The groups together may form a ring having 5 to 10 atoms and may be ringed by one or more R 1 Preferably, all R d radicals are identical or different in each case and are H, straight-chain alkyl radicals having 1 to 10 carbon atoms, branched or cyclic alkyl radicals having 3 to 12 carbon atoms, wherein the alkyl radicals may be replaced by one or more R in each case. 1 A phenyl group is substituted with one or more R 1 More preferably, R d The radicals are in each case identical or different and are H, D or phenyl.

[0106] In a particularly preferred embodiment, it is possible that R c and at least one, preferably all, R d The groups are the same and are each H or D. In another particularly preferred embodiment, it is possible that R c Group and R d The groups together form a ring having 5 to 10 ring atoms.

[0107] In another preferred configuration, it is possible that the compound of the present invention comprises a structure of formula (IV-1) or (IV-1a) to (IV-1f), wherein the compound of the present invention may be more preferably selected from compounds of formula (IV-1) or (IV-1a) to (IV-1f),

[0108]

[0109]

[0110] The symbol R a , R b , Y 1 , Y 2 and L have the meanings given above, in particular for formula (I), wherein Y 1 Preferably S or Se, more preferably S, symbol X 1 , X 2 and X 3 has the definitions given above, especially for formula (Z-1), and the other symbols have the following definitions:

[0111] Y 3 are in each case identical or different and are O, S, Se, Te, NAr', NR 1 , B.R. 1 , C(R 1 )2,Ge(R 1 )2,Si(R 1 )2, -CR 1 =CR 1 -, C=NR 1 , P(O)R 1 , S=O, SO2, or having 5 to 14 aromatic ring atoms and may be replaced by one or more R 1 A radical-substituted ortho-linked aromatic or heteroaromatic substituent group, wherein Ar' and R 1 The radicals have the meanings given above, in particular for formula (I); preferably Y 3 C(R 1 )2, O, S, Se, NAr';

[0112] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0113] n is 0, 1, 2 or 3, preferably 0, 1 or 2.

[0114] In a preferred configuration, the compound of the present invention may comprise the structure of formula (V-1a) to (V-32c); more preferably, the compound of the present invention may be selected from the compounds of formula (V-1a) to (V-32c),

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121] The symbol R a , R b , R c , Y 2 and L have the meanings given above, in particular for formula (I), the symbol X 1 , X 2 and X 3 Having the definitions given above, especially for formula (Z-1), the symbol L 1 have the definitions given above, especially for formula (II), and the other symbols have the following definitions:

[0122] Y 3 are in each case identical or different and are O, S, Se, Te, NAr', NR 1 , B.R. 1 , C(R 1 )2,Ge(R 1 )2,Si(R 1 )2, -CR 1 =CR 1 -, C=NR 1 , P(O)R 1 , S=O, SO2, or having 5 to 14 aromatic ring atoms and may be replaced by one or more R 1 A radical-substituted ortho-linked aromatic or heteroaromatic substituent group, wherein Ar' and R 1 The radicals have the meanings given above, in particular for formula (I), Y 3 Preferably C(R 1 )2, O, S, Se, NAr';

[0123] l is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2;

[0124] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0125] n is 0, 1, 2 or 3, preferably 0, 1 or 2.

[0126] Preferably Y 1 = structure or compound of S or Se; in particular, Y 1 =S.

[0127] Preferred here are structures or compounds of formula (V-2a), (V-2b), (V-6a), (V-6b), (V-26a), (V-26b), (V-30a) and / or (V-30a), particularly preferred are structures or compounds of formula (V-2a), (V-2b), (V-6a) and / or (V-6b), especially structures or compounds of formula (V-2a) and (V-6a).

[0128] In another very particularly preferred embodiment, the present invention relates to structures or compounds of the formula (V-2a) or (V-2b), in particular of the formula (V-2a).

[0129] In a further very particularly preferred embodiment, the invention relates to structures or compounds of formula (V-6a) or (V-6b), in particular formula (V-6a).

[0130] In a further very particularly preferred embodiment, the present invention relates to structures or compounds of formula (V-26a) or (V-26b), in particular formula (V-26a).

[0131] In a further very particularly preferred embodiment, the present invention relates to structures or compounds of formula (V-30a) or (V-30b), in particular formula (V-30a).

[0132] For Y of Formula (I), (II), (III), (IV), (IVa) to (IVf), (IV-1) or (IV-1a) to (IV-1f) above 2 R e The preferences detailed for the radicals also apply correspondingly to formulae (V-1a) to (V-32c).

[0133] It is also possible that, especially for formula (IV), (IVa) to (IVf), (IV-1), (IV-1a) to (IV-1f) and / or formula (V-1a) to (V-32a), the sum of the markers l, m and n is not greater than 10, preferably not greater than 8, particularly preferably not greater than 6, and more preferably not greater than 4.

[0134] In addition, the above description of formula (Z-1) and L 1 The preferred options described for the group also apply to formulas (V-1a) to (V-32c) accordingly, but it should be noted that X in formulas (V-1a) to (V-32c) 1 To X3 At least one of the groups has a CN group.

[0135] It is preferred that, especially for formulae (V-1a) to (V-32c), X 1 , X 2 , X 3 At least one of the groups is N or C-CN, preferably CN.

[0136] A more preferred situation is that, especially for formulae (V-1a) to (V-32c), X 1 , X 2 , X 3 Exactly one of the groups is C-CN.

[0137] It is also possible that, especially for formulae (V-1a) to (V-32c), X 1 , X 2 , X 3 Exactly two of the groups are C-CN.

[0138] It is also possible that, especially for formulae (V-1a) to (V-32c), X 1 , X 2 , X 3 Exactly one of the groups is N.

[0139] It is preferred that, especially for formulae (V-1a) to (V-32c), X 1 , X 2 , X 3 At least one of the groups is N and X 1 , X 2 , X 3 At least one of the groups is C-CN.

[0140] It is also possible that, especially for formulae (V-1a) to (V-32c), X 1 , X 2 , X 3 At least one, preferably at least two, of the groups are CR d .

[0141] In a preferred embodiment of the present invention, it is feasible that at least two R, R a , R b The group and the two R, R a , R b The other groups to which the group is combined together form a condensed ring, in which the two R, R a , R b The groups form at least one structure of formula (RA-1) to (RA-12),

[0142]

[0143]

[0144] Where R 1 has the above definition, and the dotted bond represents the two R, R a , R b The attachment point of the atom of the group to which the group is attached, and other symbols are defined as follows:

[0145] Y 4 are identical or different in each case and are C(R 1 )2、(R 1 )2C-C(R 1 )2、(R 1 )C=C(R 1 ), NR 1 , NAr', O or S, preferably C(R 1 )2、(R 1 )2C-C(R 1 )2、(R 1 )C=C(R 1 ), O or S;

[0146] R f are identical or different in each case and are F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be replaced by one or more R in each case 2 group, wherein one or more non-adjacent CH2 groups may be replaced by R 2 C=CR 2 、C≡C、Si(R 2 )2. C=O, C=S, C=Se, C=NR 2 、-C(=O)O-、-C(=O)NR 2 -、NR 2 、P(=O)(R 1 ), -O-, -S-, SO or SO2, or has 5 to 60 aromatic ring atoms and can be replaced by one or more R in each case 2 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 substituted aryloxy or heteroaryloxy groups; at the same time, the two R f Group together or one R fGroup and R 1 The groups together or with other groups may also form a ring system, wherein R 2 The radicals have the definitions given above, in particular for formula (I);

[0147] s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0148] t is 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0149] v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2.

[0150] Preference is given here to structures of the formulae RA-1, RA-3, RA-4 and RA-5, particular preference to structures of the formulae RA-4 and RA-5.

[0151] In a preferred embodiment of the present invention, it is feasible that at least two R, R a , R b The group and the two R, R a , R b The other groups to which the group is combined together form a condensed ring, in which the two R, R a , R b The groups form structures of formula (RA-1a) to (RA-4f),

[0152]

[0153]

[0154] The dotted bond represents the two R, R a , R b The attachment site of the atom of the group to which the group is attached, the symbol m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the symbol R 1 , R 2 , R g and the indices s and t have the definitions given above, in particular for formula (I) and / or formulae (RA-1) to (RA-12).

[0155] Preferred here are structures of formula RA-4f.

[0156] It is also possible that at least two R, R a , R b The group is from the adjacent X aand X b The R and R a , R b group, or R, R each bonded to an adjacent carbon atom a , R b A group in which the carbon atoms are preferably connected via a bond.

[0157] In another preferred configuration, it is feasible that at least two R, R a , R b The group and the two R, R a , R b The other groups to which the group is combined together form a condensed ring, in which the two R, R a , R b The group forms a structure of formula (RB),

[0158]

[0159] Where R 1 has the definitions given above, especially for formula (I), the dashed bond represents the two R, R a , R b The attachment site of the atom of the group to which the group is attached, the label m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 5 C(R 1 )2. NR 1 、NAr'、BR 1 , BAr', O or S, preferably C(R 1 )2, NAr' or O, more preferably C(R 1 )2 or O, wherein Ar' has the meaning given above, in particular the meaning given for formula (I).

[0160] Here, it is feasible that at least two R, R a , R b The group is from the adjacent X a and X b The R and R a , R b group, or R, R each bonded to an adjacent carbon atom a , R b A group in which the carbon atoms are preferably connected to one another via bonds.

[0161] More particularly, it is possible that in preferred structures or compounds the sum of the indices r, s, t, v, m and n is preferably 0, 1, 2 or 3, more preferably 1 or 2.

[0162] More preferably, the compound comprises at least one structure of formula (VI-1) to (VI-5); more preferably, the compound is selected from compounds of formula (VI-1) to (VI-5), wherein the compound has at least one fused ring,

[0163]

[0164] The symbol R a , R b , R c , Y 1 , Y 2 and L have the meanings given above, in particular for formula (I), the symbol X 1 , X 2 and X 3 Having the definitions given above, especially for formula (Z-1), the symbol L 1 has the definitions given above, in particular for formula (II), the symbol o represents the fusion site of at least one fused ring, and the other symbols have the following definitions:

[0165] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0166] n is 0, 1, 2 or 3, preferably 0, 1 or 2.

[0167] i is 0, 1 or 2, preferably 0 or 1;

[0168] k is 0 or 1.

[0169] It is also possible that the fused ring consists of at least two R a , R b group and the two R a , R b The other groups to which the group is combined form at least two R a , R b The groups form structures of formula (RA-1) to (RA-12) and / or formula (RB), preferably structures of formula (RA-1) to (RA-12).

[0170] Furthermore, it is possible, in particular, in the formulae (VI-1) to (VI-5) for the sum of the indices k, i, n and m to be 0, 1, 2 or 3, preferably 1 or 2.

[0171] Preferably, the compound has at least two fused rings, wherein at least one fused ring is formed by the structure of formula (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f), and the other ring is formed by the structure of formula (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB).

[0172] Another possible situation is that the substituents R, R a , R b , R c , R d , R e , R f and R 1 Not with the substituents R, R a , R b , R c , R d , R e , R f and R 1 The ring atoms of the ring systems to which they are bonded form a fused aromatic or heteroaromatic ring system. This includes ring atoms that can be bonded to substituents R, R a , R b , R c , R d , R e , R f and R 1 Possible substituents R 1 and R 2 A fused aromatic or heteroaromatic ring system is formed.

[0173] When in particular it can be selected from R, R a , R b , R c , R d , R e , R f , R 1 and / or R 2 When two groups in form a ring system with each other, the ring system may be monocyclic or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. In this case, the groups that together form the ring system may be adjacent, which means that these groups are bonded to the same carbon atom or to carbon atoms that are directly bonded to each other, or they may be further away from each other. a , R b , R c , R d , R e , R f , R 1 and / or R 2 The ring systems of can also be connected to one another via bonds so that this can result in a closed ring. In this case, each corresponding bonding site preferably has a substituent R, R a , R b , R c , R d , R e , R f , R 1 and / or R2 .

[0174] In a preferred configuration, the compound of the present invention can be represented by at least one of the structures of formula (I), (II), (III), (IV), (IVa) to (IVf), (IV-1), (IV-1a) to (IV-1f) and / or (V-1a) to (V-32c). Preferably, the compound of the present invention preferably comprising the structure of formula (I), (II), (III), (IV), (IVa) to (IVf), (IV-1), (IV-1a) to (IV-1f) and / or (V-1a) to (V-32c) has a molecular weight of not more than 5000 g / mol, preferably not more than 4000 g / mol, particularly preferably not more than 3000 g / mol, especially preferably not more than 2000 g / mol, most preferably not more than 1200 g / mol.

[0175] In addition, a feature of the preferred compounds of the present invention is that they are sublimable. The molar mass of these compounds is generally less than about 1200 g / mol.

[0176] Preferred aromatic or heteroaromatic ring systems Ar, R, R a , R b , R c , R d , R e , R f and / or Ar' is selected from: phenyl; biphenyl, especially o-biphenyl, m-biphenyl or p-biphenyl; terphenyl, especially o-terphenyl, m-terphenyl or p-terphenyl or branched terphenyl; quaterphenyl, especially o-quaterphenyl, m-quaterphenyl or p-quaterphenyl or branched quaterphenyl; fluorene which may be attached via the 1-, 2-, 3- or 4-position; spirobifluorene which may be attached via the 1-, 2-, 3- or 4-position; naphthalene, especially 1-bonded naphthalene or 2-bonded naphthalene; indole; benzofuran; benzothiophene; carbazole which may be attached via the 1, 2, 3, 4 or 9 position; dibenzofuran which may be attached via the 1, 2, 3 or 4 position; dibenzothiophene which may be attached via the 1, 2, 3 or 4 position; indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or terphenylene, each of which may be substituted by one or more R, R 1 or R 2 Group substitution.

[0177] Preferably, at least one of R, R a , R b , R c , R d , R eThe radicals are identical or different in each case and are selected from H, D, branched or cyclic alkyl, alkoxy or thioalkoxy radicals having 3 to 20 carbon atoms, or aromatic or heteroaromatic ring systems selected from the following formulae Ar-1 to Ar-78; preferably, R, R a , R b , R c , R d , R e The group forms a condensed ring, preferably according to the structure of formula (RA-1) to (RA-12) or (RB), or R, R a , R b , R c , R d , R e are identical or different in each case and are selected from H, D or an aromatic or heteroaromatic ring system selected from the following formulae Ar-1 to Ar-78, and / or Ar' groups are identical or different in each case and are selected from the following formulae Ar-1 to Ar-78,

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205] Where R 1 Having the definitions given above, the dashed bonds indicate the site of attachment to the corresponding group, and in addition:

[0206] Ar 1 are identical or different in each case and are aromatic rings having 6 to 18 atoms and may be replaced by one or more R 1 a divalent aromatic or heteroaromatic ring system substituted with a radical;

[0207] A is identical or different in each case and is C(R 1 )2. NR 1 , O or S;

[0208] p is 0 or 1, where p=0 means Ar 1 The group is absent and the corresponding aromatic or heteroaromatic group is directly bonded to the corresponding group;

[0209] q is 0 or 1, where q=0 means that no A group is bonded to this position, and R 1 The groups are bonded to the corresponding carbon atoms.

[0210] In this case, the structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar40), (Ar-41), (Ar-42), (Ar-43), (Ar-44), (Ar-45), (Ar-46), (Ar-69), (Ar-70), and (Ar-75) are preferred, and the structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), and (Ar-16) are particularly preferred.

[0211] When the above groups have two or more A groups, all possible options include all combinations from the definition of A. In this case, a preferred embodiment is that one of the A groups is NR 1 and the other A group is C(R 1 )2 or both A groups are NR 1 Or the case where both A groups are O.

[0212] When A is NR 1 When the substituent R bonded to the nitrogen atom 1 Preferably, the aromatic ring has 5 to 24 atoms and may also be replaced by one or more R 2 In a particularly preferred embodiment, the R 1 The substituents are identical or different in each case and are aromatic or heteroaromatic ring systems having 6 to 24 aromatic ring atoms, in particular 6 to 18 aromatic ring atoms, which do not have any fused aryl groups and any fused heteroaryl groups in which two or more aromatic or heteroaromatic 6-membered ring groups are directly fused to one another, and which may in each case also be replaced by one or more R 2 Phenyl, biphenyl, terphenyl and quaterphenyl groups having the bonding modes listed above for Ar-1 to Ar-11 are preferred, wherein these structures may be substituted by one or more R 2 The group is not replaced by R 1 Also preferred are triazines, pyrimidines and quinazolines as listed above for Ar-47 to Ar-50, Ar-57 and Ar-58, wherein these structures may be replaced by one or more R 2 The group is substituted instead of R 1 replace.

[0213] Preferred substituents R, R a , R b , R c , R d , R e and Rf .

[0214] In a preferred embodiment of the present invention, R, R a , R b , R c , R d , R e are in each case identical or different and are selected from H, D, F, CN, NO2, Si(R 1 )3,B(OR 1 )2, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group may be replaced by one or more R 1 or have 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and may in each case be substituted with one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0215] In another preferred embodiment of the present invention, the substituents R, R a , R b , R c , R d , R e are identical or different in each case and are selected from H, D, F, a straight-chain alkyl radical having 1 to 20 carbon atoms or a branched or cyclic alkyl radical having 3 to 20 carbon atoms, wherein the alkyl radical may be replaced by one or more R 1 or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case being substituted by one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0216] It is also possible that at least one substituent R, R a , R b , R c , R d , R e are identical or different in each case and are selected from H, D, having 6 to 30 aromatic ring atoms and may be replaced by one or more R 1 In another preferred embodiment of the present invention, the substituents R, R a , R b , R c , R d , R e The rings forming the structures according to formula (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), or the substituents R, Ra , R b , R c , R d , R e are identical or different in each case and are selected from H, D, having 6 to 30 aromatic ring atoms and may be replaced by one or more R 1 More preferably, the substituents R, R a , R b are identical or different in each case and are selected from H or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, more preferably having 6 to 13 aromatic ring atoms, which can each be replaced by one or more R 1 Group substitution.

[0217] Preferably, at least one of the substituents R, R a , R b , R c , R d , R e is selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene and terphenylene, each of which may be substituted by one or more R 1 Here, the term "substituent" more specifically refers to R, R a , R b , R c , R d , R e is not H. In addition, if two or more substituents are present from the aromatic or heteroaromatic groups mentioned, the substituents R, R a , R b , R c , R d , R e Can be the same or different.

[0218] In another embodiment, it is possible that at least one substituent R, R a , R b , R c , R d , R eis selected from o-biphenyl, o,o'-terphenyl, o,o',p-quaterphenyl, 4,6-diphenylpyrimidin-2-yl, 4,6-diphenyltriazine-2-yl, naphthalene, phenanthrene, lettuce, spirobifluorene, terphenylidene, anthracene, benzanthracene, fluorene and / or pyrene, preferably selected from naphthalene, phenanthrene, lettuce, spirobifluorene, terphenylidene, anthracene, benzanthracene, fluorene and / or pyrene, each of which may be substituted by one or more R 1 Preference is given here to spirobifluorene, o-biphenyl, o,o'-terphenyl, o,o',p-quaterphenyl, 4,6-diphenylpyrimidin-2-yl, 4,6-diphenyltriazin-2-yl radicals. If two or more substituents are present from the aromatic radicals mentioned, the substituents R, R a , R b , R c , R d , R e Can be the same or different.

[0219] In a preferred embodiment of the present invention, R f are identical or different in each case and are selected from linear alkyl radicals having 1 to 20 carbon atoms or branched or cyclic alkyl radicals having 3 to 20 carbon atoms, wherein the alkyl radicals may be replaced by one or more R 1 or having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case being substituted by one or more R 2 Aromatic or heteroaromatic ring systems substituted with radicals.

[0220] In another preferred embodiment of the present invention, R f are identical or different in each case and are selected from linear alkyl radicals having 1 to 10 carbon atoms or branched or cyclic alkyl radicals having 3 to 10 carbon atoms, wherein the alkyl radicals may be replaced by one or more R 2 substituted with 6 to 30 aromatic ring atoms and may be substituted with one or more R 2 More preferably, R f are identical or different in each case and are selected from straight-chain alkyl radicals having 1 to 5 carbon atoms or branched or cyclic alkyl radicals having 3 to 6 carbon atoms, wherein the alkyl radicals may be replaced by one or more R 2 substituted, but preferably unsubstituted, or having 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms and in each case being substituted by one or more R 2 Most preferably, R fare identical or different in each case and are selected from straight-chain alkyl groups having 1, 2, 3 or 4 carbon atoms or branched alkyl groups having 3 to 6 carbon atoms. Most preferably, R f is a methyl group or a phenyl group, wherein two phenyl groups together can form a ring system, and relative to the phenyl group, the methyl group is preferred.

[0221] Substituents R, R a , R b , R c , R d , R e , R f Alternatively, the preferred aromatic or heteroaromatic ring system represented by Ar or Ar' is selected from phenyl; biphenyl, especially o-, m- or p-biphenyl; terphenyl, especially o-, m- or p-terphenyl or branched terphenyl; quaterphenyl, especially o-, m- or p-quaterphenyl or branched quaterphenyl; fluorene which may be attached via the 1-, 2-, 3- or 4-position; spirobifluorene which may be attached via the 1-, 2-, 3- or 4-position; naphthalene , in particular 1- or 2-bound naphthalene; indole; benzofuran; benzothiophene; carbazole which may be attached via the 1, 2, 3 or 4 position; dibenzofuran which may be attached via the 1, 2, 3 or 4 position; dibenzothiophene which may be attached via the 1, 2, 3 or 4 position; indenocarbazole; indolocarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; isoquinoline; quinazoline; quinoxaline; phenanthrene or terphenylene, each of which may be substituted by one or more R, R 1 or R 2 The structures Ar-1 to Ar-78 listed above are particularly preferred, and the structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16), (Ar-69), (Ar-70), (Ar-75) are preferred, and the structures of formula (Ar-1), (Ar-2), (Ar-3), (Ar-12), (Ar-13), (Ar-14), (Ar-15), (Ar-16) are particularly preferred. Regarding the structures Ar-1 to Ar-78, it should be noted that these are structures with substituents R 1 In the case of the ring system Ar, these substituents R 1 should be replaced by R, and in R f In the case of these substituents R 1 Should be replaced by R 2 .

[0222] Also suitable for R, R a , R b , R c , R dThe group is of formula -Ar 4 -N(Ar 2 )(Ar 3 ) group, wherein Ar 2 ,Ar 3 and Ar 4 are identical or different in each case and are aromatic rings having 5 to 24 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a radical. 2 ,Ar 3 and Ar 4 The total number of aromatic ring atoms in is not more than 60, preferably not more than 40.

[0223] In this Ar 4 and Ar 2 It can also be selected from C(R 1 )2. NR 1 , O and S groups are bonded to each other, and / or Ar 2 and Ar 3 By selecting C(R 1 )2. NR 1 , O and S groups are bonded to each other. Preferably, Ar 4 and Ar 2 Ar is connected to each other at each adjacent position to the nitrogen atom. 2 and Ar 3 In another embodiment of the present invention, Ar 2 ,Ar 3 and Ar 4 The groups are not bonded to each other.

[0224] Preferably, Ar 4 is a radical having 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms and which may in each case be replaced by one or more R 1 More preferably, Ar 4 is selected from o-phenylene, m-phenylene or p-phenylene or o-biphenylene, m-biphenylene or p-biphenylene, each of which may be replaced by one or more R 1 Most preferably, Ar 4 is an unsubstituted phenylene group.

[0225] Preferably, Ar 2 and Ar 3 are identical or different in each case and are aromatic rings having 6 to 24 atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with groups. Particularly preferred Ar2 and Ar 3 The radicals are in each case identical or different and are selected from benzene; o-, m- or p-biphenyl; o-, m- or p-terphenyl or branched terphenyl; o-, m- or p-quaterphenyl or branched quaterphenyl; 1-, 2-, 3- or 4-fluorenyl; 1-, 2-, 3- or 4-spirobifluorenyl; 1- or 2-naphthyl; indole; benzofuran; benzo[pi] Thiophene; 1-carbazole, 2-carbazole, 3-carbazole or 4-carbazole; 1-dibenzofuran, 2-dibenzofuran, 3-dibenzofuran or 4-dibenzofuran; 1-dibenzothiophene, 2-dibenzothiophene, 3-dibenzothiophene or 4-dibenzothiophene; indenocarbazole; indolocarbazole; 2-pyridine, 3-pyridine or 4-pyridine; 2-pyrimidine, 4-pyrimidine or 5-pyrimidine; pyrazine; pyridazine; triazine; phenanthrene or terphenylene, each of which may be substituted by one or more R 1 Most preferably, Ar 2 and Ar 3 are in each case identical or different and are selected from benzene; biphenyl, in particular o-, m- or p-biphenyl; terphenyl, in particular o-, m- or p-terphenyl or a branched terphenyl; quaterphenyl, in particular o-, m- or p-quaterphenyl or a branched quaterphenyl; fluorene, in particular 1-, 2-, 3- or 4-fluorene; or spirobifluorene, in particular 1-, 2-, 3- or 4-spirobifluorene.

[0226] In another preferred embodiment of the present invention, R 1 are identical or different in each case and are selected from H, D, F, CN, a straight-chain alkyl radical having 1 to 10 carbon atoms or a branched or cyclic alkyl radical having 3 to 10 carbon atoms, wherein the alkyl radical may be replaced by one or more R 2 or have 6 to 24 aromatic ring atoms and may be substituted by one or more R 2 In a particularly preferred embodiment of the present invention, R 1 are in each case identical or different and are selected from H, a linear alkyl group having 1 to 6 carbon atoms, in particular a linear alkyl group having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl group may be replaced by one or more R 5 substituted, but preferably unsubstituted, or having 6 to 13 aromatic ring atoms and in each case being substituted by one or more R 5 The invention further comprises a radically substituted, but preferably unsubstituted, aromatic or heteroaromatic ring system.

[0227] In another preferred embodiment of the present invention, R 2 are in each case identical or different and are H, D, an alkyl radical having 1 to 4 carbon atoms or an aryl radical having 6 to 10 carbon atoms, which may be substituted by an alkyl radical having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0228] At the same time, in the compounds of the invention processed by vacuum evaporation, the alkyl group preferably has no more than 5 carbon atoms, more preferably no more than 4 carbon atoms, and most preferably no more than 1 carbon atom. For compounds processed from solution, suitable compounds are also compounds substituted with alkyl groups having up to 10 carbon atoms, especially branched alkyl groups, or with oligomeric arylene groups such as o-terphenyl, m-terphenyl, p-terphenyl or branched terphenyl or quaterphenyl groups.

[0229] It is also possible that the compound contains exactly two or exactly three structures of formula (I), (II), (III), (IV), (IVa) to (IVf), (IV-1), (V-1) to (V-64) and / or (VI-1) to (VI-5).

[0230] In a preferred configuration, the compound is selected from compounds of formula (D-1),

[0231]

[0232] Where L 2 The group is a linking group, preferably a bond or a cyclic aromatic ring having 5 to 40, preferably 5 to 30, aromatic ring atoms and can be connected by one or more R 1 The aromatic or heteroaromatic ring system is substituted with a radical, and the other symbols used have the meanings given above, especially for formula (I). 2 Can bind to Ar a ,Ar b , L, Y 1 , Y 2 or Z, or combined with R c The position, in this case R c Does not exist.

[0233] In another preferred embodiment of the present invention, L 2 is 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 or a heteroaromatic ring system having 6 to 13 aromatic ring atoms, and which may in each case be replaced by one or more R 1More preferably, L 2 is an aromatic ring system having 6 to 10 aromatic ring atoms or a heteroaromatic ring system having 6 to 13 heteroaromatic ring atoms, each of which may be replaced by one or more R 1 substituted, but preferably unsubstituted, wherein R 1 may have the definitions given above, in particular for formula (I).

[0234] Also preferably, the symbol L shown in formula (D1) 2 In particular, the aromatic or heteroaromatic radicals are in each case identical or different and are a bond or an aryl or heteroaryl radical having 5 to 24 ring atoms, preferably having 6 to 13 ring atoms, more preferably having 6 to 10 ring atoms, so that the aromatic or heteroaromatic radical of the aromatic or heteroaromatic ring system is bonded directly, i.e. via an atom of the aromatic or heteroaromatic radical, to the corresponding atom of the other radical.

[0235] Another possible situation is that L shown in formula (D1) 2 The group contains an aromatic ring system with no more than two fused aromatic and / or heteroaromatic 6-membered rings, preferably does not contain any fused aromatic or heteroaromatic ring system. Therefore, naphthyl structures are preferred over anthracene structures. In addition, fluorenyl, spirobifluorenyl, dibenzofuranyl and / or dibenzothienyl structures are preferred over naphthyl structures.

[0236] Particularly preferred are unfused structures such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0237] Suitable aromatic or heteroaromatic ring systems L 2 Examples of are selected from o-phenylene, m-phenylene or p-phenylene; o-biphenylene, m-biphenylene or p-biphenylene; terphenylene, especially branched terphenylene; quaterphenylene, especially branched quaterphenylene; fluorene; spirobifluorene; dibenzofuranene; dibenzothiophene; and carbazole; each of which may be substituted by one or more R 1 The group is substituted, but is preferably unsubstituted.

[0238] The above-mentioned preferred embodiments can be combined with one another as desired within the limits defined in claim 1. In a particularly preferred embodiment of the present invention, the above-mentioned preferences occur simultaneously.

[0239] Examples of preferred compounds according to the above detailed embodiments are the compounds shown in the following table:

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251] Preferred embodiments of the compounds of the present invention are described in detail in the examples. These compounds can be used alone or in combination with other compounds for all purposes of the present invention.

[0252] The above preferred embodiments can be combined with each other as needed as long as the conditions specified in claim 1 are met. In a particularly preferred embodiment of the present invention, the above preferred embodiments are applied simultaneously.

[0253] The compounds according to the invention can in principle be prepared by various methods. However, the method described hereinafter has been found to be particularly suitable.

[0254] The present invention therefore also provides a process for preparing the compounds according to the invention, wherein a basic skeleton having an aromatic amino group is synthesized and at least one heterocyclic group is introduced, preferably by means of a nucleophilic aromatic substitution reaction or coupling reaction.

[0255] Suitable compounds comprising a basic skeleton having an aromatic amino group are commercially available in many cases, and the starting compounds detailed in the examples can be obtained by known methods, and reference is therefore made to them.

[0256] These compounds can be reacted with other compounds by known coupling reactions. The necessary conditions for this purpose are known to those skilled in the art, and the detailed description in the examples provides support for those skilled in the art to perform these reactions.

[0257] Particularly suitable and preferred coupling reactions all leading to CC bond formation and / or CN bond formation are the reactions according to BUCHWALD, SUZUKI, ULLMANN, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA and HIYAMA. These reactions are well known and the examples will provide further indications to those skilled in the art.

[0258] The compounds of the present invention can be synthesized by methods including those according to Scheme 1 below.

[0259] In the first step, the compound (1) having an aromatic amino group can be reacted with a heterocyclic compound (2); preferred heterocyclic compounds are, for example, pyrrole, furan, thiophene, selenophene or tellurophene derivatives. The resulting compound (3) can be subjected to a hydroxyalkylation reaction with a carbonyl compound (4) to produce a nitrogen-containing hydroxy compound (5), as shown in step 2 in this scheme. In step 3, the hydroxy compound (5) is cyclized and then derivatized by bromination to produce a brominated compound (8), which can be carried out, for example, with N-bromosuccinimide (7). In step 5, the brominated compound (8) can be reacted with an arylboronic acid or an ester thereof (9) in a Suzuki coupling to produce the compound of the present invention (10). The Suzuki coupling can be carried out in anhydrous form, preferably in THF using KF or Cs2CO3 as a base, or in an organic-water biphasic system, preferably in a toluene-dioxane or ethanol-water (4:1:4) system using sodium carbonate or potassium carbonate or phosphate as a base. Suitable phosphines are, in particular, triphenylphosphine, tri-o-tolylphosphine, S-Phos, X-Phos, Ru-Phos, AmPhos, etc.; suitable Pd sources are Pd2(dba)3 or palladium(II) acetate.

[0260] Scenario 1:

[0261] Step 1: Ullmann coupling

[0262]

[0263] Step 2: Hydroxyl Alkylation

[0264]

[0265] Step 3: Cyclization

[0266]

[0267] Step 4: Bromination

[0268]

[0269] Step 5: Suzuki coupling

[0270]

[0271] The compounds of the present invention can also be synthesized according to the following scheme 2, through which in particular the compounds with additional Y can be obtained. 2 Groups such as O, S, Se, Te, NAr, NR e ,BAr,BR e , Ge(R e )2、Si(R e 2. -CR e =CR e -、C=NR e , S=O, SO2 compounds.

[0272] In the first step, the compound (11) having an aromatic amino group can be reacted with a heterocyclic compound (12) by double Ullmann coupling; preferred heterocyclic compounds are, for example, pyrrole, furan, thiophene, selenophene or tellurophene derivatives. The resulting compound (13) can be converted into the compound of the present invention (15) as described in Scheme 1 by bromination (step 2) and subsequent Suzuki coupling (step 3) under the above conditions.

[0273] The aromatic amino groups (11) used may preferably be secondary amines, and the heterocyclic compounds (12) used may preferably be 1,2-bis-halogen-functionalized 5-membered heterocyclic systems known from the literature.

[0274] Scenario 2:

[0275] Step 1: Ullmann coupling

[0276]

[0277] Step 2: Bromination

[0278]

[0279] Step 3: Suzuki coupling

[0280]

[0281] The above is used to prepare 2 The group is, for example, Te, BR e , Ge(R e )2、Si(R e 2. -CR e =CR e -、C=NR e , S=O, SO2 compounds / structures Variants of the scheme shown are known to those skilled in the art.

[0282] The compounds of the present invention can also be synthesized according to the following scheme 3, through which in particular the compounds having other Y 2 Compounds containing groups such as bonds.

[0283] According to D. Bader et al., J. Org. Chem., 2020, 85(5), 3865, starting from (16) and (17), intermediate (18) can be obtained. Then, intermediate (18) can be converted into the corresponding compound (20) of the present invention through steps 2 and 3.

[0284] Scenario 3:

[0285] Step 1: Ullmann coupling

[0286]

[0287] Analogous procedure to step 2, Scheme 2: Bromination

[0288]

[0289] Analogous procedure to step 3, Scheme 2: Suzuki coupling

[0290]

[0291] The definitions of the symbols used in Schemes 1, 2 and 3 correspond essentially to the definitions for formula (I) or preferred embodiments of these structures, the numbering and complete representation of all symbols being omitted for reasons of clarity. In addition, for the sake of clarity, in many cases, in particular in formula (III) the symbols X a and X b As shown, the use of symbols to represent possible nitrogen atoms in heteroaromatic rings has been omitted. Therefore, these details should be understood by way of example; the person skilled in the art will be able to apply the syntheses described above and below, especially in the examples, to the case where the symbol X a and X b One or more of the compounds is nitrogen.

[0292] The principles of the preparation processes detailed above are known in principle from the literature for similar compounds and can be easily adopted by the person skilled in the art for the preparation of the compounds according to the invention. Further information can be found in the examples.

[0293] By these methods, if necessary, followed by purification, for example recrystallization or sublimation, a high purity, preferably greater than 99% (with the aid of 1 H NMR and / or HPLC determination) of the compounds of the present invention.

[0294] The compounds of the present invention can also be mixed with polymers. Similarly, these compounds can be covalently incorporated into polymers. This can especially be used for compounds substituted by reactive leaving groups such as bromine, iodine, chlorine, boric acid or boric esters, or by reactive polymerizable groups such as olefins or oxetanes. It is found that they can be used as monomers for producing corresponding oligomers, dendritic macromolecules or polymers. Oligomerization or polymerization is preferably achieved via halogen functional groups or boric acid functional groups or via polymerizable groups. It is also possible to crosslink polymers via this group. The compounds of the present invention and polymers can be used in the form of crosslinked or uncrosslinked layers.

[0295] The present invention therefore also provides oligomers, polymers or dendrimers containing one or more of the above detailed structures of formula (I) and preferred embodiments of the formula or compounds of the invention, wherein there are one or more bonds of the compounds of the invention or the structures of formula (I) and preferred embodiments of the formula to the polymer, oligomer or dendrimer. According to the connection of the structures of formula (I) and preferred embodiments of the formula or compounds, they thus form side chains of the oligomer or polymer or are bonded within the main chain. The polymer, oligomer or dendrimer may be conjugated, partially conjugated or non-conjugated. The oligomer or polymer may be linear, branched or dendritic. For the repeating units of the compounds of the invention in the oligomers, dendrimers and polymers, the same preferences as described above apply.

[0296] To prepare 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 formula (I) or the preferred embodiments described above and below are present in an amount ranging from 0.01 mol % to 99.9 mol %, preferably from 5 mol % to 90 mol %, more preferably from 20 mol % to 80 mol %. Suitable and preferred comonomers for forming the basic backbone of the polymer are selected from fluorene (for example according to EP 842208 or WO 2000 / 022026), spirobifluorene (for example according to EP 707020, EP 894107 or WO 2006 / 061181), p-phenylene (for example according to WO 92 / 18552), carbazole (for example according to WO 2004 / 070772 or WO 2004 / 113468), thiophene (for example according to EP 1028136), dihydrophenanthrene (for example according to WO 2005 / 014689), cis-indenofluorene and trans-indenofluorene (for example according to WO 2004 / 041901 or WO 2004 / 113412), ketone (for example according to WO 2005 / 040302), phenanthrene (for example according to WO 2005 / 104264 or WO 2007 / 017066) or other multiples of these units. The polymers, oligomers and dendrimers may also contain other units, for example: hole transport units, especially units based on triarylamines; and / or electron transport units.

[0297] In addition, compounds of the invention characterized by a high glass transition temperature are of particular interest. In this regard, compounds of the invention comprising the structure of formula (I) or the preferred embodiments described above and below are particularly preferred, and having a glass transition temperature of at least 70° C., more preferably at least 110° C., even more preferably at least 125° C., and particularly preferably at least 150° C., as determined according to DIN 51005 (2005-08 version).

[0298] In order to process the compounds of the invention from the liquid phase, for example by spin coating or by printing, preparations of the compounds of the invention are required. These preparations may be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents may preferably be used. Suitable and preferred solvents are, for example: toluene; anisole; o-xylene, m-xylene or p-xylene; methyl benzoate; mesitylene; tetralin; o-dimethoxybenzene; THF; methyl-THF; THP; chlorobenzene; dioxane; phenoxytoluene, especially 3-phenoxytoluene; (-)-fennel; 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; isopropylbenzene; cyclohexanol ; cyclohexanone; cyclohexylbenzene; decalin; dodecylbenzene; ethyl benzoate; indane; NMP; p-cymene; phenethyl ether; 1,4-diisopropylbenzene; dibenzyl ether; diethylene glycol butyl methyl ether; triethylene glycol butyl methyl ether; diethylene glycol dibutyl ether; triethylene glycol dimethyl ether; diethylene glycol monobutyl ether; tripropylene glycol dimethyl ether; tetraethylene glycol dimethyl ether; 2-isopropylnaphthalene; pentylbenzene; hexylbenzene; heptylbenzene; octylbenzene; 1,1-bis(3,4-dimethylphenyl)ethane; 2-methylbiphenyl; 3-methylbiphenyl; 1-methylnaphthalene; 1-ethylnaphthalene; ethyl octanoate; diethyl sebacate; octyl octanoate; heptylbenzene; menthyl isovalerate; cyclohexyl hexanoate; or a mixture of these solvents.

[0299] Therefore, the present invention also provides a preparation or composition comprising at least one compound of the present invention and at least one other compound. The other compound can be, for example, a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents. If the other compound contains a solvent, the mixture is referred to as a preparation in this article. The other compound can alternatively be at least one other organic or inorganic compound that is also used in electronic devices, such as a co-material, wherein these compounds are different from the compounds of the present invention. Suitable co-materials are listed later in conjunction with organic electronic devices. The other compound can also be polymeric.

[0300] Therefore, the present invention also provides a composition comprising the compounds of the present invention and at least one other organic functional material. Functional materials are generally organic or inorganic materials introduced between anode and cathode. The organic functional material is preferably selected from photosensitizers, electron transport materials, electron injection materials, hole conduction materials, hole injection materials, electron blocking materials and hole blocking materials, preferably selected from photosensitizers, electron transport materials, electron injection materials, hole blocking materials.

[0301] The present invention further provides the use of the compounds of the present invention in electronic devices, preferably in organic optoelectronic devices, especially in organic photodetectors, preferably as photosensitizers, more preferably as green, red, infrared or blue photosensitizers, especially preferably as blue or green photosensitizers.

[0302] The present invention also provides an electronic device comprising at least one compound according to the invention. An electronic device in the context of the present invention is a device comprising at least one layer comprising at least one organic compound. The component may also comprise other layers formed entirely of inorganic materials or of inorganic materials.

[0303] The electronic device is preferably selected from: organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), preferably organic light emitting diodes (OLED), small molecule-based organic light emitting diodes (sOLED), polymer-based organic light emitting diodes (PLED), light emitting electrochemical cells (LEC), organic laser diodes (O-lasers), organic plasma light emitting devices (DM Koller et al., Nature Photonics 2008, 1-4), organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs) and organic electrical sensors, preferably organic photodetectors, organic photoreceptors, organic electrical sensors, organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), more preferably organic photodetectors.

[0304] The organic photodetector comprises a cathode, an anode and at least one light absorbing layer. In addition to these layers, the organic photodetector 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 and / or charge generation layers. It is also possible to introduce an intermediate layer between two light absorbing layers, which has, for example, an exciton blocking function. However, it should be pointed out that each of these layers does not necessarily have to be present. The organic photodetector may contain one light absorbing layer, or it may contain two or more light absorbing layers.

[0305] Depending on the exact structure, the compounds of the invention can be used in different layers. Preferably, the organic photodetector comprises a compound of formula (I) or of the preferred embodiments detailed above as a photosensitizer in a light-absorbing layer, preferably an infrared, red, green or blue photosensitizer, more preferably as a green photosensitizer, wherein the color in each case refers to the color of the light absorbed by the photosensitizer.

[0306] When the compounds of the invention are used as photosensitizers in a light-absorbing layer, preference is given to using suitable co-materials known from this point on. The co-materials can be used as a mixture with the photosensitizer or in a layer adjacent to the layer comprising the photosensitizer.

[0307] Suitable co-materials which can be used in combination with the compounds according to the invention, i.e. as a mixture or in a layer adjacent to a layer containing the compounds according to the invention, are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones, for example according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680; triarylamines; carbazole derivatives, for example CBP (N,N-dicarbazolylbiphenyl) or those of WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176; for example according to WO 2007 / 063754 or WO 2008 / 056746; indolecarbazole derivatives, for example, according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, for example, according to EP 1617710, EP1617711, EP 1731584, JP 2005 / 347160; bipolar co-materials, for example, according to WO 2007 / 137725; silanes, for example, according to WO 2005 / 111172; borazolidines or boric acid esters, for example, according to WO 2006 / 117052; for example, according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877; zinc complexes, for example, according to EP 652273 or WO 2009 / 062578; siladiazacyclopentane or siladiazacyclopentane derivatives, for example, according to WO 2010 / 054729; phosphodiazacyclopentane derivatives, for example, according to WO 2010 / 054730; bridged carbazole derivatives, for example, according to WO 2011 / 042107, WO 2011 / 060867, WO 2011 / 088877 and WO 2012 / 143080; terphenylidene derivatives, for example, according to WO 2012 / 048781; 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565; or biscarbazoles, for example according to JP 3139321 B2.

[0308] In a particularly preferred embodiment, it is possible that one or more compounds of the invention of formula (I) or the preferred embodiments are used in combination with an electron transport material, an electron injection material, a hole blocking material. Particularly preferably, subphthalocyanines, subphthalocyanine derivatives, fullerenes or fullerene derivatives are used. It is known to those skilled in the art that such compounds can be used in organic photodetectors.

[0309] Such a configuration is particularly preferred if the compounds according to the invention can be used as hole-conducting material, hole-injecting material and / or electron-blocking material.

[0310] Subphthalocyanines, subphthalocyanine derivatives, fullerenes or fullerene derivatives that can be preferably used are described in particular in European patent application EP 3848374 A1 with application number EP 21151295.9 filed in the European Patent Office on January 13, 2021, wherein this publication is hereby incorporated by reference for the purpose of disclosure. These materials are particularly described in detail on pages 84 to 86 (see paragraphs

[322] to

[332] ).

[0311] In addition, the co-material used may be a compound that participates in charge transport but not to a significant extent, as described, for example, in WO 2010 / 108579. Particularly suitable as a co-material in combination with the compounds of the present invention are compounds that have a large band gap and that themselves participate in the charge transport of the light absorbing layer but at least not to a significant extent. Such materials are preferably pure hydrocarbons. Examples of such materials can be found, for example, in WO 2009 / 124627 or WO 2010 / 006680.

[0312] In another embodiment of the present invention, the organic photodetector 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 absorption layer is directly adjacent to the hole injection layer or the anode, and / or the light absorption layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode.

[0313] In the other layers of the organic photodetector of the present invention, any material commonly used according to the prior art can be used. Therefore, without paying creative labor, those skilled in the art will be able to use any known material for organic photodetectors in combination with the compounds of the present invention of formula (I) or the preferred embodiments described above.

[0314] Also preferred is an organic photodetector, characterized in that one or more layers are applied by sublimation. In this case, the organic photodetector is applied by sublimation in a vacuum sublimation system at a temperature of less than 10 -5 mbar, preferably less than 10 -6 The material is applied by vapor deposition at an initial pressure of 10 mbar. However, even lower pressures, such as less than 10-7 Initial pressures of millibars are also feasible.

[0315] Likewise preferred is an organic photodetector, characterized in that one or more layers are applied by the OVPD (organic vapor phase deposition) method or by means of carrier gas sublimation. -5 The material is applied at a pressure of mbar to 1 bar. A special case of this method is the OVJP (Organic Vapor Phase Jet Printing) method, in which the material is applied directly through a nozzle and thus structured.

[0316] Furthermore, preference is given to an organic photodetector, 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, LITI (light-induced thermography, thermal transfer), inkjet printing or nozzle printing. For this purpose, soluble compounds are required, for example obtained by appropriate substitution.

[0317] The formulations using the compounds of formula (I) or preferred embodiments thereof as described in detail above are novel. Therefore, the present invention also provides a formulation containing at least one solvent and the compound according to formula (I) or preferred embodiments thereof as described in detail above.

[0318] Furthermore, hybrid methods are possible, for example in which one or more layers are applied from solution and one or more other layers are applied by vapor deposition.

[0319] The person skilled in the art is generally aware of these methods and can apply them to organic photodetectors comprising the compounds according to the invention without inventive step.

[0320] Further details of preferred electronic devices, in particular organic photodetectors and their manufacture are known from the prior art. These are described in particular in European patent application EP 3848374 A1 with application number EP 21151295.9 filed on January 13, 2021 in the European Patent Office, wherein this publication is hereby incorporated by reference for the purpose of disclosure. In this regard, particular reference is made to Figures 1 to 10 described in EP 3848374 A1, which are described in particular on pages 83 to 90 of document EP 3848374 A1.

[0321] Compared with the prior art, the electronic device of the present invention, especially the organic photodetector, has one or more of the following surprising advantages:

[0322] 1. Electronic devices, in particular organic photodetectors, which comprise compounds of the formula (I) or the preferred embodiments described above and below, especially as photosensitizers, have very good lifetimes.

[0323] 2. Electronic devices, in particular organic photodetectors, comprising compounds of formula (I) or preferred embodiments as described above and below as photosensitizers have excellent efficiency. In this case, the compounds of formula (I) or preferred embodiments as described above and below lead to low operating voltages when used in electronic devices.

[0324] 3. The compounds of the invention of the formula (I) or of the preferred embodiments described above and below exhibit very high stability, in particular thermal stability, and relatively low vapour deposition temperatures.

[0325] 4. By using the compounds of formula (I) or the preferred embodiments described above and below, the formation of optical loss channels in electronic devices, especially organic photodetectors, can be avoided. As a result, these devices are characterized by high PL efficiency, and therefore high EL efficiency of the photosensitizer, and excellent energy transport.

[0326] 5. The compounds of formula (I) or the preferred embodiments described above and below have excellent glass film formation.

[0327] 6. The compounds of formula (I) or the preferred embodiments described above and below form very good films from solvents and show excellent solubility.

[0328] These above-mentioned advantages are not accompanied by very serious degradation of other electronic properties.

[0329] It should be noted that the changes of the embodiments described in the present invention are covered by the scope of the present invention. Unless any feature disclosed in the present invention is explicitly excluded, it can be exchanged with an alternative feature having the same purpose or an equivalent or similar purpose. Therefore, unless otherwise stated, any feature disclosed in the present invention should be regarded as an example of a general series or as an equivalent or similar feature.

[0330] Unless specific features and / or steps are mutually exclusive, all features of the present invention can be combined with each other in any way. This is especially true for the preferred features of the present invention. Similarly, features of non-essential combinations can be used alone (and not in combination).

[0331] It should also be noted that many features of the present invention, especially the features of the preferred embodiments, should be considered creative in themselves, rather than just being some embodiments of the present invention. For these features, independent protection may be sought to supplement or replace any currently claimed invention.

[0332] The technical teachings disclosed in the present invention can be refined and combined with other embodiments.

[0333] The present invention is illustrated in detail by the following examples, but it is not intended to be limited thereby. Those skilled in the art will be able to use the information provided to implement the present invention within the entire scope disclosed without inventive effort, and to prepare other compounds of the present invention and use them in electronic devices or employ the methods of the present invention. Example

[0334] Unless otherwise stated, the following syntheses were carried out in anhydrous solvents under a protective gas atmosphere. Solvents and reagents can be purchased from, for example, Sigma-ALDRICH or ABCR. The corresponding numbers in square brackets or the numbers quoted for individual compounds are related to the CAS numbers of the compounds known in the literature. In the case of compounds that can have multiple enantiomers, diastereomers or tautomeric forms, one form is shown in a representative manner.

[0335] Synthons known from the literature:

[0336]

[0337]

[0338] Synthesis of synthons

[0339] Example S1:

[0340] Synthesis of the compounds of the present invention:

[0341] Heterocyclic compound (6) can be prepared by the following steps: similar to US 2021 / 0234103, page 70, using the corresponding reactants listed below, o-bromoamine (1), 5-membered heterocycle (2) (pyrrole, furan, thiophene, selenophene, tellurophene), ketone (4), and then dehydration cyclization of alcohol (5). In step 4, (6) is NBS brominated to bromide (8), and then converted into the compound of the present invention (10) in Suzuki coupling (step 5).

[0342] Scenario 1:

[0343] Step 1: Ullmann coupling

[0344]

[0345] Step 2: Hydroxyl Alkylation

[0346]

[0347] Step 3: Cyclization

[0348]

[0349] Step 4: Bromination

[0350]

[0351] Step 5: Suzuki coupling

[0352]

[0353] Alternative to Step 2: Suzuki coupling

[0354]

[0355] A well-stirred mixture of 100 mmol of (3), 120 mmol of alkenyl-BF3K salt, 250 mmol of cesium carbonate, 3 mmol of palladium(II) acetate, 9 mmol of triphenylphosphine, 1000 ml of THF and 200 ml of water is heated under reflux for 16 hours. After cooling, 500 ml of ethyl acetate (EA) are added, the aqueous phase is separated off, the organic phase is washed three times with 300 ml of water each time, once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of an EA slurry, and the solvent is removed under reduced pressure. The residue can be reacted further without further purification.

[0356] Alternative method for step 3: cyclization

[0357]

[0358] A well-stirred mixture of 100 mmol of (11) and 400 g of polyphosphoric acid is heated to 90° C. for 1 hour. The reaction mixture is cooled to 60° C., poured onto 5 l of ice water while stirring well, stirred for a further 30 minutes, and the precipitated solid is filtered off with suction or extracted with EA or dichloromethane (DCM). The crude product is recrystallized from DCM / acetonitrile or chromatographed.

[0359] Alternative methods for the introduction of BR, SiR2, GeR2, NR and S bridging groups:

[0360]

[0361] Embodiment B1:

[0362] Step 4:

[0363]

[0364] To a well-stirred solution of 3.36 g (10.0 mmol) of LS1 in 100 ml of dichloromethane (DCM) cooled to 0°C, 1.78 g (10.0 mmol) of N-bromosuccinimide were added portionwise and the mixture was stirred for 1 hour. Subsequently, the reaction mixture was allowed to warm to room temperature, stirred for a further 2 hours, washed three times with 100 ml of water each time, washed once with 100 ml of saturated saline solution and dried over sodium sulfate. The desiccant was filtered off, 50 ml of ethanol were added to the filtrate, which was then gradually concentrated to a volume of 30 ml under reduced pressure. The crystalline product was filtered off with suction, washed twice with 10 ml of ethanol and dried under reduced pressure. Yield: 4.03 g (9.7 mmol), 97%, purity: about 95%, according to 1 H NMR.

[0365] Step 5:

[0366]

[0367] A mixture of 4.15 g (10.0 mmol) of B1, step 4, 1.89 g (11.0 mmol) of LS 10, 4.25 g (20 mmol) of potassium phosphate tripotassium, 347 mg (0.3 mmol) of tetrakis(triphenylphosphine)palladium(0), 80 ml of toluene, 20 ml of dioxane and 80 ml of water was heated under gentle reflux and stirred vigorously for 16 h. After cooling, the aqueous phase was separated off, the organic phase was concentrated to dryness, the residue was extracted by stirring with 50 ml of ethanol, the solid was washed twice with 10 ml of water each time and the product was dried under reduced pressure. Further purification was carried out by chromatography (Torrent automated column system from A. Semrau) or hot extractive crystallization (conventional organic solvents, preferably acetonitrile or acetonitrile-DCM mixtures (4:1-1:2 by volume)) and by high vacuum (p about 10 -5 The reaction mixture was prepared by fractional sublimation at 400 mbar (0.1 % NH 2 O). Yield: 3.37 g (7.3 mmol), 73%; purity: about 99.9% according to HPLC.

[0368] The following compounds can be prepared similarly, with yields reported in 5 stages:

[0369]

[0370]

[0371]

[0372]

[0373]

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392] Thermal stability of the compounds of the present invention:

[0393] The results of the thermal storage test are summarized in Table 1. For this purpose, 500 mg of compound B were placed under reduced pressure (p about 10 -4 The mixture was sealed by melting in a 20 ml Duane glass ampoule at 260° C. and then stored in the dark for 10 days at 260° C. Subsequently, the ampoule was opened and an olfactory evaluation was performed by sniffing, because even if very small amounts of volatile organic sulfur compounds, organic selenium compounds and organic tellurium compounds were formed by thermal decomposition, the characteristic smell of rotten eggs or radishes was easily evident through them. Subsequently, the purity was determined by HPLC and compared with the purity of the starting material with a purity of >99.9%.

[0394] Table 1:

[0395]

[0396] Photodiode Example:

[0397] 1) Fabrication of single layer photodiode (MLPD)

[0398] Device Type 1:

[0399] A clean quartz substrate (sonicated for 15 min in an acetone / isopropanol / water bath (1:1:1 vol:vol:vol) followed by UV-ozone treatment) was provided with a 150 nm thick indium tin oxide anode (ITO) via sputtering. Compounds B and C of the invention were produced thereon in a 1:1 volume ratio by co-evaporation under high vacuum. 60 A 150 nm thick layer was applied. Finally, a 10 nm thick ITO cathode was applied by sputtering. Subsequently, the IPCE (incident photon-charge carrier efficiency) of the initial device was determined in the wavelength range of 400 nm-700 nm with the aid of a PTS-2-QE from PhotonicSolutions (UK) (Table 2). The device was then thermally stored at a temperature of 180°C for 10 minutes and the IPCE was then determined again (Table 2).

[0400] Table 2:

[0401]

[0402] Device Type 2:

[0403] A cleaned quartz substrate (sonicated for 15 min in an acetone / isopropanol / water bath (1:1:1 vol:vol:vol) and then UV-ozone treated) was provided with a 150 nm thick indium tin oxide anode (ITO) via sputtering. A 30 nm thick layer of HTM2 (Table 5) was applied thereto under high vacuum and then the compounds B and C according to the invention were deposited by vapor phase in a 1:1 volume ratio by coevaporation. 60 A 80 nm thick layer was applied. Subsequently, a 1.5 nm thick ytterbium layer was applied by vapor deposition. Finally, a 10 nm thick ITO cathode was applied by sputtering. Subsequently, the IPCE (incident photon-charge carrier efficiency) of the initial device was determined at a voltage of 3 V at the maximum absorption in the wavelength range of 400 nm-700 nm with the help of a PTS-2-QE from Photonic Solutions (UK) (Table 3).

[0404] Table 3:

[0405]

[0406] 2) Fabrication of double-layer photodiode (BLPD)

[0407] A clean quartz substrate (sonicated for 15 min in an acetone / isopropanol / water bath (1:1:1 vol:vol:vol) followed by UV ozone treatment) was provided with a 150 nm thick indium tin oxide anode (ITO) via sputtering. All other materials were applied by thermal vapor deposition in a vacuum chamber. The materials used to make the BLPDs are shown in Table 5. The electron transport layer 2 (ETL2) can be made by co-evaporation of two materials; an entry such as ETM1:EIL (50:50) means that the co-evaporated layer contains 50% by volume of each individual material.

[0408] The structure of BLPD:

[0409] ITO substrate BLPD

[0410] Hole injection layer (HIL) consisting of HTM1 doped with 5% NDP-9 (available from Novaled), 10 nm

[0411] Hole transport layer 1 (HTL1), see Table 4

[0412] Hole transport layer 2 (HTL2), see Table 4

[0413] Electron donor layer (EDL), see Table 4

[0414] Electron Acceptor Layer (EAL), see Table 4

[0415] Electron transport layer 1 (ETL1), see Table 4

[0416] Electron transport layer 2 (ETL2), see Table 4

[0417] Electron injection layer 1 (EIL1), 3 nm EIM

[0418] Mg:Ag (10:90) cathode, 100 nm

[0419] Subsequently, the IPCE (Incident Photon-Charge Carrier Efficiency) of the initial devices was determined at 3 V at the maximum absorption in the wavelength range of 400 nm-700 nm with the aid of a PTS-2-QE from Photonic Solutions (UK) (Table 4).

[0420] Table 4: Structure of a double-layer photodiode (BLPD)

[0421]

[0422]

[0423] Table 5: Materials used

[0424]

Claims

1. A compound comprising at least one structure of formula (I), The symbols used are as follows: Ar a are identical or different in each case and are aromatic rings having 5 to 60 atoms and may be replaced by one or more Ar or R a group-substituted aromatic or heteroaromatic ring systems; Ar b are identical or different in each case and are aromatic rings having 5 to 60 atoms and may be replaced by one or more Ar or R b group-substituted aromatic or heteroaromatic ring systems; Z is identical or different in each case and is a moiety having 5 to 60 aromatic ring atoms and can be replaced by one or more R d An aromatic or heteroaromatic ring system substituted with a group, and the aromatic or heteroaromatic ring system forms a ring system with other groups, characterized in that The Z group has a strong electron-withdrawing effect; Y 1 are in each case identical or different and are O, S, Se, Te, NAr, NR, C(R)2, Ge(R)2 or Si(R)2; Y 2 are in each case identical or different and are a bond, O, S, Se, Te, NAr, NR e ,BAr,BR e , C(R e )2、Ge(R e )2、Si(R e 2. -CR e =CR e -、C=NR e , S=O or SO2; L is in each case identical or different and is a linking group, preferably a bond, C(R)2, O, S, NR, NAr, C(═O), BAr, B(R), Si(R)2, C═NR, C═C(R)2, S═O, SO2, P(R) and P(═O)R, -CR═CR- or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which may be substituted by one or more R groups; Ar is in each case identical or different and is an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more R groups; the Ar groups may be substituted with at least one Ar, R, R a , R b , R c , R d , R e Groups or other groups form a ring system; R, R a , R b , R c , R d , R e are in each case identical or different and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)N(Ar')2,C(=O)N(R 1 )2,C(Ar')3,C(R 1 )3,Si(Ar')3,Si(R 1 )3,B(Ar')2,B(R 1 )2,C(=O)Ar',C(=O)R 1 , P(=O)(Ar')2, P(=O)(R 1 )2,P(Ar')2,P(R 1 )2,S(=O)Ar',S(=O)R 1 ,S(=O)2Ar',S(=O)2R 1 , OSO2Ar', OSO2R 1 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, wherein the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by R 1 C=CR 1 、C≡C、Si(R 1 )2. C=O, C=S, C=Se, C=NR 1 、-C(=O)O-、-C(=O)NR 1 -、NR 1 、P(=O)(R 1 )、-Se-、-Te-、NAr'、BR 1 , Ge(R 1 )2, -O-, -S-, SO or SO2, or has 5 to 60 aromatic ring atoms and can be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 A substituted aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms and which may be substituted by one or more R 1 substituted arylthio or heteroarylthio groups, or having 5 to 60 aromatic ring atoms and may be replaced by one or more R 1 A diarylamino, arylheteroarylamino, diheteroarylamino group substituted with a group, or a diarylamino group having 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl group and being substituted with one or more R 1 an aralkyl or heteroaralkyl group substituted with a group; two R, R a , R b , R c , R d , R e The groups together or with other groups here can also form a ring system; Ar' is identical or different in each case and is a ring having 5 to 60 aromatic ring atoms and may be replaced by one or more R 1 At the same time, two Ar' groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom may also be bridged to each other by a single bond or a bridging group selected from the following groups: B(R 1 )、C(R 1 )2、Si(R 1 )2. C=O, C=NR 1 、C=C(R 1 )2, O, S, S=O, SO2, N(R 1 )、P(R 1 ) and P(=O)R 1 ; R 1 are in each case identical or different and are H, D, F, Cl, Br, I, CN, NO2, N(Ar'')2, N(R 2 )2,C(=O)Ar'',C(=O)R 2 ,P(=O)(Ar'')2,P(Ar'')2,B(Ar'')2,B(R 2 )2,C(Ar'')3,C(R 2 )3,Si(Ar'')3,Si(R 2 )3, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R 2 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2. C=O, C=S, C=Se, C=NR 2 、-C(=O)O-、-C(=O)NR 2 -、NR 2 、P(=O)(R 2 ), -O-, -S-, SO or SO2, and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, or having 5 to 60 aromatic ring atoms and in each case by one or more R 2 An aromatic or heteroaromatic ring system substituted with a radical, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 substituted aryloxy or heteroaryloxy groups, or having 5 to 60 aromatic ring atoms and may be replaced by one or more R 2 substituted aralkyl or heteroaralkyl groups, or combinations of these systems; at the same time, two or more preferably adjacent R 1 The groups may form a ring system together; at the same time, one or more R 1 The group and the other parts of the compound can form a ring system; Ar'' is identical or different in each case and is a cyclic aromatic ring having 5 to 30 atoms and may be replaced by one or more R 2 At the same time, two Ar'' groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom may also be bridged to each other by a single bond or a bridging group selected from the following groups: B(R 2 )、C(R 2 )2、Si(R 2 )2. C=O, C=NR 2 、C=C(R 2 )2, O, S, S=O, SO2, N(R 2 )、P(R 2 ) and P(=O)R 2 ; R 2 are in each case identical or different and are selected from H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN, and which may be substituted by one or more alkyl radicals each having 1 to 4 carbon atoms; at the same time, two or more preferably adjacent substituents R 2 Together they can form a ring system.

2. The compound according to claim 1, characterized in that The Z group has a LEeV value of less than -0.20 eV, preferably less than -0.40 eV, more preferably less than -1.00 eV, and most preferably less than -1.40 eV.

3. The compound according to claim 1 or 2, characterized in that The Z group has at least one selected from CN, NO2, C(=O)R d , B(R d )2, preferably at least one CN group, more preferably at least two CN groups.

4. Compounds according to one or more of claims 1 to 3, characterized in that The Z group is a substructure of formula (Z-1), or contains a substructure of formula (Z-1), Where X 1 , X 2 , X 3 are the same or different in each case and are N, CZ 2 or CR d , where R d Having the definition given in claim 1, Z 2 is CN or NO2, and the dotted bond indicates the attachment site, where X 1 , X 2 , X 3 At least one, preferably at least two, of the groups are N or CZ 2 .

5. Compound according to one or more of claims 1 to 4, characterized in that The Z group is a substructure of formula (Z-1a) to (Z-1n), or contains a substructure of formula (Z-1a) to (Z-1n), Where R d has the definitions given in claim 1, the dashed bond indicates the attachment site, and the other labels have the following definitions: n is 0, 1, 2 or 3; o is 0, 1, or 2.

6. Compounds according to one or more of claims 1 to 5, comprising at least one structure of formula (II), The symbol Ar a ,Ar b , R c , Y 1 , Y 2 and L have the meaning given in claim 1, and the symbol X 1 , X 2 and X 3 has the definition given in claim 4, and L 1 is a bond or an aromatic or heteroaromatic ring system having 6 to 40 aromatic ring atoms and which may be substituted by one or more R groups.

7. The compound according to claim 6, characterized in that L 1 The group represents a bond or is identical or different in each case and is selected from the structures of the formulae (Ar-1) to (Ar-9), The symbols and notations used are as follows: i is 0, 1, or 2; j is independently 0, 1, 2 or 3 in each case; h is independently at each occurrence 0, 1, 2, 3 or 4; R has the meaning given in claim 1; And the dotted key marks the connection location.

8. The compound according to one or more of claims 1 to 7, comprising at least one structure of formula (III), The symbol R c , Y 1 , Y 2 and L has the meaning given in claim 1, the symbol X 1 , X 2 and X 3 The symbol L has the definition given in claim 4. 1 has the meaning given in claim 6, and other symbols have the following definitions: X a are the same or different in each case and are N or CR a , provided that there are no more than two X in a ring a The group is N, where R a has the definition detailed in claim 1; or two adjacent X a The groups together are of the formula: wherein dashed bonds represent the connection of the groups within the structure; X b are the same or different in each case and are N or CR b , provided that there are no more than two X in a ring b The group is N, where R b has the definition detailed in claim 1; or two adjacent X b The groups together are of the formula: The dashed bonds represent the connection of the groups within the structure.

9. The compound according to one or more of claims 1 to 8, comprising at least one structure of formula (IV) or (IVa) to (IVf), The compounds may also be partially or fully deuterated, symbol R a , R b , R c , Y 1 , Y 2 and L has the meaning given in claim 1, the symbol X 1 , X 2 and X 3 The symbol L has the definition given in claim 4. 1 has the meaning given in claim 6, and other symbols and indices have the following definitions: m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3.

10. Compounds according to one or more of claims 1 to 9, characterized in that L group is a bond, C(R)2, O, S, NAr or NR, Y 2 The group is C(R e )2 and Y 1 The group is O, S, Se, Te, NR or NAr.

11. A compound according to one or more of claims 1 to 10, comprising at least one structure of formula (IV-1) or (IV-1a) to (IV-1f), preferably selected from compounds of formula (IV-1), The symbol R a , R b , Y 1 , Y 2 and L has the meaning given in claim 1, the symbol X 1 , X 2 and X 3 has the meaning given in claim 4, and other symbols and indices have the following definitions: Y 3 are in each case identical or different and are O, S, Se, Te, NAr', NR 1 , B.R. 1 , C(R 1 )2,Ge(R 1 )2,Si(R 1 )2, -CR 1 =CR 1 -, C=NR 1 , P(O)R 1 , S=O, SO2, or having 5 to 14 aromatic ring atoms and may be replaced by one or more R 1 A radical-substituted ortho-linked aromatic or heteroaromatic substituent group, wherein Ar' and R 1 The groups have the definitions given above in claim 1; m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3.

12. A compound according to one or more of claims 1 to 11, comprising at least one structure of formula (V-1a) to (V-32c), The symbol R a , R b , Y 2 and L has the meaning given in claim 1, the symbol X 1 , X 2 and X 3 The symbol L has the definition given in claim 4. 1 has the meaning given in claim 6, and other symbols and indices have the following definitions: Y 3 are in each case identical or different and are O, S, Se, Te, NAr', NR 1 , B.R. 1 , C(R 1 )2,Ge(R 1 )2,Si(R 1 )2, -CR 1 =CR 1 -, C=NR 1 , P(O)R 1 , S=O, SO2, or having 5 to 14 aromatic ring atoms and may be replaced by one or more R 1 A radical-substituted ortho-linked aromatic or heteroaromatic substituent group, wherein Ar' and R 1 The groups have the definitions given above in claim 1; l is 0, 1, 2, 3, 4 or 5; m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3.

13. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 12, wherein: One or more bonds of the compound to the polymer, oligomer or dendrimer are present in place of a hydrogen atom or a substituent.

14. A preparation containing at least one compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13 and at least one further compound, wherein the further compound is selected from one or more solvents and / or from at least one further compound selected from electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials and hole blocking materials, preferably electron transport materials, electron injection materials, hole blocking materials, more preferably subphthalocyanines, subphthalocyanine derivatives, fullerenes or fullerene derivatives.

15. A process for preparing a compound according to one or more of claims 1 to 12, characterized in that A basic skeleton having an aromatic amino group is synthesized and at least one heterocyclic group is introduced, preferably by means of a nucleophilic aromatic substitution reaction or a coupling reaction.

16. Use of a compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13 in electronic devices, preferably as photosensitizer. 17 . An electronic device comprising at least one compound according to one or more of claims 1 to 12 or an oligomer, polymer or dendrimer according to claim 13 .

18. The electronic device according to claim 17, characterized in that The compounds according to one or more of claims 1 to 12 or the oligomers, polymers or dendrimers according to claim 13 are used as photosensitizers in light-absorbing layers.

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