Boron-nitrogen doped fluoranthene compound as well as preparation method and application thereof

Abstract

The invention relates to a boron-nitrogen doped fluoranthene compound as well as a preparation method and application thereof. The structural formula of the boron-nitrogen doped fluoranthene compound is as shown in a formula 1 or a formula 2, and a boron-nitrogen unit is embedded in a molecular central axis; 1, 8-dibromo-boron aza-naphthalene is used as a raw material, and the boron-nitrogen-doped fluoranthene compound and the derivative thereof are synthesized by a one-pot method through a palladium-catalyzed Suzuki-Miyaura coupling reaction. The method is simple and convenient to operate and mild in reaction condition, and has good structural adjustability and applicability; the obtained compound shows excellent photoelectric properties and can be applied to the field of organic photoelectric functional materials.

Description

Technical Field

[0001] This invention belongs to the field of optoelectronic materials technology, and in particular relates to a boron-nitrogen-doped fluoranthene compound, its preparation method, and its application. Background Technology

[0002] Polycyclic aromatic hydrocarbons (PAHs) possess significant research and application value in the field of organic optoelectronic materials due to their rigid planar structure and extended π-conjugated system. Among them, fluoranthene and its derivatives are widely used in organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic photovoltaic devices due to their excellent conjugation, high carrier mobility, and superior optical properties. Modifying the electronic structure and optoelectronic properties of fluoranthene compounds through molecular structure modification is one of the important directions in current organic semiconductor material research. In recent years, the introduction of heteroatoms into the PAH framework to regulate their electronic structure and physicochemical properties has received widespread attention. Boron-nitrogen (B–N) doping, as an important structural modification strategy, introduces a significant electronic difference while maintaining the overall conjugated structure of the aromatic system by isoelectronically replacing carbon-carbon bonds. Boron atoms have empty p orbitals, which can act as good electron acceptors, while trivalent nitrogen atoms have lone pairs of electrons, which can act as electron donors. The boron-nitrogen bond formed by these two atoms has a certain polarity due to the difference in electronegativity. In boron-nitrogen-doped aromatics, the empty p orbitals on boron atoms can interact with the π* orbitals of the aromatic π-conjugated system via P–π* interactions, thereby effectively regulating the electron distribution of the molecule, promoting intramolecular charge transfer, and enabling the compound to exhibit unique photoelectric physical properties that distinguish it from all-carbon aromatics.

[0003] Boron-nitrogen-doped polycyclic aromatic hydrocarbons (PAHs) have shown promising applications in organic optoelectronic materials, exhibiting advantages in luminous efficiency, energy level modulation, and carrier transport performance. However, current research mainly focuses on boron-nitrogen-doped naphthalene, anthracene, and other simple PAH systems. Reports on boron-nitrogen-embedded fluoranthene skeletons, especially the structural isomers of boron-nitrogen-doped fluoranthene and complex fused aromatic hydrocarbon systems doped with two boron-nitrogen units, remain scarce. Furthermore, existing synthetic methods for the all-carbon acenaphthene[1,2-k]fluoranthene suffer from cumbersome steps and demanding reaction conditions, limiting the expansion of structural diversity and further application of this class of compounds in organic optoelectronic devices.

[0004] Therefore, developing a method for preparing boron-nitrogen-doped fluoranthene compounds with a simple synthetic route, mild reaction conditions, and precise introduction of boron-nitrogen units, and systematically studying their structure and optoelectronic properties, especially their application performance in devices such as organic field-effect transistors, is of great scientific significance and application value for expanding the molecular design strategies of boron-nitrogen-doped polycyclic aromatic hydrocarbons and promoting their practical application in the field of optoelectronic materials.

[0005] Existing methods for preparing boron-nitrogen-doped fluoranthene can only introduce boron-nitrogen units to the edge of the fluoranthene framework. There is a lack of methods for constructing a fluoranthene framework with boron-nitrogen units embedded in it, as well as methods for constructing bis-boron-nitrogen-doped acenaphthene[1,2-k]fluoranthene compounds. In addition, there is a lack of simpler methods for constructing acenaphthene[1,2-k]fluoranthene. References (E. Li, M. Jin, R. Jiang, L. Zhang, Y. Zhang, M. Liu, X. Wu and X. Liu. Synthesis, Characterization, and Properties of BN-Fluoranthenes [J]. Org. Lett. 2022, 24, 5503-5508) and (Y. Wang, S. Liu, P. Yang, T. Shi, J. Fan, G. Zhou and B. Su. BN-Benzo[b]fluoranthenes: facile synthesis, characterization, and optoelectronic properties [J]. Org. Chem. Front., 2024, 11, 2548-2553) report a method for synthesizing boron-nitrogen units at the edge of the fluoranthene framework using a pyrrole-type nitrogen-directed CH borylation / cyclization strategy, with boron trichloride as the boron source, and using a sterically hindered Grignard reagent to stabilize the boron center. However, this method cannot achieve internal doping of boron-nitrogen units. The literature (G. Wang, Q. Guo, Y. Xin, Z. Qi, S. Cao, D. Tian and B. Zhu. Synthesis, Structure, and Properties of Two Planar BN-Benzofluorenes [J]. Org. Lett. 2025, 27, 15, 3844–3850) achieved the preparation of partially boron-nitrogen-embedded fluoranthene compounds, but it could not obtain the target product in one step, nor could it obtain symmetrical boron-nitrogen-doped fluoranthene parent compounds with boron-nitrogen units embedded in the central axis. This greatly limits the application of the corresponding boron-nitrogen-embedded fluoranthene and acenaphthene[1,2-k]fluoranthene in the field of organic optoelectronic materials. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a boron-nitrogen-doped fluoranthene compound, its preparation method, and its applications.

[0007] The technical solution adopted in this invention is: a boron-nitrogen-doped fluoranthene compound, the structure of which is shown in Formula 1 or Formula 2;

[0008] Formula 1;

[0009] Formula 2;

[0010] Among them, R 1 - R 10 For substituted or unsubstituted aryl, heteroaryl, C1-C 12 Straight-chain or branched alkyl, methoxy, ethoxy, n-propoxy, isopropoxy, vinyl, allyl, ethynyl, propynyl, triarylamine, hydrogen or halogen atom; R 1 - R 10 Same, partially the same, or different;

[0011] The halogen atom is F, Cl, Br, or I;

[0012] Ar represents substituted or unsubstituted benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, thiophene, furan, pyrrole, pyridine, benzothiophene, benzofuran, benzopyrrole, or benzopyridine.

[0013] Preferably, the boron-nitrogen-doped fluoranthene compounds have structures as shown in formula C1, formula C2, or formula C3;

[0014] ;

[0015] Alternatively, the structure of the bis-boron nitrogen-doped acenaphthene[1,2-k]fluoranthene parent compound is shown in formula C4;

[0016] ;

[0017] Among them, R 7 – R 18 For substituted or unsubstituted aryl, heteroaryl, C1-C 12 Straight-chain or branched alkyl, methoxy, ethoxy, n-propoxy, isopropoxy, vinyl, allyl, ethynyl, propynyl, triarylamine, hydrogen or halogen atom; R 7 - R 18 Same, partially the same, or different;

[0018] The halogen atom is F, Cl, Br, or I;

[0019] Ar represents substituted or unsubstituted benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, thiophene, furan, pyrrole, pyridine, benzothiophene, benzofuran, benzopyrrole, or benzopyridine.

[0020] Preferably, the structure is as shown in any of formulas A1-A11;

[0021] .

[0022] A method for preparing boron-nitrogen-doped fluoranthene compounds involves using 1,8-dibromoborazonaphthalene and aryl o-diboronate or aryl tetraboronate as raw materials, and synthesizing boron-nitrogen-doped fluoranthene compounds with embedded boron-nitrogen units in a one-pot reaction via palladium-catalyzed Suzuki–Miyaura coupling reaction.

[0023] Preferably, under inert gas protection conditions, 1,8-dibromoborazonaphthalene, aryl o-diboronate or aryl tetraboronate, palladium catalyst, phosphine ligand and base are added to a mixture of organic solvent and water, and the mixture is heated to prepare boron nitrogen-doped fluoranthene compounds.

[0024] Preferably, the palladium catalyst is one or a combination of tetra(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, and tris(dibenzylacetone)palladium;

[0025] The phosphine ligand is one or more of the following: triphenylphosphine, tricyclohexylphosphine, tributylphosphine, tritert-butylphosphine, tri(o-methoxyphenyl)phosphine, and tri(p-methoxyphenyl)phosphine;

[0026] The molar ratio of palladium catalyst to phosphine ligand is 1:1 to 1:2.

[0027] Preferably, the base is one or a combination of potassium carbonate, potassium phosphate, potassium acetate, sodium carbonate, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, and triethylamine; the concentration of the base in the reaction system is 1.0–2.0 mol / L.

[0028] The organic solvent is one or more of toluene, tetrahydrofuran, 1,4-dioxane and ethanol;

[0029] The inert gas is argon or nitrogen; the reaction temperature is 80-130℃.

[0030] A method for preparing acenaphthene[1,2-k]fluoranthene compounds, using 1,8-dibromonaphthalene and aryltetraborate esters as raw materials, synthesizes acenaphthene[1,2-k]fluoranthene compounds in a one-pot manner via a palladium-catalyzed Suzuki–Miyaura coupling reaction;

[0031] Preferably, under inert gas protection conditions, 1,8-dibromonaphthalene, aryl o-diboronate or aryl tetraboronate, palladium catalyst, phosphine ligand and base are added to a mixture of organic solvent and water, and the mixture is heated to prepare boron nitrogen-doped fluoranthene compounds.

[0032] Preferably, the palladium catalyst is one or a combination of tetra(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, and tris(dibenzylacetone)palladium;

[0033] The phosphine ligand is one or more of the following: triphenylphosphine, tricyclohexylphosphine, tributylphosphine, tritert-butylphosphine, tri(o-methoxyphenyl)phosphine, and tri(p-methoxyphenyl)phosphine;

[0034] The molar ratio of palladium catalyst to phosphine ligand is 1:1 to 1:2;

[0035] Preferably, the base is one or a combination of potassium carbonate, potassium phosphate, potassium acetate, sodium carbonate, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, and triethylamine; the concentration of the base in the reaction system is 1.0–2.0 mol / L.

[0036] The organic solvent is one or more of toluene, tetrahydrofuran, 1,4-dioxane and ethanol;

[0037] The inert gas is argon or nitrogen; the reaction temperature is 80-130℃.

[0038] Application of boron-nitrogen-doped fluoranthene compounds in organic optoelectronic materials.

[0039] Preferably, the organic semiconductor material is used in an organic field-effect transistor.

[0040] The advantages and positive effects of this invention are: it provides a boron-nitrogen-doped fluoranthene compound, which achieves effective regulation of molecular structure and electronic properties by introducing boron-nitrogen units into the fluoranthene and acenaphthene[1,2-k]fluoranthene skeletons; this compound exhibits good photoelectric properties, such as the double boron-nitrogen-doped acenaphthene[1,2-k]fluoranthene compound showing high hole mobility in organic field-effect transistors, reaching up to 0.8 cm⁻¹. 2 V -1 s -1 Based on their excellent photoelectric properties, the boron-nitrogen-doped fluoranthene compounds shown in Formula 1 or Formula 2 are suitable for organic field-effect transistors and other organic optoelectronic functional materials.

[0041] In addition, the synthesis method of this boron-nitrogen-doped fluoranthene compound is easy to implement, with mild reaction conditions, simple operation, good functional group compatibility and structural scalability; it also has good structural tunability and applicability. Attached Figure Description

[0042] Figure 1 This is the proton NMR spectrum of compound A1 prepared in Example 1;

[0043] Figure 2 This is the proton NMR spectrum of compound A2 prepared in Example 2;

[0044] Figure 3 This is the proton NMR spectrum of compound A3 prepared in Example 2;

[0045] Figure 4 This is the proton NMR spectrum of compound A4 prepared in Example 2;

[0046] Figure 5 This is the proton NMR spectrum of compound A5 prepared in Example 2;

[0047] Figure 6 This is the proton NMR spectrum of compound A6 prepared in Example 2;

[0048] Figure 7 This is the proton NMR spectrum of compound A7 prepared in Example 2;

[0049] Figure 8 This is the proton NMR spectrum of compound A8 prepared in Example 2;

[0050] Figure 9 This is the proton NMR spectrum of compound A9 prepared in Example 2;

[0051] Figure 10 This is the proton NMR spectrum of compound A10 prepared in Example 3;

[0052] Figure 11 This is the proton NMR spectrum of compound A11 prepared in Example 4;

[0053] Figure 12 These are the (a) normalized UV absorption spectrum and (b) normalized fluorescence emission spectrum of compound A1 in different solvents;

[0054] Figure 13 The normalized UV absorption spectrum and normalized fluorescence emission spectrum of compound A2 in different solvents are shown in (a) and (b) respectively.

[0055] Figure 14 These are the (a) normalized UV absorption spectrum and (b) normalized fluorescence emission spectrum of compound A11 in different solvents;

[0056] Figure 15 The TG curves are based on compounds (a) A1 and (b) A11;

[0057] Figure 16 These are (a) typical output curves and (b) transfer characteristic curves of an organic field-effect transistor (OFET) based on compound A11. Detailed Implementation

[0058] The embodiments of the present invention will now be described with reference to the accompanying drawings.

[0059] This invention relates to a boron-nitrogen-doped fluoranthene compound, its preparation method, and its application. The structural formula of the boron-nitrogen-doped fluoranthene compound is shown in Formula 1 or Formula 2; its boron-nitrogen unit is embedded in the central axis of the molecule;

[0060] Formula 1;

[0061] Formula 2;

[0062] Among them, R 1 - R 10 Selected independently from substituted or unsubstituted aryl, heteroaryl, C1-C 12 Straight-chain or branched alkyl, methoxy, ethoxy, n-propoxy, isopropoxy, vinyl, allyl, ethynyl, propynyl, triarylamine, hydrogen or halogen atom; preferably hydrogen, C1-C3 straight-chain or branched alkyl, methoxy, ethoxy or halogen atom; the halogen atom is F, Cl, Br or I; Ar is independently selected from substituted or unsubstituted benzene ring, naphthyl ring, anthracene ring, phenanthrene ring, thiophene, furan, pyrrole, pyridine, benzothiophene, benzofuran, benzopyrrole or benzopyridine.

[0063] In some embodiments of the present invention, the boron-nitrogen-doped fluoranthene compounds have structures as shown in any of compounds A1-A10, or as shown in compound A11.

[0064]

[0065] In preparing boron-nitrogen-doped fluoranthene compounds as shown in Formula 1 or 2, a one-pot synthesis of boron-nitrogen-embedded fluoranthene parent compounds and their derivatives is achieved via a palladium-catalyzed Suzuki–Miyaura coupling reaction. Specifically, under inert gas protection, 1,8-dibromoborazanaphthalene, aryl o-diboronate or aryl tetraboronate, palladium catalyst, phosphine ligand, and base are added to a mixture of organic solvent and water, and the reaction is heated. Following post-treatment and purification, the target boron-nitrogen-doped fluoranthene compounds are obtained. Different substituents are introduced using different types of aryl o-diboronate or aryl tetraboronate to obtain structurally diverse boron-nitrogen-doped fluoranthene compounds.

[0066] Among them, the structural formulas of aryl o-diboronate or aryl tetraboronate are shown in B1-B4; when any of the aryl o-diboronate compounds shown in B1-B3 are used as raw materials, boron nitrogen-doped fluoranthene compounds shown in C1-C3 can be prepared respectively; when the aryl tetraboronate compound shown in B4 is used as raw material, the diboron nitrogen-doped acenaphthene[1,2-k]fluoranthene parent compound shown in C4 can be prepared.

[0067]

[0068] Among them, R 7 -R 18 Selected independently from substituted or unsubstituted aryl, heteroaryl, C1-C 12Straight-chain or branched alkyl, methoxy, ethoxy, n-propoxy, isopropoxy, vinyl, allyl, ethynyl, propynyl, triarylamine, hydrogen or halogen atom, R 7 -R 18 The same, partially the same, or different; the halogen atom is F, Cl, Br, or I; Ar is independently selected from substituted or unsubstituted benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, thiophene, furan, pyrrole, pyridine, benzothiophene, benzofuran, benzopyrrole, or benzopyridine.

[0069] In the synthesis reaction, the palladium catalyst is selected from at least one of tetra(triphenylphosphine)palladium, di(triphenylphosphine)palladium dichloride, and tris(dibenzylacetone)palladium; the organophosphine ligand is selected from at least one of triphenylphosphine, tricyclohexylphosphine, tributylphosphine, tri-tert-butylphosphine, tris(o-methoxyphenyl)phosphine, and tris(p-methoxyphenyl)phosphine; the molar ratio of palladium catalyst to organophosphine is 1:1 to 1:2. The base is selected from at least one of potassium carbonate, potassium phosphate, potassium acetate, sodium carbonate, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, and triethylamine, and the concentration of the base compound in the solvent is 1.0 to 2.0 mol / L. The concentration of 1,8-dibromoborazonaphthalene in the solvent is 0.1–1.0 mol / L. When the starting material also includes aryl o-diboronate, the molar ratio of aryl o-diboronate to the 1,8-dibromoborazonaphthalene substrate is 1–1.1:1; when the starting material also includes aryl tetraboronate, the molar ratio of aryl tetraboronate to the 1,8-dibromoborazonaphthalene substrate is 2–2.2:1. The inert gas is argon or nitrogen, and the solvent is selected from at least one of toluene, tetrahydrofuran, 1,4-dioxane, and ethanol. The reaction temperature is 80–130 °C, and the reaction time is 12–72 h. Preferably, the palladium catalyst is tris(dibenzylacetone)dipalladium, the organophosphine ligand is tricyclohexylphosphine, the base is potassium carbonate, and the solvent is a mixture of tetrahydrofuran and water or a mixture of toluene and water.

[0070] In some embodiments of the present invention, acenaphthene[1,2-k]fluoranthene compounds can also be synthesized by this method. Specifically, under inert gas protection, 1,8-dibromonaphthalene, aryltetraborate ester, palladium catalyst, phosphine ligand and base are added to a mixture of organic solvent and water, heated to react, and after post-treatment and purification, acenaphthene[1,2-k]fluoranthene compounds as shown in Formula C5 are obtained.

[0071]

[0072] The palladium catalyst is selected from at least one of tetra(triphenylphosphine)palladium, di(triphenylphosphine)palladium dichloride, and tris(dibenzylacetone)palladium; the organophosphine ligand is selected from at least one of triphenylphosphine, tricyclohexylphosphine, tributylphosphine, tri-tert-butylphosphine, tris(o-methoxyphenyl)phosphine, and tris(p-methoxyphenyl)phosphine; the molar ratio of the palladium catalyst to the organophosphine is 1:1 to 1:2. The base is selected from at least one of potassium carbonate, potassium phosphate, potassium acetate, sodium carbonate, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, and triethylamine, and the concentration of the base compound in the solvent is 1.0 to 2.0 mol / L. The concentration of 1,8-dibromoborazonaphthalene in the solvent is 0.1–1.0 mol / L. When the starting material also includes aryl o-diboronate, the molar ratio of aryl o-diboronate to the 1,8-dibromoborazonaphthalene substrate is 1–1.1:1; when the starting material also includes aryl tetraboronate, the molar ratio of aryl tetraboronate to the 1,8-dibromoborazonaphthalene substrate is 2–2.2:1. The inert gas is argon or nitrogen, and the solvent is selected from at least one of toluene, tetrahydrofuran, 1,4-dioxane, and ethanol. The reaction temperature is 80–130 °C, and the reaction time is 12–72 h. Preferably, the palladium catalyst is tris(dibenzylacetone)dipalladium, the organophosphine ligand is tricyclohexylphosphine, the base is potassium carbonate, and the solvent is a mixture of tetrahydrofuran and water or a mixture of toluene and water.

[0073] The boron-nitrogen-doped fluoranthene compounds of Formula 1 or Formula 2 prepared by the above method exhibit excellent photoelectric properties. The boron-nitrogen-doped fluoranthene compound of Formula 1 shows a redshift in emission compared to all-carbon fluoranthene, while the bis-boron-nitrogen-doped acenaphthene[1,2-k]fluoranthene compound of Formula 2 shows a significant redshift in absorption and emission spectra compared to all-carbon acenaphthene[1,2-k]fluoranthene; both also exhibit good thermal stability. Furthermore, the prepared boron-nitrogen-doped fluoranthene compounds were used to fabricate bottom-gate top-contact (BGTC) single-crystal devices, grown using the air-gap sublimation method, revealing excellent charge transport performance. In particular, the device containing compound Al1 exhibits p-type transport behavior with a hole mobility as high as 0.8 cm⁻¹. 2 V -1 s -1 The on / off ratio is approximately 10. 6 This level is relatively high among boron-nitrogen-doped cyclopentanoic fused-ring aromatics (CPPAHs) to date. This indicates that this class of boron-nitrogen-doped fluoranthene compounds can be applied in the field of organic optoelectronic functional materials.

[0074] The present invention will now be described with reference to the accompanying drawings. Experimental methods not specifically described in terms of operation steps are performed in accordance with the corresponding product manuals. Unless otherwise specified, the instruments, reagents, and consumables used in the embodiments can be purchased from commercial companies.

[0075] Example 1: Preparation of boron-nitrogen-doped fluoranthene compounds

[0076] A1; D1;

[0077] Compound A1 (3a-aza-3a) 1 Preparation of -borafluoranthene.

[0078] In a two-necked flask equipped with a reflux apparatus, add aryl o-diboronic acid pinacol ester (structure shown in D1, 0.74 mmol, 1.05 equiv.), 1,8-dibromo-9,10-borazonaphthalene (200.0 mg, 0.70 mmol, 1.00 equiv.), tris(dibenzylideneacetone)palladium (Pd2dba3, 64.1 mg, 0.07 mmol, 0.10 equiv.), tris(o-methylphenyl)phosphine (P(o-OMePh)3, 98.7 mg, 0.28 mmol, 0.40 equiv.), potassium carbonate (583.6 mg, 4.2 mmol, 6.00 equiv.), purged with argon, add 25 mL of tetrahydrofuran and 2.5 mL of water, and reflux the mixture at 85 °C for 24 hours. The reaction was monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature, the solvent was removed by rotary evaporation, 150 mL of ethyl acetate was added to extract the product, the organic phases were combined, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the crude product was separated by column chromatography (evolving solvent: petroleum ether / dichloromethane = 4 / 1). The product obtained was compound A1, a yellow solid with a yield of 82%.

[0079] The compound was characterized, and its proton NMR spectrum was obtained as follows: Figure 1 As shown, the characterization data is as follows:

[0080] 1 H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 7.34 (dd, J = 5.6, 3.2 Hz, 2H; Ar-H), 7.23 (d, J = 5.6 Hz, 2H; Ar-H), 7.13 (d, J = 6.8 Hz, 2H; Ar-H), 6.97 (dd, J = 5.6, 3.2 Hz, 2H; Ar-H), 6.34 (t, J = 6.4 Hz, 2H; Ar-H); 13C NMR (101 MHz, CDCl3, 298 K, ppm): δ = 146.4 (s; CCH), 129.6 (s; CCH), 127.98 (s; CCH), 127.84 (s; CCH), 123.5 (s; CCH), 117.8 (s; CCH), (B-aryl carbons werenot observed); 11 B NMR (128 MHz, CDCl3, 298 K, ppm): δ = 35.24; HRMS (ESI): m / z calcd for C 14 H 11 BN + 204.0985 [M+H] + Found: 204.0991.

[0081] Example 2: Preparation of boron-nitrogen-doped fluoranthene compounds

[0082] Compounds 2-9 were prepared using the same method as in Example 1, except that the aryl o-diboronate compounds in Example 1 were replaced with other types of aryl o-diboronate compounds (such as dimethyl phenyl borate D5, which corresponds to product A5). The structural formulas of compounds A2-A9 and the structures of the aryl o-diboronate compounds D1-D8 used as raw materials are shown below.

[0083]

[0084]

[0085] Compound A2 (3a-aza-3a) 1 -borabenzo[k]fluoranthene) is a pale yellow-green solid with a yield of 44%. The proton NMR spectrum is as follows: Figure 2 As shown, the characterization data is as follows:

[0086] 1H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 7.86 (s, 2H; Ar-H), 7.71 (dd,J = 6.0, 3.2 Hz, 2H; Ar-H), 7.56 (d, J = 5.6 Hz, 2H; Ar-H), 7.44 (d, J = 6.4Hz, 2H; Ar-H), 7.36 (dd, J = 6.0, 3.2 Hz, 2H; Ar-H), 6.62 (t, J = 6.4 Hz, 2H; Ar-H); 13 C NMR (101 MHz, CDCl3, 298 K, ppm): δ = 144.3 (s; CCH), 134.2 (s; CCH), 129.5 (s; CCH), 128.6 (s; CCH), 127.9 (s; CCH), 126.1 (s; CCH), 121.9 (s; CCH), 118.2 (s; CCH), (B-aryl carbons were not observed); 11 B NMR (128MHz, CDCl3, 298 K, ppm) δ = 35.77. HRMS (ESI): m / z calcd for C 18 H 13 BN + :254.1141 [M+H] + Found: 254.1140.

[0087] Compound A3 (3a-aza-3a) 1 -borabenzo[j]fluoranthene) is an orange-red solid with a yield of 51%. The proton NMR spectrum is as follows: Figure 3 As shown, the characterization data is as follows:

[0088] 1H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 8.27 (d, J = 8.4 Hz, 1H; Ar-H), 7.73 (d, J = 8.0 Hz, 1H; Ar-H), 7.70 (d, J = 6.0 Hz, 1H; Ar-H), 7.64–7.56 (m, 2H; Ar-H), 7.45 (t, J = 7.6 Hz, 1H; Ar-H), 7.35 (t, J = 7.2 Hz, 1H; Ar-H), 7.29 (d, J = 6.0 Hz, 1H; Ar-H), 7.16 (t, J = 6.0 Hz, 2H; Ar-H), 6.44(t, J = 6.4 Hz, 1H; Ar-H), 6.38 (t, J = 6.4 Hz, 1H; Ar-H); 13 C NMR (101 MHz, CDCl3, 298 K, ppm): δ = 134.4 (s; CCH), 132.5 (s; CCH), 131.0 (s; CCH), 130.0 (s; CCH), 129.6 (s; CCH), 129.0 (s; CCH), 128.5 (s; CCH), 128.0 (s; CCH), 126.7 (s; CCH), 125.5 (s; CCH), 122.0 (s; CCH), 118.1 (s; CCH), 117.8 (s; CCH), (B-aryl carbons were not observed); 11 B NMR (128 MHz, CDCl3, 298 K, ppm)δ = 36.59; HRMS (ESI): m / z calcd for C 18 H 13 BN + : 254.1141 [M+H] + ; found: 254.1140.

[0089] Compound A4 (8,9-dimethoxy-3a-aza-3a) 1 -borafluoranthene is a yellow solid with a yield of 23%. The proton spectrum is as follows: Figure 4 As shown, the characterization data is as follows:

[0090] 1H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 7.16 (d, J = 6.0 Hz, 2H; Ar-H), 7.14 (d, J = 6.8 Hz, 2H; Ar-H), 7.02 (s, 2H; Ar-H), 6.37 (t, J = 6.4 Hz, 2H; Ar-H), 3.93 (s, 6H; OCH3) ppm. 13 C NMR (101 MHz, CDCl3, 298 K): δ 129.0(s; CCH), 126.2 (s; CCH), 118.0 (s; CCH), 117.7 (s; CCH), 107.6 (s; CCH), 100.1 (s; CCH), 56.2 (s; OCH3), (B-aryl carbons were not observed); 11 B NMR(128 MHz, CDCl3, 298 K, ppm) δ = 35.68; HRMS (ESI): m / z calcd for C 16 H 15 BNO2: 264.1196 [M+H] + Found: 264.1198.

[0091] Compound A5 (8,9-dimethyl-3a-aza-3a) 1 -borafluoranthene is a yellow solid with a yield of 70%. Its proton NMR spectrum is as follows: Figure 5 As shown, the characterization data is as follows:

[0092] 1 H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 7.35 (t, J = 6.4 Hz, 2H; Ar-H), 7.31–7.21 (m, 3H; Ar-H), 7.12 (dd, J = 9.2, 2.2 Hz, 1H; Ar-H), 6.74 (td,J = 9.2, 2.2 Hz, 1H; Ar-H), 6.49–6.42 (m, 2H; Ar-H); 1313C NMR (101 MHz, CDCl3, 298 K, ppm): δ = 130.3 (s; CCF), 129.2 (s; CCH), 128.8 (s; CCH), 127.4 (s; CCH), 124.1 (s; CCH), 124.0 (s; CCH), 118.0 (s; CCH), 117.7 (s; CCH), 113.9 (s; CCH), 113.7 (s; CCH), 111.4 (s; CCH), 111.2 (s; CCH), (B-aryl carbons were not observed); 11 11B NMR (128 MHz, CDCl3, 298 K, ppm) δ = 35.51; 19 19F NMR(376 MHz, CDCl3, 298 K) δ = 114.63 (dd, J = 9.02, 5.64 Hz) ppm. HRMS (ESI): m / z calcd for C 14 H 10 BFN + : 222.0890 [M+H] + ; found: 222.0888.

[0093] Compound A6 (9-fluoro-3a-aza-3a 1 -borafluoranthene) is a yellow solid with a yield of 69%. The 1H NMR spectrum is as Figure 6 shown, and the characterization data are as follows:

[0094] 1 1H NMR (400 MHz, CDCl3, 298 K): δ = 7.26–7.18 (m, 6H; Ar-H), 6.41 (t, J = 6.2 Hz, 2H; Ar-H), 2.23 (s, 6H; CH3); 13 13C NMR (101 MHz, CDCl3, 298 K, ppm): δ = 144.1 (s; CCH), 136.1 (s; CCH), 129.2 (s; CCH), 126.9 (s; CCH), 125.1 (s; CCH), 117.7 (s; CCH), 20.2 (s; CCH3), (B-aryl carbons were not observed); 11B NMR (128 MHz, CDCl3, 298 K, ppm) δ = 35.55; HRMS (ESI): m / zcalcd for C 16 H 15 BN + : 232.1298 [M+H] + Found: 232.1300.

[0095] Compound A7 (9-methyl-3a-aza-3a) 1 -borafluoranthene is a yellow solid with a yield of 67%. Its proton NMR spectrum is as follows: Figure 7 As shown, the characterization data is as follows:

[0096] 1 H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 7.32 (t, J = 6.0 Hz, 2H; Ar-H), 7.28–7.22 (m, 4H; Ar-H), 6.87 (d, J = 7.6 Hz, 1H; Ar-H), 6.43 (td, J =6.4, 3.2 Hz, 2H; Ar-H), 2.31 (s, 3H; CH3); 13 C NMR (101 MHz, CDCl3, 298 K,ppm): δ = 146.5 (s; CCH), 143.6 (s; CCH), 137.8 (s; CCH), 129.6 (s; CCH), 129.2 (s; CCH), 128.5 (s; CCH), 127.6 (s; CCH), 127.0 (s; CCH), 124.6 (s; CCH), 123.3 (s; CCH), 117.9 (s; CCH), 117.7 (s; CCH), 21.7 (s; CCH3), (B-arylcarbons were not observed); 11 B NMR (128 MHz, CDCl3, 298 K, ppm) δ = 35.34; HRMS (ESI): m / z calcd for C 15 H 12 BN: 217.1063 [M]; found: 217.1061.

[0097] Compound A8 (2-bromo-3a-aza-3a) 1-borafluoranthene is a yellow solid with a yield of 30%. The proton NMR spectrum is as follows: Figure 8 As shown, the characterization data is as follows:

[0098] 1 H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 7.51 (s, 1H; Ar-H), 7.45–7.39(m, 2H; Ar-H), 7.38 (s, 1H; Ar-H), 7.32 (d, J = 5.6 Hz, 1H; Ar-H), 7.19 (d, J= 6.8 Hz, 1H; Ar-H), 7.14–7.03 (m, 2H; Ar-H), 6.46 (t, J = 6.4 Hz, 1H; Ar-H); 13 C NMR (101 MHz, CDCl3, 298 K, ppm): δ = 131.9 (s; CCH), 129.3 (s; CCH), 128.90 (s; CCH), 128.85 (s; CCH), 128.4 (s; CCH), 128.2 (s; CCH), 124.1(s;CCH), 123.7 (s; CCH), 118.3 (s; CCH), (B-aryl carbons were not observed); 11 BNMR (128 MHz, CDCl3, 298 K, ppm) δ = 34.80; HRMS (ESI): m / z calcd forC 14 H 10 BNBr + : 282.0090 [M+H] + Found: 282.0085.

[0099] Compound A9 (8-thia-3a-aza-3a 1 (-boracyclopenta[a]acenaphthylene) is a pale orange-yellow solid with a yield of 79%. Its proton NMR spectrum is as follows: Figure 9 As shown, the characterization data is as follows:

[0100] 1H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 7.37 (d, J = 6.0 Hz, 2H; Ar-H), 7.33 (d, J = 6.0 Hz, 2H; Ar-H), 7.10 (s, 2H; Ar-H), 6.54 (t, J = 6.4 Hz, 2H; Ar-H); 13 C NMR (101 MHz, CDCl3, 298 K, ppm): δ = 150.0 (s; CCH), 128.8 (s; CCH), 127.3 (s; CCH), 117.5 (s; CCH), 116.0 (s; CCH), (B-aryl carbons were not observed); 11 B NMR (128 MHz, CDCl3, 298 K) δ = 37.51 ppm; HRMS (ESI): m / zcalcd for C 12 H9BNS + : 210.0549 [M+H] + Found: 210.0544.

[0101] Example 3: Preparation of boron-nitrogen-doped fluoranthene compounds

[0102] A10;

[0103] Compound A10 (7,9-dibromo-8-thia-3a-aza-3a) 1 Preparation of -boracyclopenta[a]acenaphthylene.

[0104] Compound A9 (8-thia-3a-aza-3a) obtained in Example 2 1 1-Boracyclopenta[a]acenaphthylene (248.6 mg, 1.19 mmol, 1.00 equivalent) was dissolved in chloroform, and the solution was then cooled in an ice bath for 10 minutes. A solution of liquid bromine in chloroform (110 μL, 2.44 mmol, 2.05 equivalent) was then slowly added dropwise. The mixture was stirred for 30 minutes, quenched with saturated sodium bisulfite solution, and extracted with chloroform (50 mL). The combined organic phases were dried over anhydrous sodium sulfate and concentrated by rotary evaporation to remove the solvent. The crude product was purified by preparative HPLC to give compound A10 as a light brown solid (98.5 mg, 23% yield). The 1H NMR spectrum is shown below. Figure 10 As shown, the characterization data is as follows:

[0105] 1 H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 7.62 (d, J = 6.0 Hz, 2H; Ar-H), 7.48 (d, J = 6.4 Hz, 2H; Ar-H), 6.63 (t, J = 6.4 Hz, 2H; Ar-H); 13 C NMR (101 MHz, CDCl3, 298 K): δ = 129.5 (s; CCH), 128.7 (s; CCH), 117.8 (s; CCH), (B-aryl carbons were not observed); 11 B NMR (128 MHz, CDCl3, 298 K, ppm) δ =36.70; HRMS (ESI): m / z calcd for C 12 H7BNSBr2 + 365.8759 [M+H] + ; found: 365.8761.

[0106] Example 4: Preparation of the parent compound of bis-boron nitrogen-doped acenaphthene[1,2-k]fluoranthene

[0107] A11;

[0108] Preparation of compound A11 (BN-doped acenaphtho[1,2-k]fluoranthene).

[0109] In a glove box, phenyl tetraborate pinacol ester (98.8 mg, 0.17 mmol, 0.5 equiv.), 1,8-dibromo-9,10-borazanaphthalene (100.0 mg, 0.35 mmol, 1.0 equiv.), tris(dibenzylacetone)palladium (Pd2dba3, 32.0 mg, 0.035 mmol, 0.10 equiv.), tris(cyclohexyl)phosphine (P(Cyc)3, 39.2 mg, 0.14 mmol, 0.40 equiv.), and potassium carbonate (580.5 mg, 4.2 mmol, 12.00 equiv.) were added to a sealed tube. A mixed solution of 2 mL toluene and 0.2 mL water was added, and the reaction was heated at 130 °C for 24 h. The reaction was monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature, and the product was extracted with 300 mL of dichloromethane. The organic phases were combined, dried over anhydrous Na₂SO₄, and filtered to remove impurities. The solvent was removed by concentration under reduced pressure, followed by sonication for 5 minutes with the addition of 2 ml of cold anhydrous methanol, and then filtered. The filter cake was collected and washed twice with anhydrous methanol to give compound A11 as a red solid, in 54% yield. Characterization data are as follows:

[0110] 1 H NMR (400 MHz, CD2Cl2, 298 K, ppm): δ = 7.60 (s, 2H; Ar-H), 7.35 (d,J = 5.2 Hz, 4H; Ar-H), 7.31 (d, J = 6.4 Hz, 4H; Ar-H), 6.49 (t, J = 6.4 Hz,4H; Ar-H); 1 H NMR (400 MHz, DMSO-d6, 298 K, ppm): δ = 7.66 (s, 2H; Ar-H), 7.63 (d, J = 5.8 Hz, 4H; Ar-H), 7.40 (d, J = 6.0 Hz, 4H; Ar-H), 6.56 (t, J = 6.2Hz, 4H; Ar-H); 13 C NMR (101 MHz, CD2Cl2, 298 K): δ = 131.9 (s; CCH), 130.0 (s; CCH), 127.8 (s; CCH), 126.0 (s; CCH), 118.2(s; CCH), (B-aryl carbons were notobserved); 11B NMR (128 MHz, CD2Cl2, 298 K, ppm) δ = 35.43; HRMS (ESI): m / zcalcd for C 22 H 15 B2N2 + 329.1421 [M+H] + Found: 329.1422.

[0111] Example 5: Preparation of acenaphthene[1,2-k]fluoranthene parent compound

[0112] A12;

[0113] Preparation of compound A12 (acenaphtho[1,2-k]fluoranthene).

[0114] In a glove box, phenyl tetraborate pinacol ester (308.4 mg, 0.53 mmol, 0.5 equiv.), 1,8-dibromonaphthalene (300.0 mg, 1.05 mmol, 1.0 equiv.), tris(dibenzylacetone)palladium (Pd2dba3, 96.2 mg, 0.11 mmol, 0.10 equiv.), tris(cyclohexyl)phosphine (P(Cyc)3, 117.8 mg, 0.42 mmol, 0.40 equiv.), potassium carbonate (1.74 g, 12.6 mmol, 12.00 equiv.), and a mixture of 5 mL toluene and 0.5 mL water were added to a sealed tube. The reaction was heated at 130 °C for 24 hours. The reaction was monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature, and the product was extracted with 300 mL of dichloromethane. The organic phases were combined, dried over anhydrous Na₂SO₄, and filtered to remove impurities. The solvent was removed by concentration under reduced pressure, followed by sonication for 5 minutes with the addition of cold anhydrous methanol (2 ml), and then filtered. The filter cake was collected and washed twice with anhydrous methanol to give compound A12 as a yellow-green solid in 44% yield. Characterization data are as follows:

[0115] 1 H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 8.44 (s, 2H; Ar-H), 8.05 (d,J = 6.8 Hz, 4H; Ar-H), 7.87 (d, J = 8.0 Hz, 4H; Ar-H), 7.69 (t, J = 7.4 Hz,4H; Ar-H); 13C NMR (101 MHz, CD2Cl2, 298 K, ppm): δ = 139.4 (s; CCH), 137.3 (s; CCH), 128.2 (s; CCH), 126.8 (s; CCH), 120.2 (s; CCH), 115.1 (s; CCH). 3

[0116] Example 6: Performance Analysis of Boron-Nitrogen-Doped Fluoranthracite Compounds

[0117] Photophysical studies were conducted on compounds A1, A2, and A11, and their absorption and emission spectra were obtained, as shown in the attached figures. Figure 12-14 As shown, analysis revealed a redshift in emission of boron-nitrogen fluoranthene A1 compared to all-carbon fluoranthene, possibly due to the increased band gap caused by the introduction of boron-nitrogen units. The absorption and emission of bis-boron-nitrogen-doped acenaphthene [1,2-k]fluoranthene are shown in the attached figure. Figure 14 As shown, the absorption spectrum exhibits strong absorption between 325 nm and 375 nm, while weaker absorption occurs between 400 nm and 450 nm. The emission spectrum is between 500 nm and 800 nm. Compared with the absorption and emission spectrum of the all-carbon structure acenaphthene[1,2-k]fluoranthene, it shows a significant red shift, which is due to the intramolecular charge transfer phenomenon in the extended conjugated structure or the double boron nitrogen doped structure.

[0118] In addition, thermogravimetric analysis was performed on compounds A1 and A11, and the results are as follows: Figure 15 As shown, when the thermogravimetric loss of the compounds is 5%, the corresponding temperature for compound A1 is 192℃, and the corresponding temperature for compound A11 is 355℃, indicating that compound A11 has higher thermal stability.

[0119] Example 7:

[0120] The charge transport properties of compound Al1 were evaluated, and a bottom-gate top-contact (BGTC) single-crystal device containing compound Al11 was fabricated. The crystal was grown using an air-gap sublimation method. Figure 16 As shown, the representative transfer and output characteristics of the device, measured under environmental conditions, are illustrated. The device exhibits p-type transport behavior with a hole mobility as high as 0.8 cm⁻¹. 2 V -1 s -1 The on / off ratio is approximately 10. 6 This demonstrates that compound A11 possesses superior charge transport properties and can be applied in the field of organic optoelectronic functional materials.

[0121] The embodiments of the present invention have been described in detail above, but the content described is only a preferred embodiment of the present invention and should not be considered as limiting the scope of the present invention. All equivalent changes and improvements made in accordance with the scope of the present invention should still fall within the patent coverage of the present invention.

Claims

1. A boron-nitrogen-doped fluoranthene compound, characterized in that: The structure is shown in Equation 1 or Equation 2; Formula 1; Formula 2; Among them, R 1 - R 10 For substituted or unsubstituted aryl, heteroaryl, C1-C 12 Straight-chain or branched alkyl, methoxy, ethoxy, n-propoxy, isopropoxy, vinyl, allyl, ethynyl, propynyl, triarylamine, hydrogen or halogen atom; R 1 -R 10 Same, partially the same, or different; The halogen atom is F, Cl, Br, or I; Ar represents substituted or unsubstituted benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, thiophene, furan, pyrrole, pyridine, benzothiophene, benzofuran, benzopyrrole, or benzopyridine.

2. The boron-nitrogen-doped fluoranthene compound according to claim 1, characterized in that: The structures of boron-nitrogen-doped fluoranthene compounds are shown in formula C1, formula C2 or formula C3; ； Alternatively, the structure of the bis-boron nitrogen-doped acenaphthene[1,2-k]fluoranthene parent compound is shown in formula C4; ； Among them, R 7 – R 18 For substituted or unsubstituted aryl, heteroaryl, C1-C 12 Straight-chain or branched alkyl, methoxy, ethoxy, n-propoxy, isopropoxy, vinyl, allyl, ethynyl, propynyl, triarylamine, hydrogen or halogen atom; R 7 -R 18 Same, partially the same, or different; The halogen atom is F, Cl, Br, or I; Ar represents substituted or unsubstituted benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, thiophene, furan, pyrrole, pyridine, benzothiophene, benzofuran, benzopyrrole, or benzopyridine.

3. The boron-nitrogen-doped fluoranthene compound according to claim 1, characterized in that: The structure is shown in any of the formulas A1-A11; 。 4. The method for preparing the boron-nitrogen-doped fluoranthene compound according to any one of claims 1-3, characterized in that: Boron-nitrogen-doped fluoranthene compounds with embedded boron-nitrogen units were synthesized in a one-pot manner via palladium-catalyzed Suzuki–Miyaura coupling reaction using 1,8-dibromoborazane and aryl o-diboronate or aryl tetraboronate as raw materials.

5. The method for preparing boron-nitrogen-doped fluoranthene compounds according to claim 4, characterized in that: Under inert gas protection, 1,8-dibromoborazonaphthalene, aryl o-diboronate or aryl tetraboronate, palladium catalyst, phosphine ligand and base are added to a mixture of organic solvent and water, and the mixture is heated to prepare boron nitrogen-doped fluoranthene compounds.

6. The method for preparing boron-nitrogen-doped fluoranthene compounds according to claim 5, characterized in that: The palladium catalyst is one or a combination of tetra(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride and tris(dibenzylacetone)palladium; The phosphine ligand is one or more of the following: triphenylphosphine, tricyclohexylphosphine, tributylphosphine, tritert-butylphosphine, tri(o-methoxyphenyl)phosphine, and tri(p-methoxyphenyl)phosphine; The molar ratio of palladium catalyst to phosphine ligand is 1:1 to 1:

2.

7. The method for preparing boron-nitrogen-doped fluoranthene compounds according to claim 5 or 6, characterized in that: The base is one or more of potassium carbonate, potassium phosphate, potassium acetate, sodium carbonate, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, and triethylamine; the concentration of the base in the reaction system is 1.0–2.0 mol / L; The organic solvent is one or more of toluene, tetrahydrofuran, 1,4-dioxane and ethanol; The inert gas is argon or nitrogen; the reaction temperature is 80-130℃.

8. A method for preparing an acenaphthene[1,2-k]fluoranthene compound, characterized in that: Anenaphthene[1,2-k]fluoranthene was synthesized in a one-pot reaction via palladium-catalyzed Suzuki–Miyaura coupling from 1,8-dibromonaphthene and aryltetraborate esters. Preferably, under inert gas protection conditions, 1,8-dibromonaphthalene, aryl o-diboronate or aryl tetraboronate, palladium catalyst, phosphine ligand and base are added to a mixture of organic solvent and water, and the mixture is heated to prepare boron nitrogen-doped fluoranthene compounds. Preferably, the palladium catalyst is one or a combination of tetra(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, and tris(dibenzylacetone)palladium; The phosphine ligand is one or more of the following: triphenylphosphine, tricyclohexylphosphine, tributylphosphine, tritert-butylphosphine, tri(o-methoxyphenyl)phosphine, and tri(p-methoxyphenyl)phosphine; The molar ratio of palladium catalyst to phosphine ligand is 1:1 to 1:2; Preferably, the base is one or a combination of potassium carbonate, potassium phosphate, potassium acetate, sodium carbonate, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, and triethylamine; the concentration of the base in the reaction system is 1.0–2.0 mol / L. The organic solvent is one or more of toluene, tetrahydrofuran, 1,4-dioxane and ethanol; The inert gas is argon or nitrogen; the reaction temperature is 80-130℃.

9. The application of the boron-nitrogen-doped fluoranthene compounds according to any one of claims 1-3 in organic optoelectronic materials.

10. The application according to claim 9, characterized in that: Organic semiconductor materials used in organic field-effect transistors.

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