A kind of pillar aromatic derivative embedded with diphenylmethylenefluorene and preparation method thereof

Abstract

The present invention provides a columnar aromatic derivative embedded with dibenzhydrylfluorene and a preparation method thereof, which relates to the technical field of organic synthesis, and also relates to a fluorescence control method and application of the columnar aromatic derivative. The columnar aromatic derivatives A and B in the present invention are synthesized by modifying the bridge methylene (meso) position of [15]para-cyclic aromatic hydrocarbons and ethoxy columnar [5] aromatic hydrocarbons, respectively. The embedding of the dibenzhydrylfluorene structure not only does not destroy the skeleton structure of the two macrocyclic rings, but also retains their host-guest properties and enables them to have efficient aggregation-induced luminescence performance. Ethoxy columnar [5] aromatic hydrocarbons have better host-guest properties than [15]para-cyclic aromatic hydrocarbons, and their fluorescence emission intensity can be controlled by complexing with specific guest molecules.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, in particular to a diphenylmethylenefluorene embedded pillar aromatic derivative and a preparation method thereof, and further to a method for regulating the fluorescence intensity of the pillar aromatic derivative and an application thereof. Background Art

[0002] Pillarene, as a new generation of supramolecular macrocyclic host molecules, has many excellent properties compared to the previous four generations of macrocyclic hosts. First, compared with crown ethers and calixarenes, pillararenes have better symmetry and stronger rigidity, which makes them more selective when binding to guest molecules. Secondly, compared with cucurbiturils, pillararenes are easier to functionalize some substituent groups on their benzene ring positions, which enriches the host-guest recognition properties of pillararenes. Finally, compared with cyclodextrins, pillararenes have better solubility in organic solvents. Combining the above advantages of pillararenes, they have broad application value in the fields of ion recognition, fluorescence sensing and artificial transmembrane channels.

[0003] Aggregation-induced emission (AIE) refers to a photophysical phenomenon in which molecular aggregates exhibit stronger emission than single molecules. The emergence of aggregation-induced emission (AIE) materials has greatly promoted the development of supramolecular luminescent materials, because the strong luminescence phenomenon they exhibit in the aggregated state solves the long-standing obstacles brought about by the aggregation fluorescence quenching (ACQ) effect, thereby bringing broad application prospects for AIE-based supramolecular materials in the fields of luminescent materials, sensors, bioimaging, drug delivery and treatment. In addition, compared with traditional fluorescent molecules, the configuration of AIE materials is highly distorted in space, so the study of AIE materials and corresponding supramolecular materials provides a basis for studying the self-assembly of non-planar molecules, greatly expands the building blocks of supramolecular materials, and promotes the development of the frontier of supramolecular chemistry.

[0004] By utilizing the easy-to-modify property of pillararenes, aggregation-induced emission elements (AIEgens) are modified onto pillararene derivatives. This not only gives pillararenes AIE properties and enriches their applications in fluorescent materials, but also allows them to complex with specific guest molecules using the excellent host-guest properties of pillararenes, thereby regulating their fluorescence emission. This has potential application prospects in the field of fluorescence sensing based on pillararenes. Summary of the invention

[0005] In view of the defects in the prior art, the purpose of the present invention is to provide a diphenylmethylenefluorene embedded pillar aromatic derivative and its preparation method and fluorescence regulation.

[0006] The object of the present invention is achieved through the following solutions:

[0007] In a first aspect, the present invention provides a pillar aromatic derivative embedded with dibenzhydrylfluorene, wherein the structural formula of the pillar aromatic derivative is shown in A or B:

[0008]

[0009] In a second aspect, the present invention provides a method for preparing a dibenzhydrylfluorene embedded pillar aromatic derivative A, the preparation method comprising the following steps:

[0010] S1. Synthesis of intermediate A-1: ​​1,4-diethoxybenzene and polyformaldehyde are added to organic solvent I, and reacted under the action of catalyst I. After the reaction, deionized water is added and stirred to obtain intermediate A-1;

[0011] S2. Synthesis of intermediate A-2: Add catalyst II to organic solvent II, and continue to react the intermediate A-1 obtained in step S1 to obtain intermediate A-2;

[0012] S3, synthesis of intermediate A-3: add intermediate A-2 to organic solvent III, adjust pH, introduce sulfuryl fluoride gas, and react to obtain intermediate A-3;

[0013] S4, synthesis of intermediate A-4: adding catalyst III to organic solvent IV, and sequentially adding formic acid and triethylamine to react to obtain intermediate A-4;

[0014] S5. Synthesis of intermediate A-5: Add intermediate A-4 and N-bromosuccinimide to organic solvent V, then add initiator, react under inert gas protection, add silica gel after the reaction is completed and continue stirring to obtain intermediate A-5;

[0015] S6, synthesis of intermediate A-6: adding intermediate A-5 and an oxidant to an organic solvent VI, and reacting to obtain intermediate A-6;

[0016] S7. Synthesis of pillar aromatic derivative A: intermediate A-6 and 9-fluorenone are added to organic solvent VII, and catalyst IV is added to react to obtain the pillar aromatic derivative A embedded with dibenzhydrylfluorene.

[0017] Preferably, in step S1, the reaction time is 1-3 hours, and the stirring time is 1-3 hours. The reaction is carried out at room temperature. The organic solvent I is 1,2-dichloroethane or chloroform; the catalyst I includes one or more of boron trifluoride ether complex and ferric chloride. The molar ratio of catalyst I to 1,4-diethoxybenzene is 1:1-2:1; the molar ratio of paraformaldehyde to 1,4-ethoxybenzene is 1:1-1.5:1.

[0018] Preferably, in step S2, the reaction time is 3-4 days. The reaction is carried out at room temperature, and after the reaction is completed, suction filtration is performed to obtain intermediate A-2. The organic solvent II is chloroform; the catalyst II is boron tribromide, and the molar ratio of catalyst II to intermediate A-1 is 20:1-25:1.

[0019] Preferably, in step S3, the molar ratio of sulfuryl fluoride gas to intermediate A-2 is 20:1-30:1; the reaction time is 10-15 hours. The organic solvent III is acetonitrile or acetone. The pH is adjusted by adding an acid binding agent to make the pH reach 10-11, and the acid binding agent includes solids such as sodium carbonate, potassium carbonate, and cesium carbonate. The reaction is carried out at room temperature, and after the reaction is completed, the filter is sucked and the solvent is dried to obtain intermediate A-3.

[0020] Preferably, in step S4, the reaction time is 14-16 hours; the molar ratio of intermediate A-3, formic acid and triethylamine is 1:50:50-1:60:60. The organic solvent IV is dimethyl sulfoxide; the catalyst III includes palladium acetate and 1,3-bis(diphenylphosphino)propane, the molar ratio of palladium acetate to intermediate A-3 is 0.7:1-1:1, and the molar ratio of 1,3-bis(diphenylphosphino)propane to intermediate A-3 is 1:1-1.2:1. The reaction is carried out at room temperature.

[0021] Preferably, in step S5, the reaction temperature is 70-80°C, and the reaction time is 10-14 hours. The molar ratio of N-bromosuccinimide to intermediate A-4 is 0.7:1-1.5:1. The organic solvent V is carbon tetrachloride; the initiator is azobisisobutyronitrile. The inert gas is preferably nitrogen. The amount of silica gel is 1-2 equivalents of intermediate A-4, and the stirring time is 2-4 hours. After stirring, the solvent is dried to obtain intermediate A-5.

[0022] Preferably, in step S6, the reaction temperature is 70-80°C, the reaction time is 3-4 hours, and the molar ratio of the oxidant to the intermediate A-5 is 2:1-4:1. The oxidant is pyridinium dichromate. The organic solvent VI is dichloromethane.

[0023] Preferably, in step S7, the reaction temperature is 70-80°C, the reaction time is 12-15 hours, and the molar ratio of 9-fluorenone to intermediate A-6 is 5:1-10:1. Catalyst IV is a mixed catalyst of zinc powder and titanium tetrachloride, wherein the molar ratio of zinc powder to intermediate A-6 is 10:1-40:1, and the molar ratio of titanium tetrachloride to intermediate A-6 is 4:1-10:1. Organic solvent VII is tetrahydrofuran.

[0024] The present invention also provides a method for preparing a dibenzylidenefluorene embedded pillar aromatic derivative B, the preparation method comprising the following steps:

[0025] T1. Synthesis of intermediate B-1: Add an initiator to an organic solvent V, and react the intermediate A-1 with N-bromosuccinimide under the protection of an inert gas. After the reaction is completed, add silica gel and continue stirring to obtain intermediate B-1; pillar aromatic hydrocarbon A is the same as that in pillar aromatic hydrocarbon derivative A;

[0026] T2, synthesis of intermediate B-2: adding an oxidant to an organic solvent VI to react the intermediate B-1 in step T1, and obtaining intermediate B-2 after the reaction is completed;

[0027] T3. Synthesis of pillar aromatic derivative B: Add catalyst IV to organic solvent VII to react the intermediate B-2 in step T2 with 2,7-dibromo-9-fluorenone to obtain the pillar aromatic derivative B embedded with dibenzhydrylfluorene.

[0028] Preferably, in step T1, the molar ratio of N-bromosuccinimide to intermediate A-1 is 0.7:1-1.5:1. The reaction time is 10-14 hours, and the reaction temperature is 70-80°C. The inert gas is preferably nitrogen. The stirring time is 2-4 hours, and the solvent is dried after stirring.

[0029] Preferably, in step T1, the synthesis of intermediate A-1 is as follows: 1,4-diethoxybenzene and polyformaldehyde are added to an organic solvent I, reacted under the action of a catalyst I, and after the reaction, deionized water is added and stirred to obtain intermediate A-1. The reaction time is 1-3 hours, and the stirring time is 1-3 hours. The reaction is carried out at room temperature. The organic solvent I is 1,2-dichloroethane or chloroform; the catalyst I includes one or more of a boron trifluoride ether complex and ferric chloride. The molar ratio of catalyst I to 1,4-diethoxybenzene is 1:1-2:1; the molar ratio of polyformaldehyde to 1,4-ethoxybenzene is 1:1-1.5:1.

[0030] Preferably, in step T2, the molar ratio of the oxidant to the intermediate B-1 is 2:1-5:1. The oxidant is pyridinium dichromate; the reaction time is 2-4 hours, and the reaction temperature is set at 70-80°C.

[0031] Preferably, in step T3, the molar ratio of 2,7-dibromo-9-fluorenone to intermediate B-2 is 10:1-20:1. Catalyst IV uses zinc powder and titanium tetrachloride, the molar ratio of zinc powder to intermediate B-2 is 10:1-40:1, and the molar ratio of titanium tetrachloride to intermediate B-2 is 4:1-10:1. The reaction time is 12-16 hours, and the reaction temperature is set to 70-80°C.

[0032] In a third aspect, the present invention provides a method for regulating the fluorescence intensity of a dibenzhydrylfluorene-embedded pillar aromatic derivative B, wherein the fluorescence regulation method includes weakening the fluorescence intensity or enhancing the fluorescence intensity;

[0033] The fluorescence intensity reduction is specifically as follows: adding a guest C containing a pyrazine group to the pillar aromatic hydrocarbon derivative B, and as the content of the guest C increases, the fluorescence emission intensity of the pillar aromatic hydrocarbon derivative B gradually decreases;

[0034] The fluorescence intensity enhancement is specifically as follows: a guest D containing a dinitrile group is added to the pillar aromatic derivative B, and as the content of the guest D increases, the fluorescence emission intensity of the pillar aromatic derivative B gradually increases.

[0035] Preferably, the molecular structures of the guests C and D are as follows:

[0036]

[0037] Preferably, the molar ratio of pillar[5]arene derivative B to guest C is 1:0-1:9.

[0038] Preferably, the molar ratio of pillar[5]arene derivative B to guest D is 1:0-1:500.

[0039] The pillararene derivative B achieves regulation of its fluorescence emission intensity through complexation with specific guest molecules C and D. The fluorescence regulation principle is as follows:

[0040] After the guest C is complexed with the pillararene derivative B, charge transfer occurs between the pyrazine cation group and the electron-rich cavity of the pillararene, which has a certain quenching effect on the fluorescence emission.

[0041] After the guest D is complexed with the pillararene derivative B, a dipole-dipole interaction occurs between the dinitrile group and the pillararene, which restricts the rotation of the pillararene itself, thereby enhancing the fluorescence emission to a certain extent.

[0042] The present invention also provides an application of the pillar aromatic hydrocarbon derivative B in detecting pyrazine cationic group and dinitrile group guest molecules in a solution. The present invention realizes the enhancement and reduction of the fluorescence emission intensity through complexation with specific guest molecules, thereby serving as a fluorescent probe for detecting guest molecules containing pyrazine cationic group and dinitrile group in a solution.

[0043] The columnar [5]arene derivative B embedded with diphenylethylene fluorene is a structure formed by locking the external benzene ring structure of the columnar [5]arene derivative E embedded with tetraphenylethylene. Compared with the columnar arene derivative B, the wavelength of the fluorescence emission peak of the columnar arene derivative E is significantly blue-shifted, the fluorescence color changes from yellow to blue, and the fluorescence emission intensity is significantly enhanced. The yellow fluorescence wavelength of the columnar arene derivative B of the present invention is longer, the energy is weaker, the light emission is relatively softer, the human eye is more sensitive to yellow light, and it is suitable for use as a fluorescent indicator.

[0044] The structure of the pillar[5]arene derivative E is as follows:

[0045]

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] (1) The present invention obtains diphenylmethylenefluorene-embedded pillar aromatic derivatives A and B and obtains their single crystal structures. Both A and B have excellent aggregation-induced emission effects, providing more application prospects for functionalized luminescent supramolecular macrocyclic hosts.

[0048] (2) A diphenylmethylenefluorene group was embedded in the bridge methylene (meso) position of the columnar aromatic hydrocarbon, retaining the original skeletal structure of the columnar aromatic hydrocarbon. The resulting columnar aromatic hydrocarbon derivative B has excellent host-guest properties compared with A. The host-guest complex crystal structure of the columnar aromatic hydrocarbon derivative B and guest D was obtained. In addition, the fluorescence emission intensity can be effectively controlled by adding different guest molecules, enriching the application of columnar aromatic hydrocarbons in fluorescent materials.

[0049] (3) The method of the present invention compares the fluorescence emission properties of pillar aromatic hydrocarbon derivatives embedded with different AIEgens. Through simple structural adjustments, the fluorescence emission of pillar aromatic hydrocarbons is regulated, which provides the possibility for the preparation of more different luminescent supramolecular macrocyclic hosts. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Other features, objects and advantages of the present invention will become more apparent from the detailed description of non-limiting embodiments made with reference to the following drawings:

[0051] Figure 1 is the compound A in Example 1 1 H NMR spectrum;

[0052] Figure 2 is the compound A in Example 1 13 C NMR spectrum;

[0053] Figure 3 is a high-resolution mass spectrum of compound A in Example 1;

[0054] Figure 4 is a single crystal structure diagram of compound A in Example 1;

[0055] Figure 5 is the compound B in Example 2 1 H NMR spectrum;

[0056] Figure 6 is the compound B in Example 2 13 C NMR spectrum;

[0057] Figure 7is a high-resolution mass spectrum of compound B in Example 2;

[0058] Figure 8 is a single crystal structure diagram of compound B in Example 2;

[0059] Fig. 9 is the fluorescence spectrum of compound B after adding different equivalents of compound C in Example 3;

[0060] Fig.10 is the fluorescence spectrum of compound B after adding different equivalents of compound D in Example 3;

[0061] Fig.11 is the host-guest complex in Example 3 Single crystal structure diagram of

[0062] Fig.12 is the compound E in Example 3 1 H NMR spectrum;

[0063] Fig.13 is the compound E in Example 3 13 C NMR spectrum;

[0064] Fig.14 is a high-resolution mass spectrum of compound E in Example 3;

[0065] Fig.15 It is the fluorescence spectrum of compound B and compound E in Example 3. DETAILED DESCRIPTION

[0066] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. The following examples are implemented on the premise of the technical solution of the present invention, provide detailed implementation methods and specific operation processes, and will help those skilled in the art to further understand the present invention. It should be pointed out that the protection scope of the present invention is not limited to the following embodiments, and several adjustments and improvements made under the premise of the concept of the present invention all belong to the protection scope of the present invention.

[0067] Example 1

[0068] The present invention discloses a dibenzhydrylfluorene embedded pillar aromatic derivative A, the structure of which is as follows:

[0069]

[0070] By modifying the meso position of the bridge of

[15] paracyclic aromatic hydrocarbon to form a diphenylmethylenefluorene-embedded pillar aromatic hydrocarbon derivative, the skeleton structure of

[15] paracyclic aromatic hydrocarbon is retained while giving it an aggregation-induced emission effect.

[0071] Among them, a preparation method of a dibenzhydrylfluorene embedded pillar aromatic derivative A comprises the following steps:

[0072] S1. Synthesis of intermediate A-1: ​​Using 1,2-dichloroethane as solvent and boron trifluoride ether complex as catalyst, 1,4-diethoxybenzene, boron trifluoride ether complex and paraformaldehyde were added in a molar ratio of 1:1.2:1.2, and reacted at room temperature for 2 hours. After the reaction, deionized water was added and stirred for 1 hour, and the liquids were separated. The organic phase was dried over anhydrous sodium sulfate and separated by column chromatography to obtain a white solid A-1.

[0073] S2. Synthesis of intermediate A-2: Under nitrogen protection, chloroform was used as solvent, and boron tribromide in an amount 20 times the molar equivalent of intermediate A-1 was added, with boron tribromide as catalyst, and intermediate A-1 was reacted at room temperature for 3 days. After the reaction was completed, water was added to quench the reaction, and the mixture was filtered and dried in vacuo to obtain white solid A-2;

[0074] S3, synthesis of intermediate A-3: under nitrogen protection, acetonitrile is used as solvent, potassium carbonate in an amount of 25 times the molar equivalent of intermediate A-2 is added, sulfuryl fluoride gas is introduced, and the molar ratio of sulfuryl fluoride to intermediate A-2 is 20:1. Intermediate A-2 is reacted at room temperature for 18 hours. After the reaction is completed, the solvent is dried, dichloromethane is added to dissolve the obtained solid, and the solid is filtered and separated by column chromatography to obtain a white solid A-3;

[0075] S4. Synthesis of intermediate A-4: Under nitrogen protection, dimethyl sulfoxide was used as solvent, palladium acetate, 1,3-bis(diphenylphosphino)propane and intermediate A-3 were added in a molar ratio of 0.8:1:1, palladium acetate and 1,3-bis(diphenylphosphino)propane were used as catalysts, and after reacting for 10 minutes, triethylamine and formic acid were added in a molar ratio of 50 times the equivalent of intermediate A-3 in sequence, and intermediate A-3 was reacted at room temperature for 14 hours. After the reaction, the reaction solution was washed with distilled water, and white solid A-4 was obtained by column chromatography.

[0076] S5. Synthesis of intermediate A-5: Under nitrogen protection, with carbon tetrachloride as solvent and azobisisobutyronitrile as initiator, intermediate A-4 and N-bromosuccinimide were added in a molar ratio of 1:1.2, and reacted at 75°C for 12 hours. After the reaction, silica gel with a molar ratio of 2 times that of intermediate A-4 was added and continued to stir. After 2 hours, the solvent was dried by spin drying and separated by column chromatography to obtain a light yellow solid A-5;

[0077] S6. Synthesis of intermediate A-6: Using dichloromethane as solvent, add 3 times the molar equivalent of pyridinium dichromate of intermediate A-5, and use pyridinium dichromate as oxidant, and react intermediate A-5 at 60°C for 3 hours. After the reaction is completed, filter and separate by column chromatography to obtain light yellow solid A-6;

[0078] S7. Synthesis of column [5] aromatic derivative A embedded with diphenylmethylenefluorene: Under nitrogen protection, tetrahydrofuran was used as solvent, 9-fluorenone, zinc powder, titanium tetrachloride and intermediate A-6 were added in a molar ratio of 10:40:10:1, zinc powder and titanium tetrachloride were used as catalysts, and the mixture was stirred for 3 hours at a temperature below 0°C, then the temperature was raised to 75°C and refluxed for 12 hours. After the reaction was completed, saturated sodium bicarbonate solution was added to quench the reaction, and the mixture was filtered and separated to obtain an organic phase. After drying, column chromatography was performed to obtain a yellow solid diphenylmethylenefluorene embedded with column [5] aromatic derivative A.

[0079] More specifically, in step S1, the organic solvent I is 1,2-dichloroethane, and the catalyst I is boron trifluoride ether complex; in step S2, the organic solvent II is chloroform, and the catalyst II is boron tribromide; in step S3, the organic solvent III is acetonitrile; in step S4, the organic solvent IV is dimethyl sulfoxide, and the catalyst III is palladium acetate and 1,3-bis(diphenylphosphino)propane; in step S5, the organic solvent V is carbon tetrachloride, and the initiator is azobisisobutyronitrile; in step S6, the organic solvent VI is dichloromethane, and the oxidant is pyridinium dichromate; in step S7, the organic solvent VII is tetrahydrofuran, and the catalyst IV is zinc powder and titanium tetrachloride.

[0080] The synthetic route of the dibenzhydrylfluorene-embedded pillar[5]arene derivative A is as follows:

[0081]

[0082] The H NMR spectrum of the pillararene derivative A embedded with dibenzhydrylfluorene is shown in Figure 1 As shown, the carbon spectrum is Figure 2 As shown in the high-resolution mass spectrometry Figure 3 The single crystal structure is shown in Figure 4 (a) Top view, (b) front view. 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 7.70 (d, J = 7.4Hz, 4H), 7.11 (s, 8H), 7.02 (s, 8H), 6.99 (s, 4H), 6.80 (d, J = 7.9Hz, 4H), 3.89 (s, 4H), 3.80 (s, 4H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 145.6, 141.3, 140.8, 140.3, 139.6, 139.5, 139.1, 138.7, 133 .0,129.1,129.0,128.8,128.6,128.6,127.5,126.4,124.9,119.2,41.7,41.5.HR-ESI-MS:m / z calcd.[M+Na] +:635.2715,found:635.2746.

[0083] Example 2

[0084] The present invention discloses a dibenzhydrylfluorene embedded pillar aromatic derivative B, the structure of which is as follows:

[0085]

[0086] By modifying the meso position of ethoxylated columnar[5]arene to form a columnar[5]arene derivative embedded with diphenylmethylenefluorene, the skeleton structure of ethoxylated columnar[5]arene is retained while giving it an aggregation-induced emission effect.

[0087] Among them, a preparation method of a dibenzhydrylfluorene embedded pillar aromatic derivative B comprises the following steps:

[0088] T1. Synthesis of intermediate B-1: Under nitrogen protection, with carbon tetrachloride as solvent and azobisisobutyronitrile as initiator, intermediate A-1 and N-bromosuccinimide were added in a molar ratio of 1:1.2, and reacted at 75°C for 12 hours. After the reaction, silica gel with a molar ratio of 2 times the equivalent of intermediate A-4 was added and continued to stir. After 2 hours, the solvent was dried by spin drying and separated by column chromatography to obtain a light yellow solid B-1;

[0089] T2, synthesis of intermediate B-2: using dichloromethane as solvent, adding 3 times the molar equivalent of pyridinium dichromate of intermediate B-1, using pyridinium dichromate as oxidant, allowing intermediate B-1 to react at 75°C for 3 hours, after the reaction is completed, filtering, column chromatography separation to obtain light yellow solid B-2;

[0090] T3. Synthesis of column [5] aromatic derivative A embedded with diphenylmethylenefluorene: Under nitrogen protection, tetrahydrofuran was used as solvent, 2,7-dibromo-9-fluorenone, zinc powder, titanium tetrachloride and intermediate B-2 were added in a molar ratio of 20:40:10:1, zinc powder and titanium tetrachloride were used as catalysts, and the reaction was maintained below 0°C for 3 hours, then the temperature was raised to 75°C and refluxed for 12 hours. After the reaction was completed, saturated sodium bicarbonate solution was added to quench the reaction, and the reaction was filtered and separated to obtain an organic phase. After drying, column chromatography was performed to obtain a yellow solid diphenylmethylenefluorene embedded with column [5] aromatic derivative B.

[0091] More specifically, in step T1, the organic solvent V is carbon tetrachloride, and the initiator is azobisisobutyronitrile; in step T2, the organic solvent VI is dichloromethane, and the oxidant is pyridinium dichromate; in step T3, the organic solvent VII is tetrahydrofuran, and the catalyst IV is zinc powder and titanium tetrachloride.

[0092] The synthetic route of the dibenzhydrylfluorene-embedded pillararene derivative B is as follows:

[0093]

[0094] The H NMR spectrum of the pillararene derivative B embedded with dibenzhydrylfluorene is shown in Figure 5 As shown, the carbon spectrum is Figure 6 As shown in the high-resolution mass spectrometry Figure 7 The single crystal structure is shown in Figure 8 (a) Top view, front view (b) 1 H NMR (400MHz, CDCl3, 298K) δ7.50(d,J=8.2Hz,2H),7.35(d,J=8.0Hz,2H),7.01(s,2H),6.85(s,2H),6.79–6.74 (m,6H),6.67(s,2H),3.86(m,20H),3.64–3.53(m,4H),3.46–3.33(m,4H),1.30(m,24H),0.67(t,J=6.9Hz,6H); 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 150.3, 150.3, 149.9, 140.5, 137.9, 132.4, 130.0, 128.9, 128.7, 128.3, 128.2, 128.0, 120.7,120.2,116.0,115.7,115.1,115.1,64.7,63.9,63.8,30.3,29.7,29.3,15.6,15.2,15.1,15.0.MALDI-TOF-MS:m / z calcd.[M+Na] + :1209.3727,found:1209.3717.

[0095] Example 3

[0096] The fluorescence emission of the dibenzhydrylfluorene embedded pillar arene derivative B mentioned in the present invention is regulated as follows:

[0097] 1. Study on the attenuation effect of guest C containing pyrazine group on the fluorescence emission of column[5]arene derivative B

[0098] The column [5] was prepared with chloroform, aromatic derivative B (0.02 mM), guest C containing pyrazine group (2 mM), and mixed solutions with molar ratios of host B to guest C of 1:0, 1:1, 1:3, 1:5, 1:7, and 1:9 were prepared, and the changes in fluorescence emission intensity in the mixed solutions were detected. The results are shown in Fig. 9As shown, the guest C containing pyrazine groups has a certain quenching effect on the fluorescence emission of the host B, and with the increase of the guest C content, the fluorescence emission intensity of the mixed solution gradually decreases. When the guest C is added to 7 times the equivalent of the host B, the fluorescence emission intensity remains almost unchanged.

[0099] 2. Study on the enhancement of fluorescence emission of column[5]arene derivative B by guest D containing dinitrile group

[0100] The column [5] was prepared with chloroform, aromatic derivative B (0.1 mM), guest D containing dinitrile group (0.1 M), and mixed solutions with molar ratios of host B to guest D of 1:0, 1:10, 1:50, 1:100, 1:200, 1:300, 1:400, and 1:500 were prepared, and the change of fluorescence emission intensity in the mixed solution was detected. The results are shown in Figure 2. Fig.10 As shown, the guest D containing a dinitrile group has a significant enhancing effect on the fluorescence emission of the host B, and with the increase of the content of guest C, the fluorescence emission intensity of the mixed solution gradually increases. When the guest D is added to 400 times the equivalent of the host B, the fluorescence emission intensity remains almost unchanged.

[0101] At the same time, in order to verify the host-guest interaction between subject B and object D, the host-guest complex was cultured and obtained. The single crystal structure is as follows Fig.11 As shown in (a) top view and (b) front view, guest D completely enters the cavity of host B, the binding ratio between the two is 1:1, and they are stabilized by multiple non-covalent bonds.

[0102] Therefore, if Fig. 9 and Fig.10 As shown, the pillar aromatic derivative B realizes the enhancement and attenuation of the fluorescence emission intensity by complexing with specific guest molecules, and thus can be used as a fluorescent probe for detecting guest molecules containing pyrazine cationic groups and dinitrile groups in the solution.

[0103] 3. Comparison of fluorescence emission properties of tetraphenylethylene embedded pillar arene derivative E and diphenylmethylenefluorene embedded pillar arene derivative B

[0104] Comparing the structures of pillar aromatic derivatives B and E, the main difference between the two is that, relative to E, the benzene ring of the AIEgen on the non-embedded pillar aromatic side of pillar aromatic derivative B is completely locked, thereby restricting the rotation of AIEgen, resulting in significant differences in the fluorescence emission properties of the two.

[0105] Among them, the synthesis route of the tetraphenylethylene embedded pillar aromatic derivative E is as follows:

[0106]

[0107] Under nitrogen protection, tetrahydrofuran was used as solvent, 4,4'-dibromobenzophenone, zinc powder, titanium tetrachloride and intermediate B-2 were added in a molar ratio of 20:40:10:1, zinc powder and titanium tetrachloride were used as catalysts, the reaction was maintained below 0°C for 3 hours, and then the temperature was raised to 75°C and refluxed for 12 hours. After the reaction was completed, a saturated sodium bicarbonate solution was added to quench the reaction, the reaction was filtered, and the organic phase was separated. After drying, column chromatography was performed to obtain a tetraphenylethylene embedded pillar aromatic derivative E as a white solid.

[0108] The H NMR spectrum of the tetraphenylethylene embedded pillararene derivative E is shown in Fig.12 As shown, the carbon spectrum is Fig.13 As shown in the high-resolution mass spectrometry Fig.14 shown. 1 H NMR (400MHz, CDCl3, 298K) δ7.20(d,J=7.8Hz,4H),6.92(d,J=8.0Hz,4H),6.76(d,J=11.6Hz,4H),6.59(s,2H),6.32(s,2H),6.19(s,2H),3. 91–3.70(m,20H),3.60(d,J=6.1Hz,4H),3.12(s,4H),1.37(t,J=6.7Hz,6H),1.27(t,J=13.7Hz,14H),1.13(t,J=6.7Hz,6H),0.32(brs,4H); 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 150.1, 150.1, 15.96, 150.0, 149.3, 142.2, 138.7, 132.5, 130.8, 130.6, 130.3, 129.1, 128.8, 128.5,120.3,117.4,115.4,115.3,115.2,115.1,64.1,64.0,63.9,29.9,29.7,29.0,15.3,15.1,15.0,14.7.MALDI-TOF-MS:m / z calcd.[M+Na] + :1211.3883,found:1211.3883.

[0109] The fluorescence emission spectra of pillar aromatic derivatives B (0.1 mM) and E (0.1 mM) in chloroform solution are shown in Figure 2. Fig.15 As shown, the fluorescence emission intensity of E is much stronger than that of B, and the fluorescence emission peak undergoes an obvious blue shift, and the fluorescence color changes from yellow to blue.

[0110] The columnar aromatic diffractor embedded with diphenylmethylenefluorene in the present invention is formed by connecting columnar aromatics at the bridging methylene position (i.e., meso position) with 9-fluorene through a carbon-carbon double bond. It successfully solves the problem that columnar aromatics themselves have no fluorescent chromophores, endows columnar aromatics with aggregation-induced emission effect, and at the same time retains the original skeleton structure of columnar aromatics, so that its fluorescence emission intensity can be regulated by complexing with guest molecules. The columnar [5] aromatic diffractor B in the present invention can be complexed with guest molecule C to weaken its fluorescence emission intensity, and can also be complexed with guest molecule D to enhance its fluorescence emission intensity, and its fluorescence emission properties are significantly different from those of the columnar aromatic diffractor E embedded with tetraphenylethylene. The compound molecule has the advantages of stable structure, simple synthesis, and low raw material price, and has potential application prospects in the fields of fluorescent probes based on columnar aromatics.

[0111] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various changes or modifications within the scope of the claims, which does not affect the essence of the present invention. In the absence of conflict, the embodiments of the present application and the features in the embodiments can be combined with each other arbitrarily.

Claims

1. A pillararene derivative embedded with dibenzhydrylfluorene, characterized in that: It is a pillar aromatic derivative A or a pillar aromatic derivative B. The structural formula of the pillar aromatic derivative A is shown in the following formula A, and the structural formula of the pillar aromatic derivative B is shown in the following formula B: 。 2. A method for preparing a pillar aromatic derivative as claimed in claim 1, characterized in that: The preparation method of the pillararene derivative A comprises the following steps: S1. Synthesis of intermediate A-1: ​​1,4-diethoxybenzene and polyformaldehyde are added to organic solvent I, and reacted under the action of catalyst I. After the reaction, deionized water is added and stirred to obtain intermediate A-1; S2. Synthesis of intermediate A-2: Add catalyst II to organic solvent II, and continue to react the intermediate A-1 obtained in step S1 to obtain intermediate A-2; S3, synthesis of intermediate A-3: add intermediate A-2 to organic solvent III, adjust pH, introduce sulfuryl fluoride gas, and react to obtain intermediate A-3; S4, synthesis of intermediate A-4: adding catalyst III to organic solvent IV, and sequentially adding formic acid and triethylamine to react to obtain intermediate A-4; S5. Synthesis of intermediate A-5: Add intermediate A-4 and N-bromosuccinimide to organic solvent V, then add initiator, react under inert gas protection, add silica gel after the reaction is completed and continue stirring to obtain intermediate A-5; S6, synthesis of intermediate A-6: adding intermediate A-5 and an oxidant to an organic solvent VI, and reacting to obtain intermediate A-6; S7, synthesis of pillar aromatic derivative A: adding intermediate A-6 and 9-fluorenone to organic solvent VII, adding catalyst IV, and reacting to obtain the pillar aromatic derivative A embedded with dibenzhydrylfluorene; The structural formulas of intermediates A-1 to A-6 are shown below: 、 、 、 、 、 。 3. The method for preparing a pillararene derivative according to claim 2, characterized in that: In step S5, the reaction temperature is 70-80° C., the reaction time is 10-14 hours, and the molar ratio of N-bromosuccinimide to intermediate A-4 is 0.7:1-1.5:

1.

4. The method for preparing a pillararene derivative according to claim 2, characterized in that: In step S7, the reaction temperature is 70-80° C., and the reaction time is 12-15 hours; the molar ratio of the 9-fluorenone to the intermediate A-6 is 5:1-10:

1.

5. A method for preparing a pillar aromatic derivative as claimed in claim 1, characterized in that: The preparation method of the pillararene derivative B comprises the following steps: T1. Synthesis of intermediate B-1: adding an initiator to an organic solvent V, allowing intermediate A-1 to react with N-bromosuccinimide under the protection of an inert gas, adding silica gel after the reaction is completed and continuing to stir to obtain intermediate B-1; wherein intermediate A-1 is obtained by adding 1,4-diethoxybenzene and polyformaldehyde to an organic solvent I, reacting under the action of a catalyst I, and adding deionized water after the reaction is completed and stirring; T2, synthesis of intermediate B-2: adding an oxidant to an organic solvent VI to react the intermediate B-1 in step T1, and obtaining intermediate B-2 after the reaction is completed; T3, synthesis of pillar aromatic derivative B: adding catalyst IV to organic solvent VII, allowing the intermediate B-2 in step T2 to react with 2,7-dibromo-9-fluorenone to obtain the pillar aromatic derivative B embedded with dibenzhydrylfluorene; The structural formulas of intermediates B-1 and B-2 are shown below: 、 。 6. The method for preparing a pillararene derivative according to claim 5, characterized in that: In step T1, the molar ratio of N-bromosuccinimide to intermediate A-1 is 0.7:1-1.5:1; the reaction time is 10-14 hours, and the reaction temperature is 70-80°C.

7. The method for preparing a pillararene derivative according to claim 5, characterized in that: In step T2, the molar ratio of the oxidant to the intermediate B-1 is 2:1-5:1; the reaction time is 2-4 hours, and the reaction temperature is 70-80°C.

8. The method for preparing a pillararene derivative according to claim 5, characterized in that: In step T3, the molar ratio of 2,7-dibromo-9-fluorenone to intermediate B-2 is 10:1-20:1; the reaction time is 12-16 hours, and the reaction temperature is 70-80°C.

9. A method for controlling the fluorescence intensity of a pillararene derivative as claimed in claim 1, characterized in that: Fluorescence regulation methods include reducing fluorescence intensity or increasing fluorescence intensity; The fluorescence intensity reduction is specifically as follows: adding a guest C containing a pyrazine cationic group to the pillar aromatic hydrocarbon derivative B, and as the content of the guest C increases, the fluorescence emission intensity of the pillar aromatic hydrocarbon derivative B gradually decreases; The fluorescence intensity enhancement is specifically as follows: a guest D containing a dinitrile group is added to the pillar aromatic derivative B, and as the content of the guest D increases, the fluorescence emission intensity of the pillar aromatic derivative B gradually increases. 10 . Use of the pillararene derivative as claimed in claim 1 in detecting pyrazine cationic group and dinitrile group guest molecules in a solution, wherein the pillararene derivative is pillararene derivative B.

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