A diaryl-substituted cyclopentadienyl fused hexabenzoxamethylene derivative and its synthesis method

Abstract

This invention discloses a diaryl-substituted cyclopentadienyl fused hexabenzoxamethylene derivative and its synthesis method, belonging to the field of organic optoelectronic functional materials technology. This invention utilizes the unique five-membered ring structure to introduce a positive curvature similar to fullerenes into the molecular skeleton by fused cyclopentadienyl groups onto the hexabenzoxamethylene skeleton, thus suppressing excessive molecular aggregation in the solid state. Simultaneously, the introduction of sterically hindered substituents such as mesitylene, triphenylmethyl, and tert-butylphenyl onto the five-membered ring further increases the π-π planar spacing, weakens intermolecular π-π stacking, significantly improves the solubility, film-forming properties, and solid-state luminescence performance of the derivative, and effectively suppresses aggregation-induced fluorescence quenching.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic functional materials technology, specifically to a diaryl-substituted cyclopentadienyl fused hexabenzoxamethylene derivative and its synthesis method. Background Technology

[0002] Hexabenzo[a]oxane (HBC), a typical all-benzene polycyclic aromatic hydrocarbon, exhibits strong π-π stacking effects, good thermochemical stability, and tunable photoelectric properties due to its highly symmetrical planar conjugated structure and large π-conjugated system, making it a promising candidate for applications in organic optoelectronics and liquid crystal materials. However, unsubstituted HBC molecules suffer from inherent drawbacks such as poor solubility, difficulty in solution processing, and limited methods for performance tuning. These drawbacks severely restrict its practical industrial applications in organic field-effect transistors, organic photovoltaic cells, energy storage devices, bioimaging, and nano-optoelectronic devices.

[0003] Existing technologies focus on the structural design and functional modification of hexabenzoxanone molecules, developing various modification strategies such as alkyl / alkoxy substitution, heteroatom doping, and donor-acceptor (DA) unit composites. Through precise modification of the hexabenzoxanone skeleton, a series of hexabenzoxanone derivatives with tunable properties have been obtained, broadening its application scenarios. Current modification strategies mainly fall into two categories: The first category introduces long-chain alkyl groups such as dodecyl and octadecyl groups into the L-region of the hexabenzoxanone molecule. Utilizing the flexibility and hydrophobic properties of long alkyl chains, the solubility of the molecule and the stability of the material are improved, while also inducing ordered self-assembly of the hexabenzoxanone molecule and optimizing charge transport efficiency. The second category introduces planar aromatic groups such as benzene rings and naphthalene rings into the L-region. Through conjugation fusion, the π-conjugated system of the molecule is strengthened. The structural characteristics of the planar aromatic rings enhance the intermolecular π-π stacking interaction, improving the charge mobility of the material. Simultaneously, the sterically hindered aromatic rings can suppress excessive aggregation while broadening the light absorption range of the molecule and optimizing the molecular orbital structure.

[0004] However, the two existing L-region modification strategies for hexabenzoxanthium still have significant technical drawbacks: On the one hand, while the long-chain alkyl modification strategy improves the solubility and processability of hexabenzoxanthium molecules, the aliphatic long chains excessively weaken the intermolecular interaction forces, resulting in a significant decrease in the crystallinity of the hexabenzoxanthium material and damage to its mechanical properties. Furthermore, it cannot increase the spacing between the π-planes of hexabenzoxanthium molecules in the aggregated or solid state, leading to significant fluorescence quenching. This strategy sacrifices the material's potential as a light-emitting functional material, making it unsuitable for organic light-emitting devices. On the other hand, the planar aromatic group modification strategy, due to the strong planarity and rigidity of the substituent groups themselves, further strengthens the π-π stacking and charge transfer interactions between molecules. This not only fails to suppress the aggregation-induced quenching effect commonly found in polycyclic aromatic hydrocarbons, but also exacerbates the process of excited-state molecules returning to the ground state through non-radiative transitions, leading to rapid fluorescence decay in the aggregated or solid state. This is also difficult to apply to organic optoelectronic devices that require high luminescence performance. Summary of the Invention

[0005] The purpose of this invention is to solve the above-mentioned technical problems and provide a diaryl-substituted cyclopentadienyl fused hexabenzoxamethylene derivative and its synthesis method.

[0006] The above-mentioned objective of the present invention is achieved through the following technical solution:

[0007] A cyclopentadienyl fused hexabenzo[a]oxane derivative, wherein the structural formula of the cyclopentadienyl fused hexabenzo[a]oxane derivative is selected from one of the following structural formulas:

[0008] , , , , , , ;

[0009] Ar is selected from one or more of trimethylbenzyl, triphenylmethyl and tert-butylphenyl.

[0010] This invention fuses cyclopentadiene groups onto the basic hexabenzo[a]oxane (HBC) skeleton, such as... , , By utilizing the unique structure of the five-membered ring, a positive curvature similar to that of fullerenes is introduced into the HBC molecular skeleton, effectively preventing excessive aggregation of hexabenzo[a]oxane molecules caused by their planar structure. Furthermore, introducing sterically hindered substituents, such as mesitylene (Mes), triphenylmethyl, and tert-butylphenyl, onto the five-membered ring yields diaryl-substituted cyclopentadienyl-fused hexabenzo[a]oxane derivatives, such as... , , This further increases the distance between the π-π planes of HBC molecules, inhibiting intermolecular aggregation. By introducing tert-butyl ( t Bu can further increase the steric hindrance between molecules, effectively suppress the intermolecular π-π stacking effect of hexabenzoxan derivatives, thereby improving their solubility and film-forming properties, and enhancing their photophysical properties in solution and solid state.

[0011] A diaryl-substituted cyclopentadienyl fused hexabenzoxan derivative The synthesis method includes the following steps:

[0012] S1. 4-Bromo-9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene (structural formula: Cuprous iodide and palladium bis(triphenylphosphine)dichloride are dissolved in triethylamine, and triisopropylsilylacetylene is added to react and give ((9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene-4-yl)acetylenyl)triisopropylsilane (structural formula: ); where Ar is tert-butylphenyl;

[0013] S2. Dissolve ((9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene-4-yl)ethynyl)triisopropylsilane in an organic solvent, add tetrabutylammonium fluoride and react to obtain 9,9-bis(4-(tert-butyl)phenyl)-4-ethynyl-9H-fluorene (structural formula: );

[0014] S3. 9,9-bis(4-(tert-butyl)phenyl)-4-ethynyl-9H-fluorene and 2,3,4,5-tetratetra(4-tert-butylphenyl)cyclopentan-2,4-dien-1-one were dissolved in an organic solvent to obtain 9,9-bis(4-(tert-butyl)phenyl)-4-(4,4''-di-tert-butyl-5',6'-bis(4-(tert-butyl)phenyl)-[1,1':2',1''-terphenyl]-3'-yl)-9H-fluorene (structural formula: );

[0015] S4. Dissolve 9,9-bis(4-(tert-butyl)phenyl)-4-(4,4''-di-tert-butyl-5',6'-bis(4-(tert-butyl)phenyl)-[1,1':2',1''-terphenyl]-3'-yl)-9H-fluorene and 2,3-dichloro-5,6-dicyanobenzoquinone in an organic solvent, add trifluoromethanesulfonic acid, and react to obtain the diaryl-substituted cyclopentadienyl fused hexabenzoquinone derivative. (5,8,11,14-tetratert-butyl-1,1-bis(4-tert-butylphenyl)-1H-tetrabenzo[ef,hi,kl,no]fluoren[3,4,5,6-qrabc]cor).

[0016] Further, in S1, the molar ratio of 4-bromo-9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene, cuprous iodide, bis(triphenylphosphine)palladium dichloride and triisopropylsilylacetylene is 1:(0.08-0.12):(0.08-0.12):(3-5).

[0017] Furthermore, in S1, the reaction temperature is 80-100 °C and the time is 16-20 h.

[0018] Furthermore, in S2, the organic solvent is tetrahydrofuran (THF); the reaction time is 3-5 h.

[0019] Further, in S3, the molar ratio of 9,9-bis(4-(tert-butyl)phenyl)-4-ethynyl-9H-fluorene to 2,3,4,5-tetra(4-tert-butylphenyl)cyclopentan-2,4-dien-1-one is (3-5):(5-7).

[0020] Furthermore, in S3, the organic solvent is o-xylene; the reaction is carried out under an argon atmosphere for 20-24 h.

[0021] Further, in S4, the molar ratio of 9,9-bis(4-(tert-butyl)phenyl)-4-(4,4''-di-tert-butyl-5',6'-bis(4-(tert-butyl)phenyl)-[1,1':2',1''-terphenyl]-3'-yl)-9H-fluorene to 2,3-dichloro-5,6-dicyanobenzoquinone is 1:(5-7).

[0022] Furthermore, in S4, the organic solvent is dichloromethane; the reaction temperature is 15-25 °C, and the reaction time is 1-3 h.

[0023] A diaryl-substituted cyclopentadienyl fused hexabenzoxan derivative The synthesis method includes the following steps:

[0024] P1. 4-Bromo-9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene (structural formula: Pinaryl diborate, potassium acetate, and [1,1′-bis(diphenylphosphine)ferrocene]palladium dichloride are dissolved in an organic solvent to react and yield 2-(9,9-bis(4-(tert-butyl)phenyl)-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxane (structural formula: );

[0025] P2. Dissolve 2-(9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxane-pentaborane, 1,3,5-tribromobenzene, and barium hydroxide in a solvent, then add tetra(triphenylphosphine)palladium to react and obtain 4,4'-(5-bromo-1,3-phenylene)bis(9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene) (structural formula: );

[0026] P3. 4,4'-(5-bromo-1,3-phenylene)bis(9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene), pinacol biphenyl-2-borate, and barium hydroxide were dissolved in a solvent, and tetrakis(triphenylphosphine)palladium was added to react and yield 3,5-bis(9,9-bis(4-tert-butylphenyl)-9H-fluorene-4-yl)-1,1':2',1''-terphenyl (structural formula: );

[0027] P4. 3,5-bis(9,9-bis(4-tert-butylphenyl)-9H-fluoren-4-yl)-1,1':2',1''-terphenyl and 2,3-dichloro-5,6-dicyanobenzoquinone were dissolved in an organic solvent, and trifluoromethanesulfonic acid was added to react and obtain the diaryl-substituted cyclopentadienyl fused hexabenzoquinone derivative. (1,1,6,6-Tetra(4-tert-butylphenyl)-1,6-dihydrodibenzo[kl,no]difluoren[3,4,5,6-efghi:3',4',5',6'-qrabc]).

[0028] Further, in P1, the molar ratio of 4-bromo-9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene, pinacol diborate, potassium acetate and [1,1′-bis(diphenylphosphine)ferrocene]palladium dichloride is (0.3-0.5):(5-7):(1-3):(0.06-0.08).

[0029] Furthermore, in P1, the organic solvent is 1,4-dioxane; the reaction temperature is 90-110 °C, and the reaction time is 12-16 h.

[0030] Further, in P2, the molar ratio of 2-(9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxacyclopentaborane, 1,3,5-tribromobenzene, barium hydroxide and tetra(triphenylphosphine)palladium is (1-3):(0.8-1.2):(5-7):(0.12-0.15).

[0031] Furthermore, in P2, the solvent is a mixed solvent of 1,4-dioxane and water; the reaction time is 14-18 h.

[0032] Further, in P3, the molar ratio of 4,4'-(5-bromo-1,3-phenylene)bis(9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene), biphenyl-2-borate pinacol ester, barium hydroxide and tetra(triphenylphosphine)palladium is (8-10):(12-14):(90-100):(2-4).

[0033] Furthermore, in P3, the solvent is a mixed solvent of 1,4-dioxane and water; the reaction time is 12-16 h.

[0034] Further, in P4, the molar ratio of 3,5-bis(9,9-bis(4-tert-butylphenyl)-9H-fluorene-4-yl)-1,1':2',1''-terphenyl to 2,3-dichloro-5,6-dicyanobenzoquinone is 1:(5-7).

[0035] Furthermore, in P4, the organic solvent is dichloromethane (DCM); the reaction temperature is 15-25 °C, and the time is 1-3 h.

[0036] A diaryl-substituted cyclopentadienyl fused hexabenzoxan derivative The synthesis method includes the following steps:

[0037] (1) 9,9-bis(4-(tert-butyl)phenyl)-4-ethynyl-9H-fluorene (structural formula: Cobalt salt, zinc powder, and zinc salt are dissolved in an organic solvent to react and yield 1,3,5-tris(9,9-bis(4-tert-butylphenyl)-9H-fluorene-4-yl)benzene (structural formula: );

[0038] (2) 1,3,5-tris(9,9-bis(4-tert-butylphenyl)-9H-fluoren-4-yl)benzene and 2,3-dichloro-5,6-dicyanobenzoquinone were dissolved in an organic solvent, and trifluoromethanesulfonic acid was added to react and obtain the diaryl-substituted cyclopentadienyl fused hexabenzoquinone derivative. (1,1,6,6,11,11-hexa(4-tert-butylphenyl)-6,11-dihydro-1H-trifluoren[3,4,5,6-efghi:3',4',5',6'-klmno:3'',4'',5'',6''-qrabc]).

[0039] Further, in step (1), the molar ratio of 9,9-bis(4-(tert-butyl)phenyl)-4-ethynyl-9H-fluorene, cobalt salt, zinc powder and zinc salt is (60-80):(6-8):(6-8):(6-8).

[0040] Further, in step (1), the cobalt salt is cobalt bromide, the zinc salt is zinc iodide, the organic solvent is acetonitrile, and the reaction is carried out under degassing conditions for 40-56 h.

[0041] Further, in step (2), the molar ratio of 1,3,5-tris(9,9-bis(4-tert-butylphenyl)-9H-fluorene-4-yl)benzene to 2,3-dichloro-5,6-dicyanobenzoquinone is 1:(4-6).

[0042] Further, in step (2), the organic solvent is 1,1,2,2-tetrachloroethane; the reaction temperature is 40-60 °C and the time is 1-3 h.

[0043] Furthermore, in step (2), the reaction is carried out under an argon atmosphere.

[0044] The above-described technical solution of the present invention has the following beneficial effects:

[0045] This invention addresses the problem of excessive aggregation of HBC molecules due to their planar structure by fused cyclopentadiene groups onto the HBC backbone, utilizing the unique structure of the five-membered ring to introduce a positive curvature similar to that of fullerenes. Simultaneously, the introduction of sterically hindered substituents such as mesitylene, triphenylmethyl, and tert-butylphenyl onto the five-membered ring further increases the π-π planar spacing of the HBC molecule, enhancing the inhibition of molecular aggregation. Through the synergistic effect of the positive curvature structure and the sterically hindered substituents, this invention significantly suppresses the aggregation-induced fluorescence quenching effect of HBC molecules, improves the solubility, processability, and charge transport properties of the derivative, and enables it to exhibit excellent photophysical properties in both solution and solid states. Attached Figure Description

[0046] Figure 1 This is a schematic diagram of substituent modification in the L region of an HBC molecule; where a) is an HBC molecule modified with dodecyl groups and b) is an HBC molecule modified with aromatic groups.

[0047] Figure 2 The UV-Vis absorption spectra (solid lines) and photoluminescence spectra (dashed lines) of TTC prepared in Example 1 and TDC prepared in Example 2 in chloroform solution are shown.

[0048] Figure 3 The solid-state UV-Vis absorption spectra (solid lines) and photoluminescence spectra (dashed lines) of TTC and TDC thin films are shown. Detailed Implementation

[0049] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0050] A schematic diagram of existing techniques for substituent modification of the L region of HBC molecules is shown below. Figure 1 As shown, a) is a dodecyl-modified HBC molecule, and b) is an aromatic-modified HBC molecule. However, simply introducing long-chain alkyl or aromatic groups cannot effectively inhibit the aggregation-induced quenching of HBC molecules, which limits their application in organic optoelectronic devices.

[0051] Therefore, the present invention provides a cyclopentadienyl fused hexabenzo[a]oxane derivative, wherein the structural formula of the cyclopentadienyl fused hexabenzo[a]oxane derivative is selected from one of the following structural formulas:

[0052] , , , , , , ;

[0053] Ar is selected from one or more of trimethylbenzyl, triphenylmethyl and tert-butylphenyl.

[0054] This invention designs and synthesizes a series of cyclopentadienyl fused hexabenzo[a]oxane derivatives, and by introducing sterically hindered aryl-substituted cyclopentadienyl groups into the bay region of the HBC molecule, diaryl-substituted cyclopentadienyl fused hexabenzo[a]oxane derivatives can be formed.

[0055] The cyclopentadienyl fused hexabenzoxan derivatives provided by this invention are hexabenzoxan derivatives with a large π-conjugated system, and also involve derivatives with diaryl-substituted cyclopentadienyl structural units fused to their HBC backbone.

[0056] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.

[0057] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the materials and reagents used are commercially available.

[0058] In the following examples, 4-bromo-9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene (structural formula: It is prepared by the following method:

[0059]

[0060] a. After three evacuations in a 100 mL Schlenk tube, 1,2-dibromobenzene (2.01 g, 8.47 mmol) and THF (21 mL) were added. The reaction system was cooled to -78 °C (liquid nitrogen / acetone bath), and at this temperature, n-butyllithium solution (1.6 M, 2.7 mL) was slowly added dropwise. After the addition was complete, the mixture was stirred at this temperature for 30 min. The reaction mixture was then transferred to an ice-water bath, and the reaction was continued for 16 h. The reaction was quenched with 10% hydrochloric acid solution and stirred for 5 min. The product was then extracted and separated by column chromatography using pure petroleum ether as the eluent to obtain 2,2'-dibromobiphenyl in 53% yield. NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.69 (d, J = 7.9 Hz, 2H), 7.40(td, J = 7.4, 1.2 Hz, 2H), 7.28 (ddd, J = 9.6, 7.5, 1.8 Hz, 4H); 13 C NMR (101 MHz, Chloroform- d ) d 142.07, 132.61, 131.01, 129.43, 127.16, 123.54.

[0061] b. Weigh 0.213 g (0.680 mmol) of 2,2'-dibromobiphenyl into a 50 mL dry Schlenk tube. After three evacuations, add 6 mL of THF as a solvent. Cool the reaction system to -78 °C (liquid nitrogen / acetone bath). At this temperature, slowly add 0.4 mL of 1.6 M n-butyllithium solution. After the addition is complete, maintain the reaction temperature for 1 h. Take another dry 50 mL Schlenk tube, weigh 0.193 g (0.654 mmol) of di(4-tert-butylphenyl) ketone into the Schlenk tube, add a magnetic stir bar, evacuate the gas three times, and add 2 mL of THF. After 1 h, transfer the di(4-tert-butylphenyl) ketone solution to the above low-temperature reaction system and continue to maintain the reaction temperature at -78 °C for 2.5 h. Quench the reaction with 10% hydrochloric acid solution and stir for 5 min. Subsequently, extraction and separation were performed using DCM and saturated brine. The product was then purified by column chromatography using DCM / petroleum ether (volume ratio 1:3) as the eluent to obtain (6-bromo-[1,1'-biphenyl]-2-yl)bis(4-(tert-butyl)phenyl)methanol, with a yield of 52%. NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.58 (dd, J = 8.0, 1.2 Hz, 1H),7.36 – 7.23 (m, 6H), 7.17 – 7.12 (m, 2H), 7.06 (ddd, J = 8.2, 4.4, 1.8 Hz, 4H),6.97 (dd, J = 7.9, 1.4 Hz, 1H), 6.88 (td, J = 7.5, 1.3 Hz, 1H), 6.37 (dd, J = 7.7, 1.7 Hz, 1H), 2.64 (s, 1H), 1.35 (s, 9H), 1.32 (s, 9H); Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS) data are: MALDI-TOF·MS: m / z cald for C 33 H 35 BrO: 528.19, [M-OH] + = 510.18.

[0062] c. (6-Bromo-[1,1'-biphenyl]-2-yl)bis(4-(tert-butyl)phenyl)methanol (783 mg, 1.39 mmol) was added to a dried Schlenk tube, followed by DCM (7.23 mL). Boron trifluoride diethyl ether complex (0.250 mL) was dissolved in the DCM solution of (6-bromo-[1,1'-biphenyl]-2-yl)bis(4-(tert-butyl)phenyl)methanol in the Schlenk tube. The mixture was stirred at room temperature for 24 h. After the reaction was complete, ethanol (5 mL) and water (5 mL) were added sequentially to quench the reaction. The reaction product was extracted with DCM and saturated brine. The organic extract was dried and purified by recrystallization using a mixed solvent of DCM and methanol to obtain 4-bromo-9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene (574 mg, 1.125 mmol), with a yield of 81%. NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 8.62 (d, J = 7.8 Hz, 1H), 7.50(d, J = 8.0 Hz, 1H), 7.41 (dd, J = 7.2, 3.7 Hz, 1H), 7.37 (d, J = 7.3 Hz, 1H), 7.31(t, J = 7.4 Hz, 1H), 7.24 – 7.15 (m, 6H), 7.08 (h, J = 4.3, 3.0 Hz, 4H), 1.27 (d, J = 2.6 Hz, 18H); 13 C NMR (101 MHz, CDCl3) d 154.73, 152.20, 149.46, 142.35, 139.32, 138.35, 132.29, 129.12, 128.39, 128.28, 128.19, 127.83, 127.04, 126.15, 125.35, 125.09, 124.45, 124.17, 123.70, 116.90, 77.35, 77.03, 76.71, 64.67, 34.37, 31.33; Mass spectrometry data: MALDI-TOF·MS: m / z cald for C 33 H 33 Br: 508.510, [M]+ = 509.391.

[0063] Example 1

[0064] A 5,8,11,14-tetratert-butyl-1,1-bis(4-tert-butylphenyl)-1H-tetrabenzo[ef,hi,kl,no]fluoren[3,4,5,6-qrabc]coryl ( The synthesis method of ) includes the following steps:

[0065]

[0066] S1. 4-Bromo-9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene (51.2 mg, 100 μmol), cuprous iodide (1.87 mg, 9.82 μmol), and bis(triphenylphosphine)palladium dichloride (6.91 mg, 9.84 μmol) were dissolved in triethylamine (0.5 mL), and the system was degassed. Subsequently, triisopropylsilylacetylene (0.1 mL, 446 μmol) was added, and the reaction mixture was heated to 90 °C and refluxed for 18 h. After the reaction was complete, the solvent was removed under reduced pressure. The residue was purified by preparative rapid silica gel column chromatography using petroleum ether / DCM (volume ratio 10:1) as eluent to give 32.9 mg of a viscous oily liquid product ((9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene-4-yl)ethynyl)triisopropylsilane, in 54% yield. NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 8.83 – 8.79 (m, 1H), 7.53 (dd, J = 7.6, 1.1 Hz, 1H), 7.48 (dt, J = 7.2, 0.9 Hz, 1H), 7.45 (dd, J = 7.7, 1.1 Hz, 1H), 7.42 – 7.33 (m,2H), 7.30 (d, J = 8.4 Hz, 1H), 7.29 – 7.26 (m, 4H), 7.19 – 7.14 (m, 4H), 1.33(s, 21H), 1.28 (d, J = 3.9 Hz, 18H).

[0067] S2. A stir bar was added to a clean, dry 25 mL round-bottom flask, followed by the addition of ((9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene-4-yl)ethynyl)triisopropylsilane (32 mg, 53.3 μmol) and dry THF (2 mL). The mixture was stirred until the starting material was completely dissolved. Tetrabutylammonium fluoride (0.1 mL) was added to the system, and the reaction was continued to be stirred at room temperature for 4 h. After the reaction was completed, the reaction mixture was concentrated under nitrogen protection and purified by rapid silica gel short column chromatography using petroleum ether / DCM (8:1 v / v) as the eluent to give 17.8 mg of the white solid product 9,9-bis(4-(tert-butyl)phenyl)-4-ethynyl-9H-fluorene, with a yield of 74%. NMR data were as follows: 1 H NMR (400 MHz, Chloroform- d ) d 8.68 – 8.62 (m, 1H), 7.53(dd, J = 7.6, 1.1 Hz, 1H), 7.48 (dd, J = 7.7, 1.1 Hz, 2H), 7.43 (td, J = 7.5, 1.3Hz, 1H), 7.36 (td, J = 7.5, 1.3 Hz, 1H), 7.31 (s, 1H), 7.30 – 7.23 (m, 4H), 7.18 – 7.12 (m, 4H), 3.56 (s, 1H), 1.33 (s, 18H).

[0068] S3. 2,3,4,5-Tetra(4-tert-butylphenyl)cyclopentane-2,4-dien-1-one (35.2 mg, 57.9 μmol) and 9,9-bis(4-(tert-butyl)phenyl)-4-ethynyl-9H-fluorene (20.2 mg, 44.5 μmol) were dissolved in o-xylene (4 mL) and refluxed at 144 °C for 22 h under an argon atmosphere. After the reaction was completed, the reaction solution was cooled to room temperature, and the solvent was removed by rotary evaporation under vacuum. The crude product was purified by column chromatography using DCM / petroleum ether (volume ratio 1:6) as the eluent to obtain a light white powder product 9,9-bis(4-(tert-butyl)phenyl)-4-(4,4''-di-tert-butyl-5',6'-bis(4-(tert-butyl)phenyl)-[1,1':2',1''-terphenyl]-3'-yl)-9H-fluorene (29.4 mg, 34.7 μmol), with a yield of 78%. NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.60 (s, 1H), 7.37 (dd, J = 6.6,2.1 Hz, 1H), 7.25 – 7.20 (m, 2H), 7.17 (td, J = 6.8, 2.0 Hz, 6H), 7.14 – 7.08(m, 4H), 7.05 – 7.00 (m, 2H), 6.96 (d, J = 8.0 Hz, 2H), 6.94 – 6.90 (m, 2H), 6.85 (d, J = 8.0 Hz, 4H), 6.78 – 6.62 (m, 8H), 1.28 (d, J = 2.1 Hz, 18H), 1.25 (s, 9H), 1.19 (s, 9H), 1.11 (s, 9H), 1.09 (s, 9H).

[0069] S4. Under an argon atmosphere, trifluoromethanesulfonic acid (0.02 mL) was added to a 2 mL DCM mixture containing 9,9-bis(4-(tert-butyl)phenyl)-4-(4,4''-di-tert-butyl-5',6'-bis(4-(tert-butyl)phenyl)-[1,1':2',1''-terphenyl]-3'-yl)-9H-fluorene (4.10 mg, 3.86 μmol, 1.0 equivalent) and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ, 5.21 mg, 22.9 μmol, 6.0 equivalent). The mixture was stirred at room temperature for 2 h. After the reaction was complete, the reaction solution was cooled to room temperature, and the reaction was quenched with triethylamine (5 mL). The reaction solution was then extracted with DCM (3 × 10 mL) and water. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to remove the solvent. The crude product was purified by silica gel column chromatography using petroleum ether / DCM (8:1 v / v) as eluent to give 0.95 mg of a yellow powder, 5,8,11,14-tetratert-butyl-1,1-bis(4-tert-butylphenyl)-1H-tetrabenzo[ef,hi,kl,no]fluoren[3,4,5,6-qrabc]cort, denoted as TTC, in 24% yield. 1 H NMR (400 MHz, Chloroform- d ) d 9.36 – 9.30 (m, 6H), 9.22 (d, J = 1.7Hz, 2H), 9.04 (d, J = 8.0 Hz, 2H), 8.24 (d,J = 7.9 Hz, 2H), 7.50 – 7.45 (m, 4H), 7.29 – 7.26 (m, 4H), 1.85 (s, 18H), 1.82 (s, 18H), 1.29 (s, 18H); 13 C NMR (101MHz, Chloroform- d ) d 149.66, 149.45, 149.14, 148.49, 141.41, 135.22, 131.33, 131.01, 130.63, 130.55, 129.04, 127.72, 125.34, 125.07, 124.24, 124.04, 122.50, 121.24, 120.78, 120.36, 120.24, 119.53, 119.33, 119.03, 71.43, 35.83, 34.42, 32.05, 31.55, 31.37, 1.03; Mass spectrometry data: MALDI-TOF MS: m / z cald forC 79 H 74 1022.58, [M] + =1022.31.

[0070] Example 2

[0071] A 1,1,6,6-tetra(4-tert-butylphenyl)-1,6-dihydrodibenzo[kl,no]difluoren[3,4,5,6-efghi:3',4',5',6'-qrabc]codon ( The synthesis method of ) includes the following steps:

[0072]

[0073] P1. In an oven-dried Schlenk tube, 4-bromo-9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene (21.3 mg, 0.0419 mmol), pinacol diborate (151 mg, 0.594 mmol), potassium acetate (KOAc, 15.4 mg, 0.157 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium dichloride (5.11 mg, 0.00701 mmol) were added sequentially. After purging the reaction tube three times with argon, 1,4-dioxane (0.7 mL) was added. The reaction mixture was heated to 95 °C and maintained at this temperature for 16 h. After the reaction was completed, the solvent was removed by concentration, and the crude product was purified by silica gel column chromatography using DCM / petroleum ether (volume ratio 1:3) as eluent to give 11.0 mg of 2-(9,9-bis(4-(tert-butyl)phenyl)-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxane, with a yield of 47%. NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 8.70 (d, J = 7.8 Hz, 1H), 7.81 – 7.73 (m, 1H), 7.49 (dt, J = 7.7, 1.2 Hz,1H), 7.39 (d, J = 7.5 Hz, 1H), 7.33 (td, J = 7.5, 1.2 Hz, 1H), 7.23 (dd, J =7.4, 2.5 Hz, 1H), 7.21–7.15 (m, 4H), 7.14–7.02 (m, 5H), 1.47 (s, 12H), 1.26 (d, J = 2.1 Hz, 18H).

[0074] P2. 2-(9,9-bis(4-(tert-butyl)phenyl)-9H-fluoren-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxane (134 mg, 0.241 mmol), 1,3,5-tribromobenzene (31.5 mg, 0.101 mmol), and barium hydroxide octahydrate (Ba(OH)2·8H2O, 192 mg, 0.609 mmol) were dissolved in a mixed solvent of 1.6 mL of 1,4-dioxane and 0.3 mL of water. The reaction system was degassed. Then, Pd(PPh3)4 (16.10 mg, 13.9 μmol) was added, and the mixture was stirred and mixed thoroughly. The mixture was then heated to 80 °C and refluxed for 15 h. After the reaction was complete, the solvent was evaporated, and the residue was purified by rapid silica gel preparative column chromatography using petroleum ether / DCM (volume ratio 3:1) as eluent to give a white solid product 4,4'-(5-bromo-1,3-phenylene)bis(9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene) (61.9 mg, 61.1 μmol), with a yield of 63%. NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.78 (d, J = 1.5 Hz, 2H), 7.65 – 7.57 (m,2H), 7.49 – 7.35 (m, 6H), 7.32 – 7.22 (m, 9H), 7.22 – 7.13 (m, 7H), 7.10 (d, J = 7.9 Hz, 6H), 6.99 (t, J = 7.7 Hz, 1H), 1.29 (s, 18H), 1.24 (s, 18H); Mass spectrometry data: MALDI-TOF·MS: m / z cald for C 72 H 69 Br: 1014.46, [M] + = 1014.32.

[0075] P3. 4,4'-(5-bromo-1,3-phenylene)bis(9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene) (91.3 mg, 90.0 μmol), biphenyl-2-borate pinacol (373 mg, 133 μmol), and barium hydroxide octahydrate (Ba(OH)2·8H2O, 312 mg, 0.991 mmol) were dissolved in a mixed solvent of 3 mL 1,4-dioxane and 1 mL water. The reaction system was degassed. Then, Pd(PPh3)4 (32.3 mg, 28.0 μmol) was added, and the mixture was stirred and mixed thoroughly. The mixture was then heated to 80 °C and refluxed for 15 h. After the reaction was complete, the solvent was evaporated, and the residue was purified by rapid silica gel preparative column chromatography using petroleum ether / DCM (8:1 v / v) as eluent to give 31.8 mg of a white solid product, 3,5-bis(9,9-bis(4-tert-butylphenyl)-9H-fluorene-4-yl)-1,1':2',1''-terphenyl, in 33% yield. NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.81 – 7.51 (m, 2H), 7.45 (dd, J = 17.8, 8.7 Hz, 4H), 7.41 – 7.27(m, 8H), 7.28 – 7.00 (m, 24H), 6.96 (q, J = 10.1, 8.1 Hz, 4H), 1.32 – 1.26 (m, 18H), 1.24 (s, 18H); Mass spectrometry data: MALDI-TOF·MS: m / z cald for C 84 H 78 1086.61, found [M] + = 1087.35.

[0076] P4. Under an argon atmosphere, trifluoromethanesulfonic acid (0.02 mL) was added to a 2 mL DCM mixture containing 3,5-bis(9,9-bis(4-tert-butylphenyl)-9H-fluorene-4-yl)-1,1':2',1''-terphenyl (5.31 mg, 4.88 μmol, 1.0 equivalent) and DDQ (6.63 mg, 29.2 μmol, 6.0 equivalent). The mixture was stirred at room temperature for 2 h. After the reaction was complete, the reaction solution was cooled to room temperature, and the reaction was quenched with triethylamine (5 mL). The reaction solution was then extracted with DCM (3 × 10 mL) and water. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to remove the solvent. The crude product was purified by silica gel column chromatography using petroleum ether / DCM (8:1 v / v) as eluent to give 0.78 mg of a yellow powder product, 1,1,6,6-tetrakis(4-tert-butylphenyl)-1,6-dihydrodibenzo[kl,no]difluoren[3,4,5,6-efghi:3',4',5',6'-qrabc]codon, denoted as TDC, with a yield of 15%. NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 9.00(d, J = 7.9 Hz, 2H), 8.69 (d, J = 7.7 Hz, 2H), 8.64 (d, J = 7.9 Hz, 2H), 8.56 (d, J =8.1 Hz, 2H), 8.32 (d, J = 7.8 Hz, 2H), 8.11 (d, J = 7.9 Hz, 2H), 7.65 (t, J = 7.8Hz, 2H), 7.56 (d, J = 8.3 Hz, 8H), 7.39 – 7.32 (m, 8H), 1.31 (s, 36H); Mass spectrometry data: MALDI-TOF·MS: m / z cald for C 84 H 66 : 1074.52, [M] + = 1074.16.

[0077] Figure 2 The UV-Vis absorption spectra (solid lines) and photoluminescence spectra (dashed lines) of TTC prepared in chloroform solution are shown for TTC prepared in Example 1 and TTC prepared in Example 2. All spectra were measured at room temperature. Figure 2As can be seen from this, when the concentrations of TTC molecules and TDC molecules in chloroform are 1.15 × 10⁻⁶, respectively... -5 M and 1.04×10 -5 At wavelength M, the maximum absorption wavelength of TTC molecules in chloroform is 361 nm, while that of TDC molecules is 360 nm. TTC molecules exhibit a slight redshift compared to the previously reported HBC molecules without fluorene modification (356 nm). Based on Beer-Raybould's law, the molar extinction coefficient of TTC molecules at the maximum absorption wavelength is calculated to be 8.23 ​​× 10⁻⁶. 4 M -1 ·cm -1 Similarly, the molar extinction coefficient at the maximum absorption wavelength of the TDC molecule can be obtained as 8.74 × 10⁻⁶. 4 M -1 ·cm -1 .

[0078] Dissolve 1 mg of TTC prepared in Example 1 or TDC prepared in Example 2 in 1 mL of tetrahydrofuran. Take 100 μL of the solution and drop it onto a quartz glass slide. Spin coat the solution using a spin coater under the following conditions: spin coat at 500 rpm for 60 s, followed by spin coat at 1500 rpm for 60 s to obtain a TTC film or a TDC film. Figure 3 The solid-state UV-Vis absorption spectra (solid lines) and photoluminescence spectra (dashed lines) of TTC and TDC films are shown. All spectra were measured at room temperature. Figure 3 As can be seen, the maximum absorption wavelengths of the films made of TTC molecules and TDC molecules are 362 nm and 360 nm, respectively, which are almost consistent with the absorption wavelengths of their solutions. The maximum emission wavelength of the TTC film is 465 nm, and the maximum emission wavelength of the TDC film is 500 nm.

[0079] Fluorescence quantum yield tests were performed on chloroform solutions and thin films containing TTC and TDC molecules. The results showed that the fluorescence quantum yield of TTC molecules in chloroform solution was 6.35%, while that of the TTC thin film was 8.02%. Similarly, the fluorescence quantum yield of TDC molecules in chloroform solution was 5.64%, while that of the TDC thin film was 6.00%. These results confirm that the present invention significantly suppresses the aggregation-induced quenching effect of HBC molecules, enabling them to exhibit excellent photophysical properties in both solution and solid states.

[0080] Example 3

[0081] A 1,1,6,6,11,11-hexa(4-tert-butylphenyl)-6,11-dihydro-1H-trifluorenano[3,4,5,6-efghi:3',4',5',6'-klmno:3'',4'',5'',6''-qrabc] guano The synthesis method of ) includes the following steps:

[0082]

[0083] (1) 9,9-bis(4-(tert-butyl)phenyl)-4-ethynyl-9H-fluorene (304 mg, 66.9 μmol), cobalt(II) bromide (CoBr2, 15.3 mg, 6.69 μmol), zinc powder (6.41 mg, 6.68 μmol), and zinc iodide (ZnI2, 21.2 mg, 6.71 μmol) from Example 1 were dissolved in acetonitrile (CH3CN, 1.2 mL), and the reaction system was degassed. The mixture was then refluxed at room temperature for 48 h. After the reaction, the solvent was evaporated, and the residue was purified by rapid silica gel preparative column chromatography using petroleum ether / DCM (8:1 v / v) as eluent to obtain 154 mg of the white solid product 1,3,5-tris(9,9-bis(4-tert-butylphenyl)-9H-fluorene-4-yl)benzene, with a yield of 52%. NMR data were as follows: 1 H NMR (400 MHz, Chloroform- d ) d 7.79 (s, 3H), 7.58 (d, J = 9.2 Hz, 3H), 7.53 – 7.47 (m, 3H), 7.43 – 7.39 (m,3H), 7.39 – 7.35 (m, 3H), 7.35 – 7.31 (m, 3H), 7.18 (d, J = 4.1 Hz, 6H), 7.12(d, J = 2.8 Hz, 6H), 7.06 (d, J = 6.1 Hz, 6H), 6.92 (d, J = 8.2 Hz, 3H), 6.86 (d, J =4.1 Hz, 3H), 6.77 (d, J = 7.4 Hz, 3H), 6.63 (dd, J = 14.1, 7.5 Hz, 3H), 1.25 (s, 54H); Mass spectrometry data: MALDI-TOF·MS: m / zcald for C 105 H 102 1363.80, found [M] + =1363.07.

[0084] (2) Under an argon atmosphere, trifluoromethanesulfonic acid (0.07 mL) was added to a mixed solution of 1,1,2,2-tetrachloroethane (6.50 mL) containing 1,3,5-tris(9,9-bis(4-tert-butylphenyl)-9H-fluorene-4-yl)benzene (10.3 mg, 7.34 μmol, 1.0 equivalent) and DDQ (8.33 mg, 36.7 μmol, 5.0 equivalent). The resulting mixture was heated to 50 °C and stirred for 2 h. After the reaction was completed, the mixture was cooled to room temperature and then triethylamine (5 mL) was added to quench the reaction. Subsequently, the mixture was extracted with DCM (3 × 10 mL) and water. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to remove the solvent. The crude product was purified by silica gel column chromatography using petroleum ether / DCM (8:1 v / v) as eluent to give 0.2 mg of a yellow powder product, 1,1,6,6,11,11-hexa(4-tert-butylphenyl)-6,11-dihydro-1H-trifluorenano[3,4,5,6-efghi:3',4',5',6'-klmno:3'',4'',5'',6''-qrabc], denoted as HBC-Ar, with a yield of 2%. Mass spectrometry data were obtained using MALDI-TOF·MS. m / z cald for C 105 H 90 1351.70, found [M] + = 1350.81.

[0085] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art should understand that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A diaryl-substituted cyclopentadienyl fused hexabenzoxan derivative The synthesis method is characterized by, Includes the following steps: (1) Cobalt salt, zinc powder, and zinc salt are dissolved in an organic solvent and reacted to obtain... Wherein, Ar is mesitylene or tert-butylphenyl; (2) 2,3-Dichloro-5,6-dicyanobenzoquinone was dissolved in an organic solvent, and then reacted with trifluoromethanesulfonic acid to obtain the diaryl-substituted cyclopentadienyl fused hexabenzoquinone derivative. .

2. The synthesis method according to claim 1, characterized in that, In step (1), the The molar ratio of cobalt salt, zinc powder and zinc salt is (60-80):(6-8):(6-8):(6-8); the cobalt salt is cobalt bromide and the zinc salt is zinc iodide; the organic solvent is acetonitrile.

3. The synthesis method according to claim 1 or 2, characterized in that, In step (2), the The molar ratio of 2,3-dichloro-5,6-dicyanobenzoquinone is 1:(4-6); the organic solvent is 1,1,2,2-tetrachloroethane; the reaction temperature is 40-60 °C; and the reaction is carried out under an argon atmosphere.

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