Boron-based framework compound as well as preparation method and application thereof

Abstract

The invention relates to the field of organoboron chemistry and material chemistry. The invention discloses a boron-based framework compound as well as a preparation method and application thereof. The compound is characterized by having a specific skeleton structure formed by coordination of an N, O-bidentate ligand and a boron center. The preparation method adopts a one-pot method or a fractional step method, the key point is that hexafluoroisopropanol is used as a single reaction solvent, or a mixed solvent system of perfluorinated pinacoline alcohol and chloroform is used, and the system obviously improves the chemical stability of the product. The method is simple in synthesis process, high in yield and easy to purify. The obtained series of compounds have good solubility in organic solvents and show excellent fluorescence properties, the highest fluorescence quantum yield can reach 75.48%, and the emission wavelength is adjustable. The compounds have wide application prospects in the fields of photoelectric materials such as organic light emitting diodes, fluorescence sensing, biological imaging and solar cells.

Description

Technical Field

[0001] This invention relates to the fields of organoboron chemistry and materials chemistry, specifically to a boron-based framework compound, its preparation method, and its applications. Background Technology

[0002] Boron-based framework compounds are composite materials composed of boron and framework groups. Their structure typically involves boron atoms linked to the framework groups via covalent and coordinate bonds, forming a framework with unique properties. This structure not only exhibits good thermal stability, corrosion resistance, and plasticity, but also allows for the modulation of fluorescence properties by adjusting the structure of the framework groups and the arrangement of boron atoms. Therefore, boron-based framework compounds have broad application prospects in materials science and related fields, particularly in self-organized materials, fluorescent materials, and catalytic systems.

[0003] With the widespread application of boron-based frameworks in drug design, materials chemistry, and other fields, the high fluorescence intensity of boron-based framework compounds makes them ideal candidate materials for organic light-emitting diodes, photochromic materials, chemical sensors, sensitive solar cells, and biofluorescent probes. The development of boron-based frameworks in the materials field is rapid, currently focusing mainly on difluoroboron complexes. In contrast, research on other boron-based frameworks is relatively limited; therefore, research on novel boron-based frameworks is essential. Traditional organic synthesis methods often involve cumbersome multi-step reactions and impose certain environmental burdens. Therefore, developing an efficient and green synthetic method is particularly important. Summary of the Invention

[0004] The purpose of this invention is to provide a boron-based framework compound, its preparation method, and its application, in order to solve the technical problem of the stability of boron-based fluorescent materials.

[0005] The technical solution of the present invention is as follows: A boron-based skeleton compound having a general structural formula as shown in one of the following formulas 1a, 1b, and 1c: ; Wherein R A1 The connection structure is one of the following: , ; R B1 The connection structure is one of the following: , ; In this context, * indicates a connection site.

[0006] Further optimization is achieved by the structure of the R1 group in general formula 1a as one of the following formulas A1-A5: , , , ,

[0007] In this context, * indicates a connection site.

[0008] Further optimization is made by having R2 group in general formula 1b be either a hydrogen atom or a tert-butyl group with ortho- or para-disubstituted tert-butyl groups.

[0009] Further optimization is made, wherein the R3 group in the general formula 1c is any one of H atom, fluorine atom, bromine atom, ortho-substituted methoxy, para-substituted methoxy, ortho-substituted tert-butyl, or ortho-para-disubstituted tert-butyl.

[0010] Further optimization is achieved by the boron-based framework compound being any one of the following structures: 1aa-1ac, 1ba-1be, 2aa-2ac, 2ba-2bd, and 3ba-3bg. , , , , , , , , , , , , , , , , , , , , , .

[0011] A method for preparing a boron-based skeleton compound, wherein the compound is prepared by a one-step or stepwise method, and the reaction formula for the one-step method is shown below: , The one-step preparation method is as follows: salicylaldehyde compound, amine compound, boric acid and molecular sieve are added to the reaction tube, and then the reaction solvent is added and reacted at 60-100℃ for 7-12h. After the reaction is completed, the target product is obtained after post-treatment. The reaction formula for the step-by-step method is shown below: , The stepwise preparation method is as follows: add salicylaldehyde imine compound or phenoxyoxazoline compound, boric acid and molecular sieve into the reaction tube, then add reaction solvent, react at 60~100℃ for 7~12h, and after the reaction is completed, the target product is obtained after post-processing. The reaction solvent is a mixture of hexafluoroisopropanol or perfluorophenyl alcohol and chloroform.

[0012] Further optimization resulted in the molecular sieve being a type 4A molecular sieve.

[0013] Further optimization involves using boric acid in the one-step method at a rate of 1.0 to 4 times the amount of salicylaldehyde compound, and using alkali at a rate of 2 times the amount of salicylaldehyde compound; when using perfluoroquinolone, the amount of perfluoroquinolone is 3.0 to 6.0 times the amount of salicylaldehyde compound or salicylaldehyde imine compound.

[0014] Further optimization involves post-processing including diatomaceous earth filtration, thin-layer chromatography separation, and drying. The solvent used for filtration is ethyl acetate, and the eluent used for thin-layer chromatography separation is ethyl acetate and petroleum ether or pure dichloromethane in a volume ratio of 0:1 to 5:1.

[0015] Application of a boron-based framework compound in the preparation of light-emitting diodes, photoluminescent materials, chemical sensors, biofluorescent probes, or energy-controlled battery devices.

[0016] The beneficial effects of this technical solution are: This invention constructs a stable chelate structure formed by N,O-bident ligands and boron atoms. This framework structure differs from common difluoroboron complexes in the prior art, broadening the chemical diversity of boron-based functional materials. By systematically and flexibly modifying its substituents (such as R1, R2, R3, RA1, RB1), the electronic effects and spatial configuration of the molecule can be precisely controlled, thereby achieving effective "tailoring" of its photophysical properties, especially the fluorescence emission wavelength and intensity, providing a rich material library to meet the needs of different application scenarios. This invention employs two synthetic routes, a one-step method and a multi-step method, offering high operational flexibility. The one-step method is concise, starting directly from commercially available raw materials such as salicylaldehyde and amines, reducing intermediate separation and purification steps, improving synthetic efficiency, and meeting the requirements of atom economy. More importantly, it innovatively uses a fluorinated alcohol solvent system and discovers the unique advantages of two specific combinations: hexafluoroisopropanol as a single solvent and perfluoroquinol-chloroform mixed solvent. The latter not only efficiently promotes the reaction, but its perfluoroquinol component also participates in coordination as a reactant, replacing the unstable borate ester group in situ with the more sterically hindered and electronegative perfluoroquinol borate ester structure, fundamentally and significantly improving the chemical and light stability of the final product, and solving the common problem of easy hydrolysis or degradation of such materials in practical applications. The series of compounds prepared in this invention exhibit good solubility and film-forming properties in common organic solvents, facilitating subsequent device fabrication. Their fluorescence performance is particularly outstanding, with a quantum yield of up to 75.48%, indicating extremely high luminous efficiency. Simultaneously, the fluorescence emission range covers 385-484 nm, demonstrating excellent spectral tunability. These superior comprehensive properties make them ideal candidate materials for the preparation of organic light-emitting diodes, fluorescent chemical sensors, biofluorescent probes, and for improving the performance of solar cells, demonstrating enormous application potential and market value in the field of optoelectronic materials and devices. Attached Figure Description

[0017] Figure 1-4 The boron-based skeleton compound 1aa obtained in Example 1 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 F NMR and 11 B NMR spectrum; Figure 5-8 The boron-based skeleton compound 1ab obtained in Example 5 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 F NMR and 11 B NMR spectrum; Figure 9-12 The boron-based framework compound 1ac obtained in Example 6 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figure 13-16 The boron-based framework compound 1ba obtained in Example 8 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19FNMR and 11 B NMR spectrum; Figure 17-20 The boron-based framework compound 1bb obtained in Example 9 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figure 21-24 The boron-based framework compound 1bc obtained in Example 10 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figure 25-28 The boron-based framework compound 1bd obtained in Example 11 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figure 29-32 The boron-based framework compound 1be obtained in Example 12 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figure 33-36 The boron-based skeleton compound 2aa obtained in Example 13 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figure 37-40 The boron-based skeleton compound 2ab obtained in Example 14 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figures 41-44 The boron-based framework compound 2ac obtained in Example 15 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figures 45-48 The boron-based skeleton compound 2ba obtained in Example 16 of this invention 1 H NMR spectrum, 13C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figures 49-52 The boron-based framework compound 2bb obtained in Example 17 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figures 53-56 The boron-based framework compound 2bc obtained in Example 18 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figures 57-60 The boron-based framework compound 2bd obtained in Example 19 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figures 61-64 The boron-based framework compound 3ba obtained in Example 20 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figures 65-68 The boron-based framework compound 3bb obtained in Example 21 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figures 69-72 The boron-based framework compound 3bc obtained in Example 22 of this invention 1 H NMR spectrum, 13 C NMR spectrum 19 FNMR and 11 B NMR spectrum; Figure 73 The fluorescence emission spectrum (a) and fluorescence absorption spectrum (b) of the boron-based skeleton compound 1aa-1ac prepared in Examples 1-3 of this invention in ultradry acetonitrile are shown. Figure 74 The fluorescence emission spectrum (a) and fluorescence absorption spectrum (b) of the boron-based skeleton compound 1ba-1be prepared in Examples 4-8 of this invention in ultradry acetonitrile; Figure 75The fluorescence emission spectrum (a) and fluorescence absorption spectrum (b) of the boron-based skeleton compound 2aa-2ac prepared in Examples 9-11 of this invention in ultradry acetonitrile are shown. Figure 76 The fluorescence emission spectrum (a) and fluorescence absorption spectrum (b) of the boron-based skeleton compound 2bb-2bd prepared in Examples 13-15 of this invention in ultradry acetonitrile are shown. Figure 77 The fluorescence emission spectrum (a) and fluorescence absorption spectrum (b) of the boron-based skeleton compound 3ba-3bg prepared in Examples 16-22 of this invention in ultradry acetonitrile; Figure 78 The quantum yield of the boron-based skeleton compound 1ab prepared in Example 2 of this invention in dichloromethane; Figure 79 The quantum yield of the boron-based skeleton compound 1ac prepared in Example 3 of this invention in dichloromethane; Figure 80 The quantum yield of the boron-based skeleton compound 1bb prepared in Example 5 of this invention in dichloromethane; Figure 81 The quantum yield of the boron-based skeleton compound 1bc prepared in Example 6 of this invention in dichloromethane; Figure 82 The quantum yield of the boron-based skeleton compound 1be prepared in Example 8 of this invention in dichloromethane; Figure 83 The quantum yield of the boron-based skeleton compound 3ba prepared in Example 16 of this invention in dichloromethane; Figure 84 The quantum yield of the boron-based skeleton compound 3bd prepared in Example 19 of this invention in dichloromethane; Figure 85 The quantum yield of the boron-based skeleton compound 2aa prepared in Example 9 of this invention in dichloromethane; Figure 86 The quantum yield of the boron-based skeleton compound 2ab prepared in Example 10 of this invention in dichloromethane; Figure 87 The quantum yield of the boron-based framework compound 2ac prepared in Example 11 of this invention in dichloromethane; Figure 88 The quantum yield of the boron-based skeleton compound 2ba prepared in Example 12 of this invention in dichloromethane; Figure 89 The quantum yield of the boron-based skeleton compound 2bc prepared in Example 13 of this invention in dichloromethane; Figure 90The quantum yield of the boron-based skeleton compound 2bd prepared in Example 14 of this invention in dichloromethane. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention; that is, the described embodiments are merely some embodiments of the invention, and not all embodiments. The components of the embodiments of the invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0019] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0020] It should be noted that relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0021] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0022] Example 1 The structural formula of compound 1aa in this embodiment is:

[0023] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.1 mmol of (R)-(+)-1-phenylethylamine, 0.2 mmol of boric acid, 2 mL of hexafluoroisopropanol, and 1 g of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and heated at 60 °C. oThe reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a pale yellow oil with a yield of 76%. 1 H NMR (600 MHz, CD3CN) δ 8.6 (q, J = 3.9 Hz, 1H), 7.6 (ddd, J = 8.8, 7.4, 1.7 Hz, 1H), 7.5 (dd, J = 8.1, 1.7 Hz, 1H), 7.5 – 7.4 (m, 2H), 7.4 – 7.4 (m, 2H), 7.4 – 7.3(m, 1H), 7.0 (dd, J = 8.0, 6.4 Hz, 2H), 5.4 (q, J = 7.1 Hz, 1H), 4.9 (h, J =6.2 Hz, 1H), 4.8 (h, J = 6.5 Hz, 1H), 1.8 (d, J = 7.1 Hz, 3H). 13 C NMR (151MHz, CD3CN) δ 165.1, 157.9, 140.5, 139.2, 133.2, 129.3(q, 1 J C-F = 289.0 Hz),128.9, 128.2, 121.2, 119.1, 117.9, 116.3, 70.8 – 68.5 (m, 2 J C-F =32.7 Hz), 59.6, 21.3. 19 F NMR (565 MHz, CD3CN) δ -75.1 (q, J = 9.6 Hz), -75.2 (td, J =13.9, 8.2 Hz). 11 B NMR (193 MHz, CD3CN) δ 2.1. HRMS (positive ESI) Calcd. ForC 21 H 16 BF 12 NO3Na (M + Na + ) 592.1382, Found: 592.0888. The maximum fluorescence excitation wavelength is 273 nm, and the maximum fluorescence emission wavelength is 441 nm.

[0024] Example 2

[0025] The structural formula of compound 1ab in this embodiment is:

[0026] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.1 mmol of cyclohexylamine, 0.2 mmol of boric acid, 2 mL of hexafluoroisopropanol, and 1 g of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and heated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a white solid with a yield of 75%. 1 H NMR (600 MHz, CDCl3) δ 8.2 (d,J = 6.8 Hz, 1H), 7.6 (ddd, J = 8.8, 7.3, 1.7 Hz, 1H), 7.4 (dd, J = 7.8, 1.7Hz, 1H), 7.1 – 7.0 (m, 2H), 4.6 (dd, J = 11.0, 5.8 Hz, 2H), 3.9 (tt, J = 8.3,3.8 Hz, 1H), 2.2 (d, J = 9.2 Hz, 2H), 1.9 – 1.9 (m, 2H), 1.8 – 1.7 (m, 1H),1.4 (td, J = 11.9, 6.2 Hz, 4H), 1.2 (dt, J = 12.8, 3.9 Hz, 1H). 13 C NMR (151MHz, CDCl3) δ 161.2, 157.8, 138.0, 131.4, 121.4 (q, 1 J C-F = 294.9 Hz), 120.3,119.0, 115.5, 69.1 (m, 2 J C-F = 32.6 Hz), 59.3, 34.1, 25.6, 25.3. 19 F NMR (565MHz, CDCl3) δ -74.8 (q, J = 9.4 Hz), -74.9 (q, J = 9.4 Hz). 11 B NMR (193 MHz, CDCl3) δ 2.0.HRMS (positive ESI) Calcd. For C 19 H 18 BF 12 NO3Na (M + Na +570.1327, Found: 570.0609. Maximum fluorescence excitation wavelength is 257 nm, and maximum fluorescence emission wavelength is 449 nm. The quantum yield measured in dichloromethane is 67.08%.

[0027] Example 3

[0028] The structural formula of compound 1ac in this embodiment is:

[0029] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.1 mmol of cyclohexylamine, 0.2 mmol of boron-10 acid, 2 mL of hexafluoroisopropanol, and 1 g of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and heated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a white solid with a yield of 74%. 1 H NMR (600 MHz, CDCl3) δ 8.2 (d,J = 4.7 Hz, 1H), 7.6 – 7.5 (m, 1H), 7.4 (dd, J = 7.8, 1.7 Hz, 1H), 7.1 – 7.0(m, 2H), 4.7 (h, J = 6.8 Hz, 2H), 3.9 (tt, J = 8.1, 3.7 Hz, 1H), 2.2 (d, J =10.3 Hz, 2H), 1.9 – 1.9 (m, 2H), 1.8 – 1.7 (m, 1H), 1.5 – 1.4 (m, 4H), 1.2(ddd, J = 12.6, 8.3, 4.3 Hz, 1H). 13 C NMR (151 MHz, CDCl3) δ 161.2, 157.8,138.0, 131.4, 121.4 (q, 1 J C-F = 280.5 Hz), 120.3, 119.0, 115.5, 69.1 (m, 2 J C-F =32.6 Hz), 59.3, 34.1, 25.6, 25.3. 19 F NMR (565 MHz, CDCl3) δ -74.8 (q, J = 9.4Hz), -74.9 (q, J = 9.4 Hz). 11B NMR (193 MHz, CDCl3) δ 2.0. 11 B NMR (193 MHz, CDCl3) δ 2.0.HRMS (positive ESI) Calcd. For C 19 H 18 10 BF 12 NO3Na (M + Na + 569.1327, Found: 569.3545. Maximum fluorescence excitation wavelength is 273 nm, and maximum fluorescence emission wavelength is 432 nm. The quantum yield measured in dichloromethane is 29.48%.

[0030] Example 4 The structural formula of compound 1ba in this embodiment is:

[0031] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.1 mmol of (R)-(+)-1-phenylethylamine, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA=10 / 1), which was dried to obtain a pale yellow solid with a yield of 88%. 1 HNMR (600 MHz, CD3CN) δ 8.59 – 8.54 (m, 1H), 8.30 – 8.25 (m, 1H), 7.97 (d, J =8.3 Hz, 1H), 7.96 – 7.93 (m, 1H), 7.70 (d, J = 7.2 Hz, 1H), 7.64 (ddd, J =8.7, 7.2, 1.7 Hz, 1H), 7.59 (t, J = 7.8 Hz, 1H), 7.55 – 7.51 (m, 2H), 7.44 (dd, J = 7.9, 1.7 Hz, 1H), 7.02 (d, J = 8.5 Hz, 1H), 7.01 –6.96 (m, 1H), 6.08(q, J = 6.8 Hz, 1H), 1.98 (d, J = 6.8 Hz, 3H). 13C NMR (151 MHz, CD3CN) δ167.9, 159.0, 140.5, 139.9, 133.3, 129.7, 129.1, 127.8, 123.5 (d, 1 J C-F =290.7 Hz), 121.6, 119.2, 117.9, 117.2, 90.4 (q, 2 J C-F = 32.7 Hz), 58.9, 20.7. 19 F NMR (565 MHz, CD3CN) δ -67.7 – -68.0 (m), -68.8 – -69.0 (m), -69.3 – -69.5(m). 11 B NMR (193 MHz, CD3CN) δ 7.3. HRMS (positive ESI) Calcd. ForC 21 H 15 BF 12 NO3 (M + H + ) 568.1405, Found: 568.0929. The maximum fluorescence excitation wavelength is 279 nm, and the maximum fluorescence emission wavelength is 445 nm.

[0032] Example 5 The structural formula of compound 1bb in this embodiment is:

[0033] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.1 mmol of (S)-(-)-1-phenylethylamine, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and heated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a pale yellow solid with a yield of 80%. 1HNMR (600 MHz, CD3CN) δ 8.77 (d, J = 6.0 Hz, 1H), 7.68 (ddd, J = 8.7, 7.2, 1.7Hz, 1H), 7.62 (dd, J = 7.9, 1.7 Hz, 1H), 7.44–7.33 (m, 5H), 7.08 (t, J = 7.6Hz, 1H), 7.03 (d, J = 8.4 Hz, 1H), 5.47 (q, J = 7.0 Hz, 1H), 1.81 (d, J = 7.0Hz, 3H). 13 C NMR (151 MHz, CD3CN) δ 167.9, 159.0, 140.5, 139.9, 133.3, 129.7,129.1, 127.8, 123.5 (q, 1 J C-F = 290.3 Hz), 121.6, 119.2, 117.9, 117.2, 90.2(q, 2 J C-F = 32.7 Hz), 58.9, 20.6. 19 F NMR (565 MHz, CD3CN) δ -68.1 – -68.5 (m), -68.8 – -69.1 (m), -69.7 – -70.0 (m). 11 B NMR (193 MHz, CD3CN) δ 7.0. HRMS(positive ESI) Calcd. For C 21 H 15 BF 12 NO3 (M + H + 568.1405, Found: 568.0923. Maximum fluorescence excitation wavelength is 278 nm, and maximum fluorescence emission wavelength is 456 nm. The quantum yield measured in dichloromethane is 8.98%.

[0034] Example 6 The structural formula of compound 1bc in this embodiment is:

[0035] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.1 mmol of (S)-1-naphthylethylamine, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C.o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a pale yellow oil with a yield of 91%. 1 HNMR (600 MHz, CD3CN) δ 8.77 (d, J = 6.1 Hz, 1H), 7.68 (ddd, J = 8.6, 7.2, 1.7Hz, 1H), 7.62 (dd, J = 7.8, 1.7 Hz, 1H), 7.44–7.33 (m, 5H), 7.08 (t, J = 7.6Hz, 1H), 7.03 (d, J = 8.4 Hz, 1H), 5.47 (q, J = 7.1 Hz, 1H), 1.81 (d, J = 7.0Hz, 3H). 13 C NMR (151 MHz, CD3CN) δ 167.7, 159.0, 140.0, 134.9, 134.6, 133.3,131.2, 130.5, 129.7, 127.5, 126.9, 126.6, 126.0, 123.7, 123.6 (d, 1 J C-F =289.4 Hz), 121.5, 119.0, 117.9, 116.8, 90.4 (q, 2 J C-F = 32.7 Hz), 56.9, 20.9. 19 F NMR (565 MHz, CD3CN) δ -68.1 – -68.5 (m), -68.8 – -69.1 (m), -69.7 – -70.0 (m). 11 B NMR (193 MHz, CD3CN) δ 7.0. HRMS (positive ESI) Calcd. ForC 25 H 17 BF 12 NO3 (M + H + 618.1992, Found: 618.4500. Maximum fluorescence excitation wavelength is 280 nm, and maximum fluorescence emission wavelength is 445 nm. The quantum yield measured in dichloromethane is 9.71%.

[0036] Example 7 The structural formula of compound 1bd in this embodiment is:

[0037] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.1 mmol of (R)-1-naphthylethylamine, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a pale yellow oil with a yield of 87%. 1 HNMR (600 MHz, CD3CN) δ 8.58–8.54 (m, 1H), 8.30–8.25 (m, 1H), 7.99–7.92 (m,2H), 7.70 (d, J = 7.2 Hz, 1H), 7.64 (ddd, J = 8.7, 7.2, 1.7 Hz, 1H), 7.59(dd, J = 8.2, 7.3 Hz, 1H), 7.57–7.49 (m, 2H), 7.44 (dd, J = 7.9, 1.7 Hz, 1H), 7.04–6.95 (m, 2H), 6.08 (q, J = 6.8 Hz, 1H), 1.98 (d, J = 6.8 Hz, 3H). 13 C NMR (151 MHz, CD3CN) δ 167.7, 159.0, 139.9, 134.9, 134.5, 133.3, 131.2, 130.5,129.6, 127.5, 126.9, 126.6, 125.9, 123.7, 123.6 (d, 1 J C-F = 287.5 Hz), 121.5,119.0, 117.9, 116.7, 90.6 (q, 2 J C-F = 32.7 Hz), 56.9, 20.9. 19 F NMR (565 MHz, CD3CN) δ -67.7 – -68.0 (m), -68.8 – -69.0 (m), -69.2 – -69.5 (m). 11 B NMR (193MHz, CD3CN) δ 7.2. HRMS (positive ESI) Calcd. For C 25 H17 BF 12 NO3 (M + H + )618.1992, Found: 618.4490. The maximum fluorescence excitation wavelength is 280 nm, and the maximum fluorescence emission wavelength is 440 nm.

[0038] Example 8 The structural formula of compound 1be in this embodiment is:

[0039] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.1 mmol of cyclohexylamine, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a white solid with a yield of 70%. 1 H NMR (600 MHz, CD3CN) δ 8.87 (d, J = 6.5 Hz, 1H), 7.68 (ddd, J = 7.2, 4.1, 2.4 Hz, 2H), 7.14–7.08 (m, 1H), 7.02 (d, J = 8.8 Hz, 1H), 3.91 (tt, J = 12.3, 3.5 Hz, 1H),2.02 – 1.96 (m, 2H), 1.91 (dt, J = 13.6, 3.3 Hz, 3H), 1.75–1.68 (m, 1H), 1.61(qd, J = 12.3, 3.5 Hz, 2H), 1.35 (qt, J = 13.0, 3.4 Hz, 2H), 1.30–1.19 (m,2H). 13 C NMR (151 MHz, CD3CN) δ 166.7, 158.6, 139.4, 133.0, 123.5 (d, 1 J C-F =292.4 Hz), 121.4, 119.0, 117.9, 117.0, 90.1 (q, 2 J C-F = 32.7 Hz), 59.5, 34.1,26.1, 25.4. 19F NMR (565 MHz, CD3CN) δ -68.3 – -68.4 (m), -69.4 – -69.5 (m). 11 B NMR (193 MHz, CD3CN) δ 6.89. HRMS (positive ESI) Calcd. For C 19 H 16 BF 12 NO3Na(M + Na + 568.1168, Found: 568.7789. Maximum fluorescence excitation wavelength is 277 nm, and maximum fluorescence emission wavelength is 434 nm. The quantum yield measured in dichloromethane is 6.17%.

[0040] In summary, all derivatives in Examples 1-8 were monoamines. Based on this, perfluorophenylamine (HFP) generally yielded higher yields (80-91%), while hexafluoroisopropanol (HFIP) yielded moderate yields (70-76%). The quantum yield varied considerably (6.17-67.08%) between emission wavelengths of 432-456 nm, with 1ab showing the highest yield at 67.08%.

[0041] Example 9 The structural formula of compound 2aa in this embodiment is:

[0042] Preparation methods are divided into one-pot method and stepwise method: One-pot method: Add 0.1 mmol of 3,5-di-tert-butylsalicylaldehyde, 0.05 mmol of (1S,2S)-(+)-1,2-cyclohexanediamine, 0.2 mmol of boric acid, 0.1 mmol of potassium acetate, 1 g of type 4A molecular sieve, and 3 mL of hexafluoroisopropanol to separate 15 mL pressure-resistant tubes, and incubate at 100°C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (pure PE), which was dried to obtain a pale blue solid with a yield of 65%.

[0043] Stepwise method: Add 0.05 mmol of (S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicylic acid)-1,2-cyclohexane, 0.1 mmol of boric acid, 0.1 mmol of potassium acetate, 1 g of type 4A molecular sieve, and 3 mL of hexafluoroisopropanol to 15 mL pressure-resistant tubes respectively, and incubate at 100°C. oThe reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (pure PE), which was dried to obtain a pale blue solid with a yield of 55%. 1 H NMR (600 MHz, CDCl3) δ 8.30 (d, J = 45.6 Hz, 2H), 7.55 (d, J = 23.6 Hz, 2H), 7.13 (s, 1H), 6.86 (s, 1H), 4.86 (d, J = 57.7 Hz, 2H), 4.55 (s, 1H),4.34 (s, 1H), 4.09 (d, J = 62.2 Hz, 2H), 2.68 (s, 1H), 2.23 (s, 2H), 1.95 (s,2H), 1.49 (s, 2H), 1.37 (d, J = 16.8 Hz, 1H), 1.18 (d, J = 45.0 Hz, 36H). 13 CNMR (151 MHz, CDCl3) δ 168.7, 164.7, 154.3, 143.1, 137.6, 134.7, 126.5, 123.1(q, 1 J C-F = 285.5 Hz), 73.1, 70.3(m), 59.6, 37.0 – 32.9 (m), 30.9, 29.2 (d, J= 88.8 Hz), 24.9 (d, J = 79.3 Hz). 19 F NMR (565 MHz, CDCl3) δ -72.8 (t, J =10.8 Hz), -73.0 (t, J = 10.8 Hz), -73.6 (dd, J = 84.5, 11.1 Hz), -73.9, -74.4(d, J = 11.5 Hz), -74.6 (d, J = 11.3 Hz). 11 B NMR (193 MHz, CDCl3) δ 2.1 (d, J= 64.5 Hz). HRMS (positive ESI) Calcd. For C 48 H 56 B2F 24 N₂O₆Na (M + Na) +1257.5414, Found: 1257.5897. Maximum fluorescence excitation wavelength is 283 nm, and maximum fluorescence emission wavelength is 475 nm. The quantum yield measured in dichloromethane is 31.32%.

[0044] Example 10

[0045] The structural formula of compound 2ab in this embodiment is:

[0046] Preparation methods are divided into one-pot method and stepwise method: One-pot method: Add 0.1 mmol of 3,5-di-tert-butylsalicylaldehyde, 0.05 mmol of (1R,2R)-(-)-1,2-cyclohexanediamine, 0.2 mmol of boric acid, 0.1 mmol of potassium acetate, 1 g of type 4A molecular sieve, and 3 mL of hexafluoroisopropanol to 15 mL pressure-resistant tubes respectively, and incubate at 100°C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (pure PE), which was dried to obtain a pale blue solid with a yield of 64%.

[0047] Stepwise method: Add 0.05 mmol of (R,R)-(-)-N,N-bis(3,5-di-tert-butylsalicylic acid)-1,2-cyclohexane, 0.1 mmol of boric acid, 0.1 mmol of potassium acetate, 1 g of type 4A molecular sieve, and 3 mL of hexafluoroisopropanol to 15 mL pressure-resistant tubes respectively, and incubate at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (pure PE), which was dried to obtain a pale blue solid with a yield of 56%. 1 HNMR (600 MHz, CDCl3) δ 8.31 (d, J = 45.5 Hz, 2H), 7.55 (d, J = 24.9 Hz, 2H), 7.13 (s, 1H), 6.86 (s, 1H), 4.87 (d, J = 57.4 Hz, 2H), 4.55 (s, 1H), 4.34 (s,1H), 4.09 (d, J = 62.2 Hz, 2H), 2.69 (s, 1H), 2.23 (s, 2H), 1.95 (s, 2H),1.50 (s, 2H), 1.35 – 1.32 (m, 1H), 1.28–1.14 (m, 36H). 13C NMR (151 MHz, CDCl3)δ 168.6, 164.7, 154.3, 143.3, 137.6, 134.7, 126.5, 123.1 (q, 1 J C-F = 282.1Hz), 73.1, 70.1 (m), 59.7, 36.3 – 32.9 (m), 30.9, 30.5 – 28.2 (m), 24.9 (d, J= 79.1 Hz). 19 F NMR (565 MHz, CDCl3) δ -72.7 (q, J = 10.3 Hz), -73.0 (q, J =10.4 Hz), -73.5 (dq, J = 83.3, 9.4 Hz), -73.9, -74.4 (q, J = 9.9 Hz), -74.6(q, J = 10.2 Hz). 11 B NMR (193 MHz, CDCl3) δ 2.1 (d, J = 64.4 Hz). HRMS(positive ESI) Calcd. For C 48 H 56 B2F 24 N₂O₆Na (M + Na) + 1257.5414, Found: 1257.3813. Maximum fluorescence excitation wavelength is 284 nm, and maximum fluorescence emission wavelength is 480 nm. The quantum yield measured in dichloromethane is 32.57%.

[0048] Example 11

[0049] The structural formula of compound 2ac in this embodiment is:

[0050] Preparation method: 0.05 mmol of (S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicyl)-1,2-cyclohexane, 0.1 mmol of boric acid, 0.1 mmol of potassium acetate, 1 g of type 4A molecular sieve, and 3 mL of hexafluoroisopropanol were added to 15 mL pressure-resistant tubes respectively, and incubated at 100 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (pure PE), which was dried to obtain a pale blue solid with a yield of 60%. 1H NMR (600 MHz, CDCl3) δ 8.30 (d, J = 44.3 Hz, 2H), 7.58 – 7.51 (m, 2H), 7.13 (s, 1H), 6.86 (s, 1H), 4.86 (d, J = 57.1 Hz, 2H), 4.55 (s, 1H), 4.34 (s,1H), 4.09 (d, J = 62.7 Hz, 2H), 2.68 (s, 1H), 2.30 – 2.20 (m, 2H), 1.94 (d, J= 7.7 Hz, 2H), 1.52 (d, J = 30.5 Hz, 3H), 1.27 – 1.13 (m, 36H). 13 C NMR (151MHz, CDCl3) δ 168.7, 164.7, 154.3, 143.3, 134.7, 126.5, 123.1 (q, 1 J C-F = 282.8Hz), 73.1, 70.56 – 68.4 (m), 59.7, 34.8(m), 30.9, 29.5 (d, J = 86.4 Hz), 24.62 (d, J = 76.0 Hz). 19 F NMR (565 MHz, CDCl3) δ -72.7 (q, J = 10.7 Hz), -73.0 (d, J = 11.6 Hz), -73.4 – -73.7 (m), -73.9, -74.4 (q, J = 10.2 Hz), -74.6 (d, J = 10.9 Hz). 11 B NMR (193 MHz, CDCl3) δ 2.1 (d, J = 64.6 Hz). HRMS(positive ESI) Calcd. For C 48 H 56 10 B2F 24 N₂O₆Na (M + Na) + 1255.5414, Found: 1255.6181. Maximum fluorescence excitation wavelength is 283 nm, and maximum fluorescence emission wavelength is 476 nm. The quantum yield measured in dichloromethane is 45.24%.

[0051] Example 12

[0052] The structural formula of compound 2ba in this embodiment is:

[0053] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.05 mmol of (1S,2S)-(+)-1,2-cyclohexanediamine, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 500 mg of type 4A molecular sieve, and 2 mL of chloroform are added to 15 mL pressure-resistant tubes respectively, and the mixture is heated at 100 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA=10 / 1), which was dried to obtain a white solid with a yield of 60%. 1 H NMR (600 MHz, CDCl3) δ 8.57 (s, 2H), 7.63 – 7.58 (m, 2H), 7.42 (d, J =7.9 Hz, 2H), 7.01 (t, J = 7.5 Hz, 2H), 6.94 (d, J = 8.5 Hz, 2H), 4.20 (d, J =8.9 Hz, 2H), 2.41 (d, J = 12.8 Hz, 2H), 2.05 – 2.01 (m, 2H), 1.75 – 1.70 (m,2H), 1.52 (d, J = 10.0 Hz, 2H). 13 C NMR (151 MHz, CDCl3) δ 166.5, 159.3,139.8, 132.0, 122.2 (q, 1 J C-F = 291.5 Hz,), 120.7, 119.3, 115.7, 89.2 (q, J =33.1 Hz), 61.2, 34.4, 24.8. 19 F NMR (565 MHz, CDCl3) δ -68.8 – -67.1 (m), -67.4 – -67.7 (m), -67.9 – -68.2 (m). 11 B NMR (193 MHz, CDCl3) δ 6.4. HRMS(positive ESI) Calcd. For C 32 H 20 B2F 24 N₂O₆Na (M + Na) +1029.0844, Found: 1029.6969. Maximum fluorescence excitation wavelength is 284 nm, and maximum fluorescence emission wavelength is 453 nm. The quantum yield measured in dichloromethane is 8.22%.

[0054] Example 13

[0055] The structural formula of compound 2bb in this embodiment is:

[0056] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.05 mmol of (1R,2R)-(-)-1,2-cyclohexanediamine, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 500 mg of type 4A molecular sieve, and 2 mL of chloroform are added to 15 mL pressure-resistant tubes respectively, and the mixture is heated at 100 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA=10 / 1), which was dried to obtain a white solid with a yield of 96%. 1 H NMR (600 MHz, CDCl3) δ 8.6 (s, 2H), 7.6 (ddd, J = 8.7, 7.2, 1.7 Hz,2H), 7.4 (d, J = 7.9 Hz, 2H), 7.0 (t, J = 7.5 Hz, 2H), 6.9 (d, J = 8.5 Hz,2H), 4.2 (d, J = 9.3 Hz, 2H), 2.4 (d, J = 12.9 Hz, 2H), 2.1 – 2.0 (m, 2H),1.7 (d, J = 10.9 Hz, 2H), 1.5 (d, J = 10.0 Hz, 2H). 13 C NMR (151 MHz, CDCl3) δ166.5, 159.3, 139.8, 132.0, 121.1 (q, 1 J C-F = 290.4 Hz), 120.7, 119.3, 115.7, 89.2 (m), 61.2, 34.4, 24.8. 19 F NMR (565 MHz, CDCl3) δ -66.8 – -67.1 (m), -67.9 – -68.2 (m), -70.0 – -70.2 (m). 11B NMR (193 MHz, CDCl3) δ 6.4. HRMS(positive ESI) Calcd. For C 32 H 20 B2F 24 N₂O₆Na (M + Na) + ) 1029.0844, Found:1029.5953. The maximum fluorescence excitation wavelength is 283 nm, and the maximum fluorescence emission wavelength is 455 nm.

[0057] Example 14

[0058] The structural formula of compound 2bc in this embodiment is:

[0059] The preparation method is as follows: 0.05 mmol of (S,S)-(+)-N,N-bis(3,5-di-tert-butylsalicyl)-1,2-cyclohexane, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 500 mg of type 4A molecular sieve, and 2 mL of ultradry chloroform are added to 15 mL pressure-resistant tubes respectively, and incubated at 100 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA=100 / 1), which was dried to obtain a pale blue solid with a yield of 22%. 1 H NMR (600 MHz, CDCl3) δ 8.5 (s, 2H), 7.6 (d, J = 2.4 Hz,2H), 7.1 (d, J = 2.5 Hz, 2H), 4.2 (d, J = 9.0 Hz, 2H), 2.4 (d, J = 12.8 Hz,2H), 1.9 (d, J = 9.6 Hz, 2H), 1.7 – 1.6 (m, 2H), 1.5 (d, J = 9.7 Hz, 2H), 1.2(s, 18H), 1.1 (s, 18H). 13 C NMR (151 MHz, CDCl3) δ 167.1, 156.1, 143.0, 139.1,135.7, 126.1, 120.6 (q, 1 J C-F = 291.9 Hz), 115.0, 90.7 – 89.0 (m), 60.8, 35.1,34.7, 34.2, 30.7, 28.8, 24.9. 19F NMR (565 MHz, CDCl3) δ -65.6 – -65.8 (m), -68.8 – -67.0 (m), -67.6 – -67.8 (m), -69.6 – -69.9 (m). 11 B NMR (193 MHz, CDCl3) δ 7.0. HRMS (positive ESI) Calcd. For C 48 H 52 B2F 24 N₂O₆Na (M + Na) + 1253.5097, Found: 1253.3390. Maximum fluorescence excitation wavelength is 292 nm, and maximum fluorescence emission wavelength is 477 nm. The quantum yield measured in dichloromethane is 31.02%.

[0060] Example 15

[0061] The structural formula of compound 2bd in this embodiment is:

[0062] The preparation method is as follows: 0.1 mmol of salicylaldehyde, 0.05 mmol of 2,2-biphenyldiamine, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 500 mg of type 4A molecular sieve, and 2 mL of chloroform are added separately to 15 mL pressure-resistant tubes, and then incubated at 100 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA=10 / 1), which was dried to obtain a pale blue solid with a yield of 23%. 1 H NMR (600 MHz, Acetone) δ 9.06 (s, 2H), 7.97 (d, J = 2.5 Hz, 2H), 7.82 (dd, J =8.1, 1.4 Hz, 2H), 7.76 (d, J = 2.5 Hz, 2H), 7.63 (dd, J = 8.0, 1.6 Hz, 2H), 7.53 (td, J = 7.7, 1.4 Hz, 2H), 7.44 (td, J = 7.8, 1.7 Hz, 2H), 1.49 (s, 18H), 1.36 (s, 18H). 13C NMR (151 MHz, Acetone) δ 174.0, 156.8, 143.4, 141.7,138.9, 136.1, 133.4, 130.5, 129.3, 127.8, 127.5, 119.8, 115.0, 76.2, 34.8,34.1, 30.4. 19 F NMR (565 MHz, Acetone) δ -67.7 – -68.0 (m), -68.0 – -68.2 (m), -68.2 – -68.4 (m), -70.3 – -70.5 (m). 11 B NMR (193 MHz, Acetone) δ 7.1. HRMS(positive ESI) Calcd. For C 54 H 50 B2F 24 N₂O₆Na (M + Na) + 1323.5580, Found: 1323.0671. Maximum fluorescence excitation wavelength is 292 nm, and maximum fluorescence emission wavelength is 484 nm. The quantum yield measured in dichloromethane is 51.07%.

[0063] In summary, in Examples 9-15, all amine derivatives used were diamines, and the yields were generally lower than those of monoamines (22-65%). This was especially true for the sterically hindered structures 2bc and 2bd, which had emission wavelengths between 453-484 nm and generally higher quantum yields (31.02-51.07%), with 2bd showing particularly significant yields of 51.07%. Tert-butyl substitution (2aa-2ac) enhanced fluorescence stability. 2aa and 2ab were prepared using a one-step method and a stepwise method, respectively. The one-step method (yields of 65% and 64%, respectively) yielded boron-based framework compounds with higher yields than the stepwise method (yields of 55% and 56%, respectively).

[0064] Example 16 The structural formula of compound 3ba in this embodiment is:

[0065] The preparation method is as follows: 0.1 mmol of (S)-2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenol, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C. oThe reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a colorless oil with a yield of 98%. 1 H NMR (600 MHz, CD3CN) δ 7.84 (dd, J = 8.0, 1.7 Hz, 1H), 7.77 – 7.73 (m, 1H), 7.38 – 7.33 (m, 3H), 7.20 (d, J = 8.0 Hz, 2H), 7.14 (t, J = 7.6 Hz, 1H), 7.10(d, J = 8.5 Hz, 1H), 5.65 (dd, J = 9.6, 4.4 Hz, 1H), 5.25 (t, J = 9.3 Hz,1H), 4.69 (dd, J = 9.2, 4.4 Hz, 1H). 13 C NMR (151 MHz, CD3CN) δ 171.8, 160.9,139.7, 139.4, 129.3, 129.2, 128.3, 126.7, 123.4 (q, 1 J C-F = 289.0 Hz), 121.5,121.3, 119.6, 117.9, 107.0, 89.4 – 88.2 (m), 80.5, 63.2. 19 F NMR (565 MHz, CD3CN) δ -67.9 – -68.4 (m), -69.6 – -69.8 (m), -70.1 – -70.2 (m). 11 B NMR (193MHz, CD3CN) δ 7.15. HRMS (positive ESI) Calcd. For C 21 H 12 BF 12 NO4Na (M + Na + 604.1059, Found: 604.0542. Maximum fluorescence excitation wavelength is 255 nm, and maximum fluorescence emission wavelength is 385 nm. The quantum yield measured in dichloromethane is 25.12%.

[0066] Example 17

[0067] The structural formula of compound 3bb in this embodiment is:

[0068] The preparation method is as follows: 0.1 mmol of (S)-4-fluoro-2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenol, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinol, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a pale yellow solid with a yield of 99%. 1 H NMR (600 MHz, CD3CN) δ 7.57 (t, J = 8.3 Hz, 2H), 7.42 – 7.37 (m, 3H), 7.26 – 7.22 (m, 2H), 7.15 (ddd, J = 8.4, 4.3, 1.4 Hz, 1H), 5.73 – 5.68 (m,1H), 5.30 (t, J = 9.4 Hz, 1H), 4.75 (dd, J = 9.1, 4.5 Hz, 1H). 13 C NMR (151MHz, CD3CN) δ 171.3, 157.5, 157.2, 155.6, 139.1, 129.3 (d, J = 10.5 Hz), 127.5 (d, J = 24.9 Hz), 126.7, 121.6 (q, 1 J C-F = 289.3 Hz), 117.9, 112.9 (d, J =24.9 Hz), 107.0 (d, J = 10.0 Hz), 89.4 – 88.4 (m), 80.7, 63.4. 19 F NMR (565MHz, CD3CN) δ -68.1 – -68.3 (m), -69.6 – -68.8 (m), -70.0 – -70.2 (m). 11 B NMR(193 MHz, CD3CN) δ 7.2. HRMS (positive ESI) Calcd. For C 21 H 12 BF 13 NO4 (M + H + )600.1145, Found: 600.0202. The maximum fluorescence excitation wavelength is 255 nm, and the maximum fluorescence emission wavelength is 398 nm.

[0069] Example 18

[0070] The structural formula of compound 3bc in this embodiment is:

[0071] The preparation method is as follows: 0.1 mmol of (S)-4-bromo-2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenol, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a pale yellow oil with a yield of 99%. 1 H NMR (600 MHz, CD3CN) δ 7.96 (d, J = 2.5 Hz, 1H), 7.84 (dd, J = 9.0,2.5 Hz, 1H), 7.36 (qd, J = 4.8, 1.3 Hz, 3H), 7.20 (dd, J = 7.3, 2.2 Hz, 2H), 7.04 (d, J = 9.0 Hz, 1H), 5.66 (dd, J = 9.7, 4.5 Hz, 1H), 5.26 (t, J = 9.4Hz, 1H), 4.71 (dd, J = 9.1, 4.5 Hz, 1H). 13 C NMR (151 MHz, CD3CN) δ 170.9,159.9, 142.2, 139.0, 130.2, 129.3 (d, J = 8.3 Hz), 126.7, 123.3 (q, 1 J C-F =289.0 Hz), 121.9, 121.4, 117.9, 112.3, 108.7, 89.2 (q, 2 J C-F = 32.7 Hz), 80.7, 63.4. 19 F NMR (565 MHz, CD3CN) δ -68.0 – -68.3 (m), -69.5 – -69.8 (m), -70.1 –-70.2 (m). 11B NMR (193 MHz, CD3CN) δ 7.1. HRMS (positive ESI) Calcd. ForC 21 H 12 BBrF 12 NO4 (M + H + ) 661.0201, Found: 661.9887. The maximum fluorescence excitation wavelength is 255 nm, and the maximum fluorescence emission wavelength is 401 nm.

[0072] Example 19

[0073] The structural formula of compound 3bd in this embodiment is:

[0074] The preparation method is as follows: 0.1 mmol of (S)-4-methoxy-2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenol, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a pale yellow oil with a yield of 99%. 1 H NMR (600 MHz, CD3CN) δ 7.42 – 7.37 (m, 4H), 7.26 – 7.22 (m, 3H), 7.08 (d, J = 9.1 Hz, 1H), 5.69 (dd, J = 9.6, 4.3 Hz, 1H), 5.29 (t, J = 9.3Hz, 1H), 4.73 (dd, J = 9.1, 4.3 Hz, 1H), 3.84 (s, 3H). 13 C NMR (151 MHz, CD3CN)δ 171.7, 155.8, 153.9, 139.4, 129.4, 129.2, 129.0, 126.6, 123.4 (q, 1 J C-F =289.3 Hz), 121.0, 117.9, 108.6, 106.4, 89.0 (q, 2 J C-F = 32.7 Hz), 80.5, 63.2, 56.4. 19F NMR (565 MHz, CD3CN) δ -68.0 – -68.4 (m), -69.5 – -69.8 (m), -70.0 –-70.2 (m). 11 B NMR (193 MHz, CD3CN) δ 7.2. HRMS (positive ESI) Calcd. ForC 22 H 14 BF 12 NO5Na (M + Na + 634.1318, Found: 634.0651. Maximum fluorescence excitation wavelength is 260 nm, and maximum fluorescence emission wavelength is 433 nm. The quantum yield measured in dichloromethane is 75.48%.

[0075] Example 20

[0076] The structural formula of compound 3be in this embodiment is:

[0077] The preparation method is as follows: 0.1 mmol of (S)-2-methoxy-2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenol, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a white solid with a yield of 99%. 1 H NMR (600 MHz, CD3CN) δ 7.43 (dd, J = 8.1, 1.4 Hz, 1H), 7.38 (tt, J =9.3, 3.4 Hz, 4H), 7.23 (dd, J = 7.5, 2.1 Hz, 2H), 7.09 (t, J = 8.0 Hz, 1H), 5.69 (dd, J = 9.6, 4.3 Hz, 1H), 5.27 (t, J = 9.3 Hz, 1H), 4.71 (dd, J = 9.1, 4.3 Hz, 1H), 3.90 (s, 3H). 13 C NMR (151 MHz, CD3CN) δ 172.0, 151.8, 151.5,139.4, 129.3, 129.2, 126.6, 123.4 (q,1 J C-F = 289.9 Hz), 121.1, 120.9, 119.1,117.9, 107.3, 88.6 (q, 2 J C-F = 32.7 Hz), 80.4, 63.2, 56.9. 19 F NMR (565 MHz, CD3CN) δ -68.0 – -68.4 (m), -69.4 – -69.7 (m), -70.0 – -70.3 (m). 11 B NMR (193MHz, CD3CN) δ 7.3. HRMS (positive ESI) Calcd. For C 22 H 14 BF 12 NO5Na (M + Na + )634.1318, Found: 634.0667. The maximum fluorescence excitation wavelength is 260 nm, and the maximum fluorescence emission wavelength is 433 nm.

[0078] Example 21

[0079] The structural formula of compound 3bf in this embodiment is:

[0080] The preparation method is as follows: 0.1 mmol of (S)-2-tert-butyl-2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenol, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinolone, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a colorless oily substance with a yield of 44%. 1H NMR (600 MHz, CD3CN) δ 7.78 (dd, J = 7.7, 1.7 Hz, 1H), 7.74 (dd, J =7.9, 1.7 Hz, 1H), 7.38 – 7.33 (m, 3H), 7.17 (dd, J = 7.5, 2.0 Hz, 2H), 7.09 (t, J = 7.8 Hz, 1H), 5.64 (dd, J = 9.4, 3.8 Hz, 1H), 5.19 (t, J = 9.2 Hz, 1H), 4.68 (dd, J = 9.1, 3.8 Hz, 1H), 1.39 (s, 9H). 13 C NMR (151 MHz, CD3CN) δ172.1, 159.6, 140.4, 139.6, 136.6, 129.3, 129.1, 126.5, 126.4, 123.6 (q, 1 J C-F = 289.9 Hz), 120.9, 117.9, 107.1, 89.2 (q, 2 J C-F = 32.7 Hz), 80.0, 63.3, 35.3,28.9. 19 F NMR (565 MHz, CD3CN) δ -68.0 – -68.3 (m), -68.4 – -68.8 (m), -69.9 –-70.2 (m). 11 B NMR (193 MHz, CD3CN) δ 7.3. HRMS (positive ESI) Calcd. ForC 25 H 20 BF 12 NO4Na (M + Na + ) 660.2122, Found: 660.1171. The maximum fluorescence excitation wavelength is 261 nm, and the maximum fluorescence emission wavelength is 396 nm.

[0081] Example 22

[0082] The structural formula of compound 3bg in this embodiment is:

[0083] The preparation method is as follows: 0.1 mmol of (S)-2,4-di-tert-butyl-2-(4-phenyl-4,5-dihydrooxazol-2-yl)phenol, 0.2 mmol of boric acid, 0.3 mmol of perfluoroquinol, 2 mL of chloroform, and 500 mg of type 4A molecular sieve are added to 15 mL pressure-resistant tubes respectively, and incubated at 60 °C. o The reaction was carried out at C for 7 hours. After the reaction was completed, the reaction solution was filtered through diatomaceous earth and the filtrate was concentrated. The crude product was purified by column chromatography to obtain the target product (PE / EA = 10 / 1), which was dried to obtain a pale yellow solid with a yield of 88%. 1 H NMR (600 MHz, CD3CN) δ 7.87 (d, J = 2.5 Hz, 1H), 7.70 (d, J =2.5 Hz, 1H), 7.40 – 7.36 (m, 3H), 7.21 – 7.18 (m, 2H), 5.67 (dd, J = 9.3, 3.8Hz, 1H), 5.22 (t, J = 9.2 Hz, 1H), 4.71 (dd, J = 9.1, 3.8 Hz, 1H), 1.44 (s,9H), 1.37 (s, 9H). 13 C NMR (151 MHz, CD3CN) δ 172.1, 157.8, 143.5, 139.9,139.7, 134.7, 129.3, 129.1, 126.5, 123.7 (q, 1 J C-F = 289.5 Hz), 121.7, 117.8,106.4, 89.3 (q, 2 J C-F = 32.7Hz), 79.9, 63.3 (q, J = 4.5 Hz), 35.5, 34.8, 31.0,29.0. 19 F NMR (565 MHz, CD3CN) δ -68.1 – -68.3 (m), -68.4 – -68.8 (m), -70.0 –-70.2 (m). 11 B NMR (193 MHz, CD3CN) δ 7.3. HRMS (positive ESI) Calcd. ForC 29 H 28 BF 12 NO4Na (M + Na +) 716.3185, Found: 716.1864. The maximum fluorescence excitation wavelength is 263 nm, and the maximum fluorescence emission wavelength is 409 nm.

[0084] In summary, in Examples 16-22, using phenoxyoxazoline compounds as raw materials, the yield of 3bf was 44%, due to steric hindrance. The yields of the other compounds were all above 88%, and the yields of 3ba, 3bb, 3bc, and 3bd were all above 98%. The quantum yield varied greatly between 385-433 nm, reaching 75.48% for 3bd.

[0085] In this invention, regarding the preparation method, the boron-based framework compounds are prepared using either a one-pot or stepwise method. The one-pot method is simpler, while the stepwise method is suitable for complex substrates. Regarding the selection of fluorinated alcohols, fluorinated groups (CF3 derived from HFIP / HFP) enhance the stability and solubility of the compounds. Both HFIP and HFP can promote the reaction, but HFP is often used in combination with chloroform to more effectively improve the yield and stability.

[0086] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. The scope of patent protection of the present invention shall be determined by the claims. Similarly, any equivalent structural changes made based on the description and drawings of the present invention shall also be included within the scope of protection of the present invention.

Claims

1. A boron-based skeleton compound, characterized in that, The general structural formula of the compound is one of the following formulas 1a, 1b, and 1c: ； Wherein R A1 The connection structure is one of the following: 、 ； R B1 The connection structure is one of the following: 、 ； In this context, * indicates a connection site.

2. The boron-based framework compound according to claim 1, characterized in that, The structure of the R1 group in general formula 1a is as shown in one of the following formulas A1-A5: 、 、 、 、 ； In this context, * indicates a connection site.

3. The boron-based framework compound according to claim 1, characterized in that, In general formula 1b, the R2 group is either a hydrogen atom or a tert-butyl group with ortho- or para-disubstituted tert-butyl groups.

4. A boron-based framework compound according to claim 1, characterized in that, In the general formula 1c, the R3 group is any one of H atom, fluorine atom, bromine atom, ortho-substituted methoxy group, para-substituted methoxy group, ortho-substituted tert-butyl group, ortho-para-disubstituted tert-butyl group.

5. A boron-based framework compound according to claim 1, characterized in that, The boron-based skeleton compound is any one of the following structures: 1aa-1ac, 1ba-1be, 2aa-2ac, 2ba-2bd, 3ba-3bg. 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 6. A method for preparing a boron-based framework compound, characterized in that, This compound uses ； The one-step preparation method is as follows: salicylaldehyde compound, amine compound, boric acid and molecular sieve are added to the reaction tube, and then the reaction solvent is added and reacted at 60-100℃ for 7-12h. After the reaction is completed, the target product is obtained after post-treatment. The reaction formula for the step-by-step method is shown below: ； The stepwise preparation method is as follows: add salicylaldehyde imine compound or phenoxyoxazoline compound, boric acid and molecular sieve into the reaction tube, then add reaction solvent, react at 60~100℃ for 7~12h, and after the reaction is completed, the target product is obtained after post-processing. The reaction solvent is a mixture of hexafluoroisopropanol or perfluorophenyl alcohol and chloroform.

7. The preparation method according to claim 6, characterized in that, The molecular sieve is a type 4A molecular sieve.

8. The preparation method according to claim 6, characterized in that, In the one-step method, the amount of boric acid used is 1.0 to 4 times the amount of salicylaldehyde compound, and the amount of alkali used is 2 times the amount of salicylaldehyde compound. When using perfluoroquinol, the amount of perfluoroquinol should be 3.0-6.0 times the amount of salicylaldehyde or salicylaldehyde imine compounds.

9. The preparation method according to claim 6, characterized in that, The post-processing includes diatomaceous earth filtration, thin-layer chromatography separation, and drying. The solvent used for filtration is ethyl acetate, and the eluent used for thin-layer chromatography separation is ethyl acetate and petroleum ether or pure dichloromethane in a volume ratio of 0:1 to 5:

1.

10. The use of any boron-based framework compound as described in any one of claims 1-5 in the preparation of light-emitting diodes, photoluminescent materials, chemical sensors, biofluorescent probes, or energy-regulating battery devices.

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