A planar-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance, preparation method and application

Abstract

The present invention provides a face-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance, a preparation method and applications, relating to the field of organic light-emitting materials. The face-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance provided by the present invention has the following molecular structural formula: ; The face-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance of the present invention introduces a donating group diphenylamino and an electron-withdrawing group [(2-dimesitylboryl)phenyl]ethynyl at the pseudo-meta positions of the two benzene rings of [2.2]paracyclophane, and has a high solid-state fluorescence quantum yield and a high solid-state luminescence asymmetry factor, showing excellent circularly polarized luminescence properties.

Description

Technical Field

[0001] The present invention relates to the field of organic light-emitting materials, and particularly to a planar chiral [2.2] paracyclophane organic small molecule with high solid-state luminescence performance, a preparation method and an application thereof. Background Art

[0002] Polarization is one of the important inherent properties of light. According to the different trajectories of the endpoints of the light vector, polarized light is mainly divided into linearly polarized light, circularly polarized light and elliptically polarized light. Among them, circularly polarized light is closer to natural light, can effectively reduce people's visual fatigue and achieve the purpose of protecting eyes healthily.

[0003] Circularly polarized luminescence (CPL) refers to the phenomenon that a chiral luminescence system or a non-chiral luminescence system emits different left-handed or right-handed circularly polarized light in a chiral environment. Such materials have potential application prospects in the fields of three-dimensional display, optical information storage and processing, biological probes, CPL sensors, asymmetric photochemical synthesis, etc. At present, the most studied CPL materials are transition metal complexes, organic polymers and organic small molecules; in contrast, organic small molecules have the advantages of easy derivatization, adjustable emission wavelength, simple preparation process, easy determination of structure, etc. Therefore, the research on organic small molecule CPL materials has become an important topic at present. Fluorescence quantum yield (Φ F ) and luminescence asymmetry factor (g lum ) are two important parameters for measuring the luminescence performance of circularly polarized luminescence materials; at the same time, since the prepared devices are often in a solid state, high solid-state luminescence performance is a very important reference index for circularly polarized luminescence materials.

[0004] Due to the aggregation-induced quenching phenomenon caused by the intermolecular interaction, the fluorescence quantum yield of organic small molecules in the solid state is generally low; moreover, the luminescence asymmetry factors of the currently disclosed CPL organic small molecules are also generally low (less than 5×10 -3 ). Especially in the solid state, it more restricts the improvement of the fluorescence quantum yield and luminescence asymmetry factor of CPL organic small molecules. Therefore, it is very challenging to obtain organic small molecules with both high fluorescence quantum yield and high luminescence asymmetry factor.

[0005] "Research on Boron-Modified [2.2]Paracyclophane Organic Luminescent Materials" (Doctoral Dissertation of Shandong University, Zhang Mengyuan, etc.) discloses a pseudo-meta-substituted [2.2]paracyclophane derivative m-BPhNPh2-Cp. The fluorescence quantum yield of this compound in the powder state is 0.19. Although the luminescence asymmetry factor of this molecule is relatively high in solution, the luminescence asymmetry factor in its solid state cannot be detected, and its fluorescence quantum yield is also relatively low. Based on the current research progress, it is of great technical significance and broad application prospects to provide a CPL organic small molecule with high solid-state luminescence performance, especially a CPL organic small molecule with both a high fluorescence quantum yield and a high luminescence asymmetry factor in the solid state. Summary of the Invention

[0006] To solve the technical problems existing in the prior art, the present invention provides a face-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance, which can simultaneously have a high fluorescence quantum yield and a high luminescence asymmetry factor in the solid state; the present invention also provides a preparation method of the face-chiral [2.2]paracyclophane organic small molecule; the present invention also provides an application of the face-chiral [2.2]paracyclophane organic small molecule.

[0007] To solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0008] A face-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance, the molecular structural formula is shown as follows:

[0009] ;

[0010] In the formula, -BMes2 is a dimesitylboron group, and -NPh2 is a diphenylamino group.

[0011] A preparation method of a face-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance, including the following steps:

[0012] Using 4-iodo-1,5-diphenylamino[2.2]paracyclophane as the starting material, first carrying out a coupling reaction to obtain 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane; then through a borylation reaction, a face-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance is prepared.

[0013] Further, the method of the coupling reaction is that in a solvent environment, in the presence of copper iodide and bis(triphenylphosphine)palladium dichloride, 4-iodo-1,5-diphenylamino[2.2]paracyclophane reacts with 2-bromophenylethyne to obtain 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane;

[0014] The method of the boronation reaction is as follows: in a solvent environment, 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane first reacts with n-butyllithium and then reacts with dimethylboron fluoride to obtain a planar chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance.

[0015] Preferably, in the coupling reaction, the molar ratio of 4-iodo-1,5-diphenylamino[2.2]paracyclophane, 2-bromophenylethyne, bis(triphenylphosphine)palladium dichloride, and cuprous iodide is 1:1 - 1.3:0.05 - 0.1:0.06 - 0.09.

[0016] Preferably, in the coupling reaction, the reaction time of 4-iodo-1,5-diphenylamino[2.2]paracyclophane and 2-bromophenylethyne is 12 - 18 h.

[0017] Preferably, in the boronation reaction, the molar ratio of 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane to n-butyllithium is 1:1.8 - 2.2;

[0018] The molar ratio of 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane to dimethylboron fluoride is 1:2 - 3.

[0019] Preferably, in the boronation reaction, the reaction time of 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane and n-butyllithium is 1.5 - 2 h.

[0020] Preferably, in the boronation reaction, the reaction time for contacting and reacting with dimethylboron fluoride is 10 - 15 h.

[0021] The synthetic route of the planar chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance is as follows:

[0022] 。

[0023] An application of the aforementioned planar chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance or a planar chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance prepared by the aforementioned preparation method as a circularly polarized luminescence material.

[0024] An application of the aforementioned planar chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance or a planar chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance prepared by the aforementioned preparation method in the fields of three-dimensional display, optical information storage and processing, biological probes, and CPL sensors.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] (1) The planar-chiral [2.2]paracyclophane organic small molecule m-BPhANPh2-Cp with solid-state luminescence properties of the present invention uses [2.2]paracyclophane as a structural unit, and a donating group diphenylamino and an electron-withdrawing group [(2-dimesitylboryl)phenyl]ethynyl are introduced at the pseudo-meta positions of the two benzene rings of [2.2]paracyclophane respectively; the fluorescence of the planar-chiral [2.2]paracyclophane organic small molecule arises from the intramolecular space charge transfer between the donating group diphenylamino and the electron-withdrawing group [(2-dimesitylboryl)phenyl]ethynyl; in the planar-chiral [2.2]paracyclophane organic small molecule, the [2.2]paracyclophane structural unit has stable planar chirality, and the dimesitylboryl group with large steric hindrance can effectively inhibit the aggregation-induced quenching phenomenon caused by intermolecular interactions, and can have a high fluorescence quantum yield and luminescence asymmetry factor in the solid state.

[0027] (2) Compared with the [2.2]paracyclophane derivative m-BPhNPh2-Cp disclosed in the prior art, the planar-chiral [2.2]paracyclophane organic small molecule m-BPhANPh2-Cp with solid-state luminescence properties of the present invention has a strong solid-state circularly polarized luminescence signal, and higher solid-state fluorescence quantum yield and luminescence asymmetry factor.

[0028] (3) The preparation method of the planar-chiral [2.2]paracyclophane organic small molecule m-BPhANPh2-Cp with solid-state luminescence properties of the present invention is simple, the preparation process is easy to control, the reaction yield is high, and it is conducive to large-scale production.

[0029] (4) The planar-chiral [2.2]paracyclophane organic small molecule m-BPhANPh2-Cp with solid-state luminescence properties of the present invention can be used as a circularly polarized luminescence material in the fields of three-dimensional display, optical information storage and processing, biological probes, CPL sensors, etc., and has a wide application prospect. Brief Description of the Drawings

[0030] Figure 1 It is the synthetic route diagram of m-BPhANPh2-Cp in Example 1.

[0031] Figure 2 It is the high-resolution mass spectrum of m-BrPhANPh2-Cp prepared in Example 1.

[0032] Figure 3 It is the 1H nuclear magnetic resonance spectrum of m-BrPhANPh2-Cp prepared in Example 1.

[0033] Figure 4 It is the high-resolution mass spectrum of m-BPhANPh2-Cp prepared in Example 1.

[0034] Figure 5 It is the 1H nuclear magnetic resonance spectrum of m-BPhANPh2-Cp prepared in Example 1.

[0035] Figure 6 Fluorescence emission spectra of the m-BPhANPh2-Cp powder and thin film prepared in Example 1.

[0036] Figure 7 HPLC chromatogram of m-BPhANPh2-Cp prepared in Example 1.

[0037] Figure 8 Circularly polarized luminescence spectrum of the m-BPhANPh2-Cp thin film prepared in Example 1. Detailed implementation manners

[0038] For a clearer understanding of the technical features, objectives, and effects of the present invention, the specific implementation manners of the present invention are now described. It should be noted that the following detailed descriptions are all exemplary and are intended to provide further explanations of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.

[0039] It should be noted that the terms used herein are only for describing specific implementation manners and are not intended to limit the exemplary implementation manners according to the present invention. As used herein, "first", "second", etc. are used to distinguish similar objects and are not used to describe a specific order or sequence. In addition, it should also be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0040] An embodiment of the present invention provides a planar chiral [2.2] paracyclophane organic small molecule with high solid-state luminescence performance. The planar chiral [2.2] paracyclophane organic small molecule is named m-BPhANPh2-Cp and has the following molecular structural formula:

[0041] ;

[0042] In the formula, -BMes2 is a dimesitylboron group, and -NPh2 is a diphenylamino group.

[0043] An embodiment of the present invention also provides a preparation method for a planar chiral [2.2] paracyclophane organic small molecule with high solid-state luminescence performance, including:

[0044] Using 4-iodo-1,5-diphenylamino[2.2]paracyclophane as the starting material, first performing a Sonogashira coupling reaction to obtain 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane, and then through a borylation reaction, preparing a planar chiral [2.2] paracyclophane organic small molecule with high solid-state luminescence performance.

[0045] Further, the method of the Sonogashira coupling reaction is that in a solvent environment, in the presence of cuprous iodide and bis(triphenylphosphine)palladium dichloride, 4-iodo-1,5-diphenylamino[2.2]paracyclophane reacts with 2-bromoacetylene to prepare 4-(2-bromoethynyl)-1,5-diphenylamino[2.2]paracyclophane;

[0046] The method of the borylation reaction is that in a solvent environment, 4-(2-bromoethynyl)-1,5-diphenylamino[2.2]paracyclophane first reacts with n-butyllithium and then reacts with dimethylphenylboron fluoride to prepare a planar chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance.

[0047] Further, the method of the Sonogashira coupling reaction is that in a solvent environment, in the presence of cuprous iodide and bis(triphenylphosphine)palladium dichloride, 4-iodo-1,5-diphenylamino[2.2]paracyclophane reacts with 2-bromoacetylene at room temperature, and after extraction with an extractant, the extraction phase is dried, desolvated and then purified to prepare 4-(2-bromoethynyl)-1,5-diphenylamino[2.2]paracyclophane.

[0048] The method of the borylation reaction is that in a solvent environment, 4-(2-bromoethynyl)-1,5-diphenylamino[2.2]paracyclophane first reacts with n-butyllithium at low temperature and then reacts with dimethylphenylboron fluoride at room temperature, and after extraction with an extractant, the extraction phase is dried, desolvated and then purified to prepare a planar chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance.

[0049] Preferably, in the Sonogashira coupling, the molar ratio of 4-iodo-1,5-diphenylamino[2.2]paracyclophane, 2-bromoacetylene, bis(triphenylphosphine)palladium dichloride, and cuprous iodide is 1:1-1.3:0.05-0.1:0.06-0.09

[0050] Preferably, in the Sonogashira coupling, the reaction time is 12-18 h; for example, the reaction time can be 12 h, 14 h, 16 h or 18 h.

[0051] Preferably, in the borylation reaction, the molar ratio of 4-(2-bromoethynyl)-1,5-diphenylamino[2.2]paracyclophane to n-butyllithium is 1:1.8-2.2.

[0052] Preferably, in the borylation reaction, the reaction time of 4-(2-bromoethynyl)-1,5-diphenylamino[2.2]paracyclophane and n-butyllithium is 1.5-2 h; for example, the reaction time can be 1.5 h, 1.7 h or 2 h.

[0053] Preferably, in the borylation reaction, the molar ratio of 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane to dimethylphenylboron fluoride is 1:2-3; for example, the molar ratio can be 1:2, 1:2.5 or 1:3.

[0054] Preferably, in the borylation reaction, the reaction time of 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane and dimethylphenylboron fluoride is 10-15 h; for example, the reaction time can be 10 h, 12 h, 13 h or 15 h.

[0055] The present invention also provides the application of the above-mentioned axially chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance or the axially chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance prepared by the above-mentioned preparation method as a circularly polarized luminescence material.

[0056] The present invention also provides the application of the above-mentioned axially chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance or the axially chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance prepared by the above-mentioned preparation method in the fields of three-dimensional display, optical information storage and processing, biological probes, and CPL sensors.

[0057] The following further illustrates the present invention in conjunction with some specific embodiments.

[0058] Example 1

[0059] This example provides an axially chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance. The organic small molecule is named m-BPhANPh2-Cp and has the following molecular structural formula:

[0060] ;

[0061] In the formula, -BMes2 is a dimethylphenylboron group, and -NPh2 is a diphenylamino group.

[0062] The embodiment of the present invention also provides a preparation method of an axially chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance. The specific synthesis route is as Figure 1 shown, and the specific steps are as follows:

[0063] 1. Coupling reaction

[0064] Prepare 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane (m-BrPhANPh2-Cp) by Sonogashira coupling reaction:

[0065] 4-Iodo-1,5-diphenylamino[2.2]paracyclophane (m-INPh2-Cp) (413 mg, 0.824 mmol), 2-bromophenylacetylene (178 mg, 0.989 mmol), copper(I) iodide (11 mg, 7% mmol), and bis(triphenylphosphine)palladium(II) dichloride (28.8 mg, 5% mmol) were added to a sealed tube. Diethylamine (12 mL) was used as the solvent. The tube was purged with nitrogen and the reaction was carried out at room temperature for 12 h under a nitrogen atmosphere. After the reaction was completed, the reaction mixture was quenched with saturated sodium chloride solution and extracted with ethyl acetate. The separated organic layer was dried over anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure. The product was purified by silica gel column chromatography (petroleum ether:dichloromethane = 30:1, R f = 0.60); a yellow solid, 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane (m-BrPhANPh2-Cp) (228 mg, 0.44 mmol, 63% yield), was obtained. Melting point M.p.: 132.5–133.2 °C; 1 1H NMR (400 MHz, CDCl3): δ 7.64 (dd, J = 8.1, 1.0 Hz, 1H), 7.57 (dd, J = 7.7, 1.6 Hz, 1H), 7.35–7.28 (m, 5H), 7.21–7.15 (m, 5H), 7.11 (t, J = 7.3 Hz, 2H), 7.03 (d, J = 7.9 Hz, 1H), 6.94 (d, J = 7.7 Hz, 1H), 6.85 (d, J = 1.7 Hz, 1H), 6.34 (dd, J = 7.9, 1.8 Hz, 1H), 6.23 (dd, J = 7.7, 1.6 Hz, 1H), 5.81 (d, J = 1.6 Hz, 1H), 3.65–3.48 (m, 1H), 3.06–2.66 (m, 7H); HRMS (ESI): 554.1478 [M + H] + , C 36 H 29 BrN found: 554.1477. The starting material 4-iodo-1,5-diphenylamino[2.2]paracyclophane (m-INPh2-Cp) used in this example is an existing compound. The preparation method can be referred to "Study on Boron-Modified [2.2]Paracyclophane Organic Light-Emitting Materials" (Ph.D. thesis of Shandong University, Zhang Mengyuan et al.), P63-65.

[0066] The high-resolution mass spectrum of the prepared 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane (m-BrPhANPh2-Cp) is as shown in Figure 2 Figure, and the 1H NMR spectrum is as shown in Figure 3 Figure.

[0067] 2. Boronation Reaction

[0068] Preparation of 4-[(2-dimesitylboranyl)phenyl]ethynyl-15-diphenylamino[2.2]paracyclophane (m-BPhANPh2-Cp) by boronation reaction:

[0069] Dissolve the previously prepared m-BrPhANPh2-Cp (228 mg, 0.411 mmol) in anhydrous tetrahydrofuran (THF), displace with nitrogen, and under a nitrogen atmosphere, add a n-hexane solution of n-butyllithium (0.33 mL, 2.5 mol / L, 0.82 mmol) dropwise via syringe at -78 °C. After the addition is completed in 10 min, keep the reaction at -78 °C for 1.5 h, then add a solution of dimesitylboron fluoride (275 mg, 1.03 mmol) in anhydrous THF (5 mL) via syringe. After addition, allow the reaction to warm up to room temperature naturally and react at room temperature for 12 h. After the reaction is completed, quench with saturated sodium chloride solution and extract with ethyl acetate. After liquid separation, dry the extract phase with anhydrous sodium sulfate, then filter to remove sodium sulfate, and remove the solvent by rotary evaporation under reduced pressure. Purify by silica gel column chromatography (petroleum ether:dichloromethane = 5:1, R f = 0.45); obtain the yellow solid target molecule, namely 4-[(2-dimesitylboranyl)phenyl]ethynyl-15-diphenylamino[2.2]paracyclophane (m-BPhANPh2-Cp) (235 mg, 0.325 mmol, yield 79%), melting point M.p.: 134.7 - 135.2 °C; 1 1H NMR(400 MHz, CDCl3): δ 7.57 (d, J = 7.6 Hz, 1H), 7.39 (td, J = 8.0, 2.4 Hz, 1H), 7.31 (s, 1H), 7.29–7.25 (m, 5H), 7.14 (d, J = 7.5 Hz, 4H), 7.09 (t, J = 7.3 Hz, 2H), 6.89 (d, J = 7.9 Hz, 1H), 6.82 (s, 4H), 6.58 (d, J = 7.6 Hz, 1H), 6.22 (dd, J = 7.9, 1.6 Hz, 1H), 5.98 (d, J = 1.4 Hz, 1H), 5.91 (d, J = 7.4 Hz, 1H), 5.75 (d, J = 1.5 Hz, 1H), 3.38–3.29 (m, 1H), 2.99–2.58 (m, 7H), 2.32 (s, 6H), 2.05 (s, 12H); HRMS (ESI): 724.4109 [M + H] + , C 54 H 51 BN found: 724.4104.

[0070] The high-resolution mass spectrum of 4-[(2-dimesitylboryl)phenyl]ethynyl-1,5-diphenylamino[2.2]paracyclophane (m-BPhANPh2-Cp) prepared in this example is as Figure 4 shown, and the 1H nuclear magnetic resonance spectrum is as Figure 5 shown.

[0071] Example 2

[0072] Determination of the relevant properties of 4-[(2-dimesitylboryl)phenyl]ethynyl-1,5-diphenylamino[2.2]paracyclophane (m-BPhANPh2-Cp) in the powder / thin film state:

[0073] It was determined that the fluorescence emission wavelength of m-BPhANPh2-Cp (prepared according to Example 1) in the powder state is located at 473 nm, and the fluorescence quantum yield is as high as 0.64. The fluorescence emission wavelength and fluorescence quantum yield of m-BPhANPh2-Cp (prepared according to Example 1) in the thin film state are basically the same as those in its powder state. The fluorescence emission wavelength is 465 nm (as Figure 6 shown), and the fluorescence quantum yield is also as high as 0.64. Since the aggregation-induced quenching phenomenon generally exists in organic small molecules, the m-BPhANPh2-Cp of the present invention has a relatively high fluorescence quantum yield in the solid state among organic small molecules.

[0074] Example 3

[0075] Determination of the solid-state circularly polarized luminescence properties of 4-[(2-dimesitylboryl)phenyl]ethynyl-1,5-diphenylamino[2.2]paracyclophane (m-BPhANPh2-Cp) in the thin film state:

[0076] In view of the fact that the target molecule m-BPhANPh2-Cp (prepared according to Example 1) of the present invention has a relatively high fluorescence quantum yield, the target molecule m-BPhANPh2-Cp was resolved (as Figure 7 shown, Figure 7 the upper figure in the middle is the HPLC chromatogram of racemic m-BPhANPh2-Cp, the middle figure is the HPLC chromatogram of m-BPhANPh2-Cp with the R p configuration, and the lower figure is the HPLC chromatogram of m-BPhANPh2-Cp with the S p configuration), and the circularly polarized luminescence spectrum of the target molecule m-BPhANPh2-Cp in the thin film state was tested (as Figure 8 shown). It can be seen that the m-BPhANPh2-Cp with the Sp configuration in the thin film state has a positive signal peak at 475 nm (the maximum fluorescence emission wavelength), and its luminescence asymmetry factor reaches +5.4×10 -3。In the thin film state, m-BPhANPh2-Cp with the Rp configuration has a negative signal peak at 469 nm (the maximum fluorescence emission wavelength), and its luminescence asymmetry factor reaches -4.3×10 -3 。Therefore, m-BPhANPh2-Cp of the present invention has excellent solid-state circularly polarized luminescence performance.

[0077] Therefore, the planar chiral [2.2] paracyclophane organic small molecule m-BPhANPh2-Cp with high solid-state luminescence performance of the present invention has important value in the field of organic small molecule circularly polarized luminescence materials, and has broad application prospects in the fields of three-dimensional display, optical information storage and processing, biological probes, CPL sensors, etc.

[0078] Unless otherwise specified, the percentages used in the present invention are all mass percentages.

[0079] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A planar-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance, characterized in that, The planar-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance has the following molecular structural formula: ； In the formula, -BMes2 is a dimesitylboron group, and -NPh2 is a diphenylamino group.

2. Preparation method of a planar chiral [2.2] paracyclophane organic small molecule with high solid-state luminescence performance, characterized in that, It includes the following steps: Using 4-iodo-1,5-diphenylamino[2.2]paracyclophane as the starting material, first carrying out a coupling reaction to obtain 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane; then through a borylation reaction, preparing the planar-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance; The method of the coupling reaction is that in a solvent environment, in the presence of copper(I) iodide and bis(triphenylphosphine)palladium(II) dichloride, 4-iodo-1,5-diphenylamino[2.2]paracyclophane reacts with 2-bromophenylethyne to obtain 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane; The method of the borylation reaction is that in a solvent environment, 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane first reacts with n-butyllithium and then reacts with dimesitylboron fluoride to prepare the planar-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance.

3. The preparation method of the planar chiral [2.2] paracyclophane organic small molecule with high solid-state luminescence performance according to claim 2, characterized in that, In the coupling reaction, the molar ratio of 4-iodo-1,5-diphenylamino[2.2]paracyclophane, 2-bromophenylethyne, bis(triphenylphosphine)palladium(II) dichloride, and copper(I) iodide is 1:1 - 1.3:0.05 - 0.1:0.06 - 0.

09.

4. The preparation method of the planar chiral [2.2] paracyclophane organic small molecule with high solid-state luminescence performance according to claim 2, wherein, In the coupling reaction, the reaction time of 4-iodo-1,5-diphenylamino[2.2]paracyclophane and 2-bromophenylethyne is 12 - 18 h.

5. The preparation method of the planar chiral [2.2] paracyclophane organic small molecule with high solid-state luminescence performance according to claim 2, characterized in that, In the borylation reaction, the molar ratio of 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane to n-butyllithium is 1:1.8 - 2.2; The molar ratio of 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane to dimesitylboron fluoride is 1:2 - 3.

6. The preparation method of the planar chiral [2.2] paracyclophane organic small molecule with high solid-state luminescence performance according to claim 2, characterized in that, In the borylation reaction, the reaction time of 4-(2-bromophenylethynyl)-1,5-diphenylamino[2.2]paracyclophane and n-butyllithium is 1.5 - 2 h.

7. The preparation method of the planar chiral [2.2] paracyclophane organic small molecule with high solid-state luminescence performance according to claim 2, characterized in that, In the borylation reaction, the reaction time of contacting with dimesitylboron fluoride is 10 - 15 h.

8. Application of the planar-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance as claimed in claim 1 or the planar-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance prepared by the preparation method as claimed in any one of claims 2 - 7 as a circularly polarized luminescence material.

9. Application of the planar-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance as claimed in claim 1 or the planar-chiral [2.2]paracyclophane organic small molecule with high solid-state luminescence performance prepared by the preparation method as claimed in any one of claims 2 - 7 in the fields of three-dimensional display, optical information storage and processing, and CPL sensors.

Images