WO2015144133A1 - Aryl borane compound, method for the production thereof and use thereof - Google Patents

Abstract

The invention relates to aryl borane compounds, to methods for the production thereof and to the use thereof in semi-conductive organic materials.

Description

 "Arylborane compound, its method of preparation and its use"

The present invention relates to arylborane compounds, their method of preparation and their use.

Organic light emitting diodes (OLEDs) are based on a relatively new technology. For some years the first electronic devices with OLED screen are commercially available, typically mobile phones with relatively small display. In televisions and as lighting elements in lamps, OLEDs have not yet prevailed. In order to become competitive with the established technologies, there is still a need for research regarding the materials used and production processes. Against this backdrop, numerous institutes and companies are exploring new fluorescent dyes based on organic compounds with extended, conjugated sr systems. These emitters are needed in different colors of the visible spectrum. The selection of blue luminous substances that are suitable for OLEDs is currently comparatively low. In addition, blue light, unlike lower energy colors (at least so far) can not be produced by phosphorescence, since corresponding emitter substances are not stable in use for a long time. A comprehensive review by M. Zhu and C. Yang from 2013 discusses the basic requirements for fluorescent emitters and lists many previously known and tested substances (M. Zhu, C. Yang, Chem. Soc. Rev. 2013, 42, 4963).

The fluorescence properties of organic molecules are essentially determined by the size of their respective conjugated nr-electron system. Due to its blue fluorescence, anthracene is often used as a lead structure for the design of fluorescent emitters. By extension of the α-system and in particular by introduction of suitable substituents, derivatives have been obtained, among others, which are now accepted as fluorescent standards, such as 9,10-diphenylanthracene. The aim of an application-oriented structural design is usually to combine the desired fluorescence dye with a high quantum yield. Another advantageous feature of OLED Emittersub punch is in ensuring a sufficiently high charge carrier mobility. Particularly in demand are blue emitters, which due to their molecular structure are electron-deficient and therefore suitable as electron acceptors and conductors.

Three-coordinate boron atoms are good electron acceptors because of their empty p orbital. In the last few years, molecules containing boron atoms have been increasingly tested in the search for electron-deficient, blue-fluorescent emitters. In these compounds, the boron atoms carry almost two mesityl groups, which provide excellent spatial protection and are protected against hydrolysis / oxidation on contact with air. However, a major drawback of this molecular design is that the boron atom can only undergo another bond and thus the orientation of its empty p orbital relative to the organic jr system can not be fixed. Due to the free rotation around the B-C bond, which connects the boryl substituent with the rest of the jr system, optimal interaction of the two molecular fragments is not guaranteed. In contrast, perfect conjugation of the p orbital at the boron atom with the jr system of the molecule can be achieved by inserting the boron atom into the molecular skeleton via two or three bonds. Substances of this kind are so far little known.

M. Wagner et al. Wagner et al., J. Am. Chem. Soc., 2013, 135, 12892) describe a compound of the formula A in which boron atoms have two bonds in an anthracene backbone are integrated. The substance is air-stable, but shows little fluorescence and a low quantum yield of about 3%. The fluorescence quantum yield increases as the TOS system is increased by substituents on the phenyl rings.

[Formula A]

 Mes

CN 102977129 A, CN 103183691 A, CN 10383692 A, CN 10318692 A describe derivatives of benzopyreneborane compounds of formula B with a high electron mobility. In CN 102977129 A, the synthesis of this molecule takes place in seven slides with an overall yield of only 6%. In addition, expensive reagents (Pd (PPh3) ₄ ) and highly carcinogenic solvents (HMPT) are required. A representation on a large scale would therefore be complicated and expensive.

[Formula B]

 JP 20130356859 A describes an air-stable compound of the formula C which shows blue fluorescence. However, the quantum yield is very low at 10%.

[Formula C]

 C. Dou et al, Angew. Chem. Int. Ed. 2012, 51, 12206, describe a compound of formula D which contains two boron atoms which are integrated into the JI system of the compound. As is typical of large polycyclic aromatic hydrocarbons, the compound absorbs visible light. The fluorescence is very weak from red to infrared with a quantum efficiency of 4% and a fluorescence maximum of 679 μm.

[Formula D]

Furthermore, also exclusively carbon-containing compounds such as those of the formulas E to G are known.

[Formula E]

[Formula F]

[Formula G]

A. Konishi et al, Chem. Lett. 2013, 42, 592, describe a carbon-containing compound of the formula E which absorbs in the visible spectral range and fluoresces red at an emission maximum of a wavelength of 705 nm,

Chaudhuri et al, Org. Lett. 2008, 10, 3053, and EP 21 12214 A1 describe a dibenzo [g, p] chrysene compound of the formula F. The compound fluoresces blue in a Wavelength of about 400 nm. The quantum yield is 1%. Furthermore, substituted dibenzo [g, p] chrysene derivatives were also investigated, with the strongest fluorescent compound having four methoxy substituents and a quantum yield of 49%.

WO 2010013006 A3 describes perylene (formula G), which fluoresces most strongly at a wavelength of 435 nm with a quantum yield of 94% and is therefore frequently used in OLEDs.

The compound of the formula H is from S.-L. Lin et al, Adv. Mater. 2008, 20, 3947 and H, Doi et al, Chem. Lett. 2003, 15, 1080 known. It has been tested for suitability as a bipolar emitter for OLEDs.

[Formula H]

Organic light emitting diodes require three electroluminescent (ELM) materials in red, yellow and blue to produce white light. According to their function, the components which make up these electroluminescent materials are subdivided into hollow substances and dopants. Many ELMs consist of a host substance that has been added to small amounts of a dopant (usually less than 5%). The dopant has the function of producing light by electroluminescence, while the host substance gives the material a good electrical conductivity. Some ELMs combine both functions and can therefore be used without host substance.

An organic light-emitting diode is made up of several layers: on a carrier material, an anode and a cathode layer are applied, between which at least one layer of the ELM is located. In operation, electrons are injected from the cathode and holes are injected from the anode into the ELM. These electrons and holes recombine in the electroluminescent material and emit light of a particular wavelength, which is a characteristic material property.

Often, in OLEDs, additional layers are used in addition to those mentioned, for example, materials that assist in the injection of electrons or holes into the ELM. Often one also integrates a hole-line layer, which improves the transport of holes between the anode and the ELM, or between a hole injection layer and the ELM. The additional layers can significantly improve the function of the OLED, in particular with regard to efficiency and service life. However, as the number of layers increases, the construction of such OLEDs becomes more complicated and the manufacturing cost becomes higher. To counteract this, electroluminescent materials are needed that require no or as few additional layers as possible, yet allow the construction of efficient OLEDs. In the best case, these materials must therefore be able to absorb both holes from the anode and electrons from the cathode equally well and forward them within the layer. Considering the organic ELMs known today, there is the greatest shortage of such materials that are able to absorb and conduct electrons well.

It is an object of the present invention to provide an arylborane compound which overcomes the disadvantages known from the prior art. In particular, a blue fluorescent arylborane compound of high efficiency, i. high fluorescence quantum yield and good electronic properties are provided. Likewise, the arylborane compound should have a certain stability to environmental influences, show a corresponding solubility in organic solvents and be electrochemically reversibly oxidizable and reversibly reducible. A further object is to provide a process for preparing the arylborane compound which, in particular by slight modification and variation of the synthesis building blocks used, ensures the preparation of a large number of arylborane derivatives having optimized properties. Another object of the present invention is to provide an arylborane compound which finds use in electronic and optoelectronic materials.

The first object is achieved by an arylborane compound represented by one of the following formulas 1 to 5: [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

where X = B, CH, CR ₅ , N, O without R ₂ or S without R ₂ ,

R 1, R ₂ , R ₃ , R ₄ and R 5 are the same or different and each independently selected from hydrogen, electron accepting substituent, preferably fluorine or CN, electron donating substituent, preferably C 1 -C 20 alkyl, C 1 -C 10 alkoxy, and unsubstituted or substituted Amine, unsubstituted or substituted C ₆ -C ₂ o ~ aryl, preferably phenyl, and unsubstituted or substituted C ₄ -C] g heteroaryl, and / or

R 1 to R _{5 are} attached directly or via a linker, preferably bridging atoms or groups, more preferably phenyl, to the arylborane skeleton and / or at least two of R 1, R ₂ , R _3; R 4 and R _5, preferably neighboring, are bonded together directly or via a Bmcke, and / or at least one of _R]} R _2, R, R4 integrated into a polymer backbone to R ₅ or bound to a side chain of a polymer, wherein the Polyraer main chain itself and also a linker optionally used for interaction is conjugated or non-conjugated. Ralimen in the present invention are the definitions for the radicals to "equal to or different from each other" and be each be independently selected, "will be understood that each residue R j, R _2, R _3, R _4, 5, etc. different or identical can be selected, so that a single radical, such as R ₄ , in each case can be chosen differently in one and the same molecule, if it occurs several times.

In the context of the present invention, it should be. an "electron-accepting substituent" is a substituent capable of accepting electrons by inductive or mesomeric means, preferably N0 ₂ , CN, S0 ₃ H, CHO, COOH, F, Cl, Br and I, preferably fluorine and CN.

Furthermore, in the context of the present invention, an "electron-donating substituent" is a substituent which is capable of giving off electrons by inductive or mesomeric means, such substituents preferably being a hydroxy group, C] -Ci _0- alkyl, Cj-Cio-alkoxy and unsubstituted and substituted amine, preferably unsubstituted and substituted amine.

The term "heteroaryl" includes aromatic cyclic radicals whose unsubstituted or substituted monocyclic or polycyclic ring skeleton contains one or more heteroatoms selected from O, S, N, Si or P. Examples of heteroaryl compounds are pyrrole, furan, thiophene, imidazole, pyrazine, pyridine , Pyrimidine, purine or indole.

A Ausruhrangs form is characterized in that when X = B or N, Ri and R _{2 are} alkyl-substituted phenyl groups, preferably Mesityl or 2,4,6-Triisopropylphenyl, are.

Furthermore, it is preferably provided that R _{4 is} a C 1 -C 8 -alkyl-bridged or an electron donor bonded directly or via a linker, preferably a substituted amine, preferably tert-butyl, methyl and / or diphenylamine.

In a further embodiment, it is preferred that one or more phenyl rings in Arylgrandgerüst the arylborane compound by one or more heteroaromatics, preferably pyridine, pyrimidine, pyrazine, dioxin, thiazine and oxazine, more preferably pyridine, is replaced. Furthermore, it is preferred according to the invention for the compound to be reversibly oxidizable and reversibly reducible (doubly).

The second object is achieved by a process for preparing the inventive arylborane compound comprising the steps: a) providing a compound of formula 6

[Formula 6]

wherein R ₃ and R _{4 are the} same or different from each other and are each independently selected from hydrogen, electron-accepting substituent, preferably fluorine or CN, electron-donating substituent, preferably Ci-Qo-alkyl, C _I -CJ _O - alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C _ö - ^ o-aryl, preferably phenyl, and unsubstituted or substituted C4-C ₁ 8-heteroaryl,

Reacting the compound of formula 6 to give a compound of formula 7 by lithiation followed by silylation and re-lithiation

[Formula 7]

c) reacting the compound of the formula 7 with at least one compound of the formula 8, 9 and / or 10 [Formula 8]

[Formula 9]

Formula 10]

where Y is either absent, a carbonyl group, CR ₂ R ₅ , NR ₂ , S, O or SiMe ₂ ,

R ₂ and R _{5 are the} same or different from each other and each independently selected from hydrogen, electron accepting substituent, preferably fluorine or CN, electron donating substituent, preferably C 1 -C 10 alkyl, C 1 -C 10 alkoxy and unsubstituted or substituted amine, unsubstituted or substituted QC ^ -Aryl, preferably phenyl, and unsubstituted or substituted C ₄ -C 18 heteroaryl,

R ₆ is selected from hydrogen, unsubstituted or substituted Cj-Cio-alkyl, unsubstituted or substituted C ₂ -Cio-alkenyl, unsubstituted or substituted C ₂ -C ₀ alkynyl, unsubstituted and substituted C6-C ₂₀ ~ aryl, preferably substituted phenyl , and unsubstituted or substituted C4-C18 heteroaryl, d) reacting the compound obtained in step c), preferably a Schöll reaction or, more preferably, a photocyclic reaction is carried out, and e) borylating the compound obtained in step d), preferably by transmetallation with boron tribromide.

Likewise, the second object is achieved by a process for preparing an inventive Arylboranverbindung of formula 5 comprising the steps: a) providing a compound of formula 1]

[Formula 1 1]

wherein R4 are the same or different from each other and each independently selected from hydrogen, electron-accepting substituent, preferably fluorine or CN, electron-donating substituent, preferably Cj-Cio-alkyl, Cs-Cio-alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C _f , -C 2o-aryl, preferably phenyl, and unsubstituted or substituted C ₄ -C ₄ heteroaryl,

Reacting the compound of formula 1 1 to a compound of formula 12 by lithiation and subsequent silylation

[Formula 12]

c) lithiating the compound of formula 12 and reacting with two compounds of formula 8 Formula 8]

where Y is either absent, a carbonyl group, CR ₂ R ₅ , NR ₂ , S, O or SiMe ₂ , and

R ₂ , R ₃ and R _{5 are the} same or different and each independently selected from hydrogen, electron accepting substituent, preferably fluorine or CN, electron donating substituent, preferably C 1 -C 20 alkyl, C 1 -C 10 alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C ₍ C ₂ -C 20 aryl, preferably phenyl, and unsubstituted or substituted C ₄ -C 1 g heteroaryl, d) reacting the compound obtained in step c), preferably a Schöll reaction or, more preferably, a photocyclic Reaction is carried out, and e) borylation of the compound obtained in step d), preferably by transmetalation with boron tribromide.

In the above formulas, Me = methyl, in formulas 6 and 7, on the silicon atom incorporated in the ring, the bond lines are also methyl.

It is further preferred that R, * in the. Formulas 6 to 12 is a Ci-Ci-alkyl group or an electron donor bonded directly or via a linker, preferably substituted amine, preferably ferf-butyl, methyl and / or diphenylamine.

It is preferred that the reaction in step c) is a Petersen olefination.

Further, it is preferred that the photo-cyclic reaction in step d) be carried out using iodine and propylene oxide with UV light.

In addition, it can preferably be provided that, after the borylation in step e), an arylation or alkylation is carried out. Furthermore, it is preferably provided that the compound of the formula 8 is prepared from the compound of the formula 6, preferably by oxidation.

In the context of the present invention, it is further preferred that the compound of the formula 6 is obtained starting from bis (4-yl-butylphenyl) methane by electrophilic substitution on the aromatic, preferably bromination, and subsequent lithium-halogen exchange and ring closure reaction by transmetallation.

For example, for the preparation of an arylborane compound of formula 5 in which X is Φ B, the compounds of formulas 7, 8 and 10 are needed. In this case, Y in the structure of the formula 8 is a carbonyl group.

The second object is alternatively achieved by a method for producing the arylborane compound according to the invention, comprising the steps: a) providing a compound of the formula 6

[Formula 6]

wherein _R3 and R4 are the same or different and elektronenakzeptierendem substituent are each independently selected from hydrogen, preferably fluorine or CN, elektronendonierendem substituent, preferably Cj-Cio-alkyl, C _J -C _J O alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C ₆ -C 20 -aryl, preferably phenyl, and unsubstituted or substituted C ₄ -C] _. gH heteroaryl, b) borylating the compound obtained in step a), preferably by transmetalation with boron tribromide, c) reacting the compound obtained in step b) to give a compound of formula 13 by lithiation, subsequent silylation and re-lithiation [Fonnel 13]

Ri is selected from hydrogen, electron-accepting substituent, preferably fluorine or CN, electron-donating substituent, preferably Ci-Cto-alkyl, Ci-Qo-alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C ₆ -C ₂ o-aryl, preferably phenyl, and unsubstituted. or substituted C 4 -C 8 -heteroaryl, d) reacting the compound of formula 13 with at least one compound of formula 8, 9 and / or 10

[Fonnel 8]

[Formula 9]

[Formula 10] R

where Y is either absent, a carbonyl group is CR ₂ R 5, NR ₂ , S, O or SiMe ₂ ,

R ₂ and R are the same or different from each other and are each independently selected from hydrogen, electron-accepting substituents, preferably fluorine or CN, electron-donating substituents, preferably Ci-Cio-alkyl, Ci-Cio-alkoxy and unsubstituted or substituted amine, unsubstituted or substituted Q-Qo-aryl, preferably phenyi, and unsubstituted or substituted Gj-Cig-heteroaryl,

R _f is selected from hydrogen, unsubstituted or substituted Ci-Cio-alkyl, unsubstituted or substituted C ₂ -Cio-alkenyl, unsubstituted or substituted C ₂ - Cio-Alkiny !, unsubstituted or substituted Ce-Qo-aryl, preferably substituted phenyl and unsubstituted or substituted C 4 -C 18 g heteroaryl, e) reacting the compound obtained in step d), preferably a Schöll reaction or, more preferably, a photo-cyclic reaction. In a preferred embodiment, R] in the compound of the formula 13 is selected from unsubstituted or substituted C 1 -C 10 -alkoxy and unsubstituted or substituted C 6 -C ₂₀ -aryl, preferably alkyl-substituted phenyl groups.

It is further preferred that after the borylation in step b) an arylation or alkylation is carried out directly.

In a further embodiment, it is preferred that steps b) and c) take place in the reverse order, so that the compound obtained in step a) is first reacted by means of lithiation, subsequent silylation and renewed lithiation, and the compound of formula 13 is then reacted in a subsequent step Step by borylation, preferably by transmetallation with boron tribromide, is obtained.

Furthermore, it is also preferred that the borylation at any other point of the process according to the invention for the preparation of the arylborane compound, where it is synthetically possible and useful, can be carried out.

In a further preferred embodiment, one or more phenyl rings in each case in a compound of the formulas 6 to 13 are replaced by one or more heteroaromatics, preferably pyridine, pyrimidine, pyrazine, dioxin, thiazine and oxazine, more preferably pyridine. The third object is achieved according to the invention by the use of the arylborane compound according to the invention in semiconducting organic materials, preferably organic light-emitting diodes (OLED), photosensitive materials, preferably organic solar cells or electronic components. In a further preferred embodiment, the compound is used in electroluminescent materials (ELM), preferably as doping and / or host substance.

Surprisingly, it was found that the arylborane compound according to the invention fluoresces blue with an emission maximum at a wavelength between 400 and 500 nm, preferably 450 nm, and a quantum yield in solution of 92%. Since the pure substance even in the solid state still has a quantum yield of 90%, it is not only suitable as a dopant of a suitable host substance, but can also be used without a host substance. Investigations show that the arylborane compound is electrochemically reversibly oxidizable and reversibly reducible. On the other hand, the cyclic voltammogram of Dibenzo [g, jo] chrysene (formula F) in CH ₂ Cl _{2 shows} signs of irreversible oxidation. With regard to the reduction of the compound, nothing is disclosed. In comparison, 2,5,9,12-tetra-tert-butyl-7,14-dihydro-7,7,14,14-tetramethyl-7,14-disilabisanthene shows a reversible oxidation at E _{ä / 2} = 0, 81 V (vs. FcH / FcH ⁺ ; CH ₂ Cl ₂ ). Up to a potential of -2.3 V (limit of the potential window of CH ₂ C1 ₂ ), no reduction can be seen. In stark contrast, 2,5,9,12-tetra-fert-butyl-7,14-dihydro-7,14-dimesityl-7,14-diborabisanthene, in addition to reversible oxidation at Ei _/ 2 = 1.09V two more reversible reductions at Ei / ₂ - 1.85 V and -2.14 V. This is directly related to the boron atoms, which make the electron-deficient molecule a good electron acceptor, and means that the compound in an ELM has holes as well can also conduct electrons. The substance ensures a high charge carrier mobility. In addition, the arylborane compound according to the invention shows a high stability to environmental influences, since it is air and water stable. This means that the compound can be handled without problems, both as a solid and in solution under normal conditions, ie at 20 ° C., contact with air and water (at a pH of the aqueous phase of about 7). The arylborane compound shows no change under these conditions for at least 3 days. The solubility of the arylborane compound is in organic solvents such as hexane, dichloromethane and aromatic solvents excellent as benzene. In water and alcohols, however, the arylborane compound of the invention is not or only slightly soluble.

The excellent optoelectronic properties of the arylborane compound according to the invention are also related to the fact that the boron atoms are bonded via two bonds to the dibenzo [g, p] chrysene framework. As a result, there is maximum conjugation of the empty p orbitals of the boron atoms with the π system of the molecule at all times. Compared to dibenzo [g, p] chrysene (formula F) with an emission wavelength of 396 nm, the maximum fluorescence for 2,5,9, 12-tetra-ter / -butyl-7,14-dihydro-7,14 -dimesityl-7,14-diborabisanthene with an emission wavelength of 449 nm bathochromically shifted. However, the fluorescence quantum yield of 92%, which is drastically increased in comparison with dibenzoylglycene, is particularly surprising. The fluorescence quantum yield of

is only 1%. Also of interest is the comparison with the synthetic precursor 2,5,9,12-tetra-ii-r-butyl-7,14-dihydro-7,7,14,14-tetramethyl-7,14-disilabisanthene. The latter is also planarized by the heteroaromatic bridge, but shows no outstanding quantum yield (35%). It can be concluded that the superior fluorescence quantum yield of the target molecule is due to the specific electronic nature of the boron atoms with their empty p _z -qualitates. This structural feature differs from the vast majority of the known Boron-containing substances used in ELM so far.

In addition, it has been found that a large number of arylborane compounds with optimized optoelectronic properties can be prepared in a simple manner by the process according to the invention for preparing the arylborane compound by slight modification and variation of the synthesis units used.

Due to the excellent optical and electronic properties of the arylborane compound according to the invention, these can be used particularly well in optoelectronic materials such as organic light-emitting diodes, organic solar cells or electronic components. The material may consist mainly of at least one of the arylborane compounds of the invention, but need not. However, the optoelectronic material may also preferably consist of a host substance which is doped with one or more of the arylborane compounds according to the invention. Host substances such as Alq ₃ (aluminum tris (8-hydroxyquinoline)), and CBP (4,4'-bis (N-carba-zolyl) -l, l ^'diphenyl) experts in the field are well known. Furthermore For example, the optoelectronic material is overall luminescent, wherein it may contain other substances which can change the properties of the material, ie luminescence, charge carrier mobility, glass transition temperature. Due to the good properties of the compound, ie the ability to absorb and deliver electrons well, no or only a few additional layers are needed to construct the OLEDs. As a result, the production costs are kept low. Optionally, however, multiple layers can be used to increase, for example, the life in addition.

Furthermore, the arylborane compound according to the invention can also be used to influence the conductivity of electronic materials which are used, for example, as an electron conduction layer in OLEDs or organic solar cells.

In addition, it is possible to use the arylborane compound in photosensitive materials. This includes, in particular, the use in monolayer or multilayer organic solar cells in which they function, for example, as photon absorbers and / or improve the charge separation.

Further features and advantages of the invention will become apparent from the following description, schematic drawings and Ausführangsbeispielen. Showing:

Fig. 1 is a UV / Vis and fluorescence spectrum of an arylborane compound of

 Compound 2,5,9,12-tetra-tertiarybutyl-7,1-dihydro-7,14-dimesityl-7,14-diborabisanthene in cyclohexane (blue) and in the solid state (green).

Fig. 2 is a cyclic voltammogram of an arylborane compound of the compound

2,5,9, 12-tetra-tert-butyl-7,1-dihydro-7,14-dimesityl-7,14-diborabisanthene (CH ₂ Cl ₂ , ("Bu) NPF ₆ 0,1 M, 200 mV / s).

3 shows a MALDI-MS of an arylborane compound of the compound 2,5,9,12-tetra- ter / -butyl-7,14-dihydro-7,14-dimesityl-7,1,4-diborabisanthene.

4 shows a MALDI-HRMS of an arylborane compound of compound 2,5,9,12-

Tetra-tert-butyl-7,14-dihydro-7,1-4-dimesityl-7,14-diborabisanthene. Fig. 5 is a simulation of the isotopic pattern of an arylborane compound of

Compound 2,5,9,12-tetra-ferro-butyl-7,14-dihydro-7,14-dimesityl-7,1,1-diborabisanthene.

Fig. 6 is an ORTEP plot of X-ray structural analysis of the molecular structure of an arylborane compound of 2,5,9,12-tetra-butyl-7,14-dihydro-7,14-diraesityl-7,14-diborabisanthene, wherein hydrogen atoms and cocrystallized benzene are not shown, the probability of residence is 50% and the main orientation of the disordered iBu substituent is shown.

7 UV / Vis absorption and emission spectrum of 6,10-di-uf-butyl-8-mesityl

8-hydro-8-borabenzo [gA] naphtho [l, 2,3,4-p] r] tetraphene in cyclohexane.

8 shows a cyclic voltammogram of an arylborane compound of the compound 6,10-di-tert-butyl-8-mesityl-8-hydro-8-borabenzo [g / [...] Naphtho [1, 2, 3, 4-pr] tetraph (CH ₂ Cl ₂ , ("Bu) ₄ PF ₀ 0.1 .VI. 200 mV / s).

FIG. 9 MALDf-HRMS of an arylborane compound of the compound 6,10-di-tert-butyl-8-mesityl-8-hydro-8-borobenzene [g / i] naphtho [1,2,3,4 / -] r] tetraphene.

Fig. 10 ORTEP representation of an X-ray structure analysis of the molecular structure of a

 Arylborane compound of the compound 6,10-di-feri-butyl-8-mesityl-8-hydro-8-borabenzo [gA] naphtho [l, 2,3,4 - /? ^ R] tetraphene, wherein hydrogen atoms are not shown and the residence probability is 50%.

FIG. 1 1 UV / Vis absorption and emission spectrum of an arylborane compound of the compound 8-mesityl-3-methyl-6,10-di-eri-butyl-8-hydro-8-boradibenzo [a, isfe] anthracene in cyclohexane.

FIG. 12 shows a cyclic voltammogram of an arylborane compound of the compound 8-mesityl

3-methyl-6,10-di-tert-butyl-8-hydro-8-boro-dibenzo [a, e] anthracene (CH ₂ Cl ₂ , ( ^,! Bu) ₄ PF ₆ 0,1 M, 400 mV / s).

Fig. 13 MALDI-HRMS of an arylborane compound of the compound 8-mesityl-3-methyl-6,10-di-r-butyl-8-hydro-8-boro-dibenzo [o, iie] anthracene. Fig. 14 ORTEP representation of an X-ray structure analysis of the molecule structure of a

Arylborane compound of the compound 8-MesityI-3-methyl-6,10-di-fcrf-butyl-8-hydro-8-boradibenzo [a, t e] anthracene, wherein hydrogen atoms are not shown and the residence probability is 50%.

Fig. 15 UV / Vis absorption and emission spectrum of an arylborane compound of

 Compound 6,10-di- / eri-butyl-3- (4-diphenylamino) phenyl-8-mesityl-8-hydro-8-boro-dibenzo [ö, c / t '] anthracene in cyclohexane.

Fig. 16 a cyclic voltammogram Arylboranverbindung the compound 6,10-di-teri-butyl-3- (4-diphenylamino) phenyl-8-mesityl-8-hydro-8- boradibenzo [i7 ₅ tfc] anthracene (CH ₂ CI _2, ("Bu) ₄ PF ₆ 0.1 M, 400 mV / s).

Fig. 17 MALD1-HRMS of an arylborane compound of the compound

 6,10-Di-tert-butyl-3- (4-diphenylamino) -phenyl-8-mesityl-8-hydoO-8-boro-dibenzo [a, hexa] anthracene.

1 ORTEP representation of an X-ray structure analysis of the molecular structure of a

 Arylborane compound of the compound 6,10-di-tert-butyl-3- (4-diphenylamino) phenyl-8-mesityl-8-hydro-8-boradibenzo [ö, ie] anthracene, wherein hydrogen atoms are not shown and the probability of residence 50 % is.

19 MALDI-HRMS of an arylborane compound of the compound 5,9-di-tert-butyl

7-mesityl-1-phenyl-7-hydro-7-borabenzo [iv] anthracene.

20 MALDI-HRMS of an arylborane compound of the compound 2,6-di-ieri-butyl

4-mesityl-4-hydro-4-boradibenzo [gA, / j <5 ^, r] tetraphene.

embodiments

General working conditions

Unless otherwise noted, the experiments described below were carried out under a dry nitrogen protection atmosphere by Schlenk technique. Hexane, Et ₂ O, THF, benzene and toluene were dried over sodium / B enzophenone before use and distilled prior to use. Dichloromethane (DCM) and DMSO and Et ₃ N, Me ₃ SiCl and Me ₂ SiCl ₂ were dried over CaH ₂ and distilled. Benzoyl chloride was distilled before use, BBr ₃ was stored above Hg. The microwave-heated reactions were carried out in a Biotage Initiator "microwave." For the photochemical reactions, a medium pressure mercury vapor lamp from Heraeus Noblelight (TQ 1.50, 150 W) was used NMR spectra were recorded with the following spectrometers: Bruker DPX-250, AM - 250, Avance-300, Avance-400, Avance-50 The chemical shifts are given in parts per million (ppm, <5) and were calibrated to the residual signals of the respective deuterated solvent ('H / ^{, 3} C { 1H}: CDC1 ₃ , 7.26 / 77.16 ppm, C ₆ D ₆ , 7.16 / 128.06 ppm) or to the external standards BFyEt ₂ O ( ^H B {'H}: 0.00 ppm), Si (CH) ₄ ( ²⁹ Si INEPT : 0.00 ppm) and CFC1 ₃ ( ¹⁹ F: 0.00 ppm) Abbreviations: s = singlet, d = dubiett, t = triplet, vt = virtual triplet, q = quartet, quint = quintet, m = multiplet, br. = broad, no = not observed, no = the expected multiplet is not resolved The resonances boron-bound carbon Fatomas were often not observed due to quadrupole relaxation or were very low in intensity. The B resonances of the triarylboranes are detectable only for samples of high concentration and as very broad signals with half height widths greater than 1000 Hz at about 65 ppm UV / Vis absorption and fluorescence spectra were measured with a Varian Gary 50 Scan UV / The fluorescence quantum yields were measured with an integrating sphere (Jasco ZLF-835, 100 mm Integrating Sphere) and Jasco's FWQE-880 program, and the solvent used immediately became Following this procedure, a quantum yield of 96% was obtained for the fluorescence standard diphenylanthracene (reference: 97%). For cyclic voltammetry, an EC & G Princeton Applied Research 263A potentiostat with a platinum working electrode (diameter 2.00 mm) The reference electrode consisted of silver wire, which was immersed in HCl / HN0 ₃ (3: 1) was coated with AgCl. The solvent DCM was dried as described above and degassed by an argon stream (injected with a capillary, 15 min.). The main salt used was (nBu) ₄ NPF ₆ (0.1 mol / L). The potentials were measured against FeiTocen / ferrocenium. Precision masses were determined using the MALDI LTQ Orbitrap XL mass spectrometer from Thermo Fisher Scientific. The matrix used for the MALDI mass spectra was 2,5-dihydroxybenzoic acid. Given is the exact mass of the molecule with the most common natural isotope combination. Bis (4-tert-butylphenyl) methane (99%) was purchased from Alfa Aesar and used without additional purification. Ausfuhrungsbeispicic

1.) Bis (2-bromo-4-tert-butylphenyl) methane

In a 250 mL two-necked flask with dropping funnel and drying tube, bis (4-tert-butylphenyl) methane (10.02 g, 35.73 mmol) was dissolved in DCM (50 mL) and extracted with iron powder (about 0.2 g, 4 mmol ). When cooled by an ice bath, a solution of Br ₂ (4.00 mL, 12.5 g, 78.2 mmol) in DCM (15 mL) was added dropwise. The ice bath was removed and the reaction solution stirred for 2 h. The solution was decolorized with aqueous Na ₂ S ₂ (V solution and the phases were separated, the aqueous phase was extracted twice with DCM, the combined organic phases were dried with MgSO ₄ and the solvent was removed under reduced pressure to leave an orange oil (15.7 g) For purification, the crude product was taken up in a little hexane / DCM (1: 1) and filtered through a short column of silica gel After removal of the solvent the product (15.19 g, 34.66 mmol, 97%) as a light yellow oil which crystallized over time.

1H-NR (250.13 MHz, CDC1,): δ 7.60 (d, ⁴ J _HH ^~ 2.0 Hz. 2H), 7.24 (dd, J _H11

= 8.0 Hz, 2H), 6.93 (d, ³ J _H H = 8, 1 Hz, 2H), 4.14 (s, 2H), 1 .31 (s, 18H).

C {'H} NMR (62.9 MHz, CDCl ₃ ): δ 151.6, 136.1, 130.4, 129.9, 125.0, 124.8, 41.2, 34.7, 31.4.

2.) 2,7-Di-ieri-butyl-9,10-dihydro-9,9-dimethyl-9-silaanthracene

In a 500 mL three-necked flask with reflux condenser and two dropping funnels, bis (2-bromo-4-tert-butylphenyl) methane (12.42 g, 28.34 mmol) was dissolved in Et ₂ O (200 mL). Cooled through an ice bath, a solution of "BuLi in" hexane (40.0 mL, 1.51 M, 59.5 mmol) was added dropwise and heated to reflux for 1 h .The yellow reaction solution was cooled again by an ice bath A solution of dichlorodimethylsilane (4.80 mL, 39.7 mmol) in Et ₂ O (10 mL) was slowly added dropwise, forming a colorless precipitate. The reaction mixture was refluxed for 0.5 h. Subsequently, slowly at room temperature, saturated aqueous NaHC0 ₃ solution (50 mL) and dist. H ₂ 0 (50 mL) was added. The phases were separated and the aqueous phase extracted twice with Et ₂ O (50 mL). The combined organic phases were washed twice with dist. H ₂ 0 (100 mL), dried with MgS0 ₄ and concentrated. The crude product was purified by a short filter column (about 5 cm silica gel, hexane / EA 10: 1). Removal of the solvent under reduced pressure left a light yellowish oil (9.85 g, 103%). The Ή-NMR spectrum showed low impurities in the alkyl and silyl range. By crystallization from hexane, the product can be obtained as a colorless, analytically pure solid.

Ή-NMR (400.13 MHz, CDCl ₃ ): δ 7.62 (d, ⁴ J _HH - 2, 1 Hz, 2H, H-1, 8), 7.34 (dd, V _HH = 8.0 Hz, ⁴ J _HH = 2, 1 Hz, 2H, H-3.6), 7.26 (d, V _HH = 8.0 Hz, 2H, U-4.5, 4.07 (s, 2H, H- / O), 1.34 (s, in, 'Bu-CH ₃ ), 0.50 (s, 6H, Me ₂ Si).

¹³ C { ¹ H} NMR (100.6 MHz, CDC1 ₃ ): δ 148.2 (2, 7), 143.4 (4a, l () a), 135.5 (8a, 9a), 129.8 (1.8), 127.7 {3.6), 126.3 (4.6), 40.6 (10), 34.6 Bu-C), 31.6 (Bu-CHi), -2.7 (Me ₂ Si).

²⁹ Si NMR (79.5 MHz, CDCl ₃ ): d - 1 8. 1.

EA (%): Calculated for C ₂₃ H ₃₂ Si [336.59]: C 82.07, H 9.58; found: C 82.26, H 9.14. 3.) 2,7-di-ferric-butyl-9,30-dihydro-9,9-dimethyiyl-9-silaanthracene-10-one

In a 250 mL one-necked flask with reflux condenser was added 2,7-di-tert-butyl-9,10-dihydro-9,9-dimethyl-9-silaanthracene (1. 58 g, 40.35 mmol) in acetic acid (100 mL). solved. Cr0 ₃ (4.4 g, 44 mmol) was added and the reaction mixture heated to 70 ° C for 1 h. The deep green reaction solution was then poured into a stirred mixture of hexane (100 mL) and dist. Poured H ₂ 0 (200 mL). The aqueous phase was separated and extracted twice with hexane. The combined organic phases were washed twice with dist. H ₂ 0 washed and dried with Na ₂ S0 ₄ . Removal of the solvent under reduced pressure left the crude product as a brown oil (32.8 g, 36.5 mmol, 90%). By column chromatography on silica gel (eluent hexane / EA 25: 1, Rf = 0.4) and recrystallization from hexane, the product can be obtained in the form of colorless crystals.

1 H NMR (400.13 MHz, CDCl ₃ ): δ 8.39 (d, V _HH - 8.4 Hz, 2H, H-4.5), 7.67 (d, ⁴ J _HH = 2.0 Hz, 2H, Yi-1.8% 7.61 fdd, ³ J _HH = 2.0 Hz, ⁴ J _HH = 8.4 Hz, 2H, H-5.6), 1.40 (s, 1 8H, ¹ Bu-CH ₃ ), 0.52 (s, 6H, Me ₂ Si).

¹³ C {'H} -NMR (75.44 MHz, CDCl ₃ ): δ 1 87.6 {10), 154.9 (2, 7), 139.0 (8a, 9a), 138.8 (4a 0a), 129.7 (AS), 129.6 (4.5), 127.5 (.? />). 35.2 (Bu-C), 3 1.3 (Bu-CH _} ), -1.1 (IfcS).

^M Si-NM (59.6 MHz, CDCl ₃ ): -23.7.

EA (%): Calculated for C ₂₃ H ₃₀ OS1 [350.57]: C 78.80, H 8.63; found: C 78.68, H 8.78.

4.) 2,7-di-tert-butyl-9,10-dihydro-9,9-dimethyl-l 0-trimethylsilyi-9-silaanthraeen

In a 100 mL two-necked flask with reflux condenser, 2,7-di-tert-butyl-9,10-dihydro-9,9-dimethyl-9-silaanthracene (2.01 g, 5.97 mmol) in Et 2 O ( 40 mL). On cooling through an ice bath, "BuLi solution (4.3 mL, 1.6 M in" hexane, 6.6 mmol) was added slowly via syringe and then heated to reflux for 1 h. The deep red reaction solution was again cooled by an ice bath While Me ₃ Si-Cl (1.0 mL, 7.8 mmol) was slowly added via syringe, the ice bath was removed and the reaction mixture was refluxed for 1.5 h After stirring overnight, the colorless suspension became saturated Aqueous NaHCO ₃ solution (40 mL) was added to dissolve the colorless precipitate and the organic phase turned neo yellow, the aqueous phase was separated and extracted twice with Et ₂ O (30 mL) washed with distilled H ₂ O (20 mL), dried with MgS0 ₄ and the solvent removed under reduced pressure The partly colored impurities were separated by column chromatography (10 cm silica gel, eluent hexane, R _f = 0.4) pr The product was obtained as a colorless oil (1.93 g, 4.72 mmol, 79%), which solidified after some time. Ή-NMR (400.13 MHz, CDCl ₃ ): δ 7.53 (d, ⁴ J _HH = 2.1 Hz, 211, U-1.8), 7.28 (dd, V _HH = 8.2 Hz, ⁴ JHH = 2.1 Hz, 2H, B-3.6), 7.01 (d, ³ J _HH = 8.2 Hz, 2H, U-4.5), 3.90 (s, 1H, iÖ), 1.33 (s, 18H, ^l-Bu CH _3), 0:46 (s, 3H, Me ₂ Si), 0:42 (s, 3H, Me ₂ Si), -0.15 (s, 9H, Me ₃ Si).

¹³ C {'H}' M (75.4 MHz, CDCl ₃ ): Ö 146.4 (2, 7), 144.8 (4a ⁽ ) a), 131.7 130.4 (7.5),

127.8 (4.5), 125.8 (3.6), 46.2 (70), 34.4 (Bu, 31.6 ( ^! Bu-CH ₃ ), 0.7 (Afe ₂ Si), 0.6 (e ₂ S), - 1.4 (e ^j S ⁱ ) -

²⁹ Si NMR (59.6 MHz, CDCl 3): δ 5.1 (Me ₎ Si), -19.5 (e A).

EA (%): Calculated for C26H40S12 [408.77]: C 76.40, H 9.86; found: C 77.18, H 9.89.

5.) 9,9'-Bi (3,6-di-ferf-butyl-10,10-dimethyl-10-silaanthracenylidene)

In a 100 mL two-necked flask, 2,7-di-tert-butyl-9,10-dihydro-9,9-dimethyl-10-trimethylsilyl-9-silaanthracene (1.00 g, 2.45 mmol) in THF ( 25 mL) and cooled to -78.degree. At this temperature, ^K BuLi solution (1.5 mL, 1.6 M in hexane, 2.45 mmol) was added and the reaction solution warmed to room temperature, turning red. The temperature was lowered again to -78 C and a solution of 2,7-di-t-butyl-9,10-dihydro-9-dimethyl-9-silaanthracene-10-one (847 mg, 2.42 mmol) in THF (about 3 mL) injected. The red reaction solution was slowly warmed to room temperature, the color becoming darker. The reaction mixture was stirred overnight and then decolorized with methanol (1 mL) (colorless precipitate). The solvent was removed under reduced pressure and the residue was purified through a broad filter column (5 cm silica gel, 2 cm sand, eluent DCM). The solvent was removed and the residue was taken up with hexane (ca 10 mL), filtered and washed twice with hexane / 7 (about 10 mL). After drying in an oil pump vacuum, the product (879 mg, 1.31 mmol, 54%) was obtained as an analytically pure colorless powder. Ή-NMR (400.13 MHz, CDCl ₃ ): S 7.55 (d, ⁴ J _HH = 2, 1 Hz, 4H, H / J 8.8% 6.90 (dd, J _{) m} = 8.2 Hz, ⁴ J _HH = 2.1 Hz, 4H, K-3, 3 ', 6.6% 6.65 (d, ³ J _HH = 8.2 Hz, 4H, H-4, 4', 5.5% 1.26 ( s, 36H, 'Bu-CHj), 0.72 (s, 6H, Me ₂ Si), 0.64 (s, 6H, Me ₂ Si).

^I3C {1H} ~ NMR (75.4 MHz, CDCfe): δ 147.7 (2.2 ', 8.8% 144.9 (4a, 4a 10a)% 138.0 (7%), 137.2 (8a, 8a', 9a , 9a% 129.5 (V, 5.5 '), 128.2 (7.7', 5.5 '), 125.0 (3.3', 6.6% 34.6 C'ÄM-). 31 .5 (Bu CHs), - 1.6 (e ₂ 5i), -5.6 (Afe ₃ Sz).

²⁹ Si NMR (59.6 MHz, CDCh): 5 -17.1.

EA (%): Calculated for C ₄ 6H ₆ oSi ₂ [669, 14]: C 82.57, H 9.04; found: C 83.02, H 8.97. HRMS: calculated for C, _(, H _{(OSI 2:} 668.42281, found: 668.42208 UV absorption (CHCI _3, 20 nM, 25 ° C):. _{Max =} 319 nm; ε ₃₁₉ = 19900 l-mor '-cm ^"1 .

6.) 10-diphenylmethylene-2,7-di-i-butyl-9,9-dimethyl-9,10-dihydro-9-silaanthracene

in a 100 mL two-necked flask with reflux condenser, 2,7-di-ieri-butyl-9,10-dihydro-9-dimethyl-10-trimethylsilyl-9-silaanthracene (250 mg, 610 μηιοΐ) in Et ₂ O (15 mL) dissolved and cooled by an ice bath. At this temperature, "BuLi solution (0.40 mL, 1.6 M in" hexane, 640 μmol) was added and stirred for 0.5 h The ice bath was removed and the orange reaction solution heated to reflux for 1 h. The temperature was lowered again to 0 ° C and a solution of benzophenone (1 1 1 mg, 610 μπιοΐ) in Et ₂ 0 (2 mL) was added through a syringe, whereupon the solution turned deep green The reaction was for 21 h to Subsequently, saturated aqueous NaHCO solution (20 mL), distilled H ₂ O (10 mL) and Et ₂ O (20 mL) were added to give two clear, almost colorless, phases extracted twice with Et ₂ O. The combined organic phases were dried with MgSO ₄ and the solvent was removed under reduced pressure to leave a glassy solidified, colorless solid (about 270 mg), which was purified by column chromatography (15 cm silica gel, eluent Hexane / EA 50: 1), the second fraction (243 mg, 7 _f = 0.2 with hexane / EA 50: 1) contained mainly product but was still slightly contaminated. By primary crystallization from n-hexane (about 1 mL), the product could be obtained in 53% yield (162 mg, 323 μηιοΐ). X-ray diffraction crystals were obtained by recrystallization from methanol.

1 H-NMR (500.18 MHz, CDCl ₃ ): δ 7.52 (d, ⁴ J _HH = 2.1 Hz, 2H, H- / ,, <?), 7.24-7.22 (m, 411, Ph-CH ° ^rtho ), 7.16-7.13 (m, 4H, Ph-CH " ^{ie, a} ), 7.09-7.05 (m, 2H, Ph-CPf ^ar 7.00 (d, ³ J _HH = 8.2 Hz, 2H, H-4 , 5), 6.94 (dd,

2.1 Hz, 2H, H-3.6), 1.23 (s, 18H, ¹ Bu-CH ₃ ), 0.68 (br, 3H, Me ₂ Si% 0.64 (br, 3H, Me ₂ Si), ⁱ C {'H} -NMR (125.8 MHz, CDC1 ₃ ): δ 147.7 (2,7), 144.3 (4a 0a \ 143.0 (Ph-C), 140.2 (10), 140.1 (Ph ₂ C =), 136.4 (8a, 9a), 129.8 (Ph-CH ^orlh0 ) ₎ 129.4 (4), 128.5 (/, £), 127.8 (Ph-CH ^{, a} ), 126.1 (Ph-CH ^para ), 125.1 (3.6), 34.5 ('BM-Q, 31.5 (Bu-CH ₃ ), - 1 .26 (Me ₃ Si), -5.4 (Afe Si).

²⁹ Si NMR (99.4 MHz, CDCl ₃ ): δ - 17.2.

EA (%): Calculated for C ₃₆ H ₄ oSi [500.79]: C 86.34, H 8.05; found: C 84.81, H 7.91. 7.) 2,5,9,12-Tetra-butyl-7,14-dih ^

In an exposure apparatus, 9,9'-Bi (3,6-di-er-butyl-10,10-dimethyl-10-silaanthracenylidene) (833 mg, 1.24 mmol) in toluene (ca. 800 mL, as purchased) and added with propylene oxide (20 mL). Argon was bubbled through a cannula for one hour to remove dissolved oxygen. The solution was exposed to a mercury vapor lamp while iodine (650 mg, 2.55 mmol) was added portionwise over about 3 hours. Subsequently, the reaction solution was filtered through A1 ₂ 0 ₃ (2 cm, neutral) and the solvent was removed under reduced pressure. The brownish, solid residue was taken up in n-hexane (12 ml), suspended in an ultrasound bath and treated with cold methanol (50 ml). The precipitate was filtered off, washed twice with cold methanol (20 mL) and dried in an oil pump vacuum. The Product (588 mg, 884 μηιοΐ, 71%) was obtained as a colorless powder which was contaminated with traces of the starting material. In order to obtain crystals suitable for X-ray structure analysis, the substance was dissolved in benzene and coated with methanol.

Ή MR (500, 18 MHz, CDCl ₃ ): S 8.80 (d, ⁴ J _HH = 2, 1 Hz, 4H, H-3.4, 0.11), 8.02 (d, ⁴ J _HH = 2, 1 Hz, 4H, HI, 6, 8, 13), 1.56 (s, 36R, ¹ Bu-CH ₃ ), 0.57 (s, 12H, Me ₂ Si). ⁱ³ C {'H} -NMR (125.7 MHz, CDCl ₃ ): δ 147.8 (2, 5, 9, 12), 134.3 (6a, 7a, 13a, 14a), 132.2 (7b, 13b, 14b, 14e ), 130.9 (3a, 3b, 10o 0b), 130.2 (1, 6, 8, 13), 127.6 (14c, 14d), 120.6 (3, 4, 10, 11), 35.0 ('tftt-Q, 31.5 ( Bu-CH ₃ ), -0.8 (AfejSi).

²⁹ Si NMR (99.4 MHz, CDCU): δ - 19.9.

EA (%): Calculated for C ₄₆ H ₅₆ Si ₂ [665.1 1]: C 83.07, H 8.49, found: C 83.31, H 8.49. HRMS: Calculated for C, "H _v , Si ₂ : 664.39151, found: 664.391 15.

UV absorption (cyclohexane, 9 μΜ, 25 ° C): X _max = 347 nm, 361 nm; ε ₃₄₇ = 21900 L mol ^{" '•} cm. ¹

Fluorescence (cyclohexane, 9 μΜΜ, λ _Εχ = 351 nm, 25 ° C): λ _ιτιΆΧ = 390 nm, 407 nm; <P _F = 25%.

Cyclic voltammetry (CH ₂ Cl ₂ , [nBu ₄ N] [PF ₆ ] 0.1 M, 20 μM xs ^" ', vs FcH / FcH):

8.) 2,5,9,12-Tetra-tert-butyl-7,14-dihydro-7,14-dimesityl-7,14-diborabisanthene

In a fusible ampoule was 2,5, 9, 12-tetra-feri-hutyi-7,14-dihydro-7, 7, 14, 14-tetramethyl-7, 14-disilabisanthen (300 mg, 451 μηιοΐ) in BBr _3rd (0.8 mL, 8 mmol) and heated in the oven for 4 d at 200 ° C. The vial was opened and the dark solution transferred to a Schlenk vessel with dropping funnel. The BBr ₃ was removed under reduced pressure and heated to 60 ° C. The remaining solid was dissolved in toluene (20 mL). at Cooled through an ice-bath, a solution of mesityl-MgBr (1, 6 mL, 0.87 M in THF, 1.4 mmol) was added dropwise. The reddish solution was stirred overnight at room temperature. Subsequently, the reaction solution was poured into a stirred mixture of half-diluted aqueous NaHCO ₃ solution (100 mL) and toluene (30 mL). The phases were separated and the aqueous phase extracted twice with toluene (50 mL). The combined organic phases were washed with dist. H ₂ 0 (50 mL), dried with MgS0 ₄ and the solvent removed under reduced pressure. The crude product was purified first by column chromatography on silica gel (applied and washed with hexane, then eluted with hexane / EA 25: 1). The first colored fraction contained the product. After removal of the solvent, slightly bleached, neon yellow solid (244 mg, 67%) remained. By recrystallization in hexane (3.5 mL, washed with MeOH), the impurities were separated, there were obtained 1 16 mg of pure product (131 μηιοΐ, 29%, one equivalent of hexane co-crystallized). To grow suitable X-ray crystallographic crystals, 10 mg were dissolved in 1 mL of benzene and overlaid with 5 mL of methanol. The neon yellow, clear crystals contained 2 equivalents of benzene.

Ή-NMR (300.03 MHz, CDCl _3): δ 9:41 (d, V _HH = 2.0 Hz, 4H, H-3 0 I), 8:47 (d, ⁴ J _in - 2.0 Hz, 4 H ₅ H- / A <V), 7.03 (s, 4H _, Mes-C ^{m ta} ) _> 2.50 (s, 6H, Mes-C hf ^ra ), 2.09 (s, 12H, Mes-CH ₃ ^ortho ), L56 (s, 36H, 'Bu-CH ₃ ).

¹³ C {'H} - MR (125.7 MHz, CDCl ₃ ): δ 149.1 (2, 5, 9, 12), 140.8 (MesC-1), 139.0 (MesC-2, Mes-C6), 138.5 ( 1,6,8,13), 136.5 (MesC-4), 136.3 (14c 4d), 130.5 (7b, 13b, 14b, 14e), 129.9 (3a, 3b, If Yes Ob), 128.3 (6a, 7a, 13a , 14a), 127.1 (MesC-3, Mes-C5), 125.3 (3,4,10,11), 35.3 (Bu-C), 31.6 Bu-Cl-), 23.8 (Mes-CHf ^lho ), 21. 6 {Mes-CHf ").

^I3 B {'H} NMR (160.5 MHz, CDC1 ₃ ): δ 66.0 (h _Vl ~ 2500 Hz).

EA (%): Calculated for C ₆ oH ₆₆ B ₂ x 2 C ₆ H ₆ [965.01]: C 88.61, H 8.15; found: C 89.10, H 8.14.

1IRMS: Calculated for C ₆ oH ₆₆ B2: 808.54451, found: 808.53687.

UV absorption (cyclohexane, 7 μM, 25 ° C): / _max - 264 nm, 419 nm, 432 nm; ε _{1 (Α} = 73900 L-mor ^l * cm ^" ', £ -432 = 42300 L-mof'-cm ^{" 1} .

Fluorescence (cyclohexane, 3 μΜ, λ _Έχ = 400 nm, 25 ° C): / l _max = 449 nm, 475 nm; Φ _ν = 60%. Cyclic voltammctric (CH ₂ Cl ₂ , ('Bu) ₄ NPF ₆ 0.1 M, 200 mV / s, vs. Fe / F <T): E [V] 1.09, -1.85, -2.14 ,

Solubility: The compound shows good solubility in organic solvents such as hexane, dichloromethane and aromatic solvents such as benzene: hexane:> 15 mg / ml; Dichloromethane:> 25 mg / ml and benzene: 10 mg / ml.

Optoelectronic characterization of 2,5,9,12-tetra-iiTf-but-l-7,14-dihydro-7,14-dimesityl-7,14-diborabisanthene

The compound already shows strong fluorescence upon irradiation with a UV hand lamp (365 nm). In addition, it is very soluble in non-polar solvents. Diluted solutions of the substance radiate blue under UV light, crystals show an intense green light emission. To further investigate the optical properties of the compound, absorbance and fluorescence spectra of dilute solutions in cyclohexane were measured (Figure 1). In the UV range from 250 nm to 310 nm, the substance absorbs strongly. In addition, an absorption band in the blue region of the spectrum is visible with a maximum at λ = 432 nm. The emission maximum is at a wavelength of 449 nm. It can be seen a Sehwingungsfemstrukiur with a local maximum at 475 nm and a shoulder at about 505 nm. Noticeable is the low Stokes size of only 880 cm ^-1 . Since the absorption and emission of the compound overlap, a shift of the measured centroid wavelength into the green region of the spectrum is evident in the fluorescence spectrometer at higher concentrations blue area emitted photons.

Reabsorption also decreases the measured fluorescence quantum yield at higher concentrations. In the concentration range from 1 μΜ to 13 μΜ, the quantum yield was determined to be 60% (excitation at 425 nm, transmittances between 0.3 and 0.9). The solid state fluorescence was measured with crystals placed on the inner wall of the cuvette. The crystals were in the beam path and absorbed between 15% and 30% of the excitation light. For the quantum yield, a value of 44% was obtained. When considering the Festköiper emission spectrum, it is striking that it barely overlaps with the absorption spectrum. In addition, the compound was investigated by cyclic voltammetry. It turned out that the compound can be reduced relatively easily and reversibly twice (FIG. 2). Even oxidation is possible without immediate decomposition.

The half-wave potentials of the compound are listed in the table of FIG. The potential difference between the first reduction potential and the oxidation potential is 2.94 V. This variable is approximately a measure of the FIOMO-LUMO distance. If an electron falls from the LUMO back to the HOMO, an energy of about 2.94 eV is released. Converted to the wavelength of an emitted photon, this corresponds to 422 nm.

A solution of n-butyllithium in hexane (1.52 mL, 1.61 M, 2.45 mmol) was added at 0 ° C to a solution of 2,7-di-tert-butyl-9,10-dihydro Add 9,9-dimethyl-10-trimethylsilyl-9-silaneanthracene (1.00 g, 2.45 mmol) in diethyl ether (20 mL) and stir for 0.5 h. The orange solution was heated to reflux for 1 h. Upon addition of a solution of p-tolualdehyde (3.20 mL, 2.69 mmol) in diethyl ether (5 mL) with ice cooling, the red reaction solution decolorized, which was then stirred at room temperature for 1.5 h. Saturated aqueous sodium bicarbonate solution (20 mL) was added. The aqueous phase was separated from the organic and extracted with diethyl ether (50 mL). The combined organic phases were washed with water (100 mL), dried with magnesium sulfate and the solvent removed under reduced pressure. The colorless crude product was purified by column chromatography (10 cm silica gel, eluent: cyclohexane) (1, 02 g, 2.32 mmol, 95%). Pure white colorless crystals were obtained by crystallization from methanol at 0 ° C.

1 H-NMR (500.18 MHz, CDC): 3.74 (d, ³ J _HH = 8.0 Hz, 1 H), 7.62 (d, ⁴ J -1 "- 2.3 Hz, 111) .

7.59 (d, ⁴ J _HH = 2, 1 Hz, 1 H), 7.43 (dd, ³ J _HH = 8.2 Hz, ⁴ J _HH = 2.2 Hz, 1H), 7.21 ( d, ³ J " _H = 8.2 Hz, 1H), 7, 1 1 (dd, V _HH = 8.2 Hz, ⁴ J _HH = 2.2 Hz, 1 H), 7.09 (d, ³ J _HH = 8.0 Hz, 2H), 7.00 (d, ³ J _HH = 8.0 Hz, 2H), 6.84 (s, 1H), 2.30 (s, 3H), 1, 35 (s, 9H), 1, 31 (s, 9H), 0.53 (s, 6H). ^{! 3} CfH} -NMR (125.8 MHz, CDCl ₃ ): S 148.9, 148.5, 146.9, 141.7, 141.2, 136.4, 136.3, 135.1, 134 , 8, 129.6, 129.3, 129.2, 129.2, 128.8, 128.8, 126.6, 125.7, 124.9, 34.7, 31, 6, 31, 5 ,. _^ ^ ^ - ^ --- ^ »

²⁹ Si NMR (99.4 MHz, CDC1,): δ - 7.6.

EA (%): Calculated for C ₃ H ₃₈ Si [276.53]: C, 84.87, H, 8.73; found: C 85.07, H 8.95.

HRMS: For C _3] H ₃₈ Si calculated: 438.27373, found: 438.27392.

10.) 3-Methyl-6,10-di-tert-butyl-8,8-dimethyl-8-hydro-8-sil- dibenzo [ii, cfe] anthracene

A solution of 2,7-di-tert-butyl-9,9-dimethylH, 0-tolylmethylene-9,10-dihydro-9-silaanthracene (61.0 mg, 1.39 mmol) and propylene oxide (20 mL) in cyclohexane (ca. 700 mL) was exposed to a mercury-vapor lamp for 5 h, with portions of iodine (0.54 g, 2.13 mmol) being added over the reaction time. The reaction solution was then filtered through alumina and the solvent removed under reduced pressure. Purification of the crude product by column chromatography (7 cm silica gel, eluent cyclohexane / ethyl acetate 50: 1) gave a colorless oil (450 mg, 1:03 mmol, 74.1%) *, in which residual educt was still present. Colorless, reagent grade solid was obtained by precipitating the product with ethanol from a dichloromethane solution. * The yield is corrected for the ratio of product / solvent in Ή-NMR.

Ή NMR (500.18 MHz, CDCS ₃ ): δ 8.80 (d, ⁴ J _HH = 2.0 Hz, 1H), 8.46 (s, 1H), 8.42 (s, 1H) , 8.17 (d, _HH = 8.6 Hz, 1H), 7.96 (d, ⁴ J _HH = 2.0 Hz, 1H), 7.86 (d, _HH = 8.0 Hz, 1H) , 7.73 (d, V _HH = 2.3 Hz, 1H), 7.57 (dd, J _HH = 8.6 Hz, ⁴ J _HH = 2.3 Hz, 1 H), 7.42 (d , ³ J _HH = 8.0 Hz, 1H), 2.65 (s, 3H), 1.55 (s, 9H), 1.42 (s, 9H), 0.51 (s, 6H). fHJ NMR (125.8 MHz, CDCl): δ 149.2, 147.6, 140.6, 136.4, 134.1, 133.3, 132.2, 131, 9, 131, 1, 130 , 7, 130.3, 130.2, 130.0, 129.1, 128.5, 127.4, 126.5, 125, 1, 122.2, 120.5, 35.1, 34.6 , 3 1, 7, 31, 5, 22, 4, -0, 1.

²⁹ Si NMR (99.4 MHz, CDC1,): δ -20.6.

EA (%): Calculated for C ₃ iH ₃₆ Si [436.70] C 85.26, H 8.31; Found: C 85.24, H 8.25. HRMS: For C ₃ iih Si calculated: 436.25808, found: 436.25800.

1 1.) 6,10-Di-tert-butyl-8-mesityl-3-methyl-8-hydro-8-boradibenzo [ö, l / e] anthracene

In a tapping flask was added 3-methyl-6,10-di-tert-butyl-8,8-dimethyl-8-hydro-8-siladibenzo [δ, e] anthracene (105 mg, 0.24 mmol) Dissolved BBr (2.5 ml) and stirred at 50 ° C overnight. The solution was cooled to room temperature, whereupon a precipitate formed. Excess BBr ₃ was condensed into a cold trap and the remaining solid dried for 0.5 h in an oil pump vacuum. To remove residual BBr ₃ , the solid was suspended in benzene (1.5 ml) and dried again. Then toluene (10 ml) was added and stirred for 0.5 h at ca. 35 torr. At 0 ° C, a solution of Mes-MgBr (0.6 mL, 0.87 M in THF) was added, with the solution beginning to fluoresce. The ice bath was removed and stirred for a further 1 h at room temperature. Then MeOH (5 mL) was added and the solvent removed. The solid residue was extracted with hexane and filtered. Concentration of the filtrate left the product as a neon-green solid (0.13 g, 106%). Overlayering a solution of the product (25 mg) in benzene (0.5 ml) with MeOH (3 ml) gave analytically pure crystals.

1 H-NMR (500.18 MHz, CDCl 3): δ 9.1 0 (d, ⁴ J _HH = 2.0 Hz, 1H, H-5), 8.93 (s, 1H, H-13), 8.62 (d, HH = 8.6 Hz, 1H, H-12), 8.58 (br, 1H, H-4), 8.25 (d, ⁴ J _HH = 2, 1 Hz, 1 H, H-7), 8.01 (d, ³ J _HH = 8, 1 Hz, 1 H, HI), 7.86 (d, ⁴ J _HH = 2.3 Hz, 1H, H-9), 7.82 (dd, V _HH = 8.5 Hz, ⁴ J _HH = 2.4 Hz, 1H, H-7 /), 7.49-7.52 (m, 1 Η, H-2), 6 , 95 (s, 2Η, Mes-Clf ^{1 £} 2.71 (s, 3Η, CH ₃ in pos. 3), 2.44 (s, 3H, Mes-CH ₃ ^pam 2.01 (s, 6H, Mes-CH ₃ ^ortho ), 1, 47 (s, 9H, 'Bu in pos. 6), 1, 33 (s, 9H, ^r Bu in pos. 10).

¹³ C {'11} NMR (125.7 MHz, CDCl,): δ 149.6 (10), 148.5 (6), 140.5 (Mes-C l), 139.6 (12a), 138 , 8 (Mes-C2.6), 138.4 (7), 137.5 (2a), 136.4 (Mes-C3.5), 135.0 (9), 131, 4 (4a), 130 , 6 (11), 130.2 (12c), 130.1 (13a), 129.8 (1), 129.8 (12b), 129.4 (4b), 128.6 (2), 127 , 0 (Mes-C3.5), 126.2 (13), 1.25.2 (5), 123.4 (12), 122.3 (4), 35.2 ( ¹ Bu-C in pos. 6 ), 34.6 (C in Pos. 10), 31.6 (Bu-CH ₃ in pos. 6), 31.4 (C-Bu ₃ in pos. 10), 23.4 (Mes-CH ₃ ⁽ . observed "^'lho \ 22.6 (. _CH3 in position 3), 21, 5 (Mes-CH ^{pai a),} C-7a B ⁿ {1 H] -NMR (160.5 MHz, CDC1 _3): δ 65.0 (h _Vl ~ 2500 Hz).

EA. (%): Calculated for C ₃ 8H _4I B [508.54]: C, 89.75, H, 8.13; Found: C 89.91, H 7.95. HRMS: Calculated for C38H41B: 508.33024, found: 508.33017.

UV absorption (cyclohexane, 7 μΜΜ, 25 ° C): X _max ^~~ 416 nm, 395 μm; i? 4i = 30000 L-mor '-cm ^"1 , e _m = 18000 L-mor'-cm ^{" 1} .

Fluorescence (cyclohexane, 1 μΜ, _λΕχ = 375 nm, 25 ° C): X _{m: a} = 428 nm, 450 nm; </> ,. - 88%.

Cyclic voltammetry (CH ₂ Cl ₂ , ("Bu) ₄ NPF ₆ 0.1 M, 400 mV / s, vs. Fc / Fc *): E _Vl [V] 0.99, -2, 17.

Optoelectronic characterization of 8-mesityl-3-niethyl-6, 10-di-ifriphenyl 1-8-hydro-8-boradibenzo [i, t] -lanthracene.

The compound is stable against air, moisture, water, acids and bases. It shows strong fluorescence and can be used as a blue emitter in organic light emitting diodes. It dissolves very well in most organic solvents, the solubility in benzene is about 50 mg / ml. Dilute solutions show an intense blue fluorescence (FIG. 11),

As the absorption and fluorescence of the compound overlap, higher concentrations result in a change in the emission spectrum due to reabsorption. The fluorescence quantum yield of dilute solutions in cyclohexane is 88%. The compound was studied by cyclic voltammetry to determine the energetic location of the frontier orbitals. The cyclic voltammogram suggests that the substance can be reversibly oxidized in solution (Figure 12).

From the half-wave potentials of oxidation and reduction, the energy levels of the frontier orbitals can be calculated. The highest occupied molecular orbital (HOMO) is -5.8 eV, the lowest unoccupied molecular orbital (LUMO) at -2.6 eV versus vacuum level (calculated as Fc / Fc ⁺ - 4.8 eV).

12.) 2,7-di- / eri-butyl-9,9-dimethyL10- (p-bromophenyl) methylene-9,10-dihydro-9-silaanthracene

einemη one. 100 mL two-neck flask with reflux condenser was charged with 2,7-di-tert-butyl-9,10-dihydro-9-dimethyl-10-trimethylsilyl-9-silaanthracene (1.25 g, 3.06 mmol) in Et ₂ O (22 mL) and cooled by an ice bath. At this temperature, "BuLi solution (1.88 mL, 1.63 M in n-hexane, 3.06 mmol) was added, the ice bath was removed and the orange reaction solution heated to reflux for 1.5 h again lowered to 0 ° C and a solution of p-bromobenzaldehyde (567 mg, 3.06 mmol) in Et ₂ O (8 mL) was added The reaction solution decolorized and was heated to reflux for 0.5 h, then became saturated aqueous NaHCO ₃ solution (30 mL), distilled H ₂ O (50 mL) and Et ₂ O (20 mL) was added and the aqueous phase was separated and extracted twice with Et ₂ O (50 mL) to give the combined organic layers dried with MgS0 and the solvent was removed under reduced pressure Residues of the aldehyde used were separated by a short silica gel column (eluent cyclohexane / ethyl acetate 25: 1) to give the product as a colorless solid (1.40 g, 91%) Residues of the silyl compound used can be removed by washing with methanol n.

1 H NMR (500.18 MHz, CDCl ₃ ): δ 7.64-7.61 (m, 3H), 7.44 (dd, ³ J _HH = 8.2 Hz, ⁴ J _HH = 2.2 Hz , 1H), 7,31 (d, ³ J _HH = 8,5 Hz, 2H), 7,14 (d, ³ J _HH = 8,2 Hz, 1H), 7,12 (dd, ³ J _HH = 8.2 Hz, V _HH = 1, 9 Hz 1H), 7.05 (d, ³ J _HH = 8.5 Hz, 2H), 6.79 (s, 1H), 1.36 (s, 9H) , 1, 32 (s, 9H), 0.54 (s, 6H). C {H NMR (125.8 MHz, CDCl3): S149.3, 148.9, 146.4, 142.7, 141, 1.137, 1, 136.4, 134.7, 131, 3, 129.4, 129.2, 128.9, 128.0, 126.7, 125.9, 124.9, 120.4, 34.7, 31, 6, 33, 5, -3, 1.

²⁹ Si NMR (99.4 MHz, CDCl ₃ ): δ -17.6.

EA (%): Calculated for C ₃ oH ₃ 5SiBr [503.59]: C 71, 55, H 7.01; found: C 71, 69, H 7.08. HRMS: Calculated for CsoHjsSiBr: 502, 16859, found: 502, 16796.

13.) 3-Bromo-6,10-di-tert-butyl-8,8-dimethyl-8-hydro-8-sila-dibenzo [a, i c] anthracene

A solution of 2,7-di-tri-butyl-9,9-dimethyl-10- (p-bromophenyl) methylene-9, 10-dihydro-9-saccharide acetic acid (500 mg, 0.99 mmol) and propylene oxide ( 10 mL) in toluene (about 700 mL) was exposed to a mercury-vapor lamp for 10 h, with iodine (1.13 g, 4.45 mmol) being added in portions over the reaction time. The reaction solution was stirred with aqueous 10% sodium sulfite solution. The resulting precipitate was filtered off and the phases were separated. The yellow organic phase was washed with water (50 mL), dried with magnesium sulfate and the solvent removed under reduced pressure. The brown residue was purified by column chromatography (7 cm silica gel, eluent cyclohexane / ethyl acetate 100: 1) to isolate a colorless solid (about 500 mg, product / starting material> 9: 1). By washing with cold methanol, colorless, analytically pure solid was obtained (337 mg, 671 mmol, 69%).

Ή-NMR (500.18 MHz, CDCl ₃ ): δ 8.80 (d, ⁴ J _HH = 1, 2 Hz, 1 H), 8.69 (d, ³ J _HH = 2.0 Hz, 1H) , 8.39 (s, 1H), 8.15 (d, ³ J _HH = 8.6 Hz, 1H), 8.01 (d, ⁴ J _HH = 2.0 Hz, 1H), 7.82 ( d, J _HH = 8.5 Hz, 1H), 7.74 (dd, JHH ^~ 2.3 Hz, ³ J _HH = _1.8 Hz, 1 H), 7.58 (dd, ³ J _HH = 8 , 6 Hz, ⁴ J _HH = 2.3 Hz, 1 H), 1, 55 (s, 9H), 1, 43 (s, 9H), 0.52 (s, 6H).

^{, 3} C! HS-NMR (125.8 MHz, CDCl ₃ ): S 149.7, 148.3, 140, 1, 1 34.4, 133.7, 1 3.4, 132.5,

132.2, 131, 5, 130.9, 130.7, 130.3, 129.9, 129.3, 127.5, 126.7, 125.3, 124.4, 120.9, 120, 5, 35, 2, 34, 7, 31, 6, 31, 4, -0, 1. Si NMR (99.4 MHz, CDCl ₃ ): δ -20.5. EA (%): _Calculated for C _{3 u} H ₃₃ SiBr [501, 57]: C 71, 84, H 6.63; found: C 71, 97, Ff 6,65. HRMS: For C _H , H _3? SiBr calculates: 502.15137, found: 502.1.5120.

14.) 3-BiOra-6, 10-di-tertiarybutyl-8-mesityl-8-hydro-8-boradibenzo [ö, £ e3anthracene

In a Schlenk flask, 3-bromo-6,10-di-terti-butyl-8,8-dimethyl-8-hydro-8-siladibenzo [β, iie] anthracene (102 mg, 0.203 mmol) in BBr ₃ ( 1 ml) and stirred at 50 ° C overnight. The solution was cooled to room temperature, whereupon a precipitate formed. Excess BBr ₃ was condensed into a refrigerator and the remaining solid was vacuum dried for 0.5 h in the oil pump. To remove residual BBr ₃ , the solid was suspended in benzene (1.5 ml) and dried again. Then toluene (20 ml) was added, the precipitate was dissolved in the heat (60 ° C) and cooled to 0 ° C. At this temperature, first 0.5 h at about 20 Ton- stirred, then at Norraaldruck a solution of Mes-MgBr (0.5 ml, 0.87 M in THF) was added, whereby the precipitate dissolved. The ice bath was removed and stirred for 0.5 h at room temperature. Then MeOH (4 ml) was added and the solvent removed. The solid residue was extracted with cyclohexane and filtered. Concentration of the filtrate left a neon yellow solid (0.13 g) which was dissolved in benzene (2.5 ml) and overlaid with methanol (15 ml). In the refrigerator (8 ° C), the product (107 mg, 0.226 mmol, 92%) crystallized from an analytical grade.

1 H-NMR (500.18 MHz, CDCl ₃ ): δ 8.98 (d, J _HH = 2.1 Hz, 1H), 8.92 (d, ⁴ J _HH = 1.4 Hz, 1 H), 8.88 (s, 1H), 8.59 (d, ³ J _UH = 8.6 Hz, 1 H), 8.27 (d, ⁴ Jnn ^™ 2, 1 Hz, 1 H), 7.96 ( d, ³ J _HH = 8.52 Hz, 1 H), 7.87 (d, ⁴ JHH = 2.3 Hz, IH), 7.83 (dd, V _HH = 8.5 Hz, ⁴ J _m = 2.4 Hz, 1 H), 7.75 (dd, ³ J _HH = 8.5 Hz, V _HH = 1.8 Hz, IH), 6.95 (s, 2H), 2.44 (s, 3H), 2.01 (s, 6H), 1, 46 (s, 9H), 1, 33 (s, 9H).

¹³ C {1 H NMR (125.7 MHz, CDCl ₃ ): δ 150.1.9, 149.30, 140.1 1, 139.18, 139.06, 138.67, 136.58, 135.15, 135 , 00, 132, 61, 131, 31, 131, 22, 130, 78, 130, 64, 130, 29, 130, 102, 128, 61 127.05, 125.46, 125.35, 125.36, 123.60, 121.79, 77.41, 77.16, 76.91, 35.27, 34.71, 31.56, 31, 39,23,41,21,53.

"B {1H} NR (160.5 MHz, CDCI ₃ ): 665.9 { _h " 2000 Hz).

EA (%): Calculated for C ₃₇ H ₃₈ BBr [573.41]: C, 77.50, H, 6.68; Found: C 77.82, H 6.79. HRMS: Calculated for C ₃₇ H _3g BBr: 574.22364, found: 574.22207.

15.) 6, 10-Di-tert-butyl-3- (4-diphenylamino) -phenyl-8-mesityl-8-hydro-8-boro-dibenzo [ö, ce] anthracene

In a Schlenk olben under nitrogen atmosphere 3-bromo-6,10-di-terti-butyl-8-inesityl-8-hydro-8-boradibenzo [<3!, Ife] anthraccn (44 mg, 77 μηιοΐ), 4 - (Tri - "- Buiylstannyl) - triphenylamine (104 mg, 194 pmoi) and bis [tri (teri-butyl) phosphine] palladium (2 mg, 4 μηιοΐ) in 1.5 ml of toluene for 48 h at 100 ° C. heated. The solvent was removed and the reaction mixture was separated by column chromatography on silica gel. The first fraction was eluted with cyclohexane / toluene (10: 1) and discarded. The second fraction was obtained with cyclohexane / ethyl acetate (10: 1) as eluent. Removal of the solvent left a neon yellow solid which, according to ¹ H-NMR, still contained about 10% starting material (35 mg, 56%) *. By recrystallization in hexane, the product was obtained in high purity. * The stated yield is around the ratio of product to educt in the ^! H-NMR corrected.

Ίΐ-NMR (500.18 MHz, CDC1 ₃ ): δ 9.17 (d, ⁴ J _HH ^" 1.9 Hz, 1H), 8.96 (s, 1H), 8.95 (s, 1H), 8.64 (d, ³ J _HH = 8.6 Hz, 1H), 8.26 (d, ⁴ J _HH = 1.9 Hz, 1H), 8.15 (d, ³ J _HH = 8.3 Hz , 1H), 7.90 (d, ³ J _HH = 8.3 Hz, 1H), 7.87 (d, ⁴ J _HH ^ 2.3 Hz, 1H), 7.83 (d, V _HH = 8 , 5 Hz, ⁴ J _HH = 2.3 Hz, 1H), 7.73 (d, ³ J _HH = 8.5 Hz, 2H), 7.33-7.30 (m, 4H), 7.26 (d, ³ J _HH = 8.5 Hz, 2H), 7.21 to 7.20 (m, 4H), 7.09 to 7.06 (m, 2H), 6.95 (s, 2H), 2.44 (s, 3H) ₅ 2.01 (s, 6H), 1.46 (s, 9H), 1.33 (s, 9H). ° C {1H} NMR (125.7 MHz, CDCl3): δ 149.8, 148.8, 147.8, 147.7, 140.4, 139.7, 139.5, 138.7, 138.6, 136.5, 136.5, 1.35.4, 135.0, 131, 6, 131, 0, 1 30.7, 1 30.5, 130.4, 130.4, 129.7, 129.5, 128.4, 127.0, 126.0, 126.0, 125.2, 124.8, 124.0, 123.6, 123.3, 120.3, 35.3, 34, 7, 31, 6, 31, 4, 23, 4, 21, 5.

EA (%): Calculated for C55H42BN [737.82]: C, 89.53, H, 7.10, N, 1.90; found: C 90.00, H 7.27, N 1.46.

1IRMS: Calculated for C ₅₅ H ₅₂ BN: 737.41964, found: 737.41916. UV absorption (cyclohexane): _maii - 434 nm.

Fluorescence (cyelohexane, λ _ΐΛ = 415 nm): _max = 471 nm, 498 nm; Φ _ν = 92%.

Fluorescence (other solvents, _ex = 435 nm): λ _{Β & χ} ( _Ρ ) = C l le-501 nm (93%), CHCh:

534 nm (89%), THF: 555 nm (88%), acetone: 609 nm (73%), CH ₃ CN: 646 nm (48%).

Cyclic voltammetry (CII ₂ C1 ₂ , | «Bu ₄ NJ [PF ₆ | 0.1 M, 400 mV s vs. FcH / FcH): E _Vl = 0.94,

0.48, -2.10 V.

16.) 6,10-Di-ieri-butyl-3- (thien-2-yl) -8-mesityl-8-hydro-8-boro-dibenzo [a, ejanthracene

In a Schlenk tube under nitrogen were added 3-bromo-6,10-di-tert-butyl-8-mesityl-8-hydro-8-boradibenzo [ö, ie] anthracene (40 mg, 70 mmol) and w-butylthien-2-yl-stannane (31 mg, 84 mmol) in toluene (1 ml). The solution was degassed by bubbling nitrogen through for 5 minutes, and bis [tri (eri-butyl) phosphine] palladium (1 mg, 2 μιηοΐ) was added. The reaction mixture was heated to 90 ° C for 5 h. After 3 h, stannane (13 mg, 35 mmol) and catalyst (1 mg, 2 μτηοΐ) were added again. Subsequently, the solvent was removed under reduced pressure and the neon-green residue was purified by column chromatography on silica gel (eluent cyclohexane / toluene 25: 1). The product was obtained as a neon yellow solid (26 mg, 64%). Ή-NMR (500.18 MHz, CDCl 3): δ 9.14 (d, J _HH = 2.0 Hz, 1H), 9.00 (s, 1H), 8.93 (s, 1H) , 8.62 (d, ³ J _{H, H} = 8.6 Hz, 1H), 8.27 (d, ⁴ J _HH = 2.1 Hz, 1H), 8.11 (d, ³ J _HH = 8 , 3 Hz, 1H), 7.93 (dd, J _HH = 1.6 Hz, ³ J _HH = 8.3 Hz, 1H), 7.88 (d, ⁴ Jim = 2.3 Hz, 1H), 7.83 (d, ⁴ J _HH = 2.38 Hz, 1H), 7.58 (dd, J _HH = 3.6 Hz, V _HH = 1.0 Hz, 1H), 7.41 (dd, ³ J _HH = 5.1 Hz, ⁴ J _HH = 1.0 Hz, 1H), 7.21 (dd, V _HH = 5.0 Hz, ³ J _HH = 3.6 Hz, 1H), 6.96 ( s, 2H), 2.44 (s, 3H), 2.02 (s, 6H), 1.48 (s, 9H), 1.34 (s, 9H).

^{, 3} C {'H} -NMR (125.8 MHz, CDCl ₃ ): δ 149.9, 148.9, 145.0, 140.3, 139.3, 138.8, 138.7,

136.6, 136.5, 135.1, 133.4, 131.6, 131.4, 130.8, 130.7, 130.5, 129.5, 129.2, 128.5, 128, 4, 127.0, 125.8, 125.6, 125.1, 125.1, 124.0, 123.6, 119.6, 77.4, 77.2, 76.9, 35.2, 34.7, 31.6, 31.4, 23.4, 21.5.

EA (%): Calculated for C ₄₁ H _4] BS [576.64]: C, 85.40, H, 7.17, S, 5.56; found: C 85.36, H 7.08, N 5.64.

IIRMS: Calculated for C ₄ | H ₄ | BS: 576.30236, found: 576.30165. UV absorption (cyclohexane): / l _max = 429 nm.

Fluorescence (cyclohexane, λ _Εχ = 400 nm): A _max . = 447 nm; Φ _Ρ = 73%. Cycovoltammetry (CH ₂ Cl ₂ , ('Bu) ₄ NPF ₆ 0.1 M, 400 mV / s, vs. Fc / Fc ⁺ ): E _Vl [V] -2.09.

17.) 6,10-Di-tert-butyl-3- (3,5-bis (trifluoromethyl) phenyl) -8-mesityl-8-hydro-8-boro-dibenzo [β, cfe] anthracene

3-bromo-6,10-di- / er-butyl-8-mesityl-8-hydro-8-boro-dibenzo [fl, i / e] anthracene (60 mg, 100 μπιοΐ) were prepared in a Schlenk tube under a nitrogen atmosphere. Tri-n-butyl-3,5-bis (trifluoromethyl) phenylstannane (80 mg, 150 μηιοΐ) and bis [tri (ieri-butyl) phosphine] - palladium (1 mg, 2 μιηοΐ) in toluene (1.5 ml) heated to 100 ° C for 30 h. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel (eluent cyclohexane / ethyl acetate 50: 1) separated. The product (36 mg, 49%) was obtained as a neon-green solid.

'II NMR (500.2 MHz, CDC1 _3): S 9.14 (br s, 1H.), 8.99 (s, 1 H), 8.94 (br s, 1H.), 8.65 (d, ³ J _HH = 8.6 Hz, 1H), 8.30 (br s, 1H.), 8.26 to 8.24 (m, 3H), 7.96 (br s, 1H.), 7.90-7.87 (m, 2H), 7.85 (dd, V _HH = 8.5 Hz, ⁴ JHH ™ 2, 1 Hz, 1H), 6.96 (s, 2H), 2.45 (s, 3H), 2.02 (s, 6H), 1.48 (s, 9H), 1.34 (s, 9H).

^{, 3} C {'H} -NMR (125.8 MHz, CDCl ₃ ): δ 150.3, 149.4, 144.0, 140.1, 139.1, 138.7, 137.2, 136, 7, 136.6, 135.2, 132.5 (q, ² J _Hr = 33 Hz), 132.1, 131.8, 131, 6, 131.0, 130.8, 130.5, 129, 5, 128.0 - 127.8 (m), 127.1, 125.9, 125.4, 124.9, 123.7, 123.6 (q, ^x J _m = 273 Hz), 122.5 , 121, 5, 121, 4 - 121.2 (m), 35.3, 34.7, 31.6, 31, 4, 23, 4, 21, 5.

¹⁹ F-NMR (470.6 MHz, CDCl _3): -62.7.

EA (%): _Calculated for C ₄₅ H _4i BF ₆ [706.61]: C, 76.49; H, 5.85; found: C 76.08, H 6.1 1.

HRMS: Calculated for C45H41BF6: 706.32077, found: 706.32059.

UV absorption (cyclohexane): λ _max = 413 nm.

Fluorescence (cyclohexane, ΛΕΧ = 370 nm): A _max = 427 nm; Φ ₍ - 89%.

Cyclovolammetry (CH ₂ Cl ₂ , ( ^r Bu) ₄ NPF ₆ μL, 200 mV / s, vs. Fc / Fc ⁺ ): Ey ₂ [V] 1, 1 1, -2.05.

18.) 1-Phenyl-3- (trimethylsilyl) prop-2-yn-1-one

PdCl ₂ (PPh ₃ ) ₂ (200 mg, 0.29 mmol) and Cul (109 mg, 0.57 mmol) in THF (50 mL) were suspended in a 250 mL Schlenk flask. Et ₃ N (2.2 mL, 1.59 g, 16 mmol), benzoyl chloride (1.7 mL, 2.0 g, 14 mmol) and trimethylsilylacetylene (2.0 mL, 1.4 g, 14 mmol ) via a syringe at room temperature. The Reaktionswämie was discharged through a water bath. After 2.5 hours, the green suspension was quenched with Et ₂ O (10 mL) and dist. Diluted water (150 mL). The phases were separated and the aqueous phase extracted with Et ₂ O (2 x 50 mL). The combined organic phases were washed with saturated aqueous NaHCO ₃ solution (50 mL) and brine (50 mL), dried with MgSO ₄ and the solvent is removed under reduced pressure. The crude product was purified by column chromatography on silica gel (diameter 5 cm, length 15 cm, eluent cyclohexam ethyl acetate = 25: 1). The first fraction contained the product. Yield: 2.58 g (89%) of colorless liquid.

1H-NMR (250.13 MHz, CDCl ₃ ): 6 8.17-8.12 (m, 2H), 7.62 (tt, ³ V _HH = 7.3 Hz, ⁴ J _HH = 1.3 Hz, 1 H), 7.53 -7.45 (m, 2H), 0.32 (s, 9H).

19.) 2,7-di-it-ti-butyl ~ 9,9-dimethyl-10- (1-phenyl-3- (trimethylsilyl) prop-2-yn-1-ylidene) -9, 10 ~ dihydro- 9-silaanthracen

In a 100 mL two-necked flask with reflux condenser was added 2,7-di-tert-butyl-9,10-dihydro-9,9-dimethyl-10-trimethylsilyl-9-silaanthracene (2.40 g, 5.93 mmol) in Et ₂ 0 (50 mL) dissolved. At room temperature, "BuLi solution (3.9 mL, 1.53 M in n-hexane, 5.9 mmol) was added via syringe and heated to reflux for 1 h, during which time the solution turned red Phenyl-3- (trimethylsilyl) prop-2-yn-1-one (1.26 g, 6.22 mmol) was added via syringe and stirred for 20 h at room temperature (red), followed by saturated aqueous NaHCO 3. Solution (40 mL), Et ₂ O (40 mL) and distilled water (40 mL) were added and the aqueous phase was separated and extracted with Et ₂ O (50 mL) The combined organic phases were washed with saturated aqueous NaCl. Solution (2 x 50 mL), triturated with MgSO ₄ and the solvent removed under reduced pressure The crude product was purified by column chromatography (silica gel, length 20 cm, diameter 5 cm, eluent cyclohexane: CHCl ₃ = 4: 1) : 2.30 g (74%) of a colorless solid.

11-NMR (500.2 MHz, CDCl ₃ ): δ 8.10 (d, ³ J _HH = 8.2 Hz, 1H), 7.62 (d, ⁴ J _HH = 2.0 Hz, 1H), 7.55 (d, ⁴ J _HH = 2.0 Hz, 1H), 7.37 (dd, ³ J _HH = 8.2 Hz ₅ ⁴ J _H H = 2.1 Hz, 1H), 7.23-7.19 (m, 2H), 7.17-7.13 (m, 3H), 6.92 (dd, ³ J _H H = 8.2 Hz, ⁴ J _H H = 2.1 Hz, 1H), 6.73 (d, ³ J _HH = 8.2 Hz, 1H ), 1 .35 (s, 9H), 1.24 (s, 9H), 0.68 (s, 3H), 0.48 (s, 3H), 0.15 (s, 9H). ¹³ C {'H} -NMR (125.8 MHz, CDCl3): δ 148.8, 148.7, 147.4, 143.7, 142.8, 139.8, 136.8, 136.2, 130.5, 129.6, 128.8, 128.8, 128.5, 127.7, 126.8, 125.3, 125.0, 120.9, 107.4, 99.9, 34.8, 34.6, 31.5, 31.4, -0.1, 4.0, -5.4.

²⁹ Si-NM (99.4 MHz, CDC1 ₃ ): S - 17.2, - 1 8. 1.

EA (%): calculated for C ₃₅ H44Si2 [520.89]: C 80.70, H 8:51; found: C 80.64, H 8.63. HRMS: Calculated for C35H44S12: 520.29761, found: 520.29648.

2,7-di-ieri-butyl-9,9-dimethyl-10- (1-phenylprop-2-yn-1-ylidene) -9,10-dihyd:

9-silaanthracen

In a 100 mL Schlenk flask, 2,7-di-tert-butyl-9,9-dimethyl-10- (1-phenyl-3- (trimethylsilyl) piOp-2-yn-1-ylidene) -9 , 10-dihydro-9-silaanthracene (1.20 g, 2.30 mmol) in THF (20 mL). On cooling through an ice-bath, tetra ("- butyl) ammonium fluoride solution in THF (2.76 mL, 1.0 M, 2.76 mmol) was added. The solution turned deep green. After stirring for 1 h, the solvent was removed under reduced pressure. The residue was extracted with cyclohexane (10 mL) and purified by column chromatography (silica gel, 10 cm length, eluent cyclohexane: EtOAc = 25: 1). Yield: 1.05 g glassy solidified solid, slightly orange, residues of cyclohexane can still be seen in Ή-NM. The substance was immediately used for the next reaction.

Ή-NMR (250.1 MHz, CDCl ₃ ): δ 8.05 (d, ³ J _HH = 8.2 Hz, 1 H), 7.63 (d, ⁴ J _HH = 2.1 Hz, 1 H), 7.55 ( d, ⁴ J _HH = 2.1 Hz, 1 H), 7.40 (dd, ³ J _HH = 8.2 Hz, ⁴ J _HH = 2.2 Hz, 1H), 7.27-7.13 (m, 5H), 6.92 (dd, ³ J _HH = 8, Hz, ⁴ J _HH = 2.2 Hz, 1H), 6.73 (d, ³ J _HH = 8.2 Hz, 1H), 3.15 (s, 1H), 1.35 (s, 9H), 1 .24 (s, 9H), 0.69 (s, 3H), 0.47 (s, 3H). 21.) 5,9-di-he-butyl-7,7-dimethyl-1-phenyl-7-hydro-7-silabenzo [ci]? Anthracene

In a 50 mL two-necked flask with reflux condenser and dropping funnel, PPh ₃ Ru (cymene) Cl ₂ (62 mg, 0.38 mmol) and NH ₄ PF ₆ (107 mg, 0.189 mmol) were suspended in 1, 2-dichloroethane (20 mL) , The suspension was heated through a 75 ° C oil bath. At this temperature a solution of 2,7-di-tert-butyl-9,9-dimethyl-10- (1-phenylprop-2-yn-1-ylidene) -9,10-dihydro-9-silaanthracene was obtained (850 mg, 1.89 mmol) in 1, 2-dichloroethane (10 mL) was added dropwise over 1 h. After complete addition, the mixture was heated to reflux for 1 h. Subsequently, the solvent was removed under reduced pressure at room temperature. The crude product was purified by column chromatography (silica gel, length 25 cm, eluent CydohexamCHC ^ = 15: 1, R {= 0.25). Yield: 615 mg (70%) of light yellow solid.

MJV1D (f \ (\ t U ₇ f 'I. Λ 7 ß7 l A / .... _ 1 1 II ·, 1 \ 7 ST.7 70 in 1U l 7 A4 (A

V _HH = 2.3 HZ, 1H), 7.61 (d, ³ J _HH = 8.3 Hz, 1H), 7.45 (d, ³ J _HH = 7.3 Hz, 2H), 7.32 (vt, J _HH = 7.2 Hz (2H), 7.25 (m, 1H), 7.03 (d, ³ J _HH = 8.6 Hz, 1H), 6.92 (dd, ³ J _H H = 8.6 Hz, ⁴ J _HH = 2.3 Hz, 1H), 1.45 (s, 9H), 1.28 (s, 9H), 0.53 (s, 6H).

¹³ C {'H} -NMR (125.8 MHz, CDCl ₃ ): δ 148.0, 147.3, 145.2, 140.6, 139.0, 135.5, 134.3, 134.0, 134.0, 133.4, 132.7, 130.9, 130.7, 130.2, 129.3, 128.6 , 128.4, 126.4, 125.5, 124.8, 34.7, 34.5, 31.4, -1.57 (only one zBu-CH ₃ resonance visible).

²⁹ Si NMR (99.4 MHz, CDC1 _3): δ -19.6.

 22.) 5,9-Di-tert-butyl-7-mesityl-1-phenyl-7-hydro-7-borabenzo [i / e] anthracene

In a small Schlenk flask, 5,9-di-tert-butyl-7,7-dimethyl-1-phenyl-7-hydro-7-silabenzo [ire] anthracene (50 mg, 0.1 mmol) in pure BBr ₃ (0.3 mL) and stirred for 16 h at room temperature. Excess BBr ₃ was removed under reduced pressure and the glassy solidified dark residue dried for 1, 5 h in an oil pump vacuum. Toluene (2.5 mL) was added and the solution was stirred for 1 h at 25 torr to remove residual BBr ₃ (the volume only slightly decreased). A MesMgBr solution in THF (0.20 mL, 0.87 M, 0.17 mmol) was added at room temperature and stirred for 2 h. The solution turned from orange to yellow. MeOH (0.5 mL) was added and all volatiles removed under reduced pressure. The residue was extracted with n-hexane (20 mL), filtered and the filtrate concentrated (crude yield 66 mg). The crude product was dissolved in CH ₂ Cl ₂ (0.7 mL) and overlaid with CH ₃ CN (3 mL). After 2 days, the supernatant was removed and the crystals were dried under reduced pressure. Yield 35 mg (60%) yellow solid.

Ή-NMR (500.2 MHz, CDCl ₃ ): δ 8.21 (d, V _H ii = 2.3 Hz, 1H), 8.14 (d, ⁴ J _HH = 2.3 Hz, 1 H), 7.97 (d, _HH = 8.3 Hz, 1 H), 7.79 (d, ⁴ J _HH = 2.4 Hz, 1 H), 7.63 (d, ³ J _HH = 8.3 Hz, 1 H), 7.54-7.51 (m, 2H), 7.48-7.44 (m, 3H), 7.42-7.39 (m, 1H), 7.17 (dd, ³ J _HH = 8.7 Hz, ⁴ J _HH = 2.5 Hz, 3 H),

QA from A'X io Wi Ί m 1 is (at 1 0 1 r _a om

^, C { ^! H} NMR (125.8 MHz, CDCl3): δ 148.6, 148.3, 145.9, 141.5, 140.6, 140.3, 140.0,

138.8, 138.7, 1 36.3, 134.9, 134.6, 132.2, 131.4, 131.2, 131.2, 131.0, 130.8, 130.0, 129.1,

128.9, 128.6, 127.1, 126.9, 34.8, 34.5, 31.3, 23.5, 21.5 (only one rBu-CH ₃ resonance visible).

HRMS: Calculated for C ₃₉ H ₄₁ B: 520.33026, found: 520.32847.

23.) 2,6-Di-feri-butyl-4-mesityl-4-hydro-4-boradibenzo [g ^' ^, / g ⁱ i "] tetraphene

A solution of 5 _} 9-di-tert-butyl-7-mesityl-1-phenyl-7-hydro-7 "borabenzo [ies] anthracene (0.26 g, 0.50 mmol) and propylene oxide (10 mL). in toluene (about 700 mL) was exposed to a mercury-vapor lamp for 8 h, with iodine (195 mg, 0.75 mmol) being added in portions over the reaction time, the reaction solution being replaced by Al ₂ O ₃ (3 cm, neutral.) and the solvent is removed under reduced pressure. Yield: 0.25 g (0.48 mmol, 96%) of yellow solid.

1 H NMR (250.1 MHz, CDCl ₃ ): δ 9.21 (d, ⁴ J _HH = 2.0 Hz ₎ 1 H), 8.78-8.93 (m, 3H), 8.42 (d, ⁴ J _HH = 2, 3 Hz, 1H), 8.38 (d, ⁴ / _ΗΗ = 2.1 Η.ζ, 1H), 8.36 (d, ⁴ J _HH = 2.3 Hz, 1 H), 8.29 (d, ³ J _HH = 9 , 0Hz, 1H), 7.83-7.79 (m, 2H), 6.99 (s, 2H), 2.47 (s, 3H), 2.04 (s, 6H), 1.50 (s, 9H), 1.46 (s, 9H) ,

HRMS: For C ₃₉ H ₃₉ B calculated: 518.31461, found: 518.31346.

24.) 2,7-Di- / erf-butyl-9-mesityl-10-pyridinylmethylene-9,10-dihydro-9-boraanthracene

 Nie Mes

In a 50 mL two-necked flask with reflux condenser, 2,7-di-ieri-butyl-9,10-dihydro-9-mesityl-10-trimethylsilyl-9-boraanthracene (500 mg, 1.04 mmol) in Et ₂ O (15 mL). At 0 ° C, "BuLi solution in n-hexane (0.70 mL, 1.56 M, 1.1 mmol) was added and the orange solution heated to reflux for 30 min. At 0 ° C, 2-pyridinylcarboxaldehyde ( 0.1 1 mL, 0.12 g, 1.1 mmol) was added and the solution became deep red, heated to reflux for 30 min, then saturated aqueous NaHCO ₃ solution (20 mL) was added and the phases The aqueous phase was extracted with Et ₂ O (2 x 30 mL) and the combined organic phases were washed with distilled water (50 mL) and saturated aqueous NaCl (20 mL), dried with MgSO ₄ , and the solvent The crude product was purified by column chromatography (10 cm silica gel, eluent cyclohexane / ethyl acetate 5: 1, λ _f = 0.35) Yield: 310 mg (0.62 mmol, 60%) yellow solid.

Ή NMR (500.2 MHz, CDCl,): δ 8.71 (m, 1H), 8.06 (d, ³ J _HH = 8.2 Hz, 1H, H-4 or 5), 7.64-7.63 (m, 2H; Hl and 8), 7.61 (dd, ³ J _HH = 8.2 Hz, ⁴ J _HH = 2.3 Hz, 1H, H-3 or 6), 7.46 (dt, ³ J _HH = 7.7 Hz, ⁴ J _HH = 1.8 Hz, 1H), 7.43 (s, 1H, ArC // =), 7.39 (d, ³ J _HH = 8.3 Hz, 1H, H-4 or 5), 7.17 (dd, ³ J _HH = 8.3 Hz, ⁴ J _HH = 2.3 Hz, 1H, H-3 or 6), 7.16-7.1 1 (m, 2H), 6.92 (s, 2H, Mes-Cm), 2.40 (s , 3H, Mes-CH ₃ -p), 2.06 (s, 6H, Mes-CH ₃ -ö), 1.26 (s, 9H, iBu-CH ₃ ), 1.20 (s, 9H, iBu-CH ₃ ). ¹ C { ^! H NMR (125.8 MHz, CDCl ₃ ): S 158.4, 1 50.6, 150.0, 1.49.8, 144.7, 141.7, 139.7, 138.1, 136.5, 135.8, 134.2 (Cl or 8), 133.9 (C-1 or 8), 1 30.4 (ArCH =), 130.1 (C-3 or 6), 129.5 (C-4 or 5), 128.1 (C-3 or 6), 127.0 (Mes-CH-m), 125.6, 123.6 ( C-4 or 5), 121.6, 34.7, 34.6, 31 .4 (Bu-CH _3), 31.3 (iBu-CH _{3) 5} 22.9 (Mes-CH ₃ -O), 21.5 (Mes-CH ₃ ->) , three resonances (C-B) not observed.

EA (%): _Calculated for C ₃ H ₄₀ BN [497.52]: C 86.91, H 8.10, N 2.82; found: C 86.20, H 8.34, N 2.54.

HRMS: Calculated for C ₃₆ H ₄ iBN: 498.33328, found: 498.33238.

25.) 6, 10-Di-ieri-butyl-8-mesityl-8-hydro-1 -aza-8-boradibenzof a, the anthracene

 In an exposure apparatus, 2,7-di-tert-butyl-9-mesityl-10-pyridinylmethylene-9, 10-dihydro-9-boraanthracene (0.174 g, 0.350 mmol) was added under argon atmosphere in toluene (700 mL). dissolved and mixed with propylene oxide (20 mL). For degassing, argon was introduced through a cannula for 15 minutes. The solution was exposed to a mercury vapor lamp while iodine (0.133 g, 0.525 mmol) was added portionwise over about 2 h. After 5 h, all volatiles were removed under reduced pressure. The residue was taken up in hexane (30 mL), suspended in an ultrasonic bath and filtered, the filtrate was concentrated to dryness and the residue was taken up in MeOH (5 mL), suspended in an ultrasonic bath, cooled to 8 ° C. and filtered while cold The resulting solid was dried in an oilpurapen vacuum.Yield: 100 mg (0.202 mmol, 58%) of yellow solid, crystals suitable for X-ray diffraction analysis were obtained by recrystallization from hexane.

^! H NMR (500.2 MHz, CDQ ₃ ): δ 9.21. (s, 1 H, H-1), 9.10 (br d, ³ J _HH = 8.3 Hz, 1H, H-2 or 4), 9.06 (dd, V _HH = 4.3 Hz, J _HH = 1, 5 Hz, 1 H, H-2 or 4), 9.02 (d, ⁴ J _HH = 2.1 Hz, 1 H, H-5), 8.70 (d, ³ J _HH = 8.2 Hz, 1H H-12), 8.29 (d, V _HH = 2.1 Hz, 1H, H-7), 7.89-7.85 (m, 2H, H-9 and 1 1), 7.64 (dd, ³ J _HH = 8 , 3 Hz, ³ J _HH = 4.3 Hz, 1 H, H-3), 6.95 (s, 2H, Mes-CH-m), 2.44 (s, 1H, Mes-CH ₃ -), 2.01 (s , 6H, Mes-CH ₃ -o), 1.46 (s, 9H, iBu-CH ₃ ), 1.33 (s, 9H, iBu-CH ₃ ). ¹³ C {\ H} NMR (125.8 MHz, CDCh): S 150.8 (C-10), 150.3 (C-2 or 4), 149.6 (C-6), 148.4, 140.0 (Mes-Ci), 139.2 (C-7), 138.9 (C-12a), 138.7 (Mes-Co), 136.8 (C-8a), 136.7 (Mes-C-p), 135.2 (C-9), 135.1 (C-7a), 134.6 (C-12b), 131.1 (Cl l), 130.6 (C-2 or 4), 129.9 (C-12c), 129.0, 127.1 (Mes-CH-m), 126.8 (C-13), 126.4 (C -4a), 124.9 (C-5), 124.3 (CI), 121.9 (C-3), 35.3 (Bu-C at pos. 10), 34.8 (iBu-C at pos. 6), 31.5 (fBu ~ CH ₃ at pos. 6), 31.4 (* Bu-CH ₃ at pos. 10), 23.4 (Mes-CH ₃ -o), 21 .5 (Mes-CH ₃ -p).

"ß NMR (160.5 MHz, CDCl _3): Ö 66 (h _Vt ~ 1500 Hz).

EA (%); Calculated for C ₃₆ H ₃₈ BN [495.50]: C 87.26, H 7.73, N 2.83; found: C 86.42, H 7.76, N 2.76.

HRMS: FÜ1- C ₃ 6H ₃ 9BN calcd: 496.31763, found: 496.31749. UV absorption (cyclohexane): _max (ε) - 397 nm (14,000), 378 11m (13,000). Fluorescence; (Cyclohexane, κ _Εχ = 370 nm): X _nw - 412 nm, 432 nm; Φγ = 73%. Cyclic voltammetry (CH ₂ C1 ₂ , ("Bu) NPF ₆ 0, 1 vi, 200 mV / s, vs. Fc / Fc ⁺ ): Ey ₂ [V] -2.03.

26.) 2,7-Di-t-i-butyl-9,10-dihydro-9-mesityl-9-boraanthracene

2,7-Di-1-Butyl-9,10-dihydro-9,9-dimethyl-9-silaanthracene (4.00 g, 11 mmol, 9 mmol) was dissolved in a heated Schlenk tube with dropping funnel at room temperature (water bath) pure BBr ₃ (3 mL). The solution was stirred for 16 h, then excess BBr ₃ was removed under reduced pressure to give a dark solid. Toluene (20 mL) was added and the resulting suspension was stirred at 25 torr for 1 h to remove residual BBr. Via the dropping funnel, a solution of mesitylmagnesium bromide (MesMgBr) in tetrahydrofuran at room temperature was added dropwise over 30 minutes (0.87 M, 16.4 mL, 14.3 mmol) and stirred for 1 h. The reaction mixture was transferred to a beaker with cyclohexane (100 mL) and saturated aqueous NaHCO ₃ solution (1.00 mL). It was dest. Water (100 mL) was added and the phases were separated. The aqueous phase was extracted with cyclohexane (50 mL), the combined organic phases with dist. Washed water (100 mL) and dried with MgS0 ₄ . The solvent was removed under reduced pressure and the crude product was purified by column chromatography (8 cm Silica gel, eluent cyclohexane). The eluate was concentrated to a volume of 20 ml and freeze-dried. Yield: 3.60 g (8.81 mmol, 73%) of a colorless solid.

1H NMR (500.2 MHz, CDCl ₃ ): δ 7.71 (no 2H, H-1, 8), 7.63 (dd, ³ J (H, H) = 8, 1 Hz, ⁴ J (H, H) = nr 2H, H-3.6), 7.51 (d, ³ J (H, H) = 8, 1 Hz, 2H, H-4.5), 6.90 (s, 2H, Mes-CH), 4.49 ( s, 2H, H-10), 2.41 (s, 3H, Mes-CH ₃ - />), 1.98 (s, 6H, Mes-CH ₃ -o), 1.27 (s, 18H, iBu-CH ₃ ).

° C {1H} NMR (125.8 MHz, CDCl3): δ 148.2, 145.0, 140.2, 138.2, 136.6, 136.3, 134.6 (C-1, 8), 129.9 (C-3.6), 127.8 (C -4.5), 126.9 (Mes-CH), 37.5 (C-10), 34.5 (iBu-C), 31.5 (fBu-CH ₃ ), 23.0 (Mes-CH ₃ -o), 21.5 (Mes -CH ₃ - /?).

^Ϊ! Β NMR (160.5 MHz, CDC1 ₃ ): S 66 {h _Vl 1500 Hz).

EA (%): Calculated for C ₃₀ H ₃₇ B [408.43]: C 88.22, H 9.1 3; found: C 87.91, H 9.12. HRMS: Calculated for C ₃₀ H ₃₆ B: 407.29099, found: 407.29021.

2,7-di-ietf-butyl-9, 10-dihydro ~ 9 ^{»mesityl-10-trimethyisilyl-9-boraanthracene}

In a two-necked flask with reflux condenser, 2,7-di-teft-butyl-9,10-dihydro-9-mesityl-9-boraanthracene (3.25 g, 7.47 mmol) was dissolved in Et 2 O (50 mL). When cooled by an ice bath, "BuLi solution in hexane (6.6 mL, 1.56 M, 10 mmol) was added slowly via syringe, the ice bath was removed, and the red reaction mixture was stirred at room temperature for 30 min a syringe was slowly added to Me ₃ Si-Cl (1.5 mL, 1.3 g, 12 mmol) and the reaction mixture heated to reflux for 5.5 h The colorless suspension was washed with saturated aqueous NaHCO ₃ solution (50 mL The aqueous phase was then separated off and extracted with Et ₂ O (2 × 50 ml) and the combined organic phases were washed with distilled water (50 ml) and saturated aqueous NaCl solution (50 ml) over MgS0 dried ₄ and filtered. from the filtrate, all volatiles were removed under reduced pressure. after purification by column chromatography (8 cm silica gel, eluent cyclohexane), the eluate was concentrated to 30 mL and the product after freeze-drying as a colorless solid in a yield of 3 , 51 g (7.30 mmol, 92%). Ή NMR (500.2 MHz, CDCl ₃ ): δ 7.68 (nr, 2H, H-1, 8), 7.51 (dd, ³ J (H, H) = 8.2 Hz, V (J IH) = nr , 2H, H-3.6), 7.33 (d, J (H, H) = 8.2, 2H, H-4.5), 6.90 (s, 1H, Mes-CH), 6.88 (s, 1 H, Mes-CH), 4.39 (s, 1H, H-10), 2.40 (s, 3H, Mes-CH ₃ -), 2. 1 (s, 3H, Mes-CH ₃ -o), 1.81 (s , 3H, Mes-CH ₃ -o), 1.24 (s, 18H, iBu-CH ₃ ), -0.15 (s, 9H, SiMe ₃ ).

^I C {'H} NMR (125.8 MHz, CDCl ₃ ): δ 148.7 (C-4a, 10a), 146.5 (C-2,7), 140.7 (Mes-C), 139.1 (Mes-Co) , 138.1 (Mes-Co), 136.3 (C-8a, 9a), 136.0 (Mes-C-?), 1 34.7 (C-1, 8), 128.6 (C-3.6), 127.3 (C-). 4.5), 127.0 (Mes-CH-w), 126.8 (Mes-CH-w), 47.0 (C-10), 34.4 (/ Bu-C), 31.6 (/ Bu-CH _3), 23.7 (Mes -CH ₃ -o), 23.0 (Mes-CH ₃ -o), 21.5 (Mes-CH ₃ - //>, -1.7 (SiMe ₃ ).

^U B NMR (160.5 MHz, CDCl ₃ ): δ 65 (h _Vl ~ 1500 Hz). ²⁹ Si NMR (99.5 MHz, CDCl ₃ ): 3 7.5.

EA (%): Calculated for C33H ₄₅ BS1 [480.61]: C 82.47, H 9.44; found: C 82.70, H 9.62. HRMS: Calculated for C ₃₃ H ₄₄ BSi: 479.33059, found: 479.32982.

28.) 3-Trifluoromethyl-6,10-di-terti-butyl-8-mesityl-8-hydro-8-boradibenzo, de] anthracene

In a two-necked flask with reflux condenser, 2,6-di-tert-butyl-9,10-dihydro-9-mesityl-10-trimethylsilyl-9-boraanthracene (0.80 g, 1.7 mmol) in Et ₂ O ( 15 mL). At room temperature, "BuLi solution (1, 1 mL, 1, 54 M in hexane, 1.7 mmol) was added with stirring and heated to reflux for 0.5 h. The temperature was lowered to 0 ° C and 4- (trifluoromethyl) benzaldehyde (0.24 mL, 310 mg, 1.8 mmol) added dropwise. The reaction was heated to reflux for 1.5 h. After cooling to room temperature, the colorless suspension was treated with saturated, aqueous NaHCO ₃ solution (30 ml). Subsequently, the aqueous phase was separated and extracted with Et ₂ O (30 mL). The combined organic phases were washed with distilled H ₂ O (50 mL) and saturated aqueous NaCl solution (30 mL), dried over MgSO ₄ and filtered. From the filtrate, all volatiles were removed under reduced pressure. The resulting solid (about 900 mg) was purified by column chromatography (25 cm silica gel, eluent cyclohexane). cleaned. Only pure fractions were combined and the solvent removed in vacuo. Yield: 0.24 g (0.43 mmol, 25%) yellow powder.

Ή NMR (500.2 MHz, CDCl ₃ ): δ 7.97 (d, ³ J (H, H) = 8.3 Hz, 1H, H-4 or 5), 7.66 (d, J (H, H) = 2, 2 Hz, 1H, H or 8), 7.64 (d, ⁴ J (H, H) = 2.2 Hz, 1H, H or 8), 7.61 (dd, (H, H) = 8.3 Hz, ⁴ J (H, H) = 2.2 Hz, 1H, H-3 or 6), 7.53 (d, ³ J (H, H) = 8.2 Hz, 2H, Ar-Hm), 7.42 (d, ³ J (H, H) = 8.2 Hz, 2H, Ar-Ho), 7.40 (d, ³ J (H, H) = 8.3 Hz, 1H, H-4 or 5), 7.37 (s, 1H ; ArCH =), 7.20 (dd, ³ J (H, H) = 8.3 Hz, ⁴ J (H, H) = 2.2 Hz, 1H, H-3 or 6), 6.92 (s, 2H; Mes-CH-m), 2.41 (s, 31 1: Mes-CH ₃ -p), 2.06 (s, 6H, Mes-CH ₃ -o), 1.27 (s, 9H, Bu-CH ₃ ), 1.22 ( s, 9H; iBu-CH ₃ ).

¹ C {'H} NMR (125.8 MHz, CDQ ₃ ): δ 150.5, 149.9, 144.8, 142.7, 141.0, 139.7 (br, CB), 139.5, 138.2 (br, CB), 138.0, 136.6, 135.9 (br, CB), 134.2 (Cl or 8), 134.0 (Cl or 8), 130.0 (Ar-Co), 130.0 (C-3 or 6), 129.5 (C-4 or 5), 129.1 (ArCH =), 128.8 (q, ² J (C, F) = 32.7 Hz, Ar-Cp), 128.2 (C-3 or 6), 127.1 (Mes-CH-m), 125.4 (q, ³ J (C, F) = 3.6 Hz; Ar-Cw), 123.3 (C-4 or 5), 34.7 (tBu-C), 34.6 (iBu-C), 31.4 (iBu-CH _3), 31.3 (iBu-CH _3), 22.9 (Mes-CH ₃ -o), 21.5 (Mes-CH ₃ - /?), A carbon resonance (CF ₃ ) not observed.

^{, 9} Ε I Vi D (Λ Ί (for MH, Γ Ύ \ Γ Λ. \. X -ΑΊ A

EA (%): Calculated for C _3S H ₄₀ BF ₃ [564.53]: C 80.85, H 7.14; Found: C 80.25, H 7.35. HRMS: Calculated for C ₃₈ H ₄ iBF ₃ : 565.32545, found: 565.32338.

3-trifluoromethyl-6,10-di-er-butyl-8-mesityl-8-hydro-8-borodibenzo [a, de] anthracene

A solution of 3-trifluoromethyl-6,10-di-tert-butyl-8-mesityl-8-hydro-8-borodibenzo [,] fe] anthracene (145 mg, 0.257 mmol) in cyclohexane (approximately 700 mL ) was added with propylene oxide (5 mL). For degassing, argon was introduced through a cannula for 15 minutes. The solution was exposed to a mercury-vapor lamp while iodine (103 mg, 0.406 mmol) was added portionwise over about 1.5 h. After another 2 After exposure to light, the solvent was removed under reduced pressure. The solid residue was purified by column chromatography (5 cm silica gel, eluent cyclohexane: dichloromethane = 25: 1) to give a yellow solid. Yield: 0.1 15 g (0.204 mmol, 80%) of a colorless solid.

Ή NMR {500.2 MHz, C ₆ D ₆ ): δ 9.16 (no, 1 H, H-4), 9.01 (d, ⁴ J (H, H) - 2.1 Hz, 1 H, H-5 ), 8.78 (s, 1H, H-13), 8.62 (d, ⁴ J (H, H) = 2, 1 Hz, 1 H, H-7), 8.50 (d, V (H, H) - 8 , 6 Hz, 1 H; H-12), 8.29 (d, ⁴ J (H, H) = 2.4 Hz, 1H, H-9), 7.78 (dd, J (H, H) = 8.6 Hz, ⁴ J (H, H) - 2.4 Hz, 1H, H-1 1), 7.70 (d, ³ J (H, H) = 8.4 Hz, ΪΗ; HI), 7.65 (dd, ³ J (H, H) = 8.4 Hz, ⁴ J (H, H) = no, 1 H; H-2), 7:04 (s, 2H, Mes-CH-zw), 2:32 (s, 3H, Mes -CH ₃ ->), 2.19 (s, 6H, Mes-CH ₃ -o), 1 .26 (s, 9H, fBu-CH ₃ at C-10), 1.21 (s, 9H; iBu-CH ₃ at C-6).

^, C { ^! H NMR (125.8 MHz, C ₆ D ₆ ): 6 151.0 (C-10), 150.0 (C-6), 140.6 (br, Mes-C-), 139.7 (C-7), 139.5 ( C-12a), 138.9 (Mes-Co), 137.4 (br, C-8a), 137.3 (Mes-Cp), 135.6 (br, C-7a), 135.5 (C-9), 334.2 (C). 13a), 133.4 (C-12b), 131.3 (C-1 1), 131.0 (C-4a or 12c), 130.9 (C-4a or 1.2c), 130.9 (CI), 130.1 (C-4b) , 129.0 (q, ² J (C, F) = 32.0 Hz, C-3), 127.8 (Mes-CH-m), 125.5 (q, ^S J (C, F) = 272.2 Hz, CF ₃ ) , 125.5 (C-5), 125.4 (C-13), 124.6 (Cl 2), 122.7 (q, ³ J (C, F) = 3.1 Hz, C-2), 120.2 (q, ³ J (C , F) = 4.2 Hz, C-4), 35.0 (/ Bu-C at C-6), 34.7 (iBu-C at C-10), 31.3 (/ Bu ~ CH ₃ at C-10), 31.2 ( iBu-CH ₃ at C-6), 23.5 (Mes-CH ₃ -o), 21 .5 (Mes-CH ₃ -jP).

¹³ B NMR (160.5 MHz, C ₆ D ₆ ): δ 67 (hy ₂ × 1500 Hz). ¹⁹ F NMR (470.6 MHz, C ₆ D ₆ ): δ 61 .5.

EA (%): Calculated for C ₃₈ H ₃₈ BF ₃ [562.51]: C 81.14, H 6.81; found: C 80.82, H 6.81.

ERMS: Calculated for C _3g H _3S BF ₃ : 562.30197, found: 562.30097.

UV / Vis (cyclohexane): _max (ε) = 401 (30,000), 381 nm (21,000).

Fluorescence (cyclohexane, λ = 370 nm, 25 ° C): A _max = 434, 412 nm; Φ _Γ · = 79%.

Cyclic voltammetry (CH ₂ C1 ₂ , | iBu ₄ N] [PF ₆ ], 0.1 M, 200 mV / s, vs. FcH / FcH): E _Vt = -2.01 V.

In a two necked flask with reflux condenser, 2,7-di-tert-butyl-9,10-dihydro-9-mesityl-10-trimethylsilyl-9-boraanthracene (0.525 g, 1.09 mmol) in Et ₂ O (15 mL). At room temperature, "BuLi solution (0.70 mL, 1.56 M in hexane, 1.1 mmol) was added with stirring and heated to reflux for 0.5 h. The temperature was lowered to 0 ° C and benzophenone (200 mg, 1, 10 mmol) was added. The reaction was heated to reflux for 2 h. After cooling to room temperature, the colorless suspension was treated with saturated, aqueous NaHCO ₃ solution (20 ml). Subsequently, the aqueous phase was separated and extracted with Et ₂ O (40 mL). The combined organic phases were washed with distilled H ₂ 0 (50 mL) and saturated aqueous NaCl solution (40 mL), dried over MgS <3 ₄ and filtered. From the filtrate, all volatiles were removed under reduced pressure. The resulting solid (about 640 mg) was purified by column chromatography (25 cm silica gel, eluent cyclohexane / ethyl acetate 50: 3, R _f = 0.45). By recrystallization from n-hexane (about 1 mL), the product was obtained in 53% yield (362 mg, 323 μηαοΐ). X-ray diffraction crystals were obtained by recrystallization from methanol. After removal of the solvent, the product was taken up in methanol (10 mL), suspended in an ultrasonic bath, isolated by filtration, washed with methanol (5 mL) and dried in vacuo. Yield: 0.336 g (0.587 mmol, 54%) of colorless powder.

Ή NMR (500.2 MHz, CDCl 3): δ 7.54 (d, ⁴ J (H, H) = 2.2 Hz, 2H, H-1, 8), 7.25-7.19 (m, 8H, Ph-CH -ι, ι »), 7.14 (m, 2H, Ph-CH-p), 7.1 1 (d, V (H, H) = 8.3 Hz, 2H, H-4.5), 7.00 (dd, ³ J (H, H) = 8.3 Hz, ⁴ J (H, H) = 2.2 Hz, 2H, H-3.6), 6.95 (s, 2H, Mes-CH-m), 2.41 ( s, 3H; Mes-CH ₃ - />), 2.17 (s, 6H, Mes-CH ₃ -o), 1 .16 (s, 18H, iBu-CH ₃ ).

^I C {1 H} NMR (125.8 MHz, CDCl 2): S 148.6 (C-2,7), 144.2, 143.4, 142.6, 140.3 (br., Mes-C-i), 138.6 (br., C -8a, 9a), 138.5, 137.7, 136.4, 132.6 (C-1, 8), 129.8 (Ph-CH-o), 129.3 (C-4.5), 128.2 (Ph-Hw), 127.5 (C-) 3.6), 127.0 (Mes-CH-m), 126.4 (m, 2H; -CR P-p), 34.4 (iBu-C), 31.3 (iBu-CH _3), 22.7 (Mes-CH ₃ -O ), 21 .5 (Mes-CH ₃ -p). B NMR (160.5 MHz, C ₆ D ₆ ): d 69 (b _A ~ 1500 Hz). EA (%): Calculated for C43H45B [572.63]: C 90.19, H 7.92; found: C 90.09, H 7.94. HRMS; Calculated for C ₄ 3H ₄₅ B: 572.36162, found: 572.36100. 1) 6,10-di-tert-butyl-8-mesityl-8-hydro-8-borabenzo [gA] naphtho [l ₅ 2,3 _s 4-

rjtetraphen ^

In an exposure apparatus, 2,7-di-tert-butyl-9-mesityl-10-diphenylmethylene-9,10-dihydro-9-bora-a-anthracene (0.165 g, 0.288 mmol) was dissolved under argon in cyclohexane (700 mL). dissolved and mixed with propylene oxide (20 mL). For degassing, argon was introduced through a cannula for 15 minutes. The solution was exposed to a mercury-vapor lamp while iodine (0.190 g, 0.749 mmol) was added portionwise over about 1.5 hours. After 4 h, the reaction solution was filtered through A1 ₂ 0 (3 cm, neutral) and the solvent removed under reduced pressure. The residue was taken up in methanol (20 mL), suspended in an ultrasonic bath, isolated by filtration, washed with methanol (5 mL) and dried in vacuo. Yield: 0.103 g (0.181 mmol, 63%) of yellow solid.

Ή NMR (500.2 MHz, CDCl ₃ ): 0.116 (d, ⁴ J (H, H) = 2, 1 Hz, 2H, H-5, 1 1 or 7.9), 8.92 (m, 4H; H-1, 4, 12, 15), 8.34 (d, J (H, H) = 2, 1 Hz, 2H, H-5.1, 1 or 7.9), 7.78 (vt, 2H, H-2 , 14 or 3, 13), 7.68 (vt, 2H, H-2.14 or 3.13), 6.98 (s, 2H, Mes-CH-m), 2.46 (s, 3H, Mes-CH ₃ -p ), 2.03 (s, 6H, Mes-CH ₃ -o), 1 .50 (s, 18H, iBu-CH ₃ ). C { ^v E NMR (125.8 MHz, CDCl ₃ ): δ 149.1 (C-6,10), 140.4 (br., Mes-Cz), 138.9 (Mes-C-o), 138.1 (C-5, 1 1 or 7.9), 136.4 (Mes-C-?), 135.4 (br., C-7a, 8a), 131.8, 130.7, 130.1 (C-1, 15 or 4,12), 130.1 (C -8b, 8d), 129.6, 129.0, 126.9 (C-2,14 or 3, 13), 126.9 (Mes-CH-m), 125.7 (C-2,14 or 3,13), 125.1, 125.0 (C -5.1 1 or 7.9), 123.3 (C-1, 15 or 4.12), 35.1 (iBu-C), 31.5 (r Bu -CH ₃ ), 23.6 (Mes-C-), 21.5 (Mes C- /?).

"B NMR (160.5 MHz, CDCl3): δ 65 { _h ~ 1500 Hz). EA (%): Calculated for C ₄₃ H ₄ , B [568.60]: C 90.83, H 7.27; found: C 90.13, H 7.32. HRMS: Calculated for C43H41B: 568.33032, found: 568.32910. ÜV / Vis (cyclo exane): _{m &} * (ε) = 429 (22,000), 407 nm (14,000). Fluorescence (cyclohexane, x _E = 400 nm): 465, 439 nm: Φγ = 70%.

Cyciovoltammetrie (CH ₂ CI ₂ ( "Bu ₄ N | [PF _6] 0.1 vi, 200 mV / s, vs. FcH / FcH): E _Vl = 1, 00, ^™ 2.01 V.

Further synthesis examples

In the following, further synthesis examples for the preparation of individual arylborane compounds of the formulas 1 to 5 are shown schematically. a) Synthesis scheme of an oxygen- or sulfur-containing arylborane compound of formula 1

 Synthetic Scheme of an Arylborane Compound of Formula 5, Scheme 2 a]

c) Synthetic Scheme of an Arylborane Compound of the Formula 5 [Scheme 2 b]

The features of the invention disclosed in the foregoing description, the claims and the drawings may be essential both individually and in any combination for the realization of the invention in its various embodiments.

Claims

Expectations

Arylborane compound represented by one of the following formulas 1 to 5: [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Funnel 5]

where X = B, CH, CR ₅ , N, O without R ₂ or S without R ₂ ,

Ri, R ₂ , R ₃ , R4 and R ₅ are the same or different from one another and are each independently selected from hydrogen, electron-accepting substituent, preferably fluorine or CN, electron-donating substituent, preferably Ci-C ₁₀ -alkyl, Ci-Cio-alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C ₆ -C ₂ o-aryl, preferably phenyl, and unsubstituted or substituted C ₄ -cis-heteroaryl, and/or

Ri to R are connected to the arylborane skeleton directly or via a linker, preferably bridging atoms or groups, more preferably phenyl, and/or at least two of Rj, R ₂ , R ₃ , R and R5, preferably adjacent, directly or connected to one another via a bridge, and/or at least one of Rj, R ₂ , R , R4 and R ₅ is integrated into a polymer main chain or on a side chain of a polymer is bound, the polyiner main itself and also a linker optionally used for interaction being conjugated or not conjugated.

Arylborane compound according to claim 1, wherein when X = B or N, R] and R ₂ are alkyl-substituted phenyl groups, preferably mesityl or 2,4,6-triisopropylphenyl.

Arylborane compound according to one of the preceding claims, wherein R ₄ is a C _{ - C 10 -alkyl group or an electron donor bound directly or via a linker, preferably substituted amine, preferably tert-butyl, methyl and / or diphenylamine.

Arylborane compound according to one of the preceding claims, wherein the compound is reversibly oxidizable and reversibly reducible.

A process for producing the arylborane compound according to any one of claims 1 to 4, comprising the steps: a) providing a compound of formula 6

[Formula 6]

where R ₃ and R4 are the same or different from one another and are each independently selected from hydrogen, electron-accepting substituent, preferably fluorine or CN, electron-donating substituent, preferably Cj-Cio-alkyl, Ci-Cio-alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C ₆ -C2o-aryl, preferably phenyl, and unsubstituted or substituted C ₄ -Ci 8-heteroaryl, b) Converting the compound of formula 6 to a compound of formula 7 by lithiation, subsequent silylation and renewed lithiation

[Funnel 7]

c) reacting the compound of formula 7 with at least one compound of formula 8, 9 and/or 10

[Formula 8]

[Formula 9]

[Formula 10]

where Y is either omitted, a carbonyl group, CR2R ₅ , R2, S, O or SiMe ₂ ,

R ₂ and R5 are the same or different from one another and are each independently selected from hydrogen, electron-accepting substituent, preferably fluorine or CN, electron-donating substituent, preferably Ci-Cio-alkyl, Cj-Cio-alkoxy and unsubstituted or substituted amine, unsubstituted or substituted Cö- C^-aryl, preferably phenyl, and unsubstituted and substituted C^C^-heteroaryl,

R(, is selected from hydrogen, unsubstituted or substituted C>-Cjo-alkyl, unsubstituted or substituted C ₂ -Cjo-alkenyl, unsubstituted or substituted C ₂ -Cjo-alkynyl, unsubstituted or substituted C ₆ -C?o-aryi, preferably substituted phenyl, and unsubstituted or substituted C4-Ci s-heteroaryl, d) reacting the compound obtained in step c), preferably carrying out a Schöll reaction or, more preferably, a photocyclic reaction, and e) borylating the compound obtained in step d) compound obtained, preferably by transmetalation with boron tribromide.

6. A process for producing an aryiboran compound of the formula 5 comprising the steps: a) providing a compound of the formula 1 1

[Formula 1 1 ]

where R ₄ are the same or different from one another and are each independently selected from hydrogen, electron-accepting substituent, preferably fluorine or CN. electron-donating substituent, preferably C _\ - C io-alkyl, Ci-Cio-alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C ₆ -C ₂ o-ary], preferably phenyl, and unsubstituted and substituted C -Ci 8-heteroaryl, b) converting the compound of formula 1 1 to a compound of formula 12 by lithiation and subsequent silylation

[Formula 12]

c) lithiating the compound of formula 12 and reacting it with two compounds of formula 8

[Formula 8]

where Y is either omitted, a carbonyl group, CR2R5, NR ₂ , S, O or SiMe ₂ , and

R-2, R3 and R ₅ are the same or different from one another and are each independently selected from hydrogen, electron-accepting substituent, preferably fluorine or CN, electron-donating substituent, preferably Ci-Cjo-alky], Ci-Cio-alkoxy and unsubstituted or substituted amine , unsubstituted or substituted C6-C ₂ -aryl, preferably phenyl, and unsubstituted or substituted C ₄ -Ci 8-heteroaryl, d) reacting the compound obtained in step c), preferably a Schöll reaction or, even more preferably, a photocyclic one Reaction is carried out, and b) borylating the compound obtained in step a), preferably by transmetalation with boron tribromide, c) converting the compound obtained in step b) to a compound of formula 13 by lithiation, subsequent silylation and renewed lithiation

[Formula 13]

where Ri is selected from hydrogen, electron-accepting substituent, preferably fluorine or CN, electron-donating substituent, preferably CpCio-Alkyh C] _. -Cio-alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C _f ,-C2o~aryl, preferably phenyl, and unsubstituted or substituted C4-C 1 8-heteroaryl, d) reacting the compound of the formula 13 with at least one compound of the formula 8, 9 and/or 10

[Formula 8]

[Formula 9]

e) borylation of the compound obtained in step d), preferably by transmetalation with boron tribromide.

7. A process for producing the arylborane compound according to claim 5 or 6, wherein the reaction in step c) is a Petersen oil refinement,

8. Process for producing the arylborane compound according to one of claims 5, 6 or 7, wherein the photocyclic reaction in step d) is carried out using iodine and propylene oxide with UV light.

9. A process for producing the arylborane compound according to any one of claims 5-8, wherein after the borylation in step e), an arylation or alkylation is carried out.

10. A process for producing the arylborane compound according to any one of claims 5-9, wherein the compound of formula 8 is prepared from the compound of formula 6, preferably by oxidation.

1 1. Process for producing the arylborane compound according to one of claims 1 to 4, comprising the steps: a) providing a compound of formula 6

[Formula 6]

where R ₃ and R ₄ are the same or different from each other and are each independently selected from hydrogen, electron-accepting substituent. preferably fluorine or CN, electron-donating substituent, preferably Ci-Cio-alkyl, Cj-Cio-alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C _< s-C2o-aryl, preferably phenyl, and unsubstituted or substituted C ₄ -C] g -heteroaryl, [Formula 10]

where Y is either omitted, is a carbonyl group CR ₂ R ₅ , NR ₂ , S, O or SiMe ₂ ,

R2 and R ₅ are the same or different from one another and are each independently selected from hydrogen, electron-accepting substituent, preferably fluorine or CN, electron-donating substituent, preferably Ci-Cio-alkyl Ci-C _fo -alkoxy and unsubstituted or substituted amine, unsubstituted or substituted C ₆ ~ C ₂ o-aryl, preferably phenyl, and unsubstituted or substituted C ₄ -C _{] 8} - heteroaryl,

R& is selected from hydrogen, unsubstituted or substituted Ci-Cio-alkyl, unsubstituted or substituted C ₂ -Ci ₀ -alkenyl, unsubstituted or substituted C ₂ -Ci ₀ -alkynyl and unsubstituted or substituted C6-C ₂ o-aryl, preferably substituted phenyl, and unsubstituted or substituted C ₄ -C ₁₈ heteroaryl, and e) reacting the compound obtained in step d), preferably a Schöll reaction or, more preferably, a photocyclic reaction being carried out.

Process for producing the arylborane compound according to claim 1 1, wherein after the borylation in step b), an arylation or alkylation is carried out directly,

Process for producing the arylborane compound according to claims 1 1 and 12, wherein steps b) and c) take place in reverse order, so that the compound obtained in step a) is first reacted by lithiation, then silylation and renewed lithiation and the compound of the formula 13 is obtained in a subsequent step by borylation, preferably by transmetalation with boron tribromide.

14. Use of the arylborane compound according to one of claims 1-4 in semiconducting organic materials, preferably organic light-emitting diodes (OLED), photosensitive materials, preferably organic solar cells or electronic components.

15. Use of the arylborane compound according to claim 13, wherein the compound is used in electroluminescent materials (ELM), preferably as a dopant and/or host substance.