KR20190114018A - Spirobifluorene compounds for organic electroluminescent devices - Google Patents

Abstract

The present invention relates to compounds of formula (1) suitable for use in electronic devices, in particular organic electroluminescent devices, and electronic devices comprising such compounds.

Description

Spirobifluorene compounds for organic electroluminescent devices {SPIROBIFLUORENE COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT DEVICES}

The present invention relates to materials for use in electronic devices, in particular organic electroluminescent devices, and electronic devices comprising such materials.

The structure of an organic electroluminescent device (OLED) in which an organic semiconductor is used as a functional material is described, for example, in US 4,539,507, US 5,151,629, EP 0676461 and WO 98/27136. Radioactive materials used here are increasingly organo-metallic complexes that display phosphorescence instead of fluorescence (see M. A. Baldo et al., Appl. Phys. Lett. 1999 , 75, 4-6).

According to the prior art, the hole-transport material used in the hole-transport layer or the hole-injection layer is in particular a triaryl-amine which frequently contains at least two triarylamino groups or at least one triarylamino group and at least one carbazole group. Such compounds are often derived from diarylamino-substituted triphenyl-amines (TPA type), diarylamino-substituted biphenyl derivatives (TAD type) or combinations of these base compounds. Also used are spirobifluorene derivatives substituted at the 2,7- or 2,2 ', 7,7'-position, for example by 2 or 4 diarylamino groups (for example EP 676461 or US). According to 7,714,145). Also known are spirobifluorene derivatives which in each case are substituted at the 4,4'-position by diphenylamino groups. In the case of such compounds, improvements are needed, both in the case of fluorescent and phosphorescent OLEDs, in terms of efficiency, lifetime and operating voltage, when used in organic electroluminescent devices.

It is an object of the present invention to provide compounds suitable for use in fluorescent or phosphorescent OLEDs, in particular phosphorescent OLEDs, for example as hole-transport materials in hole-transport or exciton-blocking layers or as matrix materials in emissive layers.

Surprisingly, it has been found that certain compounds, described in more detail below, achieve this goal and yield significant improvements in life, efficiency and operating voltage, especially in organic electroluminescent devices. This applies in particular to phosphorescent and fluorescent electroluminescent devices in the use of the compounds according to the invention as hole-transport materials or matrix materials. The materials generally have high thermal stability and can therefore be sublimed without decomposition and residues. Accordingly, the present invention relates to electronic devices comprising such materials and compounds of this type.

In particular, it is surprisingly surprising that very good results are also obtained using aromatic monoamines, especially since hole-transport materials containing at least two nitrogen atoms are generally used in organic electroluminescent devices.

The present invention therefore relates to compounds of the formula (1)

[Wherein the following applies to symbols and exponents used:

Ar ¹ is the same or different at each occurrence, having 6 to 60 carbon atoms selected from the group consisting of fluorene, spirobifluorene, biphenyl, terphenyl, quarterphenyl, carbazole, dibenzofuran and dibenzothiophene Aromatic or heteroaromatic ring systems, each of which may also be substituted with one or more radicals R ⁵ ; Wherein Ar ¹ and Ar ² may also be connected to each other by a group E;

Ar ² is the same or different at each occurrence, an aromatic or heteroaromatic ring system having 6 to 60 carbon atoms, which in each case may also be substituted by one or more radicals R ⁵ ; Ar ¹ and Ar ² here may also be connected to one another by the group E;

Ar ^S is the same or different at each instance, an aromatic or heteroaromatic ring system having 6 to 60 carbon atoms, which in each case may also be substituted with one or more radicals R ⁵ ;

E is the same or different at each occurrence, a single bond, C (R ⁵ ) ₂ , NR ⁵ , O or S;

R ¹ , R ² , R ³ , R ⁴ are the same or different at each occurrence, H, D, F, Cl, Br, I, CN, Si (R ⁶ ) ₃ , linear alkyl of 1 to 40 carbon atoms, alkoxy Or a thioalkyl group or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms, each of which may be substituted by one or more radicals R ⁶ , in which case at least one non-adjacent CH ₂ group is Si (R ⁶ ) ₂ , C = NR ⁶ , P (= O) (R ⁶ ), SO, SO ₂ , NR ⁶ , O, S or CONR ⁶ and at least one H atom may be D, F, Cl , May be substituted with Br or I), aromatic or heteroaromatic ring system having 6 to 60 carbon atoms, which may in each case be substituted by one or more radicals R ⁶ , aryl having 5 to 60 aromatic ring atoms aryloxy or heteroaryloxy group having an aralkyl (which may be substituted by one or more radicals that R ^6), or from 5 to 60 ring atoms Kill or heterocyclic aralkyl group is selected from the group consisting of (which may be substituted by one or more radicals R ⁶ in each case), where the substituent two or more adjacent R ¹ or R ² or R ³ or R ⁴ are optionally mono- or Can form poly-cyclic, aliphatic ring systems, which may be substituted with one or more radicals R ⁶ ;

R ⁵ is the same or different at each occurrence, H, D, F, Cl, Br, I, CN, Si (R ⁶ ) ₃ , a straight chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or 3 to 40 carbon atoms Branched or cyclic alkyl, alkoxy or thioalkyl groups of each of which may be substituted by one or more radicals R ⁶ , where in each case one or more non-adjacent CH ₂ groups are Si (R ⁶ ) ₂ , C═NR ⁶ , P (= 0) (R ⁶ ), SO, SO ₂ , NR ⁶ , O, S or CONR ⁶ , and one or more H atoms can be replaced with D, F, Cl, Br or I ), Aromatic or heteroaromatic ring systems having 6 to 60 carbon atoms, which in each case may be substituted by one or more radicals R ⁶ , aryloxy or heteroaryloxy groups having 5 to 60 aromatic ring atoms may be substituted by one or more radicals R ⁶ Yes), or aralkyl or H. having 5 to 60 aromatic ring atoms Loa Le alkyl group is selected from the group consisting of a (which may be substituted with one or more radicals R ⁶ in each case), in which two or more adjacent substituents R ⁵ are optionally mono-or polycyclic, aliphatic ring system (which is one or more radicals May be substituted with R ⁶ );

R ⁶ is selected from the group consisting of H, D, F, aliphatic hydrocarbon radicals of 1 to 20 carbon atoms or aromatic or heteroaromatic ring systems of 5 to 30 carbon atoms, where one or more H atoms may be replaced by D or F Wherein two or more adjacent substituents R ⁶ may form a mono- or polycyclic, aliphatic ring system with one another;

i is equal or different at each occurrence, 0 or 1;

m is 0, 1 or 2;

n is the same or different at each occurrence, 0, 1, 2, 3 or 4;

p, q are the same or different at each occurrence, 0 or 1;

r, s are the same or different in each case 0, 1, 2, 3 or 4, where p + r <4 and q + s <4;

The invention also relates to compounds of formula (1), except that the following definitions apply to groups Ar ¹ and Ar ² instead of the above definitions:

Groups Ar ¹ and Ar ² are connected to one another via group E as defined above,

The groups Ar ¹ and Ar ² in each case are the same or differently aromatic or heteroaromatic ring systems having 6 to 60 carbon atoms, which in each case may also be substituted with one or more radicals R ⁵ .

An aryl group in the sense of the present invention means a simple aromatic ring, ie a benzene, or a condensed (anellate) aryl group, for example naphthalene or phenanthrene. In contrast, aromatic rings connected to each other by a single bond, for example biphenyl or fluorene, are not represented by aryl groups but instead by aromatic ring systems.

Heteroaryl groups in the sense of the present invention comprise at least one heteroatom in the aromatic ring, preferably a heteroatom selected from N, O and S. Heteroaryl groups can include simple heteroaromatic rings such as pyridine, triazine or thiophene, or they can be condensed (annelate) heteroaryl groups such as quinoline or carbazole.

In the sense of the present invention an aromatic ring system contains 6 to 60 carbon atoms in the ring system, wherein the aromatic ring system is for example from benzene, naphthalene, phenanthrene, fluorene and spirobifluorene or combinations of such groups Can be built. In particular, an aromatic ring system in the sense of the present invention is also intended to mean a system in which a plurality of aryl groups are connected to each other directly or through a carbon atom. Thus, for example, systems such as biphenyl, terphenyl, quarterphenyl, fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene and the like, in particular also refer to aromatic ring systems in the sense of the present invention. It is intended to mean. Here, the aromatic ring system does not contain amino groups by definition. Triarylamino groups are therefore not included in the definition of aromatic ring systems.

Similar definitions apply to the term heteroaromatic ring system, which is a combination of two or more interconnected aryl or heteroaryl groups, at least one of which is understood to be a heteroaryl group.

An aralkyl group is understood to be an alkyl group substituted by an aryl group, where the aryl group is as defined above, the alkyl group may have from 1 to 20 carbon atoms, may be substituted as defined above for an alkyl group, and an alkyl group It may have one or more CH ₂ groups replaced as defined above for. In an aralkyl group, an alkyl group is a group that binds to the rest of the compound. Similar definitions apply to the term heteroaralkyl group only if heteroaryl groups are present instead of aryl groups.

An aryloxy group is understood to be an aryl group bonded via a divalent (ether) oxygen atom. Similar definitions apply to the term heteroaryloxy group only if a heteroaryl group is present instead of an aryl group.

For the purposes of the present invention, aliphatic hydrocarbon radicals or alkyl groups or alkenyl or alkynyl groups (which may typically contain 1 to 40 or also 1 to 20 carbon atoms, and also individual H atoms or CH ₂ groups are May be substituted with the groups mentioned), preferably the radical methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl , s-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl , Propynyl, butynyl, pentynyl, hexynyl, heptynyl or octinyl.

Alkoxy groups having 1 to 40 carbon atoms are preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy , n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy In the sense, pentafluoroethoxy or 2,2,2-trifluoroethoxy.

Thioalkyl groups having 1 to 40 carbon atoms are especially methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio , Octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

In general, alkyl, alkoxy or thioalkyl groups according to the invention can be straight chain, branched or cyclic wherein one or more non-adjacent CH ₂ groups can be replaced with the abovementioned groups; One or more H atoms may also be replaced with D, F, Cl, Br, I, CN or NO ₂ , preferably F, Cl or CN, and also preferably F or CN, particularly preferably CN.

In a preferred embodiment of the invention, p + q = 0 or 1. The compound according to the invention thus preferably contains one or two diarylamino groups.

In a preferred embodiment, m, s, r and n are the same or different in each case 0 or 1, more preferably 0.

According to a more preferred embodiment of the invention, at most one index i in formula (1) is 1. More preferably, the index i is generally zero. When the index i is zero, it is understood that spirobifluorene and the nitrogen atom are directly connected.

In a preferred embodiment of the invention, the compound of formula (1) is selected from compounds of formula (2) to (10):

Wherein the symbols and indices used have the meanings given above.

In the case of the compounds according to the above formulas (2) to (10), it is preferable that i = 0.

In a particularly preferred embodiment of the invention, the compounds of the formulas (2) to (10) are selected from the compounds of the formulas (2a) to (10a):

Wherein the symbols and indices used have the meanings given above.

In the case of the compounds according to the above formulas (2a) to (10a), it is preferable that i = 0.

Very particular preference is given to compounds of the formulas (2b) to (10b):

Wherein the symbols used have the meanings given above.

In a particularly preferred embodiment of the invention, the compounds according to the invention contain only one diarylamino group -NAr ¹ Ar ² . It therefore preferably relates to compounds of the formulas (2), (5) and (8) or (2a), (5a) and (8a) or (2b), (5b) and (8b).

In a more preferred embodiment of the invention, the diarylamino group -NAr ¹ Ar ² is bonded at the 4-position or 4- and 4'-position of spirobifluorene. Thus, it preferably relates to compounds of the formulas (2) and (3) or (2a) and (3a) or (2b) and (3b).

Very particular preference is given to compounds of the formula (2) or (2a) or (2b).

In a more preferred embodiment of the invention, Ar ² is identically or differently selected from the group consisting of fluorene, spirobifluorene, biphenyl, terphenyl, quarterphenyl, carbazole, dibenzofuran and dibenzothiophene Each of which may be substituted with one or more radicals R ⁵ .

The groups Ar ¹ and Ar ^{2 here} are preferably selected from the groups of the formulas (11) to (66) below, identically or differently in each case, wherein the dotted bond represents a bond to nitrogen and the group is at least one It may be substituted with a radical R ⁵ but is preferably unsubstituted:

R ⁵ in the groups of the formulas (20) to (23), (53) and (54) are preferably the same or differently, an alkyl group having 1 to 10 carbon atoms, in particular a methyl or phenyl group, which is one or more radicals R ⁶ May be substituted).

Preferred groups Ar ¹ and Ar ² are the same or different in each case, as mentioned above in the formulas (11), (13), (16), (20), (28), (29), (33), (34). ), (35), (37), (38), (39), (40), (44), (48), (49), (51) and (59). All possible combinations of these groups are the same possible here.

Ar ¹ and Ar ² are the same or different in each case, and as mentioned above, in formulas (11), (13), (20), (29), (35), (38), (39), (49), It is especially preferable to select from the group which consists of (51) and (59).

Further, in the groups of the formulas (28) to (31) and (40) to (43) and (55) to (58) and (63) to (66), R ⁵ is preferably a phenyl group, an ortho-biphenyl group , Meta-biphenyl group, para-biphenyl group, terphenyl group, 1-naphthyl group or 2-naphthyl group, which may be substituted with one or more radicals R ⁶ .

Preferably, Ar ¹ and Ar ² are the same or different in each case selected from the groups of the formulas (11), (20) and (24), which may be substituted with one or more radicals R ⁵ .

At least one of the groups Ar ¹ and Ar ² is particularly preferably a group of the formula (11) or (20). Very particularly preferably, Ar ¹ represents a group of formula (11) and Ar ² represents a group of formula (20).

The two groups Ar ¹ and Ar ² of the above-mentioned formulas (11) to (66) bonded to nitrogen may be combined with one another as desired.

In a preferred embodiment of the invention, the groups Ar ¹ and Ar ² are selected differently from each other.

When the groups Ar ¹ and Ar ² in the compounds of the formulas (1) and (2) to (10) or a preferred embodiment are connected to each other by a group E, the group -NAr ¹ Ar ² is preferably the following formulas (67) to Has a structure of one of 74:

Wherein the symbols used have the meanings given above and the dashed bonds represent the bonds to spirobifluorene. Such groups may also be substituted with one or more radicals R ⁵ , but are preferably unsubstituted.

R ⁵ in the groups of the formulas (68) to (72) preferably represent the same or differently an alkyl group having 1 to 10 carbon atoms, in particular a methyl or phenyl group, which may be substituted with one or more radicals R ⁶ .

In addition, in the groups of the formulas (71) and (73) R ⁵ preferably denotes a phenyl group, which may be substituted by one or more radicals R ⁶ .

Preferred substituted embodiments of formula (13) are the following formulas (13a) to (13f), preferred embodiments of formula (16) are formulas (16a) and (16b), and preferred embodiments of formula (20) are Formulas (20a) to (20l), preferred embodiments of formula (21) are the following formulas (21a) to (21g), and preferred embodiments of formula (22) are formulas (22a), (22b), ( 22c) and (22d), and preferred embodiments of formula (23) are the following formulas (23a), (23b), (23c) and (23d):

Wherein the dotted line bond represents the bond to nitrogen.

The group Ar ^S is preferably selected identically or differently in each case from an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, which in each case may also be substituted with one or more radicals R ⁵ .

In particular to the preferred groups Ar are selected from groups of the formula ^S (Ar ^S -1) to ^(S AR -15), wherein the dashed line represents the bond by bonding to the lobby RY fluorene and amine, the group R ⁵ group It may be substituted at each free position but is preferably unsubstituted:

In a preferred embodiment of the invention, R ¹ to R ⁴ are the same or different at each occurrence, H, F, CN, straight chain alkyl or alkoxy group having 1 to 10 carbon atoms or branched or cyclic alkyl having 3 to 10 carbon atoms. Or alkoxy groups, each of which may be substituted by one or more radicals R ⁶ , wherein one or more non-adjacent CH ₂ groups may be replaced by O and one or more H atoms may be replaced by F, 6 to 24 Or heteroaromatic ring systems having 2 aromatic ring atoms, which in each case may be substituted with one or more radicals R ⁶ .

In a particularly preferred embodiment of the invention, R ¹ to R ⁴ are the same or different at each occurrence, H, F, a straight chain alkyl group of 1 to 5 carbon atoms or branched or cyclic alkyl of 3 to 6 carbon atoms, 5 to 18 Or heteroaromatic ring systems having 2 aromatic ring atoms, which in each case may be substituted by one or more radicals R ⁶ .

Most preferably, R ¹ to R ⁴ are the same or differently selected from H, F, phenyl, methyl and tert-butyl.

R ¹ to R ⁴ in the compounds of the formulas (1) and (2) to (10) and (2a) to (10a) are very particularly preferably identical or different in each case H, F, methyl, tert- It is selected from the group consisting of butyl and phenyl.

In a more preferred embodiment of the invention, the radicals R ⁵ bonded to Ar ¹ or Ar ² or Ar ^S are the same or different in each case H, F, CN, a straight alkyl group of 1 to 10 carbon atoms, 3 to 10 carbon atoms Branched or cyclic alkyl groups of or aromatic or heteroaromatic ring systems having from 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R ⁶ .

In a particularly preferred embodiment of the invention, the radicals R ⁵ bonded to Ar ¹ or Ar ² or Ar ^S are the same or different at each occurrence: H, straight chain alkyl groups having 1 to 5 carbon atoms, branched form having 3 to 6 carbon atoms or Or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R ⁶ .

The radicals R ¹ to R ⁶ herein preferably do not contain condensed aryl or heteroaryl groups, ie anthracene or pyrene groups, in which more than two aromatic or heteroaromatic six-membered rings are directly condensed with one another. The radicals R ¹ to R ⁶ particularly preferably do not contain condensed aryl or heteroaryl groups, ie also naphthalene groups, in which the aromatic or heteroaromatic six-membered ring is directly condensed with one another.

It may be preferable for the two substituents R ⁵ at the 9-position of fluorene together to form a cycloalkyl ring, preferably having 3 to 8 carbon atoms, particularly preferably 5 or 6 carbon atoms.

Likewise, two substituents R ⁵ of formulas (68) and (72) may form a ring system and thus a spiro system, for example a cycloalkyl ring having 3 to 8 carbon atoms, particularly preferably 5 or 6 carbon atoms, to each other. have.

In the case of compounds which are processed by vacuum evaporation, the alkyl group preferably has up to 4 carbon atoms, particularly preferably up to 1 carbon atom. In the case of compounds to be processed from solution, suitable compounds are also substituted with linear, branched or cyclic alkyl groups having up to 10 carbon atoms, or oligoarylene groups, for example ortho-, meta-, para- or branched terphenyl or quarterphenyl. Compound substituted with a group.

In a preferred embodiment of the invention, R ⁶ is the same or different at each occurrence consisting of H, a straight alkyl group of 1 to 10 carbon atoms or a branched or cyclic alkyl group of 3 to 10 carbon atoms or an aromatic ring system of 6 to 24 carbon atoms Selected from the group. R ⁶ is particularly preferably the same or different in each case H or a methyl group, very particularly preferably H.

Particular preference is given to compounds of the formulas (1) and (2) to (10) and (2a) to (10a) and (2b) to (10b), in which the above-mentioned preferred embodiments occur equally. Thus, the following compounds are particularly preferred:

Ar ¹ , Ar ² , identically or differently, are a group of one of formulas (11) to (66); Or -NAr ¹ Ar ² represents a group of one of the formulas (67) to (74);

E is the same or different at each instance, a single bond or C (R ¹ ) ₂ , N (R ¹ ), O or S;

R ¹ to R ⁴ are the same or different at each occurrence, H, F, CN, a straight chain alkyl or alkoxy group having 1 to 10 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, each of which is one above it can be optionally substituted with a radical R ^6, where one or more non-adjacent CH ₂ groups may be replaced by O, one or more H atoms may be replaced by F), 6 to 24 aromatic aromatic or heterocyclic having ring atoms Aromatic ring systems, which in each case may be substituted by one or more radicals R ⁶ ;

R ⁵ is the same or different in each case when the radical R ⁵ is bonded to Ar ¹ or Ar ² or Ar ^S , H, F, CN, a straight alkyl group having 1 to 10 carbon atoms, branched form having 3 to 10 carbon atoms or A cyclic alkyl group or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R ⁶ ; or

R ⁵ bonded to the carbon crosslink in the formulas (20) to (23), (53), (54), (68) and (72) is the same or differently an alkyl group having 1 to 10 carbon atoms, in particular a methyl or phenyl group Which may be substituted by one or more radicals R ⁶ ; or

In formulas (28) to (31), (40) to (43) or (55) to (58), (63) to (66), (71) and (73), R ⁵ is one Phenyl group which may be substituted by the above radical R ⁶ ;

R ⁶ is the same or different at each occurrence is selected from the group consisting of H, a straight chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms or an aromatic ring system having 6 to 24 carbon atoms;

i is 0;

m is 0 or 1, preferably 0;

n is 0 or 1;

p + q is 0 or 1;

r is 0 or 1;

s is 0 or 1

Examples of preferred structures of the compounds according to formula (1) are listed below. The compound is based on the basic structures of the formulas (2a), (5a) and (8a).

The compounds in the list preferably have as preferred embodiments of these groups described above as Ar ^S and R ¹ to R ⁴ . More preferably in the compounds listed above, Ar ^S is selected from the groups Ar ^S -1 to Ar ^S -15 as defined above. More preferably, R ¹ to R ⁴ in the compounds listed above are the same or differently selected from H, F, phenyl, methyl and tert-butyl.

Examples of suitable compounds according to the invention are the compounds shown in the following table:

The compounds according to the invention can be prepared by synthetic steps known to those skilled in the art, for example bromination, ulman arylation, Hartwig-Buchwald coupling and the like.

Synthesis generally starts from 1-, 3- or 4-halogenated, especially brominated, spirobifluorene derivatives, and then the CN coupling reaction, for example Hartwig-Buchwald coupling or Ulmann coupling, is a diarylamino group. Follow for the introduction of. Similarly, other suitable leaving groups such as tosylate or triflate can be used instead of halogen. The synthesis of 1-diarylaminospirobifluorene is shown in Scheme 1, where the access route to two different brominated starting compounds is shown.

Scheme 1:

a) Traditional Spiro Synthesis:

b) aromatic lithium substitution of fluorenol:

Similar to the traditional spiro synthesis shown above, the corresponding spirobifluorene derivative halogenated at the 3- or 4-position can be synthesized using the corresponding 3- or 4-halogen-substituted fluorenone as starting material. Likewise, the corresponding substitution structures can also be synthesized completely similarly.

In a variant of the method shown in Scheme 1a, it is likewise possible to carry out Buchwald coupling in the first step for fluorenone, followed by addition of metallized biphenyl and then ring closure to spirobifluorene. For further details, the synthesis method is shown in the working example.

Spirobifluorene-carbazole compounds can be synthesized by Buchwald coupling of halogen-substituted spirobifluorene and carbazole as shown in the working examples.

The present invention therefore also provides a process for the preparation of the compound of formula (1), wherein the diarylamino group is introduced by a CN coupling reaction between 1- or 3- or 4-halogenated spirobifluorene and diarylamine. It is about.

The compounds according to the invention described above, in particular compounds substituted by reactive leaving groups such as bromine, iodine, boronic acid or boronic acid esters, can be used as monomers for the preparation of the corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization herein is preferably carried out via halogen functional groups or boronic acid functional groups.

The present invention therefore also relates to oligomers, polymers or dendrimers comprising at least one compound of formula (1) wherein the bond (s) to the polymer, oligomer or dendrimer is substituted by R ¹ to R ⁵ ) May be localized at any desired position. According to the linkage of the compound of formula (1), the compound is part of the main chain or part of the side chain of the oligomer or polymer. Oligomer in the sense of the present invention means a compound constructed from three or more monomer units. Polymer in the sense of the present invention means a compound constructed from at least 10 monomer units. The polymers, oligomers or dendrimers according to the invention may be conjugated, partially conjugated or nonconjugated. The oligomers or polymers according to the invention can be linear, branched or dendritic. In the structure connected in a linear manner, the units of the formula (1) may be directly connected to each other or to each other via a divalent group, for example a substituted or unsubstituted alkylene group, a heteroatom or a divalent aromatic or heteroaromatic group. In branched and dendritic structures, three or more units of formula (1) are linked, for example, via a trivalent or polyvalent group, such as a trivalent or polyvalent aromatic or heteroaromatic group, to form a branched or dendritic oligomer or polymer. Can be calculated. The same preferences as described above for the compounds of formula (1) apply to the repeat units of formula (1) in oligomers, dendrimers and polymers.

For the preparation of oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with further monomers. Suitable and preferred comonomers are fluorene (eg according to EP 842208 or WO 00/22026), spirobifluorene (eg according to EP 707020, EP 894107 or WO 06/061181), para-phenylene ( For example according to WO 92/18552), carbazole (for example according to WO 04/070772 or WO 04/113468), thiophene (for example according to EP 1028136), dihydrophenanthrene (for example According to WO 05/014689 or WO 07/006383), cis- and trans-indenofluorene (eg according to WO 04/041901 or WO 04/113412), ketones (eg WO 05/040302) ), Phenanthrene (eg according to WO 05/104264 or WO # 07/017066) or also many of these units. Polymers, oligomers and dendrimers are generally also further units, for example radiation (fluorescent or phosphorescent) units, for example vinyltriarylamine (for example according to WO 07/068325) or phosphorescent metal complexes (for example WO 06/003000), and / or charge-transporting units, in particular those based on triarylamines.

The polymers, oligomers and dendrimers according to the invention have advantageous properties, in particular long life, high efficiency and good color coordinates.

Polymers and oligomers according to the invention are generally prepared by the polymerization of one or more types of monomers, at least one of which yields repeating units of formula (1) in the polymer. Suitable polymerization methods are known to those skilled in the art and are described in the literature. Particularly suitable and preferred polymerization reactions yielding C-C or C-N are as follows:

(A) Suzuki polymerization;

(B) Yamamoto polymerization;

(C) steel polymerization; And

(D) Hardwig-Buchwald polymerization.

How the polymerization can be carried out by this method and how the polymer can then be separated and purified from the reaction medium are known to those skilled in the art and are described in the literature, for example WO 2003/048225, WO 2004/037887 and WO 2004/037887. It is described in detail in.

The invention therefore also relates to a process for the preparation of the polymers, oligomers and dendrimers according to the invention, characterized in that they are produced by Suzuki polymerization, Yamamoto polymerization, steel polymerization or Hartwig-Buchwald polymerization. Dendrimers according to the invention can be prepared by methods known to those skilled in the art or by analogous methods. Suitable methods are described in, for example, Frechet, Jean M. J .; Hawker, Craig J., "Hyper-branched polyphenylene and hyperbranched polyesters: new soluble, three-dimensional, reactive poly-mers", Reactive & Functional Polymers (1995), 26 (1-3), 127-36; Janssen, H. M .; Meijer, E. W., "The synthesis and characterization of dendritic molecules", Materials Science and Technology (1999), 20 (Synthesis of Polymers), 403-458; Tomalia, Donald A., "Dendrimer molecules", Scientific American (1995), 272 (5), 62-6; WO 02/067343 A1 and WO # 2005/026144 A1.

The compounds according to the invention are suitable for use in electronic devices. By electronic device is meant herein a device comprising at least one layer comprising at least one organic compound. However, the constituents herein may comprise an inorganic material or also a layer completely constructed from an inorganic material.

The invention therefore also relates to the use of the compounds according to the invention in electronic devices, in particular organic electroluminescent devices.

The invention further relates to an electronic device comprising at least one compound according to the invention. The above mentioned preferences likewise apply to electronic devices.

The electronic device is preferably an organic electroluminescent device (organic light emitting diode, OLED), organic integrated circuit (O-IC), organic field-effect transistor (O-FET), organic thin film transistor (O-TFT), organic light emitting transistor (O-LET), organic solar cell (O-SC), organic dye-sensitized solar cell (ODSSC), organic optical detector, organic photoreceptor, organic field-quench device (O-FQD), luminescent electrochemical cell (LEC) ), Organic laser diodes (O-lasers) and organic plasmon radiating elements (D. M. Koller et al., Nature Photonics 2008, 1-4), preferably organic electroluminescent elements (OLEDs), particularly preferably phosphorescent It is selected from the group which consists of OLED.

Organic electroluminescent devices and luminescent electrochemical cells can be used in a variety of applications such as mono or multicolor displays, lighting applications or medical and / or cosmetic applications such as phototherapy.

The organic electroluminescent device comprises a cathode, an anode and one or more emitting layers. Apart from this layer, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking Layers, electron-blocking layers, and / or charge-generating layers. For example, an interlayer having an exciton-blocking function can likewise be introduced between two emitting layers. However, it should be pointed out that each of these layers need not necessarily exist.

The organic electroluminescent device herein may comprise one emitting layer or multiple emitting layers. If multiple emitting layers are present, this preferably has a large number of emission maximums of 380 nm to 750 nm in total, yielding white radiation as a whole, i.e. various emitting compounds capable of fluorescence or phosphorescence are used in the emitting layer. . Particular preference is given to systems having three emitting layers, where the three layers show blue, green and orange or red emission (see eg WO # 2005/011013 for the basic structure). Wherein all emitting layers may be fluorescent, all emitting layers may be phosphorescent, or one or more emitting layers may be fluorescent and one or more other layers may be phosphorescent.

The compounds according to the invention according to the embodiments shown above can be used here in different layers depending on the precise structure. Compounds of formula (1) or preferred embodiments are employed as hole-transporting materials in hole-transporting or hole-injecting or exciton-blocking or electron-blocking layers or as fluorescent or phosphorescent emitters in the emitting layer, in particular matrix materials for phosphorescent emitters The organic electroluminescent element containing is preferable. The preferred embodiments shown above also apply to the use of materials in organic electronic devices.

In a preferred embodiment of the invention, the compound of formula (1) or preferred embodiment is used as a hole-transporting or hole-injecting material in a hole-transporting or hole-injecting layer. The emissive layer herein can be fluorescent or phosphorescent. In the sense of the present invention, the hole-injecting layer is a layer directly adjacent to the anode. In the sense of the present invention, the hole-transport layer is a layer located between the hole-injection layer and the emission layer.

In a still more preferred embodiment of the invention, the compound of formula (1) or preferred embodiment is used in the exciton-blocking layer. An exciton-blocking layer means a layer directly adjacent to the emissive layer on the anode side.

Compounds of formula (1) or preferred embodiments are particularly preferably used in hole-transporting or exciton-blocking layers.

In an embodiment of the invention, the compound of formula (1) or preferred embodiment is used in a layer comprising a hexaazatriphenylene derivative, in particular hexacyanohexaazatriphenylene together with a hole-transporting or -injection layer (For example according to EP 1175470). Thus, for example, combinations that look as follows are preferred: anode-hexaazatriphenylene derivative-hole-transport layer, wherein the hole-transport layer comprises at least one compound of formula (1) or a preferred embodiment. It is also possible to use a plurality of continuous hole-transport layers in this structure, wherein the at least one hole-transport layer comprises at least one compound of formula (1) or a preferred embodiment. More preferred combinations are represented as follows: anode-hole-transport layer-hexaazatriphenylene derivative-hole-transport layer, wherein at least one of the two hole-transport layers comprises at least one compound of formula (1) or a preferred embodiment ). It is also possible to use multiple continuous hole-transporting layers in this structure instead of one hole-transporting layer, wherein the one or more hole-transporting layers comprise at least one compound of formula (1) or a preferred embodiment.

When the compound according to formula (1) is used as a hole transporting material in a hole transporting layer, a hole injection layer, an exciton blocking layer or an electron blocking layer, the compound may be used as a pure material, ie in a layer at a rate of 100% or one It can be used together with the other materials. According to a preferred embodiment, in this case one or other compound used with the compound according to formula (1) is p-dopant. Preferred p-dopants used are electron acceptor compounds, preferably those electron acceptor compounds capable of oxidizing one or more other compounds of the mixture.

The p-dopant is preferably 0.1 to 20% by volume, preferably 0.5 to 12% by volume, more preferably 1 to 8% by volume and most preferably 2 to 6% by volume in the layer comprising the compound according to the invention. It is present at a concentration of%.

Particularly preferred p-dopants for use with the compounds according to the invention are the compounds disclosed in one or more of the following documents: WO 2011/073149, EP # 1968131, EP # 2276085, EP 2213662, EP 1722602, EP 2045848, DE # 102007031220, US 8044390 , US 8057712, WO 2009/003455, WO 2010/094378, WO 2011/120709, US 2010/0096600 and WO 2012/095143.

Very preferred p-dopants for use in the devices according to the invention are quinodimethane, azaindenofluorenedione, azafenalene, azatriphenylene, I ₂ , metal halogenides, preferably transition metal halogenides , A metal oxide, preferably a transition metal oxide or a metal oxide comprising at least one third main group metal and a transition metal complex, preferably Cu, Co, Ni, Pd or Pt, with a ligand having at least one bonded oxygen atom It is a complex. Preferred are also transition metal oxides such as rhenium oxide, molybdenum oxide and tungsten oxide, more preferably Re ₂ O _7, MoO ₃ , WO ₃ and ReO ₃ .

Preferred p-dopants are also the following compounds:

In a more preferred embodiment of the invention, the compound of formula (1) or preferred embodiment is used as matrix material for fluorescent or phosphorescent compounds, in particular phosphorescent compounds, in the emitting layer. The organic electroluminescent device herein can comprise one emitting layer or a plurality of emitting layers, wherein at least one emitting layer comprises at least one compound according to the invention as matrix material.

When the compound of formula (1) or preferred embodiment is used as matrix material for the radioactive compound in the emitting layer, it is preferably used together with one or more phosphorescent materials (triple emitters). Phosphorescence in the sense of the present invention means light emission from an excited state, in particular an excited triplet state, having a spin multiplicity of greater than one. For the purpose of this application, all luminescent complexes containing transition metals or lanthanide elements, in particular all luminescent iridium, platinum and copper complexes, are considered phosphorescent compounds.

The mixture comprising the compound of formula (1) or preferred embodiment and the radioactive compound is 99.9 to 1% by weight, preferably 99 to 10% by weight, particularly preferably 97, based on the total mixture comprising the emitter and the matrix material. To 60% by weight, in particular 95 to 80% by weight of the compound of formula (1) or preferred embodiment. Correspondingly, the mixture comprises from 0.1 to 99% by weight, preferably from 1 to 90% by weight, particularly preferably from 3 to 40% by weight, in particular from 5 to 20% by weight, based on the total mixture comprising the emitter and the matrix material. It includes a radiator. In particular, the limitations indicated above apply when the layer is applied from solution. If the bed is applied by vapor evaporation, the numerical value is applied in this case in percentage in this case, expressed in volume% in each case.

A particularly preferred embodiment of the present invention is the use of a compound of formula (1) or a preferred embodiment as an additional matrix material together with a matrix material for phosphorescent emitters. Particularly suitable matrix materials which can be used with the compounds of formula (1) or preferred embodiments are aromatic ketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones (for example WO 2004/013080, WO 2004/093207, WO 2006/005627). Or according to WO 2010/006680), triarylamines, carbazole derivatives, for example CBP (N, N-biscarbazolylbiphenyl), m-CBP or carbazole derivatives (WO 2005/039246, US 2005 / 0069729, JP 2004/288381, EP 1205527 or WO 2008/086851), indolocarbazole derivatives (for example according to WO 2007/063754 or WO 2008/056746), indenocarbazole derivatives (for example According to WO 2010/136109 or WO 2011/000455), azacarbazole derivatives (for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160), bipolar matrix materials (for example WO 2007 / 137725), silane (for example according to WO 2005/111172), Zaborol or boronic acid esters (eg according to WO 2006/117052), triazine derivatives (eg according to WO 2010/015306, WO 2007/063754 or WO 08/056746), zinc complexes (eg , According to EP 652273 or WO 2009/062578), fluorene derivatives (for example according to WO 2009/124627), diazasilol or tetraazasilol derivatives (for example according to WO 2010/054729), diazapo Spol derivatives (for example according to WO # 2010/054730), or crosslinked carbazole derivatives (for example according to US 2009/0136779, WO 2010/050778, WO 2011/042107 or WO 2011/088877). Electrically neutral co-hosts with hole-transport or electron-transport properties as described, for example, in WO 2010/108579 can also be used.

Particularly preferably, the compound according to formula (1) is used as matrix material for at least one triplet emitter together with a second host material selected from lactam compounds. Especially preferred are the lactam compounds disclosed in WO 2011/116865, WO 2011/137951, unpublished EP 12007040.7 and unpublished EP 11008708.7. Most preferred are the compounds shown in the working examples of this application.

Examples of preferred lactam compounds used with materials according to formula (1) in the emissive layer are shown in the table below.

It is likewise possible to use two or more phosphorescent emitters in a mixture. In this case, the emitter emitting at shorter wavelengths acts as a co-host in the mixture.

Suitable phosphorescent compounds (= triplet emitters) emit light in a particularly suitable excitation, preferably in the visible region, and also atoms of more than 20, preferably more than 38 and less than 84, particularly preferably more than 56 and less than 80 Compounds containing at least one atom having a number, in particular a metal having such an atomic number. The phosphorescent emitters used are preferably compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium, platinum or copper to be.

Examples of the radiators described above are described in applications WO # 2000/70655, WO # 2001/41512, WO # 2002/02714, WO # 2002/15645, EP # 1191613, EP 1191612, EP 1191614, WO 2005/033244, WO # 2005/019373, 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 2011/157339 or WO 2012/007086 Revealed by In general, all phosphorescent complexes used according to the prior art with respect to phosphorescent OLEDs and known to those skilled in the organic electroluminescent area are suitable, and one skilled in the art will be able to use additional phosphorescent complexes without the inventive steps.

Examples of triplet emitters used in the device according to the present application are shown in the table below.

In a further embodiment of the invention, the organic electroluminescent device according to the invention does not comprise separate hole-injecting layers and / or hole-transporting layers and / or hole-blocking layers and / or electron-transporting layers, ie emitting layers Is directly adjacent to the hole-injecting layer or anode and / or the emitting layer is directly adjacent to the electron-transporting layer or electron-injecting layer or cathode (as described for example in WO 2005/053051). It is also possible to use the same or similar metal complexes as the metal complexes in the emissive layer as hole-transport or hole-injecting materials directly adjacent to the emissive layer as described, for example, in WO # 2009/030981.

It is also possible to use compounds of the formula (1) or preferred embodiments in the hole-transporting layer or the exciton-blocking layer and as the matrix in the emitting layer.

In a further layer of the organic electroluminescent device according to the invention, all materials generally used according to the prior art can be used. Those skilled in the art will therefore be able to use all materials known for organic electroluminescent devices with the compounds of formula (1) or preferred embodiments according to the invention without the inventive step.

Preferred fluorescent emitter materials are selected from the class of arylamines. An arylamine or aromatic amine in the sense of the present invention means a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to nitrogen. At least one of the aromatic or heteroaromatic ring systems is particularly preferably a condensed ring system having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthraceneamine, aromatic anthracenediamine, aromatic pyrenamine, aromatic pyrendiamine, aromatic chryseneamine or aromatic chrysenediamine. By aromatic anthraceneamine is meant a compound in which one diarylamino group is bonded directly to the anthracene group, preferably at the 9-position. Aromatic anthracenediamine means a compound in which two diarylamino groups are bonded directly at the anthracene group, preferably at the 9,10-position. Aromatic pyrenamines, pyrendiamines, chryseneamines and chrysenediamines are similarly defined, wherein the diarylamino groups are preferably attached to the pyrene at the 1-position or 1,6-position. More preferred emitter materials are indenofluoreneamine or indenofluorenediamine (for example according to WO 06/122630), benzoindenofluoreneamine or benzoindenofluorenediamine (for example in WO 08/006449 ) And dibenzoindenofluoreneamine or dibenzoindenofluorenediamine (for example according to WO-07 / 140847). Examples of emitter materials from the class of styrylamines are substituted or unsubstituted tristilbenamines or emitter materials described in WO 06/000388, WO06 / 058737, WO06 / 000389, WO07 / 065549 and WO 07/115610. . Also preferred are the condensed hydrocarbons disclosed in the application WO # 10/012328.

Suitable radiator materials are also the structures shown in the following table, derivatives of which are disclosed in JP 06/001973, WO04 / 047499, WO06 / 098080, WO 07/065678, US 2005/0260442 and WO 04/092111. have.

Preferably the matrix material that can be used in the fluorescent dopant is a material from various classes of components. Preferred matrix materials are oligoarylenes (for example 2,2 ', 7,7'-tetraphenylspirobifluorene or dinaphthylanthracene according to EP 676461), in particular oligoarylenes containing condensed aromatic groups, oligos Arylenevinylene (for example DPVBi or Spiro-DPVBi according to EP 676461), polypodal metal complexes (for example according to WO 04/081017), hole-conducting compounds (for example according to WO 04/058911) , Electron-conducting compounds, in particular ketones, phosphine oxides, sulfoxides and the like (eg according to WO 05/084081 and WO 05/084082), atropisomers (eg according to WO 06/048268), boron Acid derivatives (eg according to WO 06/117052) or benzanthracene (eg according to WO 08/145239). Suitable matrix materials are also preferably compounds according to the invention. Apart from the compounds according to the invention, particularly preferred matrix materials are selected from naphthalene, anthracene, benzanthracene and / or pyrene or a class of atropisomers, oligoarylenevinylenes, ketones, phosphine oxides and sulfoxides of such compounds. do. Very particularly preferred matrix materials are selected from the class of oligoarylenes comprising anthracene, benzanthracene, benzophenanthrene and / or pyrene or an atropisomer of such compounds. Oligoarylene in the sense of the present invention means a compound in which three or more aryl or arylene groups are bonded to each other.

Preferably the matrix material suitable for the fluorescent dopant is, for example, the material shown in the table below, and derivatives of such materials are WO 04/018587, WO 08/006449, US 5935721, US 2005/0181232, JP 2000/273056, EP 681019, US 2004/0247937 and US 2005/0211958.

In addition to the compounds according to the invention, suitable charge-transport materials which can be used in the hole-injection or hole-transport layer or the electron-transport layer of the organic electroluminescent device according to the invention are described, for example, in [Y. Shirota et al., Chem. Rev. 2007, 107 (4), 953-1010 or other materials used in such layers according to the prior art.

In addition, at least one layer of material is generally less than 10 ^-5 mbar, preferably from 10 to ^- is an organic electroluminescent device, characterized in that applied by the sublimation process to be deposited in a vacuum sublimation apparatus at an initial pressure of less than 6 mbar preferably . However, the initial pressure can also be lower, for example less than 10 ⁻⁷ mbar.

Organic electroluminescent devices are preferred wherein at least one layer is applied by an OVPD (organic vapor phase deposition) process or with the aid of a carrier-gas sublimation, where the material is applied at a pressure of 10 ⁻⁵ mbar to 1 bar. Do. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, where the material is applied directly through the nozzle and structured accordingly (eg MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

In addition, one or more layers may be removed from the solution, for example by spin coating or in any desired printing process such as LITI (light induced thermal imaging, thermal transfer printing), inkjet printing, screen printing, flexographic printing, offset printing or Organic electroluminescent devices characterized by being produced by nozzle printing are preferred. Soluble compounds, for example obtained by suitable sublimation, are necessary for this purpose. This process is also particularly suitable for the compounds according to the invention since they generally have very good solubility in organic solvents.

Also possible is a hybrid process in which, for example, one or more layers are applied from solution and one or more additional layers are applied by vapor deposition. Thus, for example, the emissive layer can be applied from the electron-transport layer and the solution by vapor deposition.

Such a process is generally known to the person skilled in the art and can be applied by the person skilled in the art without an inventive step for organic electroluminescent devices comprising the compounds according to the invention.

Processing of the compounds according to the invention from the liquid phase, for example by spin coating or printing processes, requires the formulation of the compounds according to the invention. Such formulations can be, for example, solutions, dispersions or mini-emulsions. It may be desirable to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, dimethylanisole, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, Chlorobenzene, dioxane or mixtures of these solvents. Preferably, the solvent disclosed in WO 2010/093592 is used for this purpose.

The present invention therefore also relates to formulations, in particular solutions, dispersions or mini-emulsions, comprising at least one compound of the formula (1) or preferred embodiment indicated above and at least one solvent, in particular at least one organic solvent. Methods by which solutions of this type can be prepared are known to the person skilled in the art and are described, for example, in WO 2002/072714, WO 2003/019694, WO # 2010/093592 and the references cited therein.

The invention also relates to a mixture comprising at least one compound of the formula (1) or preferred embodiment as indicated above and at least one additional compound. For example, the further compound can be for example a fluorescent or phosphorescent dopant when the compound according to the invention is used as matrix material. The mixture may then further comprise further materials as further matrix materials.

The compounds according to the invention and the organic electroluminescent devices according to the invention are distinguished by advantages over the following surprising prior art:

1. The compounds according to the invention are very suitable for use in hole-transport or hole-injection layers in organic electroluminescent devices. It is also particularly suitable for use in layers directly adjacent to the phosphorescent emitting layer, since the compounds according to the invention do not dissipate luminescence.

2. The compounds according to the invention used as matrix materials for fluorescent or phosphorescent emitters yield very high efficiencies and long lifetimes. In particular, this applies when the compound is used as a matrix material together with further matrix materials and phosphorescent emitters.

3. The compounds according to the invention used in organic electroluminescent devices yield low use and operating voltages with high efficiency and steep current / voltage curves.

This above mentioned advantage is not accompanied by obstacles in other electrical properties.

The invention is illustrated in more detail by the following examples, which are not intended to limit the invention. Based on the description, those skilled in the art will be able to carry out the invention throughout the disclosed ranges, to prepare further compounds according to the invention without the inventive steps and to use them in electronic devices or to use the processes according to the invention.

Example

A) Synthesis Example

The following synthesis was carried out under a protective-gas atmosphere unless otherwise indicated. Starting materials can be purchased from ALDRICH or ABCR. In the case of starting materials known in the literature, the numbers in square brackets correspond to the CAS number.

Example 1: Synthesis of brominated spirobifluorene derivative (starting material)

1a) Synthesis of 1-bromosspiro-9,9'-bifluorene

2.7 g (110 mmol) of iodine-activated magnesium turning and 25.6 g (110 mmol) of 2-bromobiphenyl, 0.8 ml of 1,2-dichloroethane, 50 ml with secondary heating using an oil bath at 70 ° C. The corresponding Grignard reagent was prepared from a mixture of 1,2-dimethoxyethane, 400 ml of THF and 200 ml of toluene. Once the magnesium has reacted completely, the mixture is cooled to room temperature, a solution of 25.9 g (100 mmol) of 1-bromofluorenone [36804-63-4] in 500 ml of THF is then added dropwise and the reaction mixture is 4 hours. Warmed at 50 ° C. and then stirred for additional 12 h at room temperature. 100 ml of water were added, the mixture was briefly stirred, the organic phase was separated and the solvent was removed in vacuo. The residue was suspended in 500 ml of glacial acetic acid at 40 ° C., 0.5 ml of concentrated sulfuric acid was added to the suspension, and the mixture was then stirred at 100 ° C. for a further 2 hours. After cooling, the precipitated solid was filtered off with suction, washed once with 100 ml of glacial acetic acid, three times with 100 ml of ethanol each, and finally recrystallized from dioxane. Yield: 26.9 g (68 mmol), 68%; Purity about 98% according to ¹ H-NMR.

1b) Synthesis of 4-bromosspiro-9,9'-bifluorene

A solution of 2,2'-dibromo-biphenyl (250 g, 785 mmol) in THF (1900 ml) was converted to 318 mL of n-BuLi (2,5 M in hexane, 785 mmol) under argon at -78 ° C. Treated. The mixture was stirred for 30 minutes. A solution of fluoren-9-one (144 g, 785 mmol) in 1000 mL THF was added dropwise. The reaction proceeded at -78 ° C for 30 minutes and then stirred at room temperature overnight. The reaction was quenched with water and the solid was filtered off. Without further purification, a mixture of alcohol (299 g, 92%), acetic acid (2200 mL) and concentrated HCl (100 mL) was refluxed for 2 hours. After cooling, the mixture was filtered, washed with water and dried in vacuo. The product was isolated in the form of a white solid (280 g, 98% of theory).

The synthesis of further brominated spirobifluorene derivatives was performed similarly:

Example 2: Synthesis of 4-biphenyl-2- (9,9'-dimethylfluorenyl) -1-spiro-9,9'-bifluorenylamine

Synthesis of 1- (1-biphen-4-yl)-(9,9'-dimethylfluoren-2-yl) amine-9H-fluoren-9-one

Tri-tert-butylphosphine (4.5 ml of 1.0 M solution in toluene, 1,9 mmol), palladium acetate (217 mg, 0.97 mmol) and sodium tert-butoxide (13.9 g, 145 mmol) were degassed toluene (200 ml 1-biphenyl-yl- (9,9-dimethyl-9H-fluoren-2-yl) amine (40.0 g, 111 mmol), 1-bromo-fluoren-9-one (25 g, 96 mmol) and the mixture was heated at reflux overnight. The reaction mixture was cooled to room temperature, concentrated with toluene and filtered through celite. The filtrate was evaporated in vacuo and the residue was crystallized from toluene / heptane. The product was isolated in the form of a pale yellow solid (43 g, 82% of theory).

Synthesis of 4-biphenyl-2- (9,9'-dimethylfluorenyl) -1-spiro-9,9'-bifluorenylamine

A solution of 2-bromobiphenyl (17 g, 70 mmol) in THF (90 ml) was treated with 35 mL of n-BuLi (2,1 M in hexane, 70 mmol) under argon at -78 ° C. The mixture was filtered for 30 minutes. A solution of 1- (1-biphen-4-yl)-(9,9'-dimethylfluoren-2-yl) amine-9H-fluoren-9-one (38 g, 70 mmol) in 90 mL THF Added dropwise. The reaction was allowed to proceed at -78 ° C for 30 minutes, then stirred at room temperature overnight. The reaction was quenched with water and extracted with ethyl acetate. Intermediate alcohol was obtained after the solvent was removed (31 g, 64%). Without further purification, a mixture of alcohol, acetic acid (700 mL) and concentrated HCl (62 mL) was refluxed for 2 hours. After cooling, the mixture was filtered and washed with water. The residue was crystallized from toluene. The crude product was extracted in a Soxhlet extractor (toluene) and purified by zone sublimation under vacuum. The product was isolated in the form of a pale yellow solid (13 g, 43% of theory, purity> 99.99% according to HPLC).

Example 3a: Synthesis of 4-biphenyl-2- (9,9'-dimethylfluorenyl) -1-spiro-9,9'-bifluorenylamine

Biphenyl-2-yl- (9,9-dimethyl-9H-fluoren-2-yl) amine (40.0 g, 111 mmol) and 4-bromo-9,9'-spire in degassed toluene (500 mL) To a solution of ubifluorene (56.9 g, 144 mmol) tri-tert-butylphosphine (1.0 M solution in 4.4 ml of toluene, 4.4 mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide ( 16.0 g, 166 mmol) was added and the mixture was heated at reflux for 2 hours. The reaction mixture was cooled to room temperature, concentrated with toluene and filtered through celite. The filtrate was evaporated in vacuo and the residue was crystallized from ethyl acetate / heptane. The crude product was extracted in a Soxhlet extractor (toluene) and purified twice by zone sublimation under vacuum (p = 3 × 10 ⁻⁴ mbar, T = 298 ° C.). The product was isolated in the form of a pale yellow solid (20.4 g, 27% of theory, purity> 99.99% according to HPLC).

The following compounds were similarly obtained:

Example 4a: Synthesis of Biphenyl-2-yl- (9,9-dimethyl-9H-fluoren-2-yl)-(9,9'-spirobifluoren-4-yl) -amine

a) Synthesis of Biphenyl-2-yl- (9,9-dimethyl-9H-fluoren-2-yl) amine

1,1'-bis (diphenylphosphino) ferrocene (1.5 g, 2.7 mmol), palladium acetate (616 mg, 2.7 mmol) and sodium tert-butoxide (22.9 g, 238 mmol) were degassed toluene (400 ml) To a solution of biphenyl-2-ylamine (31.0 g, 183 mmol) and 2-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol) and the mixture was refluxed for 20 hours Under heating. The reaction mixture was cooled to room temperature, concentrated with toluene and filtered through celite. The filtrate was concentrated with water, reextracted with toluene, the combined organic phases were dried and evaporated in vacuo. The residue was filtered through silica gel (heptane / dichloromethane) and crystallized from isopropanol. Biphenyl-2-yl- (9,9-dimethyl-9H-fluoren-2-yl) amine was obtained in the form of a pale yellow solid (63.0 g, 95% of theory).

b) Synthesis of biphenyl-2-yl- (9,9-dimethyl-9H-fluoren-2-yl)-(9,9'-spirobifluoren-4-yl) amine

Tri-tert-butylphosphine (4.4 ml of 1.0 M solution in toluene, 4.4 mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide (16.0 g, 166 mmol) were degassed toluene (500 ml) Biphenyl-2-yl- (9,9-dimethyl-9H-fluoren-2-yl) amine (40.0 g, 111 mmol) and 4-bromo-9,9'-spirobifluorene (56.9 g 144 mmol), and the mixture was heated at reflux for 2 hours. The reaction mixture was cooled to room temperature, concentrated with toluene and filtered through celite. The filtrate was evaporated in vacuo and the residue was crystallized from ethyl acetate / heptane. The crude product was extracted in a Soxhlet extractor (toluene) and purified twice by zone sublimation under vacuum (p = 3 × 10 ⁻⁴ mbar, T = 298 ° C.). The product was isolated in the form of a pale yellow solid (20.4 g, 27% of theory, purity> 99.99% according to HPLC).

The following compounds were similarly obtained:

Example 5a Biphenyl-4-yl- (9,9-dimethyl-9H-fluoren-2-yl)-[4- (9,9'-spiro-bifluoren-4-yl) -phenyl] Synthesis of Amine

Biphenyl-4-yl- (9,9-dimethyl-9H-fluoren-2-yl (4,4,5,5tetramethyl- [1,3,2] dioxaborolan-2-yl)- Synthesis of Phenyl] -amine

102 g (198 mmol) of biphenyl-4-yl- (4-bromo-phenyl)-(9,9-dimethyl-9H-fluoren-2-yl) -amine, 4,8 g (5,9 mmol) of Pd (dppf) Cl ₂ , 61,6 g (238 mmol) of bis (pinacolato) diboron and 58,3 g (594 mmol) of potassium acetate in 1300 mL of 1,4-dioxane Dissolved. The reaction mixture was refluxed, shaken for 12 h under argon atmosphere, and after cooling to room temperature the mixture was filtered through celite. The filtrate was evaporated in vacuo and the residue was crystallized from heptane. The product was isolated in the form of a pale yellow solid (87 g, 78% of theory).

Synthesis of Biphenyl-4-yl- (9,9-dimethyl-9H-fluoren-2-yl)-[4- (9,9'-spiro-bifluoren-4-yl) -phenyl] -amine

28 g (49,4 mmol) of biphenyl-4-yl- (9,9-dimethyl-9H-fluoren-2-yl (4,4,5,5-tetramethyl- [1,3,2] Dioxaborolan-2-yl) -phenyl] -amine, 20 g (49,4 mmol) of 4-bromspirobifluorene, 1,8 g (2,5 mmol) of PdCl ₂ (Cy) ₃ , 15 g (99 mmol) cesium fluoride was dissolved in 500 mL of toluene The reaction mixture was refluxed, shaken for 12 hours under argon atmosphere, and cooled to room temperature, then the mixture was filtered through celite. The residue was evaporated in vacuo and the residue crystallized from heptane The crude product was extracted in a Soxhlet extractor (toluene) and purified twice by zone sublimation under vacuum The product was isolated in the form of a pale yellow solid (9 g, 24% of theory, purity according to HPLC> 99.99%).

The following compounds were similarly synthesized:

Example 6a: 9-spiro-4-yl-3,6-diphenyl-9H-carbazole

250 mL p-xylol of 19.2 g (47 mmol) 4-brom-9-spirobifluorene, 15 g (47 mmol) 3,6-diphenyl-9-H-carbazole and 29.2 g Rb ₂ CO ₃ Suspended in. The suspension was given 0.95 g (4,2 mmol) Pd (OAc) ₂ and 12.6 ml of tri-tert-butylphosphine 1 M solution. The mixture was stirred at reflux for 24 h. After cooling the organic phase was separated, washed three times with 150 mL water, then concentrated to dryness in vacuo. The residue was heated to extract with toluene, recrystallized three times from toluene and then sublimed under high vacuum. The yield is 19.6 g (30.9 mmol), corresponding to 66% of theory. Purity is 99.9% according to HPLC.

The following compounds were similarly obtained:

B) Device example

OLEDs according to the invention and OLEDs according to the prior art were prepared by the general method according to WO # 2004/058911, which is adapted to the situation (layer-thickness change, material) described herein.

Data on various OLEDs are shown in Examples 1-5 below (see Tables 1-7).

The substrate used was a glass plate coated with structured ITO (indium tin oxide) of 50 nm thickness. OLEDs basically have the following layer structure: substrate / hole-injection layer (IL) / hole-transport layer (HTL) / hole-injection layer (IL) / electron-blocking layer (EBL) / emission layer (EML) / electron Transport layer (ETL) and finally cathode. In the device structure according to Table 3, a similar structure is used except that the first hole injection layer is omitted.

Other examples are shown in the following general device structure shown in Table 6: Substrate / p-doped hole transport layer (HIL1) / hole-transport layer (HTL) / p-doped electron blocking layer (HIL2) / electron-blocking layer (EBL) / Emission layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) and finally the cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm.

Other examples are shown in the following general device structure shown in Table 7. This structure differs from the structure of the example of Table 6 in that the second p-doped electron blocking layer is omitted and the hole blocking layer (HBL) is present between the emissive layer and the electron transport layer.

The exact structure of all OLEDs made in the examples of the present invention are shown in Tables 1, 3, 6 and 7. Materials required for the manufacture of OLEDs are shown in Table 5. The data obtained are specified and / or shown in Tables 2 and 4.

All materials are applied by thermal deposition in a vacuum chamber. The emitting layer here always consists of at least one matrix material (host material) and radioactive dopant (emitter), which are mixed with the matrix material (s) in a certain proportion by volume by co-evaporation. The expression H1: SEB1 (95%: 5%) here means that the substance H1 is present in the layer by the volume of 95% and SEB1 is present in the layer by the ratio of 5%. Similarly, the electron-transporting layer can also consist of a mixture of two materials.

OLEDs feature standard methods. For this purpose, the electroluminescent spectrum, current efficiency (measured in cd / A), power efficiency (measured in lm / W), and external quantum efficiency (EQE, measured in percentage) (currents assuming Lambert emission characteristics) / Voltage / light emission density feature line (as a function of light emission density calculated from the IUL feature line), and lifetime. The electroluminescent spectrum is measured at an emission density of 1000 cd / m ² and the CIE 1931 x and y color coordinates are calculated therefrom. The expression EQE @ 1000 cd / m ² represents the external quantum efficiency at an operating luminous density of 1000 cd / m ² . LT80 @ 6000 cd / m ² is the lifetime from the emission of 6000 cd / m ² to the 80% of the initial intensity, ie 4800 cd / m ² . LT80 @ 60 mA / cm ² is the lifespan from the initial emission of the OLED to 80% of the initial emission at a constant current of 60 mA. The data obtained for the various OLEDs are summarized and / or shown in Tables 2 and 4.

Use of the compounds according to the invention as hole-transport materials in fluorescent and phosphorescent OLEDs

In particular the compounds according to the invention are suitable as HIL, HTL or EBL in OLEDs. It is suitable as a single layer but also as HIL, HTL, EBL or as a mixed component in EML.

Example 1

Single blue devices are shown in Tables 1 and 2, and triplet green devices are shown in Tables 3 and 4.

Compared to devices comprising NPB as reference (V1, V3), the samples comprising the compounds according to the invention show high efficiency and significantly improved lifetimes in both singlet blue and also triplet green devices. In comparison to the reference substances HTMV1 (V2, V4), the compounds according to the invention HTM1 have significantly improved efficiency and a fairly good lifetime.

Table 5: Structure of materials used

Example 2

In different blue fluorescent device structures (Table 6), reference devices V5 and V6 (NPB and HTMV1) using materials according to the state of the art are compounds E3 (8.5%), E4 (8.3%), E5 according to the invention. Lower efficiency (V5) compared to devices containing (7.9%), E6 (7.6%), E7 (7.8%), E8 (8.9%), E9 (8.4%), E10 (8.1%) and E11 (8.2%) EQE @ 10 mA / cm ² ) of 6.2% for V6 and 5.8% for V6.

Reference samples V5 and V6 also include samples E3 (305 h), E4 (290 h), E5 (320 h), E6 (390 h), E7 (365 h), E8 (165 h), E9 (280 h), It has a lower lifespan (120 hours of V5 (LT80 @ 60 mA) and 105 hours of V6) compared to E10 (285 h) and E11 (340 h).

Example 3

In the different green phosphor structure (Table 6), the reference element V7 represents compounds E12 (20.0%), E13 (19.6%), E14 (18.9%), E15 (19.2%) and E16 (20.2%) according to the invention. It has a low 11.7% efficiency (EQE @ 2mA / cm ² ) compared to the containing sample. Reference sample V6 also has a lower lifetime of 80 h (LT80 @ 20 mA) compared to samples E12 (90 h), E13 (185 h), E14 (105 h), E15 (205 h) and E16 (185 h). .

Use of the compounds according to the invention as matrix material in phosphorescent OLEDs

Example 4

In different green phosphorescent device structures (Table 7), the reference device V8, which does not have a compound according to the invention as the matrix material of the emitting layer, is used as a mixed matrix material in EML, the compound HTM3 according to the invention (16.1% EQE @ 2 mA / cm ² ) with lower efficiency (14.4% EQE @ 2 mA / cm ² ) compared to sample E17. Reference sample V8 also has a low lifespan of 305 hours (LT80 @ 20 mA) compared to 330 hours of sample E17.

Example 5

In different green phosphorescent device structures (Table 7), the compounds according to the invention have been shown to combine with lactam compound H4 and have a beneficial effect as mixed matrix components in the emitting layer. Reference element V9 has an efficiency of 17.6% (EQE @ 2 mA / cm ² ) and a lifetime of 255 hours. As shown by Examples E18 and E19 compared to V9, the lifetime can be improved by adding the compounds according to the invention to the emissive layer as co-matrix materials. Device E18 exhibits an efficiency of 13.4% and a life of 400 hours, and device E19 exhibits an efficiency of 17.9% and a life of 270 hours, all of which are improvements over the reference device V9.

Claims (16)

A compound of formula (1)

[Wherein the following applies to symbols and exponents used:
Ar ¹ is the same or different at each occurrence, having 6 to 60 carbon atoms selected from the group consisting of fluorene, spirobifluorene, biphenyl, terphenyl, quarterphenyl, carbazole, dibenzofuran and dibenzothiophene Aromatic or heteroaromatic ring systems, each of which may also be substituted with one or more radicals R ⁵ ; Wherein Ar ¹ and Ar ² may also be connected to each other by a group E;
Ar ² is the same or different at each occurrence, an aromatic or heteroaromatic ring system having 6 to 60 carbon atoms, which in each case may also be substituted by one or more radicals R ⁵ ; Ar ¹ and Ar ² here may also be connected to one another by the group E;
Ar ^S is the same or different at each instance, an aromatic or heteroaromatic ring system having 6 to 60 carbon atoms, which in each case may also be substituted with one or more radicals R ⁵ ;
E is the same or different at each occurrence, a single bond, C (R ⁵ ) ₂ , NR ⁵ , O or S;
R ¹ , R ² , R ³ , R ⁴ are the same or different at each occurrence, H, D, F, Cl, Br, I, CN, Si (R ⁶ ) ₃ , linear alkyl of 1 to 40 carbon atoms, alkoxy Or a thioalkyl group or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 carbon atoms, each of which may be substituted by one or more radicals R ⁶ , in which case at least one non-adjacent CH ₂ group is Si (R ⁶ ) ₂ , C = NR ⁶ , P (= O) (R ⁶ ), SO, SO ₂ , NR ⁶ , O, S or CONR ⁶ and at least one H atom may be D, F, Cl , May be substituted with Br or I), aromatic or heteroaromatic ring system having 6 to 60 carbon atoms, which may in each case be substituted by one or more radicals R ⁶ , aryl having 5 to 60 aromatic ring atoms aryloxy or heteroaryloxy group having an aralkyl (which may be substituted by one or more radicals that R ^6), or from 5 to 60 ring atoms Kill or heterocyclic aralkyl group is selected from the group consisting of (which may be substituted by one or more radicals R ⁶ in each case), where the substituent two or more adjacent R ¹ or R ² or R ³ or R ⁴ are optionally mono- or Can form poly-cyclic, aliphatic ring systems, which may be substituted with one or more radicals R ⁶ ;
R ⁵ is the same or different at each occurrence, H, D, F, Cl, Br, I, CN, Si (R ⁶ ) ₃ , a straight chain alkyl, alkoxy or thioalkyl group having 1 to 40 carbon atoms or 3 to 40 carbon atoms Branched or cyclic alkyl, alkoxy or thioalkyl groups of each of which may be substituted by one or more radicals R ⁶ , where in each case one or more non-adjacent CH ₂ groups are Si (R ⁶ ) ₂ , C═NR ⁶ , P (= 0) (R ⁶ ), SO, SO ₂ , NR ⁶ , O, S or CONR ⁶ , and one or more H atoms can be replaced with D, F, Cl, Br or I ), Aromatic or heteroaromatic ring systems having 6 to 60 carbon atoms, which in each case may be substituted by one or more radicals R ⁶ , aryloxy or heteroaryloxy groups having 5 to 60 aromatic ring atoms may be substituted by one or more radicals R ⁶ Yes), or aralkyl or H. having 5 to 60 aromatic ring atoms Loa Le alkyl group is selected from the group consisting of a (which may be substituted with one or more radicals R ⁶ in each case), in which two or more adjacent substituents R ⁵ are optionally mono-or polycyclic, aliphatic ring system (which is one or more radicals May be substituted with R ⁶ );
R ⁶ is selected from the group consisting of H, D, F, aliphatic hydrocarbon radicals of 1 to 20 carbon atoms or aromatic or heteroaromatic ring systems of 5 to 30 carbon atoms, where one or more H atoms may be replaced by D or F Wherein two or more adjacent substituents R ⁶ may form a mono- or polycyclic, aliphatic ring system with one another;
i is equal or different at each occurrence, 0 or 1;
m is 0, 1 or 2;
n is the same or different at each occurrence, 0, 1, 2, 3 or 4;
p is 1;
q is 0;
r, s are the same or different in each case 0, 1, 2, 3 or 4, wherein p + r <4 and q + s <4;
Or a compound of formula (1) in which the following definitions apply to the groups Ar ¹ and Ar ² instead of the above definitions:
Ar ¹ and Ar ² are connected to each other via the group E as defined above,
The groups Ar ¹ and Ar ² in each case are the same or differently aromatic or heteroaromatic ring systems having 6 to 60 carbon atoms, which in each case may also be substituted with one or more radicals R ⁵ . The compound of claim 1, wherein the index i is zero. A compound according to claim 1 selected from compounds of the formulas (3), (6) and (9):

Wherein the symbols and indices used are as defined in claim 1. The compound of claim 1 selected from compounds of the formulas (3a), (6a) and (9a):

Wherein the symbols and indices used are as defined in claim 1. A compound according to claim 1 selected from compounds of formulas (3b), (6b) and (9b):

Wherein the symbols used are as defined in claim 1. The process according to claim 1, wherein the groups Ar ¹ and Ar ² are not connected to each other via group E and are the same or different in each case from the group of formulas (11) to (66), wherein the dotted line is a bond to nitrogen Wherein the group may be substituted with one or more radicals R ⁵ :

. 7. A compound according to claim 6, wherein Ar ¹ and Ar ² are the same or different in each case selected from the group of formulas (11), (20) and (24), which may be substituted by one or more radicals R ⁵ . Compound characterized by the above-mentioned. The compound of claim 1, wherein the groups Ar ¹ and Ar ² are selected differently from each other. The process according to claim 1, wherein R ¹ to R ⁴ are the same or different at each occurrence, H, F, CN, a straight alkyl or alkoxy group having 1 to 10 carbon atoms or a branched or cyclic alkyl or alkoxy having 3 to 10 carbon atoms. Groups (each of which may be substituted by one or more radicals R ⁶ , where one or more non-adjacent CH ₂ groups may be replaced by O and one or more H atoms may be replaced by F), 6 to 24 aromatic A compound characterized in that it is selected from the group consisting of aromatic or heteroaromatic ring systems having ring atoms, which in each case may be substituted by one or more radicals R ⁶ . 2. A radical according to claim 1, wherein the radicals R ⁵ bonded to Ar ¹ or Ar ² or Ar ^S are the same or different at each occurrence: H, F, CN, straight chain alkyl groups having 1 to 10 carbon atoms, branched form having 3 to 10 carbon atoms Or an cyclic alkyl group or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R ⁶ . 2. Compounds according to claim 1, wherein Ar ¹ and Ar ² are not linked to each other via the group E. 2. Compounds according to claim 1, characterized in that the indices m, s, r and n are zero. A compound according to claim 6 characterized in that
R ⁵ is the same or different in each case when the radical R ⁵ is bonded to Ar ¹ or Ar ² or Ar ^S , H, F, CN, a straight alkyl group having 1 to 10 carbon atoms, branched form having 3 to 10 carbon atoms or A cyclic alkyl group or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R ⁶ ; or
R ⁵ bonded to the carbon crosslink in the formulas (20) to (23), (53) and (54) is the same or differently, an alkyl group having 1 to 10 carbon atoms, a methyl group, or a phenyl group, which is formed by one or more radicals R ⁶ May be substituted); or
R ⁵ bonded to a nitrogen bridge in formulas (28) to (31), (40) to (43) or (55) to (58) and (63) to (66) may be substituted with one or more radicals R ⁶ Phenyl group;
R ⁶ is the same or different at each occurrence is selected from the group consisting of H, a straight chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms or an aromatic ring system having 6 to 24 carbon atoms;
i is 0;
m is 0;
n is 0;
r is 0;
s is 0. 14. A compound according to claim 1, wherein the diarylamino group is introduced by a CN coupling reaction between 1- or 3- or 4-halogenated spirobifluorene and diarylamine. Manufacturing method. Organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic dye-sensitive solar cells, organic optical detectors, organic photoreceptors, organic electro-quenching devices, luminescent electricity An electronic device comprising at least one compound according to any one of claims 1 to 13 selected from the group consisting of chemical cells, organic laser diodes and organic plasmon radiating devices. An electronic device comprising at least one compound according to claim 1, wherein said compound is included as a hole-transport material in a hole-transport or hole-injection or exciton-blocking or electron-blocking layer And an organic electroluminescent device, characterized in that it is included as a matrix material for fluorescent or phosphorescent emitters in the emitting layer.