Perylene boron-nitrogen doped fused ring aromatic hydrocarbon, synthesis method and application thereof

Abstract

The application discloses a boron-nitrogen doped condensed aromatic hydrocarbon of perylene, and a general structure of the boron-nitrogen doped condensed aromatic hydrocarbon is as follows: The application is a boron-nitrogen doped condensed aromatic hydrocarbon, and the introduction of a boron-nitrogen unit effectively improves P-pi conjugation in a perylene molecule, so that the delocalization of pi electrons is increased. Absorption spectra of most materials show a long absorption band at 300-500 nm, a strong absorption band extending from the ultraviolet region to the visible region, and a maximum absorption peak at 390-465 nm. The boron-nitrogen doped perylene derivative materials have a very short excited state lifetime, that is, tau is about 0.5. The properties described in the application are all conducive to the use of the boron-nitrogen doped perylene derivative in luminescent materials.

Description

Technical Field

[0001] This invention belongs to the field of boron-nitrogen doped large conjugated molecular technology, and in particular to a perylene-based boron-nitrogen doped fused-ring aromatic hydrocarbon, its synthesis method, and its application. Background Technology

[0002] In recent years, the widespread application of polycyclic aromatic hydrocarbons (PAHs) containing BN units in fields such as biology and medicine, organic chemistry, and materials chemistry has attracted great interest. In the periodic table, the boron atom has three valence electrons in its outermost shell, the carbon atom has four, and the nitrogen atom has five. Therefore, both the BN and CC units have stable octet structures, and they are isoelectronic and isostructural. Although replacing the CC unit with a BN unit in a PAH has little impact on its structure, the presence of a BN unit in a PAH exhibits unique properties completely different from its all-carbon structure. This is because the empty p orbital of the BN unit can form p-π conjugation with the π orbital of the PAH, thereby effectively regulating the orbital energy levels, band gap, and photoelectric properties, making it promising for various optoelectronic applications.

[0003] The first boron-acid heteroaromatic compounds were reported in 1958 by the Dewar group (Dewar, MJS; Kubba, VP; Pettit, RJ Chem. Soc. 1958, 3073). They synthesized 5,6-boronazphenanthrene using o-vinylaniline and boron trichloride in excess aluminum trichloride via the Friedel-Crafts reaction. In 1959, the Dewar group (Dewar, MJS; Dietz, RJ Chem. Soc. 1959, 2728) prepared boronazenanes via an electrophilic cyclization reaction using o-vinylaniline and boron trichloride. In 1963, the White group (MJS Dewar, VP Kubba, R. Pettit, J. Chem. Soc. 1958, 3073–3076) synthesized 1-H-2-phenyl-1,2-azaboron, opening a new chapter in the field of boron-acid compounds. However, due to limitations in experimental conditions, the field of boron-nitrogen synthesis experienced a brief period of stagnation until 2000, when Ashe's group (J. Ashe, Fang. Org. Lett. 2000, 2089-2091.) synthesized boron-nitrogen-doped compounds using a ring-closing metathesis oxidation method. In 2010, Perepichka's group (Lepeltier, M.; Lukoyanova, O.; Jacobson, A.; Jeeva, S.; Perepichka, DFChem. Commun. 2010, 46, 7007.) first achieved an aromatic electrophilic substitution reaction on a thiophene ring, synthesizing a class of boron-nitrogen compounds fused with a thiophene ring. In 2011, Nakamura's group (Hatakeyama, T.; Hashimoto, S.; Seki, S.; Nakamura, MJAm. Chem. Soc. 2011, 133, 18614.) successfully synthesized boron-aza-tetraphenyl fused-ring molecules by simultaneously carrying out aromatic electrophilic substitution reactions on three aromatic rings under Lewis acid catalysis. In 2015, Liu's group (Brown, AN; Li, B.; Liu, SYJAm. Chem. Soc. 2015, 137, 8932.) also synthesized boron-aza-anthracene and diboron-aza-anthracene using the same method.

[0004] The insertion of BN units into classic polycyclic aromatic hydrocarbons (PAHs) perylene has also received considerable attention in recent years. In 2019, the Wagner group (T. Kaehler.; M. Wagne. Angew. Chem. Int. Ed. 2019, 58, 11379-11384.) efficiently prepared blue luminescent boronazine using a gold-catalyzed Wacker-type addition reaction between NH and C≡C bonds, providing a new approach for the synthesis of boronazine. In 2021, the Pei group (PF. Zhang.; J. Pei. Chem. Int. Ed. 2021, 60, 23313–23319.) started from known BN-embedded naphthalene precursors and synthesized boronazine with different BN orientations using synthetic methods commonly used in PAH chemistry, providing an efficient synthetic strategy for larger BN-embedded PAHs based on existing BN-containing molecules. In the same year, Fang's research group (Fang.Molecules 2021,26,7148.) synthesized two perylene matrixes, one doped with BN and the other doped with BN, starting from halo-BN naphthalene derivatives, thus providing a new and valuable platform for the application of novel organic materials.

[0005] In recent years, research on boron-nitrogen-doped polycyclic aromatic hydrocarbons (PAHs) has made great progress. Researchers have synthesized various forms of boron-nitrogen-doped PAHs using different methods and found that boron-nitrogen doping can effectively modulate the photoelectric physical properties of aromatic systems. The success of boron-nitrogen-doped PAHs has attracted research interest, and their potential applications in electronic devices have been extensively studied. However, their potential applications in luminescent materials have not yet been widely developed.

[0006] In summary, boronazine and its derivatives can be used to synthesize a variety of novel conjugated structures by modifying the conjugated framework. The unique photoelectric properties and supramolecular characteristics of these structures have significant application value in organic optoelectronic materials, energy storage, field emission, and other fields. They also have potential applications in organic semiconductor devices (such as organic field-effect transistors (OFETs)). S Organic photovoltaic devices (OPV) S ) and organic light-emitting diodes (OLEDs) S The practical applications of this technology have also attracted attention, and due to its unique properties, it is of great significance for the future application of solar energy and the development of fields such as photocatalysis.

[0007] At the same time, there is an urgent shortage of deep blue light materials and main body materials.

[0008] A search revealed no patent publications related to this invention's patent application. Summary of the Invention

[0009] The purpose of this invention is to overcome the shortcomings of the prior art and provide a perylene boron nitrogen-doped fused-ring aromatic hydrocarbon, its synthesis method, and its application.

[0010] The technical solution adopted by this invention to solve its technical problem is:

[0011] A perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbon, wherein the general structural formula of the boron-nitrogen-doped fused-ring aromatic hydrocarbon is as follows:

[0012]

[0013] Where R1, R2, R 3, R5,R 6, R7, R8, R9, R 10 It is independent, being a substituted or unsubstituted aryl, heteroaryl, alkene, or alkyne, or being hydrogen, alkyl, aldehyde, or ketone, or being hydrogen or a single-substituted halogen atom X: F, Cl, Br, I; wherein R4 and R9 are independent, being substituted or unsubstituted hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, ether, heterocyclic, phenyl, aryloxy, halogen, cyano, benzene ring, thiophene ring, furan ring, pyrrole ring, pyridine ring, benzothiophene, benzofuran, benzopyrrole, benzopyridine, naphthyl ring, anthracene ring, phenaene, carbazolyl, pyrazinyl, triphenyl, tetraphenyl, pyrene, Linear or angular pentadienylbenzene, hexabenzene, indene, fluorene.

[0014] Furthermore, the boron-nitrogen-doped fused-ring aromatic hydrocarbon has a structure selected from one of BN1 to BN54:

[0015]

[0016]

[0017]

[0018] The synthetic route for perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons described above is as follows:

[0019]

[0020] Furthermore, the method includes the following steps:

[0021] Synthesis of Compound 3: Compound 1 (containing R group molecules), Compound 2 (containing R group molecules), and an organic base with pH 8.0-8.5 were weighed into a round-bottom flask with a ratio of Compound 1:Compound 2 of equiv:equiv of 1.0:1.0 under nitrogen protection. After adding solvent to the system, the reaction system was stirred at -78°C for 1-1.5 hours. Then the cold bath was removed, and the product temperature was allowed to return to room temperature. The product was extracted with an organic solvent and a saturated sodium bicarbonate aqueous solution. The obtained organic phase was dried over anhydrous magnesium sulfate and filtered. After removing the solvent under reduced pressure, Compound 3 was purified by column chromatography.

[0022] Synthesis of Compound 4: Compound 3 and N,O-bistrimethylsilylacetamide (BSA) were added to a pressure-resistant sealed tube. The ratio of Compound 3 to N,O-bistrimethylsilylacetamide was equiv:equiv 1.0:5.0 under nitrogen protection. After adding solvent to the system, the mixture was heated to 100°C and stirred in an oil bath for 12 hours. After the reaction was completed, the product was allowed to cool to room temperature, filtered, and washed with cold methanol to obtain Compound 4.

[0023] Synthesis of compound 5: Compound 4 and strong reducing agent sodium dithionite (Na2S2O4) were added to a flask. The ratio of compound 4 to sodium dithionite was equiv:equiv 1.0:10.0. Nitrogen protection was applied. Then, solvent was added, and the mixture was heated to 80°C and stirred for 12 hours. After the reaction was completed, the product was allowed to cool to room temperature, filtered, and washed with cold water to obtain compound 5.

[0024] Synthesis of Compound 6: Compound 5, di-tert-butyl dicarbonate ((Boc)₂O), and 4-dimethylaminopyridine (DMAP) catalyst were added to a flask. The ratio of compound 5: di-tert-butyl dicarbonate: 4-dimethylaminopyridine was 1.0:3.0:0.7 (equiv:equiv:equiv). Nitrogen protection was maintained. After adding solvent to the system, the reaction was carried out in the presence of an organic base at pH 8.0-8.5 and stirred at room temperature for 8 hours. After the reaction was completed, the organic phase was extracted with organic solvent and saturated brine. The organic phase was dried with anhydrous magnesium sulfate, filtered, and purified by column chromatography after removing the solvent under reduced pressure to obtain compound 6.

[0025] Synthesis of Compound 7: Compound 6 and tributylvinyltin were added to a flask with a ratio of 1.0:3.0 (equiv:equiv) under nitrogen protection. After adding solvent to the system, the reaction was carried out under palladium catalyst and heated to 110°C with stirring for 12 h. After the reaction was completed, the product was cooled to room temperature and extracted with organic solvent and saturated brine. The obtained organic phase was dried with anhydrous magnesium sulfate, filtered, and purified by column chromatography after removing the solvent under reduced pressure to obtain Compound 7.

[0026] Synthesis of Compound 8: Compound 7 and boron trichloride (BCl3) were added to a flask with a ratio of 1.0:4.0 (equiv:equiv) under nitrogen protection. After adding solvent, the mixture was heated to 110°C and stirred for 12 h in the presence of an organic base at pH 8.0-8.5. After the reaction was complete, the product was allowed to cool to room temperature, and the corresponding Grignard reagent was added. The mixture was then reacted at room temperature for 12 h. After the reaction was complete, the product was extracted with organic solvent and saturated brine. The resulting organic phase was dried with anhydrous magnesium sulfate, filtered, and purified by column chromatography after removing the solvent under reduced pressure to obtain Compound 8.

[0027] Furthermore, the method also includes the following synthetic route:

[0028]

[0029] Furthermore, the method includes the following steps:

[0030] Synthesis of compound 9: Compound 8 was added to a round-bottom flask under nitrogen protection; the reactants were placed at 0°C, and after adding solvent, Br2 was slowly added to the system. The ratio of compound 8 to Br2 was equiv:equiv of 1.0:0.55. The mixture was stirred for 1 hour. After the product cooled to room temperature, it was extracted with an organic solvent and a saturated sodium carbonate aqueous solution. The resulting organic phase was dried with anhydrous magnesium sulfate, filtered, and after removing the solvent under reduced pressure, compound 9 was obtained by column chromatography.

[0031] Synthesis of Compound 10: The corresponding boric acid of Compound 9 was added to a round-bottom flask, with the ratio of Compound 9 to boric acid being 1.0:1.5 under nitrogen protection. After adding solvent to the system, the mixture was heated to 100°C and stirred for 12 hours in the presence of a palladium catalyst and an inorganic base at pH 8.0-8.5. After the reaction was completed, the product was allowed to cool to room temperature, filtered, and washed with cold methanol to obtain Compound 10.

[0032] Further, the solvent includes one of toluene, chlorobenzene, cyclopentylmethyl ether, tetrahydrofuran, water, dichloromethane, ethanol, ethyl acetate, and diethyl ether; the organic base includes one of dimethylamine, pyridine, aniline, triethylamine, potassium tert-butoxide, and diisopropylethylamine; the inorganic base includes one of potassium carbonate, potassium hydroxide, and aluminum hydroxide; the palladium catalyst includes one of tetrakis(triphenylphosphine)palladium, 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride, and bis(dibenzylidene)acetone palladium; and the Grignard reagent includes one of magnesium methyl bromide, magnesium phenyl bromide, magnesium methyl bromide, and magnesium allyl bromide.

[0033] As mentioned above, perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons are used in optics and / or optoelectronics.

[0034] As described above, perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons are used as luminescent materials and / or host materials in the preparation of optical or optoelectronic devices.

[0035] Furthermore, the optical or optoelectronic device includes organic light-emitting diodes, organic field-effect transistors, and organic solar cells.

[0036] The advantages and positive effects of this invention are as follows:

[0037] 1. This invention relates to perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons. The introduction of boron-nitrogen units effectively improves the p-π conjugation within the perylene molecule, increasing the delocalization of π electrons. Furthermore, most of these materials exhibit a long absorption band in the 300-500 nm range, extending strongly from the ultraviolet to the visible light region, with a maximum absorption peak at 390-465 nm. Moreover, these boron-nitrogen perylene derivatives all possess very short excited-state lifetimes, i.e., τ is around 0.5. These properties described in this invention are advantageous for the application of these boron-nitrogen perylene derivatives in luminescent materials.

[0038] 2. This invention uses commercially available 1-bromo-2-nitrobenzene and 2-bromoaniline as raw materials, and through a series of coupling reactions, reduction reactions, and electrophilic borylation reactions, it can simply and rapidly synthesize borazine and its derivatives. Furthermore, the luminescent properties can be effectively adjusted by regulating the substituents on the boron. This invention features simple operation and mild reaction conditions.

[0039] 3. The blue organic light-emitting diode made from perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons as the light-emitting host described in this invention has an excellent low onset voltage of less than 6V and a maximum onset voltage of greater than 10V. 3 cd / m 2 The brightness of the light-emitting device demonstrates the potential application value of perylene boron-nitrogen-doped fused-ring aromatic hydrocarbons in organic electrochemistry.

[0040] 4. This invention expands upon a novel method for synthesizing boron-nitrogen-doped fused-ring aromatic hydrocarbons (FJHNCHes), and simultaneously provides luminescent materials based on this method using FJHNCHes containing a perylene matrix. These materials can be fluorescent, delayed-fluorescence, and / or phosphorescent emitters. The compounds of this invention have the following characteristics: First, boron-nitrogen-doped FJHNCHes and their derivatives can be rapidly synthesized using a series of simple methods under mild reaction conditions. Second, the emission bands of these perylene-based boron-nitrogen-doped FJHNCHes are located in the 300-500 nm range, and they exhibit a quantum yield of up to 91.81%. These properties are advantageous for the application of these boron-nitrogen-doped FJHNCHes in luminescent materials, greatly promoting the development of the blue light emission materials field. Attached Figure Description

[0041] Figure 1 This is the 1H NMR spectrum of compound 3 in this invention;

[0042] Figure 2 This is the 1H NMR spectrum of compound 4 in this invention;

[0043] Figure 3 This is the 1H NMR spectrum of compound 5 in this invention;

[0044] Figure 4 This is the 1H NMR spectrum of compound 6 in this invention;

[0045] Figure 5 This is the 1H NMR spectrum of compound 7 in this invention;

[0046] Figure 6 This is the 1H NMR spectrum of compound 8 in this invention;

[0047] Figure 7 This is the 1H NMR spectrum of compound 9 in this invention;

[0048] Figure 8 This is the 1H NMR spectrum of compound 10 in this invention;

[0049] Figure 9 This is the 1H NMR spectrum of compound 11 in this invention;

[0050] Figure 10 This is the 1H NMR spectrum of compound 12 in this invention;

[0051] Figure 11 This is the carbon NMR spectrum of compound 5 in this invention;

[0052] Figure 12 This is the carbon NMR spectrum of compound 6 in this invention;

[0053] Figure 13 This is the carbon NMR spectrum of compound 7 in this invention;

[0054] Figure 14 This is the carbon NMR spectrum of compound 8 in this invention;

[0055] Figure 15 This is the carbon NMR spectrum of compound 9 in this invention;

[0056] Figure 16 This is the carbon NMR spectrum of compound 11 in this invention;

[0057] Figure 17 The diagram shows the single-crystal structure of compound 8 in this invention; the left diagram is a front view of the single-crystal structure of compound 8, and the right diagram is a top view of the single-crystal structure of compound 8.

[0058] Figure 18 Compound 8 in this invention is at a concentration of 1×10⁻⁶. -5Absorption spectrum of M in dichloromethane solution;

[0059] Figure 19 Compound 8 in this invention is at a concentration of 1×10⁻⁶. -5 Emission spectrum of M in dichloromethane solution;

[0060] Figure 20 Compound 9 in this invention is at a concentration of 1×10⁻⁶. -5 Absorption spectrum of M in dichloromethane solution;

[0061] Figure 21 Compound 9 in this invention is at a concentration of 1×10⁻⁶. -5 Absorption spectrum of M in dichloromethane solution;

[0062] Figure 22 Compound 11 in this invention is at a concentration of 1×10⁻⁶. -5 Absorption spectrum of M in dichloromethane solution;

[0063] Figure 23 Compound 11 in this invention is at a concentration of 1×10⁻⁶. -5 Emission spectrum of M in dichloromethane solution;

[0064] Figure 24 The diagrams show the current density-voltage relationship and the brightness-voltage relationship of compound 8 in this invention.

[0065] Figure 25 The graphs show the current efficiency-current density relationship and the power efficiency-current density relationship for compound 8 in this invention.

[0066] Figure 26 This is a schematic diagram of the structure of the blue-emitting OLED device prepared in this invention. Detailed Implementation

[0067] The present invention will be further described below with reference to the embodiments. The following embodiments are descriptive and not limiting, and should not be used to limit the scope of protection of the present invention.

[0068] The various experimental operations involved in the specific embodiments are all conventional techniques in the field. For parts not specifically annotated in this document, those skilled in the art can refer to various commonly used reference books, scientific and technological documents or related instructions and manuals prior to the filing date of this invention to carry out the operations.

[0069] A perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbon, wherein the general structural formula of the boron-nitrogen-doped fused-ring aromatic hydrocarbon is as follows:

[0070]

[0071] Where R1, R2, R3, R5,R 6, R7, R8, R9, R 10 It is independent, being a substituted or unsubstituted aryl, heteroaryl, alkene, or alkyne, or being hydrogen, alkyl, aldehyde, or ketone, or being hydrogen or a single-substituted halogen atom X: F, Cl, Br, I; wherein R4 and R9 are independent, being substituted or unsubstituted hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, ether, heterocyclic, phenyl, aryloxy, halogen, cyano, benzene ring, thiophene ring, furan ring, pyrrole ring, pyridine ring, benzothiophene, benzofuran, benzopyrrole, benzopyridine, naphthyl ring, anthracene ring, phenaene, carbazolyl, pyrazinyl, triphenyl, tetraphenyl, pyrene, Linear or angular pentadienylbenzene, hexabenzene, indene, fluorene.

[0072] Preferably, the boron-nitrogen-doped fused-ring aromatic hydrocarbon has a structure selected from one of BN1 to BN54:

[0073]

[0074]

[0075]

[0076] The synthetic route for perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons described above is as follows:

[0077]

[0078] Preferably, the method includes the following steps:

[0079] Synthesis of Compound 3: Compound 1 (containing R group molecules), Compound 2 (containing R group molecules), and an organic base with pH 8.0-8.5 were weighed into a round-bottom flask with a ratio of Compound 1:Compound 2 of equiv:equiv of 1.0:1.0 under nitrogen protection. After adding solvent to the system, the reaction system was stirred at -78°C for 1-1.5 hours. Then the cold bath was removed, and the product temperature was allowed to return to room temperature. The product was extracted with an organic solvent and a saturated sodium bicarbonate aqueous solution. The obtained organic phase was dried over anhydrous magnesium sulfate and filtered. After removing the solvent under reduced pressure, Compound 3 was purified by column chromatography.

[0080] Synthesis of Compound 4: Compound 3 and N,O-bistrimethylsilylacetamide (BSA) were added to a pressure-resistant sealed tube. The ratio of Compound 3 to N,O-bistrimethylsilylacetamide was equiv:equiv 1.0:5.0 under nitrogen protection. After adding solvent to the system, the mixture was heated to 100°C and stirred in an oil bath for 12 hours. After the reaction was completed, the product was allowed to cool to room temperature, filtered, and washed with cold methanol to obtain Compound 4.

[0081] Synthesis of compound 5: Compound 4 and strong reducing agent sodium dithionite (Na2S2O4) were added to a flask. The ratio of compound 4 to sodium dithionite was equiv:equiv 1.0:10.0. Nitrogen protection was applied. Then, solvent was added, and the mixture was heated to 80°C and stirred for 12 hours. After the reaction was completed, the product was allowed to cool to room temperature, filtered, and washed with cold water to obtain compound 5.

[0082] Synthesis of Compound 6: Compound 5, di-tert-butyl dicarbonate ((Boc)₂O), and 4-dimethylaminopyridine (DMAP) catalyst were added to a flask. The ratio of compound 5: di-tert-butyl dicarbonate: 4-dimethylaminopyridine was 1.0:3.0:0.7 (equiv:equiv:equiv). Nitrogen protection was maintained. After adding solvent to the system, the reaction was carried out in the presence of an organic base at pH 8.0-8.5 and stirred at room temperature for 8 hours. After the reaction was completed, the organic phase was extracted with organic solvent and saturated brine. The organic phase was dried with anhydrous magnesium sulfate, filtered, and purified by column chromatography after removing the solvent under reduced pressure to obtain compound 6.

[0083] Synthesis of Compound 7: Compound 6 and tributylvinyltin were added to a flask with a ratio of 1.0:3.0 (equiv:equiv) under nitrogen protection. After adding solvent to the system, the reaction was carried out under palladium catalyst and heated to 110°C with stirring for 12 h. After the reaction was completed, the product was cooled to room temperature and extracted with organic solvent and saturated brine. The obtained organic phase was dried with anhydrous magnesium sulfate, filtered, and purified by column chromatography after removing the solvent under reduced pressure to obtain Compound 7.

[0084] Synthesis of Compound 8: Compound 7 and boron trichloride (BCl3) were added to a flask with a ratio of 1.0:4.0 (equiv:equiv) under nitrogen protection. After adding solvent, the mixture was heated to 110°C and stirred for 12 h in the presence of an organic base at pH 8.0-8.5. After the reaction was complete, the product was allowed to cool to room temperature, and the corresponding Grignard reagent was added. The mixture was then reacted at room temperature for 12 h. After the reaction was complete, the product was extracted with organic solvent and saturated brine. The resulting organic phase was dried with anhydrous magnesium sulfate, filtered, and purified by column chromatography after removing the solvent under reduced pressure to obtain Compound 8.

[0085] Preferably, the method further includes the following synthetic route:

[0086]

[0087] Preferably, the method includes the following steps:

[0088] Synthesis of compound 9: Compound 8 was added to a round-bottom flask under nitrogen protection; the reactants were placed at 0°C, and after adding solvent, Br2 was slowly added to the system. The ratio of compound 8 to Br2 was equiv:equiv of 1.0:0.55. The mixture was stirred for 1 hour. After the product cooled to room temperature, it was extracted with an organic solvent and a saturated sodium carbonate aqueous solution. The resulting organic phase was dried with anhydrous magnesium sulfate, filtered, and after removing the solvent under reduced pressure, compound 9 was obtained by column chromatography.

[0089] Synthesis of Compound 10: The corresponding boric acid of Compound 9 was added to a round-bottom flask, with the ratio of Compound 9 to boric acid being 1.0:1.5 under nitrogen protection. After adding solvent to the system, the mixture was heated to 100°C and stirred for 12 hours in the presence of a palladium catalyst and an inorganic base at pH 8.0-8.5. After the reaction was completed, the product was allowed to cool to room temperature, filtered, and washed with cold methanol to obtain Compound 10.

[0090] Preferably, the solvent includes one of toluene, chlorobenzene, cyclopentylmethyl ether, tetrahydrofuran, water, dichloromethane, ethanol, ethyl acetate, and diethyl ether; the organic base includes one of dimethylamine, pyridine, aniline, triethylamine, potassium tert-butoxide, and diisopropylethylamine; the inorganic base includes one of potassium carbonate, potassium hydroxide, and aluminum hydroxide; the palladium catalyst includes one of tetratetraphenylphosphine palladium, 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride, and bis(dibenzylacetone) palladium; and the Grignard reagent includes one of magnesium methyl bromide, magnesium phenyl bromide, magnesium methyl bromide, and magnesium allyl bromide.

[0091] As mentioned above, perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons are used in optics and / or optoelectronics.

[0092] As described above, perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons are used as luminescent materials and / or host materials in the preparation of optical or optoelectronic devices.

[0093] Preferably, the optical or optoelectronic device includes an organic light-emitting diode, an organic field-effect transistor, or an organic solar cell.

[0094] Specifically, the relevant preparation and testing methods are as follows:

[0095] The following examples are provided to provide those skilled in the art with a complete disclosure and description of how to manufacture and evaluate the compounds, compositions, articles, devices, and / or methods described in this invention, and these examples are intended to be illustrative of the present disclosure only and are not intended to limit the scope of the invention. Although efforts have been made to ensure the accuracy of numerical values ​​(e.g., amounts, temperatures, etc.), some errors and deviations should be taken into account. Unless otherwise stated, parts are by weight, temperatures are in °C or at ambient temperature, and pressures are at or near atmospheric pressure.

[0096] Various methods for preparing the disclosed compounds described in this invention are described in the embodiments. These methods are provided to illustrate various preparation methods, but this disclosure is not intended to limit it to any of the methods described in this invention. Therefore, those skilled in the art to which this disclosure pertains can readily modify the described methods or use different methods to prepare one or more of the disclosed compounds. The following methods are merely exemplary and do not limit the scope of this disclosure. Temperature, catalyst, concentration, reactant composition, and other process conditions can be varied, and those skilled in the art to which this disclosure pertains can readily select suitable reactants and conditions for the desired complexes.

[0097] Recorded at 400 MHz in CDCl3 or DMSO-d6 solution on a Varian Liquid State NMR instrument. 1 H-graph, recorded at 100 MHz 13 C10 NMR spectra, with chemical shifts referenced to the residual protiated solvent. If CDCl3 is used as the solvent, tetramethylsilane (δ = 0.00 ppm) is recorded as an internal standard. 1 1H NMR spectra; DMSO-d6 (δ = 77.00 ppm) was used as an internal standard for recording. 13 C10 NMR spectra. If H2O (δ = 3.33 ppm) is used as the solvent, the residual H2O (δ = 3.33 ppm) is used as the internal standard for recording. 1 1H NMR spectra; DMSO-d6 (δ = 39.52 ppm) was used as an internal standard for recording. 13 1H NMR spectra. Use the following abbreviations (or combinations thereof) to interpret the multiplicity of 1H NMR: s = singlet, d = doublet, t = triplet, q = tetrad, p = quintuplets, m = multiply, br = broad.

[0098] Those skilled in the art can use a variety of methods to prepare the compounds of the present invention, including but not limited to those methods listed in the examples provided herein.

[0099] This invention discloses a method for the overall synthesis of boron-nitrogen-doped polycyclic aromatic hydrocarbons, comprising the following synthetic route and steps:

[0100] Synthesis route:

[0101]

[0102] Examples of the above compounds are given below:

[0103] Example 1:

[0104] 1) Synthesis of Compound 3: Weigh potassium tert-butoxide (t-BuOK) (3.0 equiv, 22.1 nmol, 2.5 g) into a 500 mL round-bottom flask, purge three times, and protect under nitrogen. Add 20 mL of tetrahydrofuran (THF) solvent to the system using an injectable syringe, and then stir the reaction system at -78 °C for 15 min. After the potassium tert-butoxide has completely dissolved, slowly add a 5 mL solution of tetrahydrofuran (THF) containing 1.0 equiv, 7.4 nmol, 1.2 g of 2-bromoaniline and a 5 mL solution of tetrahydrofuran (THF) containing 1.0 equiv, 7.4 nmol, 1.5 g of 2-bromonitrobenzene using a syringe. Stir the mixture at this temperature for 1–1.5 hours (controlled by column chromatography). Then remove the cooling zone and pour in a saturated ammonium chloride (NH4Cl) solution (approximately 20 mL). Continue stirring at room temperature for 30 min. After the system was brought to room temperature, the solvent was suspended, water and ethyl acetate (EA) were added, and the mixture was extracted three times. The organic layers were combined and dried with anhydrous sodium sulfate (Na2SO4), and filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product, which was then separated by silica gel column chromatography (elution buffer: PE:EA = 20:1) to finally obtain compound 3 (956.2 mg, 36.7%) as a brick-red solid.

[0105] 1 H NMR (400MHz, CDCl3): δ12.52(s,1H,NH),7.68(d,J=8.0Hz,1H,Ar),7.34-7.39(m,3H,Ar),7.17(t,J=8.0Hz,2H,Ar),6.91(d,J=8.8Hz,1H,Ar).

[0106] Figure 1 This is the 1H NMR spectrum of compound 3 in this invention.

[0107] 2) Synthesis of Compound 4: Compound 3 (1.0 equiv, 0.9 nmol, 319.6 mg) was weighed into a 75 mL sealed tube. The system was transferred to a glove box, and acetonitrile (MeCN) (10 mL) was added to the system using a syringe. After compound 4 was completely dissolved, N,O-dimethylsilane (BSA) (5.0 equiv, 4.5 nmol, 1.2 mL) was added to the system, and the system was removed from the glove box. The system was then placed in an oil bath and slowly heated to 100 °C for 12 h. After the reaction was complete, the precipitate in the system was separated by filtration, washed with cold methanol, and dried under vacuum. Compound 4 (219.0 mg, yield 72.2%) was obtained as a yellow solid.

[0108] 1H NMR (400MHz, CDCl3): δ8.38 (dd, J1=8.8Hz, J2=1.2Hz, 2H, Ar), 8.24 (dd, J1=7.2Hz, J2=1.2Hz, 2H, Ar), δ7.76 (dd, J1=8.8Hz, J2=7.2Hz, 2H, Ar).

[0109] Figure 2 This is the 1H NMR spectrum of compound 4 in this invention.

[0110] 3) Synthesis of Compound 5: Compound 4 (1.0 equiv, 0.987 nmol, 331.6 mg) was weighed into a 250 mL round-bottom flask, and the mixture was purged three times under nitrogen protection. Ethanol (EtOH) (15 mL) was added to the system using a syringe. After the addition was complete, the reaction system was placed in an oil bath and slowly heated to 80 °C with stirring for 15 min. Then, a solution of sodium dithionite (Na₂S₂O₄) (10.0 equiv, 9.675 nmol, 1.7 g) in water (H₂O) (10 mL) was added using a syringe. The system was then slowly heated to 100 °C and stirred for 3 h. After the reaction was complete, the precipitate was separated by filtration, washed with cold water, and dried under vacuum. Compound 5 (248.0 mg, 74.3%) was obtained as a green solid.

[0111] 1 H NMR (400MHz, CDCl3): δ6.66 (d, J=8.0Hz, 2H, Ar), 6.33 (dd, J1=8.0Hz, J2=7.6Hz, 2H, Ar), 6.10 (d, J=7.6Hz, 2H, Ar), 5.33 (br, 2H, NH). 13 C NMR (101MHz, CDCl3): δ133.1,130.5,124.9,122.0,111.5,106.8.

[0112] Figure 3 This is the 1H NMR spectrum of compound 5 in this invention. Figure 11 This is the carbon NMR spectrum of compound 5 in this invention.

[0113] 4) Synthesis of Compound 6: Compound 5 (1.0 equiv, 4.21 nmol, 976.3 mg) and 4-dimethylaminopyridine (DMAP) (0.7 equiv, 2.95 nmol, 361.3 mg) were weighed into a 500 mL round-bottom flask, and the mixture was evacuated three times under nitrogen protection. Dichloromethane (CH2Cl2) (60 mL) was added to the system using a syringe. After the addition was complete, the system was placed at 37 °C and stirred for 15 min. Then, triethylamine (TEA) (3.0 equiv, 12.62 nmol, 1.7 mL) and di-tert-butyl dicarbonate ((BOC)2O) (3.0 equiv, 12.62 nmol, 2.9 mL) were added to the system using a syringe, and the mixture was reacted at this temperature for 40 min. After the reaction was complete, the system was allowed to return to room temperature, the solvent was suspended, water and dichloromethane (CH2Cl2) were added, and the mixture was extracted three times. The organic layers were combined and dried with anhydrous sodium sulfate (Na2SO4), and filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product, which was then separated by silica gel column chromatography (elution buffer: PE:EA = 30:1) to finally obtain compound 6 (1.92 g, 84.5%) as a white solid.

[0114] 1 H NMR (400MHz, CDCl3): δ7.58 (d, J=6.8Hz, 2H, Ar), 7.45 (dd, J1=8.0Hz, J2=0.8Hz, 2H, Ar), 7.13 (dd, J1=8.0Hz, J2=8.0Hz, 2H, Ar), 1.45 (s, 18H, CH3). 13 C NMR (101MHz, CDCl3): δ151.0,139.7,136.1,130.4,127.0,125.5,119.2,82.9,27.9.

[0115] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of compound 6 in this invention. Figure 12 This is the carbon NMR spectrum of compound 6 in this invention.

[0116] 5) Synthesis of Compound 7: Compound 6 (1.0 equiv, 2.83 nmol, 1.5 g) and tetrakis(triphenylphosphine)palladium (0.1 equiv, 0.28 nmol, 327.2 mg) were weighed into a 250 mL round-bottom flask, and the mixture was purged three times under nitrogen protection. Toluene (25 mL) was added to the system using a syringe, and after it was completely dissolved in 1 day, tributylvinyl selenide (3.0 equiv, 8.50 nmol, 2.49 mL) was added to the system. After the addition was complete, the reaction system was placed in an oil bath and the temperature was slowly raised to 110 °C and stirred for 3 h. After the reaction was completed, the system was allowed to return to room temperature, the solvent was suspended, water and ethyl acetate (EA) were added, and the mixture was extracted three times. The organic layers were combined, dried with anhydrous sodium sulfate (Na₂SO₄), and filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain a crude product, which was then separated by silica gel column chromatography (elution buffer: PE:EA = 30:1) to finally obtain compound 7 (667.2 mg, 54.3%) in the form of a light yellow solid.

[0117] 1 H NMR (400MHz, CDCl3): δ7.49 (d, J=7.6Hz, 2H, Ar), 7.44 (dd, J1=8.0Hz, J2=1.2Hz, 2H, Ar), 7.23 (dd, J1=8.0Hz, J2=8.0Hz, 2H, Ar), 6.87 (dd, J1=1 7.6Hz, J2=11.2Hz, 2H, CH=CH2), 5.79(dd, J1=17.6Hz, J2=0.8Hz, 2H, CH=CH2), 5.34(dd, J1=11.2Hz, J2=0.8Hz, 2H, CH=CH2), 1.41(s, 18H, CH3). 13 C NMR (101MHz, CDCl3): δ152.1,138.6,134.8,133.4,132.8,125.8,125.1,122.7,114.5,82.2,27.9.

[0118] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of compound 7 in this invention. Figure 13 This is the carbon NMR spectrum of compound 7 in this invention.

[0119] 6) Synthesis of Compound 8: Weigh Compound 7 (1.0 equiv, 0.494 nmol, 241.6 mg) into a 75 ml sealed tube. Transfer the system to a glove box, add toluene (10 ml) to the system using a syringe, and after Compound 8 is completely dissolved, add triethylamine (TEA) (4.0 equiv, 1.977 nmol, 0.27 ml) and boron tribromide (BCl3) (4.0 equiv, 1.977 nmol, 2.0 ml). Then remove the system from the glove box and place it in an oil bath, slowly heating it to 110 °C and reacting for 12 h. After the reaction was complete, the solvent was removed under vacuum using a double-cold hydrazine solution, and the system was then transferred back into a glove box. Toluene (10 ml) and 2,4,6-trimethylbenzene magnesium bromide (MesMgBr) (5.0 equiv, 5.94 nmol, 6.0 ml) were added to the system using a syringe. The system was then removed from the glove box and allowed to react at room temperature for 12 h. After the reaction was complete, the system was allowed to return to room temperature, the solvent was suspended, and water and ethyl acetate (EA) were added. The mixture was extracted three times, the organic layers were combined, and dried with anhydrous sodium sulfate (Na2SO4). The organic phase was then filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product. The crude product was then separated by silica gel column chromatography (elution buffer: PE:EA = 80:1) to finally obtain compound 8 (73.3 mg, 26.9%) as a white solid.

[0120] 1 H NMR (400MHz, CDCl3): δ7.89(d,J=11.2Hz,2H,Ar),7.26(d,J=7.2Hz,2H,Ar),6.96(d,J=11.2Hz,2H,Ar),6.93(d ,J=8.0Hz,2H,Ar),6.83(s,4H,Ar),6.76(dd,J1=8.0Hz,J2=7.6Hz,2H,Ar),2.31(s,6H,CH3),2.19(s,12H,CH3). 13 C NMR (101MHz, CDCl3): δ143.7,138.8,137.3,135.8,133.2,132.1,127.8,126.7,125.5,122.2,121.5,22.5,21.2(B-aryl carbons were not observed).

[0121] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of compound 8 in this invention. Figure 14 This is the carbon NMR spectrum of compound 8 in this invention. Figure 17The images show the single-crystal structure of compound 8 in this invention; the left image is a front view of the single-crystal structure of compound 8, and the right image is a top view of the single-crystal structure of compound 8. The single-crystal structure images show that the conformation of compound 8 is slightly distorted, and the BN bond length is... Significantly shorter than the common BN single bond length This indicates that the BN unit in BN hybrid perylene contributes to the delocalization of π electrons, which is beneficial for the application of this matrix in the currently scarce blue-emitting organic light-emitting diodes. Figure 18 Compound 8 in this invention is at a concentration of 1×10⁻⁶. -5 Absorption spectrum of M in dichloromethane solution; Figure 19 Compound 8 in this invention is at a concentration of 1×10⁻⁶. -5 The emission spectrum of M in dichloromethane solution. Its emission peak at room temperature is 389 nm, and the spectrum shows a long absorption band in the 300-500 nm range, extending from the ultraviolet region to the visible light region. It is a blue light emitting material that is in short supply in this field.

[0122] 7) Synthesis of Compound 9: Weigh Compound 7 (1.0 equiv, 0.307 nmol, 133.3 mg) into a 75 ml sealed tube. Transfer the system to a glove box, add toluene (13 ml) to the system using a syringe, and after all 1e has dissolved, add triethylamine (TEA) (4.0 equiv, 1.228 nmol, 0.18 ml) and boron tribromide (BCl3) (4.0 equiv, 1.228 nmol, 0.13 ml). Then remove the system from the glove box and place it in an oil zone, slowly heat to 110 °C, and react for 12 h. After the reaction was complete, the solvent was removed under vacuum using hydrazine, and the system was then transferred back into a glove box. Toluene (13 ml) was added to the system using a syringe, followed by methyl magnesium bromide (CH3MgBr) (5.0 equiv, 1.228 nmol, 1.0 ml). The system was then removed from the glove box and allowed to react at room temperature for 12 h. After the reaction was complete, the system was allowed to return to room temperature, the solvent was suspended, and water and ethyl acetate (EA) were added. The mixture was extracted three times, the organic layers were combined, and dried over anhydrous sodium sulfate (Na2SO4). The organic phase was then filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product. The crude product was then separated by silica gel column chromatography (elution buffer: PE:CH2Cl2 = 25:1), finally yielding compound 9 (11.7 mg, 13.6%) as a white solid.

[0123] 1H NMR (400MHz, CDCl3): δ7.77(d,J=11.2Hz,2H,Ar),7.31(dd,J1=6.8Hz,J2=2.4Hz,2H,Ar),7.08-7.14(m,4H,Ar),6.86(d,J=11.2Hz,2H,Ar),1.08(s,6H,BCH3). 13 CNMR(101MHz, CDCl3):142.4,136.8,133.1,132.0,126.6,124.9,121.8,121.7,6.0.

[0124] Figure 7 This is the 1H NMR spectrum of compound 9 in this invention. Figure 15 This is the carbon NMR spectrum of compound 9 in this invention. Figure 20 Compound 9 in this invention is at a concentration of 1×10⁻⁶. -5 Absorption spectrum of M in dichloromethane solution. Figure 21 Compound 9 in this invention is at a concentration of 1×10⁻⁶. -5 The absorption spectrum of M in dichloromethane solution. Its emission spectrum peaks at room temperature at 382 nm, and the spectrum exhibits a long absorption band in the 300-500 nm range, extending from the ultraviolet region to the visible light region. It is a blue light emitting material that is urgently needed in this field.

[0125] 8) Synthesis of Compound 10: Weigh Compound 7 (1.0 equiv, 0.75 nmol, 324.6 mg) into a 75 mL sealed tube. Transfer the system to a glove box, add toluene (13 mL) using a syringe, and after all 1e has dissolved, add triethylamine (TEA) (4.0 equiv, 3.0 nmol, 0.42 mL) and boron tribromide (BCl3) (4.0 equiv, 3.0 nmol, 3.0 mL). Then remove the system from the glove box and place it in an oil zone, slowly heating to 110 °C and reacting for 12 h. After the reaction is complete, remove the solvent from the system under vacuum using hydrazine, then transfer it back to the glove box, add toluene (13 mL) using a syringe, then add phenyl magnesium bromide (PhMgBr) (4.0 equiv, 3.0 nmol, 3.0 mL), remove the system from the glove box and continue reacting at room temperature for 12 h. After the reaction was complete, the system was allowed to return to room temperature, the solvent was suspended, water and ethyl acetate (EA) were added, and the mixture was extracted three times. The organic layers were combined and dried with anhydrous sodium sulfate (Na2SO4), and filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product, which was then separated by silica gel column chromatography (elution buffer: PE:CH2Cl2 = 25:1) to finally obtain compound 10 (21.3 mg, 7%) as a white solid.

[0126] 1 H NMR (400MHz, CDCl3): δ7.97(d,J=11.2Hz,2H,Ar),7.65-7.69(m,4H,Ar),7.32-7.35(m,4H,Ar),7.27(d,J=9.2Hz, 2H, Ar), 7.16 (d, J = 11.2Hz, 2H, Ar), 6.91 (dd, J1 = 8.0Hz, J2 = 1.2Hz, 2H, Ar), 6.77 (dd, J1 = 8.0Hz, J2 = 7.6Hz, 2H, Ar).

[0127] Figure 8 This is the 1H NMR spectrum of compound 10 in this invention.

[0128] 9) Synthesis of Compound 11: Weigh Compound 7 (1.0 equiv, 0.75 nmol, 324.6 mg) into a 75 mL sealed tube. Transfer the system to a glove box, add toluene (13 mL) using a syringe, and after all 1e has dissolved, add triethylamine (TEA) (4.0 equiv, 3.0 nmol, 0.42 mL) and boron tribromide (BCl3) (4.0 equiv, 3.0 nmol, 3.0 mL). Then remove the system from the glove box and place it in an oil zone, slowly heating to 110 °C and reacting for 12 h. After the reaction is complete, remove the solvent from the system under vacuum using hydrazine, then transfer it back to the glove box, add toluene (13 mL) using a syringe, then add water (H2O) (4.0 equiv, 3.0 nmol, 3.0 mL), remove the system from the glove box, and continue the reaction at room temperature for 12 h. After the reaction was complete, the system was allowed to return to room temperature, the solvent was suspended, water and ethyl acetate (EA) were added, and the mixture was extracted three times. The organic layers were combined and dried with anhydrous sodium sulfate (Na2SO4), and filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product, which was then separated by silica gel column chromatography (elution buffer: PE:CH2Cl2 = 25:1), finally yielding compound 11 (33.6 mg, 15.7%) as a white solid.

[0129] 1 H NMR (400MHz, CDCl3): δ7.37(d,J=3.2Hz,2H,Ar),7.06(d,J=8.0Hz,2H,Ar),6.92(d ,J1=8.0Hz,J2=7.6Hz,2H,Ar),6.71(d,J=7.2Hz,2H,Ar),6.47(d,J=3.2Hz,2H,Ar). 13CNMR (101MHz, CDCl3): δ129.3,128.2,127.3,122.7,119.7,116.5,104.8,102.9.

[0130] Figure 9 This is the 1H NMR spectrum of compound 11 in this invention. Figure 16 This is the carbon NMR spectrum of compound 11 in this invention. Figure 22 Compound 11 in this invention is at a concentration of 1×10⁻⁶. -5 Absorption spectrum of M in dichloromethane solution. Figure 23 Compound 11 in this invention is at a concentration of 1×10⁻⁶. -5 The emission spectrum of M in dichloromethane solution shows three emission peaks at room temperature, with peak values ​​of 252, 370, and 389 nm. The spectrum exhibits a long absorption band in the 300-500 nm range, extending from the ultraviolet region to the visible light region, and it is a blue light emitting material that is in high demand in this field.

[0131] The following analysis of the photoelectric physical properties of the compounds prepared in the above embodiments of the present invention is presented. We performed ultraviolet absorption, fluorescence emission tests, electrochemical property tests, and single-crystal diffraction structure characterization on these compounds.

[0132] The following is a photophysical property analysis of the complexes prepared in the above embodiments of the present invention:

[0133] Photophysical analysis: Emission and absorption spectra were measured using a HORIBA FL3-11 spectrometer. Test conditions: In the room temperature emission spectra, all samples were prepared as a dilute solution of dichloromethane (chromatographic grade) (10...). -5 -10 -6 M), and all samples were prepared in a glove box and purged with nitrogen for 5 minutes.

[0134] Combined with X-ray single crystal diffraction ( Figure 17Analysis revealed that the obtained compound was the target compound. To investigate the changes in photophysical properties with increasing molecular conjugation, we studied the UV-Vis absorption spectra of this series of compounds. Compound 8 had a maximum emission wavelength of 385 nm and a solution-state absolute quantum yield of 30%; compound 9 had a maximum emission wavelength of 380 nm and a solution-state absolute quantum yield of 27%; and compound 11 had a maximum emission wavelength of 370 nm and a solution-state absolute quantum yield of 91%. The intercalation of boron-nitrogen bonds endows polycyclic aromatic hydrocarbons with excellent photoelectric properties, making them suitable as the emitting layer of organic light-emitting diodes (OLEDs). The emission color of the compounds disclosed in this invention can be easily controlled by adjusting the donor structure. They can be used as host materials or luminescent materials in a variety of optical and electro-optical devices, including but not limited to light-absorbing devices such as solar cells and photosensitive devices, organic light-emitting diodes (OLEDs), light-emitting devices, or markers capable of both light absorption and emission, as well as bio-applications. Compared with traditional materials, these compounds can improve device performance, such as improving the efficiency of organic light-emitting devices.

[0135] The method of the present invention also includes the following synthetic route:

[0136]

[0137] Examples of the above compounds are given below:

[0138] Example 2:

[0139] 1) Synthesis of Compound 12: Compound 7 (1.0 equiv, 0.10 nmol, 49.1 mg) was weighed into a 50 mL round-bottom flask. Dichloromethane (CH2Cl2) (5 mL) was added to the system using an injectable syringe, and the mixture was stirred for 15 min. Liquid bromine (0.55 equiv, 0.05 nmol, 3 μL) was injected dropwise into the system using a microsyringe. The reaction system was stirred at 0 °C for 1 h. After the reaction was completed, the system was allowed to return to room temperature, the solvent was suspended, water and dichloromethane (CH2Cl2) were added, and the mixture was extracted three times. The organic layers were combined and dried with anhydrous sodium sulfate (Na2SO4). The organic phase was filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product. The crude product was separated by silica gel column chromatography (elution: PE) to finally obtain compound 12 (45 mg, 79.5%) as a white solid.

[0140] 1H NMR (400MHz, CDCl3): δ8.32(d,J=11.7Hz,1H),7.89(d,J=11.3Hz,1H),7.28(s,1H),7.09(d,J=11.7Hz,1H),7.02(d,J=8.6Hz,1H),6.94(d, J=11.3Hz,1H),6.92–6.88(m,1H),6.82(s,2H),6.81(s,2H),6.78(s,1H),6.76(s,1H),2.30(s,3H),2.29(s,3H),2.16(s,6H),2.15(s,6H).

[0141] Figure 10 This is the 1H NMR spectrum of compound 12 in this invention.

[0142] 2) Synthesis of Compound 13: Compound 8 (1.0 equiv, 0.17 nmol, 100 mg), phenylboronic acid (1.5 equiv, 0.26 nmol, 31.7 mg), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (0.17 equiv, 0.03 nmol, 34.6 mg), and potassium carbonate (K2CO3) (1.5 equiv, 62.4 nmol, 9.1 g) were weighed into a 150 mL round-bottom flask. A reflux purging device was added, and the mixture was evacuated three times under nitrogen protection. Solvent 1,4-dioxane (10 mL) and water (H2O) (2.5 mL) were added to the system using an injectable reagent. The reaction system was then stirred in an oil bath at 100 °C for 12 h. TLC monitoring was performed. After the reaction was complete, the oil bath was removed, and the system was allowed to slowly return to room temperature. The solvent was suspended, and water and ethyl acetate (EA) were added. The mixture was extracted three times, and the organic layers were combined and dried with anhydrous sodium sulfate (Na2SO4). The organic phase was then filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product. The crude product was separated by silica gel column chromatography (elution buffer: PE:EA = 50:1) to finally obtain compound 13 (43.6 mg, 45.3%) as a yellow solid.

[0143] Performance Example:

[0144] OLED devices consist of an anode and a cathode, and one or more organic compound layers disposed between the anode and the cathode. The organic compound layers include a light-emitting layer, an electron and hole injection layer, and a transport layer.

[0145] This invention provides an example of a thin-film OLED device using boron-nitrogen perylene compounds as the light-emitting host material, which incorporates blue and deep blue light-emitting host materials. The device structure and performance are described in detail below:

[0146] The structure of the blue-emitting OLED device prepared in this example is: ITO / PEDOT:PSS (30nm) / Active layer:compound 8 / TPBi (70nm) / Al (120nm), as shown in the figure. Figure 26 As shown. The active layer material of this example device is compound 8. Among them, PEDOT is the hole transport layer, TPBi is the electron transport layer, and LiF / Al is the composite cathode.

[0147] The thin-film device prepared using boron-nitrogen perylene compounds as the luminescent host material in this invention exhibits the following performance characteristics: Figure 24 As shown in Figure 25, the blue light material is compound 8:

[0148]

[0149] Depend on Figure 24 Figure 25 shows that the device based on compound 8 has a moderate startup voltage (6V), indicating that the material has good carrier mobility. In addition, the brightness of the light-emitting device is about 1000 cd / m². 2 Meanwhile, the device exhibits a maximum quantum efficiency of 3.29 cd / A and a maximum power efficiency of 3.1 Lm / W. This indicates that compound 8 undergoes efficient energy transfer from the host to the guest material in the excited state under energized conditions, demonstrating that compound 8 is entirely feasible as a host material for blue light. This application provides an effective approach to address the current shortage of deep blue light materials and host materials, thereby significantly promoting the development of the blue light materials field.

[0150] Figure 24 The figures show the current density-voltage relationship and brightness-voltage relationship for compound 8 in this invention. (Attached) Figure 25 The graphs show the current efficiency-current density relationship and the power efficiency-current density relationship of compound 8 in this invention.

[0151] Although embodiments of the invention have been disclosed for illustrative purposes, those skilled in the art will understand that various substitutions, variations, and modifications are possible without departing from the spirit and scope of the invention and the appended claims. Therefore, the scope of the invention is not limited to the contents disclosed in the embodiments.

Claims

1. A perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbon, characterized in that: The structural formula of the perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbon is as follows: 。 2. The method for synthesizing perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons according to claim 1, characterized in that: The method includes the following steps: 1) Synthesis of Compound 3: Weigh 2.5 g of potassium tert-butoxide into a 500 ml round-bottom flask, purge three times, and protect with nitrogen. Add 20 ml of tetrahydrofuran solvent to the system using an injectable syringe, and then stir the reaction system at -78 °C for 15 min. After the potassium tert-butoxide has completely dissolved, slowly add 5 ml of tetrahydrofuran solution containing 1.2 g of 2-bromoaniline and 5 ml of tetrahydrofuran solution containing 1.5 g of 2-bromonitrobenzene using a syringe. Stir the mixture at this temperature for 1-1.5 hours, and control the reaction by column chromatography. Then remove the cooling zone, pour in 20 ml of saturated ammonium chloride solution, and continue stirring at room temperature for 30 minutes. min; after the system returned to room temperature, the solvent was suspended, water and ethyl acetate were added, and the mixture was extracted three times. The organic layers were combined and dried with anhydrous sodium sulfate, and filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product. The crude product was separated by silica gel column chromatography with PE:EA = 20:1 as the eluent, and finally, 3,956.2 mg (36.7%) of the compound was obtained as a brick-red solid. The structural formula of compound 3 is as follows: ； 2) Synthesis of Compound 4: Weigh 319.6 mg of Compound 3 into a 75 ml sealed tube; transfer the system to a glove box, add 10 ml of acetonitrile to the system using a syringe, and after Compound 3 is completely dissolved, add 1.2 ml of N,O-dimethylsilane to the system, and remove the system from the glove box; then place the system in an oil bath and slowly heat to 100°C. o C, reacted for 12 h; after the reaction was complete, the precipitate in the system was separated by filtration, washed with cold methanol, and dried under vacuum; 4,219.0 mg of the compound was obtained as a yellow solid, yield 72.2%; The structural formula of compound 4 is as follows: ； 3) Synthesis of Compound 5: Weigh 331.6 mg of Compound 4 into a 250 ml round-bottom flask, purge three times, and protect with nitrogen; add 15 ml of ethanol solvent to the system using a syringe; after the addition is complete, place the reaction system in an oil bath and slowly heat to 80°C. o Stir at C for 15 min; then add a solution of 1.7 g sodium dithionite in 10 ml of water using a syringe, and slowly heat the system to 100 °C and stir for 3 h; after the reaction is complete, filter to separate the precipitate, wash with cold water, and dry under vacuum; obtain 5,248.0 mg (74.3%) of the compound in green solid form. The structural formula of compound 5 is as follows: ； 4) Synthesis of Compound 6: 976.3 mg of Compound 5 and 361.3 mg of 4-dimethylaminopyridine were weighed into a 500 ml round-bottom flask, and the mixture was purged three times under nitrogen protection. 60 ml of dichloromethane was added to the system using a syringe. After the addition was complete, the system was placed at 37 °C and stirred for 15 min. Then, 1.7 ml of triethylamine and 2.9 ml of ditert-butyl dicarbonate were added to the system using a syringe, and the mixture was reacted at this temperature for 40 min. After the reaction was complete, the system was allowed to return to room temperature, the solvent was suspended, water and dichloromethane were added, and the mixture was extracted three times. The organic layers were combined and dried with anhydrous sodium sulfate. The organic phase was filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product. The crude product was separated by silica gel column chromatography with an eluent of PE:EA = 30:

1. Finally, Compound 6 was obtained as a white solid, 1.92 g, 84.5%; The structural formula of compound 6 is as follows: ； 5) Synthesis of Compound 7: Weigh 1.5 g of Compound 6 and 327.2 mg of tetraphenylphosphine palladium into a 250 ml round-bottom flask, purge three times, and protect under nitrogen atmosphere; add 25 ml of toluene to the system using a syringe, and after it is completely dissolved in 1 day, add 2.49 ml of tributylvinyl selenide to the system; after the addition is complete, place the reaction system in an oil bath and slowly heat to 110 °C. o C, stirred for 3 h; after the reaction was complete, the system was allowed to return to room temperature, the solvent was suspended, water and ethyl acetate were added, and the mixture was extracted three times. The organic layers were combined and dried with anhydrous sodium sulfate, and filtered to obtain the organic phase. The organic phase was concentrated by rotary evaporation to obtain the crude product. The crude product was separated by silica gel column chromatography with the eluent being PE:EA = 30:1, and finally, 7,667.2 mg (54.3%) of the compound in the form of a light yellow solid was obtained. The structural formula of compound 7 is as follows: ； 6) Synthesis of Compound 8: Weigh 241.6 mg of Compound 7 into a 75 ml sealed tube; transfer the system to a glove box, add 10 ml of toluene to the system using a syringe, and after Compound 7 is completely dissolved, add 0.27 ml of triethylamine and 2.0 ml of boron tribromide. Then remove the system from the glove box and place it in an oil bath, slowly heating to 110°C. o C, react for 12 h; after the reaction is complete, the solvent is removed under vacuum using hydrazine, and then the system is transferred back into a glove box. 10 ml of toluene and 6.0 ml of 2,4,6-trimethylbenzene magnesium bromide are added to the system using a syringe. The system is then removed from the glove box and the reaction continues at room temperature for another 12 h; after the reaction is complete, the system is allowed to return to room temperature, the solvent is suspended, water and ethyl acetate are added, and the mixture is extracted three times. The organic layers are combined, dried with anhydrous sodium sulfate, and filtered to obtain the organic phase. The organic phase is concentrated by rotary evaporation to obtain the crude product. The crude product is separated by silica gel column chromatography with an eluent of PE:EA = 80:1, finally yielding a white solid compound 8, 73.3 mg, 26.9%; The structural formula of compound 8 is as follows: 。 3. The application of perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons as described in claim 1 in optical and / or optoelectronic fields.

4. The use of perylene-based boron-nitrogen-doped fused-ring aromatic hydrocarbons as described in claim 1 in their role as luminescent materials and / or host materials for the preparation of optical or optoelectronic devices.

5. The application according to claim 4, characterized in that: The optical or optoelectronic device is selected from organic light-emitting diodes, organic field-effect transistors, and organic solar cells.

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