WO2019229134A1 - Multi-functionalized [cd,lm]-annellated perylenes and their homologs - Google Patents

Abstract

The invention relates to multi-functionalized [CD,LM]-annellated perylenes and 2,9-diazaperylenes and their lower and higher homologs, the efficient preparation thereof via triflates and other intermediates of formula (I) wherein X = -OSO2R, and to their use in the field of molecular electronics.

Description

 Patent application

Multifunctionalized [cd, lm] -annulated perylenes and their homologues

description

 Heteroaromatics were early used as dyes and pigments, for example in the form of the synthetic aniline purple (PERKIN, 1856) and indigo (BAYER, 1878). Current research investigates organic dyes for a much broader field of application. In addition to fluorescence applications in lasers and in medicine, heteroaromatic dyes are used because of their electronic properties in photovoltaics and organic electronics.

 For photophysical applications, such as in organic photovoltaics, two general approaches to increase the solubility of PDIs have been developed. The first approach relies on the attachment of sterically demanding residues on the imide nitrogen atom. The second approach requires substitution on the perylene backbone. Both functionalizations serve to reduce the tt-tt interactions between the molecules and increase their solubility.

 A synthesis of 2,9-diazadibenzoperylene (DDP) was achieved by STANG et al. 1995 by hydrogenation of / V, / V'-dimethyl-perylenediimide to the corresponding tetrahydro-2,9-diazadibenzoperylene (THDAP) followed by aromatization and dealkylation under harsh reaction conditions.

 A major disadvantage of this method is the low yields of DDP, which was obtained due to its low solubility by means of SoxHLETT extraction with pyridine.

 A functionalization of DDPs on the aromatic framework to influence the optical and electronic properties has not previously been reported. It was found that the aromatization reaction leads to a decomposition of the THDAP and only / V-Benzylsubstituenten could be selectively removed.

Two other functionalized DDPs are described in patents. They are obtained by reacting PTCDI with PCI3 and chlorine gas or by reducing the carbonyl functions. The optical and electronic properties of this Compounds are not thoroughly studied and their further chemical functionalization is not described. In this work, based on the first work of SACHDEV, the further functionalization of DDP silyl ether N (DDP 1) and the properties of new DDPs are investigated. a / pfta-functionalized 2,9-diazadibenzoperylenes and dibenzoperylenes tetrasilyl ether-2,9-diazadibenzoperylene

 Perylene diimides (PDIs) have established themselves as phthalocyanines as one of the most important classes of dyes and as a polyaromatic model system for photophysical and electrochemical investigations in the last three decades. The substitution capabilities of the aromatic periphery allow control of versatile electronic, optical, and structural properties for organic electronic applications. In this work, 1, 3,8,10-tetrafunctionalized, also known as a / p / 7a-functionalized 2,9-diazadibenzoperylenes (DDPs) were investigated. The synthesis of 1, 3,8,10-tetrakis (trimethylsilyloxy) -2,9-diazadibenzoperylene DDP 1 was described for the first time in a patent by SACHDEV. (EP2390253A1) The synthesis was carried out in two ways: via the reduction of perylene-3,4,9,10-tetracarboxylic acid diimide (PTCDI) with n-BuLi in THF (lithium organyl route) or with sodium and sodium amide in liquid ammonia at - 78 ° C (alkali metal route). The alkali metal route is proposed for the synthesis of diazapyrene by reduction of naphthalene tetracarboxylic diimide (NTCDI). For DDP 1, a yield of 57% is reported via the lithium organyl route.

To find out what role the degree of reduction of the PTCDI plays, instead of a two-step reaction procedure, a one-pot synthesis was carried out with simultaneous use of sodium and MesSiCl. By way of example, this reaction also serves to advantageously avoid the use of the expensive reducing agent BuLi, and therefore also according to the invention. Surprisingly, the product was obtained in a yield of 51%. The highest yield achieved was 55%.

 > 150 mmol

 Optimized synthesis of DDP 1.

In addition to sodium, the intercalation compound CsK was investigated as a reducing agent. It was found that CsK yields similar high yields as sodium. The advantage of using CsK is the shorter reaction time at a lower reaction temperature and the use of THF as a low-boiling solvent (example experiment: 1.6 mmol starting material, 1.) 5 eq. CsK, 2h, 80 ° C, 2.) 6 eq. Me ₃ SiCl, 1 h, 80 ° C -> 2 h, rt in THF gives about 55% yield).

 In summary, the use of elemental sodium and, at the same time, as coordinating and high boiling solvents allows a convenient, simple and scalable synthesis. The largest batch size so far was 186 mmol from PTCDI. This synthesis optimization, by displaying DDP 1 in large quantities, allows for a variety of advanced synthetic modifications of the DDP framework, which will be described throughout this work.

Tetrasulfonyl-2,9-diazadibenzoperylenes - The key to a / pfta-functionalized 2,9-diazadibenzoperylenes

 While DDP silyl ethers are a storable form of reduced PTCDI and are available in sufficient quantity by the described methodology for laboratory scale studies and reactions, their functionalizability is limited. In addition, the electron-rich silyl ether functions in the a / p / 7a positions result in an oxidation sensitivity that makes DDP silyl ethers less attractive for potential applications.

 This chapter describes the synthesis of DDP-sulfonic acid esters, specifically the conversion to the triflyl- and tosyl-functionalized DDPs.

Two general methods for preparing triflates are known from the literature. Both methods were examined, adapted and optimized for the system of DDPs in this thesis. The higher sensitivity of 2-pyridinyl trifluoromethanesulfonate compared to phenyl triflates against hydrolysis and oxidation requires a significant modification of the literature procedures, especially during the work-up of the product.

Synthesis of DDP tetratriflate via the lithium salt route

1, 3,8,10-Tetrakis (trifluoromethylsulfonate) -2,9-diazadibenzoperylene, short DDP (OTf) 4 or tetratriflate DDP (DDP 8) was in a one-pot synthesis via the lithium salt route analogous to the method of KOBAYASHI et al. receive. For this purpose, first DDP 1 was deprotected with four equivalents of n-BuLi to Tetralithiumsalz DDP 7 and reacted without further workup by slowly adding Tf ₂ 0 to Tetratriflat DDP 8. Scheme 1 shows the optimized reaction conditions for the synthesis of DDP 8 via the lithium salt route. Further selected reaction conditions for the preparation of DDP 8 via the lithium salt route are summarized in Table 4.

Scheme 1: Optimized synthetic procedure for DDP 8 via the lithium salt route starting from DDP 1.

While the first step of lithiation occurs selectively at room temperature in diethyl ether and is completed after several hours by formation of an intense red solid, some aspects must be considered in the reaction with Tf ₂ O. Some problems could be eliminated by choosing a suitable solvent. For example, THF is often used as the solvent in aryne synthesis. However, it turned out that it is not suitable for the synthesis of DDP 8.

 For these reasons, especially diethyl ether was used as a solvent, which is suitable for both lithiation and triflylation.

To avoid the ether cleavage of diethyl ether, methyllithium (MeLi) was used as lithiating agent (Table 4, # 12). Slow addition of ThO should keep its concentration low in the course of the reaction and prevent reaction of the product with ThO. By means of a syringe pump, the best yields were obtained at a dropping rate of 2 ml per hour with repeated passage. After a successful course of the reaction, which can easily be monitored by ¹ H and ¹⁹ F NMR spectroscopy, the next challenge is the isolation of DDP 8. While aromatic triflates can often be worked up in water in air, such a procedure leads to DDP 8 often to complete decomposition of the product. Numerous experiments have shown that the product can be obtained in pure form in low yields by rapid work-up by column chromatography (drying the silica gel for several days at 160 ° C. and 10 ^-3 mbar within a few minutes). However, removal of the solvent on a rotary evaporator common to organic products inevitably results in the decomposition of the product, which is accompanied by a pungent odor and the formation of a dark insoluble solid. As a dried solid, however, the product is stable in air for several days. Overall, it is not advisable to carry out a purification by column chromatography, since the yields vary widely with this method. Instead, it has been found that under inert conditions, first a hot extraction with nonpolar solvents (hexane, pentane) leads to the removal of soluble by-products and then a hot extraction with moderately polar solvents (toluene, THF) gives the product in good purity and yield. The purity of the product is further improved by recrystallization from chloroform or DCM.

Table 4: Reactions of DDP 1 and DDP 7 via the lithium salt route to DDP 8.

# Reaction conditions result

 1. 4.2 eq n-BuLi, THF, 1h, 0 ° C

 Polymerization of the solvent

2. 4.5 e Tf ₂ 0, 0 ° C -> rt _

 1. 4.5 eq n-BuLi, THF, 1h, -78 ° C

2. 4.0 eq Tf ₂ 0, 2.5 h, -78 ° C - »rt

 DDP 8 included, not isolable

3. Aqueous worked up, extraction with

 DCM

3 DDP (OLi) _4, 4.0 eq Tf ₂ 0, -100 ° C □ 18 h, rt Polymerization of the solvent

1. 4.2 eq n-BuLi, Et ₂ 0, 15 min, 0 ° C

4 2. 4.5 eq Tf ₂ 0, 0 ° C -> 18 h, rt DDP 8 received in traces

3. CC ^*

 1. 4.2 eq n-BuLi, THF, 1 h, 0 ° C Rapid lithiation, none

Polymerization, product formation, 5 2. 4.5 eq Tf ₂ 0, Et ₂ 0, 1 h, 0 ° C - »4 h, rt

 Decomposition of the product

3. Aqueous worked up, CC ^* aqueous work-up and CC ^*

 Product formation, decomposition of g reaction conditions identical to # 5,

Upon aqueous work-up, both steps were carried out in Et ₂ O.

and CC ^*

1. 4.0 eq n-BuLi, Et ₂ 0, 4 h, 0 ° C

7 2. 4.4 eq Tf ₂ 0, rt, mixed with silica gel, 27% yield

eluted with DCM / pentane

 2 d, r.t.

 h, r.t.

 33% yield

 3. mixed with silica gel, dried, with

 DCM / pentane 1/2 eluted

1. 4.8 eq n-BuLi, Et ₂ 0, 30 min, -30 ° C ->

 2 d, r.t.

49% crude, slightly contaminated u 2. 4.8 eq Tf ₂ 0, 5 h, -20 ° C

3. mixed with silica gel, dried, CC ^*

1. 4.8 eq n-BuLi, Et ₂ 0, 18 h, rt decomposition on removal of

H 2. 5.0 eq Tf ₂ 0, 3 d, rt solvent at

3. Aqueous worked up, organic rotary evaporator, 2% yield _ solvent removed at 40 ° C, CC ^* after CC ^*

 1. 5.0 eq MeLi, 30 min, -28 ° C -> 2 d, r.t.

Very slow lithiation, 6% 12 2. 5.0 eq Tf ₂ 0, -50 ° C - »4 d, rt

Product after CC ^*

3. CC ^*

CC = column chromatographic purification, eluent DCM Base-catalyzed one-pot synthesis of DDP tetratriflate

 Without a preceding lithiation, DDP 8 was obtained from DDP 1 in the presence of Tf 2+. Table 5 summarizes selected reaction conditions.

Table 5: Selected base-catalyzed reactions of DDP (OSiMe3) 4 with ThO

DDP 8.

 # Reaction conditions result

4.0 eq pyridine, 4 eq Tf ₂ 0, DCM,

 1 formation of L / -T riflyl pyridinium triflate

 15.6 eq Tf2Ü, 18 h, r.t. -> 6 h, no sales at r.t. without base, decomposition at

85 ° C 85 ° C, no product formation

1.0 eq DMAP, 4 eq Tf ₂ 0, DCM,

 3 Image of a product mixture containing DDP 8

 2 h, -78 ° C - »24 h, r.t.

 Formation of TMSOTf containing product mixture

0.9 eq DMAP, 10 eq Tf ₂ 0, DCM,

4 DDP 8, CC ^* over basic Al ₂ O ₃ leads to

20 h, CC ^*

 decomposition

 Upon addition of fluoride, formation of a blue

8.0 eq / 7-Bu ₄ NF @ Si02, 4.0 eq

Suspension, with Tf ₂ 0 addition formation of a Tf ₂ 0, DCM, 20 h, rt

 violet suspension, no product formation

8.0 eq DMAP, 9.6 eq Tf ₂ 0, DCM, formation of a black suspension, too much 20 h, rt DMAP and Tf ₂ 0 used

0.4 eq DMAP, 4.2 eq Tf ₂ 0, DCM,

 8 72 h, r.t., aqueous workup 3% yield isolated

and CC ^*

 0.4 eq DBU, 4.2 eq Tf2 <D, 40 h, r.t., product formed after 40 h; Decomposition on aqueous workup

CC = column chromatographic purification, eluent DCM However, the use of stronger bases such as DMAP and DBU led to the formation of DDP 8 in comparatively high yields (up to 64%), with DMAP typically yielding higher yields than DBU. Although catalytic amounts of a base (0.4 equivalent) are sufficient for complete conversion to the product, in an equimolar reaction the reaction time can be reduced from several days to about one day. The use of such bases is essential, since without them even at elevated temperatures of up to 85 ° C, no formation of DDP 8 takes place. Thus, this method is slower in the reaction than the reaction via the lithium salt route. However, the higher yields compensate for this disadvantage. Scheme 35 shows the reaction conditions of an optimized synthesis of DDP 8. It should be noted that the reaction solution in this method is intensely green and a rapid color change to orange is observed in targeted air contact, without any change in the NMR spectrum takes place.

Scheme 35: Representation of DDP 8 from DDP 1 in a one-pot synthesis in the presence of DMAP.

The described synthetic routes provide sufficient amounts of DDP 8 for further functionalizations. However, a direct synthesis from the DCD (ONa) ₄ generated from PTCDI in situ would be desirable, without a detour via DDP 1 and DDP 7. However, in the context of the synthesis optimizations it was found that a one-pot reaction gives the product only in low yields. Although the formation of a green-blue fluorescent solution is observed upon the addition of Tf ₂ O to reduced PTCDI and the product detected by ¹ H NMR spectroscopy, the higher reactivity of DDP 8 compared to DDP 1 results in the product formed Tf ₂ 0 are decomposed by not fully reacted sodium. Also, a reaction of DDP (ONa) ₄ with triflylated DDP to DDP ethers can contribute to lowering the yield. On the other hand, using isolated reduced PTCDI from which unreacted sodium has been removed yields DDP 8 in a yield of about 5%. The yield and selectivity of the reaction in DCM is higher than in diethyl ether. Although the yield is relatively low, in this case a simple work-up by filtration of the reaction solution and subsequent removal of the solvent justifies a future optimization of this synthesis route, so that the route via the DDP 1 is no longer necessary. High priority should be given to a one-pot synthesis with CsK as the reducing agent, since this may reduce the decomposition of Tf ₂ 0 by the reducing agent.

Attempts to prepare further sulfonic acid derivatives

Triflates are versatile and reactive starting compounds for further functionalization. Their disadvantage is a relatively high price of triflation reagents. Therefore, the introduction of, for example, tosylates starting from p-toluenesulfonyl chloride (TsCl) or p-toluenesulfonic anhydride is an interesting alternative to the use of Tf ₂ O.

It was found that TsCI is not sufficiently reactive for reaction with reduced PTCDI (with both lithium and sodium salts). Therefore, Ts ₂ 0 was reacted as a more reactive tosylating agent with DDP 7 at 80 ° C in toluene, so that the tetratosylate DDP 10 was detected by mass spectrometry from the green fluorescent reaction solution (see Scheme 58). As part of this work, no functionalizations of the DDP 10 were performed. However, the potential access to this compound opens up, so that further work can be carried out on the use of DDP 10 in coupling reactions and for nucleophilic substitution in alpha position. Further attempts should be devoted to the use of reactive active esters such as [Ts-DMAP] OTs or [Ts-DMAP] CI.

Scheme 58: Representation of DDP 10 from DDP 7. Tetraarylsubstituted 2.9-diazadibenzoperylene

 The synthesis of polycyclic heteroaromatic hydrocarbons (PAHs) and molecular nanographers has received increasing attention in the literature over the past decade. PDIs are well-established building blocks for the synthesis of larger PAHs. It is shown below that also DDPs starting from DDP 8 are suitable as building blocks for the construction of larger heteroaromatic structures whose optical and electronic properties can be influenced by the introduction of various aryl substituents.

 As a C-C coupling method of first choice, the SUZUKI-MIYAURA cross-coupling reaction is suitable for the reaction of DDP 8 (Scheme 2).

 Aryl derivatives are used as versatile starting materials in coupling reactions, but have been investigated much less frequently compared to halides. Their reactivity for the Suzuki-MiYAURA reaction follows roughly the series Ar-I »Ar-Br> Ar-OTf» Ar-Cl »Ar-OTs. Therefore, synthetic protocols based on the reaction of aryl bromides were used in this work. Another peculiarity of DDP triflates is the fourfold cross-coupling of a molecule that has rarely been described before.

 Pd catalyst

' ^{x +} _R' ^{b (0h} »= base

 X = Ci, Br, i, R = aryl, alkyl

 OTf, OTs

Scheme 2: Simplified presentation of the SUZUKI-MiYAURA reaction used in this work.

The synthetic conditions of the aryl DDPs were initially optimized most simply aryl DDP by introduction of phenyl substituents (DDP 12) and led in this work to the electron-rich and electron-poor aryl DDPs shown in Scheme 3.

 Scheme 3: Overview of synthesized aryl DDPs

Synthesis and properties of tetraaryl-2,9-diazadibenzoperylenes

Synthesis of the first tetraaryl DDP was achieved by reacting DDP 8 with phenylboronic acid in the presence of Pd (PPh ₃ ) ₄ and Na ₂ C0 ₃ in toluene / water (1: 1). It provided a product mixture from which 1, 3,8,10-tetraphenyl-2,9-diazadibenzoperylene DDP 12 was detected by mass spectrometry (Table 1, # 1). However, the crude product contained at least two different DDP compounds which could not be separated due to almost identical R _f values. Scheme 4 shows the work-optimized synthesis of DDP 12.

 Scheme 4: Synthesis of tetraphenyl DDP DDP 12.

 In order to avoid the formation of by-products, various catalysts, bases and solvents were investigated (summary in Table 1). However, it has been shown that in the reactions carried out, the formation of by-products can not be avoided so far. Reliable predictions of the reaction outcome of an unknown system are difficult because the choice of base in the Suzuki-MiYAURA reaction is generally empirical. It became clear that the reactive tert-butanolates frequently used for the coupling of aromatic hydrocarbons are unsuitable for the reaction with DDP 8 since they lead to the decomposition of the starting material DDP 8 and formation of a violet solid (Table 1, # 3 and # 4 ).

 The milder (hydrogen) carbonate and phosphate bases, however, lead to the formation of DDP 12 in good yields. The influence of the catalyst under these conditions seems to play a minor role, since both Pd (0) - with monodentate and Pd (II) catalysts with bidentate phosphine ligands and allyl and NHC ligands for the product provided. The reaction time can be shortened and the reaction temperature lowered when the NHC-stabilized palladium complex CX 31 (see Fig. 1) is used. The reaction with NiChidppe) as a catalyst led to the formation of product in traces. It is known from the literature that reactions in the presence of water give better results in reactions of heteroaromatics. One possible reason for this is that / V heteroaromatics preferentially form hydrogen bonds instead of deactivating them by coordination to the catalyst. It was also found that the highest yields in a solvent mixture of toluene, ethanol and water are obtained after two to three days at 95 ° C. To increase the yield of the change to an anhydrous reaction medium may be useful, since a possible hydrolysis of Tetratriflats DDP 8 could be avoided.

A simple workup was developed in which the reaction solution was eluted through silica gel with DCM and the resulting product was washed with hot toluene and recrystallized. Filtration over silica gel allows the separation of decomposed, insoluble DDP and inorganic base while passing through Recrystallization arylboronic acids and the palladium catalyst are removed. Although some of the product remains in the toluene filtrate, all impurities can be removed. This simple work-up method has been successfully applied to the synthesis of DDP 12 to DDP 18. A column chromatographic purification is also possible and was carried out predominantly for DDP 19 - DDP 23.

Table 1: Investigated reaction conditions of the Suzuki-MiYAURA reaction for the preparation of DDP 12.

 # Catalyst Base solvent conditions Yield

Toluene / EtOH / H ₂ 0

8 Pd (PPh ₃ ) ₄ NaHCOs 24 h, 90 ° C 39%

(5/2/2)

 Toluene / EtOH / FHO

10 Pd (PPh ₃ ) ₄ NaHCO ₃ 42 h, 95 ° C 40%

 (5/2/2)

Thermal stability of DDP 12

DDP 12 can be sublimated in a fine vacuum (> 350 ° C, 10 ³ mbar). Thermogravimetric analysis (TGA) shows a one-step thermal decomposition of DDP 12 from 519 ° C with a mass loss of 58%, which can be interpreted as a cleavage of the four phenyl substituents (52% mass fraction).

The simultaneous differential thermal analysis shows an endothermic process at about 420 ° C, which is determined as the melting point. Thus, between melting point and decomposition point about 100 ° C, so that DDP 12 could be evaporated without decomposition. The thermal stability of the lower homologs, ie the corresponding tetra-substituted pyrene compounds and / or diazapyrene compounds, is generally even higher, melting and sublimation points lower due to the lower molecular weight than the DDP derivatives. These properties allow a particularly good processability of the lower homologs in the technical organic

Molecular Beam Epitaxy (OMBE) from the gas phase under reduced pressure.

 Although the production of tetra-substituted pyrene, or diazapyrene, is already known to a limited extent in the prior art, it undergoes an extremely advantageous expansion / improvement by the process disclosed here. Thus, a Japanese working group around Y. Miyake et al. (Chem. Commun .: DOI:

10.1039 / c8cc01937a) the synthesis of quadruply aryl-su bstituierten diazapyrenes via pivaloate intermediate, but the process described there is much more complicated, expensive and more expensive than the inventive method, since for example no substoichiometric, but significantly lower amounts of a catalyst and a much lower reagent excess needed. The C-C bond is more selective at much lower temperatures. The scope of application of the tetra-O-sulfonates according to the invention is significantly greater, because it was also possible for the first time to introduce 1-alkynyl groups via a SONOGASHIRA protocol on the diazapyrene skeletons, not just aryl groups. Also, those of Müllen et al. (Chem. Rev. 201 1, 1 11, 7260-7314) described method for the preparation of four-substituted pyrenes are fundamentally different (via tetrabromo-perylene) of the disclosed method according to the invention here and with greater disadvantages this opposite afflicted.

Based on the synthetic optimization of DDP 12, three additional aryl-substituted DDPs were prepared (Scheme 5) and characterized by crystallographic characterization. For the synthesis of DDP 13 and DDP 18 the system of Pd (PPh ₃ ) ₄ / NaHCO ₃ (A) and for DDP 14 the system Pd (dppf) Cl ₂ / K ₃ PO ₄ (B) was used. ("A" and "B" respectively with reference to Scheme 64) A Pd (PPh ₃₎ 4, ArB (OH) _2,

NaHCO ₃

Toluene / EtOH / H ₂ 0, 90 ° C

 DDP 8

B Pd (dppf) Cl ₂ , ArB (OH) ₂ ,

K ₃ P0 ₄ in THF,

18 h, rt 4 h, 60 ° C

 DDP 13 DDP 18 DDP 14

 69% 35%

 Scheme 5: Synthesis of DDP 13, DDP 14 and DDP 18.

Synthesis of functional tetraaryl-2,9-diazadibenzoperylenes

Four further functional aryl-DDPs with thienyl (DDP 19), ferrocenyl (DDP 20), phenylnaphthalenimide (DDP 22) and perylenemonoimide substituents (DDP 23) were prepared. In contrast to the aryl DDPs already described, their synthesis is more complicated. By introducing electron-rich 2-thienyl groups, DDP 19 is a promising candidate for investigation as an organic (semi) conducting donor material with energetically high HOMO and LUMO. The remaining DDPs are suitable candidates for the electron-rich (DDP 20) and electron-deficient (DDP 22 and 23) character of the substituents to investigate energy and charge transfer processes between DDP core and substituents, as already explored for PDIs. In addition, DDP 23 is a promising synthetic compound, as it is converted into a potentially fully conjugated and planar heteroaromatic Cio ₄ framework by oxidative C [BOND] C coupling (SCHOLL reaction) and thus as a model system for molecular N, O-doped nanographers could be investigated.

Of course, these electronic properties are not only advantageous for experimental investigations to elucidate mechanisms of organic electronics, but also allow the advantageous use of these compounds for the preparation of corresponding electronic components based on organic compounds. Tetra (2-thienyl) -2,9-diazadibenzoperylen

DDP 19 was prepared under three different reaction conditions (Scheme 6). In the reactions, however, formed numerous by-products, which could be separated by column chromatography on the basis of similar R _f values and solubilities consuming. In the purification by column chromatography (mobile phase DCM) of the crude product mixture, DDP 19 was obtained as last fraction in 13% yield.

Scheme 6: Synthesis of DDP 19 from DDP 8. Three different reaction conditions resulted in the product: a) Pd (PPh) 4, KF, toluene / water, 8 h, 100 ° C; b) Pd (dppf) Cl ₂ , K 3 PO 4, THF, 5 h, 60 ° C and 3 h, 70 ° C; c) Pd (PPh) ₄ , NaHCOs, toluene / ethanol / water, 7d, 90 ° C, 13%.

Tetraferrocenyl-diazadibenzoperylen 2.9

 The ferrocenyl DDP 20 is accessible by reacting DDP 8 with ferrocenyl boronic acid in the presence of Pd (dppf) Cl2 (Scheme 7).

 Scheme 7: Synthesis of DDP 20.

It can be kept clean by filtration through filter paper and silica gel, but then decomposes in air. A work-up under inert conditions is necessary because DDP 20 is relatively electron-rich and therefore accessible for oxidation reactions. DDP 20 forms violet solutions in chlorinated solvents and is a black powder as a solid. The electrochemical properties of DDP 20 are discussed separately here because DDP 20 differs significantly from other aryl DDPs. In cyclovoltammetric measurements, at least one reversible oxidation potential is observed (FIG. 1B, part d). At fast scan rates of 100 mV / s and 200 mV / s, a second, 0.17 V higher, anodic peak potential can be observed, indicating a multi-step process. While the anodic peak potentials are relatively broad, the cathodic peak potential is narrower. Typically, two different electrochemical processes with different kinetics are responsible for this, in which the oxidation proceeds more slowly than the reduction and thus causes broadened anodic peak potentials. The determination of the absolute oxidation potential is difficult as the potentials of DDP 20 and the internal standard overlap (Figure 1 B, part d). Taking into account DPV measurements (see Appendix) and a two-pot calibration, there are two oxidation potentials of 0.05 V and 0.24 V relative to ferrocene / ferrocenium. Reduction potentials were not observed for DDP 20.

Phenylnaphthalene imide and perylene imide-substituted 2,9-diazadibenzoperylene

DDP 22 was obtained analogously to DDP 12 after four days of reaction time at 90 ° C. as a red solid with a yield of 21% after recrystallization from toluene (Scheme 8). The electronic and electrochemical properties are discussed in detail at the end of the chapter.

Scheme 8: Synthesis of DDP 22. The synthesis used for aryl-DDP is also suitable for the construction of large heteroaromatic systems, as shown by the example of DDP 23 (Scheme 9). DDP 23 was obtained as a dark red solid with a yield of 71%. Due to the low solubility in organic solvents, a column-chromatographic purification was possible only by using polar solvents such as acetone or methanol as eluent. In order to achieve a sufficiently high solubility for NMR spectroscopy, drJ FA is suitable as a solvent.

 Scheme 9: Synthesis of DDP 23.

 The red color of the dissolved DDP 23 indicates a low electronic interaction of the DDP core and the PMI substituents. Complete conjugation could be achieved by C-C bond formation and ring closure in the 4, 7, 11, and 14 positions (formerly ortho position on the PDI) (error! Reference could not be found).

Optical properties of tetraaryl-2,9-diazadibenzoperylenes

The optical and electrochemical properties of diazadibenzoperylene are influenced by aryl substituents in the a / p / ia position. Figure 2B and Table 2 summarize the optical properties of the aryl DDPs. DDP 12, DDP 13 and DDP 18 have in DCM absorption maxima of 490 nm and 497 nm, emission maxima between 517 nm and 528 nm and thus a STOKES shift of about 30 nm. For these compounds, a vibronic progression is observed at a distance of 30 nm.

Table 2: Optical properties of the aryl DDPs in DCM. The fluorescence spectra were measured with an excitation wavelength of A _e * = 350 nm.

 517

 DDP 12 Ph 490 86700 27

(552) ^a

 DDP 13 4-®uCeH 4 497 103400 528 31

 3,5-DDP 18 490 100500 521 31

CeH ₃ (GF ₃ ) ₂

 543 574

DDP 19 2-thienyl 120,700 31 (93) ^a

(519) = (612) ^a

 DDP 20 ferrocenyl 576 n. B. n. b. n. b.

DDP 22 Dipp-NMI 502 121800 538 36

 642

 DDP 23 PMI-Dipp 543 n. B. 99

(609) ^a

 Dipp-

507 n. B. 546 39

PMI

 a 1% TFA added.

The introduction of 3,5-bis (trifluoromethyl) phenyl substituents leads to no change in the absorption maximum compared to phenyl groups and only a small change in the emission maximum (4 nm). The substitution with terf-butylphenyl groups leads to a red shift of the absorption and emission maxima by about 10 nm. Thus, the absorption and emission of DDP 12 is about 30 nm more energetic than the unsubstituted PDIs. The addition of acids such as TFA has little effect on the location of the absorption bands. However, the emission is shifted bathochromium by 33 nm as a result of the protonation. The observed higher STOKES shift results from a greater change in the dipole moment in the excited molecule. Electron-richer thienyl groups result in a stronger bathochromic effect such that DDP 19 has a red-shift of absorption and emission maxima around 50 nm relative to DDP 12. The addition of TFA leads to a red-shift in emission by 33 nm and 40 nm, respectively, for DDP 12 and DDP 19. Unlike for DDP 12, the absorption for DDP 19 is shifted hypsochromically by 25 nm as a result of protonation.

DDP 22 has an extended aromatic system compared to phenyl-DDP. The absorption or emission maxima are 502 nm and 538 nm, respectively, and are red-shifted relative to DDP 12 by 12 nm and 19 nm, respectively. The absorption spectrum of DDP 22 is not superimposed on the absorption of the naphthalene imide substituents, since these absorb in the range of 250-300 nm.

 DDP 23 has an aromatic system with four strongly absorbing perylene monoimide (PMI) substituents. The absorption spectrum must therefore be understood as a superposition of five chromophores. The PMI substituents contribute significantly to the optical properties of DDP 23 because they are in a 4: 1 ratio to the DDP backbone and have similar extinction coefficients in the range of 500 nm to 550 nm. However, Figure 2B shows that absorption and fluorescence spectra of DDP 23 are not dominated by the PMI substituents but result in a sum of both aromatic systems. The absorption maximum of DDP 23 (543 nm) is red-shifted by approximately 40 nm relative to DDP 22 and the free PMI substituent and the emission maximum by approximately 100 nm. DDP 23 thus has a relatively large STOKES shift of 100 nm.

Electrochemical properties of T etraary I-2, 9-d i azad i benzoperylenes

The electrochemical properties of the aryl DDPs were investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). DPV measurements provide the same potential values as CV measurements. However, due to a higher sensitivity to current flow changes relative to the base current flow, they allow a more accurate identification of the redox potentials. This facilitates characterization, especially for compounds with low solubility. The redox potentials of the aryl DDPs are shown in FIG. 2

summarized and their Voltammogramme (CV and DPV) dargestelit in Fig. 3 and Fig. 4. The potentials are given relative to the redox potential of the internal standard ferrocene (vs. Fc / Fc ⁺ ), which was added to the sample in the last measurement for calibration. The redox behavior of the Aryi DDPs is usually characterized by two reversible reduction potentials and two (quasi-reversible) oxidation potentials. For DDP 12 and DDP 13, two reversible reduction processes at -2.3 V and -2.0 V are observed. The reduction potentials of the electron-poorer DDP 18 are -1 .9 V and -1 .7 V. They are lower by 0.25 V for the first reduction potential and 0.4 V for the second reduction potential than in DDP 12: electron-poor 3,5-C6H ₃ (CF ₃ ) ₂ substituents lead to DDP 18 being reduced at more positive voltages than DDP 12 and DDP 13. For DDP 12, DDP 13 and DDP 18, two partially reversible oxidation potentials are still observed. DDP 12 has oxidation potentials at 0.5 V and 1 .0 V. For DDP 12, no return wave is observed under the measurement conditions, so that a non-reversible process takes place here. The more electron-rich DDP 13 has 0.4 V and 0.6 V lower oxidation potentials than the electron-poor DDP 18 with 0.8 V and 1.1 V. Thus, the oxidation potential decreases with increasingly electron-rich aryl substituents on the DDP and increases with electron-deficient aryl substituents. This is consistent with electron-withdrawing substituents lowering the HOMO's energy. The reduction potentials follow this trend, albeit less pronounced. For the aryl DDPs they are in a narrow potential window at -1.8 V and -2.0 V for the first reduction and -2.0 V and -2.3 V for the second reduction, respectively. Electron-deficient substituents tend to lead to more positive reduction potentials and high-energy, potentially negative reduction potentials. Electron-withdrawing substituents are expected to result in lower energy of the LUMO. If one additionally considers the low oxidation potentials of the more electron-rich DDP 19 (0.4 V and 0.7 V), it becomes apparent that the alpha-aryl substituents have a strong influence on the position of the oxidation potentials and thus the HOMO energies of aryl DDPs. The more electron-rich the aryl substituent, the higher the HOMO of an aryl DDP.

The potential difference D (E _0C i - E _recji ) is identical for DDP 12 and DDP 18 at 2.47 V and decreases for the more electron-rich DDP 13 (2.33 V) and DDP 19 (2.19 V). This Trend is already reflected in the same way in the HOMO-LUMO energy differences, which are derived from the optical band gap from the absorption spectra. Thus, the frequently used approximation of A (E _L UMO - EHOMO) and A (E _0Xi - E _r0di ) is very well suited to these selected molecules. The small deviation of the absolute energy values is explained by the fact that absorption spectroscopy provides the energy difference of the electron transfer of a neutral compound. Cyclic voltammetry, however, provides, among other things, reduction potentials that are not identical to the energy of the LUMO of a molecule, because the reduced molecules contain one more electron and thus have different reorganization energies. The reduction potentials of the aryl DDPs are about 1 V lower compared to N, N'-dialkylperylene diimides, whose reductive potentials are -1..1 V and -1.3 V, respectively. The oxidation potential of PDIs at 1 .1 V is also 0.2 V to 0.6 V above those of the aryl DDPs. Thus, the aryl DDPs are harder to reduce and easier to oxidize.

For DDP 22, two reversible reduction processes at -2.2 V and -1.9 V are observed by CV. From the comparatively high current flows of the reduction potentials it can be deduced that the NMI acceptor substituents have a significant influence on the reduction (FIG. 4). The reduction potential of the free naphthalene monoimide (NMI) is given as -1.80 V in DCM and is thus very close to the reduction potentials of DDP 22. It can therefore be assumed that the reduction takes place at least partially locally on the NMI substituent and that the LU MO has the largest orbital coefficients on the NMI substituent. However, a superposition of different reduction potentials can not be excluded. The reversible oxidation potentials are comparatively high at 0.7 V and 1 .2 V and result from a low lying HOMO. They thus follow the trend described above for electron-deficient substituents. The potential difference D (E _0C i - E _re di) = 2.62V is the highest of all investigated aryl DDPs.

The redox behavior of DDP 23 is also influenced by its substituents. Three reduction potentials at -2.0 V, -1.8 V and -1 .4 V are observed. By CV two non-reversible oxidation potentials at 0.9 V and 1.1 V can be determined. DPV measurements reveal a third oxidation peak at 1 .5 V. For the free PMt substituent, redox potentials at about -1 .4 V and -2.1 V and an oxidation potential at 1 .0 V are known. Thus, at least the first and the third reduction potential as well as one of the oxidation potentials can be assigned to the PMI substituent. The absolute energies of the HOMO and the LUMO were determined by electrochemical measurements in relation to the energy level of the reference (Fc / Fc ⁺ at 4.8 eV below the vacuum level). For the energies thus obtained, it must be remembered that the electrochemical measurements always examine a reduced or oxidized species that have a different electronic ensemble than neutral compounds. The different electron-electron interactions, COULUMB interactions and reorganization processes are neglected. The spectroscopic measurements allow the determination of the optical band gap E _g.opt , which corresponds to the HOMO-LUMO distance. By combining both methods, the HOMO and LUMO energies were determined experimentally and compared with values determined by DFT calculations (FIG. 2)

) -

For electron-deficient, orffto-functionalized PDIs, HOMO energies between -6.7 eV (tetracyano-PDI) and 5.6 eV (tetraoctylamino-DPI) are reported (FIG. 5). The LUMO energies are between -4.4 eV and -3.2 eV. For / V, / V-dioctyl-1, 6,7,12-tetrachloroperylenediimide (CL-PDI), the classic of bay-substituted PDIs, the energies are given as -6.4 eV (HOMO) and -4.1 eV (LUMO) , If substituents in the ortho position are introduced starting from this tetrachloro-PDI, so that an eight-fold substitution of the PDI core is present, HOMO and LUMO can continue to be. For example, further cyano substituents in CI4CN4-PDI lead to a decrease in the HOMO to -6.8 eV and the LUMO to -4.7 eV. Electron-rich aminophenyl substituents raise the HOMO at -5.6 eV and the LUMO to -3.9 eV.

PDIs with particularly low LUMO energies are attractive molecules because they can be used as potentially air-stable nT yp semiconductor materials. High-lying LUMOs, on the other hand, promise high open-circuit voltages Voc in organic bulk heterojunction solar cells, which are characterized by the energy difference of the LUMO of the acceptor, eg. As PDIs, and the HOMOs of the donor material can be determined. Even without core substitution, aryl-DDPs are promising candidates for such applications, as the LUMO energies can be further increased by introducing more electron-rich aryl substituents, such as 4-amino and 4-methoxyphenyl substituents. Tetraalkiny (2,9-diazadibenzoperylene

 In addition to aryl substituents, alkynyl substituents provide another way to tune and expand the properties of DDPs through benzannulation. An extension of the aromatic system of DDPs is exemplified for the introduction of alkynyl substituents in the a / p / ia position by SONOGASHIRA coupling reactions. In addition, first attempts at alkenyl functionalization by Heck reactions are described.

Synthesis of tetraalkinyl-2,9-diazadibenzoperylene

 In the reaction of the tetratriflate DDP 8 with trimethylsilylacetylene, the tetraalkyne DDP 24 was obtained in 15% yield (Scheme 10). Already after three hours at room temperature in DMF complete conversion of DDP 8 is observed.

Scheme 10: Synthesis of DDP 24 by SONOGASHIRA coupling.

The use of tetrabutylammonium iodide plays a crucial role in this reaction protocol, as it leads to the formation in situ of aryl iodides, which are more reactive than terpolates in SONOGASHIRA coupling. Thus, the reaction described in Scheme 10 does not take place without tetrabutylammonium iodide. Even at an elevated temperature of 70 ° C only the decomposition of the starting material is observed. A SONOGASHIRA copper-free reaction protocol does not react at room temperature when using DDP 8 without iodide and decomposes the starting material at higher temperatures. DDP 24 is stable as an isolated solid in air. Pure DDP 24 was obtained by preparative thin layer chromatography.

DDP 24 is suitable after deprotection of the terminal alkyne for the construction of aromatic systems and for the modification of the electronic properties by introducing further substituents in the terminal alkyne position. First deprotection reactions were carried out by reaction with cesium fluoride in a DCM-methanol mixture. The slow formation of a precipitate can be observed. The soluble reaction product contains after filtration through silica gel according to ¹ H-NMR spectrum no T trimethylsilylgruppen, there is a complete deprotection instead.

 The study of copper-free SONOGASHIRA reactions, also called Heck-type alkynylation, indicates that different reaction pathways exist depending on the electronic influence of the substituents on phenylacetylene. Depending on the reaction path, the choice of base is therefore crucial for the success of cross-coupling. While high nucleophilicity of the base is important for electron-rich 1-alkynes, electron-poor acetylenes require strong, non-nucleophilic bases. The use of stronger bases than triethylamine, which do not contribute to the decomposition of the starting material by high nucleophilicity, could thus enable a more successful synthesis of DDP 26 and further 1-alkynyl DDPs in the future.

Electronic properties of tetraalkinyl-2,9-diazadibenzoperylene

Absorption and fluorescence spectroscopy, cyclic voltammetry and DFT calculations were used to investigate the influence of ethynyl substituents on DDP 24. The absorption spectrum has an intense band in the UV region at 260 nm, which is caused by rr-rf transitions on the alkyne (FIG. 6). In the visible range, an absorption maximum at 522 nm is observed in DCM with the typical vibronic progression of DDPs. The emission maximum at 528 nm is only slightly less energy-efficient. With a STOKES shift of only 6 nm, DDP 24 has the lowest STOKES shift of all DDPs studied. Accordingly, in the excited state, hardly any energy loss occurs by vibration or intramolecular rotation of the ethynyl substituents. This property makes 1-alkynediol DDPs ideal candidates for fluorescent dyes with high quantum yields. The absorption and emission maxima are red-shifted by about 30 nm and 0.1 eV, respectively, compared to the phenyl DDPs The determination of the electrochemical properties and the frontier orbital energies was carried out by cyclic voltammetry and differential pulse voltammetry.

 The energies of the frontier orbitals, which are summarized in Table 3, are determined from the optical and electrochemical measurement data. With EHOMO = -5.8 eV and ELUMO = -3.4, the energies of the frontier orbitals are 0.6 eV lower than the values for the tetraphenyl derivative DDP 12. This leads to a more electron-withdrawing character of the ethynyl substituents compared to the phenyl substituents.

Table 3: Measured and calculated energies of the frontier orbitals of DDP 24 in eV, unless stated otherwise.

Tetraamino 2,9-diazadibenzoperylene

 The proposed alkynyl and aryl DDPs are more electron-rich compounds compared to PDIs. An additional increase of the frontier orbital energies and thus a reversal and conversion in p-type semiconductor materials is expected by the introduction of donor functions at the DDP. For this reason, the amination of DDPs as a method of polarity reversal is promising.

Synthesis of tetraamino-2,9-diazadibenzoperylenes

 Without the addition of an acid, no reaction took place, as observed in the reaction of DDP 1 with sodium phenylamide.

Further amination experiments were performed in Pd- and Cu-catalyzed reactions. In a planned reaction of DDP 8 in a SONOGASHIRA reaction in DMF in the presence of copper (I) iodide, pyrrolidine was used as the base. Already before the addition of the alkyne, a color change of the brown suspension to a violet reaction solution took place. Although no etrapyrrolidine DDP could be detected However, the color of the reaction solution for the formation of an electron-rich amino-DDPs. Starting from DDP 8, a HARTWIG-BUCHWALD amination with aniline, Pd (dba) ₂ and NaOßu was investigated. Here a decomposition of the educt took place, as it was already observed in the presence of NaOßu in the SUZUKI-MIYAURA- reactions. Further Pd-catalyzed reactions were not performed as successful access to amino-DDPs was achieved by direct substitution.

 Another noteworthy reaction is the reaction of chlorinated DDPs and hexylamine. A change in color of the reaction solution from brown to an intense red violet takes place in DMF at 90 ° C. Although no amino-DDP could be detected, the color change is a promising indication for the further functionalization of chlorinated DDPs.

 Successful access to electron-rich amino DDPs is achieved by direct reaction of DDP 8 with amines in polar solvents. A series of secondary amines and an imine were reacted in DMSO with DDP 8 to form the corresponding amino DDPs. Scheme 1 1 summarizes the amines used and the reaction conditions.

 Scheme 11: Reactions of DDP 8 with secondary amines and tetramethylguanidine.

 The essential observation in the course of the reaction was the color change of the brown suspension to a violet reaction solution with the addition of the amine. Depending on the amine, the speed of the color change, which is regarded as an indicator of product formation, differed. DDP 27 and DDP 28 could not be detected, and DDP 26 and DDP 29 could only be detected by mass spectrometry. DDP 30 has been fully characterized.

Upon reaction with diethylamine at room temperature, complete reaction of DDP 8 was observed after four days. Besides DDP 26, triple-substituted amino-DDP DDP (NEt ₂ ) ₃ OH and double-substituted DDP (NEt ₂ ) ₂ (OH) _{2 were also} detected by mass spectrometry (HR-APCI). This observation leads to the conclusion that partial hydrolysis of the triflate takes place. The reaction with di-zsopropylamine shows no color change upon addition of the amine. After 18 hours at 90 ° C, a brown-violet suspension was obtained and filtered through silica gel. From the obtained brown solution no amino-DDP could be detected. The higher steric bulk of the amine compared to the other amines studied seems to be a possible cause, so that the nucleophilic substitution of the triflate under the chosen reaction conditions by this amine does not take place.

 The reaction with pyrrolidine was carried out both in DMSO and in diethyl ether, in order to investigate the influence of the solvent and, if necessary, to be able to replace DMSO. When a reaction is carried out in diethyl ether, only a slow red coloration of the reaction solution is observed when the amine is added. Nevertheless, DDP 8 is fully reacted after 24 hours at room temperature.

 After extraction of the product with DCM, pyrrolidinium triflate crystallized on cooling from the filtrate, so that separation of the organic salt is possible by precipitation.

 The previously reported reactions of DDP 8 with amines show a potential route to electron-rich DDPs. However, the properties of the products could not be described in detail. The workup of the amino DDPs is complicated and difficult. Challenging in the synthesis on the one hand is working with absolutely anhydrous amine, since otherwise kinetically preferred by attacks of hydroxides on triflate corresponding pyridones are formed as by-products. However, the oxidation sensitivity of the product, which requires a column-chromatographic purification under inert gas in the final purification, is also challenging.

Cleaning, the oxidation sensitivity of the amino-DDPs has been found. Only by filtration over dried silica gel with the exclusion of oxygen can a column-chromatographic purification take place without the amino-DDPs being decomposed immediately.

To underpin the utility of this synthetic method for the preparation of amino DDPs, DDP 30 was synthesized and fully characterized. DDP 30 was obtained by reacting DDP 8 with an excess of piperidine under a nitrogen atmosphere within one hour at 90 ° C and then washing the reaction solution with degassed water. The violet product remains intact in such aqueous workup. To confirm this, the reaction mixture was washed several times with degassed water and the product separated by centrifugation. Fig. 7 shows the ¹ H-NMR spectrum of DDP 30 after anhydrous work-up by washing with diethyl ether under a protective atmosphere (above) and after an aqueous work-up with degassed water (bottom). In both solutions, DDP 30 was detected by mass spectrometry.

 The main difference in this workup is that salt-like by-products, DMSO and piperidine can be separated and a possible protonation of DDP 30 is excluded. The chemical shift and the integrals of the signals in the upper spectrum suggest that possibly the by-product piperidinium trifluoride is observed. In an anhydrous workup can not be excluded that soluble organic salts such as piperidinium triflate are included as a byproduct.

Optical properties of tetraamino-2,9-diazadibenzoperylenes

 Amino DDPs stand out in the series of yellow and orange DDPs due to their optical properties. Their intense violet color in solution and as a solid make them optically interesting dyes. The absorption maximum of DDP 30 is in DCM at 550 nm and is lower energy by 100 nm compared to the tetratriflate DDP 8, 60 nm than tetraphenyl DDP 12 and about 30 nm lower than tetraalkynyl DDP 24. Thus, the amino form -DDPs the group with the lowest energy absorption maxima. Fig. 8 shows the absorption and fluorescence spectrum of DDP 30 in DCM.

Dibenzoperylene

 Synthesis of dibenzoperylenes

Dibenzoperylenes (DBPs) are the focus of research as potential singleton fission materials, which in the optimal case lead to a doubling of the usable excitons by splitting excited singlet states into two triplet states. So far, no easy access to functionalized dibenzoperylenes is known. In this work Analogous to diazadibenzoperylenes, a synthesis of dibenzoperylenes for further systematic functionalization is presented.

While a commercially available reactant is available for the preparation of DDPs with PTGDI, the corresponding precursor for the synthesis of DBPs has to be prepared in a two-step synthesis from naphthalene-1, 8-dicarboxylic anhydride (Scheme 12). This opens the possibility to modify the aromatic skeleton already at the beginning of the synthesis. By using 2-substituted malonic acid diesters, functional groups can be introduced in the 2- and 9-position on the DDP. The three-stage synthesis of 1, 3, 8, 10-tetrakis (trisyl! Oxy) -2,9-dimethyldibenzoperylene (DBP 1) was carried out in the final step by reduction of 3,10-dihydroxy-2,9-dimethyl-1, 8-dione dibenzoperylene and silylation analogous to the synthesis of DDP 1. Both reduction with sodium in diglyme and reduction with C ₈ K in THF led to the formation of DBP 1 in 22% yield for the first time.

 Scheme 12: Synthesis of DBP 1 by dehydrodimerization of 1-oxophenals followed by reduction.

Initial attempts to synthesize 2,9-H, H-DPB (OSiMe ₃ ) 4 did not lead to selective product formation in the silylation step, as demonstrated by ¹ H NMR spectra. Although no product could be detected by mass spectrometry, the ¹ H NMR spectra showed two doublet signals which, in comparison with DBP 1, can be assigned to the aromatic protons of 2,9-H, H-DPB (OSiMe ₃ ) ₄ . The reason for the low selectivity of the reaction is a silylation at the nucleophilic 2- and 9-positions suspected. By estimating the 2- and 9-position by methyl groups, a selective silylation to DBP 1 is achieved.

 Analogous to DDP 1, the DBP silyl ethers are only the first step

Functionalization of DBPs. To enable further functionalizations, therefore, the synthesis of 1, 3,8,10-tetratriflyl-2,9-dimethyldibenzoperylen (DBP 2) was undertaken. Synthesis and isolation have been challenging since DBP 2 is an at least solution-sensitive compound. In the absence of light, DBP 2 is stable without decomposition in DCM. The successful synthesis of DBP 2 finally succeeded in the absence of light. Scheme 13 shows the synthesis of DBP 2, and FIG. 9 shows the ¹ H NMR spectrum with the signals of the aromatic protons upfield-shifted, unlike DBP 1, compared to DDP 8. The reaction in DCM in the presence of pyridine or DMAP also leads to the formation of product.

Scheme 13: Synthesis of DBP 2

 Purification by column chromatography on DBP 2 results in the loss of most of the product to give a blue solid on silica gel. Therefore, for further cross-coupling reactions, direct reaction of DBP 2 without further purification is recommended.

Optical and electronic properties of a / pfta-substituted DBPs

With an absorption maximum of 479 nm, the absorption maximum is 11 nm and the emission maximum is 20 nm lower in energy than the related DDP (OSiMe ₃ ) 4 (DDP 1). Fig. 10 shows these for DBP 1 in DCM. The very small STOKES shift of only 9 nm is half that of DDP 1 and makes DBP 1 an ideal candidate for fluorescent dye applications. Noticeable for DBP 1 is a second structured absorption band at 340 nm, which can be compared with T etraazaperopyrenes the So - ⁺ S2 transition is assigned. However, DBF 1 decomposes slowly, like DDP 1 in air, to a purple solid.

 In DCM, DBF 2 has an absorption maximum of 457 nm, an emission maximum of 466 nm, and a small STOKES shift of 9 nm, which reflects the rigidity of the molecular backbone. DBF 2 has a 13 nm bathochromium shifted absorption maximum compared to the unsubstituted peropyrenes. The yellow solution in solution is distinguished by intense blue fluorescence under UV light (FIG. 11). DBF 2 decomposes in solution under the influence of light within a few minutes to a violet solution. Excluded from light, it can be stored in dry and oxygen-free DCM for several days without decomposition. The decomposition product was characterized spectroscopically and shows a bathochromically shifted absorption maximum of about 150 nm at 595 nm and an emission maximum of 624 nm.

The photochemical formation of the decomposition product takes place on a minute scale. By repeated exposure to ambient light and subsequent measurement of the absorption, the time course of the decomposition was observed. Fig. 12 shows a series of absorption spectra after different exposure times. Evident are the decrease of 8 _abs = 457 nm of DBF 2 and the increase of a band at 595 nm with a pronounced vibronic progression. The marked structuring of the absorption of the decomposition product and the formation of a single signal observed in several MS spectra suggest the selective formation of a new compound. The clear identification of the decomposition product is still pending. However, signals were observed mass-metric on each measurement at m / z = 548.0521 and m / z = 680.0030 assigned to the respective de-triflylated fragments [M-2 S0 ₂ CF ₃ ] ⁺ and [M-3 SO ₂ CF ₃ + H] ⁺ ,

The synthesis and characterization of DBF 1 and DBF 2 provided access to dibenzoperylenes for the first time, allowing independent functionalization at positions 2 and 9, and 1, 3, 8, and 10, thereby tuning the optical and electronic properties of DBPs allows. With DBF 2, a valuable starting material is available that allows access to functional dibenzoperylenes and a screening of their properties through a multitude of one-step modifications, as has already been demonstrated with the example of DDPs. The invention, or the subject matter of the invention, can thus be summarized as described below, it being noted that, for example, the terms "step" and "step" are used synonymously with respect to the method according to the invention. For example, "step a)" of the method also corresponds to "step a)" of the method. It should also be noted that the following description of the subject matter of the invention is not intended to be limiting, but merely describes individual embodiments. All the lists mentioned, regardless of whether substituents, structural elements or formula indices concerning, are not limiting.

A person skilled in the art is familiar with numerous list elements for each individual list, which likewise fall within the scope of the invention and its equivalents and can be used according to the invention.

In the context of the present disclosure, the term "structural segment" means an at least monatomic portion of the backbone of the compounds of the invention (or their precursors or starting materials / educts) of fused six-membered rings which consists either only of one or more carbon atoms and / or one or more heteroatoms ; If the relevant structural segment forms an edge section of the skeleton consisting of fused six-membered rings, one or all of the carbon atoms or heteroatoms of the structural segment can carry substituents instead of hydrogen atoms. For example, the formula symbol "Y" in Formula 1 is a structural segment. As substituents, therefore, individual atoms or a plurality of chemically interconnected atoms are referred to in a manner known to those skilled in the art, which atoms are linked to marginal structural segments via one or more chemical bonds, optionally double bonds. For example, the formula symbol "X" in Formula 1 is a substituent. Both types of formula symbols, or atomic / molecular components (X, Y) of the compounds according to the invention or their precursors or starting materials are summarized under the generic term "group".

By "alkali metal analogues" is meant compounds which behave at least in some properties similar to alkali metals, especially in terms of reducing properties. Examples of alkali metal analogs are carbon / graphite intercalation compounds such as CsK and complex ions such as "MgCl ⁺ ", "MgBr ⁺ ", "Mgl ⁺ ", which are known to those skilled in the art in the form of Grignard compounds, and a similar ion potential (charge per Room volume), have a similar electron density or a similar polarization capability such. B. Li ⁺ . Examples of Grignard compounds which can be used according to the invention are MgXR ^a with X = Cl, Br, I and R ^a = CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , benzyl, phenyl, cycloalkyl, etc.

The invention thus comprises both 1, 3,8,10-tetrasubstituted 2,9-diazadibenzoperylenes and 1, 3,8,10-tetrasubstituted 2,9-diorganodibenzoperylenes. In particular, it includes those tetrasubstituted compounds of the aforementioned type in which the substituents are independently selected from the list comprising triflate (-OSO ₂ CF ₃ ), nonaflate (-OSO ₂ C ₄ F ₉ ), tosylate (-OSO ₂ -C ₆ H ₄ -CH ₃ or - OTs, p-toluenesulfonate), mesylate (methylsulfonate: CH ₃ SO ₂ - or -OMs), fluorosulfonate (- OSO ₂ F). These compounds serve as starting materials for the preparation of numerous other 1, 3,8,10-tetrasubstituted compounds having dibenzo-perylene basic structure.

The invention further comprises a process for the preparation of the abovementioned compounds according to the invention, comprising the following, partly optional, steps:

 a) Reductive aromatization of Perylenetetracarbonsäurediimiden or in 1, 3,8,10- position oxo-substituted 2,9-dimethyl-dibenzo [cd, lm] perylenes by

 Reaction with alkali metals or alkali metal analogs, e.g. B. Li, Na, K, CsK and in situ conversion into the corresponding tetrakis (trimethylsiloxy compounds by reaction with trimethylsilyl chloride or other methylsilylating agents, b) conversion of the tetrakis (trimethylsiloxy compounds obtained in step a) into 1, 3, 8, 10-tetrasubstituted 2,9-Diazadibenzoperylene or 1, 3,8,10-tetrasubstituierten 2,9-Diorganodibenzoperylene by reaction with

 organometallic compounds such as butyllithium, methyllitium, propyllithium, ethyllithium and subsequent in situ reaction with a

 Acid anhydride or acid halide, wherein the corresponding acid corresponding to the acid anhydride or acid halide is an acid selected from the list comprising trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, toluenesulfonic acid, methylsulfonic acid,

 Fluorosulfonic acid.

A further embodiment of the process according to the invention provides that the salt-like compounds obtained intermediately in step a) are not first converted into the tetrakis (trimethylsiloxy compounds and then into the corresponding lithium salts (first part of step b)), but directly with one of the in step b), second part, provided acid anhydrides or acid halides implement.

A further embodiment of the invention provides for the use of the 1, 3,8,8-tetrasubstituted 2,9-diazadibenzoperylenes according to the invention and / or the 1.3.8.10-tetrasubstituted 2,9-Diorganodibenzoperylene according to formula A as starting materials for the preparation of further 1, 3,8,10-tetrasubstituted 2,9-Diazadibenzoperylene and / or

1.3.8.10-tetrasubstituted 2,9-diorganodibenzoperylenes according to formula B, wherein the groups Y, X and X 'are the specified independently selected groups, these listings are not to be understood as limiting: e

e ₃ ),

 Aryl, heteroaryl, 1-aikinyl, vinyl, acetyl.

The subject of the invention furthermore comprises a compound according to formula I,

characterized in that

 - The substituents X are independently selected from the list

comprising triflate (-OSO2CF _3), nonaflate (-OSO2C4F _9), tosylate

(-OSO ₂ -C ₆ H ₄ -CH ₃ , or also -OTs, p-toluenesulfonate abbreviated or called),

Phenylsulfonate (-OSO ₂ -C ₆ H ₅ ), mesylate (or methylsulfonate called

(in formula notation: CH ₃ SO ₂ - or -OMs abbreviated), fluorosulfonate

(-OSO ₂ F), OSO ₂ R ² , wherein the radicals R ²

are independently selected from the list comprising C _n F _{n +} 2, C _n H _{n +} 2, aryl, substituted aryl, pentafluorophenyl, para-nitrophenyl, and wherein the formula index n can assume the values 1 to 8;

- The structural segments Y are independently N or CR ¹ , wherein the

Radicals R ^{1 are} independently selected from the list comprising H, alkyl, iso-alkyl, cycloalkyl, cyclo-heteroalkyl, alkenyl, alkynyl, aryl,

 heteroaryl;

 the formula index m has one of the values 0, 1, 2 or 3.

The subject of the invention furthermore comprises a process for the preparation of the compound according to the preceding paragraph (formula I), comprising the following, partly optional, steps:

a) i) Reductive aromatization of a starting material according to formula II,

 wherein the structural segments Y are independently N or NH or

NR1 or CHR ¹ or CR ¹ ₂ are,

wherein the radicals R ^{1 are} independently selected from the list comprising H, alkyl, iso-alkyl, cycloalkyl, cyclo-heteroalkyl,

 Alkenyl, alkynyl, aryl, heteroaryl, and wherein the formula index m has one of the values 0, 1, 2 or 3, or

 at least one tautomeric form of the educt according to formula II, if at least one of them exists,

 by reaction with reducing transition metals or alkali metals or alkaline earth metals or alkali metal analogs

 from the list comprising Zn, Mg, Li, Na, K, CsK, wherein a salt-like

Compound according to formula III,

 is obtained, wherein M is independently selected from the list comprising Zn, Mg, Li, Na, K according to the choice of the reducing transition metal or alkali metal or alkaline earth metal or

 Alkali metal analogues, and p corresponds to the numerical value of the valence of the metal M,

 such as

 ii) in situ conversion of the salt-like compound from step i) into the

corresponding tetrakis (R ' ₃ SiO) compound according to formula I,

wherein Y and m have the meaning corresponding to the selected educt and X is OSiR ' ₃ , wherein R' is independently selected from the list comprising H, n-alkyl, sec-alkyl, tert-alkyl, aryl, by reaction with a Silylating agent R ' ₃ Si-halogen,

 selected from the list comprising trimethylsilyl chloride,

Triisopropylsilyl chloride, tert-butyldimethylsilyl chloride, chlorodimethylsilane Me ₂ SiHCl, chlorodimethylphenylsilane;

b) either

 iii) conversion of those obtained in stage a), substep ii)

Tetrakis (R ' ₃ SiO) compound in the corresponding tetrasubstituted compound according to formula I, wherein Y and m have the meaning corresponding to the selected educt,

 by reaction with an organometallic

 Compound selected from the list comprising butyllithium,

 Methyllitium, Propyllithium, Ethyllitium, Phenyllithium and

 iv) subsequent in situ reaction with an acid anhydride or

 Acid halide, wherein the corresponding acid corresponding to the acid anhydride or acid halide is an acid selected from the list comprising trifluoromethanesulfonic acid,

Nonafluorobutanesulfonic acid, toluenesulfonic acid, phenylsulfonic acid, Methylsulfonic acid, fluorosulfonic acid;

 or

 Reaction of the salt-like intermediates obtained in step a), substep i)

 Compound according to formula III, wherein Y and m are the chosen educt

 have meaning, directly with one of the in step b),

 Partial step iv), provided acid anhydrides or acid halides, wherein also the tetrasubstituted compound according to formula I is obtained,

 in which Y and m have the meaning corresponding to the selected educt.

The subject matter of the invention furthermore comprises a method as described in the preceding paragraph, characterized in that a further step c) is followed by step b), comprising a conversion of the in

Step b) obtained tetrasubstituted compound of formula I, wherein the Y

and m are as defined in the selected starting material, wherein step c) comprises at least one reaction by which at least one of the four substituents of the tetrasubstituted compound is chemically altered or substituted, independently selected from the list comprising the reactions nucleophilic substitution on the activated aromatic by O. Nucleophilic or N-nucleophiles or S-nucleophiles or C-nucleophiles or hydride nucleophiles or halogen nucleophiles or pseudo-halogen nucleophiles; CC cross-coupling reactions comprising Suzuki-Miyaura coupling, Sonogashira reaction, Heck reaction, Negishi reaction, Kumada coupling; Borylation (Miyaura Borylation); Amination (Buchwald-Hartwig amination);

Aryloxylation. The multiplicity of nucleophiles or reaction types that can be used in this extended process in step c) is supported, for example, by the fact that

Reactions / substitutions of the compounds of the invention such as the triflates, which are directly or initially difficult or impossible to carry out, are made possible by the addition of, for example, ammonium iodide; The reason for this is the in situ substitution, for example, of the triflate moiety by iodide, which in turn is then replaced by the substituent to be introduced and thus leads to the desired target molecule (see Scheme 70, for example, carried out there with tetrabutylammonium iodide). The person skilled in the art is familiar with further reactions known in the art, in particular also name reactions, which can be used according to the invention in step c) without departing from the scope of the invention or its equivalents. The subject of the invention further comprises the use of compounds as described above as starting materials for the preparation of compounds of the formula

I,

where the groups Y, X and X 'are independent of each other

selected groups selected, selected from the lists of groups Y, X and X ', comprising

Y = N, CR ¹ , where R ^{1 is} selected from the list comprising alkyl, alkenyl,

 Alkynyl, heteroaryl;

X = OSO ² R ² , where R ^{2 is} selected from the list comprising C _n F _{n +} 2,

C _n H _{n +} 2, aryl, substituted aryl, para-toluyl, pentafluorophenyl,

 para-nitrophenyl;

- X '= F, Cl, Br, I, CN, N _3, NCO, NCS, N0 _2, NH _2, N (alkyl) _2, N (alkylene),

NH (alkyl), N (aryl) ₂ , N (arylene), NH (aryl), N (SiMe ₃ ) ₂ , O (alkyl), O (aryl),

SH, S (alkyl), S (aryl), S (SiMe ₃ ), aryl, heteroaryl, 1-alkynyl, vinyl, acetyl,

 Acyl, allyl, substituted allyl radicals;

and the formula index m has one of the values 0, 1, 2 or 3.

 Examples of N (alkyls) include pyrrolidine, piperidine and other secondary cyclic amines; an example of an N (arylene) is N-linked carbazole; Vinyl generally also includes substituted alkylene radicals as well as higher homologues of the vinyl radical.

The subject of the invention further comprises 1, 3,8,10-tetrasubstituted 2,9-diazadibenzoperylenes and / or 1, 3,8,10-tetrasubstituted 2,9-diorganodibenzoperylenes according to formula A,

characterized in that the substituents are independently selected from the list comprising triflate (-OSO ₂ CF ₃ ), nonaflate (-OSO ₂ C ₄ F ₉ ), tosylate (-OSO ₂ - C ₆ H ₄ -CH ₃ or - OTs, p-toluenesulfonate), phenylsulfonate (-OSO ₂ -C ₆ H ₅ ), mesylate

(Methylsulfonate: CH ₃ SO ₂ - or -OMs), fluorosulfonate (-OSO ₂ F).

The subject matter of the invention furthermore comprises a process for the preparation of the 1, 3,8,10-tetrasubstituted 2,9-diazadibenzoperylenes or the 1, 3,8,10-tetrasubstituted 2,9-diorganodibenzoperylenes according to the preceding paragraph, comprising the following, in part optional, steps:

a) i) Reductive aromatization of perylenetetracarboxylic diimides or

 1, 3, 8, 10-position oxo-substituted 2,9-dimethyl-dibenzo [cd, lm] perylenes by reaction with alkali metals or alkali metal analogs,

 selected from the list comprising Li, Na, K, CsK,

 whereby salt-like compounds are obtained, as well

 ii) in situ conversion of the salt-like compounds from step i) into the

 corresponding tetrakis (trimethylsiloxy compounds by reaction with a methylsilylating agent or silylating agent selected from the

 List comprising trimethylsilyl chloride, triisopropylsilyl chloride,

 tert-butyldimethylsilyl chloride, chlorodimethylsilane Me2SiHCl,

 chlorodimethylphenylsilane;

b) either

 iii) conversion of those obtained in stage a), substep ii)

 Tetrakis (trimethylsiloxy compounds in the 1, 3, 8,10-tetrasubstituierten

 2,9-diazadibenzoperylenes or the 1,3,3,8,10-tetrasubstituted ones

 2,9-Diorganodibenzoperylenes by reaction with organometallic

 Compounds selected from the list comprising butyllithium,

 Methyllitium, Propyllithium, Ethyllitium and

iv) subsequent in situ reaction with an acid anhydride or Acid halide, wherein it is in the corresponding corresponding

 Acid to the acid anhydride or acid halide is an acid selected from the list comprising trifluoromethanesulfonic acid,

 Nonafluorobutanesulfonic acid, toluenesulfonic acid, methylsulfonic acid,

 fluorosulfonic;

 or

 Reaction of the salt-like intermediates obtained in step a), substep i)

 Compounds directly with one of those provided in step b), step iv)

 Acid anhydrides or acid halides.

The subject matter of the invention furthermore comprises the use of the 1,3,8,10-tetrasubstituted 2,9-diazadibenzoperylenes and / or the 1,3,8,10-tetrasubstituted ones

2,9-Diorganodibenzoperylenes according to formula A,

as starting materials for the preparation of further 1, 3,8,10-tetrasubstituierter

 2.9-Diazadibenzoperylenes and / or 1, 3,8,10-tetrasubstituted

 2.9-Diorganodibenzoperylenes according to formula B,

where the groups Y, X and X 'are independent of each other

selected groups selected, selected from the lists of groups Y, X and X ', comprising

Y = N, CR ¹ , where R ^{1 is} selected from the list comprising alkyl, alkenyl,

 Alkynyl, heteroaryl;

X = OSO ² R ² , where R ^{2 is} selected from the list comprising C _n F _{n +} 2, C _n H _{n +} 2, aryl, substituted aryl, para-toluyl, pentafluorophenyl,

 para-nitrophenyl

- X '= F, Cl, Br, I, CN, N _3, NCO, NCS, N0 _2, NH _2, N (alkyl) _2, N (alkylene),

NH (alkyl), N (aryl) ₂ , N (arylene), NH (aryl), N (SiMe3) 2, O (alkyl), O (aryl),

 SH, S (alkyl), S (aryl), S (SiMe3), aryl, heteroaryl, 1-alkynyl, vinyl, acetyl,

Acyl, allyl, substituted allyl radicals.

 Examples of N (alkyls) include pyrrolidine, piperidine and other secondary cyclic amines; an example of an N (arylene) is N-linked carbazole; Vinyl generally also includes substituted alkylene radicals as well as higher homologues of the vinyl radical.

The subject matter of the invention furthermore comprises preparations comprising at least one compound according to the invention as described above or prepared above which has at least one of the properties of electrically conductive, semiconducting, electron-conducting, hole-conducting, electrically insulating, photoconductive or light-emitting, wherein as a preparation both simple physical

Material mixtures and polymer composites, copolymers, compounded polymers and the like are to be regarded.

The subject matter of the invention furthermore comprises preparations comprising at least one compound according to the invention as described above or prepared above and an organic solvent or solvent mixture.

The subject of the invention further comprises the use of a

A compound of the invention as described (or prepared) or a preparation as described above as a charge transport material, semiconductor material, electrically conductive material, photoconductive or light emitting material in optical, electro-optical, electronic, electroluminescent or

photoluminescent devices or devices.

The subject matter of the invention furthermore comprises components or devices comprising at least one compound according to the invention as described above (or prepared) or a preparation according to the invention as described above, these components or these devices being selected from the list including organic field effect transistors (OFET), thin film transistors (TFT), integrated circuits (IC), logic circuits, logic devices, capacitors, radio frequency identification (RFID) chips, organic light emitting devices (OLEDs), organic light emitting transistors (OILET), flat panel displays, liquid crystal displays, backlighting of liquid crystal displays, organic

 Photovoltaic devices (OPV), organic solar cells, photodiodes, laser diodes,

Photoconductors, organic photoconductors, electrophotographic components,

electrophotographic recording components, organic storage components,

Sensor components, sensors, charge injection layers, charge transport layers or intermediate layers in polymer light-emitting diodes (PLED), Schottky diodes,

Leveling coatings, antistatic coatings and films,

Polymer electrolyte membranes (PEM), conductive substrates, conductive structures,

Electrode materials in batteries, sensors and electrolyzers, leveling layers, biosensors, biochips, security markers, security devices, and devices or devices for detecting and / or distinguishing DNA or RNA sequences.

embodiments

Synthesis instructions and analytics General remarks

 Unless otherwise stated, the syntheses of reduced, methylated and protonated perylenes were carried out by means of conventional SCHLENK technology under a protective gas atmosphere. The work-up of the neutral perylenediimides, tetraaryl-2,9-diazadibenzoperylenes and tetraalkinyl-2,9-diazadibenzoperylenes was carried out in air. The solvents used were dried according to standard procedures. Starting materials and reagents used were, unless otherwise stated, from CARBOLUTIONS CHEMICALS, FLUKA, ALDRICH, ACROS, ALFA AESAR, MERCK, TH. GEYER related. PTCDA and PTCDI were kindly provided by BASF SE.

The following compounds were prepared according to known literature procedures:

Di- / ^{'so-propylphosphinchlorid} (/ P ^ PCI), di-fe / f-butylphosphinchlorid (fBu2PCI) Perylentetracarbonsäureester, Perylentetracarbonsäurediesteranhydrid, N, N'-bis (1-hexylheptyl) perylene diimide.

The following compounds have been synthesized and provided in the working group: potassium graphite (CsK), durylboronic acid, / V- (4-phenylboronic acid ester) naphthaleneimide, bis (trifluoromethanesulfonic acid) imide (HTFSI).

Tet ras u I f oxy-2, 9 -d i azad i benzo pe ry I ne

1,3,8,10-tetrakis (trifluoromethylsulfonate) -2,9-diazadibenzoperylene DDP 8

DDP 1 (8.00 g, 11.7 mmol, 1.0 eq) was dissolved in 250 mL diethyl ether and treated at room temperature with n-BuLi (2.75 M in n-hexane, 17.1 mL, 47.0 mmol, 4.0 eq). After 18 h, Tf ₂ O (7.90 mL, 47.0 mmol, 4.0 eq) was added to the red lithium salt at -78 ° C. (1.75 mL / h by syringe pump) and stirred for 1 d at room temperature. The suspension was filtered, the solid was washed with THF and then the product was extracted by hot extraction with chloroform. The product was obtained by removal of the solvent in a fine vacuum.

 Comment: DDP 8 can be stored as a solid in air for several weeks without decomposition. In absolute solvents, it is stable to light for several days. In solutions in air and on elution over dried silica gel (neutral) or alumina (clean, neutral, basic) decomposition takes place so that only part of the product is obtained. It is not recommended to carry out a purification by column chromatography since DDP 8 obtained by extraction is sufficiently pure for further reactions and leads to good yields.

 Yield 3.66 g (0.40 mmol, 34%) orange, bright solid.

¹ H-NMR 300 MHz, CDCl ₃ : d = 9.57 (d, ³ HH = 9.6 Hz, 4H), 8.77 (d, ³ JHH = 9.5 Hz, 4H)

 ppm.

¹⁹ F NMR 282 MHz, CDCl ₃ : d = -72.0 ppm.

MS FD-HRMS (+) (DCM, C ₂ 8H8Fi 2N ₂ Oi ₂ S 4 ⁺ ): gef. (calculated) m / z = 919.8753

 (919.8768).

 IR v = 1411 (m), 1349 (m), 1214 (s), 1 168 (m), 1122 (s), 1029 (m), 947 (m), 907

(m), 831 (m), 788 (s), 751 (m), 637 (m), 597 (s), 495 (s) cm ^-1 .

 UV / Vis DCM: e (Aabs) = 56800 (455 nm), 33600 (426 nm), 17500 (402 nm), 9000

(381 nm) L-moM-cnr ¹ .

PL DCM (19.15 mM): A _ex = 400 nm, A _em = 474, 502, 540 nm. CHN (C28H8F12N2O12S4, 920.60 g / mol). (Calc.)

 C: 37.08% (36.53%), N: 3.10% (3.04%), H: 1.21% (0.88%), S: 13.99% (13.93%).

 X-ray For structural analysis, crystals were obtained from a saturated DCM solution at 4 ° C.

1,3,8,10-tetrakis (trifluoromethylsulfonate) -2,9-diazadibenzoperylene DDP 8

 DDP 2 (550 mg, 0.64 mmol, 1.0 eq) and DMAP (30 mg, 0.25 mmol, 0.4 eq) were dissolved in 30 mL DCM and Tf 2 <D (0.45 mL, 2.56 mmol, 4.0 eq) was added at room temperature a color change of the reaction solution from orange to brown was observed. The green reaction solution after 22 h was concentrated in a fine vacuum, taken up in 50 ml of n-pentane and centrifuged off.

Note: In several experiments, a green DCM solution of the crude product, which turned orange in air, formed no spectroscopic difference from ¹ H and ¹⁹ F NMR.

 Yield 0.38 g (0.42 mmol, 64%) orange, bright solid.

1,3,8,10-tetrakis (trifluoromethylsulfonate) -2,9-diazadibenzoperylene DDP 8

DDP (ONa) ₄ (0.53 g, 1.1 mmol, 1.0 eq) was stirred in 10 mL DCM at room temperature with Tf ₂ 0 (0.8 mL, 4.9 mmol, 4.4 eq) for 3 d. The solvent was removed in a fine vacuum, the residue was dissolved in 20 mL DCM and purified by column chromatography on dried silica gel (mobile phase DCM / n-pentane, 1/1).

Yield 0.06 g (0.06 mmol, 5%) orange, bright solid. 1,3,8,10-tetrakis (trifluoromethylsulfonate) -2,9-diazadibenzoperylene DDP 8

DDP 6 (80 mg, 0.19 mmol, 1.0 eq) was suspended in 5 mL of toluene and 5 mL of 30% aqueous K ₃ PO ₄ solution and incubated at 0 ° C. with Tf ₂ O (1.6 mL, 9.0 mmol, 48.0 eq ) slowly. It formed a green solution with blue fluorescence. An additional 5 mL of toluene was added in the cold and the reaction mixture warmed slowly to room temperature. After 18 h, the reaction mixture was treated with water, the green organic phase separated and dried over MgS0 ₄ . The target product was detected in traces by NMR spectroscopy. 1, 3,8,10-tetra (para-toluenesulfonate) -2,9-diazadibenzoperylene DDP 10

 DDP 7 (70 mg, 0.17 mmol, 1.0 eq) was suspended for 1 d in 2 ml diethyl ether, combined with TS 2 O (220 mg, 0.67 mmol, 4.0 eq) and stirred at room temperature. The green fluorescent solution was evaporated in a fine vacuum and the residue taken up in 10 mL toluene at 80 ° C, treated with DCM and filtered through silica gel. The target product was obtained in traces.

MS MALDI (C ₅ 2H36N ₂ Oi ₂ S 4): gef. (calculated) m / z = 1008.85 (1009.12).

Tetraarylsubstituted 2.9-diazadibenzoperylene

1, 3,8,10-tetraphenyl-2,9-diazadibenzoperylene DDP 12

DDP 8 (0.3 g, 0.32 mmol, 1.0 eq), phenyl boronic acid (0.25 g, 0.21 mmol, 6.0 eq) and Pd (PPh3) 4 (45 mg, 0.04 mmol, 0.12 eq) were dissolved in 5 mL toluene, 2 mL ethanol and 2 ml_ aqueous, saturated and degassed NaHC0 ₃ solution at 90 ° C stirred. After 2.5 days, the reaction mixture was filtered through silica gel and eluted with DCM. After removing the

Solvent in a fine vacuum, the solid was recrystallized from toluene and the

Product isolated.

 Yield 0.12 g (0.19 mmol, 59%) of a red solid.

¹ H-NMR 300 MHz, CDCl ₃ : d = 9.25 (d, ³ JHH = 9.7 Hz, 4H), 8.70 (d, ³ JHH = 9.4 Hz, 4H),

8.03 (d, ³ J _HH = 6.9 Hz, 8H), 7.69 - 7.46 (m, 12H) ppm.

¹ H-NMR 300 MHz, di-TFA: d = 9.90 (d, ³ HH = 9.8 Hz, 4H), 8.99 (d, ³ JHH = 9.6 Hz, 4H),

 8.18 - 8.00 (m, 8H), 8.01 - 7.80 (m, 12H) ppm.

¹³ C-NMR 75 MHz, di-TFA: d = 150.0, 134.8, 132.7, 132.0, 131.9, 130.3, 128.4, 128.0 ppm.

MS FD-HRMS (+) (DCM, C ₄₈ H ₂₈ N ₂ ⁺ ): gef. (calc.) m / z = 632.2261 (632.2253).

 IR v = 3026 (w), 1576 (w), 1514 (w), 1471 (w), 1443 (w), 1390 (w), 1356 (w),

1332 (w), 1287 (w), 1259 (w), 1209 (w), 1 176 (w), 1 146 (w), 1071 (w), 1025 (w), 1001 (w), 967 (w ), 912 (w), 883 (w), 840 (w), 789 (s), 771 (vs), 720 (w), 690 (vs), 641 (w), 619 (w), 598 (m ), 560 (w), 522 (w), 504 (w), 465 (w) cm ^-1 .

UV / Vis DCM: e (A _abs ) = 90900 (490 nm), 65000 (460 nm), 21700 (309 nm) L-mol

1 -crrr ¹ .

PL DCM + 5% TFA, _Aex = 350 nm: A _em = 552, 582 nm.

PL DCM, _Aex = 350 nm: A _em = 517, 550 nm.

TGA (T _s = 25 ° C, T _E = 800 ° C, 10 K / min, N ₂ ,): T = 120.3 ° C (3% degradation),

Stage 1: T _ü (onset) = 519.0 ° C, T _ü (max) = 597.2 ° C; Total mass removal: 59%.

SDTA (T _s = 25 ° C, T _E = 800 ° C, 10 K / min, N ₂ ): T _M (onset) = 412.2 ° C, T _M (max) = 422.2 ° C.

CV (DCM, vs Fc / Fc ⁺ ): E _Red 2 = -2.29V, E _Redi = -1.99V, E _0cΐ = _0.50V , E _0c2 =

 0.80 V.

1,3,8,10-tetrakis (4-fe / f-butylphenyl) -2,9-diazadibenzoperylene DDP 13

 DDP 8 (0.2 g, 0.22 mmol, 1 .0 eq), 4-fe / f-butylphenylboronic acid (0.23 g, 1 .3 mmol, 6.0 eq) and Pd (PPh3) 4 (0.03 g, 0.03 mmol, 0.12 eq). were suspended in 2 ml of ethanol, admixed with 5 ml of toluene and 1 ml of aqueous, saturated and degassed NaHCO 3 solution and stirred at 90 ° C. After 42 h, the brown reaction suspension was filtered through silica gel and eluted with DCM. After removal of the solvent, the product was purified by recrystallization from hot toluene and washed with n-pentane.

 Yield 0.13 g (0.15 mmol, 69%) of a red solid.

¹ H-NMR 300 MHz, CDCl ₃ : d = 9.09 (d, ³ HH = 9.6 Hz, 4H), 8.64 (d, ³ JHH = 9.4 Hz, 4H),

7.94 (d, ³ JHH = 8.3 Hz, 8H), 7.64 (d, ³ JHH = 8.3 Hz, 8H), 1.46 (s, 36H) ppm. ¹ H-NMR 300 MHz, di-TFA: d = 9.86 (d, ³ HH = 9.8 Hz, 4H), 9:02 (d, ³ JHH = 9.6 Hz, 4H),

8.01 (d, ³ JHH = 1 .2 Hz, 16H), 1.58 (s, 36H) ppm.

¹³ C-NMR 75 MHz, di-TFA: d = 159.9, 150.2, 134.9, 132.5, 131.7, 130.0, 129.2, 128.5,

 127.7, 125.7, 37.1, 32.0 ppm.

 A quaternary carbon signal could not be observed.

MS FD-HRMS (+) (DCM, C ₆₄ H ₆ oN ₂ ⁺ ): gef. (transl.) m / z = 856.4744 (856.4757).

 IR v = 2954 (m), 2898 (w), 2861 (w), 1579 (w), 1506 (m), 1473 (w), 1391 (m),

1358 (m), 1291 (m), 1264 (m), 1 191 (w), 1 144 (w), 1 1 12 (m), 1015 (m), 967 (m), 888 (w), 842 (s), 832 (s), 790 (vs), 748 (w), 717 (s), 644 (w), 580 (w), 561 (w), 541 (m) cm ^-1 .

UV / Vis DCM: e (A _abs ) = 73300 (273 nm), 80500 (284 nm), 30400 (326 nm), 71500

(469 nm), 103400 (497 nm) L-mol ^-1 · cm ^-1 .

PL DCM, h _ex = 350 nm: λ _em = 528, 558 nm. CV (DCM, vs Fc / Fc ^+): _Re E d2 = -2.33 V, E _Re di = -1 .97 V, E ₀ = 0.45V xi, E _0c2 = 0.72

V, Eoxs = 1.34 V.

 X-ray For structural analysis, crystals were obtained from a saturated toluene / n-pentane solution by slow evaporation.

1,3,8,10-tetrakis (3,5-bis-trifluoromethane-phenyl) -2,9-diazadibenzoperylene DDP 18

DDP 8 (0.32 g, 0.35 mmol, 1.0 eq) and Pd (PPh 3) 4 (0.05 g, 0.04 mmol, 0.15 eq) were stirred in 8 mL toluene for 10 min at room temperature. 3,5-bis-trifluoromethylphenyl boronic acid

(0.54 g, 2.1 mmol, 6.0 eq) was dissolved in 4 mL ethanol and added. The reaction solution was admixed with 2 ml of aqueous, saturated and degassed NaHCO 3 solution, stirred for 12 hours at 90 ° C. and filtered through silica gel and eluted with DCM. The DCM solution was concentrated and the product was precipitated by addition of n-pentane and isolated by filtration.

 Yield 0.14 g (0.12 mmol, 35%) of red solid.

¹ H-NMR 300 MHz, CDCl ₃ : <5 = 9.47 (d, ³ JHH = 9.7 Hz, 4H), 8.62 (d, ³ JHH = 9.5 Hz, 4H),

 8.49 (s, 8H), 8.14 (s, 4H) ppm.

¹ H-NMR 300 MHz, di-TFA: d = 7.10 (d, ³ JHH = 9.8 Hz, 4H), 8.92 (d, ³ JHH = 9.5 Hz,

 4H), 8.61 (s, 8H), 8.51 (s, 4H) ppm.

¹⁹ F NMR 282 MHz, CDCl ₃ : <5 = -62.6 (s) ppm.

¹³ C-NMR 75 MHz, di-TFA: d = 146.9, 136.8, 136.3, 133.7, 133.3, 133.2, 133.2, 132.2,

 131.7, 129.1, 127.7, 126.6 ppm.

MS FD-HRMS (+) (DCM, C ₅₆ H ₂ oF ₂₄ N ₂ ⁺ ): gef. (calc.): m / z = 1 176.1276 (1 176.1243).

IR v = 3092 (w), 1581 (w), 1382 (m), 1340 (s), 1316 (w), 1287 (s), 1274 (s),

1265 (s), 1 173 (s), 1 134 (s), 1 15 (vs), 1082 (s), 995 (w), 900 (s), 873 (m), 848 (m), 796 (s), 750 (m), 726 (m), 699 (m), 682 (s), 646 (m), 581 (w), 560 (w), 505 (w), 444 (w), 408 (w) cm ^-1 .

UV / Vis DCM: e (A _a bs) = 100500 (490 nm), 70500 (462 nm) L-mo-cm ^-1 . PL DCM, _Aex = 350 nm: A _em = 521, 551 nm.

CV (DCM, vs Fc / Fc ⁺ ): ER _ed 2 = -1.94V, ERedi = -1.71V, Eoxi = 0.75V, Eox2 =

0.98 V, E _OX3 = 1 .10 V.

 X-ray For structural analysis, crystals were obtained from a saturated toluene / n-pentane solution by slow evaporation.

1,3,8,10-T etrakis (3,5-di- / so-propyl-6- / V-1,8-naphthalimide) -phenyl-2,9-diazadibenzoperylene

DDP 22

DDP 8 (0.1 g, 0.1 1 mmol, 1 .0 eq), / V- (di- / ^{'so-propylphenyl)} naphthaleneimide (0.3 g,

0.65 mmol, 6.0 eq) and Pd (PPh3) 4 (20 mg, 0.02 mmol, 0.15 eq) were stirred in 5 ml of toluene, 2 ml of ethanol and 2 ml of aqueous, saturated and degassed NaHCO3 solution at 90.degree. After 3.5 d, the suspension was purified on silica gel (eluent n-pentane / ethyl acetate, 1/1) and recrystallized from toluene.

 Yield 0.04 g (0.02 mmol, 21%) of red solid.

¹ H-NMR 300 MHz, CD ₂ CI ₂ : d = 9.47 (d, ³ HH = 9.8 Hz, 4H), 8.93 (d, ³ JHH = 9.5 Hz, 4H),

8.76 (dd, ³ JHH = 7.3, ⁴ JHH = 0.9 Hz, 8H), 8.40 (dd, ³ HH = 8.3, ⁴ JHH = 0.8 Hz, 8H), 8.15 (s, 2H), 7.95 - 7.83 (m, 8H ), 2.98 (m, 4H), 1 .32 (d, ³ JHH = 6.8 Hz, 12H) ppm.

¹ H-NMR 300 MHz, di-TFA: d = 10.15 (d, ³ HH = 9.9 Hz, 4H), 9.30 (d, ³ JHH = 9.5 Hz,

4H), 9.03 (d, ³ JHH = 7.3 Hz, 4H), 8.65 (d, ³ JHH = 8.1 Hz, 8H), 8.25 (s, 8H), 8.09 (t, ³ J _HH = 7.8 Hz, 8H), 3.18 (m, 8H), 1.47 (d, ³ JHH = 6.8 Hz, 48H) ppm.

¹³ C-NMR 126 MHz, c / i-TFA: d = 169.2, 151.6, 149.0, 139.4, 136.2, 136.1, 134.7, 134.6, 134.3, 131.9, 130.9, 130.8, 130.0, 129.6, 129.5, 128.3, 128.0, 125.5, 122.4, 31.7, 24.6 ppm.

MS FD-HRMS (+) (DCM, CiajHgeNeOie ^* ): gef. (transl.) m / z = 1749.7304

 (1749.7322).

 IR v = 2959 (w), 1709 (m), 1670 (s), 1585 (m), 1513 (w), 1465 (w), 1434 (w),

1344 (vs), 1233 (s), 1 188 (m), 1 149 (m), 1 1 13 (m), 1069 (m), 947 (w), 893 (m), 837 (m), 814 (m), 777 (vs), 731 (m), 692 (m), 515 (m) cm ^-1 .

UV / Vis DCM: e (A _abs ) = 121800 (502 nm), 93000 (478 cm), 87800 (350 nm), 1 17700

(334nm), 105200 (323nm) L-moM -crTr ¹ .

PL DCM, K _bc = 350 nm: A _em = 538, 567 nm.

CV (DCM, vs Fc / Fc ⁺ ): E _Re d2 = -2.19 V, E _Re di = -1.91 V, E _0cΐ = 0.68 V, E _0c2 =

1.32 V

1,3,8,10-tetrakis (9- / V- (2,6-di- / ^' -propylphenyl) -perylenyl-3,4-dicarboximide)) - 2,9-diazadibenzoperylene DDP 23

DDP 8 (60 mg, 0:07 mmol, 1.0 eq), / V- (2,6-di- / ^{'so-propylphenyl)} -8- (4,4,5,5-tetramethyl- 1, 3,2-dioxaborolan -2-yl) perylene-3,4-dicarboxylic acid imide (370 mg, 0.4 mmol, 6.0 eq) and a spatula tip of Pd (PPh3) 4 were added 7 d in a mixture of 9 mL toluene, 2 mL ethanol, and 1 mL more aqueous and degassed NaHCC> 3 solution at 90 ° C stirred. By column chromatography on silica gel initially unreacted perylene imide was separated (eluent DCM). The product was eluted with DCIW acetone (100/2) as a purple solution and obtained after removal of the solvent.

 Yield 0.12 g (0.05 mmol, 71%) of a dark red solid.

¹ H-NMR 300 MHz, CDCl 3 / TFA Ö1: d 1 1 .38 - 1 1.15 (br s, 4H.), 9.73 (d, ³ J HH = 10.4 Hz,

4H), 8.94-8.81 (m, 12H), 8.81-8.64 (m, 12H), 8.30 (d, ³ JHH = 4.1 Hz, 4H), 7.80-7.56 (m, 8H), 7.52 (t, ³ J _HH = 7.8 Hz, 4H), 7:36 (d, ³ JHH = 7.6 Hz, 8H), 2.75 - 2:55 (m, 8H), 1 .17 (d, ³ JHH = 6.5 Hz, 48H) ppm. ¹ H-NMR 300 MHz, CDCl ₃ : d = 9.33 (d, JHH = 9.0 Hz, 4H DDP), 8.73 (m, 12H), 8.67 - 8.51 (m, 12H), 8.44 (t, JHH = 8.9 Hz, 4H), 8.12 (t, JHH = 8.2 Hz, 4H), 7.86 (dd, JHH = 1 1 .3, JHH = 6.6 Hz, 4H), 7.62 (d, JHH = 5.3 Hz, 4H), 7.54 - 7.44 ( m, 4H), 7.35 (dd, JHH = 7.7, JHH = 2.4 Hz, 4H), 2.90 - 2.67 (m, 8H), 1.21 (d, JHH = 6.7 Hz, 8H), 1.17 (d, JHH = 6.9 Hz , 48H) ppm.

 MS FD-HRMS (+) (DCM, CieoHnzNeCV): gef. (accounted for) m / z = 2245.8521

 (2245.8575).

 IR v = 2959 (m), 2925 (m), 2868 (m), 1700 (s), 1661 (s), 1591 (s), 1576 (s),

1466 (s), 1354 (vs), 1292 (m), 1245 (m), 1 196 (m), 1 178 (w), 987 (w), 845 (m), 81 1 (m), 794 ( m), 752 (m) cm ^-1 .

UV / Vis DCM: A _abs = 543 nm (broad absorption band between 450 and 580 nm).

PL DCM, _Aex = 350 nm: 642 nm.

DCM + 1% TFA, A _ex = 350 nm: 609 nm.

CV (DCM, vs Fc / Fc ⁺ ): E _Red 3 = -1.95 V, E _Red 2 = -1 .80 V, E _Redi = -1 .41 V, E ₀ cΐ =

0.86V, EO _X2 = 1.09V, Eoxs = 1.46V

1, 3,8,10-tetraferrocenyl-2,9-diazadibenzoperylene DDP 20

 DDP 8 (0.20 g, 0.22 mmol, 1 .0 eq), ferrocene boronic acid (0.30 g, 1.3 mmol, 6.0 eq), K 3 PO 4 (0.28 g, 1.3 mmol, 6.0 eq) and Pd (dppf) Cl 2 (64 mg, 0.09 mmol , 0.4 eq) were stirred in 8 ml of toluene and 8 ml of degassed water for 20 h at 100 ° C. The reaction solution was brought to room temperature and extracted with DCM. The red-violet organic phase was washed with water and filtered through silica gel. After removal of the solvent in a fine vacuum, the product was obtained.

 Yield 20 mg (0.02 mmol, 9%) of black solid.

¹ H-NMR 300 MHz, CDCl ₃ : d = 9.21 (d, ³ JHH = 9.6 Hz, 4H), 9.1 1 (d, ³ JHH = 9.5 Hz, 4H),

5.37 (t, ³ JHH = 1.9 Hz, 8H), 4.66 - 4.60 (m, 8H), 4.29 (s, 20H) ppm.

MS APCI-HRMS (+) (DCM, C64H _{4 4} Fe ₄ N ₂ Hi ⁺ ): gef. (calculated) m / z = 1065.0969

(1065.0983). IR v = 3088 (w), 1612 (m), 1576 (m), 1517 (m), 1479 (w), 1389 (m), 1352 (m),

1267 (m), 1212 (w), 1 147 (m), 1 103 (m), 1048 (m), 1018 (m), 997 (m), 969 (m), 899 (m), 837 (s ), 814 (s), 792 (vs), 754 (m), 730 (s), 697 (m), 615 (w), 589 (w), 561 (w), 485 (vs) cm ^-1 .

UV / Vis DCM: A _abs = 475, 499, 576 nm.

CV (DCM, vs Fc / Fc ⁺ ): Eo _xi = 0.05V, Eo _x 2 = 0.80V.

1,3,8,10-tetrakis (biphenyl) -2,9-diazadibenzoperylene DDP 14

 DDP 8 (0.11 g, 0.12 mmol, 1.0 eq), biphenylboronic acid (0.14 g, 0.72 mmol, 6.0 eq), K 3 PO 4 (0.15 g, 0.72 mmol, 6.0 eq) and Pd (dppf) Cl 2 (13 mg, 0.08 mmol, 0.2 eq) were stirred at room temperature for 18 h and at 60 ° C for 4 h. The reaction mixture was washed with

30 ml_ DCM, filtered through filter paper and washed with DCM. The residual red solid (130 mg) was washed with hot toluene and with n-pentane. The yield could not be determined because insoluble by-products could not be separated.

¹ H-NMR 300 MHz, cfi-TFA: d = 9.96 (d, ³ HH = 9.7 Hz, 4H), 9.14 (d, ³ JHH = 9.5 Hz, 4H),

8.21 (s, 16H), 7.87 (d, ³ JHH = 7.1 Hz, 4H), 7.73 - 7.49 (m, 16H) ppm.

MS FD-HRMS (C ₇₂ H ₄₄ N ₂ ⁺ ): gef. (calculated) m / z = 936.3507 (936.3505).

X-ray For the structural analysis, crystals were obtained from a solvent mixture of toluene and TFA by slow evaporation of the solvent mixture. 1, 3,8,10-tetra (2-thienyl) -2,9-diazadibenzoperylene DDP 19

 DDP 8 (0.20 g, 0.22 mmol, 1. 0 eq) and Pd (PPh 3) 4 (40 mg, 0.03 mmol, 0.2 eq) were stirred in 5 mL toluene for 15 minutes. 2-Thienylboronic acid (0.17 g, 1.32 mmol, 6.0 eq) was taken up in 4 ml of ethanol and added. The reaction mixture was admixed with 2 ml of saturated NaHCO 3 solution and stirred at 90 ° C. for 7 days. The suspension was diluted with DCM and filtered. The red-violet filtrate with orange fluorescence was purified over silica gel (mobile phase chloroform), concentrated and the product was precipitated with n-pentane at room temperature. A dark red solid was obtained.

 Yield 20 mg (0.03 mmol, 14%) of dark red solid.

¹ H-NMR 300 MHz, CD ₂ CI ₂ : <5 = 9.24 (d, ³ JHH = 9.9 Hz, 4H), 8.95 (d, ³ JHH = 9.6 Hz, 4H),

7.87 (dd, ³ JHH = 3.7, ⁴ JHH = 0.8 Hz, 4H), 7.61 (dd, ³ JHH = 5.1, ⁴ JHH = 1 .0 Hz, 4H), 7.29 (dd, ³ J _HH = 5.2, ⁴ J _HH = 3.7 Hz, 4H) ppm.

MS FD-HRMS (C ₄ oH ₂ oN ₂ S ₄ ⁺ ): gef. (calculated) m / z = 656.0498 (656.0509).

 IR v = 3062 (w), 2925 (w), 1574 (w), 1524 (m), 1464 (m), 1424 (m), 1388 (m),

1359 (m), 1327 (m), 1263 (m), 1217 (m), 1 156 (m), 1 106 (m), 1078 (m), 1047 (m), 1004 (m), 947 (w ), 896 (w), 840 (s), 788 (s), 752 (m), 712 (m), 690 (vs), 601 (w), 559 (w), 512 (w), 474 (w ) cm ^-1 .

UV / Vis DCM: e (A _abs ) = 120700 (543 nm), 100500 (508 nm), 53900 (475 nm) L-mol

1 -crrr ¹ .

DCM, 1% TFA: A _abs = 519 nm.

PL DCM, _Aex = 350 nm: A _em = 574, 612 nm.

DCM, 1% TFA: A _ex = 350 nm: A _em = 612 nm.

CV (DCM, vs Fc / Fc ⁺ ): E _Red2 = -2.01V, E _Redi = -1.75V, E _0cΐ = 0.39V, E _0c2 =

0.66 V 1,3,8,10-tetrakis (2,3,5,6-tetramethylphenyl) -2,9-diazadibenzoperylene DDP 15

DDP 8 (0.20 g, 0.22 mmol, 1.0 eq), durylboronic acid (0.24 g, 1.32 mmol, 6.0 eq) and Pd (PPh 3) ₄ (0.04 g, 0.03 mmol, 0.15 eq) were dissolved in 5 mL toluene, 2 mL ethanol and 2 ml of aqueous, saturated and degassed NaHCO 3 solution are stirred at 90 ° C. for 3.5 d. There was obtained a product mixture that could not be separated. The product could only be detected by mass spectrometry.

MS FD-HRMS (+) (DCM, C ₆ 4 H ₆₀ N ₂ ^+): Found. (transl.): m / z = 856.4744 (856.4757).

1, 3,8, 10-T etrakis (2,5-difluorophenyl) -2,9-diazadibenzoperylene DDP 16

 DDP 8 (0.10 g, 0.11 mmol, 1.0 eq), 3,5-difluorophenylboronic acid (0.10 g, 0.66 mmol, 6.0 eq) and Pd (PPh 3) 4 (0.02 g, 0.02 mmol, 0.15 eq) were mixed at room temperature suspended from 5 ml of toluene, 2 ml of ethanol and 2 ml of saturated, degassed NaHCO 3 solution and stirred at 90 ° C. for 2 days. The reaction product was taken up in DCM and filtered through silica gel. A product mixture was obtained from which the product was detected by trace mass spectrometry.

MS FD-HRMS (+) (DCM, C ₄₈ H ₂ oF ₈ N ₂ ⁺ ): gef. (transl.): m / z = 776.1509 (776.1499). Tetraamino 2,9-diazadibenzoperylene

1, 3,8,10-tetrapiperidino-2,9-diazadibenzoperylene DDP 30

DDP 8 (0.1 1 g, 0.12 mmol, 1.0 eq) was treated with piperidine (0.15 mL, 2.0 mmol, 16.6 eq) in 4 mL DMSO. A color change of the reaction mixture from brown to violet was observed. The reaction solution was stirred for 1 h at 90 ° C and volatile components were removed in a fine vacuum. The remaining violet solid was washed three times with 10 ml of degassed water and centrifuged off. After washing with 10 ml of n-pentane and drying in a fine vacuum, the product was kept clean.

 Yield 68 mg (0.10 mmol, 86%) of violet solid.

¹ H-NMR 300 MHz, C ₆ D ₆ : d = 8.73 (d, ³ HH = 9.5 Hz, 4H), 8.37 (d, ³ JHH = 9.3 Hz, 4H),

 3.63 (m, 16H), 1.78 (m, 16H), 1.57 (m, 8H) ppm.

MS FD-HRMS (+) (DCM, C ₄₄ H ₈₈ N ₆ ⁺ ): gef. (calc.) m / z = 660.3970 (660.3940).

UV / Vis DCM: A _abs = 272, 555 nm.

PL DCM, K _bc = 350 nm: A _em = 594, 632 nm.

 IR v = 3359 (s), 3310 (m), 3192 (m), 3002 (m), 2956 (vs), 2920 (s), 2850 (s),

2813 (m), 1658 (s), 1632 (s), 1580 (w), 1529 (w), 1468 (w), 141 1 (m), 1376 (m), 1263 (m), 1244 (m) , 1 190 (m), 1 153 (m), 1 134 (m), 1096 (m), 1030 (m), 792 (m), 722 (m), 698 (m), 637 (m) cm ^{- 1} .

1, 3,8,10-tetrapyrrolidino-2,9-diazadibenzoperylene DDP 29

DDP 8 (0.06 g, 0.07 mmol, 1.0 eq) was treated with pyrrolidine (0.05 ml, 0.50 mmol, 8.0 eq) in 10 ml diethyl ether and stirred at room temperature for 2 days. The reaction solution colored reddish upon addition of the amine and violet after a few hours. After removal of the solvent in a fine vacuum, the target product could be detected by mass spectrometry.

MS APCI-HRMS (+) (DCM, C ₄₀ H ₄₀ N ₆ H _I ⁺ ): m.p. (calc.) m / z = 605.3388 (605.3387).

1, 3,8,10-tetrakis (dimethylamino) -2,9-diazadibenzoperylene DDP 26

 DDP 8 (0.07 g, 0.08 mmol, 1.0 eq) was stirred in 3 mL DMSO with diethylamine (0.3 mL, 2.9 mmol, 36.0 eq) at room temperature. After 4 days, the violet solution was concentrated. A product mixture was obtained which contained two, three and four times aminated DDP.

MS APCI-HRMS (+) (DCM, C32H ₂ 8N ₄ OH _I ⁺ ): m.p. (calculated) m / z = 501.2291

 (501.2285).

APCI-HRMS (+) (DCM, C ₃₆ H ₃₈ N ₅ OH _I ⁺ ): m.p. (calc.) m / z = 557.3154 (557.3149).

APCI-HRMS (+) (DCM, C ₄ H ₄₈ N ₆ H _I ⁺ ): m.p. (calculated) m / z = 613.0418 (613.4013).

Alkynyl-2,9-Diazadibenzoperylen

1,3,8,10-tetrakis (trimethylsilylacetylene) -2,9-diazadibenzoperylene DDP24

DDP 8 (280 mg, 0.30 mmol, 1.0 eq), Cul (35 mg, 0.18 mmol, 0.6 eq), Pd (PoTol ₃ ) 2 Cl 2 (35 mg, 0.05 mmol, 0.15 mmol) and n-BuN ₄ L (660 mg , 1.8 mmol, 6.0 eq) were evacuated, flooded three times with nitrogen and suspended in DMF / Et ₃ N (5 mL / 1 mL). After Trimethylsilylacetylene (0.25 ml, 1.8 mmol, 6.0 eq) was added for 10 minutes, and the reaction solution was stirred at room temperature for 3 hours. The crude product was eluted with silica gel over DCM / n-pentane (1/1). By column chromatography by-products could not be separated, so that clean product was obtained by preparative TLC (eluent DCM / n-pentane, 2/1).

 Yield 0.04 g (0.06 mmol, 15%) of red solid.

¹ H-NMR 300 MHz, CD ₂ CI ₂ : <5 = 9.30 (d, ³ JHH = 9.5 Hz, 4H), 8.81 (d, ³ JHH = 9.3 Hz, 4H),

 0.48 (s, 36H) ppm.

¹³ C NMR 126 MHz, CD ₂ CI ₂ : d = 137.5, 128.2, 127.6, 127.1, 126.3, 125.9, 122.5, 102.6,

 101.8, 1.3 ppm.

²⁹ Si NMR 99 MHz, CD ₂ Cl ₂ : d = -15.9 ppm.

MS FD-HRMS (+) (DCMC ₄ 4H ₄ 4N ₂ Si ₄ ⁺ ): m.p. (calc.) m / z = 712.25662 (712.25815).

IR v = 3359 (m), 3358 (w), 3195 (w), 2956 (m), 2922 (vs), 2851 (s), 2185 (w),

2160 (w), 2030 (w), 1658 (m), 1632 (s), 1468 (m), 1467 (w), 1422 (w), 1411 (w), 845 (w) cm ^-1 .

UV / Vis DCM: A _abs = 522, 486, 454, 428 nm.

PL DCM, _Aex = 350 nm, A _em = 529, 567 nm.

CV (DCM, vs Fc / Fc ⁺ ): Eoxi = 1.06V, Eox2 = 1.46V.

Dibenzoperylene

2,9-dimethyl-1,3,8,10-tetrakis (trimethylsilyloxy) dibenzoperylene DBP 2

3,10-Dihydroxy-2,9-dimethyl-1,8-dione dibenzoperylene (2.5 g, 6.0 mmol, 1.0 eq) and CsK (3.5 g, 25.9 mmol, 4.3 eq) were suspended in 100 mL THF and dehydrated for 3 d at 55 ° C and 8 h at 65 ° C stirred. Trimethylsilyl chloride (4.5 mL, 36.0 mmol, 6.0 eq) was slowly added at room temperature and the reaction stirred at 60 ° C for 18 h. Volatile components were removed in a fine vacuum, the crude product was suspended in DCM, filtered off and washed with DCM until the filtrate was colorless. The solution was concentrated and filtered through dry silica gel. The filtrate was concentrated in a fine vacuum, washed with n-pentane and then dried under a fine vacuum. Yield 0.92 g (1.3 mmol, 22%) of orange solid.

¹ H-NMR 300 MHz, CDCl ₃ : d = 9.01 (d, ³ HH = 9.6 Hz, 4H), 8.42 (d, ³ HH = 9.4 Hz, 4H),

 2.59 (s, 6H), 0.41 (s, 36H) ppm.

¹³ C-NMR 126 MHz, CDCl ₃ : <5 = 149.6, 125.6, 125.1, 123.7, 121 .9, 120.4, 1 19.1, 13.2,

 1.2 ppm.

²⁹ Si NMR 99 MHz, CDCl ₃ : d = 22.4 ppm.

MS FD-HRMS (+) (DCMC ₄ OH ₅ o0 ₄ Si4 ^+): Found. (accounted for) m / z = 706.2774 (706.2786).

IR v = 2955 (w), 2900 (w), 1626 (w), 1587 (w), 1483 (m), 1405 (m), 1387 (m),

1365 (w), 1343 (w), 1304 (m), 1248 (m), 1221 (m), 1 172 (m), 1 145 (m), 1 101 (m), 1034 (w), 915 ( s), 838 (s), 787 (m), 756 (m), 705 (m), 691 (m), 657 (m), 568 (w), 457 (w) cm ^-1 .

UV / Vis DCM: e (8 _abs ) = 76900 (479 nm), 3890 (449 nm), 14300 (423 nm) L-mo-crrr

 1

PL DCM, K _bc = 350 nm: A _em = 488, 521 nm.

CHN (C ₄ oH ₅ o0 ₄ Si ₄ , 707.18 g / mol)

 gef. (calculated) C: 64.39% (67.94%), H: 6.77% (7.13%).

CV DCM vs. Fc / Fc ⁺ : E ₀ cΐ = 0.26 V, E ₀ c ₂ = 0.61 V.

2,9-dimethyl-1,3,8,10-tetratriflate-dibenzoperylene DBP 2

In a brown glass Schlenk DBP 1 (42 mg, 0.06 mmol, 1.0 eq) in 5 ml diethyl ether with n-BuLi (2.9 M in n-hexane, 0.08 ml, 0.24 mmol, 4.0 eq) slowly at 0 ° C was added. It formed an insoluble red solid, which after 4 h with Tf ₂ 0 (0.04 ml_, 0.2 mmol, 4.0 eq) was added at 0 ° C. Product formation takes place immediately, according to DC. After 2 d at room temperature, the solvent was removed in a fine vacuum and the product was dissolved in DCM, filtered and the solvent was removed in a fine vacuum. The product was washed with n-pentane and obtained as a brown solid.

¹ H-NMR 300 MHz, CDCl ₃ : d = 9.29 (d, ³ JHH = 9.4 Hz, 4H), 8.59 (d, ³ JHH = 9.8 Hz, 4H),

 2.98 (s, 6H) ppm.

¹⁹ F NMR 282 MHz, CD ₂ CI ₂ : d = -72.8 (s) ppm. UV / Vis DCM: A _abs = 457, 429, 408 nm.

PL DCM: _Aex = 350 nm: A _em = 466, 492 nm.

MS FD-HRMS (+) (DCMC32Hi ₄ Fi20i2S ₄ ⁺ ): gef. (accounted for) m / z = 945.9169 (945.9177).

Reduced naphthalenediimide derivatives - diazapyrene (DAP)

1, 3,6,8-tetrakis ((trimethylsilyl) oxy) benzo [/ mn] [3,8] phenanthroline (DAP1)

NTCDI (266 mg, 1.0 mmol, 1 eq), zinc dust (392 mg, 8.0 mmol, 8.0 eq) and trimethylsilyl chloride (1.0 mL, 8.0 mmol, 8.0 eq) were incubated at room temperature for 6 h in 20 mL THF stirred under argon atmosphere. All volatiles were removed on fine vacuum, the product was taken up with DCM and filtered. After removal of the solvent, the crude product was washed with pentane. There were obtained 390 mg (0.68 mmol, 68%) of a yellow solid.

¹ H-NMR 300 MHz, CDCl ₃ : d = 7.78 (s, 4H), 0.47 (s, 36H) ppm.

1, 3,6,8-tetrakis ((triisopropylsilyl) oxy) benzo [/ mn] [3,8] phenanthroline (DAP2)

NTCDI (266 mg, 1.0 mmol, 1.0 eq), potassium graphite (616 mg, 4.4 mmol, 4.4 eq) and triisopropylsilyl chloride (1.1 mL, 5.0 mmol, 5.0 eq) were refluxed in 20 mL THF under an argon atmosphere for 16 h. All volatiles were removed on fine vacuum, the product was dissolved in DCM and filtered through neutral alumina. After removal of the solvent in vacuo, DAP2 was recrystallized from pentane. There were obtained 268 mg (0.30 mmol, 30%) of a yellow solid. ¹ H-NMR 300 MHz, CDCl ₃ : d = 7.87 (s, 4H), 0.47 (s, 36H), 1.73 - 1.52 (m, 2H), 1.15 (t, J = 7.4 Hz, 36H) ppm.

Benzo [/ mn] [3,8] phenanthroline-1, 3,6,8-tetrayltetrakis (trifluoromethanesulfonate) (DAP3)

NTCDI (1.33 g, 5.0 mmol, 1.0 eq) and potassium graphite (2.94 g, 21.0 mmol, 4.2 eq) were stirred in 100 ml DME under an argon atmosphere for 3 h at 80 ° C. 3.6 ml (21.0 mmol, 4.2 eq) of triflate anhydride were subsequently added dropwise at -50 ° C. within 3 h and the mixture was stirred overnight at room temperature. The reaction mixture was filtered through neutral alumina and rinsed with DCM (100 mL). The product was precipitated by addition of 100 ml of pentane at -18 ° C, filtered off and dried in vacuo. There was obtained 3.05 g (3.8 mmol, 76%) of a beige solid.

¹ H-NMR 300 MHz, CDCl ₃ : d = 8.56 (s, 4H) ppm.

¹⁹ F NMR 250 MHz, CDCl ₃ : d = -71.9 ppm.

 MS

HR-FD (+) found (calculated) m / z = 795.85716 (795.85812).

1, 3,6,8-T etrakis ((trimethylsilyl) ethynyl) benzo [/ mn] [3,8] phenanthroline (DAP4)

DAP3 (80 mg, 0.1 mmol, 1.0 eq), copper iodide (4 mg, 0.02 mmol, 20 mol%) and Pd (dppf) Cl2 (7 mg, 0.01 mmol, 10 mol%) were dissolved in 2 ml THF and 2 ml triethylamine dissolved and degassed under an argon atmosphere, 0.1 ml (0.6 mmol, 6 eq) of trimethylsilylacetylene were added and the mixture was stirred at 65 ° C. for 16 h. All fleeting Ingredients were removed in a fine vacuum, the product taken with DCM filtered through silica gel. After removal of the solvent, 15 mg (0.025 mmol, 25%) of an orange solid were obtained.

¹ H-NMR 300 MHz, CDCl ₃ : d = 8.60 (s, 4H), 0.40 (s, 36H) ppm.

HR-FD (+) found (calculated) m / z = 588.22671 (588.22685).

1, 3,6,8-T etrakis ((trimethylsilyl) ethynyl) benzo [/ mn] [3,8] phenanthroline (DAP6)

DAP3 (796 mg, 1.0 mmol, 1.0 eq), tetramethylammonium iodide (804 mg, 4.0 mmol, 4.0 eq), copper iodide (38 mg, 0.2 mmol, 20 mol%) and Pd (dppf) C (71 mg, 0.1 mmol, 10 mol%) were dissolved in 30 mL 1, 4-dioxane and 10 mL triethylamine and degassed. The formation of DAP5 as an intermediate was detected after a few minutes by EI-MS. 1.1 ml (6.0 mmol, 6 eq) of 4-tert-butylphenylacetylene were added under argon atmosphere and the mixture was stirred at 85 ° C. for 16 h. All volatiles were removed in a fine vacuum, the product was purified by column chromatography on silica gel (eluent: pentane / DCM 1: 1). After removal of the solvent, 225 mg (0.27 mmol, 27%) of an orange solid DAP6 were obtained. ¹ H-NMR 300 MHz, CD ₂ CI ₂ d = 8.70 (s, 4H), 7.75 (d, J = 9.0 Hz, 8H), 7.50 (d, J = 9.0 Hz, 8H), 1.37 (s, 36H) ppm.

 io

 HR EI (+) found (calculated) m / z = 707.65250 (707.65532) for DAP5.

I O

 ° HR-FD (+) found (calculated) m / z = 828.44049 (828.44435) for DAP6.

1, 3,6,8-tetraphenylbenzo [/ mn] [3,8] phenanthroline (DAP7)

NTCDI (266 mg, 1.0 mmol, 1.0 eq) and potassium graphite (616 mg, 4.4 mmol, 4.4 eq) were stirred in 20 mL DME under argon atmosphere for 3 h at 80 ° C. 0.75 ml (4.4 mmol, 4.4 eq) of triflate anhydride were subsequently added dropwise at -50 ° C. within 3 h and the mixture was stirred at room temperature for 2 h. There were 537 mg (4.4 mmol, 4.4 eq) phenylboronic acid, 115 mg (0.1 eq, 10 mol%) of Pd (PPh3) ₄ and added to 5 ml of saturated sodium hydrogen carbonate solution degassed and stirred for 16 h at 90 ° C. The reaction solution was extracted with ethyl acetate (20 ml), dried over magnesium sulfate and purified by column chromatography on silica gel (eluent: pentane / DCM 2: 1). There were obtained 70 mg (0.14 mmol, 14%) of DAP7 as a yellow solid.

MS

HR-FD (+) found (calculated) m / z = 508.19157 (508.19395).

1, 3,6,8-tetra (piperidin-1-yl) benzo [/ mn] [3,8] phenanthroline (DAP8)

DAP3 (160 mg, 0.20 mmol, 1 eq) was stirred in 4 mL DMSO and 1 mL piperidine at 90 ° C for 1 h. Thereafter, the solvent was removed in vacuo and the crude product was washed with water and dried. There were obtained 65 mg (0.12 mmol, 60%) of DAP8 as a brown solid.

HR-FD (+) found (calculated) m / z = 536.36315 (536.36274).

Other Peropyren Derivatives - Diazadibenzopyrene (HDBP / DBP)

2,9-Dimethyldibenzo [cc /, / m] perylene-1, 3,8,10-tetrayltetrakis (trifluoromethanesulfonate) (DBP2)

Dimethyl phenalen (1.25 g, 3.0 mmol, 1.0 eq) and potassium graphite (1.70 g, 12.6 mmol, 4.2 eq) were stirred in 60 mL DME under argon atmosphere for 3 h at 80 ° C. In the course of 3 h, 2.4 mL (12.6 mmol, 4.2 eq) of triflate anhydride were added dropwise at -50 ° C. with exclusion of light and the mixture was stirred overnight at room temperature. The reaction mixture was filtered over neutral alumina and washed with DCM (50 mL). The product was precipitated by addition of 50 mL of pentane at -18 ° C, filtered off and dried in vacuo. 935 g (0.99 mmol, 33%) of a brown solid were obtained.

Derivatization of DBP2 by Suzuki-Miyaura Coupling General procedure AAV1 for Suzuki Miyaura coupling of DBP2

DBP2 (93 mg, 0.1 mmol, 1.0 eq), potassium carbonate (166 mg, 12.0 mmol, 12.0 eq) and Pd (dppf) Cl2 (7 mg, 0.02 mmol, 20 mol%) and 0.6 mmol (6.0 eq) of the corresponding arylboronic acid were dissolved in 2 ml of THF and 0.5 ml of water and degassed. The Reaction solution was stirred under exclusion of light and under argon atmosphere for 16 h at 65 ° C. All volatiles were removed in a fine vacuum, the product taken with DCM filtered through silica gel. After removal of the solvent, the Suzuki coupling products were obtained in yields of 5-10% as yellow-orange solids.

 The following compounds DBP3 to DBP8 have been presented in accordance with this General Procedure AAV1:

2,9-Dimethyl-1,3,8,10-tetraphenyldibenzo [cc /, / m] perylene (DBP3)

MS

 HR-EI (+) found (calculated) m / z = 882.51543 (882.51645).

1, 3,8,10-tetrakis (3,5-bis (trifluoromethyl) phenyl) -2,9-dimethyldibenzo [cc /, / m] perylene

HR-EI (+) found (calculated) m / z = 794.1 1019 (794.1 1016). Additions to HDBP

1, 3,8,10-T etrakis ((trimethylsilyl) oxy) dibenzo [cc /, / m] perylene (HDBP1)

Phenalen (778 mg, 2.0 mmol, 1.0 eq), zinc dust (1.05 g, 16.0 mmol, 8.0 eq) and trimethylsilyl chloride (2.0 mL, 16.0 mmol, 8.0 eq) were in 40 ° C at a temperature of 100 ° C for 3 h ml_ 1, 4-dioxane stirred under argon atmosphere. All volatiles were removed in a fine vacuum, the product was taken up with DCM and filtered. After removal of the solvent, the crude product was washed with pentane. There were obtained 647 mg (0.95 mmol, 48%) of an orange solid.

¹ H-NMR 300 MHz, CDCl ₃ : d = 8.99 (d, J = 9.6 Hz, 4H), 8.47 (d, J = 9.4 Hz, 4H), 7.42

 (s, 2H), 0.47 (s, 36H) ppm.

MS

HR-EI (+) found (calculated) m / z = 678.24409 (678.24731).

Dibenzo [cd, lm] perylene-1, 3,8,10-tetrayltetrakis (2,2-dimethylpropanoate) (HDBP2)

Phenalen (3.80 g, 9.8 mmol, 1.0 eq), zinc dust (5.18 g, 78.0 mmol, 8.0 eq) and pivalic anhydride (15.9 mL, 78.0 mmol, 8.0 eq) were submerged in 200 mL of 1, 4-dioxane for 3 d Argon atmosphere is refluxing. The reaction mixture was filtered over neutral alumina and rinsed with 200 mL dichloromethane. After removal of the volatiles in a fine vacuum, the residue was suspended in 200 ml of pentane and the precipitate was filtered. There was obtained 2.43 g (3.35 mmol, 34%) of a brown solid. ¹ H-NMR 300 MHz, CD ₂ CI ₂ : d = 8.87 (d, J = 9.6 Hz, 4H), 8.13 (d, J = 9.4 Hz, 4H), 7.69 (s, 2H), 1.63 (s, 36H ) ppm.

HR-APCI (+) found (calculated) m / z = 727.3272 (727.3265).

Dibenzo [cd, lm] perylene-1, 3,8,10-tetrayltetrakis (2,2-dimethylpropanoate) (PhDBPI)

Ph-phenals (900 mg, 1.7 mmol, 1.0 eq), zinc dust (872 mg, 13.3 mmol, 8.0 eq) and pivalic anhydride (2.7 ml, 13.3 mmol, 8.0 eq) were dissolved for 3 d in 20 ml 1, 4. Dioxane refluxed under an argon atmosphere. The reaction mixture was filtered over neutral alumina and rinsed with 20 mL dichloromethane. After removal of the volatiles in a fine vacuum, the residue was suspended in 50 ml of n-pentane and the precipitate was filtered. 252 mg (0.34 mmol, 22%) of a brown solid were obtained.

¹ H-NMR 300 MHz, CD ₂ CI ₂ : d = 9.23 (d, J = 9.4 Hz, 4H), 8.27 (d, J = 9.4 Hz, 4H),

 7.55-7.40 (m, 10H), 1.19 (s, 36H) ppm.

 I O

 ° HR-APCI (+) found (calculated) m / z = 879.3903 (879.3891).

((10- (tert-butyl) dibenzo [cd, lm] perylene-1,3,8-triyl) tris (oxy)) tris (di-tert-butylphosphane)

 (HDBP3)

Phenalen (776 mg, 2 mmol, 1.0 eq) was suspended in 40 ml of THF and treated dropwise at room temperature with 4.1 ml_ (10 mmol, 5.0 eq) of a 2.43M solution of n-butyllithium in hexane. The suspension was stirred at 50 ° C. for 2 h and, after cooling to room temperature, 2.45 ml of chlorine (di-fe / f-butyl) phosphine were added and subsequently refluxed for 18 h. After removal of the volatiles in a fine vacuum, the residue was taken up in 60 ml of dichloromethane and filtered. After removal of the solvent in vacuo, the residue was washed with n-pentane (20 mL). There was obtained 463 g (0.48 mmol, 24%) of a brown solid. ¹ H-NMR 300 MHz, CDCl ₃ : d = 8.98 (d, J = 9.6 Hz, 4H), 8.67 (d, J = 9.4 Hz, 4H), 8.52

(t, J = 5.2Hz, 4H), 1.33 (d, J = 11.8Hz, 72H) ppm. P-NMR 101 MHz, CDCl ₃ : d = 151.7 (s) ppm.

((10- (tert-butyl) dibenzo [cd, lm] perylene-1,3,8-triyl) tris (oxy)) tris (di-tert-butylphosphine) (HDBP3)

Variant A: HDBP1 (475 mg, 0.7 mmol, 1.0 eq) were dissolved in 100 mL diethyl ether and treated dropwise at 0 ° C with 1.3 mL (3.1 mmol, 4.5 eq) of a 2.43M solution of n-butyllithium in hexane. The suspension was stirred at room temperature for 2 h and treated dropwise at 0 ° C with 1.9 mL triflate anhydride (3.1 mmol, 4.5 eq). The reaction mixture was stirred at room temperature for 3 h. From the reaction solution, HDBP4 was precipitated at -18 ° C, filtered and washed with 20 mL diethyl ether. There was obtained 440 mg (0.49 mmol, 70%) of a brown solid HDBP4 after drying in vacuo.

Variant B: Phenalen (184 mg, 0.5 mmol, 1 eq) was suspended in 20 mL diethyl ether and zinc (262 mg, 4.0 mmol, 8 eq), trimethylsilyl chloride (0.5 mL, 4 mmol, 8 eq) was added. Dropwise, 1.2 mL (2.0 mmol, 4 eq) triflate anhydride was added at 0 ° C and the reaction mixture was stirred at room temperature for 2 d. All volatiles were removed in a fine vacuum and the residue in 20 mL Dichloromethane, filtered and the solvent removed in vacuo. After washing the residue with 20 mL of pentane and drying in vacuo, 1 10 mg (0.12 mmol, 23%) of HDBP4 was obtained.

¹ H-NMR 300 MHz, CDCl ₃ : d = 9.45 (d, J = 9.7 Hz, 4H), 8.67 (d, J = 9.3 Hz, 4H), 8.20

 (s, 2H) ppm.

¹⁹ F NMR 250 MHz, CDCl ₃ : d = -72.6 ppm.

 MS

HR-FD (+) found (calculated) m / z = 917.88694 (917.88635).

1, 3,8,10-tetrakis (4- (ferf-butyl) phenyl) dibenzo [cc /, / m] perylene (HDBP5)

HDBP2 (146 mg, 0.2 mmol, 1.0 eq), 570 mg 4-Fe / Butyl boronic acid (3.2 mmol, 16.0 eq), 679 mg anhydrous potassium phosphate (3.2 mmol, 16.0 eq) and 28 mg (0.04 mmol, 20 mol%). NiCl2 (PCy3) 2 was stirred in 1 mL of 1, 4-dioxane for 18 h at 110 ° C. After removal of the volatiles in a fine vacuum, the residue was taken up in dichloromethane and filtered through neutral alumina. After removal of the solvent in vacuo, the residue was crystallized from dichloromethane / n-pentane (1: 1) at -18 ° C. 75 g (0.08 mmol, 44%) of HDBP5 were obtained as orange-brown needles.

¹ H-NMR 300 MHz, CD ₂ CI ₂ : d = 9.22 (d, J = 9.6 Hz, 4H), 8.57 (d, J = 9.4 Hz, 4H),

8.12 (s, 2H), 7.69 (d, J = 8.3Hz, 8H), 7.63 (d, J = 8.3Hz, 8H), 1.33 (s, 36H) ppm. Derivatization of HDBP4 by Suzuki-Miyaura coupling

General Procedure AAV2 for Suzuki Miyaura coupling of HDBP4

 HDBP4 (184 mg, 0.2 mmol, 1.0 eq), potassium carbonate (310 mg, 3.2 mmol, 12.0 eq) and Pd (PPh3) 4 (23 mg, 0.02 mmol, 10 mol%) and 0.6 mmol (6.0 eq) of the corresponding arylboronic acid were dissolved in 3 ml_ 1, 4-dioxane and 1 ml_ of water and degassed. The reaction solution was stirred under argon atmosphere for 3 d at 1 10 ° C. The reaction solutions were diluted with 20 ml of dichloromethane, treated with magnesium sulfate and filtered. The reaction products were purified by column chromatography on neutral alumina (eluent: n-pentane / dichloromethane 2: 1).

 The following derivatives of HDBP4 have been prepared in accordance with this General Working Procedure AAV2:

1, 3,8,10-tetraphenyldibenzo [cc /, / m] perylene (HDBP6)

 Yield 15 mg (0.02 mmol, 12%), orange solid.

¹ H-NMR 300 MHz, CD ₂ CI ₂ : d = 9.23 (d, J = 9.7 Hz, 4H), 8.54 (d, J = 9.5 Hz, 4H),

8.14 (s, 2H), 7.79-7.74 (m, 8H), 7.66-7.59 (m, 8H), 7.57-7.53 (m, 4H) ppm. 1, 3,8,10-tetrakis (3,5-bis (trifluoromethyl) phenyl) dibenzo [cd, lm] perylene (HDBP7)

Yield 86 mg (0.07 mmol, 37%), orange solid. ¹ H-NMR 300 MHz, CD ₂ CI ₂ : d = 9.40 (d, J = 9.7 Hz, 4H), 8.41 (d, J = 9.5 Hz, 4H),

 8.24 (s, 8H), 8.1 1 (s, 2H), 8.10 (s, 4H) ppm.

1, 3,8,10-Tetra (thiophen-2-yl) dibenzo [cc /, / m] perylene (HDBP8)

 Yield 28 mg (0.04 mmol, 22%), dark red solid.

¹ H-NMR 300 MHz, CD2CI2: d = 9:32 (d, J = 9.7 Hz, 4H), 8.85 (d, J = 9.5 Hz, 4H),

8.36 (s, 2H), 7.62 (d, J = 4.1 Hz, 4H), 7.53 (dd, J = 3.5 Hz, J = 1 .1 Hz, 4H), 7.35 (dd, J = 5.1 Hz, J = 3.6 Hz, 4H) ppm. List of Figures

 Fig. 1: Formula of catalyst CX 31, i. of chlorophenylallyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidenes] palladium, [(IPr) Pd (cinnamyl) Cl]

Fig. 1 B: Figure 1: a) Schematic representation of the photoinduced

 Electron transfers (PET) to DDP 20 leading to fluorescence quenching and an example of a ferrocenyl-substituted PDI. b) Absorption spectrum of DDP 20 with absorption maxima at 475 nm, 499 nm and 576 nm in DCM, inserted DDP 20 in DCM under ambient light and under UV light (366 nm). c) Cyclic voltammogram of DDP 20 at different scan rates. At a scan rate of 50 mV / s only one anodic peak is observed, at higher scan rates two anodic peaks. In all cases, only one cathodic peak is observed. D) Cyclic voltammogram of DDP 20 in the presence of ferrocene as internal standard at a scan rate of

Figure 2: Table 5: Electrochemical and optical properties and experimentally determined and DFT calculated energies of the frontier orbitals of aryl-2,9-diazadibenzoperylenes.

FIG. 2B: FIG. 2: absorption and fluorescence spectra of DDP 12 (top left),

 DDP 19 (upper right), DDP 22 (lower left), and DDP 23 (lower right), including the separate aryl substituent (Dipp PMI) in DCM. Emission spectra were measured at an excitation wavelength of 8ex = 350 nm. Below are the dichloromethane solutions without addition of TFA (DDP 12, DDP 19 a) and with addition of TFA (DDP 19 b and DDP 23) under ambient light (left) and UV light (366 nm, right).

Fig. 3: Figure 3: Voltammogram (CV and DPV) of DDP 12 (upper left),

DDP 13 (top right), DDP 18 (bottom left) and DDP 19 (bottom right). All measurements were performed in DCM at room temperature and in 100 mM nBu4NPF ₆ brine at 100 mV / s (CV) and 10 mV / s (DPV). Fig. 4: Voltammogram (CV) of DDP 22 (left), DDP 23 (right). All measurements were performed in 100 mM nBu ₄ NPF ₆ brine solutions (DCM) at room temperature with a scan rate of 100 mV / s (CV) 10 mV / s (DRV).

Fig. 5: Bay- and ortho-functionalized PDIs and experimentally determined HOMO and

 LUMO energies.

Fig. 6: Left: UV / Vis spectrum of DDP 24 in DCM with an absorption band at

 260 nm and DDP 24 in DCM under ambient light and with an excitation with

366 nm (inserted). Right: Normalized absorption and fluorescence spectra of DDP 24 in DCM with a STOKES shift of 6 nm. The excitation was carried out at 8 _ex = 350 nm.

Fig. 7: ¹ H-NMR spectra of DDP 30. Top (CDCb, 300 MHz, 300 K) after filtration and washing with pentane, bottom (C ₆ D ₆ , 300 MHz, 300 K) after aqueous work-up.

Fig. 8: Absorbance and fluorescence spectra (8 _ex = 350 nm) of DDP 30 in DCM.

 Inserted is the dichloromethane solution of DDP 30 under ambient light (left) and under UV light (366 nm, right).

Fig. 9: ¹ H-NMR spectrum (CDC, 300 MHz, 300 K) of DBP 2 and DDP 8 as

 Reference.

Fig. 10: Absorbance and fluorescence spectra (8 _QC = 350 nm) of DBP 1 in DCM with

Images of the measured samples under ambient light and UV light (366 nm, left). DBP 1 as a solid under ambient light, under UV light (366 nm) and dissolved as a green solution with violet decomposition product (right). Fig. 1: Absorption and fluorescence spectra of DBF 2 (8 _ex = 350) and the

Decomposition product (8 _ex = 550 nm, right) in DCM.

Fig. 12: Time-dependent absorption spectra of DBF 2 in DCM showing decomposition of DBF 2.

List of abbreviations

 APCI Atmospheric-pressure Chemical Me Methyl

 ionization

 Ar Aryl min. Minute (s)

 Bu Butyl MS mass spectrometry

 CG column chromatography n-BuLi n-butyllithium

 COZY correlated spectroscopy n. B. not determined

 CV cyclic voltammetry NaHMDS sodium bis (trimethylsilyl) amide d day (s) NfF perfluorobutanesulfonic acid fluoride

DBU diazabicycloundecene NMR nuclear magnetic resonance

 DG thin-layer chromatography Ox oxidation

 DMAP 4- (dimethylamino) -pyridine Ph phenyl

 DCM Dichloromethane PL Photoluminescence

 DDQ 2,3-dichloro-5,6-dicyano-1,4-propyl

 benzoquinone

 DFT density functional theory p-TsCl p-toluenesulfonyl chloride

DMSO dimethyl sulfoxide Red reduction

 DPV differential pulse voltammetry r.t. room temperature

dppf 1, 1 '- TBAF tetrabutylammonium fluoride

 Bis (diphenylphosphino) ferrocene

exc. Excess TDDFT time dependent density functional theory

eq equivalent ThO T rifluoromethanesulfonic anhydride ESI electrospray ionization TFSI bis (trifluoromethylsulfonyl) imide Et ethyl TGA thermogravimetric analysis FD field desorption THF tetrahydrofuran

h hour (s) TMS trimethylsilyl

 Hex hexyl tolu toluene

 HOMO highest occupied molecular TRPL time-resolved photoluminescence orbital

 HR MS high-resolution mass Ts toluenesulfonyl

 spectrometry

HT FS I bis (trifluoromethane) sulfonimide Ts ₂ 0 p-toluenesulfonic anhydride IR infrared SuFEx sulfur (VI) fluoride exchange cat. Catalytically UV ultraviolet

 LU MO lowest unoccupied molecular Vis Visible

 orbital

 MALDI matrix assisted laser desorption PTCDI perylenetetracarboxylic acid diimide ionization

Claims

claims

1. compound according to formula I,

characterized in that

- The substituents X are independently selected from the list comprising triflate (-OSO2CF ₃ ), nonaflate (-OSO2C4F ₉ ), tosylate

 (-OSO2-C6H4-CH3), phenylsulfonate

 (-OSO2-C6H5), mesylate (CH3SO2), fluorosulfonate

(-OSO ₂ F), OSO ₂ R ² , wherein the radicals R ²

are independently selected from the list comprising C _n F _{n +2} , C _n H _{n +2} , aryl, substituted aryl, pentafluorophenyl, para-nitrophenyl, and wherein the formula index n can assume the values 1 to 8;

- The structural segments Y are independently N or CR ¹ , wherein the radicals R ^{1 are} independently selected from the list comprising H, alkyl, iso-alkyl, cycloalkyl, cyclo-heteroalkyl, alkenyl, alkynyl, aryl, heteroaryl;

 the formula index m has one of the values 0, 1, 2 or 3.

2. A process for the preparation of the compound according to claim 1, comprising the following, partly optional, steps:

a) i) Reductive aromatization of a starting material according to formula II,

wherein the structural segments Y are independently N or NH or NR1 or CHR ¹ or CR ¹ 2,

wherein the radicals R ^{1 are} independently selected from the list comprising H, alkyl, iso-alkyl, cycloalkyl, cyclo-heteroalkyl, alkenyl, alkynyl, aryl, heteroaryl, and wherein the formula index m is one of the values 0, 1, 2 or 3 has, or

 at least one tautomeric form of the educt according to formula II, if at least one of them exists,

 by reaction with reducing transition metals or alkali metals or alkaline earth metals or alkali metal analogs

 from the list comprising Zn, Mg, Li, Na, K, CeK, where a salt-like compound according to formula III,

 is obtained, wherein M is independently selected from the list comprising Zn, Mg, Li, Na, K according to the choice of the reducing transition metal or alkali metal or alkaline earth metal or

 Alkali metal analogues, and p corresponds to the numerical value of the valence of the metal M,

such as

ii) in situ conversion of the salt-like compound from step i) into the

corresponding tetrakis (R'3SiO) compound according to formula I, wherein Y and m have the meaning corresponding to the selected educt and X is OSiR'3, wherein R 'is independently selected from the list comprising H, n-alkyl, sec-alkyl, tert-alkyl, aryl, by reaction with a Silylating agent R'3Si-halogen,

 selected from the list comprising trimethylsilyl chloride,

 Triisopropylsilyl chloride, tert-butyldimethylsilyl chloride, chlorodimethylsilane Me2SiHCl, chlorodimethylphenylsilane;

 b) either

 iii) conversion of those obtained in stage a), substep ii)

 Tetrakis (R'3SiO-) compound in the corresponding tetrasubstituted

A compound according to formula I, wherein Y and m have the meaning corresponding to the selected educt,

 by reaction with an organometallic

 A compound selected from the group consisting of butyllithium, methyllitium, propyllithium, ethyllithium, phenyllithium and

 iv) subsequent in situ reaction with an acid anhydride or

 Acid halide, wherein the corresponding acid corresponding to the acid anhydride or acid halide is an acid selected from the list comprising trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, toluenesulfonic acid, phenylsulfonic acid,

Methylsulfonic acid, fluorosulfonic acid;

 or

 Reaction of the salt-like compound according to formula III obtained in step a), substep i), where Y and m have the meaning corresponding to the chosen educt, directly with one of the in step b),

 Partial step iv), provided acid anhydrides or acid halides, wherein also the tetrasubstituted compound according to formula I is obtained in which Y and m have the meaning of the selected starting material.

3. The method according to claim 2, characterized in that at step b) is followed by a further step c), comprising a conversion of in

Step b) obtained tetrasubstituierten compound according to formula I, in which Y and m have the meaning of the selected starting material, wherein step c) comprises at least one reaction, by the at least one of the four Substituents of the tetrasubstituted compound is chemically altered or substituted, independently selected from the list comprising the reactions nucleophilic substitution of the activated aromatic by O-nucleophiles or N-nucleophiles or S-nucleophiles or C-nucleophiles or hydride nucleophiles or halogenated nucleophiles or pseudo-substituted halogen nucleophiles; CC cross-coupling reactions comprising the Suzuki-Miyaura coupling, the

 Sonogashira reaction, the Heck reaction, the Negishi reaction, the Kumada coupling; Borylation (Miyaura Borylation); Amination (Buchwald-Hartwig amination); Aryloxylation.

4. Use of compounds according to claim 1 as starting materials for the preparation of compounds of formula I,

 wherein the groups Y, X and X 'are the specified independently selected groups selected from the lists of groups Y, X and X', comprising

Y = N, CR ¹ , where R ^{1 is} selected from the list comprising alkyl, alkenyl,

Alkynyl, heteroaryl;

X = OSO ² R ² , where R ^{2 is} selected from the list comprising C _n F _{n +} 2,

C _n H _{n +} 2, aryl, substituted aryl, para-toluyl, pentafluorophenyl, para-nitrophenyl;

- X '= F, Cl, Br, I, CN, N _3, NCO, NCS, N0 _2, NH _2, N (alkyl) _2, N (alkylene),

NH (alkyl), N (aryl) ₂ , N (arylene), NH (aryl), N (SiMe ₃ ) ₂ , O (alkyl), O (aryl), SH, S (alkyl), S (aryl), S (SiMe ₃ ), aryl, heteroaryl, 1-alkynyl, vinyl, acetyl, acyl, allyl, substituted allyl radicals;

and the formula index m has one of the values 0, 1, 2 or 3.

5. 1, 3,8,10-tetrasubstituted 2,9-diazadibenzoperylenes and / or 1, 3,8,10-tetrasubstituted 2,9-diorganodibenzoperylenes of formula A,

characterized in that the substituents are independently selected from the list comprising triflate (-OSO ₂ CF ₃ ), nonaflate (-

OSO ₂ C ₄ F ₉ ), tosylate (-OSO ₂ -C ₆ H ₄ -CH ₃ or -OTs, p-toluenesulfonate),

Phenyl sulfonate (-OSO ₂ -C ₆ H ₅ ), mesylate (methylsulfonate: CH ₃ SO ₂ - or -OMs), fluorosulfonate (-OSO ₂ F).

6. A process for the preparation of 1, 3, 8,10-tetrasubstituierten

 2.9-Diazadibenzoperylenes or the 1,3,8,10-tetrasubstituted

 2.9-Diorganodibenzoperylenes according to claim 3, comprising the following, partly optional, steps:

 a) i) Reductive aromatization of perylenetetracarboximides or in 1, 3, 8, 10-position oxo-substituted 2,9-dimethyl-dibenzo [cd, lm] perylenes by reaction with alkali metals or alkali metal analogues selected from the list comprising Li, Na , K, CeK,

 whereby salt-like compounds are obtained, as well

 ii) in situ conversion of the salt-like compounds from step i) into the corresponding tetrakis (trimethylsiloxy compounds by reaction with a methylsilylating agent or silylating agent selected from the list comprising trimethylsilyl chloride, triisopropylsilyl chloride,

 tert-butyldimethylsilyl chloride, chlorodimethylsilane Me2SiHCl,

 chlorodimethylphenylsilane;

 b) either

 iii) conversion of those obtained in stage a), substep ii)

 Tetrakis (trimethylsiloxy compounds in the 1, 3, 8,10-tetrasubstituierten

2.9-Diazadibenzoperylenes or the 1,3,8,10-tetrasubstituted ones

2.9-Diorganodibenzoperylenes by reaction with organometallic Compounds selected from the list comprising butyllithium,

 Methyllitium, Propyllithium, Ethyllitium and

 iv) subsequent in situ reaction with an acid anhydride or

 Acid halide, wherein the respective acid corresponding to the acid anhydride or acid halide is an acid selected from the list comprising trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, toluenesulfonic acid, methylsulfonic acid, fluorosulfonic acid;

 or

 Reaction of the salt-like compounds obtained in step a), partial step i), directly with one of the acid anhydrides or acid halides provided in step b), step iv).

7. Use of the 1, 3,8,10-tetrasubstituted 2,9-diazadibenzoperylenes and / or the 1, 3,8,10-tetrasubstituted 2,9-diorganodibenzoperylenes of the formula A,

 as starting materials for the preparation of further 1, 3,8,10-tetrasubstituierter

 2.9-Diazadibenzoperylenes and / or 1, 3,8,10-tetrasubstituted

 2.9-Diorganodibenzoperylenes according to formula B,

 wherein the groups Y, X and X 'are the specified independently selected groups selected from the lists of groups Y, X and X', comprising

Y = N, CR ¹ , where R ^{1 is} selected from the list comprising alkyl, alkenyl, Alkynyl, heteroaryl;

X = OSO ² R ² , where R ^{2 is} selected from the list comprising C _n F _{n +} 2,

C _n H _{n +} 2, aryl, substituted aryl, para-toluyl, pentafluorophenyl, para-nitrophenyl

- X '= F, Cl, Br, I, CN, N _3, NCO, NCS, N0 _2, NH _2, N (alkyl) _2, N (alkylene),

NH (alkyl), N (aryl) ₂ , N (arylene), NH (aryl), N (SiMe3) 2, O (alkyl), O (aryl), SH, S (alkyl), S (aryl), S (SiMe3), aryl, heteroaryl, 1-alkynyl, vinyl, acetyl, acyl, allyl, substituted allyl radicals.

8. A preparation comprising at least one compound according to one of

 Claims 1 or 5 or at least one compound prepared according to

 Claim 3, the at least one of the properties of electrically conductive, semiconducting, electron-conducting, hole-conducting, electrically insulating, photoconductive

 or light emitting, wherein as a preparation both simple

 physical material mixtures as well as polymer composites, copolymers, compounded polymers and the like are to be regarded.

9. A preparation comprising at least one compound according to one of

 Claims 1 or 5, or prepared according to claim 3, and an organic solvent or solvent mixture.

10. Use of a compound according to any one of claims 1 or 5 or a preparation according to any one of claims 7 or 8 or a compound prepared according to claim 3, as a charge transport material, semiconductor material, electrically conductive material, photoconductive or light-emitting material optical, electro-optical, electronic, electroluminescent or photoluminescent devices or devices.

1 1. A component or device comprising at least one compound according to any one of claims 1 or 5 or a preparation according to any one of claims 8 or 9 or a compound prepared according to claim 3, wherein said component or device is selected from the list comprising organic Field effect transistors (OFET), thin film transistors (TFT), Integrated Circuits (IC), Logic Circuits, Logic Devices, Capacitors, Radio Frequency Identification (RFID) Chips, Organic Light Emitting Diodes (OLEDs), Organic Light Emitting Transistors (OILs), Flat Panel Monitors,

Liquid crystal screens, backlights of

Liquid crystal displays, organic photovoltaic (OPV), organic

Solar cells, photodiodes, laser diodes, photoconductors, organic photoconductors, electrophotographic components, electrophotographic recording components, organic storage devices, sensor components, sensors,

 Charge injection layers, charge transport layers or intermediate layers in polymer light-emitting diodes (PLED), Schottky diodes, leveling layers, antistatic coatings and films, polymer electrolyte membranes (PEM), conductive substrates, conductive structures, electrode materials in batteries, sensors and electrolyzers, leveling layers, biosensors, biochips, security markings, Safety devices, and components or

Devices for the detection and / or differentiation of DNA or

RNA sequences.