DE4446818A1 - Spiro cpds. use in electroluminescent device, esp. 9,9'-spiro:bi:fluorene(s) - Google Patents

Abstract

The use of spiro cpds. of formula (I) in electroluminescent devices is claimed. In (I), K1, K2 = conjugated systems. Also claimed are spiro cpds. of formula (IA); electroluminescent devices contg. cpd(s). (I); and organic electroluminescent material. In (IA), A, B, K, L, M, N = R-Q-(T)m-(CH=CH)n-, R1-(T)m-(CH=CH)n-, R-Q-(CH=CH)n-(T)m-, R1-(CH=CH)n-(T)m-, R1-(T)p-(CH=CH)n-(T)m- or R2R3N-; and A, B may also = a 1-22 C alkyl, alkoxy or ester gp., CN, NO2; Ar or -O-Ar; Q = (a (het)arylene gp. of formula (II); and T = a (het)arylene gp. of formula (III): Ar = phenyl, biphenyl, 1- or 2-naphthyl, 2-thienyl or 2-furanyl, opt. mono- or di-substd. by R; m, n, p - 0, 1, 2 or 3; X, Y = CR or N; X = -O-, -S-, -CR1R4, -CH=CH- or -CH=N-; R, R1, R4 = H, a 1-22 C alkyl, alkoxy or ester gp., CN, NO2, -NR2R3, Ar or -O-Ar; R2, R3 = H, 1-22 C alkyl, Ar or 3-methylphenyl.

Description

There is a high industrial need for large-area solid-state Light sources for a number of applications, mainly in the area of Display elements, screen technology and lighting technology. The none of the requirements currently imposed on these light sources existing technologies can be solved completely satisfactorily.

As an alternative to conventional display elements such as light bulbs, Gas discharge lamps and not self-illuminating Liquid crystal display elements have been around for some time Electroluminescence (EL) materials and devices, such as light emitting Diodes (LED), known.

Electroluminescent materials are substances that are capable of creating one to emit electric field light. The physical model for Description of this effect is based on the radiative recombination of Electrons and electron gaps ("holes"). With light emitting diodes the charge carriers over the cathode or anode into the Electroluminescent material injected.

Electroluminescent devices contain a luminescent material as light emitting layer.

Generally, electroluminescent materials and devices are, for example described in Ullmann’s Encyclopedia of Industrial Chemistry, Vol A9, 5th Ed. VCH Verlag 1987 and the literature cited there.

In addition to inorganic substances such as ZnS / Mn or GaAs, there are also organic ones Connections have become known as EL materials.  

A description of EL devices that use low molecular weight organic Containing EL materials can be found, for example, in US 4,539,507.

Disadvantages of these low molecular weight organic materials are, for example the insufficient film-forming properties and a pronounced tendency to Crystallization.

Recently, polymers have also been described as EL materials (see e.g. B. WO-A 90/13148). However, the light output (quantum efficiency) is these substances are considerably lower than those of the low molecular weight Links.

It was desirable to find EL materials that have good light yields show and at the same time can be processed into thin homogeneous films, the one have a low tendency to crystallize.

It has now surprisingly been found that spiro compounds, especially derivatives of 9,9'-spirobifluorene, in an excellent manner as EL materials are suitable.

Individual compounds of this type are described, for example, in US Pat. No. 5,026,894, J.M. Tour et al. J. Am. Chem. Soc. 112 (1990) 5662 and J.M. Tour et al. Polym. Prepr. (1990) 408 as linking elements for polymeric, organic Semiconductors described and as materials for molecular electronics suggested. However, about a possible use as EL materials nothing said.

The invention therefore relates to the use of spiro compounds general formula (I),

in which
K¹ and K² mean independently conjugated systems in electroluminescent devices.

Compounds of formula (I) are characterized by good solubility in common organic solvents, improved film formation properties and a significantly reduced tendency towards crystallization. This will make the Manufacture of electroluminescent devices facilitated and their Lifespan increased. The emission properties of the invention Compounds used can be selected by choosing suitable substituents can be adjusted across the entire range of the visible spectrum. In addition, the covalently bonded arrangement of the two parts of the Spiro compound has a molecular structure in such a way that in both halves certain properties of the molecule can be set independently. So one half z. B. charge transport or Have charge injection properties while the other is light emitting Possesses properties. The spatial fixed by the covalent connection The proximity of the two halves is favorable for the energy transfer (see e.g. B. Liphardt, W. Lüttke, Liebigs Ann. Chem. (1981) 1118).

Preferred compounds of formula (I) are 9,9'-spirobifluorene derivatives Formula (II),

the benzo groups independently substituted and / or fused could be.  

Spirobifluorene derivatives of the formula (III) are particularly preferred,

where the symbols and indices have the following meanings:
K, L, M, N are the same or different

R, identical or different, has the same meanings as K, L, M, N or is -H, a linear or branched alkyl, alkoxy or ester group with 1 to 22, preferably 1 to 15, particularly preferably 1 to 12 C, Atoms, -CN, -NO₂, -NR²R³, -Ar or -O-Ar;
Ar is phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl, where each of these groups can carry one or two radicals R,
m, n, p are 0, 1, 2 or 3;
X, Y are the same or different CR or nitrogen;
Z is -O-, -S-, -NR¹-, -CR¹R⁴-, -CH = CH-, -CH = N-;
R¹, R⁴, the same or different, have the same meanings as R;
R², R³ are identical or different H, a linear or branched alkyl group with 1 to 22 carbon atoms, -Ar, 3-methylphenyl.

Preferred compounds of the formula (III) are those of the formula (IIIa) - (IIIg)
IIIa) K = L = M = N and is from the group:

R = C₁-C₂₂-alkyl, C₂H₄SO₃-
IIIb) K = M = H and N = L and is from the group:

IIIc) K = M and is from the group:

and N = L and is from the group:

IIId) K = M and is from the group:

and N = L and is from the group:

IIIe) K = L = H and M = N and is from the group:

IIIf) K = M and is from the group:

and M = N and is from the group:

IIIg) K = L and is from the group:

and M = N and is from the group:

Particularly preferred compounds of the formula (III) are those of the formulas (IIIaa) to (IIIdb):
(IIIaa) K = L = M = N and is from the group:

(IIIba) K = M = H and N = L and is from the group:

(IIIca) K = M and is from the group:

and N = L and is:

(IIIda) K = M and is from the group:

(IIIab) K = = M = N and is from the group

(IIIbb) K = L = H and M = N and is from the group:

(IIIcb) K = L and is from the group:

and M = N and is:

(IIIdb) K = L and is from the group:

and M = N and is from the group:

and N = L and is from the group:

Very particularly preferred spiro compounds are those of the formula (IV)

where the symbols have the following meanings:
K, L, M, N, R⁵, R⁶ are the same or different one of the groups G1 to G14:

and R⁵, R⁶ can also be the same or different hydrogen or a linear or branched alkyl, alkyloxy or ester group with 1 to 22 C atoms, -CN or -NO₂ mean.

Particularly preferred spiro compounds of the formula (IV) are 2,2 ′, 4,4 ′, 7,7′-hexakis (biphenylyl) -9.9′-spirobifluorene, 2,2 ′, 4,4 ′, 7,7′-hexakis (terphenylyl) -9.9′-spirobifluorene and the compounds listed in Table 1, in which the Abbreviations G1 to G14 have the meanings given in formula (IV) to have.

Table 1

Spiro compounds of the formula (IV) R⁵ = R⁶ = hydrogen

Some of the spiro compounds used according to the invention are known and partly new.

The invention therefore also relates to spiro compounds of the formula (V)

where the symbols have the following meanings:
A, B, K, L, M, N are the same or different

and A, B may also be the same or different, a linear or branched alkyl, alkyloxy or ester group having 1 to 22 carbon atoms, -CN, -NO₂, -Ar or -O-Ar;
R is -H, a linear or branched alkyl, alkoxy or ester group with 1 to 22, preferably 1 to 15, particularly preferably 1 to 12 C atoms, -CN, -NO₂₁ -NR²R³, -Ar or -O-Ar;
Ar is phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl, where each of these groups can carry one or two radicals R;
m, n, p are 0, 1, 2 or 3;
X, Y are the same or different CR, N;
Z is -O-, -S-, -NR¹-, -CR¹R⁴-, -CH = CH-, -CH = N-;
R¹, R⁴, the same or different, have the same meanings as R;
R², R³ are identical or different H, a linear or branched alkyl group with 1 to 22 carbon atoms, -Ar or 3-methylphenyl.

Compounds of the formula (V) in which K, L, M, N and optionally A, B are selected from the following groups G1 to G14:

Particularly preferred spiro compounds of the formula (V) are 2,2 ′, 4,4 ′, 7,7′-hexakis (biphenylyl) -9.9′-spirobifluorene, 2,2 ′, 4,4 ′, 7,7′-hexakis (terphenylyl) -9.9′-spirobifluorene, and the compounds listed in Tables 2 and 5, the Abbreviations G1 to G14 have the same meanings as in formula (V).  

Table 2

Spiro compounds of the formula (V) A = B = G1

Table 3

Spiro compounds of the formula (V) A = B = G2

Table 4

Spiro compounds of the formula (V) A = B = G3

Table 5

Spiro compounds of the formula (V) A = B = G12

The spiro compounds used according to the invention are produced according to methods known per se from the literature, as used in standard works for Organic synthesis, e.g. B. Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart and in the corresponding volumes of the series "The Chemistry of Heterocyclic Compounds" by A. Weissberger and E. C. Taylor (editor).

The production takes place under reaction conditions for the above Implementations are known and suitable. It can also by itself known variants not mentioned here can be used.

Compounds of formula (III) are, for example, based on Obtained 9,9'-spirobifluorene, the synthesis of z. B. by R. G. Clarkson, M. Gomberg, J.Am. Chem. Soc. 52 (1930) 2881.

The preparation of compounds of formula (IIIa) can for example starting from tetrahalogenation in positions 2.2 ′, 7.7 ′ of 9.9′- Spirobifluorens and subsequent substitution reaction take place (see e.g. US 5,026,894) or via a tetraacetylation of positions 2.2 ', 7.7' of 9,9'-spirobifluorene with subsequent C-C linkage after conversion of Acetyl groups in aldehyde groups or heterocycle structure after conversion the acetyl groups take place in carboxylic acid groups.

The preparation of compounds of the formula (IIIb) can be carried out analogously, for example to those of the formula IIIa, the stoichiometric ratios at implementation should be chosen so that positions 2.2 'and 7.7' be functionalized (see e.g. J.H. Weisburger, E.K. Weisburger, F.E. Ray, J. Am. Chem. Soc. 72 (1959) 4253; F.K. Sutcliffe, H.M. Shahidi, D. Paterson, J. Soc. Dyers Color 94 (1978) 306 and G. Haas, V. Prelog, Helv. Chim. Acta 52 (1969) 1202).  

The preparation of compounds of the formula (IIIc) can be carried out, for example, via a Dibromination in the 2,2'-position and subsequent diacetylation in the 7.7'-position of 9,9'-spirobifluorene and subsequent implementation analogous to that of Connections IIIa take place.

Compounds of the formulas (IIIe) - (IIIg) are suitable, for example, by choice Substituted starting compounds in the construction of spirobifluorene producible, e.g. B. can 2,7-dibromo spirobifluorene from 2,7-dibromo fluorenone and 2,7-dicarbethoxy-9,9-spirobifluorene by using 2,7- Dicarbethoxyfluorenon be built up. The free 2, '7' positions of the Spirobifluorens can then be independently substituted further.

For the synthesis of the groups K, L, M, N, reference is made, for example, to DE-A 23 44 732, 24 50 088, 24 29 093, 25 02 904, 26 36 684, 27 01 591 and 27 52 975 for compounds with 1,4-phenylene groups;
DE-A 26 41 724 for compounds with pyrimidine-2,5-diyl groups;
DE-A 40 26 223 and EP-A 03 91 203 for compounds with pyridine-2,5-diyl groups;
DE-A 32 31 462 for compounds with pyridazine-3,6-diyl groups; N. Miyaura, T. Yanagi and A. Suzuki in Synthetic Communications 11 (1981) 513 to 519, DE-A-39 30 663, MJ Sharp, W. Cheng, V. Snieckus in Tetrahedron Letters 28 (1987), 5093; GW Gray in J. Chem. Soc. Perkin Trans II (1989) 2041 and Mol. Cryst. Liq. Cryst. 172: 165, Mol. Cryst. Liq. Cryst. 204 (1991) 43 and 91; EP-A 0449 015; WO 89/12039; WO 89/03821; EP-A 0 354434 for the direct linking of aromatics and heteroaromatics;
The production of disubstituted pyridines, disubstituted pyrazines, disubstituted pyrimidines and disubstituted pyridazines can be found, for example, in the corresponding volumes of the series "The Chemistry of Heterocyclic Compounds" by A. Weissberger and EC Taylor (editor).

According to the invention, the spiro compounds of the formulas (I) described (II) and (III) use as electroluminescent materials, i.e. that is, they serve as active layer in an electroluminescent device. As an active layer in the For the purposes of the invention apply electroluminescent materials that are capable of Application of an electric field to emit light (light-emitting layer), as well as materials used to inject and / or transport the positive and / or improve negative charges (charge injection layers and Charge transport layers).

Electroluminescent materials according to the invention are distinguished among others also due to an exceptional temperature stability compared to known organic electroluminescent materials. This shows z. B. in that the emission maximum of the compounds after thermal Load little, in other cases not at all and that at many compounds even see an increase in the emission maximum thermal load is determined.

The invention therefore also relates to an organic Electroluminescent material, characterized in that be Emission maximum in the range from 400 to 750 nm, measured at Room temperature, by no more than 15%, relative to the initial state, diminished after the material, applied in a thickness of no more than 1 µm on a quartz substrate, in an inert atmosphere at a pressure of was not heated to 250 ° C for more than 1 mbar for 30 min.

The reduction in the emission maximum is preferably not more than 10%, particularly preferably 5%, relative to the initial state before thermal treatment.

Electroluminescent materials are very particularly preferred Reduction of the emission maximum below the above Show conditions.  

Organic electroluminescent materials are particularly preferred, which under the specified conditions an increase in the emission maximum demonstrate.

Under an inert atmosphere, a nitrogen or Understand the argon atmosphere.

The invention therefore also relates to an electroluminescent device one or more active layers comprising one or more compounds of the Formula (I), (II) and / or (III). The active layer can be, for example light-emitting layer and / or a transport layer and / or a Charge injection layer.

The general structure of such electroluminescent devices is described for example in US 4,539,507 and US 5,151,629.

They usually contain an electroluminescent layer between one Cathode and an anode, wherein at least one of the electrodes is transparent. In addition, there can be between the electroluminescent layer and the cathode an electron injection and / or electron transport layer can be introduced and / or between the electroluminescent layer and the anode Hole injection and / or hole transport layer may be introduced. As a cathode can e.g. B. Ca, Mg, Al, In, Mg / Ag serve. As an anode z. B. Au or ITO (Indium oxide / tin oxide on a transparent substrate, e.g. made of glass or a transparent polymer).

In operation, the cathode is at a negative potential with respect to the anode electrons from the cathode into the Electron injection layer / electron transport layer or directly into the light emitting layer injected. At the same time, holes from the anode are in the hole injection layer / hole transport layer or directly into the light emitting layer injected.  

The injected charge carriers move under the influence of the applied ones Tension towards each other through the active layers. This leads to the Interface between charge transport layer and light emitting layer or within the light-emitting layer to form electron / hole pairs recombine emitting light.

The color of the emitted light can by the light-emitting layer connection used can be varied.

Electroluminescent devices are used for. B. as self-luminous Display elements such as control lamps, alpha numeric displays, Information signs, and ip optoelectronic couplers.

The invention is explained in more detail by the examples, without referring to them want to restrict.

Examples A. Starting compounds

• a) Synthesis of 9,9'-spirobifluorene
• 6.3 g of magnesium shavings and 50 mg of anthracene are mixed in 120 ml dry diethyl ether in a 1 l three-neck flask with reflux condenser submitted under argon and the magnesium with ultrasound for 15 min activated.
• 62 g of 2-bromobiphenyl are dissolved in 60 ml of dry diethyl ether. About 10 ml of this solution are placed in the magnesium added to start the Grignard reaction.
• After the start of the reaction is under further ultrasound the 2-bromobiphenyl solution was added dropwise so that the solution was mild Reflux boils. When the addition is complete, the reaction mixture becomes a cooked under reflux under ultrasound for a further hour.
• 48.8 g of 9-fluorenone are dissolved in 400 ml of dry diethyl ether and added dropwise to the Grignard solution under further ultrasonication. To when the addition is complete, boil for a further 2 h. The after cooling the Reaction mixture failed yellow magnesium complex of 9- (2-biphenyl) -9-fluorenols is suctioned off and with a little ether washed. The magnesium complex is in 800 ml of ice water hydrolyzed, which contains 40 g of ammonium chloride. After 60 min The 9- (2-biphenyl) -9-fluorenol formed is suction-filtered with stirring Washed water and sucked dry.
• The dried 9- (2-biphenyl) -9-fluorenol is then in 500 ml of glacial acetic acid dissolved in the heat. 0.5 ml of conc. hydrochloric acid given. Allow the solution to boil for a few minutes and drop it formed 9,9'-spirobifluorene from the hot solution with water (Water addition until cloudiness begins). After cooling the product suctioned off and washed with water. The dried product becomes  further purification recrystallized from ethanol. 66 g (80%, bez. on 2-bromobiphenyl) 9,9'-spirobifluorene as colorless crystals mp. 198 ° C.
• b) 2,2'-Dibrnm-9,9'-spirobifluorene (F.K. Sutcliffe, H.M. Shahidi, D. Patterson, J. Soc.Dyers Color 94 (1978) 306)
• 3.26 g (10.3 mmol) of 9,9'-spirobifluorene are dissolved in 30 ml of methylene chloride dissolved and mixed with 5 mg FeCl₃ (anhydrous) as a catalyst. Of the The reaction flask is protected from light. 1.12 ml (21.8 mmol) Bromine in 5 ml of methylene chloride are stirred within 30 min dripped. After 24 h, the resulting brown solution becomes saturated aqueous NaHCO₃ solution and water washed to remove excess bromine. The organic phase is after Drying concentrated over Na₂SO₄ on a rotary evaporator. The White The residue is recrystallized from methanol, giving 3.45 g (70%) the dibromo compound as colorless crystals, mp. 240 ° C.
• c) 2,2 ', 7,7'-tetrabromo-9,9'-spirobifluorene
• To a solution of 3.16 g (10.0 mmol) of 9,9'-spirobifluorene in 30 ml Methylene chloride are given 80 mg (0.5 mmol) of anhydrous FeCl₃ and 2.1 ml (41 mmol) bromine in 5 ml methylene chloride over 10 min dripped. The solution is refluxed for 6 hours. When it cools down Product out. The precipitate is filtered off and with little cold Washed methylene chloride. After drying, 6.0 g are obtained (95%) of the tetrabromo compound as a white solid.
• d) 2-Bromo-9,9'-spirobifluorene and 2,2 ', 7-tribromo-9,9'-spirobifluorene with changed stoichiometry can be produced in an analog manner  
• e) 9,9'-spirobifluorene-2,2'-dicarboxylic acid from 2,2′-dibromo-9,9′-spirobifluorene via 2, 2′-dicyano-9,9′-spirobifluorene
• 1.19 g of 2,2'-dibromo-9,9'-spirobifluorene and 0.54 g of CuCN are in 5 ml DMF heated to reflux for 6 h. The brown mixture obtained is in a mixture of 3 g FeCl₃ (hydrate.) and 1.5 ml conc. Hydrochloric acid in Poured 20 ml of water. The mixture is 30 min at 60 to 70 ° C. held to destroy the Cu complex. The hot aqueous solution is extracted twice with toluene. The organic phases then with dilute hydrochloric acid, water and 10% aqueous NaOH washed. The organic phase is filtered and concentrated. Of the yellow residue obtained is recrystallized from methanol. You get 0.72 g (80%) of 2,2'-dicyano-9,9'-spirobifluorene as slightly yellowish Crystals (melting range 215 to 245 ° C).
• 3 g of 2,2'-dicyano-9,9'-spirobifluorene are refluxed with 25 ml of 30% aqueous NaOH and 30 ml of ethanol for 6 h. The disodium salt of spirobifluorodicarboxylic acid precipitates as a yellow precipitate, which is filtered off and heated in 25% aqueous HCl in order to recover the free acid. The spirobifluorodicarboxylic acid is recrystallized from glacial acetic acid. 2.2 g (66.6%) of white crystals are obtained (mp. 376 ° C., IR band 1685 cm ⁻¹ C = O).
• 9,9'-spirobifluorene-2,2 ', 7,7'-tetracarboxylic acid is made from 2.2', 7.7'- Tetrabromo-9,9'-spirobifluorene can be represented in an analogous manner.
• f) 9,9'-spirobifluorene-2,2'-dicarboxylic acid from 9,9'-spirofluorene over 2,2'-diacetyl-9,9'-spirobifluorene (G. Haas, V. Prelog, Helv. Chim. Acta 52 (1969) 1202; V. Prelog, D. Bedekovic, Helv. Chim. Acta 62 (1979) 2285)  
• A solution of 3.17 g of 9,9'-spirobifluorene in 30 ml of abs. Carbon disulfide is added after adding 9.0 g of finely powdered, anhydrous AlCl₃ dropwise with stirring for 10 min 1.58 g acetyl chloride in 5 ml abs. Carbon disulphide and Boiled under reflux for 1 hour. The under reduced pressure Dry evaporated mixture is at 0 ° C with 100 g of ice and 50 ml 2n hydrochloric acid added. After the usual workup, the crude product separated chromatographically with benzene / ethyl acetate (10: 1) on silica gel. 3.62 g (89%) of 2,2'-diacetyl-9.9'-spirobifluorene (recrystallized from chloroform / ethyl acetate, mp. 255 to 257 ° C) and 204 mg of 2-acetyl 9,9′-spirobifluorene (recrystallized from chloroform / benzene, mp. 225 ° C).
• [In addition, 2,2 ′, 7-triacetyl- 9,9'-spirobifluorene (mp. 258 to 260 ° C) and 2,2 ', 7,7'-tetraacetyl 9,9'-spirobifluorene (mp. <300 ° C) are isolated, recrystallized from Ethyl acetate / hexane].
• 2,2 ′, 7-triacetyl- and 2,2 ′, 7,7′-tetraacetyl-9,9′-spirobifluorene 2,2 ′, 7,7′- Tetraacetyl-9,9'-spirobifluorene can be changed as the stoichiometry changes Main product can be obtained.
• To a solution of 6.0 g of sodium hydroxide in 30 ml of water 0 ° C with stirring first 7.2 g of bromine and then a solution of 3.0 g 2,2'-diacetyl-9,9'-spirobifluorene added dropwise in a little dioxane. To Another 1 hour's stirring at room temperature turns the clear yellow Solution with 1 g of sodium bisulfite, dissolved in 20 ml of water. After acidification with conc. Hydrochloric acid becomes the precipitated colorless The product is filtered off and washed with a little water. Recrystallization from ethanol provides 9,9'-spirobifluorene-2,2'-dicarboxylic acid as water-clear Prisms (mp 352 ° C).
• 9,9′-spirobifluorene-2-carboxylic acid, 9.9′-spirobifluorene-2,2 ′, 7- tricarboxylic acid and 9,9'-spirobifluorene-2,2 ', 7,7'-tetracarboxylic acid are in can be represented in an analogous manner.  
• g) 2,2'-bis (bromomethyl) -9,9'-spirobifluorene from 2,2′-dicarboxy-9,9′-spirobifluorene over 9,9′-spirobifluorene-2,2′- dimethanol
• (V. Prelog, D. Bedekovicc, Helv. Chim. Acta 62 (1979) 2285)
• At room temperature, 10 g of a 70 wt .-% solution of Sodium dihydro-bis (2-methoxyethoxy) aluminate (Fluka) in benzene slowly to a suspension of 2.0 g of 2,2'-dicarboxy-9,9'-spirobifluorene (free Carboxylic acid) added dropwise in 20 ml of benzene. After 2 hours of cooking under Reflux, whereby the carboxylic acid dissolves, becomes the excess Reductant decomposed at 10 ° C with water, the mixture with conc. Acidified hydrochloric acid and shaken with chloroform.
• The one washed with water and dried over magnesium sulfate organic phase is evaporated and the residue from benzene recrystallized. 1.57 g of 9,9'-spirobifluorene-2,2'-dimethanol are obtained (Mp 254 to 255 ° C).
• To a solution of 13.5 g of 9,9'-spirofluorene-2,2'-dimethanol in 400 ml Benzene are 91.5 g of a 33% aqueous solution of Dropped hydrogen bromide in glacial acetic acid and the mixture under 7 h Reflux cooked. Then it is mixed with 200 ml of water and with Organic washed water and dried over magnesium sulfate Phase evaporated. Chromatography on silica gel with benzene provides 11.7 g of 2,2′-bis (bromomethyl) -9,9′-spirobifluorene as colorless platelets (Mp 175-177 ° C).
• h) A solution of 380 mg of 9,9'-spirobifluorene-2,2'-dimethanol in 15 ml Toluene is mixed with 5 g chromium (VI) oxide on graphite (Seloxcette, Alpha Inorganics) were added and the mixture was refluxed under nitrogen for 48 h. Then is sucked off through a glass filter and the filtrate evaporated. Chromatography on silica gel with chloroform and Crystallization from methylene chloride / ether yields 152 mg  9,9'-spirobifluorene-2,2'-dicarbaldehyde (mp.) 300 ° C) and 204 mg 2'-hydroxymethyl-9,9'-spirobifluorene-2-carbaldehyde (Mp 262-263 ° C).
• i) 2,2′-diamino-9,9′-spirobifluorene
• A mixture of 150 ml conc. aqueous HNO₃ and 150 ml of glacial acetic acid become a boiling solution of 15.1 g 9,9'-spirobifluorene in 500 ml of glacial acetic acid were then added dropwise over a period of 30 min the solution is refluxed for a further 75 min. After cooling and Allow the solution to stand for 1 h, the same volume of water added and thus the product precipitated. Received after suction 18.5 g of yellow crystals (mp. 220 to 224 ° C) of 2,2'-dinitro-9.9'- Spirobifluorene. Recrystallization from 250 ml glacial acetic acid gives 12.7 g light yellow crystal needles (mp. 245 to 249 ° C, analytically pure 249 to 250 ° C).
• A mixture of 4.0 ml dinitro-spriobifluorene and 4.0 g iron powder are heated in 100 ml of ethanol under reflux, while 15 ml of conc. HCl are added dropwise over a period of 30 min. After another Excess iron is filtered off for 30 minutes under reflux. The green one The filtrate is concentrated in a solution of 400 ml of water, 15 ml. NH₄OH and Given 20 g of Na, K tartrate. The white diamine is of the dark green The solution of the iron complex is filtered off. The diamine is used for cleaning diluted HCl dissolved and at room temperature with activated carbon (Darco) stirred and filtered. The filtered solution is stirred (KPG stirrer) neutralized dropwise with NH₄OH and the precipitated Aspirated product. 3.5 g of white 2,2'-diamino-9.9'- are obtained. spirobifluorene, which can be recrystallized from ethanol (Mp 243 ° C).  
• j) Synthesis of 2,2 ', 7,7'-tetrabromo-9,9'-spirobifluorene by Bromination of solid 9,9'-spirobifluorene with bromine vapor
• 3.16 g are placed in a flat porcelain evaporating dish (⌀2 approx. 15 cm) (10 mmol) of finely powdered 9,9'-spirobifuuoren. This bowl is punched in a desiccator (⌀ approx. 30 cm) Intermediate floor. There are a on the bottom of the desiccator a crystallizing dish 15.6 g (4.8 ml, 96 mmol) bromine. The desiccator is closed, but the ventilation tap is opened so that the HBr formed can escape. The desiccator is in the Deduction. The next day, the porcelain bowl with the Bromine orange colored product taken out of the desiccator, and in The trigger is left for at least 4 hours so that excess bromine and HBr can escape.
• The product is dissolved in 150 ml dichloromethane and 50 ml each Sodium sulfite solution (saturated), sodium hydrogen carbonate solution (saturated) and water washed colorless. The dichloromethane solution will dried over sodium sulfate and evaporated. For cleaning out Dichloromethane / pentane 4: 1 recrystallized. Yield 5.7 g (92%) colorless Crystals.
• 1 H-NMR (CDCl₃, ppm): 6.83 (d₁ J = 1.83 Hz, 4H, H-1,1,8,8 ′); 7.54 (dd, J = 7.93, 1.83 Hz, 4H, H-3.3 ′, 6.6 ′); 7.68 (d₁ J = 7.93 Hz, 4H, H-4.4 ′, 5.5 ′).
• k) Synthesis of 2,2 ', 4,4', 7,7'-hexabromo-9.9-spirobifluorene
• To a solution of 3.16 g (10 mmol) 9,9'-spirobifluorene in 20 ml Methylene chloride are given 200 mg of anhydrous FeCl₃ and with Treated with ultrasound. The reaction flask is covered with Al foil Light access protected. Then 9.85 g (3.15 ml, 62 mmol) bromine in 5 ml methylene chloride within 15 min  dripped. The solution is refluxed for a further 20 h and then Treated with ultrasound. After cooling, petroleum ether is added and aspirated. For further purification, THF / methanol recrystallized and dried at 80 ° C for 5 h. Yield 6.15 g (77%) colorless crystals.
• 1 H-NMR (CDCl₃, ppm): 6.76 (d, J = 1.53 Hz, 2 H, H-1.1 ′); 6.84 (d, J = 1.83 Hz, 2H, H-8.8 '); 7.60 (dd, J = 8.54.1.83 Hz, 2 H, H-6.6 ′); 7.75 (d, J = 1.53 Hz, 2H, H-3.3 ′); 8.49 (d, J = 8.54 Hz, 2 H, H-5.5 ′).
• l) Synthesis of 2,7-dibromo-9,9'-spirobifluorene
• The Grignard reagent prepares magnesium shavings from 0.72 g (30 mmol) and 5.1 ml (30 mmol) of 2-bromobiphenyl in 15 ml of diethyl ether is in Course of 2 h, with stirring (in an ultrasonic bath) to a boiling Suspension of 10.0 g (29.6 mmol) of 2,7-dibromo-9-fluorenone in 100 ml dripped dry diethyl ether. After the addition is complete, 3 hours continued to cook. After cooling overnight, the failed one The precipitate is filtered off and washed with cold ether. The vacuumed Magnesium complex is dissolved in a solution of 15 g of ammonium chloride 250 ml of ice water hydrolyzed. After 1 h, the 9- (2- Aspirated biphenylyl) -2,7-dibromo-9-fluorenol, washed with water and vacuumed dry. The dried fluorenol is used for Ring closure reaction in 100 ml glacial acetic acid after adding 3 drops of HCl conc. Cooked for 6 hours. You let it crystallize overnight, that sucks formed product and washes with glacial acetic acid and water.
• Yield: 11 g (77%) of 2,7-dibromo-9,9-spirobifluorene. For further Cleaning can be recrystallized from THF.
• 1 H-NMR (CDCl₃, ppm): 6.73 (d, J = 7.63 Hz, 2 H, H-1.8 ′); 6.84 (d. J = 1.83 Hz, 2H, H-1.8); 7.15 (td, J = 7.63.1.22 Hz., 2 H, H-2 ′, 7 ′); 7.41 (td, J = 7.63, 1.22 Hz, 2 H, H-3 ′, 6 ′); 7.48 (dd, J = 8.24, 1.83 Hz, 2H, H-3.6); 7.67 (d, J = 8.24, 2H, H-4.5); 7.85 (d, J = 7.63, 2H, H-4 ′, 5 ′).  
• m) Synthesis of 2,7-dicarbethoxy-9,9'-spirobifluorene
• The Grignard reagent prepares magnesium shavings from 0.97 g (40 mmol) and 9.32 g (6.8 ml, 40 mmol) 2-bromobiphenyl in 50 ml dry Diethyl ether becomes a boiling solution of 13 g in the course of 2 h (40 mmol) 2,7-dicarbethoxy-9-fluorenone in 100 ml dry Dropped diethyl ether. After the addition has ended, the mixture is continued for 3 hours cooked. After cooling overnight, the precipitate is precipitated suction filtered and washed with cold ether. The vacuumed Magnesium complex is dissolved in a solution of 15 g of ammonium chloride 250 ml of ice water hydrolyzed. After 1 h, the 9- (2- Biphenylyl) -2,7-dicarbethoxy-9-fluorenol suctioned off with water washed and vacuumed dry. The dried fluorenol is used for Ring closure reaction in 100 ml glacial acetic acid after adding 3 drops of HCl conc. Cooked for 6 hours. You let it crystallize overnight, that sucks formed product and washes with glacial acetic acid and water.
• Yield: 15.1 g (82%) of 2,7-dicarbethoxy-9,9'-spirobifluorene. For Further purification can be recrystallized from ethanol.
• 1 H-NMR (CDCl₃₁ ppm): 1.30 (t, J = 7.12 Hz, 6 H, ester-CH₃); 4.27 (q, J = 7.12 Hz, 4H, ester-CH₂); 6.68 (d, J = 7.63 Hz, 2H, H-1.8 ′); 7.11 (td, J = 7.48.1.22 Hz, 2H, H-2 ′, 7 ′); 7.40 (td, J = 7.48, 1.22 Hz, 4H, H-1, 8, 3 ′, 6 ′); 7.89 (dt, J = 7.63, 0.92 Hz, 2 H, H-4 ′, 5 ′); 7.94 (dd, J = 7.93, 0.6 Hz, 2H, H-4.5); 8.12 (dd, J = 7.93, 1.53 Hz, 2 H, H-3, 6).
• n) Synthesis of 2,7-dibromo, 2 ′, 7′-dÿodo-9,9′-spirobifluorene
• In a 250 ml three-necked flask with reflux condenser and dropping funnel at 80 ° C a suspension of 2.37 g of 2,7-dibromo-9,9'-spirobifluorene in 50 ml of glacial acetic acid are mixed with 5 ml of water and, after adding 2 ml of conc. Sulfuric acid, 1.27 g iodine, 0.53 g iodic acid and 5 ml  Carbon tetrachloride stirred until the iodine color disappears. It is then suctioned off and washed well with water. After this Drying the precipitate is dissolved in 150 ml dichloromethane, and successively with Na₂SO₃ solution, NaHCO₃ solution and with water washed. The dichloromethane phase is dried over Na₂SO₄ and then concentrated. Colorless crystals of 2.7- Dibromo, 2 ′, 7′-dÿodo-9,9′spirobifluorene in quantitative yield. For Further purification can be recrystallized from dichloromethane / pentane will.
• 1 H-NMR (CHCl₃, ppm):
  6.80 (d, J = 1.83 Hz, 2 H), 6.99 (d, J = 1.53 Hz, 2 H), 7.51 (dd, J = 8.24.1.83 Hz, 2 H), 7.54 (d, J = 7.93 Hz, 2 H), 7.65 (d, J = 8.24 Hz, 2 H), 7.72 (dd, J = 8.24,1.53 Hz, 2 H).

B. Synthesis Examples example 1 2,2'-bis (benzofuran-2-yl) -9,9'-spirobifluorene (analogous to W.Sahm, E. Schinzel, P. Jürges, Liebigs Ann.Chem. (1974) 523)

2.7 g (22 mmol) salicylaldehyde and 5.0 g (10 mmol) 2,2′-bis (bromomethyl) -9.9′- spirobifluorene are dissolved in 15 ml DMF at room temperature and with 0.9 g (22.5 mmol) of powdered NaOH and a spatula tip KJ. Man heated to boiling and stirred at boiling temperature for 1 h. Relocated after cooling to concentrate the reaction solution with a mixture of 0.5 ml. Hydrochloric acid, 7 ml Water and 7 ml of methanol. The mixture is stirred for a further 1 h at room temperature crystalline reaction products, washed first with cold methanol, then with water and dries in vacuo at 60 ° C. 4.6 g (79%) of the are obtained Bisbenzylphenyl ether.

5.85 g (10 mmol) of the bisbenzylphenyl ether are mixed with 2.1 g in 10 ml of toluene (22.5 mmol) freshly distilled aniline were added. You give a spatula tip p-toluenesulfonic acid and heats to boiling on the water separator until no more water separates (approx. 3 to 5 h). When cooling the The corresponding bis-benzylidene phenylamine falls into the reaction mixture in crystalline form out. It is filtered off, washed with methanol and in vacuo at 60 ° C. dried. For further purification, it can be recrystallized from DMF. 7.35 g (10 mmol) of the bis-benzylidene phenylamine and 0.62 g (11 mmol) of KOH are introduced into 30 ml of DMF under nitrogen. Then you heat with stirring at 100 ° C for 4 h. After cooling to room temperature, the The precipitate is suction filtered and washed with a little DMF and water. To Drying at 60 ° C in a vacuum drying cabinet, the 2,2′-bis (benzofuran-2- yl) -9,9'-spirobifluorene by recrystallization from methyl benzoate getting cleaned.  

Example 2 2,2 ', 7,7'-tetra (benzofuran-2-yl) -9.9'-spirobifluorene

can be produced analogously to Example 1 with a correspondingly changed stoichiometry will.

Example 3 2,2 ', 7,7'-tetraphenyl-9.9'-spirobifluorene

5 g (7.9 mmol) 2.2 ′, 7.7′-tetrabromo-9.9′-spirobifluorene, 3.86 g (31.6 mmol) Phenylboronic acid, 331 5 mg (1.264 mmol) triphenylphosphine and 70.9 mg (0.316 mmol) palladium acetate in a mixture of 65 ml of toluene and 40 ml of aqueous sodium carbonate solution (2 M) slurried. Under strong The mixture is stirred and refluxed for 24 hours. After cooling down The room temperature is filtered off, washed with water and at 50 ° C in Vacuum dried. 2.58 g are obtained. The filtrate is washed with 50 ml of toluene extracted and the dried organic phase evaporated to dryness. Man receives another 1.67 g.

Overall yield 4.25 g (86%).

Example 4 2,2 ', 7,7'-tetrakis (biphenyl) -9.9'-spirobifluorene

5 g (7.9 mmol) 2.2 ′, 7.7′-tetrabromo spirobifluorene, 6.57 g (33.2 mmol) Biphenylboronic acid, 331.5 mg (1.264 mmol) triphenylphosphine and 70.9 mg (0.316 mmol) palladium acetate in a mixture of 65 ml of toluene and 40 ml of aqueous sodium carbonate solution (2 M) slurried. Under strong The mixture is stirred and refluxed for 24 hours. After cooling down Room temperature is suctioned off with water and washed at 50 ° C in Vacuum dried.

Yield 5.95 g (81%).  

Example 5 Synthesis of 2,2 ′, 7,7′-tetrabiphenylyl-9,9-spirobifluorene

In a 250 ml two-necked flask with reflux condenser and KPG stirrer 5.5 g tetrabromovirobifluorene, 7.2 g biphenylboronic acid and 400 mg Tetrakis (triphenylphosphine) palladium, in a mixture of 100 ml of toluene and Slurried 50 ml of potassium carbonate solution. While stirring with a KPG Stirrer and protective gas blanket, the mixture is refluxed for 8 h. After cooling, the product is filtered off, the precipitate with water washed and dried. The toluene phase is separated off in the filtrate and the aqueous phase shaken once with chloroform. The United organic phases are dried over sodium sulfate and evaporated, one receives a second fraction of the product. The two product fractions are combined (8g) and dissolved in chloroform. The chloroform solution is with Activated carbon is boiled and filtered through a short column with silica gel. To the spinning in and recrystallization from chloroform / pentane are obtained colorless crystals that fluoresce blue under UV light. Melting point 408 ° C (DSC).

1 H-NMR (CDCl₃, ppm): 7.14 (d₁ J = 1.53 Hz, 4 H); 7.75 (dd, J = 7.93, 1.53 Hz, 4H); 8.01 (d, J = 7.93 Hz, 4H); 7.34 (dd, J = 7.32, 1.37 Hz, 4H); 7.42 (t, J = 7.32 Hz, 8H); 7.58 (24H).

Example 6 Synthesis of 2,2 ′, 4,4 ′, 7,7′-hexabiphenylyl-9,9-spirobifluorene

In a 250 ml two-necked flask with reflux condenser, KPG stirrer, 1.6 g Hexabromovirobifluorene and 3 g biphenylboronic acid in a mixture of 50 ml of toluene and 50 ml of 1 M potassium carbonate solution. The mixture is refluxed under nitrogen and 115 mg Tetrakis (triphenylphosphine) palladium in 5 ml of toluene was added. The mixture is refluxed with stirring for 7 h. After the reaction has ended the cooled solution is filtered off and the filtrate 2 × with water  shaken out (chloroform is added for better phase separation Organic phase is dried over sodium sulfate using a short column Filtered silica gel and then spun in. For further cleaning is made Dichloromethane / pentane recrystallized. 2 g (80%) of colorless, under UV lighting blue fluorescent crystals.

13 C-NMR [360 MHz .; ATP, broadband decoupled] (CDCl₃, ppm): 65.94 (1C, Spiro-C); 126.95 (6C, CH), 126.97 (6C, CH), 127.17 (6C, CH), 127.35 (6C, CH), 127.36 (6C, CH), 127.39 (6C, CH), 127.52 (6C, CH), 128.73 (6C, CH), 128.75 (6C, CH), 128.94 (6C, CH), 129.90 (4 C, CH), 137.77 (2 C), 137.86 (2 C), 139.43 (2 C), 139.69 (2 C), 139.89 (2 C), 140.09 (2 C), 140.17 (2 C), 140.22 (2 C), 140.30 (2 C), 140.63 (2 C), 140.64 (2 C), 140.68 (2 C), 140.72 (2 C), 140.74 (2 C), 150.45 (2C), 150.92 (2C).

Example 7 Synthesis of 2,2′-bis [(5 (p-t-butylphenyl) -1,3,4-oxadiazol-2yl] -9.9, - spirobifluorene from 9,9'-spirobifluorene-2,2'-dicarboxylic acid chloride and 5 (4-t- Butylphenyl) tetrazole a) Synthesis of 5 (4-t-butylphenyl) tetrazole

In a 250 ml round-bottom flask with a reflux condenser, 4.9 g of p-t Butylbenzonitrile, 3.82 g lithium chloride and 5.85 g sodium azide and 8.2 g Triethylammonium bromide in 100 ml DMF heated at 120 ° C for 8 h. To Cooling to room temperature, 100 ml of water is added and in an ice bath mixed with dilute hydrochloric acid until no further precipitation falls. It will suction filtered, the precipitate washed with water and dried. Recrystallization from ethanol / water gives 4.4 g of colorless crystals.

b) 9,9'-spirobifluorene-2,2'-dicarboxylic acid chloride

In a 100 ml flask with reflux condenser and drying tube, 2 g (5th mmol) 9,9'-spirobifluorene-2,2'-dicarboxylic acid with 20 ml (freshly distilled Thionyl chloride) and 3 drops of DMF, refluxed for 4 h. After cooling  the reflux condenser is replaced by a distillation bridge and Excess thionyl chloride is distilled off in vacuo, the residue 40 ml of petroleum ether (30 ° -60 ° C) are added and distilled off, remains the crystalline acid chloride.

c) 2,2'-bis [(5 (p-t-butylphenyl) -1,3,4-oxadiazol-2yl] -9,9, -spirobifluore-n

2.0 g (11 mmol) of 5 (4-t-butylphenyl) tetrazole are dissolved in the acid chloride in 20 ml of anhydrous pyridine are added and the mixture is refluxed under protective gas for 2 h heated. After cooling, the mixture is poured into 200 ml of water and 2 h ditched. The precipitated oxadiazole derivative is filtered off with water washed and dried in vacuo. Then it is over silica gel Chloroform / ethyl acetate (99: 1) chromatographed and from chloroform / pentane recrystallized. 2.4 g of colorless crystals are obtained.

1 H-NMR (CDCl₃), ppm):
1.31 (s, 18 H, t-butyl), 6.77 (d, J = 7.32 Hz, 2 H), 7.18 (td, J = 7.48, 1.22 Hz, 2 H), 7.44 (td, J = 7.40, 1.22 Hz , 2 H), 7.46 (d, J = 8.54 Hz, 4 H), 7.50 (d, J = 1.22 Hz, 2 H), 7.94 (d. J = 8.54 Hz, 4 H), 8.02 (d, J = 7.93 Hz, 6 H), 8.20 (dd, J = 7.93,1.53 Hz, 2 H).

C. Application example

2,2 ', 7,7'-tetrakis (biphenyl) -9.9'-spirobifluorene is dissolved in chloroform (30 mg / ml) and by means of spin-coating (1000 rpm) on one with indium / tin oxide (ITO) coated glass carrier applied, with a homogeneous, transparent Film is formed. A vacuum vapor deposition is applied to this film Mg / Ag (80/20) electrode applied. When creating an electrical Voltage between the ITO electrode and the metal electrode, the If the metal electrode is polarized negatively to the ITO electrode, it will turn blue Electroluminescence observed.

Claims (21)

1. Use of spiro compounds of the general formula (I), in which
K¹ and K² mean independently conjugated systems in electroluminescent devices. 2. Use according to claim 1, characterized in that a spirobifluorene of the general formula (II) is used, where the benzo groups can be independently substituted and / or fused. 3. Use according to claim 1 and / or 2, characterized in that a spirobifluorene derivative of the formula (III) is used, where the symbols and indices have the following meanings:
K, L, M, N are the same or different R, the same or different, has the same meanings as K, L, M, N or is -H, a linear or branched alkyl, alkoxy or ester group with 1 to 22 C atoms, -CN, -NO₂, -NR²R³, -Ar or -O-Ar;
Ar is phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl, where each of these groups can carry one or two radicals R,
m, n, p are 0, 1, 2 or 3;
X, Y are the same or different CR, N;
Z is -O-, -S-, -NR¹-, -CR¹R⁴-, -CH = CH-, -CH = N-;
R¹, R⁴, the same or different, have the same meanings as R.
R², R³ are identical or different H, a linear or branched alkyl group with 1 to 22 carbon atoms, -Ar, 3-methylphenyl. 4. Use according to one or more of claims 1 to 3, characterized in that a spirobifluorene derivative of the formula (IIIa) to (IIIg) is used,
IIIa) K = L = M = N and is from the group: IIIb) K = M = H and N = L and is from the group: IIIc) K = M and is from the group: and N = L and is from the group: IIId) K = M and is from the group: and N = L and is from the group: IIIe) K = L = H and M = N and is from the group: IIIf) K = M and is from the group: and M = N and is from the group: IIIg) K = L and is from the group: and M = N and is from the group: 5. Spiro compound of the formula (V), where the symbols have the following meanings:
A, B, K, L, M, N are the same or different and A, B may also be the same or different, a linear or branched alkyl, alkyloxy or ester group having 1 to 22 carbon atoms, -CN, -NO₂, -Ar or -O-Ar;
R is -H, a linear or branched alkyl, alkoxy or ester group with 1 to 22 C atoms, -CN, -NO₂, -NR²R³, -Ar or -O-Ar;
Ar is phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl, where each of these groups can carry one or two radicals R;
m, n, p are 0, 1, 2 or 3;
X, Y are the same or different CR, N;
Z is -O-, -S-, -NR¹-, -CR¹R⁴-, -CH = CH-, -CH = N-;
R¹, R⁴, the same or different, have the same meanings as R;
R², R³ are identical or different H, a linear or branched alkyl group with 1 to 22 carbon atoms, -Ar or 3-methylphenyl. 6. Use according to one or more of claims 1 to 5, characterized characterized in that the spiro compound serves as a light-emitting layer. 7. Use according to one or more of claims 1 to 5, characterized characterized in that the spiro compound serves as a transport layer. 8. Use according to one or more of claims 1 to 5, characterized characterized in that the spiro compound is used for charge injection. 9. Electroluminescent device containing an active layer, the one or more compounds of the formula (I) to (III) according to one or more of the Claims 1 to 4 contains. 10. Electroluminescent device according to claim 9, characterized in that that the active layer is a light emitting layer. 11. Electroluminescent device according to claim 9, characterized in that that the active layer is a transport layer. 12. Electroluminescent device according to claim 9, characterized in that that the active layer is a charge injection layer. 13. Organic electroluminescent material, characterized in that its emission maximum in the range from 400 to 750 nm, measured at  Room temperature, by no more than 15%, relative to the initial state, diminished after the material, applied in a thickness of no more than 1 µm on a quartz substrate, in an inert atmosphere at a pressure of was not heated to 250 ° C for more than 1 mbar for 30 min. 14. Organic electroluminescent material according to claim 13, characterized characterized in that the emission maximum by no more than 10%, relative to the initial state. 15. Organic electroluminescent material according to claim 13 and / or 14, characterized in that the emission maximum by no more than 5%, relative to the initial state. 16. Organic electroluminescent material according to one or more of the Claims 13 to 1 5, characterized in that the emission maximum, relative to the initial state, is not reduced. 17. Organic electroluminescent material according to one or more of the Claims 13 to 16, characterized in that the emission maximum, increases relative to the initial state. 18. Electroluminescent device containing an active layer, the one Electroluminescent material according to one or more of claims 13 to 17 contains. 19. Electroluminescent device according to claim 18, characterized characterized in that the active layer is a light emitting layer. 20. Electroluminescent device according to claim 18, characterized characterized in that the active layer is a transport layer. 21. Electroluminescent device according to claim 18, characterized characterized in that the active layer is a charge injection layer.