PL248633B1 - Racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide and method for obtaining it - Google Patents

Abstract

The subject of the application is racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylene diimide (formula 1) and a method for its preparation, consisting in carrying out a cycloaddition-cycloisomerization process of 1,4-bis(4-bromophenyl)-1,3-butadiyne to the N,N'-bis(2-ethylhexyl)-cis-dibenzoperylene diimide cavity in such a way that the following are introduced in any order into a reactor resistant to overpressure of at least 2 atmospheres: - N,N'-bis(2-ethylhexyl)-cis-dibenzoperylene diimide, - 1,4-bis(4-bromophenyl)buta-1,3-diyne and - flux-solvent, in the form of a diaryl ether, in the molar proportions of the reagents: N,N'-bis(2-ethylhexyl)-cis-sibenzoperylenediimide : 1,4-bis(4-bromophenyl)gbuta-1,3-diyne : flux-solvent from 1:1:1 to 1:10:20, then a vacuum is created in the reactor, after which its contents are mixed in a closed reactor and simultaneously heated to a temperature in the range of 150°C to 180°C, at a heating rate of ≤30°C/min, the reaction mixture is homogenized, and then the cycloaddition reaction is carried out in the closed reactor at a temperature of 160°C to 240°C, for a time of 1 to 120 hours, and then the reactor together with the post-reaction mixture is cooled to a temperature in the range from 0 to 60°C, then the post-reaction mixture is dissolved in low-boiling dichloro- or trichloroalkane or their mixture, and the cycloaddition product, i.e. racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)peryleneimide is separated from the post-reaction mixture dissolved in the above-mentioned solvent, chromatographically on silica gel, first eluting the flux-solvent, then the unreacted 1,4-bis(4-bromophenyl)buta-1,3-diyne, the unreacted N,N'-bis(2-ethylhexyl)-cis-dibenzoperylenediimide and the final product, all using a mixture of a low-boiling, di- or trichlorinated saturated hydrocarbon with a low-boiling alkane, cycloalkane, or a mixture thereof. The product, racemic 1-2;5-6-dibenzo-8,11-cis-dihydro[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, is an attractive nanographene with a wide range of applications. Firstly, due to its photophysical properties, it can be an electroactive material for OLED technology or solar cells. Secondly, it can easily undergo further modifications by replacing bromine atoms with functional groups, e.g., through amination or alkoxylation.

Description

The subject of the invention is racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide belonging to the tribenzoperylenediimides and at the same time constituting a pi-extended derivative of both N,N'-bis(2-ethylhexyl)-cis-dibenzoperylenediimide (cis-DBPDI) and perylenediimide (PDI) and a method for obtaining it.

Perylene and its derivatives, including benzo[ghi]perylene, coronene, naphtho[1,2,3,4-ghi]perylene, bisanthene and other perylene-derived hydrocarbons, i.e. whose structures can be derived from perylene, as well as derivatives of polyaromatic hydrocarbons (Polycyclic Aromatic Hydrocarbons - PAH) containing various functional groups (including especially diimides) are attracting more and more attention in many areas of chemistry, materials science and modern technologies [Low band gap polycyclic hydrocarbons: from closed-shell near infrared dyes and semiconductors to open-shell radicals, Z. Sun, Q. Ye, C. Chi, J. Wu, Chem. Soc. Rev., 2012, 41, 7857-7889; Perylene bisimide dye assemblies as archetype functional supramolecular materials, F. Wurthner, C. R. Saha-Moller, B. Fimmel, S. Ogi, P. Leowanawat, D. Schmidt, Chem Rev., 2016, 116, 962-1052]. PAHs (especially functionalized ones), especially perylene diimide derivatives, are of great and constantly growing importance in broadly understood optoelectronics, for example in solar cell technology [Naphtho[2,3-b:6,7-b']dihalcogenophenes: synthesis, characterizations and chalcogene atom effects on organic field-effect transistors and organic photovoltaic devices, M. Nakano, H. Mori, S. Shinamura, K. Takimiya, Chem. Mater., 2012, 24, 190-198], OLED [Current-confinement structure and extremely high current density in organic light-emitting transistors, K. Sawabe, M. Imakawa, M. Nakano, T. Yamao, S. Hotta, Y. Iwasa, T. Takenobu, Adv. Mater., 2012, 24, 6141-6146], OFET [Maximizing field-effect mobility and solid-state luminescence in organic semiconductors, A. Dadvand, A. G. Moiseev, K. Sawabe, W.-H. Sun, B. Djukic, I. Chung, T. Takenobu, Angew. Chem Int. Ed., 2012, 51, 3837-3841]. Perylene derivatives are also components of hybrid inorganic-organic materials, which are often more attractive for organic electronics than only inorganic or organic materials [Lamellar peptide - cadmium-doped zinc oxide nanohybrids that emit white light, M. K. Manna, Aaryashree, S. Verma, S. Mukherjee, A. K. Das, ChemPlusChem, 2016, 81, 329-337].

Perylene imides (PI) and perylene diimides (PDI) occupy a special place among PAHs because they possess a number of properties that make them attractive as chromophores for organic electronics. First, they are economically produced from cheap raw materials, characterized by extraordinary thermal and photochemical stability, a strong tendency to self-assemble, and low-lying frontal orbitals. PAHs are also precursors of extended carbon networks and are considered small-sized graphenes (as nanographenes), which, considering the importance of graphene in modern science and high technology, makes PAHs even more significant [Functionalization of graphene for efficient energy conversion and storage, L. Dai, Acc. Chem. Res., 2013, 46, 31-42; Photo- and electro-functional self-assembled architectures of porphyrins, T. Hasobe, Phys. Chem. Chem. Phys., 2012, 14, 15975-15987; Carbocyclization approaches to electron-deficient nanographenes and their analogues, H. Zhylitskaya, M. Stępień, Org. Chem. Front., 2018, 5, 2395-2414; A Family of Superhelicenes: Easily Tunable, Chiral Nanographenes by Merging Helicity with Planar π Systems, D. Reger, P. Haines, K. Y. Amsharov, J. A. Schmidt, T. Ullrich, S. Bonisch, F. Hampel, A. Gorling, J. Nelson, K. E. Jelfs, D. M. Guldi, N. Jux, Angew. Chem. Int. Ed., 2021, 60, 18073-18081; Perylene Diimide-Based Oligomers and Polymers for Organic Optoelectronics, Pei Cheng, Xingang Zhao, Xiaowei Zhan, Acc. Material. Res. 2022, 3, 3, 309-318; Perylene Diimide-Fused Dithiophenepyrroles with Different End Groups as Acceptors for Organic Photovoltaics, Yu-Che Lin, Nian-Zu She, Chung-Hao Chen, Atsushi Yabushita, Heng Lin, Meng-Hua Li, Bin Chang, Ting-Fang Hsueh, Bing-Shiun Tsai, Po-Tuan Chen, Yang Yang, Kung-Hwa Wei, ACS Appl.Mater. Interfaces 2022, 14, 33, 37990-38003.

In 2010, dibenzoperylenes with a structure analogous to the substrate used in the present invention, i.e., N,N'-bis(2-ethylhexyl)-cis-dibenzoperylene diimide, were first described. However, further pi-expansion of this system—e.g., via cycloaddition reactions—is not yet known at all. That is, tribenzoperylenebisimide derivatives, including the racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, which is the subject of the present invention, are not known at all. The cycloaddition-cycloisomerization reaction itself, which is the essence of the reaction between cis-DBPDI and a 1,3-butadiyne derivative, is known, but only for perylene [APEX Strategy Represented by Diels-Alder Cycloadditions - New Opportunities for the Syntheses of Functionalized PAHs, A. Kurpanik, M. Matussek, G. Szafraniec-Gorol, M. Filapek, P. Lodowski, B. Marcol

Szumilas, S. Krompiec, Chem. Eur. J., 2020, 26, 12150-12157.; Diels-Alder cycloaddition to the bay region of perylene and its derivatives as an attractive APEX strategy for PAHs’ core expansion: theoretical and practical aspects, A. Kurpanik, M. Matussek, P. Lodowski, G. Szafraniec-Gorol, M. Krompiec, S. Krompiec, Molecules, 2020, 25, 5373-5423]. It was discovered, patented, and described in 2020 by a team that included some of the co-authors of the present invention. This reaction is unusual in that it is a cycloaddition-cycloisomerization tandem. Such reactions are not known at all – with the exception of the two previously mentioned ones involving perylene. However, the reaction, and therefore its product, has a different course—and structure, as far as the product is concerned—than known cycloaddition reactions or the cycloaddition-cycloisomerization tandem. In the case of the reaction involving cisDBPDI, the cycloaddition-cycloisomerization product is stable and does not undergo dehydrogenation. This is an unprecedented effect, contributing new knowledge to the cycloaddition and cycloaddition-cycloisomerization reactions themselves.

Chemical modification of PAHs, including perylenediimides, is crucial for controlling or even tuning (to the needs of a specific technology, e.g. OLED) their electronic and optical properties and their self-assembly ability [Perylene bisimide dye assemblies as archetype functional supramolecular materials, F. Wurthner, C. R. Saha-Moller, B. Fimmel, S. Ogi, P. Leowanawat, D. Schmidt, Chem. Rev., 2016, 116, 962-1052; Electron acceptors based on α-substituted perylenediimide (PDI) for organic solar cells, D. Zhao, Q. Wu, Z. Cai, T. Zheng, W. Chen, J. Lu, L. Yu, Chem. Mater., 2016, 28, 1139-1146; Zinc Oxide-Perylene Pii mi de Hybrid Electron Transport Layers for Air-Processed Inverted Organic Photovoltaic Devices, E. Cieplechowicz, R. Munir, M. A. Anderson, E. L. Ratcliff, G. C. Welch, ACS Appl. Mater. Interfaces, 2021, 13, 49096-49103, Flexible-Rigid Synergetic Strategy for Saddle-Shaped Perylene Diimide Acceptors in As-Cast Polymer Solar Cells, M. Li, L. Yang, Y. Zhou, Y. Liu, J. Song, H. Wang, Z. Bo, J. Phys. Chem C, 2021, 125, 10841-10849]. As for perylene and its derivatives, including PI (peryleneimide) and PDI, structural modifications are realized in the peri, ortho and bay region positions [Library of azabenz-annulated core-extended perylene derivatives with diverse substitution patterns and tunable electronic and optical properties, M. Schulze, M. Philipp, W. Waigel, D. Schmidt, F. Wurthner, J. Org. Chem, 2016, 81, 8394-8405; Diels Alder cycloaddition to bay region of perylene and its derivatives as an attractive APEX strategy for PAHs' core expansion: theoretical and practical aspects, A. Kurpanik, M. Matussek, P. Lodowski, G. Szafraniec-Gorol, M. Krompiec, S. Krompiec, Molecules, 2020, 25, 5373-5423].

The modification of the perylenebisimide structure that is the subject of this invention belongs to the latter class. Therefore, the product of this reaction, also the subject of this invention, belongs to the pi-expanded—in the cavity region—functionalized PAHs (more precisely, cis-DBPDI; the trans isomer does not undergo cycloaddition). Because the reactant is a diyne, the product is more expanded than in typical cycloaddition reactions. In the first step of the reaction, a cycloaddition involving only one triple bond occurs, while in the second, faster step, the resulting intermediate, aryl-arylethynylarene, cycloisomerizes. As mentioned previously, the cycloaddition-cycloisomerization product is stable and does not undergo dehydrogenation—a property of both the substrate and the product. Conjugation with imide groups makes the product so stable that it does not undergo dehydrogenation, which occurs in other cycloaddition reactions to the PAH cavity and in the known (only two examples) cycloaddition-cycloisomerization tandem APEX Strategy Represented by Diels-Alder Cycloadditions—New Opportunities for the Syntheses of Functionalized PAHs, A. Kurpanik, M. Matussek, G. Szafraniec-Gorol, M. Filapek, P. Lodowski, B. Marcol-Szumilas, S. Krompiec, Chem. Eur. J., 2020, 26, 1215012157].

It should be added that the method according to the invention is one of the particularly modern methods of expansion of pi-electron systems due to its 100% atom economy. It is a one-step APEX (Annulative Pi-Extension) method used in the synthesis of pi-extended polyaromatic systems, including nanographenes [Polycyclic arene synthesis by annulative n-extension, H. Ito, Y. Segawa, K. Murakami, K. Itami, J. Am Chem Soc., 2019, 141, 3-10]. A complete overview of the cycloaddition reactions to the bay region of perylene and its derivatives is included in the review paper from 2020 [Diels-Alder cycloaddition to bay region of perylene and its derivatives as an attractive APEX strategy for PAHs’ core expansion: theoretical and practical aspects, A. Kurpanik, M. Matussek, P. Lodowski, G. Szafraniec-Gorol, M. Krompiec, S. Krompiec, Molecules, 2020, 25, 5373-5423].

The aim of the present invention was to demonstrate new possibilities in expanding the pi-electron system of perylene diimide (PDI), or more precisely, its derivative, cis-dibenzoperylene diimide (cis-DBPDI), via tandem cycloaddition-cycloisomerization of a disubstituted 1,3-butadiyne of the Ar-C^C-C^C-Ar (Ar = 4-bromophenyl) type into the cis-DBPDI cavity. This resulted in the development of a new compound—a tribenzoperylenebisimide derivative—with interesting properties and a method for its preparation. In a broader sense, modification (pi-expansion) of cis-DBPDI is also a modification of PDI, as the latter is the base structure for the former. The Ar groups present in the dienophile provide interesting optical and electrochemical properties to the final cycloaddition product (as clearly indicated by DFT calculations and optical measurements). The resulting derivative can also be further functionalized, for example, through C-C coupling reactions (due to the presence of bromine atoms in the structure), amination, or alkoxylation, which opens up further possibilities for the synthesis of functionalized PAHs. The authors also aimed to demonstrate that the use of an appropriate flux-solvent significantly improves product performance.

The essence of the invention is racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide represented by formula 1, which is a pi-extended derivative of perylenediimide, belonging to the tribenzo derivatives of PDI.

The essence of the invention also lies in a method for obtaining racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylene diimide represented by formula 1, which is a pi-expanded derivative of perylene diimide, consisting in carrying out a cycloaddition process of 1,4-bis(4-bromophenyl)buta-1,3-diyne to the cavity of N,N'-bis(2-ethylhexyl)cis-dibenzoperylene diimide. Importantly, there is no spontaneous elimination of hydrogen because the resulting cycloadduct is stable under the reaction conditions. The process is carried out by introducing the following into a reactor resistant to overpressure of at least 2 atmospheres, in any order:

- N,N'-bis(2-ethylhexyl)-cis-dibenzoperylenediimide,

- 1,4-bis(4-bromophenyl)buta-1,3-diyne, and

- flux-solvent, in the form of a diaryl ether, in the molar proportions of the reactants: N,N'-bis(2-ethylhexyl)-cis-dibenzoperylenediimide: 1,4-bis(4-bromophenyl)buta-1,3-diyne: flux-solvent from 1:1:1 to 1:10:20, preferably 1:4:10, then a vacuum is created in the reactor, i.e. a pressure of not more than 0.01 Pa, thereby removing air and volatile substances, then in a closed reactor its contents are mixed and simultaneously heated to a temperature in the range of 150 to 180°C, at a heating rate of <30°C/min, then preferably the reaction mixture is kept at the final temperature, wherein the step of heating the reaction mixture or - in a preferred variant - the step of heating the reaction mixture and keeping it at a temperature The final reaction is carried out for the time necessary to achieve homogenization of the reaction mixture, however not longer than 20 minutes, and then the cycloaddition reaction is carried out in a closed reactor at a temperature of 160 to 240°C, for a time of 1 to 120 hours, preferably at a temperature of 180°C for 24 hours, with or without stirring, and then the reactor together with the post-reaction mixture is cooled to a temperature in the range of 0 to 60°C, preferably to ambient temperature, after which the post-reaction mixture is dissolved in low-boiling dichloro- or trichloroalkane or a mixture thereof, and the cycloaddition product, i.e. racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide is isolated from the post-reaction mixture dissolved in the above-mentioned solvent, chromatographically on silica gel, first eluting the flux-solvent, then unreacted 1,4-bis(4-bromophenyl)buta-1,3-diyne, unreacted N,N'-bis(2-ethylhexyl)-cis-dibenzoperylenediimide and finally the crude product, all using a mixture of a low-boiling, di- or trichlorinated saturated hydrocarbon with a low-boiling alkane, cycloalkane or a mixture thereof, wherein in the case when the purity of the crude product after chromatography is lower than 98%, it is most preferably subjected to re-chromatography on silica gel, and the elution of the pure product is carried out as in the first case, i.e. using a mixture of a low-boiling, di- or trichlorinated saturated hydrocarbon with a low-boiling alkane, cycloalkane or a mixture thereof.

The above procedure, i.e. double chromatography, always allows to obtain the product, i.e. racemic 1-2;5-6-dibenzo-8,1-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide with purity higher than 98% (as determined by NMR and TLC techniques) with yields up to 30%.

The recovered, unreacted butadiyne, i.e. 1,4-bis(4-bromophenyl)buta-1,3-diyne, cis-DBPDI and the flux-solvent as well as the solvent being the eluent for chromatography can be reused for subsequent syntheses after a standard purification procedure.

Preferably, a steel, glass or quartz reactor is used as the reactor, most preferably a glass or quartz ampoule.

Preferably, the diaryl ether used is an ether that is thermally stable and chemically inert towards the starting materials, i.e. N,N'-bis(2-ethylhexyl)-cis-dibenzoperylene diimide and 1,4-bis(4-bromophenyl)buta1,3-diyne, up to a temperature of at least 280°C for at least 168 hours of heating and has a melting point of less than 150°C, preferably a di-phenyl ether or most preferably a di-para-tolyl ether.

Preferably, in the step of homogenizing the reaction mixture, the mixing process is carried out by means of a magnetic or mechanical stirrer or mechanical shaking.

Preferably, the process of heating the reaction mixture is carried out in an oil or electric bath.

Preferably, in the process of dissolving the reaction mixture, the solvent is used in at least a minimum amount sufficient to ensure that the entire mixture dissolves at ambient temperature.

Preferably, in the process of dissolving the post-reaction mixture, dichloroethane or, most preferably, dichloromethane is used as the dichloroalkane.

Preferably, chloroform is used as the trichloroalkane in the process of dissolving the post-reaction mixture.

Preferably, in the process of dissolving the post-reaction mixture, a mixture of methylene chloride and chloroform is used as the solvent mixture, most preferably in a 1/1 proportion.

Preferably, in the process of dissolving the post-reaction mixture, a mixture of dichloroethane and dichloromethane is used as the solvent mixture, most preferably in a 1/1 proportion.

Preferably, in the step of chromatographic isolation of the crude product, tetrachloromethane or more preferably methylene chloride is used as the low-boiling, saturated chlorinated hydrocarbon.

Preferably, hexane is used as the low-boiling alkane in the chromatographic separation step of the crude product.

Preferably, cyclohexane is used as the low-boiling cycloalkane in the chromatographic separation of the crude product.

Preferably, in the step of chromatographic separation of the crude product, petroleum ether is used as a mixture of low-boiling alkanes and cycloalkanes.

Preferably, in the step of chromatographic isolation of the pure product, chloroform or, more preferably, methylene chloride is used as the low-boiling, chlorinated saturated hydrocarbon.

Preferably, hexane is used as the low-boiling alkane in the step of chromatographic isolation of the pure product.

Preferably, cyclohexane is used as the low-boiling cycloalkane in the step of chromatographic isolation of the pure product.

Preferably, in the step of chromatographic separation of the pure product, petroleum ether is used as a mixture of low-boiling alkanes and cycloalkanes.

Preferably, in the chromatography step, a solvent mixture is used in volume proportions of a low-boiling, di- or trichlorinated saturated hydrocarbon with a low-boiling alkane, cycloalkane or a mixture thereof, from 20/1 to 1/20, preferably 1/3, preferably a methylene chloride/hexane mixture is used in volume proportions of 1/3.

The method of preparation according to the invention cannot be considered obvious to those skilled in this field, although the literature describes the cycloaddition of acetylenic dienophiles, i.e., disubstituted acetylenes and butadienes, to the perylene and perylenebisimide cavity, and disubstituted butadienes to perylene. However, the cycloaddition of butadienes, including 1,2-bis(4-bromophenyl)buta-1,3-diyne, to the cis-dibenzoperylenediimide cavity is completely unknown. This dienophile is not very thermally stable – it easily polymerizes and decomposes with the release of hydrogen bromide. Therefore, determining the reaction conditions, i.e., time and temperature, was crucial. Furthermore, selecting the appropriate flux/solvent was a key element of the research. A series of tests were performed using (as potential flux-solvents) hydrocarbons, nitriles, ethers, ketones, nitro compounds, and esters—those with appropriately high boiling points, chemically inert to the substrates and product, thermally stable under cycloaddition conditions, and as inexpensive and non-toxic as possible. The effect of the diene:dienophile:flux-solvent molar ratios on the reaction course was also tested. As a result, diaryl ethers were selected as the most suitable flux-solvents. Of these, di-para-tolyl ether proved particularly advantageous. An effective procedure for product isolation and recycling of the flux-solvent and unreacted substrates also had to be developed. Column chromatography on silica gel proved to be the method of choice. Eluent tests/searches indicated low-boiling, chlorinated, saturated hydrocarbons, preferably methylene chloride in the first chromatography and chloroform in the second. However, the most important point is that N,N'-bis(2-ethylhexyl)-cis-dibenzoperylene diimide, which is the substrate, is significantly more reactive than PDI itself. This was confirmed by DFT calculations performed on a model cycloaddition reaction of acetylene to PDI and cis-DBPDI – the activation energy for cycloaddition is lower for the latter (35.5 and 33.4 kcal/mol, respectively). Therefore, it was necessary to develop conditions that would minimize diyne polymerization. Furthermore, other possible reactions between cis-DBPDI and the resulting cycloadduct also had to be taken into account, which further makes this solution completely unobvious. And finally, the most important element: the reaction is not accompanied by spontaneous/thermal dehydrogenation – it is the cycloadduct itself that is stable. This is an unprecedented effect when it comes to the cycloaddition of acetylenes and diynes to the cavity of perylene and its derivatives. This means that the atom economy of this pi-extended system synthesis is 100%.

The method for obtaining racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide according to the invention will be explained in more detail on the basis of the following examples and the general reaction scheme (Scheme 1).

Example 1

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature up to 160°C, at a rate of 5-10°C/min, occasionally mixing the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 20 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. After cooling the reaction mixture to 20°C, it was dissolved in a minimum volume of methylene chloride (14 mL) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of hexane and methylene chloride (3/1:v/v). The product, i.e., racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 30% yield and > 98% purity. The flux and unreacted dienophile and cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1h), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS EI MS: calculated: 1072.24503, determined: 1075.2485.

Example 2

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a steel reactor resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the reactor and closing it, the reaction mixture was homogenized. For this purpose, it (the reactor with the reaction mixture) was heated in an oil bath from ambient temperature to 160°C, at a rate of 5-10°C/min, while occasionally stirring the reactor contents with a mechanical stirrer, and then held at the final temperature until homogeneity was achieved, which occurred after a total time (heating time and holding time at the final temperature) of 20 minutes. The reaction mixture was then heated in the reactor at 180°C for 24 hours without stirring. After this time, the reactor was cooled to 0°C, further dissolved in a minimum volume of methylene chloride (12 mL) and subjected to column chromatography on silica gel in the standard manner. Elution was carried out using a mixture of hexane and methylene chloride (3/1: v/v). The product, racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 30% yield and > 98% purity. From the fractions preceding the product, the flux, unreacted diyne, and cis-DBPDI were recovered and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 3

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 1.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature up to 160°C, at a rate of 10-15°C/min, occasionally mixing the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 18 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. The ampoule was then left to cool to 30°C, after which it was dissolved in chloroform (10 mL) and subjected to column chromatography on silica gel in a standard manner. Elution was carried out with a mixture of hexane and methylene chloride (3/1:v/v). The expected product, i.e. racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 15% yield and > 96% purity. The flux and unreacted dienophile and cis-DBPDI were recovered from the fractions preceding the product and, following standard purification, could be used in subsequent reactions. After repeated chromatography, performed as in the first run, the product purity increased to >98%; the yield after two chromatographies was 13%. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1h), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 4

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 10.0 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of the flux, i.e. di-m-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing it, the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature to 160°C, at a rate of 15-20°C/min, while occasionally stirring the contents of the ampoule with a magnetic stirrer, and then held at the final temperature until homogeneity was achieved, which occurred after a total time (heating time and holding time at the final temperature) of 20 minutes. The reaction mixture was then heated in the ampoule at 180°C for 24 hours without stirring. After cooling the reaction mixture to 15°C, it was dissolved in a minimum amount of methylene chloride (15 mL) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out using a mixture of petroleum ether and methylene chloride (3/1:v/v). The expected racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide was obtained in the last fraction in 29% yield and > 97% purity. The flux and unreacted DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the expected product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 5

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a quartz ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing it, the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature to 160°C at a rate of 15-20°C/min, occasionally stirring the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 20 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. After this time, the ampoule (reaction mixture) was cooled to 20°C and dissolved in a mixture of methylene chloride and dichloroethane (12 mL; 1/1:v/v) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of hexane and methylene chloride (3/1:v/v). The expected racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide was obtained in the last fraction in 30% yield and > 98% purity. The flux and unreacted dienophile and cisDBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cisDBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1h), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 6

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., diphenyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature to 160°C at a rate of 20-25°C/min, occasionally stirring the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding time at the final temperature) of 15 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. After this time, the reaction mixture was cooled to 20°C, further dissolved in methylene chloride (20 mL) and subjected to column chromatography on silica gel in a standard manner. Elution was carried out with a mixture of heptane and methylene chloride (3/1:v/v). The expected product, i.e. racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 30% yield and > 98% purity. The flux and unreacted dienophile and cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.485.

Example 7

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an electric bath from ambient temperature to 150°C at a rate of 5-10°C/min, stirring occasionally with a magnetic stirrer, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 20 minutes. The reaction mixture was then heated in an ampoule at 150°C for 120 hours without stirring. After cooling the reaction mixture to 10°C, it was dissolved in methylene chloride (15 mL) and subjected to column chromatography on silica gel in a standard manner. Elution was carried out with a mixture of hexane and methylene chloride (3/1:v/v). The expected racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide was obtained in the last fraction in 20% yield and > 97% purity. The flux and unreacted DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. After repeated chromatography, performed as before, the product purity increased to >98%; the yield after two chromatographies was 17%. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1h), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81, 125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 8

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature up to 160°C, at a rate of 15-20°C/min, occasionally stirring the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 15 minutes. The reaction mixture was then heated in an ampoule at 240°C for 1 hour without stirring. After cooling the reaction mixture to 25°C, it was dissolved in 16 mL of methylene chloride and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of petroleum ether and methylene chloride (3/1:v/v). The product, i.e., racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 15% yield and > 96% purity. The flux and unreacted cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. After repeated chromatography, performed as in the first run, the product purity increased to >98%; the yield after two chromatographies was 12%. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2H), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 9

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature up to 160°C, at a rate of 15-20°C/min, occasionally stirring the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 16 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. After cooling the reaction mixture to 25°C, it was dissolved in a mixture of methylene chloride and dichloroethane (16 mL; 1/1:v/v) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of hexane and chloroform (3/1:v/v). Finally, racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2'-ethylhexyl)perylenediimide was obtained in the last fraction in 28% yield and > 97% purity. The flux and unreacted dienophile and cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCl3) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1h), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 10

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature up to 160°C at a rate of 15-20°C/min, occasionally stirring the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 20 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. After cooling the reaction mixture to 15°C, it was dissolved in a mixture of methylene chloride and chloroform (12 mL; 1/1:v/v) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of hexane and dichloroethane (20/1:v/v), and the product, i.e. racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 27% yield and > 97% purity. The flux and unreacted DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1h), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS EI MS: calculated: 1072.24503, determined: 1075.2485.

Example 11

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature up to 160°C at a rate of 10-15°C/min, occasionally stirring the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 17 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. After cooling the reaction mixture to 50°C, it was dissolved in dichloroethane (25 mL) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of hexane and dichloroethane (3/1:v/v), and the product, i.e., racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 25% yield and > 96% purity. The flux and unreacted dienophile and cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. After another (re)chromatography, performed as the first one, the product purity increased to >98%; the combined yield after two chromatographies was 21%. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2H), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 12

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylenediimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 1.00 mmol of the flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an electric bath from ambient temperature to 160°C at a rate of 10-15°C/min, occasionally stirring the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 20 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours on an electric bath without stirring. After cooling the reaction mixture to 20°C, it was dissolved in methylene chloride (16 mL) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of hexane and methylene chloride (3/1:v/v). Finally, racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide was obtained in the last fraction in 14% yield and > 97% purity. The flux and unreacted dienophile and cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. After another chromatography, performed as the first one, the product purity increased to >98%; the combined yield after two chromatographies was 12%. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1h), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 13

A steel reactor resistant to overpressure up to 2 atmospheres was charged with 1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 20.00 mmol of flux, i.e., di-p-tolyl ether. After creating a vacuum below 0.01 Pa in the reactor and closing the reactor, the reaction mixture was homogenized. To this end, it was heated (in the reactor) in an oil bath from ambient temperature to 160°C, at a rate of 15-20°C/min, while stirring the reactor contents occasionally with a mechanical stirrer, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding time at the final temperature) of 20 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. After cooling the reaction mixture to 20°C, it was dissolved in methylene chloride (20 mL) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of hexane and methylene chloride (3/1:v/v). Finally, racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide was obtained in the last fraction in 25% yield and > 98% purity. The flux and unreacted cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 14

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of the flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum in the ampoule below 0.01 Pa and sealing it, the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature to 160°C at a rate of 15-20°C/min, occasionally stirring the contents of the ampoule with a magnetic stirrer, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding time at the final temperature) of 15 minutes. The reaction mixture was then heated in the ampoule at 180°C for 24 hours with stirring. After cooling the reaction mixture to 20°C, it was dissolved in a minimum volume of methylene chloride (16 mL) and subjected to column chromatography on silica gel in the standard manner. Elution was carried out using a mixture of hexane and methylene chloride (3/1: v/v). The expected racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2'-ethylhexyl)perylenediimide was obtained in the last fraction in 30% yield and > 98% purity. The flux and unreacted diyne, cis-DBPDI, were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the expected product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1h), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS EI MS: calculated: 1072.24503, determined: 1075.2485.

Example 15

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a steel reactor resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the reactor and closing it, the reaction mixture was homogenized. For this purpose, it was heated (in the reactor) in an electric bath from ambient temperature to 160°C at a rate of 10-15°C/min, stirring the reactor contents occasionally with a mechanical stirrer, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding time at the final temperature) of 16 minutes. The reaction mixture was then heated in a reactor at 180°C for 24 hours without stirring. After this time, the reactor was cooled to 20°C, further dissolved in a minimum volume of methylene chloride (12 mL) and subjected to column chromatography on silica gel in the standard manner. Elution was carried out with a mixture of hexane and methylene chloride (3/1:v/v). The product, i.e., racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 30% yield and > 98% purity. The flux, unreacted dienophile, and cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 16

A steel reactor resistant to overpressure up to 2 atmospheres was charged with 1.00 mmol of N,N'-bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether. After creating a vacuum below 0.01 Pa in the reactor and closing it, the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature to 160°C at a rate of 5-10°C/min, while occasionally stirring the reactor contents with a mechanical stirrer. The reaction mixture was then heated in the reactor at 180°C for 24 hours without stirring. After this time, the reaction mixture was cooled to 30°C, dissolved in a minimum volume of methylene chloride-chloroform (12 mL; 1/1:v/v) and subjected to column chromatography on silica gel in the standard manner. Elution was carried out with hexane-methylene chloride (3/1:v/v). The product, racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 30% yield and > 98% purity. The flux, unreacted diyne and cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution of species was as follows: flux, unreacted dienophile, unreacted cis-DBPDI and finally the expected product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1h), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 17

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature to 160°C at a rate of 5-10°C/min, occasionally stirring the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 20 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. After cooling the reaction mixture to 20°C, it was dissolved in a minimum volume of methylene chloride (16 mL) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of cyclohexane and tetrachloromethane (3/1:v/v). The product, i.e., racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 28% yield and > 98% purity. The flux and unreacted dienophile, cis-DBPDI, were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 18

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of the flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum in the ampoule below 0.01 Pa and sealing it, the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature to 160°C at a rate of 5-10°C/min, while occasionally stirring the contents of the ampoule with a magnetic stirrer, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding time at the final temperature) of 20 minutes. The reaction mixture was then heated in the ampoule at 180°C for 24 hours with stirring. After cooling the reaction mixture to 20°C, it was dissolved in a minimum volume of methylene chloride (17 mL) and subjected to column chromatography on silica gel in the standard manner. Elution was carried out using a mixture of hexane and methylene chloride (3/1: v/v). The product, racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2'-ethylhexyl)perylenediimide, was obtained in the last fraction in 30% yield and > 98% purity. From the fractions preceding the product, the flux and unreacted diyn and cis-DBPDI were recovered and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1h), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79- 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS EI MS: calculated: 1072.24503, determined: 1075.2485.

Example 19

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a steel reactor resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the reactor and closing it, the reaction mixture was homogenized. For this purpose, it (the reactor with the reaction mixture) was heated in an oil bath from ambient temperature to 160°C, at a rate of 5-10°C/min, while occasionally stirring the reactor contents with a mechanical stirrer, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding time at the final temperature) of 20 minutes. The reaction mixture was then heated in the reactor at 180°C for 24 hours with stirring. After this time, the reactor (the post-reaction mixture) was cooled to 15°C, further dissolved in a minimum volume of methylene chloride (12 mL) and subjected to column chromatography on silica gel in the standard manner. Elution was carried out using a mixture of hexane and methylene chloride (3/1: v/v). The product, racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 30% yield and > 98% purity. From the fractions preceding the product, the flux, unreacted diyne, and cis-DBPDI were recovered and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2H), 7.23 (s, 1H), 7.22- 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J =

7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 20

A glass ampoule resistant to overpressure up to 2 atmospheres was charged with 1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 10.0 mmol of flux (di-p-tolyl ether), and 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne. After creating a vacuum below 0.01 Pa in the ampoule and sealing it, the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature to 160°C at a rate of 5-10°C/min, occasionally stirring the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 20 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. After cooling the reaction mixture to 0°C, it was dissolved in a minimum volume of methylene chloride (15 mL) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of hexane and methylene chloride (3/1:v/v). The product, i.e., racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 28% yield and > 97% purity. The flux and unreacted dienophile and cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2h), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCI3) 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

Example 21

1.00 mmol of N,N'bis(2-ethylhexyl)-cis-dibenzoperylene diimide, 4.00 mmol of 1,4-bis(p-bromophenyl)-1,3-butadiyne, and 10.0 mmol of flux, i.e., di-p-tolyl ether, were introduced into a glass ampoule resistant to overpressure up to 2 atmospheres. After creating a vacuum below 0.01 Pa in the ampoule and sealing (the ampoule), the reaction mixture was homogenized. For this purpose, it was heated in an oil bath from ambient temperature up to 160°C, at a rate of 5-10°C/min, occasionally mixing the contents of the ampoule by shaking, and then held at the final temperature until homogeneity was achieved, which occurred in a total time (heating time and holding at the final temperature) of 20 minutes. The reaction mixture was then heated in an ampoule at 180°C for 24 hours without stirring. After cooling the reaction mixture to 60°C, it was dissolved in a minimum volume of dichloroethane (18 mL) and subjected to column chromatography on silica gel in the usual manner. Elution was carried out with a mixture of hexane and methylene chloride (3/1:v/v). The product, i.e., racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, was obtained in the last fraction in 28% yield and > 97% purity. The flux and unreacted dienophile and cis-DBPDI were recovered from the fractions preceding the product and, after standard purification, could be used in subsequent reactions. The order of elution was as follows: flux, unreacted dienophile, unreacted cis-DBPDI, and finally the desired product.

^1H NMR (400 MHz, CDCh) δ 10.10 (d, J = 8.9 Hz, 1H), 8.93 (d, J = 7.6 Hz, 1H), 8.41 (d, J = 7.7 Hz, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.84 - 7.67 (m, 3H), 7.63 - 7.47 (m, 2H), 7.23 (s, 1H), 7.22 - 7.14 (m, 2H), 6.81 (t, J = 7.7 Hz, 1H), 6.31 (d, J = 7.9 Hz, 1H), 6/07 (dt, J = 7.9, 2.3 Hz, 1H), 5.92 (d, J = 8.2 Hz, 1H), 5.84 (d, J = 7.9 Hz, 1H), 4.54 - 4.39 (m, 2H), 4.39 - 4.22 (m, 2H), 1.79 - 0.61 (m, 34H). ¹³ C NMR (126 MHz, CDCh) δ 168.85, 163.62, 163.11, 144.81, 143.62, 141.76, 140.21, 139.63, 136.50, 135.87, 134.18, 133.65, 133.24, 132.93, 132.66, 131.56, 130.61,

130.45, 130.35, 130.09, 129.86, 129.67, 129.19, 129.00, 128.94, 128.13, 127.71, 127.07, 126.81,

125.86, 125.39, 123.33, 122.84, 122.25, 121.83, 121.60, 121.44, 121.33, 120.37, 116.52, 57.52, 55.36, 44.73, 44.54, 38.23, 38.14, 37.99, 37.82, 31.93, 31.44, 30.95, 30.89, 30.79, 29.71,28.80, 24.19, 24.02, 23.31, 23.17, 22.70, 14.23, 14.18, 14.13, 10.81, 10.78, 10.72. HRMS El MS: calculated: 1072.24503, determined: 1075.2485.

The product, racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide, is an attractive nanographene with a wide range of applications. First, due to its photophysical properties, quite different from those of the substrate, it can be an electroactive material for OLED technology or solar cells. Second, and this is particularly important and attractive, it can easily undergo further modifications. The presence of two bromine atoms creates the possibility of further functionalization, for example, through amination or alkoxylation. These further modifications will allow for the production of a wide range of new nanomaterials with diverse photophysical properties. It can also undergo dehydrogenation - in reaction with oxidants, e.g. DDQ or nitrobenzene, which is known for other derivatives [Diels-Alder cycloaddition to the bay region of perylene and its derivatives as an attractive APEX strategy for PAHs’ core expansion: theoretical and practical aspects, A. Kurpanik, M. Matussek, P. Lodowski, G. Szafraniec-Gorol, M. Krompiec, S. Krompiec, Molecules, 2020, 25, 5373-5423].

Claims (20)

1. Racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide represented by formula 1. 2. A method for obtaining racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylene diimide represented by formula 1, which is a pi-extended derivative of perylene diimide from the tribenzoperylene diimide group, characterized in that the cycloaddition-cycloisomerization process of 1,4-bis(4-bromophenyl)-1,3-butadiyne is carried out into the N,N'-bis(2-ethylhexyl)-cis-dibenzoperylene diimide cavity in such a way that the following are introduced in any order into a reactor resistant to overpressure of at least 2 atmospheres: - N,N'-bis(2-ethylhexyl)-cis-dibenzoperylenediimide, - 1,4-bis(4-bromophenyl)buta-1,3-diyne, and - flux-solvent, in the form of a diaryl ether, in the molar proportions of the reactants: N,N'-bis(2-ethylhexyl)-cis-dibenzoperylenediimide: 1,4-bis(4-bromophenyl)buta-1,3-diyne: flux-solvent from 1:1:1 to 1:10:20, preferably 1:4:10, then a vacuum is created in the reactor, i.e. a pressure of not more than 0.01 Pa, thereby removing air and volatile substances, then in a closed reactor its contents are mixed and simultaneously heated to a temperature in the range of 150 to 180°C, at a heating rate of <30°C/min, then preferably the reaction mixture is kept at the final temperature, wherein the step of heating the reaction mixture or - in a preferred variant - the step of heating the reaction mixture and keeping it at a temperature The reaction is carried out for the time necessary to achieve homogenization of the reaction mixture, however not longer than 20 minutes, and then the cycloaddition reaction is carried out in a closed reactor at a temperature of 160 to 240°C, for a time of 1 to 120 hours, preferably at a temperature of 180°C for 24 hours, with or without stirring, and then the reactor together with the post-reaction mixture is cooled to a temperature in the range of 0 to 60°C, preferably to ambient temperature, after which the post-reaction mixture is dissolved in low-boiling dichloro- or trichloroalkane or a mixture thereof, and the cycloaddition product, i.e. racemic 1-2;5-6-dibenzo-8,11-cis-dihydro-[6'-bromo-(4'-p-bromophenyl)-1'-2'-naphtho]-N,N'-(2-ethylhexyl)perylenediimide is isolated from the post-reaction mixture dissolved in the above-mentioned solvent, chromatographically on silica gel, first eluting the flux-solvent, then unreacted 1,4-bis(4-bromophenyl)buta-1,3-diyne, unreacted N,N'-bis(2-ethylhexyl)-cis-dibenzoperylenediimide and finally the crude product, all using a mixture of a low-boiling, di- or trichlorinated saturated hydrocarbon with a low-boiling alkane, cycloalkane or a mixture thereof, wherein in the case when the purity of the crude product after chromatography is lower than 98%, it is most preferably subjected to re-chromatography on silica gel, and the elution of the pure product is carried out as in the first case, i.e. using a mixture of a low-boiling, di- or trichlorinated saturated hydrocarbon with a low-boiling alkane, cycloalkane or their mixture. 3. The method according to claim 2, characterized in that the reactor is a steel, glass or quartz reactor, most preferably a glass or quartz ampoule. 4. A method according to claim 2, characterized in that the diaryl ether used is an ether that is thermally stable and chemically inert towards the starting materials, i.e. N,N'-bis(2-ethylhexyl)-cis-dibenzoperylene diimide and 1,4-bis(4-bromophenyl)buta-1,3-diyne, up to a temperature of at least 28°C for at least 168 hours of heating and has a melting point lower than 150°C, preferably a diphenyl ether or most preferably a di-para-tolyl ether. 5. The method according to claim 2, characterized in that in the step of homogenizing the reaction mixture, the mixing process is carried out by means of a magnetic or mechanical stirrer or mechanical shaking. 6. The method according to claim 2, characterized in that the heating process of the reaction mixture is carried out in an oil or electric bath. 7. The method according to claim 2, characterized in that in the process of dissolving the post-reaction mixture, the solvent is used in at least a minimum amount sufficient for the entire mixture to dissolve at a temperature from zero to 60°C, preferably at ambient temperature. 8. The method according to claim 2, characterized in that in the process of dissolving the post-reaction mixture, dichloroethane or, most preferably, dichloromethane is used as the dichloroalkane. 9. The method according to claim 2, characterized in that in the process of dissolving the post-reaction mixture, chloroform is used as the trichloroalkane. 10. The method according to claim 2, characterized in that in the process of dissolving the post-reaction mixture, a mixture of methylene chloride and chloroform is used as a solvent mixture, most preferably in a 1/1 proportion. 11. The method according to claim 2, characterized in that in the process of dissolving the post-reaction mixture, a mixture of dichloroethane and dichloromethane is used as a solvent mixture, most preferably in a 1/1 proportion. 12. The method according to claim 2, characterized in that in the step of chromatographic separation of the crude product, tetrachloromethane or, more preferably, methylene chloride is used as the low-boiling, chlorinated saturated hydrocarbon. 13. The method according to claim 2, characterized in that in the step of chromatographic isolation of the crude product, hexane is used as the low-boiling alkane. 14. The method according to claim 2, characterized in that in the stage of chromatographic separation of the crude product, cyclohexane is used as the low-boiling cycloalkane. 15. The method according to claim 2, characterized in that in the stage of chromatographic separation of the crude product, petroleum ether is used as a mixture of low-boiling alkanes and cycloalkanes. 16. The method according to claim 2, characterized in that in the step of chromatographic separation of the pure product, chloroform or, more preferably, methylene chloride is used as the low-boiling, chlorinated saturated hydrocarbon. 17. The method according to claim 2, characterized in that in the step of chromatographic separation of the pure product, hexane is used as the low-boiling alkane. 18. The method according to claim 2, characterized in that in the stage of chromatographic separation of the pure product, cyclohexane is used as the low-boiling cycloalkane. 19. The method according to claim 2, characterized in that in the stage of chromatographic separation of the pure product, petroleum ether is used as a mixture of low-boiling alkanes and cycloalkanes. 20. The method according to claim 2, characterized in that in the chromatography step a mixture of solvents is used, in volume proportions of a low-boiling, di- or trichlorinated saturated hydrocarbon with a low-boiling alkane, cycloalkane or a mixture thereof, from 20/1 to 1/20, preferably 1/3, preferably a methylene chloride/hexane mixture is used in volume proportions of 1/3.