Heterocyclic compounds for organic electroluminescent devices

Abstract

The present invention relates to heterocyclic compounds suitable for use in electronic devices, and electronic devices, in particular organic electroluminescent devices, containing said compounds.

Description

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

[0002] The luminescent materials used in organic electroluminescent devices are typically phosphorescent organometallic complexes or fluorescent compounds.There is still a general need to improve electroluminescent devices.

[0003] WO 2010 / 104047 A1 and WO 2019 / 132506 A1 disclose polycyclic compounds that can be used in organic electroluminescent devices. However, they do not disclose compounds according to the present invention. Furthermore, Wang et al., Nature Communications | 8:1948, investigated the antiaromatic properties of these compounds. However, Wang et al. did not describe the use of these compounds in organic electroluminescent devices.

[0004] Overall, these heterocyclic compounds still need to be improved, in particular with regard to lifetime and color purity, but also with regard to efficiency and operating voltage of devices, for example for use as emitters, in particular as fluorescent emitters.

[0005] It was therefore an object of the present invention to provide compounds which are suitable for use in organic electronic devices, in particular organic electroluminescent devices, and which, when used in such devices, lead to good device properties, and to provide corresponding electronic devices.

[0006] More specifically, the problem addressed by the present invention is that of providing compounds which lead to a long lifetime, good efficiency and low operating voltage.

[0007] Furthermore, the compounds should have excellent processability and, in particular, the compounds should exhibit good solubility.

[0008] Another problem solved by the present invention can be regarded as providing compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, in particular as emitters. More specifically, the problem solved by the present invention is to provide emitters suitable for red, green and blue electroluminescent devices.

[0009] Furthermore, the compounds, in particular when they are used as emitters in organic electroluminescent devices, lead to devices having excellent color purity.

[0010] Another problem solved by the present invention can be considered to be that of providing compounds suitable for use in phosphorescent or fluorescent electroluminescent devices, in particular as host materials. More specifically, the problem solved by the present invention is that of providing host materials suitable for red, yellow and blue phosphorescent electroluminescent devices.

[0011] Furthermore, the compounds, in particular when they are used as matrix materials, as hole-transport materials or as electron-transport materials in organic electroluminescent devices, lead to devices having excellent color purity.

[0012] Another problem may be considered to be providing electronic devices with excellent performance at very low cost and of stable quality.

[0013] Furthermore, it should be possible to use or adapt the electronic device for many purposes. More particularly, the performance of the electronic device should be maintained over a wide temperature range.

[0014] Surprisingly, it has been found that this object is achieved by specific compounds, described in detail below, which are highly suitable for use in preferred electroluminescent devices and lead to organic electroluminescent devices exhibiting very good properties, in particular with regard to lifetime, color purity, efficiency and operating voltage. The present invention therefore provides these compounds and electronic devices, in particular organic electroluminescent devices, comprising these compounds.

[0015] The present invention provides a compound comprising at least one structure of formula (I), preferably a compound of formula (I),

[0016]

[0017] Among them, cyclic Ar a and Ar b is an aromatic or heteroaromatic ring system which is identical or different in each case and has 5 to 60 aromatic ring atoms and which may be substituted by one or more Ar or R groups, wherein the ring Ar a and Ar b can form a ring system together;

[0018] And other symbols and subscripts used therein are as follows:

[0019] Z 1 , Z 2 , Z 3 are the same or different in each case and are N or B;

[0020] W 1 、W 2 are identical or different in each case and are N, B, C═C(Ar), C═C(R) or C═N, wherein the two carbon atoms of the C═C(Ar) or C═C(R) group or the carbon atom and the nitrogen atom of the C═N group are each a member of the ring Ar a or Ar b wherein the carbon atom of the C=N group is adjacent to V 1 or V 4 group bonding;

[0021] V 1 、V 2 are identical or different in each case and are -N=, -B=, =C(Ar)- or =C(R)-, or V 1 、V 2 The groups form a ring of the formula,

[0022]

[0023] wherein the ring Ar c is an aromatic or heteroaromatic ring system which is identical or different in each case and has 5 to 60 aromatic ring atoms and which may be substituted by one or more Ar or R groups, wherein the ring Ar c Can be used with X 1 The groups together form a ring system, or the ring Ar a and Ar c can form a ring system together, wherein W 3 With W 1 Group bonding, W 3 are identical or different in each case and are N, B, C═C(Ar), C═C(R) or C═N, wherein the two carbon atoms of the C═C(Ar) or C═C(R) group or the carbon atom and the nitrogen atom of the C═N group are each a member of the Ar group. c part of a ring wherein the carbon atom of the C=N group is adjacent to the W 1 The dotted line represents the W 1 or Z 2 the bonds connecting the groups;

[0024] V 3 、V 4 are identical or different in each case and are -N=, -B=, (Ar)C=C(Ar) or (R)C=C(R), or said V 3 、V 4 The groups form a ring of the formula,

[0025]

[0026] wherein the ring Ar d is an aromatic or heteroaromatic ring system which is identical or different in each case and has 5 to 60 aromatic ring atoms and which may be substituted by one or more Ar or R groups, wherein the ring Ar d Can be used with X 1 The groups together form a ring system, or the ring Ar b and Ar d can form a ring system together, wherein W 4 With W 2 Group bonding, W 4are identical or different in each case and are N, B, C═C(Ar), C═C(R) or C═N, wherein the two carbon atoms of the C═C(Ar) or C═C(R) group or the carbon atom and the nitrogen atom of the C═N group are each a member of the Ar group. a or Ar b part of a ring wherein the carbon atom of the C=N group is adjacent to the W 2 The dotted line represents the W 2 or Z 3 the bonds connecting the groups;

[0027] 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 here may be combined with at least one Ar, X 1 , R group or another group to form a ring system;

[0028] X 1 In each case the same or different and N, CR a , or if by with the ring Ar c 、Ar d One or more of the groups form a ring system, then X 1 is C, preferably, X 1 Same or different in each case and CR a or C, provided that there is an X in a ring 1 、X 2 No more than two of the groups are N;

[0029] X 2 Same or different in each case and either N or CR b , preferably CR b , provided that X is in a ring 1 、X 2 No more than two of the groups are N;

[0030] R, R a 、R b are identical or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)OAr′,C(=O)OR 1 ,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 linear 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 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 substituted aryloxy or heteroaryloxy groups; at the same time, two R, R a 、R b The groups may also form a ring system together or with another group;

[0031] Ar' is identical or different in each case and is an aromatic ring having 5 to 60 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 can also be connected by a bridging group through a single bond or selected from B(R 1 )、C(R 1 )2、Si(R 1 )2. C=O, C=NR 1 、C=C(R 1 )2, O, S, S=O, SO2, N(R 1 )、P(R 1 ) and P(=O)R 1 The bridging base is connected together;

[0032] R1 are identical or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(Ar")2, N(R 2 )2, C(=O)OAr”, C(=O)OR 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, or 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 wherein 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 each of which may be replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 an aryloxy or heteroaryloxy group substituted with a group, or having 5 to 60 aromatic ring atoms and substituted 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 together form a ring system; at the same time, one or more R 1 The group may form a ring system with another part of the compound;

[0033] Ar" are identical or different in each case and are aromatic rings 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 can also be connected by a bridging group through a single bond or selected from B(R 2 )、C(R 2)2、Si(R 2 )2. C=O, C=NR 2 、C=C(R 2 )2, O, S, S=O, SO2, N(R 2 )、P(R 2 ) and P(=O)R 2 The bridging base is connected together;

[0034] R 2 are identical or different in each case 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, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and the aromatic or heteroaromatic ring system may be substituted by one or more alkyl radicals, each of which has 1 to 4 carbon atoms; at the same time, two or more preferably adjacent substituents R 2 can form a ring system together;

[0035] At least one of the V 1 、V 2 、W 1 、W 3 The group represents N or B, preferably at least one V 1 、W 1 、W 3 The group represents N or B, and at least one V 3 、V 4 、W 2 、W 4 The group represents N or B, preferably at least one V 4 、W 2 、W 4 The group represents N or B.

[0036] According to the present invention, W 1 、W 2 It can be C=C(Ar), C=C(R) or C=N, wherein the two carbon atoms of the C=C(Ar) or C=C(R) group or the carbon atom and nitrogen atom of the C=N group are each a ring of Ar. a or Ar b wherein the carbon atom of the C=N group is adjacent to V 1 or V 4 This means that when W 1 When C=C(Ar) or C=C(R), the compound of formula (I) conforms to the following formula:

[0037]

[0038] And when W 1When C=N, the compound of formula (I) conforms to the following formula:

[0039]

[0040] About Cyclic Ar b , the same applies to W 2 groups, so the corresponding chemical formula can be formed. If V 1 、V 2 Group formation includes Ar c The ring, or group V 3 、V 4 Formation containing Ar d The same applies to the ring of W 3 or W 4 group, so the corresponding chemical formula can also be formed here.

[0041] Preferably, the V 1 、V 2 No more than one of the groups is -N= or -B=. Preferably, the V 3 、V 4 No more than one of the groups is -N= or -B=.

[0042] Preferred are compounds comprising at least one structure of formula (Ia), preferably compounds of formula (Ia):

[0043]

[0044] wherein the ring Ar a 、Ar b 、Ar c 、Ar d is in each case identical or different and is an aromatic heteroaromatic ring system having 5 to 60 aromatic ring atoms and which may be substituted by one or more Ar or R groups, wherein the ring Ar c 、Ar d Can be used with X 1 The groups form a ring system, or the ring Ar a and Ar c 、the ring Ar b and Ar d and the ring Ar a and Ar b Each can form a ring system together;

[0045] And other symbols and subscripts used therein are as follows:

[0046] Z 1 , Z 2 , Z 3 are the same or different in each case and are N or B;

[0047] W 1 、W 2 、W 3 、W 4 are identical or different in each case and are N, B, C=C(Ar), C=C(R) or C=N, wherein the two carbon atoms of the C=C(Ar) or C=C(R) group or the carbon atom and nitrogen atom of the C=N group are each the same as or different from the ring Ar. a 、Ar b 、Ar c or Ar d part of which at least one W 1 、W 3 The group represents N or B, and at least one W 2 、W 4 The group represents N or B;

[0048] 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 combined with at least one Ar, X 1 , R group or another group to form a ring system;

[0049] X 1 In each case the same or different and N, CR a , or if by with the ring Ar c 、Ar d One or more of the groups form a ring system, then X 1 is C, preferably, X 1 Same or different in each case and CR a or C, provided that there is an X in a ring 1 、X 2 No more than two of the groups are N;

[0050] X 2 Same or different in each case and either N or CR b , preferably CR b , provided that X is in a ring 1 、X 2 No more than two of the groups are N;

[0051] R, R a 、R b are identical or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)OAr′,C(=O)OR 1 ,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 linear 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 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 substituted aryloxy or heteroaryloxy groups; at the same time, two R, R a 、R b The groups may also form a ring system together or with another group;

[0052] Ar' is identical or different in each case and is an aromatic ring having 5 to 60 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 can also be connected by a bridging group through a single bond or selected from B(R 1 )、C(R 1 )2、Si(R 1 )2. C=O, C=NR 1 、C=C(R 1)2, O, S, S=O, SO2, N(R 1 )、P(R 1 ) and P(=O)R 1 The bridging base is connected together;

[0053] R 1 are identical or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(Ar")2, N(R 2 )2, C(=O)OAr”, C(=O)OR 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, or 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 wherein 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 each of which may be replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 an aryloxy or heteroaryloxy group substituted with a group, or having 5 to 60 aromatic ring atoms and substituted 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 together form a ring system; at the same time, one or more R 1 The group may form a ring system with another part of the compound;

[0054] Ar" are identical or different in each case and are aromatic rings having 5 to 30 atoms and may be replaced by one or more R2 At the same time, two Ar" groups bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom can also be connected by a bridging group through a single bond or selected from B(R 2 )、C(R 2 )2、Si(R 2 )2. C=O, C=NR 2 、C=C(R 2 )2, O, S, S=O, SO2, N(R 2 )、P(R 2 ) and P(=O)R 2 The bridging base is connected together;

[0055] R 2 are identical or different in each case 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, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and the aromatic or heteroaromatic ring system may be substituted by one or more alkyl radicals, each of which has 1 to 4 carbon atoms; at the same time, two or more preferably adjacent substituents R 2 Together they can form a ring system.

[0056] In formula (I) and / or (Ia), the following may be preferred: at least one Z 1 , Z 2 or Z 3 The group is N.

[0057] In formula (I) and / or (Ia), the following may be preferred: Z 1 is N and Z 2 , Z 3 At least one, preferably both, of the groups are B.

[0058] In formula (I) and / or (Ia), the following may also be preferred: Z 1 is N and Z 2 , Z 3 At least one, preferably both, of the groups are N.

[0059] In formula (I) and / or (Ia), the following may be preferred: at least one Z 1 , Z 2 or Z 3 The group is B.

[0060] In formula (I) and / or (Ia), the following may be preferred: Z 1 It is B and Z 2 , Z 3At least one, preferably both, of the groups are N.

[0061] In formula (I) and / or (Ia), the following may also be preferred: Z 1 It is B and Z 2 , Z 3 At least one, preferably both, of the groups are B.

[0062] If the symbol W 1 、W 2 、W 3 、W 4 represents C=C(Ar), C=C(R) or C=N, then the C=C(Ar), C=C(R) or C=N group forms the ring Ar a 、Ar b 、Ar c or Ar d If W 1 is C=C(Ar) or C=C(R) and a ring Ar a represents a 6-membered ring, then in addition to Z 1 Group or W 1 and Z 2 In addition to the carbon atom to which the group is attached and the two carbon atoms from the C=C(Ar) or C=C(R) group, the ring Ar a It also contains two other atoms.

[0063] For further explanation, this will be explained in detail with reference to formulas (IIb), (IIc) and (IId) to illustrate the corresponding points. In formula (IIb), W 4 Group representation and Z 5 The carbon atom to which the group is bonded and the X bonded to the carbon atom 3 In addition, in formula (IIb), Z 5 The group corresponds to W 2 A group, wherein the ring Ar represented by formula (I) or (Ia) b Including W represented by formula (IIb) 7 、W 8 The ring Ar represented by formula (I) or (Ia) a Including W represented by formula (IIb) 5 、W 6 group, and Z 4 The group corresponds to W 1 A group, wherein W shown in formula (Ia) 3 The group represents the same as Z in formula (IIb) 4 The carbon atom to which the group is bonded and the X bonded to the carbon atom 3 In formula (IIb), ring Ar c Also includes W3 Group, and Z 2 The carbon atom to which the group is bonded and the other three X 3 group.

[0064] In formula (IIc), V represented by formula (I) 4 The group consists of W 6 Accordingly, W in formula (IIc) 5 Group represents V 3 In addition, in formula (IIc), Z 5 The group corresponds to W shown in formula (I) 2 Group, Z 4 The group corresponds to W shown in formula (I) 1 Group, wherein the ring Ar b With W 2 or Z 5 The group is combined with and includes X shown in formula (IIc) 3 、X 5 Groups and X 5 and Z 5 The carbon atom to which the group is bonded. a With W 1 or Z 4 Group combination, and including X 3 、X 5 Groups and X 5 and Z 4 The carbon atom to which the group is bonded. 1 The group in formula (IIc) is represented by W 7 The group represents, and V 2 The group consists of W 8 Group representation.

[0065] In formula (IId), W described in detail in formula (I) 2 Group representation and Z 5 The carbon atom to which the group is bonded and the X bonded to the carbon atom 3 Group. Ring Ar b Also includes X 3 Group and X 5 Group, and Z 1 and Z 3 In addition, in formula (IId), V 3 、V 4 Groups forming ring Ar d , and the group Z in formula (IId) 5 Corresponding to W in formula (I) 4 Group, wherein the ring Ar d Include X 4 、W7 、W 8 group.

[0066] The following situations are preferred: Ring Ar a 、Ar b 、Ar c and / or Ar d To form a 5- or 6-membered ring. Preferably, one W 1 、V 1 The group represents C=C(Ar) or C=C(R) or =C(Ar)- or =C(R)-, and one W 2 、V 4 The group represents C=C(Ar) or C=C(R) or =C(Ar)- or =C(R)-. Preferably, one W 1 、W 3 The group represents C=C(Ar) or C=C(R), and a W 2 、W 4 The group represents C=C(Ar) or C=C(R).

[0067] Preferably, NN bonds are excluded so that V 4 、W 2 、W 4 No more than one of the groups is N and V 1 、W 1 、W 3 More preferably, no more than one of the groups is N. 3 、V 4 、W 2 、W 4 No more than one of the groups is N and V 1 、V 2 、W 1 、W 3 No more than one of the groups is N.

[0068] Preferably BB bonds are excluded so that V 4 、W 2 、W 4 No more than one of the groups is B and V 1 、W 1 、W 3 No more than one of the groups is B. More preferably, V 3 、V 4 、W 2 、W 4 No more than one of the groups is B and V 1 、V 2 、W 1 、W 3 No more than one of the groups is B.

[0069] Preferably, BN bonds are excluded so that V 4 、W 2 、W 4 No more than one of the groups is N or B and V 1 、W 1 、W 3 No more than one of the groups is N or B. More preferably, V 3 、V 4 、W 2 、W 4 No more than one of the groups is N or B and V 1 、V 2 、W 1 、W 3 No more than one of the groups is N or B.

[0070] In another configuration, it is preferred that V 4 、W 2 、W 4 There is exactly one N in the group, and V 1 、W 1 、W 3 There is exactly one N in the group, and V 1 、V 2 、W 1 、W 3 or V 3 、V 4 、W 2 、W 4 None of the groups is B. It can also be the following: V 4 、W 2 、W 4 There is exactly one B in the group, and V 1 、W 1 、W 3 There is exactly one B in the group, and V 1 、V 2 、W 1 、W 3 or V 3 、V 4 、W 2 、W 4 None of the groups is N.

[0071] In the context of the present invention, an aryl group contains 6 to 40 carbon atoms; in the context of the present invention, a heteroaryl group contains 2 to 40 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. An aryl group or a heteroaryl group is understood here to mean a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused (annulated) aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic compounds linked to one another by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0072] In the context of the present invention, an electron-deficient heteroaryl group is a heteroaryl group having at least one heteroaromatic six-membered ring with at least one nitrogen atom. Other aromatic or heteroaromatic five-membered or six-membered rings may be fused to this six-membered ring. Examples of electron-deficient heteroaryl groups are pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, quinazoline or quinolone. phenoxylate.

[0073] In the context of the present invention, an aromatic ring system contains 6 to 60 carbon atoms in the ring system. In the context of the present invention, a heteroaromatic ring system contains 2 to 60 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. In the context of the present invention, an aromatic or heteroaromatic ring system should be understood to mean a system in which it does not necessarily contain only an aryl or heteroaryl group, but wherein two or more aryl or heteroaryl groups may also be connected by non-aromatic units, such as carbon, nitrogen or oxygen atoms. For example, in the context of the present invention, fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, etc. should also be considered as aromatic ring systems, and similar systems in which two or more aryl groups are connected by, for example, short alkyl groups should also be considered as aromatic ring systems. 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 by single bonds.

[0074] In the context of the present invention, an aliphatic hydrocarbon- or 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 above-mentioned 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, vinyl, 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. An alkylthio group having 1 to 40 carbon atoms is understood as meaning 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 alkylthio groups according to the invention may be linear, branched or cyclic, wherein one or more non-adjacent CH2 groups may be replaced by the above-mentioned groups; in addition, one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO2, preferably by F, Cl or CN, more preferably by F or CN, and particularly preferably by CN.

[0075] 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 above-mentioned 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, biphenylidene, terphenyl, biphenylidene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, 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, phenanthroline, Oxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, Azoles, benzophenones Azoles, naphtho Azoles, anthracenes azole, phenanthroline Azoles, isocyanates azole, 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, phen Oxazine, phenothiazine, fluorescent red 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.

[0076] In the context of this specification, the expression that two or more groups can together form a ring is to be understood as meaning in particular that the two groups are linked to one another by a chemical bond by formally eliminating two hydrogen atoms. This is illustrated by the following scheme:

[0077]

[0078] In addition, however, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group is bonded to the position where the hydrogen atom is bonded, thereby forming a ring. This will be illustrated by the following scheme:

[0079]

[0080] In a preferred configuration, the compound of the present invention may comprise a structure of formula (IIa), (IIb), (IIc), (IId) and / or (IIe); more preferably, the compound of the present invention may be selected from compounds of formula (IIa), (IIb), (IIc), (IId) and / or (IIe):

[0081]

[0082]

[0083] where Z 1 , Z 2 , Z 3 、X 1 and X 2 has the definitions given above, in particular for formula (I) and / or (Ia), and the further symbols are as follows:

[0084] Z 4 , Z 5 are the same or different in each case and are N or B;

[0085] W 5 、W 6 、W 7 、W 8 are the same or different in each case and are C(Ar) or X 6 , in which Ar has the definitions given above, in particular for formula (I) and / or (Ia);

[0086] X 3 Same or different in each case and either N or CR c , preferably CR c , provided that X is in a ring 3 、X 5 No more than two of the groups are N;

[0087] X 4 Same or different in each case and either N or CR d , preferably CR d , provided that X is in a ring 4 、X 6 No more than two of the groups are N;

[0088] X 5 In each case the same or different and N, CR e , or if by the Ar group or X 5 Group or X 6 The bonds of the groups form a ring system, then X 5 is C, preferably X 5 Same or different in each case and CR e or C, provided that there is an X in a ring 3 、X 5 No more than two of the groups are N;

[0089] X 6 In each case the same or different and N, CR f , or if by the Ar group, X 5 Group or X 6 The bonds of the groups form a ring system, then X 6 is C, preferably X 6 Same or different in each case and CR f or C, provided that there is an X in a ring 4 、X 6 No more than two of the groups are N;

[0090] R c 、R d 、R e 、R f are identical or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)OAr′,C(=O)OR 1 ,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 linear 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 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 substituted aryloxy or heteroaryloxy groups; at the same time, the two R c 、R d 、R e 、R f The groups may also form a ring system together or with another group; wherein the R 1 The radicals have the definitions given above, in particular for formula (I) and / or (Ia).

[0091] Preference is given here to structures of the formula (IIa), (IIb), (IIc) and / or (IId).

[0092] In a more preferred embodiment, the following situation may be possible: the compound of the present invention includes the structure of formula (III-1) to (III-25), wherein the compound of the present invention may be more preferably selected from the compounds of formula (III-1) to (III-25),

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] The symbol Z 1 , Z 2 , Z 3 、X 1 and X 2 Having the definitions given above, in particular for formula (I) and / or (Ia), the symbol Z 4 , Z 5 、X 3 、X 4 、X 5 and X 6 has the definitions given above, in particular for formulae (IIa) to (IIe), and the other symbols are defined below:

[0103] p is 0 or 1,

[0104] Y 1 are in each case identical or different and are a bond, N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R)2, Si(R)2, C═NR, C═NAr′, C═C(R)2, O, S, Se, S═O or SO2, preferably N(Ar′), N(R), B(Ar′), B(R), P(═O)R, P(═O)Ar′, C═O, C(R)2, Si(R)2, O, S, Se, S═O or SO2, more preferably C(R)2, Si(R)2, O, S, N(Ar′) or B(Ar′), wherein the symbols R and Ar′ have the meanings given in claim 1;

[0105] Y 2 、Y 3 、Y 4are identical or different in each case and are N(Ar'), N(R), P(Ar'), P(R), P(=O)Ar', P(=O)R, P(=S)Ar', P(=S)R, B(Ar'), B(R), Al(Ar'), Al(R), Ga(Ar'), Ga(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr', C=C(R)2, O, S, S e, S=O or SO2, preferably N(Ar'), N(R), B(Ar'), B(R), P(=O)R, P(=O)Ar', C=O, C(R)2, Si(R)2, O, S, Se, S=O or SO2, more preferably C(R)2, Si(R)2, O, S, N(Ar') or B(Ar'), where the symbols R and Ar' have the definitions given above, in particular for formula (I) and / or (Ia).

[0106] Preference is given here to structures / compounds of the formulae (III-1) to (III-21), particular preference to structures / compounds of the formulae (III-1) to (III-8) and (III-12) to (III-18).

[0107] Preference may be given to the following: in formulae (I), (IIa) to (IIe) and / or (III-1) to (III-25), not more than four, preferably not more than two, X 1 、X 2 、X 3 、X 4 、X 5 and X 6 The group is N; more preferably, all X 1 、X 2 、X 3 、X 4 、X 5 and X 6 The groups are all CR, CR a , CR b 、R c 、R d 、R e 、R f or in X 1 、X 5 and X 6 In the case of groups, if X 1 、X 5 and X 6 If the groups form a ring system through bonds, then it is C.

[0108] As shown in the examples, some methods for preparing the compounds of the invention give mixtures, which generally result in broadening of the emission spectrum and are therefore not preferred. Therefore, separation of these mixtures may be appropriate. The advantages of narrow emission spectra can be achieved by appropriate substitution, as shown in the examples. In this case, specifically, position X 3 or X 4 In addition, this advantage can be achieved by X 3 or X 4 To achieve N.

[0109] The following situations may be preferred: X 4 The group is CR d And R d is not H or D, preferably a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or an alkyl or alkenyl 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 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 The following situations may also be preferred: X 4 The group is N.

[0110] It can also be the following: at least one X 3 The group is CR c And R c is not H or D, preferably 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 1group, 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 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 Preferably, as CR c And R c X that does not represent H or D 3 Group in Z 2 and / or Z 3 The following situation may be more preferred: X 3 The group is N, wherein X as N 3 The group is preferably in Z 2 and / or Z 3 The ortho position of the group.

[0111] In a more preferred embodiment, the following may be the case: the compound of the present invention includes the structures of formula (IV-1) to (IV-38), wherein the compound of the present invention may be more preferably selected from the compounds of formula (IV-1) to (IV-38),

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125] The symbol Z 1 , Z 2 , Z 3 、R a and R b Having the definitions given above, in particular for formula (I) and / or (Ia), the symbol Z 4 , Z 5 、R c 、R d 、R e and R f Having the definitions given above, in particular for formulae (IIa) to (IIe), the symbol Y 1 、Y 2 、Y 3 and Y 4 has the definitions given above, especially for formulae (III-1) to (III-25), and the other symbols are defined as follows:

[0126] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0127] n is 0, 1, 2 or 3, preferably 0, 1 or 2;

[0128] j is 0, 1 or 2, preferably 0 or 1;

[0129] k is 0 or 1.

[0130] Preference is given here to structures / compounds of the formulae (IV-1) to (IV-34), particular preference to structures / compounds of the formulae (IV-1) to (IV-12) and (IV-18) to (IV-31).

[0131] The sum of the subscripts k, j, m and n in the structures / compounds of formulae (IV-1) to (IV-38) is preferably not more than 10, preferably not more than 8, particularly preferably not more than 6, and more preferably not more than 4.

[0132] Furthermore, in preferred embodiments of formulae (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Z 1 is N and Z 2 , Z 3 , Z 4 , Z 5At least one, preferably two, of the groups are B. 1 is N and Z 2 , Z 3 , Z 4 , Z 5 Configurations in which at least one, preferably both, of the radicals are B can advantageously be used as emitters.

[0133] Furthermore, in preferred embodiments of formulae (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Z 1 is N and Z 2 , Z 3 , Z 4 , Z 5 At least one, preferably two, of the groups are N.

[0134] Specifically, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 Embodiments in which a plurality, preferably all, of the radicals are N can be advantageously used as hole-conducting materials.

[0135] In another configuration, in the preferred embodiments of formulae (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Z 1 It is B and Z 2 , Z 3 , Z 4 , Z 5 At least one, preferably two, of the groups are N. 1 It is B and Z 2 , Z 3 , Z 4 , Z 5 Configurations in which at least one, preferably both, of the radicals are N can advantageously be used as emitters.

[0136] In another configuration, in the preferred embodiments of formulae (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Z 1 It is B and Z 2 , Z 3 , Z 4 , Z 5 At least one, preferably two, of the groups are B.

[0137] Specifically, Z1 , Z 2 , Z 3 , Z 4 , Z 5 Embodiments in which a plurality, preferably all, of the groups are B can be advantageously used as electron-transporting materials.

[0138] In another configuration, in the preferred embodiments of formulae (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Z 2 , Z 3 At least one, preferably two, of the groups are N, and Z 4 , Z 5 At least one, preferably two, of the groups are B.

[0139] Furthermore, in preferred embodiments of formulae (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Z 2 , Z 3 At least one, preferably two, of the groups are B, and Z 4 , Z 5 At least one, preferably two, of the groups are N.

[0140] Furthermore, in preferred embodiments of formulae (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Z 2 , Z 3 At least one, preferably two, of the groups are N, and Z 4 , Z 5 At least one, preferably two, of the groups are N.

[0141] In another configuration, in the preferred embodiments of formulae (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Z 2 , Z 3 At least one, preferably two, of the groups are B, and Z 4 , Z 5 At least one, preferably two, of the groups are B.

[0142] In another embodiment, in the preferred embodiments of formulae (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38) and / or especially these formulae described in detail below, it may be the case that: Z 2 , Z 3 At least one, preferably two, of the groups are B, and Z 4 , Z 5 At least one, preferably two, of the groups are B.

[0143] In another configuration, in the preferred embodiments of formulae (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Z 2 It's B, Z 3 is N, and Z 4 , Z 5 At least one, preferably two, of the groups are B.

[0144] Furthermore, in preferred embodiments of formulae (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that p=1 and Y 1 A group is a bond.

[0145] Furthermore, in preferred embodiments of formulae (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Y 3 and Y 4 The groups are the same.

[0146] Furthermore, in preferred embodiments of formulae (III-1) to (III-25), (IV-1) to (IV-38) and / or in particular of these formulae described in detail below, it may be the case that: Y 3 and Y 4 The groups are different.

[0147] In a preferred development of the invention, it may be the case that at least two R, R a 、R b 、R c 、R d 、R e 、R f The group and the two R, R a 、R b 、R c 、R d 、R e 、R f The other groups to which the group is combined together form a fused ring, wherein the two R, Ra 、R b 、R c 、R d 、R e 、R f The groups form at least one structure of formula (RA-1) to (RA-12):

[0148]

[0149]

[0150] where R 1 With the above definitions, the dotted bond represents the two R, R a 、R b 、R c 、R d 、R e 、R f The attachment site for group binding, and other symbols have the following definitions:

[0151] Y 5 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;

[0152] R g are identical or different in each case and are F, a linear alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, or an alkyl or alkenyl 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 2 group, wherein one or more 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 having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group, 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 g The groups can also be together or one R g Group with an R 1 The groups together or together with other groups form a ring system;

[0153] s is 0, 1, 2, 3, 4, 5 or 6, preferably 0, 1, 2, 3 or 4, more preferably 0, 1 or 2;

[0154] 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;

[0155] 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.

[0156] In a preferred embodiment of the present invention, at least two R, R a 、R b 、R c 、R d 、R e 、R f The group and the two R, R a 、R b 、R c 、R d 、R e 、R f The other groups to which the group is combined together form a fused ring, wherein the two R, R a 、R b 、R c 、R d 、R e 、R f The groups preferably form at least one structure of the formula (RA-1a) to (RA-4f),

[0157]

[0158]

[0159] The dotted line represents the two R, R a 、R b 、R c 、R d 、R e 、R fThe attachment site to which the group is attached, the subscript m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the symbol R 1 、R 2 、R g and the subscripts s and t have the definitions given above, in particular for formula (I) and / or formulae (RA-1) to (RA-12).

[0160] It can also be the following situation: the at least two R, R a 、R b 、R c 、R d 、R e 、R f The structures of formula (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) are formed in the group and a condensed ring is formed, indicating that the adjacent X 1 、X 2 、X 3 、X 4 、X 5 、X 6 R of the group a 、R b 、R c 、R d 、R e 、R f The groups, or represent R groups each bound to adjacent carbon atoms, wherein these carbon atoms are preferably connected by a bond.

[0161] In a more preferred configuration, at least two R, R a 、R b 、R c 、R d 、R e 、R f The two R, R a 、R b 、R c 、R d 、R e 、R f The other groups to which the group is combined together form a fused ring, wherein the two R, R a 、R b 、R c 、R d 、R e 、R f The structure of the group forming formula (RB):

[0162]

[0163] where R 1 As defined above, especially for formula (I), the dotted bond represents two R, Ra 、R b 、R c 、R d 、R e 、R f The attachment site to which the group is attached, the subscript m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and Y 6 It is C(R 1 )2、NR 1 、NAr'、BR 1 , BAr', O or S, preferably C(R 1 )2, NAr' or O.

[0164] Here, the following may be the case: a 、R b 、R c 、R d 、R e 、R f The group forms a structure of formula (RB) and forms a fused ring, indicating that the adjacent X 1 、X 2 、X 3 、X 4 、X 5 、X 6 R of the group a 、R b 、R c 、R d 、R e 、R f The groups, or represent R groups that are each bound to adjacent carbon atoms, wherein these carbon atoms are preferably connected to each other by a bond.

[0165] More preferably, the compound comprises at least one structure of formula (V-1) to (V-10); more preferably, the compound is selected from the compounds of formula (V-1) to (V-10), wherein the compound has at least one fused ring:

[0166]

[0167]

[0168] The symbol Z 1 , Z 2 , Z 3 and R a Having the definitions given above, in particular for formula (I) and / or (Ia), the symbol Z 4 , Z 5 、R c 、R d 、R e and R fHaving the definitions given above, in particular for formulae (IIa) to (IIe), the symbol Y 3 and Y 4 Having the definitions given above, in particular for formulae (III-1) to (III-25), the symbol o represents the site of attachment of the fused ring, and the other symbols are defined as follows:

[0169] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0170] n is 0, 1, 2 or 3, preferably 0, 1 or 2;

[0171] j is 0, 1 or 2, preferably 0 or 1;

[0172] k is 0 or 1.

[0173] Preference is given here to structures / compounds of the formulae (V-1) to (V-8).

[0174] More preferably, the compound comprises at least one structure of formula (VI-1) to (VI-9); more preferably, the compound is selected from compounds of formula (VI-1) to (VI-9), wherein the compound has at least one fused ring:

[0175]

[0176] The symbol Z 1 , Z 2 , Z 3 、R a and R b Having the definitions given above, in particular for formula (I) and / or (Ia), the symbol Z 4 , Z 5 、R c 、R d 、R e and R f Having the definitions given above, in particular for formulae (IIa) to (IIe), the symbol Y 3 and Y 4 Having the definitions given above, in particular for formulae (III-1) to (III-25), the symbol o represents the site of attachment of the fused ring, and the other symbols are defined as follows:

[0177] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0178] n is 0, 1, 2 or 3, preferably 0, 1 or 2;

[0179] j is 0, 1 or 2, preferably 0 or 1.

[0180] Preference is given here to structures / compounds of the formulae (VI-1) to (VI-7).

[0181] More preferably, the compound comprises at least one structure of formula (VII-1) to (VII-9); more preferably, the compound is selected from the compounds of formula (VII-1) to (VII-9), wherein the compound has at least one fused ring:

[0182]

[0183]

[0184] The symbol Z 1 , Z 2 , Z 3 、R a and R b Having the definitions given above, in particular for formula (I) and / or (Ia), the symbol Z 4 , Z 5 、R c 、R d 、R e and R f Having the definitions given above, in particular for formulae (IIa) to (IIe), the symbol Y 3 and Y 4 Having the definitions given above, in particular for formulae (III-1) to (III-25), the symbol o represents the site of attachment of the fused ring, and the other symbols are defined as follows:

[0185] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0186] n is 0, 1, 2 or 3, preferably 0, 1 or 2;

[0187] j is 0, 1 or 2, preferably 0 or 1.

[0188] Preference is given here to structures / compounds of the formulae (VII-1) to (VII-7).

[0189] Preferably, the fused ring, in particular in formulae (V-1) to (V-10), (VI-1) to (VI-9) and / or (VII-1) to (VII-9), is formed by at least two R, R a 、R b 、R c 、R d 、R e 、R f group and the two R, R a 、R b 、R c 、R d 、R e 、R fThe other groups to which the group is combined form, wherein the R, R a 、R b 、R c 、R d 、R e 、R f At least two of the groups form structures of formulae (RA-1) to (RA-12) and / or formula (RB), preferably structures of formulae (RA-1) to (RA-12).

[0190] The following may be preferred: the compound has at least two fused rings, wherein at least one fused ring is formed by structures of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f) and the other ring is formed by structures of formulae (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB), wherein the compound includes at least one structure of formulae (VIII-1) to (VIII-20), preferably wherein the compound is selected from compounds of formulae (VIII-1) to (VIII-20):

[0191]

[0192]

[0193]

[0194] The symbol Z 1 , Z 2 , Z 3 、R a and R b Having the definitions given above, in particular for formula (I) and / or (Ia), the symbol Z 4 , Z 5 、R c 、R d 、R e and R f Having the definitions given above, in particular for formulae (IIa) to (IIe), the symbol Y 3 and Y 4 Having the definitions given above, in particular for formulae (III-1) to (III-25), the symbol o represents the attachment site, and the other symbols are defined as follows:

[0195] m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

[0196] n is 0, 1, 2 or 3, preferably 0, 1 or 2;

[0197] j is 0, 1 or 2, preferably 0 or 1.

[0198] Preference is given here to structures / compounds of the formulae (VIII-1) to (VIII-16), particular preference to structures / compounds of the formulae (VIII-1) to (VIII-14).

[0199] In particular, in formulae (V-1) to (V-10), (VI-1) to (VI-9), (VII-1) to (VII-9) and / or (VIII-1) to (VIII-20), the sum of the subscripts k, j, l, m and n is preferably 0, 1, 2 or 3, more preferably 1 or 2.

[0200] Here, the following may be the case: Formulae (VIII-1) to (VIII-20) have at least two fused rings, wherein the fused rings are identical and are composed of two R, R a 、R b 、R c 、R d 、R e 、R f The moiety formed by the group may be represented by at least one structure of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

[0201] The following cases are also possible: Formulas (VIII-1) to (VIII-20) have at least two fused rings, wherein the fused rings are different and are composed of two R, R a 、R b 、R c 、R d 、R e 、R f The moiety formed by the radical can in each case be represented by at least one structure of the formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f).

[0202] Alternatively, the following may be the case: the formulae (VIII-1) to (VIII-20) have at least two fused rings, wherein the fused rings are different, and one of the two fused rings has a moiety formed by two R groups, which moiety can be represented by at least one of the structures of formulae (RA-1) to (RA-12) and / or (RA-1a) to (RA-4f), and one of the two fused rings has a moiety formed by two R, R a 、R b 、R c 、R d 、R e 、R f The moiety formed by the group may be represented by one of the structures of formula (RB).

[0203] In addition, the following cases may be possible: a 、Rb 、R c 、R d 、R e 、R f and R g 、R 1 and R 2 Not with R, R a 、R b 、R c 、R d 、R e 、R f and R g 、R 1 and R 2 The ring atoms of the ring systems to which they are joined form a fused aromatic or heteroaromatic ring system. This includes the formation of a fused aromatic or heteroaromatic ring system in which the possible substituents R 1 and R 2 Can be used with R, R a 、R b 、R c 、R d 、R e 、R f 、R g and R 1 Group bonding.

[0204] When in particular can be selected from R, R a 、R b 、R c 、R d 、R e 、R f 、R g 、R 1 and / or R 2 When two groups of R form a ring system with each other, this ring system can be monocyclic or polycyclic, aliphatic, heteroaliphatic, aromatic or heteroaromatic. In this case, the groups that together form the ring system can 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 can also be removed from each other. In addition, the substituents R, R a 、R b 、R c 、R d 、R e 、R f 、R g 、R 1 and / or R 2 The ring systems of can also be connected to each other via bonds, which can result in ring closure. In this case, each corresponding bonding site preferably has a substituent R, R a 、R b 、R c 、R d 、Re 、R f 、R g 、R 1 and / or R 2 .

[0205] In a preferred configuration, the compounds of the present invention can be represented by at least one of the structures of formula (I), (Ia), (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38), (V-1) to (V-10), (VI-1) to (VI-9), (VII-1) to (VII-9) and / or (VIII-1) to (VIII-20). Preferably, the molecular weight of the compounds of the present invention, preferably comprising structures of formula (I), (Ia), (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38), (V-1) to (V-10), (VI-1) to (VI-9), (VII-1) to (VII-9) and / or (VIII-1) to (VIII-20), is not more than 5000 g / mol, preferably not more than 4000 g / mol, particularly preferably not more than 3000 g / mol, particularly preferably not more than 2000 g / mol, and most preferably not more than 1200 g / mol.

[0206] Furthermore, preferred compounds of the present invention are characterized in that they are sublimable. The molar mass of these compounds is generally less than about 1200 g / mol.

[0207] Preferred aromatic or heteroaromatic ring systems R, R a 、R b 、R c 、R d 、R e 、R f , Ar' and / or Ar are 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-bound naphthalene or 2-bound 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, quinoline Phosphine, phenanthrene or terphenylene, each of which may be replaced by one or more R 1or R group substituted.

[0208] The following may be preferred: 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, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, or an aromatic or heteroaromatic ring system selected from the groups of the following formulae Ar-1 to Ar-75, wherein the substituents R, R a 、R b 、R c 、R d 、R e 、R f Preferably, the rings according to the structures of formulae (RA-1) to (RA-12), (RA-1a) to (RA-4f) or (RB) are formed, or the substituents R, R a 、R b 、R c 、R d 、R e 、R f an aromatic or heteroaromatic ring system which is identical or different in each case and is selected from H, D or a radical selected from the following formulae Ar-1 to Ar-75, and / or the Ar' radicals are identical or different in each case and are selected from the following formulae Ar-1 to Ar-75:

[0209]

[0210]

[0211]

[0212]

[0213] where R 1 As defined above, dashed bonds indicate attachment sites, and additionally:

[0214] 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 group;

[0215] A is the same or different in each case and is C(R 1 )2、NR 1 , O or S;

[0216] p is 0 or 1, wherein p=0 means that the Ar 1group is not present and the corresponding aromatic or heteroaromatic group is directly bonded to HetAr;

[0217] q is 0 or 1, where q=0 means that no A group is bonded at this position, but R 1 The groups are bonded to the corresponding carbon atoms.

[0218] When the above Ar group has two or more A groups, the possible options include all combinations of the definitions of A. In that 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 those in which both A groups are O.

[0219] When A is NR 1 When the substituent R bonded to the nitrogen atom 1 Preferably it is an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be replaced by one or more R 2 In a particularly preferred embodiment, this R 1 The substituents are identical or different in each case and are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular 6 to 18 aromatic ring atoms, which does not have any fused aryl groups and does not have any fused heteroaryl groups in which two or more aromatic or heteroaromatic 6-membered ring groups are fused directly to one another, and the aromatic or heteroaromatic ring system 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 Group substituted rather than 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 Group substituted rather than R 1 replace.

[0220] Preferred substituents R, R a 、R b 、R c 、R d 、R e 、R f and R g .

[0221] In a preferred embodiment of the present invention, R, R a 、Rb 、R c 、R d 、R e 、R f are identical or different in each case and are selected from the group consisting of H, D, F, CN, NO2, Si(R 1 )3,B(OR 1 )2, a linear 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 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.

[0222] In a more preferred embodiment of the present invention, the substituents R, R a 、R b 、R c 、R d 、R e 、R f are identical or different in each case and are selected from H, D, F, straight-chain alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, wherein the alkyl groups 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.

[0223] It is also possible that at least one substituent R, R a 、R b 、R c 、R d 、R e 、R f are identical or different in each case and are selected from H, D, a cyclopentane having 6 to 30 aromatic ring atoms and which may be replaced by one or more R 1 In a more preferred embodiment of the present invention, the substituents form a ring according to the structures of formula (RA-1) to (RA-12), (RA-1a) to (RA-4f), or R is in each case the same or different and is selected from H, D, a ring having 6 to 30 aromatic ring atoms and can be replaced by one or more R 1 More preferably, the substituents R, R a 、R b 、R c、R d 、R e 、R f are identical or different in each case and are selected from H or 6 to 24 aromatic ring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to 13 aromatic ring atoms and each of which may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0224] In a preferred embodiment of the present invention, R g are identical or different in each case and are selected from linear alkyl groups having 1 to 20 carbon atoms or branched or cyclic alkyl groups having 3 to 20 carbon atoms, wherein the alkyl groups 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.

[0225] In a more preferred embodiment of the present invention, R g are identical or different in each case and are selected from a linear alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group may be replaced by one or more R 1 substituted with a group having 6 to 30 aromatic ring atoms and may be substituted with one or more R 1 More preferably, R a are identical or different in each case and are selected from a linear alkyl group having 1 to 5 carbon atoms or a branched or cyclic alkyl group having 3 to 5 carbon atoms, wherein the alkyl group may be replaced by one or more R 1 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 1 Aromatic or heteroaromatic ring systems substituted with radicals.

[0226] In a preferred embodiment of the present invention, R g are identical or different in each case and are selected from linear alkyl groups having 1 to 6 carbon atoms or cyclic alkyl groups having 3 to 6 carbon atoms, wherein the alkyl groups may be replaced by one or more R 1 or having 6 to 24 aromatic ring atoms and in each case being substituted by one or more R 1 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two R g The groups may also form a ring system together. More preferably, Rg are identical or different in each case and are selected from 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 1 substituted but preferably unsubstituted, or having 6 to 12 aromatic ring atoms, in particular 6 aromatic ring atoms and in each case substituted by one or more preferably nonaromatic R 1 The aromatic ring system is preferably unsubstituted; at the same time, the two R g The groups may together form a ring system. Most preferably, R g are identical or different at each occurrence and are selected from a linear alkyl group having 1, 2, 3 or 4 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms. Most preferably, R g It is methyl or phenyl, wherein two phenyl groups may be taken together to form a ring system, and methyl is preferred over phenyl.

[0227] Preferred aromatic or heteroaromatic ring system substituents R, R a 、R b 、R c 、R d 、R e 、R f 、R g or Ar 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-bound naphthalene 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, quinone Phosphine, phenanthrene or terphenylene, each of which may be replaced by one or more R, R 1 or R 2The structures Ar-1 to Ar-75 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-75, it should be noted that these are shown as having a substituent R 1 In the case of the ring system Ar, these substituents R 1 can be replaced by R, and in R g In the case of these substituents R 1 Can be R 2 replace.

[0228] In addition, suitable R, R a 、R b 、R c 、R d 、R e 、R f The 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 group. 2 、Ar 3 and Ar 4 The total number of aromatic ring atoms does not exceed 60, preferably does not exceed 40.

[0229] In this case, by selecting C(R 1 )2、NR 1 , O and S groups, Ar 4 and Ar 2 They can also be bonded to each other and / or Ar 2 and Ar 3 Preferably, Ar is bonded to each other at the corresponding ortho position of the bond to the nitrogen atom. 4 and Ar 2 connected to each other and Ar 2 and Ar 3 In another embodiment of the present invention, Ar 2 、Ar 3 and Ar4 None of the groups are bonded to each other.

[0230] Preferably, Ar 4 is a ring having 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms and in each case may be replaced by one or more R 1 More preferably, Ar 4 Selected from o-phenylene, m-phenylene or p-phenylene or o-biphenyl, m-biphenyl or p-biphenyl, each of which may be replaced by one or more R 1 Groups are substituted, but preferably are unsubstituted. Most preferably, Ar 4 is unsubstituted phenylene.

[0231] Preferably, Ar 2 and Ar 3 are identical or different in each case and have 6 to 24 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with groups. Particularly preferred are Ar 2 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-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, benzothiophene phenanthene, 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 replaced by one or more R 1 Most preferably, Ar 2 and Ar 3 are in each case identical or different and are selected from phenyl, biphenyl (especially o-, m- or p-biphenyl), terphenyl (especially o-, m- or p-terphenyl or a branched terphenyl), quaterphenyl (especially o-, m- or p-quaterphenyl or a branched quaterphenyl), fluorene (especially 1-, 2-, 3- or 4-fluorene) or spirobifluorene (especially 1-, 2-, 3- or 4-spirobifluorene).

[0232] In another preferred embodiment of the present invention, R1 are identical or different in each case and are selected from H, D, F, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group may be replaced by one or more R 2 or having 6 to 24 aromatic ring atoms and in each case being substituted by one or more R 2 In a particularly preferred embodiment of the present invention, R 1 are identical or different in each case and are selected from H, a linear alkyl group having 1 to 6 carbon atoms, in particular 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 substituted by one or more R 5 The aromatic or heteroaromatic ring system may be substituted with or without substituted radicals.

[0233] In another preferred embodiment of the present invention, R 2 are in each case identical or different and are H, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be substituted by alkyl groups having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0234] At the same time, in compounds of the present invention processed by vacuum evaporation, the alkyl group preferably has no more than five 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 those substituted with alkyl groups, especially branched alkyl groups having up to 10 carbon atoms, or those substituted with oligoarylene groups such as o-, m- or p-terphenyl or branched terphenyl or quaterphenyl groups.

[0235] It may also be the case that the compound comprises exactly two or exactly three structures of formula (I), (IIa) to (IIe), (III-1) to (III-25), (IV-1) to (IV-38), (V-1) to (V-10), (VI-1) to (VI-9), (VII-1) to (VII-9) and / or (VIII-1) to (VIII-20).

[0236] In a preferred configuration, the compound is selected from compounds of formula (D-1), (D-2), (D3) or (D-4):

[0237]

[0238]

[0239] Among them L 1 The group is a linking group, preferably a bond or a cyclic aromatic group having 5 to 40, preferably 5 to 30, aromatic ring atoms and can be supported by one or more R 1 The radically substituted aromatic or heteroaromatic ring system and the other symbols and subscripts used have the meanings given above, in particular for formula (I) and / or (Ia).

[0240] In another preferred embodiment of the present invention, L 1 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, and may be replaced by one or more R 1 The group is substituted but preferably unsubstituted, wherein R 1 may have the definitions given above, in particular for formula (I). More preferably, L 1 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 2 The group is substituted but preferably unsubstituted, wherein R 2 may have the definitions given above, in particular for formula (I).

[0241] More preferably, the symbol L represented by formula (D3) or (D4) 1 are identical or different in each case and are a bond or an aryl or heteroaryl group having 5 to 24 ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ring atoms, such that the aromatic or heteroaromatic group of the aromatic or heteroaromatic ring system is bonded directly, i.e. via an atom of the aromatic or heteroaromatic group, to the corresponding atom of the further group.

[0242] In addition, the following cases may be possible: L shown in formula (D3) or (D4) 1 The group comprises an aromatic ring system having no more than two fused aromatic and / or heteroaromatic six-membered rings, and preferably does not comprise any fused aromatic or heteroaromatic ring systems. Therefore, naphthyl structures are preferred over anthracene structures. Furthermore, fluorenyl, spirobifluorenyl, dibenzofuranyl, and / or dibenzothienyl structures are preferred over naphthyl structures.

[0243] Particular preference is given to structures without condensation, such as phenyl, biphenyl, terphenyl and / or quaterphenyl structures.

[0244] Suitable aromatic or heteroaromatic ring systems L 1Examples of R 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), fluorenylene, spirobifluorenylene, dibenzofuranylene, dibenzothiophenylene and carbazolylene, each of which may be replaced by one or more R 1 The groups are substituted but preferably are unsubstituted.

[0245] 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 preferred features exist simultaneously.

[0246] Examples of preferred compounds according to the embodiments detailed above are the compounds shown in the following table:

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267] The examples detail preferred embodiments of the compounds of the present invention, which can be used alone or in combination with other compounds for all purposes of the present invention.

[0268] The above preferred embodiments can be combined with each other as needed, provided that the conditions described in claim 1 are met. In a particularly preferred embodiment of the present invention, the above preferred embodiments are applied simultaneously.

[0269] In principle, the compounds according to the invention can be prepared by various methods. However, the methods described below have been found to be particularly suitable.

[0270] Therefore, the present invention also provides a method for preparing the compounds of the present invention, wherein the synthesis of 2 , Z 3 At least one of the groups or Z 2 , Z 3 The basic skeleton of the precursor of one of the groups is introduced by metallation reaction, aromatic nucleophilic substitution reaction or coupling reaction. 1 group.

[0271] Contains Z 2 , Z 3 Suitable compounds for the basic skeleton of the radicals are in many cases commercially available, and the starting compounds detailed in the examples can be obtained by known methods, to which reference is therefore made.

[0272] 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 will assist those skilled in the art in performing these reactions.

[0273] Particularly suitable and preferred coupling reactions, which can all lead to C-C bond formation and / or C-N bond formation, are those according to BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA and HIYAMA. These reactions are well known and the examples will provide further guidance to those skilled in the art.

[0274] The principles of the above-mentioned preparation methods are known in principle from the literature for similar compounds and can be easily adapted by a person skilled in the art to prepare the compounds according to the invention. Further information can be found in the examples.

[0275] By these methods, if necessary followed by purification, for example recrystallization or sublimation, high purities, preferably exceeding 99% (by 1 H NMR and / or HPLC determination) of the compounds of the present invention.

[0276] The compounds of the present invention can also be mixed with polymers. These compounds can also be covalently bound to polymers. Compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boric acid or boric esters or with reactive polymerizable groups such as olefins or oxetanes are particularly suitable. These can be used as monomers for producing corresponding oligomers, dendrimers or polymers. Oligomerization or polymerization is preferably achieved via halogen functionality or boronic acid functionality or via polymerizable groups. Additionally, it is possible to crosslink the polymer via such groups. The compounds of the present invention and polymers can be used in the form of crosslinked or uncrosslinked layers.

[0277] Thus, the present invention also provides oligomers, polymers or dendrimers containing one or more of the above-mentioned structures of formula (I) and / or (Ia) and preferred embodiments thereof or compounds of the present invention, wherein there is a bond between one or more of the compounds of the present invention or the structures of formula (I) and / or (Ia) and preferred embodiments thereof and the polymer, oligomer or dendrimer. Depending on the bonds of the structures of formula (I) and / or (Ia) and preferred embodiments thereof or compounds, these bonds 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. With respect to the repeating units of the compounds of the present invention in the oligomers, dendrimers and polymers, the same preferred features as described above apply.

[0278] To prepare the oligomers or polymers, the monomers of the invention are homopolymerized or copolymerized with other monomers. Preference is given to copolymers in which the units of formula (I) and / or (Ia) or the preferred embodiments described above and below are present in a range of 0.01 to 99.9 mol %, preferably 5 to 90 mol %, more preferably 20 to 80 mol %. Suitable and preferred comonomers 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- 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 2004 / 070772 or WO 2004 / 113468), 2005 / 104264 or WO 2007 / 017066) or a combination of these units. The polymers, oligomers and dendrimers may contain further units, such as hole transport units, especially those based on triarylamines, and / or electron transport units.

[0279] Of particular interest are compounds of the present invention characterized by a high glass transition temperature. In this regard, particularly preferred are compounds of the present invention comprising the structures of formula (I) and / or (Ia) or the preferred embodiments described above and below, having a glass transition temperature, as measured according to DIN 51005 (2005-08 edition), 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.

[0280] In order to process the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, formulations of the compounds of the invention are required. These formulations 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, dimethylbenzene, alkane, phenoxytoluene (especially 3-phenoxytoluene), (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, para-cymene Hydrocarbons, phenetole, 1,4-diisopropylbenzene, benzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate or mixtures of these solvents.

[0281] Therefore, the present invention also provides a formulation or a composition comprising at least one compound of the present invention and at least one additional compound. The additional compound may, for example, be a solvent, in particular one of the above-mentioned solvents or a mixture of these solvents. If the additional compound comprises a solvent, then this mixture is referred to herein as a formulation. The additional compound may alternatively be at least one other organic or inorganic compound also used in electronic devices, such as a luminophore and / or a matrix material, wherein these compounds are different from the compounds of the present invention. Suitable luminophores and matrix materials are listed below in conjunction with organic electroluminescent devices. The additional compound may also be polymeric.

[0282] Therefore, the present invention also provides a composition comprising a compound of the present invention and at least one other organic functional material. The functional material is typically an organic or inorganic material introduced between the anode and cathode. Preferably, the organic functional material is selected from the group consisting of a fluorescent emitter, a phosphorescent emitter, an emitter exhibiting TADF (thermally activated delayed fluorescence), a host material, an electron transport material, an electron injection material, a hole conducting material, a hole injection material, an electron blocking material, a hole blocking material, a wide bandgap material, and an n-type dopant.

[0283] The present invention also provides the use of the compounds of the present invention in electronic devices, especially in organic electroluminescent devices, preferably as luminophores, more preferably as green, red or blue luminophores. In this case, the compounds of the present invention preferably exhibit fluorescent properties and thus preferably provide fluorescent luminophores. In addition, the compounds of the present invention can be used as host materials, electron transport materials and / or hole conducting materials. In particular, Z can be advantageously used here.1 , Z 2 , Z 3 , Z 4 , Z 5 Compounds of the invention in which several, preferably all, of the groups are N are used as hole-conducting materials. It is also particularly advantageous to use Z 1 , Z 2 , Z 3 , Z 4 , Z 5 The compounds according to the invention in which a plurality, preferably all, of the radicals are B serve as electron-transport materials.

[0284] The present invention further provides an electronic device comprising at least one compound according to the invention. In the context of the present invention, an electronic device is a device comprising at least one layer comprising at least one organic compound. The component may also comprise an inorganic material or a layer formed entirely of an inorganic material.

[0285] The electronic device is preferably selected from the following, more preferably, the electronic device is 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 optical receptors, organic field quenching devices (O-FQDs) and organic electrical sensors, preferably organic electroluminescent devices (OLED, sOLED, PLED, LEC, etc.), more preferably organic light emitting diodes (OLED), small molecule-based organic light emitting diodes (sOLED), polymer-based organic light emitting diodes (PLED), especially phosphorescent OLEDs.

[0286] The organic electroluminescent device comprises a cathode, an anode and at least one light-emitting layer. In addition to these layers, it may also include other 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. An intermediate layer having, for example, an exciton blocking function may also be introduced between the two light-emitting layers. However, it should be noted that each of these layers does not necessarily have to be present. In this case, the organic electroluminescent device may contain one light-emitting layer, or it may contain multiple light-emitting layers. If there are multiple light-emitting layers, these light-emitting layers preferably have a total of multiple light-emitting peaks between 380nm and 750nm so that the overall result is white light emission; in other words, a variety of light-emitting compounds that can emit fluorescence or phosphorescence are used in the light-emitting layer. A system with three light-emitting layers is particularly preferred, wherein the three layers exhibit blue, green and orange or red light emission. The organic electroluminescent device of the present invention may also be a tandem electroluminescent device, in particular a white light-emitting OLED.

[0287] Depending on the precise structure, the compounds according to the invention can be used in different layers. Preference is given to organic electroluminescent devices which comprise the compounds of the formula (I) or the compounds of the preferred embodiments described above as emitters, preferably red, green or blue emitters, in the emitting layer.

[0288] When the compounds according to the invention are employed as emitters in an emitting layer, preference is given to using suitable matrix materials known per se.

[0289] Preferred mixtures of the compounds according to the invention and matrix material contain from 99% to 1% by volume, preferably from 98% to 10% by volume, more preferably from 97% to 60% by volume and in particular from 95% to 80% by volume of matrix material, based on the total mixture of emitter and matrix material. Correspondingly, the mixture contains from 1% to 99% by volume, preferably from 2% to 90% by volume, more preferably from 3% to 40% by volume and in particular from 5% to 20% by volume of emitter, based on the total mixture of emitter and matrix material.

[0290] Suitable matrix materials that can be used in combination with 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-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or WO 2013 / 041176; indolocarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746; indenocarbazole derivatives, for example according to WO 2010 / 136109, WO 2011 / 000455, WO 2013 / 041176 or WO 2013 / 056776; azacarbazole derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160; bipolar matrix materials, for example according to WO 2007 / 137725; silanes, for example according to WO 2005 / 111172; borazolidines or boric acid esters, for example according to WO 2006 / 117052; triazine derivatives, for example according to WO 2007 / 063754, WO 2008 / 056746, WO 2010 / 015306, WO 2011 / 057706, WO 2011 / 060859 or WO 2011 / 060877; zinc complexes, for example according to EP 652273 or WO 2009 / 062578; siladiazacyclopentaine or silatetraazacyclopentaine derivatives, for example according to WO 2010 / 054729; phosphadiazacyclopentaine 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; dibenzofuran derivatives, for example according to WO 2015 / 169412, WO 2016 / 015810, WO 2016 / 023608, WO 2017 / 148564 or WO 2017 / 148565; or bicarbazoles, for example according to JP 3139321 B2.

[0291] Furthermore, the co-host used may be a compound that, even if it participates in charge transport, does not participate to a significant extent, as described, for example, in WO 2010 / 108579. Particularly suitable co-host materials for combination with the compounds of the present invention are compounds that have a large band gap and, even if they participate in charge transport in the light-emitting layer, do not participate 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.

[0292] In a preferred configuration, the compounds of the invention used as emitters are preferably used in combination with one or more phosphorescent materials (triplet emitters) and / or compounds serving as TADF (thermally activated delayed fluorescence) host materials. Preferably, superfluorescent and / or superphosphorescent systems are formed.

[0293] WO 2015 / 091716 A1 and WO 2016 / 193243 A1 disclose OLEDs containing both a phosphorescent compound and a fluorescent emitter in the light-emitting layer, wherein energy is transferred from the phosphorescent compound to the fluorescent emitter (superphosphorescence). In this case, the phosphorescent compound thus acts as a host material. As is known to those skilled in the art, the host material has higher singlet and triplet energies than the emitter, so that energy from the host material can also be transferred to the emitter with maximum efficiency. The systems disclosed in the prior art exhibit precisely this energy relationship.

[0294] In the context of the present invention, phosphorescence is understood to mean the emission of light from excited states with a high spin multiplicity, i.e. spin states > 1, in particular from excited triplet states. In the context of this application, all luminescent complexes containing transition metals or lanthanides, in particular all iridium, platinum and copper complexes, are to be regarded as phosphorescent compounds.

[0295] Suitable phosphorescent compounds (=triplet emitters) are, in particular, compounds which emit light upon appropriate excitation, preferably in the visible region, and which furthermore contain at least one atom, in particular a metal, having an atomic number greater than 20, preferably greater than 38 and less than 84, more preferably greater than 56 and less than 80. Preferably used phosphorescent emitters are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or platinum.

[0296] Examples of such emitters may be found in the following applications: WO 00 / 70655, WO 2001 / 41512, WO 2002 / 02714, WO 2002 / 15645, EP 1191613, EP 1191612, EP 1191614, WO 05 / 033244, WO 05 / 019373, US 2005 / 0258742, WO 2009 / 146770, WO 2010 / 015307, WO 2010 / 031485, WO 2010 / 054731, WO 2010 / 054728, WO 2010 / 086089, WO 2010 / 099852, WO 2010 / 102709, WO 2011 / 032626、WO 2011 / 066898、WO 2011 / 157339、WO 2012 / 007086、WO 2014 / 008982、WO 2014 / 023377、WO 2014 / 094961、WO 2014 / 094960、WO 2015 / 036074、WO 2015 / 104045、WO 2015 / 117718、WO 2016 / 015815、WO 2016 / 124304、WO 2017 / 032439、WO 2018 / 011186、WO 2018 / 001990、WO 2018 / 019687、WO 2018 / 019688, WO 2018 / 041769, WO 2018 / 054798, WO 2018 / 069196, WO 2018 / 069197, WO 2018 / 069273, WO 2018 / 178001, WO 2018 / 177981, WO 2019 / 020538, WO 2019 / 115423, WO 2019 / 158453 and WO 2019 / 179909. In general, all phosphorescent complexes used in phosphorescent electroluminescent devices according to the prior art and known to the person skilled in the art in the field of organic electroluminescence are suitable, and the person skilled in the art will be able to use other phosphorescent complexes without inventive step.

[0297] As mentioned above, the compounds of the present invention can preferably be used in combination with a TADF host material and / or a TADF emitter.

[0298] For example, BHUoyama et al., Nature 2012, Vol. 492, 234, describe a method called thermally activated delayed fluorescence (TADF). To achieve this method, a wavelength of less than about 2000 cm is required in the luminophore. -1In order to open the spin-forbidden T1→S1 transition and the emitter, other compounds with strong spin-orbit coupling can be provided in the matrix, so that intersystem crossing can be achieved due to spatial proximity and the resulting interactions between molecules, or other spin-orbit coupled compounds can be generated with the help of metal atoms present in the emitter.

[0299] In another embodiment of the present invention, the organic electroluminescent device according to 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, meaning that the light-emitting layer is directly adjacent to the hole injection layer or the anode, and / or the light-emitting layer is directly adjacent to the electron transport layer or the electron injection layer or the cathode, as described, for example, in WO 2005 / 053051. In addition, a metal complex identical or similar to the metal complex in the light-emitting layer can be used as a hole transport or hole injection material directly adjacent to the light-emitting layer, as described, for example, in WO 2009 / 030981.

[0300] Also preferred is an organic electroluminescent device comprising a compound of formula (I), (Ia) or the above preferred embodiments as a hole-conducting material in a hole-conducting layer. 1 is N and Z 2 , Z 3 , Z 4 , Z 5 Compounds wherein at least one, preferably two, of the groups are N. In addition, Z is particularly preferred. 2 , Z 3 At least one, preferably two, of the groups are N and Z 4 , Z 5 Compounds wherein at least one, preferably two, of the groups are N.

[0301] Also preferred is an organic electroluminescent device comprising a compound of formula (I), (Ia) or the above preferred embodiments as an electron transport material in the electron conducting layer. 1 is B and Z 2 , Z 3 , Z 4 , Z 5 Compounds wherein at least one, preferably two, of the groups are B. In addition, Z is particularly preferred 2 , Z 3 At least one, preferably two, of the groups are B and Z 4 , Z 5 Compounds in which at least one, preferably two, of the groups are B.

[0302] In the other layers of the organic electroluminescent device of the present invention, any material commonly used according to the prior art can be used. Therefore, those skilled in the art will be able to use any material known for organic electroluminescent devices in combination with the compounds of the present invention of formula (I) or the above-mentioned preferred embodiments without inventive effort.

[0303] Furthermore, an organic electroluminescent device is preferred, characterized in that one or more layers are applied by a sublimation process. In this case, the organic electroluminescent device is applied by sublimation in a vacuum sublimation system at a temperature below 10 -5 mbar, preferably below 10 -6 The material is applied by vapor deposition at an initial pressure of 10 mbar. However, the initial pressure can also be even lower, for example below 10 -7 millibar.

[0304] Likewise preferred is an organic electroluminescent device, 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 between mbar and 1 bar. A special example of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly via a nozzle and thus structured.

[0305] Furthermore, preference is given to an organic electroluminescent device, characterized in that one or more layers are produced from solution, for example by spin coating, or by any printing method, for example screen printing, flexographic printing, offset printing, LITI (light-induced thermography, thermal transfer printing), inkjet printing or nozzle printing. For this purpose, soluble compounds, obtained for example by suitable substitution, are required.

[0306] The formulations for applying compounds of formula (I) or the preferred embodiments thereof described above are novel. Therefore, the present invention also provides formulations containing at least one solvent and a compound according to formula (I) and / or (Ia) or the preferred embodiments thereof described above.

[0307] Furthermore, hybrid processes are possible, in which one or more layers are applied, for example, from solution and one or more other layers are applied by vapor deposition.

[0308] The person skilled in the art is generally aware of these processes and can apply them without inventive step to organic electroluminescent devices comprising the compounds according to the invention.

[0309] Compared to the prior art, the compounds of the present invention and the organic electroluminescent devices of the present invention have the specific feature of an improved lifespan. At the same time, other electronic properties of the electroluminescent device, such as efficiency or operating voltage, remain at least equally good. In another variant, compared to the prior art, the compounds of the present invention and the organic electroluminescent devices of the present invention are particularly characterized by improved efficiency and / or operating voltage and a longer lifespan.

[0310] Compared to the prior art, the electronic devices, in particular the organic electroluminescent devices, of the present invention are noteworthy for one or more of the following surprising advantages:

[0311] 1. An electronic device, in particular an organic electroluminescent device, comprising a compound of the formula (I) and / or (Ia) or a preferred embodiment as described above and below as an emitter, which has a very narrow emission band with a low full width half maximum (FWHM) value and leads to a particularly pure color emission that can be recognized by a low CIE y value. Particularly surprising here is that a blue emitter with a low FWHM value and an emitter with a low FWHM that emits in the green, yellow or red region of the color spectrum are provided.

[0312] 2. Electronic devices, in particular organic electroluminescent devices, comprising compounds of formula (I) and / or (Ia) or the preferred embodiments described above and below, especially as emitters, hole-conducting materials and / or electron-transporting materials, have very good lifetimes. In this case, these compounds lead in particular to low roll-off, i.e., the power efficiency of the device decreases only slightly at high brightness.

[0313] 3. Electronic devices, in particular organic electroluminescent devices, comprising compounds of formula (I) and / or (Ia) or preferred embodiments as described above and below as emitters, hole-conducting materials and / or electron-transporting materials, having excellent efficiency. In this case, the compounds of the invention having the structures or preferred embodiments of formula (I) and / or (Ia) as described above and below result in low operating voltages when used in electronic devices.

[0314] 4. The compounds of the present invention of formula (I) and / or (Ia) or preferred embodiments described above and below exhibit very high stability and longevity.

[0315] 5. The compounds of formula (I) and / or (Ia) or the preferred embodiments described above and below can be used to avoid the formation of light loss channels in electronic devices, in particular organic electroluminescent devices. These devices are therefore characterized by a high PL efficiency of the emitter and, consequently, a high EL efficiency, as well as excellent energy transfer from the host to the dopant.

[0316] 6. The compounds of the formula (I) and / or (Ia) or the preferred embodiments described above and below have excellent glass film formation.

[0317] 7. The compounds of formula (I) and / or (Ia) or the preferred embodiments described above and below form excellent films from solution and show excellent solubility.

[0318] These aforementioned advantages are not accompanied by excessive degradation of other electronic properties.

[0319] It should be noted that the scope of the present invention encompasses variations of the embodiments described herein. Unless expressly excluded, any feature disclosed herein can be interchanged with an alternative feature serving the same purpose or an equivalent or similar purpose. Therefore, unless otherwise stated, any feature disclosed herein should be considered an example of a general series or an equivalent or similar feature.

[0320] 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 (rather than in combination).

[0321] It should also be noted that many features, especially those of the preferred embodiments of the invention, should be considered inventive in themselves and should not be regarded as just some embodiments of the invention and can seek independent protection as a supplement to or alternative to any presently claimed invention.

[0322] The technical teachings disclosed in the present invention can be extracted and combined with other embodiments.

[0323] The following examples illustrate the present invention in more detail without intending to limit the invention thereby. Those skilled in the art will be able to use the information provided to implement the present invention within the entire disclosed range without inventive effort, as well as to prepare other compounds of the present invention and use them in electronic devices, or employ the methods of the present invention without inventive effort. Example:

[0324] Unless otherwise stated, the following syntheses were performed in dry solvents under a protective gas atmosphere. Metal complexes were also handled in the dark or under yellow light. 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 refer to the CAS numbers of the compounds known from the literature. Where a compound can have multiple enantiomers, diastereomers or tautomer forms, one form is shown in a representative manner.

[0325] Synthesis of synthon S:

[0326] Example S1:

[0327]

[0328] According to W. Wu et al., Frontiers in Organic Chemistry, 2019, 6(13), 2200, indole [120-72-9] and 2-iodo-4,6-dimethylaniline [4102-54-9] were used to prepare the product with a yield of 64% and a purity of about 95%. 1 H NMR.

[0329] The following compounds can be prepared similarly:

[0330]

[0331]

[0332]

[0333] Example S10:

[0334]

[0335] Prepared according to page 62 of US2019 / 0252623. Using S1 instead of compound A, the procedure of steps 1 to 3, yield: 38%; purity: about 95%, by 1 H NMR.

[0336] The following compounds can be prepared similarly:

[0337]

[0338]

[0339]

[0340] Example S100:

[0341]

[0342] A mixture of 22.7 g (110 mmol) of 10H-indolo[1,2-a]benzimidazole [2345630-10-4], 11.3 g (50 mmol) of 1-bromo-2,3-dichlorobenzene [56691-77-4], 12.5 g (130 mmol) of sodium tert-butoxide [865-48-5], 354 mg (0.5 mmol) (amphos)2PdCl2 [887919-35-9] and 200 ml of o-xylene was stirred at 80° C. for 3 hours and then at 130° C. for 6 hours. After cooling, the mixture was admixed with 500 ml of ethyl acetate and 500 ml of water, the organic phase was removed, washed once with 500 ml of water and twice with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The mixture was filtered as an ethyl acetate slurry through a silica gel bed, the filtrate was concentrated to dryness, the residue was boiled with 300 ml of ethanol, the solid was filtered off with suction, the solid was washed twice with 50 ml of ethanol, dried under reduced pressure and recrystallized from dichloromethane / acetonitrile. Yield: 15.2 g (29 mmol) 58%; purity about 95%, by 1 H NMR.

[0343] The following compounds can be prepared similarly:

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350] Example, dopants D100A, D100B, and D100C:

[0351] Step 1: Lithiation of S100

[0352]

[0353] A calcined, argon-inertized four-necked flask equipped with a magnetic stirring bar, a dropping funnel, a water separator, a reflux condenser, and an argon blanket was charged with 26.1 g (50 mmol) of S100 and 200 ml of tert-butylbenzene and cooled to -40°C. 64.7 ml (110 mmol) of tert-butyllithium (1.7 M solution in n-pentane) was added dropwise to the mixture over 10 minutes. The reaction mixture was allowed to warm to room temperature and stirred at 60°C for a further 3 hours, during which time n-pentane was distilled off through the water separator.

[0354] Step 2: Transmetallation and Cyclization

[0355]

[0356]

[0357] The reaction mixture was cooled back to -40°C. 5.7 ml (60 mmol) of boron tribromide were added dropwise over a period of about 10 minutes. After the addition was complete, the reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then cooled to 0°C and 21.0 ml (120 mmol) of diisopropylethylamine were added dropwise over a period of about 30 minutes. The reaction mixture was then stirred at 130°C for 5 hours. After cooling, the mixture was diluted with 500 ml of toluene, hydrolyzed by adding 300 ml of a 10 wt% aqueous solution of potassium acetate, the organic phase was removed and concentrated to dryness under reduced pressure. The oily residue was absorbed into the and filtered hot through a silica gel bed with an n-pentane-DCM mixture (10:1). The filtrate is concentrated to dryness. The residue is subjected to flash chromatography (silica gel, n-heptane / ethyl acetate, gradient, Torrent automated column system from A. Semrau), thereby separating the three isomeric dopants D100A, D100B and D100C. Each individual dopant can be further purified again by flash chromatography. Further purification is achieved by repeated hot extractive crystallization with a DCM / acetonitrile mixture and final fractional sublimation or reduced pressure heat treatment. Yield: D100A: 1.98 g (4.0 mmol) 8%, D100B: 4.60 g (9.3 mmol) 19%, D100C: 3.56 g (7.2 mmol) 14%; purity about 99.9%, by 1 H NMR.

[0358] The following compounds can be prepared similarly:

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367] Example, dopant D200A

[0368]

[0369] Prepared from D100A by rapid vacuum pyrolysis, carrier gas: argon, reduced pressure of about 10 -2 Torr, pyrolysis zone temperature 600°C, catalyst: 5% PdO / alumina. Yield 25%.

[0370] Example, dopant D215C

[0371]

[0372] Prepared from D115C by rapid vacuum pyrolysis, carrier gas: argon, reduced pressure of about 10 -2 Torr, pyrolysis zone temperature 550°C, catalyst: 5% PdO / alumina. Yield 30%.

[0373] Vacuum-processed OLED device fabrication:

[0374] The OLEDs according to the invention and OLEDs according to the prior art were produced by the general method according to WO 2004 / 058911, which was adapted to the cases described here (varying layer thicknesses, materials used).

[0375] In the following examples, the results of various OLEDs are presented. A clean glass plate (cleaned in a Miele laboratory glass washer, Merck Extran cleaner) coated with structured ITO (indium tin oxide) with a thickness of 50 nm was pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and, within 30 minutes, coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) as CLEVIOS in order to improve processing. TMP VP AI4083 was purchased from Heraeus Precious Metals GmbH Deutschland and was spin-coated from aqueous solution and then baked for 10 minutes at 180° C. These coated glass plates formed the substrate to which the OLEDs were applied.

[0376] The OLEDs essentially have the following layer structure: substrate / hole injection layer 1 (HIL1), consisting of Ref-HTM1 (commercially available from Novaled) doped with 5% NDP-9, 20 nm / hole transport layer 1 (HTL1), comprising: 150 nm HTM1 for UV and blue OLEDs; 50 nm for green and yellow OLEDs; 110 nm for red OLEDs / hole transport layer 2 (HTL2), comprising: 10 nm for blue OLEDs; 20 nm for green and yellow OLEDs; 10 nm for red OLEDs / emission layer (EML), comprising: 25 nm for blue OLEDs; 40 nm for green and yellow OLEDs; 35 nm for red OLEDs / hole blocking layer (HBL), 10 nm / electron transport layer (ETL), 30 nm / electron injection layer (EIL), comprising 1 nm ETM2 / and finally a cathode, which is formed from a 100 nm thick aluminum layer.

[0377] First, vacuum-processed OLEDs are described. For this purpose, all materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the light-emitting layer always consists of at least one matrix material (host material) and a luminescent dopant (luminophor) added to the matrix material in a specific volume ratio by co-evaporation. Details given in the form of SMB1:D1 (95:5%) mean here that the material SMB1 is present in the layer in a volume ratio of 95% and D1 is present in the layer in a ratio of 5%. Similarly, the electron transport layer can also consist of a mixture of two materials. The exact structure of the OLED can be seen in Table 1. The materials used to produce the OLED are shown in Table 3.

[0378] The OLEDs were characterized in a standard manner. For this purpose, the electroluminescence spectrum, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in percentage) were calculated as a function of the luminous density from the current-voltage-luminous density characteristic line (IUL characteristic line) exhibiting Lambertian luminescence. The luminous efficiency at 1000 cd / m 2 The electroluminescence spectra at the luminous density were calculated and these were used to infer the emission color and EL-FWHM values ​​(electroluminescence full width at half maximum, i.e. the width of the EL emission spectrum at half the peak height, in eV; for better comparability across the entire spectral range).

[0379] Use of the compound of the present invention as OLED material

[0380] One use of the compounds of the invention is as dopants in the light-emitting layer of OLEDs. Compound D-Ref.1 according to Table 3 was used as a comparison according to the prior art. The results for the OLEDs are summarized in Table 2.

[0381] Table 1: Structure of OLED

[0382]

[0383]

[0384]

[0385] Table 2: Results for vacuum processed OLEDs

[0386]

[0387]

[0388] Table 3: Structural formulas of the materials used

[0389]

[0390]

[0391] The A-type regioisomers of the compounds of the present invention enable blue and deep-blue OLEDs to be produced with improved efficiency and operating voltage, resulting in components with improved power efficiency. Furthermore, deep-blue OLEDs with an emission peak below approximately 440 nm cannot be produced using compounds according to the prior art. Furthermore, the A-type regioisomers of the compounds of the present invention are notable for having an emission spectrum with an extremely small EL-FWHM (full width at half maximum) of electroluminescence, which results in extremely pure emission colors and, therefore, excellent CIE X and Y values.

[0392] Furthermore, the C-type regioisomers of the compounds according to the invention are notable for their emission spectra with extremely small EL-FWHM (full width at half maximum) values, which results in extremely pure emission colors and, therefore, excellent CIE X and Y values. This allows not only the blue but also the green and yellow spectral ranges to be reached. The high EQE values ​​at reduced operating voltages result in components with excellent power efficiency.

[0393] The B-type regioisomers of the compounds of the present invention show improved efficiency and operating voltage. In addition, green, yellow and red components can be obtained with these compounds.

Claims

1. A compound comprising at least one structure of formula (IIa), (IIb), (IIc), (IId) or (IIe), The symbols used are as follows: Z 1 It is B; Z 2 、Z 3 、Z 4 、Z 5 is N; W 5 、W 6 、W 7 、W 8 are the same or different in each case and are C(Ar) or X 6 ; 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 here may be combined with at least one Ar, X 1 , R group or another group to form a ring system; X 1 In each case the same or different and N, CR a , or if by with the ring Ar c 、Ar d One or more of the groups form a ring system, then X 1 is C, provided that there is an X in a ring 1 、X 2 No more than two of the groups are N; X 2 Same or different in each case and either N or CR b , provided that X is in a ring 1 、X 2 No more than two of the groups are N; X 3 Same or different in each case and either N or CR c , provided that X is in a ring 3 、X 5 No more than two of the groups are N; X 4 Same or different in each case and either N or CR d , provided that X is in a ring 4 、X 6 No more than two of the groups are N; X 5 In each case the same or different and N, CR e , or if by the Ar group or X 5 Group or X 6 The bonds of the groups form a ring system, then X 5 is C, provided that there is an X in a ring 3 、X 5 No more than two of the groups are N; X 6 In each case the same or different and N, CR f , or if by the Ar group or X 5 Group or X 6 The bonds of the groups form a ring system, then X 6 is C, provided that there is an X in a ring 4 、X 6 No more than two of the groups are N; R, R a 、R b are identical or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)OAr′,C(=O)OR 1 ,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 linear 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 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 substituted aryloxy or heteroaryloxy groups; at the same time, two R, R a 、R b The groups may also form a ring system together or with another group; R c 、R d 、R e 、R f are identical or different in each case and are H, D, OH, F, Cl, Br, I, CN, NO2, N(Ar')2, N(R 1 )2,C(=O)OAr′,C(=O)OR 1 ,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 linear 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 ), -O-, -S-, SO or SO2, or having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 1 substituted aryloxy or heteroaryloxy groups; at the same time, the two R c 、R d 、R e 、R f The groups may also form a ring system together or with another group; Ar' is identical or different in each case and is an aromatic ring having 5 to 60 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 can also be connected by a bridging group through a single bond or selected from B(R 1 )、C(R 1 )2、Si(R 1 )2. C=O, C=NR 1 、C=C(R 1 )2, O, S, S=O, SO2, N(R 1 )、P(R 1 ) and P(=O)R 1 The bridging base is connected together; R 1 are identical or different in each case and are H, D, F, Cl, Br, I, CN, NO2, N(Ar")2, N(R 2 )2, C(=O)OAr”, C(=O)OR 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, or 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 replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 an aryloxy or heteroaryloxy group substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 substituted arylalkyl or heteroarylalkyl groups, or combinations of these systems; at the same time, two or more R 1 The groups may together form a ring system; at the same time, one or more R 1 The group may form a ring system with another part of the compound; Ar" are identical or different in each case and are aromatic rings 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 can also be connected by a bridging group through a single bond or selected from B(R 2 )、C(R 2 )2、Si(R 2 )2. C=O, C=NR 2 、C=C(R 2 )2, O, S, S=O, SO2, N(R 2 )、P(R 2 ) and P(=O)R 2 The bridging base is connected together; R 2 are identical or different in each case 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, wherein one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and the aromatic or heteroaromatic ring system may be substituted by one or more alkyl radicals, each of which has 1 to 4 carbon atoms; at the same time, two or more substituents R 2 Together they can form a ring system.

2. The compound according to claim 1, comprising at least one structure of formula (III-1) to (III-25): The symbol Z 1 , Z 2 , Z 3 、X 1 、X 2 , Z 4 , Z 5 、X 3 、X 4 、X 5 and X 6 has the definitions given in claim 1, and the other symbols are defined as follows: p is 0 or 1, Y 1 are in each case identical or different and are a bond, N(Ar′), N(R), P(Ar′), P(R), P(═O)Ar′, P(═O)R, P(═S)Ar′, P(═S)R, B(Ar′), B(R), Al(Ar′), Al(R), Ga(Ar′), Ga(R), C═O, C(R) 2 , Si(R) 2 , C═NR, C═NAr′, C═C(R) 2 , O, S, Se, S═O or SO 2 , where the symbols R and Ar′ have the definitions given in claim 1 ; Y 2 、Y 3 、Y 4 are in each case identical or different and are N(Ar'), N(R), P(Ar'), P(R), P(=O)Ar', P(=O)R, P(=S)Ar', P(=S)R, B(Ar'), B(R), Al(Ar'), Al(R), Ga(Ar'), Ga(R), C=O, C(R)2, Si(R)2, C=NR, C=NAr', C=C(R)2, O, S, Se, S=O or SO2, where the symbols R and Ar' have the definitions given in claim 1.

3. The compound according to claim 1 or 2, comprising at least one structure of formula (IV-1) to (IV-38): The symbol Z 1 , Z 2 , Z 3 、R a 、R b , Z 4 , Z 5 、R c 、R d 、R e and R f Has the definition given in claim 1, symbol Y 1 、Y 2 、Y 3 and Y 4 has the definitions given in claim 2, and the other symbols are defined as follows: m is 0, 1, 2, 3, or 4; n is 0, 1, 2, or 3; j is 0, 1, or 2; k is 0 or 1.

4. The compound according to claim 1 or 2, characterized in that At least two R, R a 、R b 、R c 、R d 、R e 、R f The group and two R, R a 、R b 、R c 、R d 、R e 、R f The other groups to which the group is combined together form a fused ring, wherein the two R, R a 、R b 、R c 、R d 、R e 、R f The groups form at least one structure of formula (RA-1) to (RA-12): where R 1 With the above definitions, the dotted bond represents the two R, R a 、R b 、R c 、R d 、R e 、R f The attachment site of the atom of the group to which the group is bound, and other symbols have the following definitions: Y 5 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; R g are identical or different in each case and are F, a linear 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 2 group, wherein one or more 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 having 5 to 60 aromatic ring atoms and in each case may be replaced by one or more R 2 An aromatic or heteroaromatic ring system substituted with a group, or having 5 to 60 aromatic ring atoms and substituted by one or more R 2 substituted aryloxy or heteroaryloxy; at the same time, the two R g The groups can also be combined or one R g Group with an R 1 The groups together or together with other groups form a ring system; s is 0, 1, 2, 3, 4, 5, or 6; t is 0, 1, 2, 3, 4, 5, 6, 7, or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

5. The compound according to claim 1 or 2, characterized in that At least two R, R a 、R b 、R c 、R d 、R e 、R f The group and two R, R a 、R b 、R c 、R d 、R e 、R f The other groups to which the group is combined together form a fused ring, wherein the two R, R a 、R b 、R c 、R d 、R e 、R f The structure of the group forming formula (RB): where R 1 Has the definition given in claim 1, and the dotted key represents the two R, R a 、R b 、R c 、R d 、R e 、R f The attachment site to which the group is attached, the subscript m is 0, 1, 2, 3 or 4, and Y 6 It is C(R 1 )2、NR 1 、NAr'、BR 1 , BAr', O or S.

6. The compound according to claim 1 or 2, comprising at least one structure of formula (V-1) to (V-10), wherein the compound has at least one fused ring, The symbol Z 1 , Z 2 , Z 3 、R a 、R b , Z 4 , Z 5 、R c 、R d 、R e and R f Has the definition given in claim 1, symbol Y 3 and Y 4 Having the definitions given in claim 2, the symbol o represents the attachment site, and the other symbols are defined as follows: m is 0, 1, 2, 3, or 4; n is 0, 1, 2, or 3; j is 0, 1, or 2.

7. The compound according to claim 1 or 2, comprising at least one structure of formula (VI-1) to (VI-9), wherein the compound has at least one fused ring, The symbol Z 1 , Z 2 , Z 3 、R a 、R b , Z 4 , Z 5 、R c 、R d 、R e and R f Has the definition given in claim 1, symbol Y 3 and Y 4 Having the definitions given in claim 2, the symbol o represents the attachment site, and the other symbols are defined as follows: m is 0, 1, 2, 3, or 4; n is 0, 1, 2, or 3; j is 0, 1, or 2.

8. The compound according to claim 1 or 2, comprising at least one structure of formula (VII-1) to (VII-9), wherein the compound has at least one fused ring, The symbol Z 1 , Z 2 , Z 3 、R a 、R b , Z 4 , Z 5 、R c 、R d 、R e and R f Has the definition given in claim 1, symbol Y 3 and Y 4 Having the definitions given in claim 2, the symbol o represents the attachment site, and the other symbols are defined as follows: m is 0, 1, 2, 3, or 4; n is 0, 1, 2, or 3; j is 0, 1, or 2.

9. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 8, wherein one or more bonds of said compounds to said polymer, oligomer or dendrimer are present instead of hydrogen atoms or substituents.

10. A preparation comprising at least one compound according to any one of claims 1 to 8 or an oligomer, polymer or dendrimer according to claim 9 and at least one further compound.

11. A composition comprising at least one compound according to any one of claims 1 to 8 or an oligomer, polymer or dendrimer according to claim 9 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters exhibiting TADF, host materials, electron transport materials, electron injection materials, hole conducting materials, hole injection materials, electron blocking materials and hole blocking materials.

12. A method for preparing a compound according to any one of claims 1 to 8, characterized in that Synthesis with Z 2 , Z 3 At least one of the groups or Z 2 , Z 3 The basic skeleton of the precursor of one of the groups is introduced by metallation reaction, aromatic nucleophilic substitution reaction or coupling reaction. 1 group.

13. Use of a compound according to any one of claims 1 to 8 or an oligomer, polymer or dendrimer according to claim 9 in an electronic device.

14. An electronic device comprising at least one compound according to any one of claims 1 to 8 or an oligomer, polymer or dendrimer according to claim 9.

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