Peripheral trifluoromethyl functionalized polybenzyl ether type dendrimer gelator as well as preparation method and application thereof

Abstract

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Description

Technical Field

[0001] The invention relates to the technical field of supramolecular chemistry, and in particular to a type of peripheral trifluoromethyl-functionalized polybenzyl ether dendrimer gel factor, and a functional supramolecular organic gel with aggregation-induced luminescence enhancement performance obtained by further functionalizing the gel factor. Background Art

[0002] Different from traditional covalently bonded polymer gels, supramolecular gels are formed by self-assembling low molecular weight gelling agent molecules into a three-dimensional network with various nanostructures through non-covalent interactions, thereby immobilizing the solvent. Due to the unique multi-level self-assembly structure and structural diversity, supramolecular gels have gradually developed into a class of intelligent / functional soft matter materials with broad application prospects. The structures and types of small molecules that can form supramolecular gels range from the simplest alkanes to sugars, oligopeptides and ureas, nucleotides, steroid compounds, metal complexes, and complex dendrimers. At present, the development of new supramolecular gel factors, the expansion of the application field of supramolecular gels, and the elucidation of their gelation mechanism are still the difficulties and hotspots in the field of supramolecular gels.

[0003] Dendrimers are a class of monodisperse macromolecules with regular and exquisite three-dimensional structures. Due to their unique characteristics such as molecular volume, shape and function that can be precisely designed and controlled at the molecular level, they have become one of the ideal molecules for constructing nanoscale soft matter materials. As a special type of supramolecular gel, dendrimer gels have the dual advantages of polymer gels and small molecule gels. At present, some dendrimer gel systems have been constructed using typical hydrogen bonds and non-covalent weak interactions such as van der Waals forces provided by typical gelling units such as amide groups and long-chain alkyl groups. However, compared with small molecule gels, there are still few reports on dendrimer gels. Therefore, it is of great significance to develop and research a new type of dendrimer gel factor with excellent gelling properties.

[0004] As an important fluorine-containing organic functional group, trifluoromethyl (CF3) has a strong electron-withdrawing inductive effect and a stable carbon-fluorine bond. Its introduction into organic molecules can significantly change the physical and chemical properties (such as acidity, dipole moment, solubility, lipophilicity, conformation, pKa and membrane permeability, etc.), metabolic stability and bioavailability of the molecules. At present, organic compounds containing trifluoromethyl are widely used in functional materials, agricultural chemicals, pharmaceuticals and other industries, and have attracted great interest from researchers in recent years. In addition, the strong electron-withdrawing trifluoromethyl group is conducive to promoting the π-π interaction between aromatic rings, and the strong electronegative fluorine atoms are conducive to the formation of multiple F...H weak hydrogen bond interactions. Based on this, it is of great significance to modify the trifluoromethyl functional group to the periphery of polybenzyl ether dendrimers and use the multiple supramolecular interactions of trifluoromethyl and the multi-bond effect of dendrimers to construct a new type of gel system with excellent gelling properties and special functions. Summary of the invention

[0005] The purpose of the present invention is to provide a new type of dendrimer gel factor with excellent gelling properties, simple and efficient synthesis and easy post-functionalization, which can form stable supramolecular organogels in a variety of organic solvents or mixed solvents, and can be easily post-functionalized to prepare functional organogel systems.

[0006] In order to achieve the above objectives, in a first aspect, the present invention provides a type of peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gel factor, whose chemical structure is any one of the following I, II, III and IV:

[0007]

[0008] in,

[0009] In formula (I) and (IV), X is independently selected from COOC n H 2n+1 , COOH, CONHNH2, CONHCH2CH2Br, CH2OH, CH2Br or CH2CN, where n is an integer greater than or equal to 1.

[0010] Preferably, X is each independently selected from COOCH3, COOH, CONHNH2, CH2OH, CH2Br or CH2CN;

[0011] In formula (II) and (III), R is independently selected from 1-pyrenyl, 9-anthryl, 9-phenanthrenyl, 3-perylenyl, 1-naphthyl, 2-naphthyl or 2-benzothiazole;

[0012] Preferably, each R is independently selected from 1-pyrenyl or 9-anthryl.

[0013] In a second aspect, the present invention provides a method for preparing a peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gel factor having a structure shown in formula (I)-(IV), comprising the following steps:

[0014] Step (1):

[0015]

[0016] Step (2):

[0017]

[0018] Step (3):

[0019]

[0020] Step (4):

[0021]

[0022] Step (5):

[0023]

[0024] Step (6):

[0025]

[0026] Step (7):

[0027]

[0028] Step (8):

[0029]

[0030] Step (9):

[0031]

[0032] In the technical scheme of the present invention, the reaction of step (1) is to etherify 3,5-bis(trifluoromethyl)benzyl bromide with 3,4,5-trihydroxybenzoic acid methyl ester by nucleophilic substitution reaction, the reaction reagent used is selected from potassium carbonate and cesium carbonate, preferably potassium carbonate; the solvent is selected from acetone, acetonitrile and DMF, preferably DMF. The molar ratio of 3,4,5-trihydroxybenzoic acid methyl ester, 3,5-bis(trifluoromethyl)benzyl bromide and potassium carbonate is 1:3-3.5:4.5-5, preferably 1:3.1:4.5.

[0033] In the technical solution of the present invention, the reaction of step (2) is a hydrolysis reaction of the dendrimer G-1 in the presence of an inorganic base and a solvent, wherein the solvent is selected from one or any combination of tetrahydrofuran, methanol and water, preferably a mixed solvent of tetrahydrofuran and water. The inorganic base is selected from one of potassium hydroxide, sodium hydroxide and lithium hydroxide, preferably potassium hydroxide. The molar ratio of the dendrimer methyl ester to potassium hydroxide is 1:5 to 10, preferably 1:5.

[0034] In the technical solution of the present invention, the reaction of step (3) is a reduction reaction of the dendrimer G-1 in the presence of a reducing agent and a solvent, wherein the solvent is selected from one of tetrahydrofuran and diethyl ether, preferably tetrahydrofuran. The reducing agent is selected from one of lithium aluminum hydride and sodium borohydride, preferably lithium aluminum hydride. The molar ratio of the dendrimer G-1 to lithium aluminum hydride is 1:1.2 to 1.5, preferably 1:1.2.

[0035] In the technical solution of the present invention, the reaction of step (4) is a bromination reaction of the dendrimer G-3 in the presence of a brominating agent PBr3 and a solvent, wherein the solvent is selected from one of dichloromethane and tetrahydrofuran, preferably dichloromethane. The molar ratio of the dendrimer G-3 to PBr3 is 1:1 to 2, preferably 1:1.5.

[0036] In the technical solution of the present invention, the reaction of step (5) is a nucleophilic substitution reaction of the dendrimer G-4 with trimethylsilyl cyanide (TMSCN) in the presence of a base, the base used is selected from potassium carbonate and cesium carbonate, preferably potassium carbonate; the solvent is selected from acetone, acetonitrile and DMF, preferably acetonitrile. The molar ratio of the dendrimer G-4, TMSCN and potassium carbonate is 1:1.5-2:1.5-2, preferably 1:2:2

[0037] In the technical solution of the present invention, the reaction of step (6) is a hydrazide reaction of the dendrimer G-1 in the presence of hydrazine hydrate, and the solvent is selected from one of tetrahydrofuran and ethanol or a mixed solvent thereof, preferably a mixed solvent of tetrahydrofuran and ethanol (1:1, v / v). The molar ratio of the dendrimer methyl ester to the hydrazine hydrate is 1:1 to 3, preferably 1:2.

[0038] In the technical solution of the present invention, the reaction of step (7) is an etherification reaction of the dendrimer G-4 and methyl 3,5-dihydroxybenzoate in the presence of a base, the base used is selected from sodium hydride, potassium carbonate and cesium carbonate, preferably potassium carbonate; the solvent is selected from acetone, acetonitrile and DMF, preferably DMF. The molar ratio of methyl 3,5-dihydroxybenzoate, dendrimer G-4 and potassium carbonate is 1:2-2.5:2-4, preferably 1:2.1:3.0.

[0039] In the technical solution of the present invention, the reaction of step (8) is a Knoevenagel condensation reaction of the dendrimer G-5 and 2-pyrene aldehyde in the presence of a base, the base used is selected from triethylamine, potassium carbonate, cesium carbonate and potassium tert-butoxide, preferably potassium tert-butoxide; the solvent is selected from ultra-dry methanol, ethanol and tert-butanol, preferably ultra-dry ethanol. The molar ratio of the dendrimer G-5, 2-pyrene aldehyde and potassium tert-butoxide is 1:1-2:1-3, preferably 1:1:2.

[0040] In the technical solution of the present invention, the reaction of step (9) is an imidization reaction carried out in the presence of an acetic acid catalyst, and the solvent is selected from one of tetrahydrofuran and ethanol or a mixed solvent thereof, preferably a mixed solvent of tetrahydrofuran and ethanol (2:1, v / v). The molar ratio of the dendrimer G-6 and 9-anthracene carboxaldehyde is 1:1 to 1.5, preferably 1:1.

[0041] The preparation method of the peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gelator provided by the present invention has mild reaction conditions, simple and easy operation for post-treatment of crude product, and high reaction yield. In addition, this type of gelator can form a stable supramolecular organogel in a variety of organic solvents or mixed solvents, with a wide range of gelling solvents and a low gelling concentration. It is worth mentioning that this type of gelator contains a variety of reactive functional groups, which facilitates the convenient and quick introduction of functional groups to prepare functional supramolecular soft matter materials.

[0042] In a third aspect, the present invention provides an organic gel material comprising a polybenzyl ether dendrimer gel factor having a structure as shown in Formula I, II, III and IV.

[0043] In a fourth aspect, the present invention provides a method for preparing an organic gel material of the polybenzyl ether dendrimer gel factor comprising the structures shown in formulas I, II, III and IV, wherein the peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gel factor is heated to 100°C in a solvent to dissolve, cooled and allowed to stand, and the gel material is obtained by judging by the bottle inversion method. The solvent includes a single organic gelling solvent and a mixed solvent, wherein the single organic gelling solvent is any one of 1,2-dichloroethane, carbon tetrachloride, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, benzyl alcohol, n-butanol, n-pentanol, n-hexanol, n-octanol, 1-decyl alcohol, acetonitrile and nitromethane, and the mixed solvent is any one of a mixed solution of anisole and n-hexane, and a mixed solution of pyridine and water. The minimum gelling concentration of the dendrimer gel factor is 3.2 mg / mL.

[0044] The polybenzyl ether dendrimer gel factor based on peripheral trifluoromethyl functionalization provided by the present invention is mainly used as a gelling (assembly) unit to prepare a functional supramolecular gel or supramolecular self-assembly system, such as a functional gel system with enhanced aggregation-induced emission prepared in an exemplary embodiment of the present invention. The compounds G-8 and G-9 synthesized by the present invention have the characteristics of aggregation-induced emission, wherein the luminescence efficiency of G-8 in the aggregated state is increased by 14.3 times compared with that in the dissolved state, and the luminescence efficiency of G-9 in the aggregated state is increased by 8.5 times compared with that in the dissolved state.

[0045] The beneficial effects of the present invention are:

[0046] 1. The present invention provides a dendrimer gel factor with a new structure, excellent gelling performance, simple and efficient synthesis, and easy post-functionalization. Through the synergistic effect of multiple π-π interactions between peripheral aromatic rings and F...H weak hydrogen bonds, it can form a stable supramolecular organogel or supramolecular self-assembly system in a variety of organic solvents or mixed solvents, and its minimum gelling concentration CGC is 3.2 mg / mL;

[0047] 2. The core of the gel factor has multiple reactive functional groups and is easy to be functionalized. For example, the functional gel system prepared by the compounds G-8 and G-9 synthesized by the present invention has the characteristics of aggregation-induced luminescence, wherein the luminescence efficiency of G-8 in the aggregated state is 14.3 times higher than that in the dissolved state, and the luminescence efficiency of G-9 in the aggregated state is 8.5 times higher than that in the dissolved state. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 The fluorescence spectrum (a) and fluorescence intensity variation trend diagram (b) of the compound G-8 prepared by the present invention in a mixed solution of tetrahydrofuran and water with a water volume content of 0-90%;

[0049] Figure 2The graphs are a fluorescence spectrum (a) and a fluorescence intensity variation trend graph (b) of the compound G-9 prepared by the present invention in a mixed solution of tetrahydrofuran and water with a water volume content of 0-95%. DETAILED DESCRIPTION

[0050] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In order to better illustrate the present invention, further examples are given below by way of embodiments.

[0051] Example 1

[0052]

[0053] In a 250mL double-necked bottle equipped with a stirring magnet, methyl 3,4,5-trihydroxybenzoate (1.84g, 10mmol), 3,5-bis(trifluoromethyl)benzyl bromide (9.52g, 31mmol), K2CO3 (6.21g, 45mmol) and ultra-dry DMF (50mL) were added in sequence. The reaction system was reacted in a metal bath at 80°C under nitrogen protection for 12h, and the reaction progress was tracked by TLC during this period. After the reaction was completed, 200mL of water was added to the reaction system to precipitate the product, which was filtered and washed with a large amount of water. The crude product was dissolved in 30mL of THF and then added dropwise to 200mL of rapidly stirred methanol solvent. During this period, a large amount of solid precipitates were precipitated, filtered, washed with methanol several times, and vacuum dried to obtain white solid G-1 with a yield of 96%. 1 H NMR (400MHz, CDCl3, δ): 3.93 (s, COOCH3, 3H), 5.21 (s, ArCH2O, 2H), 5.26 (s, ArCH2O, 4H), 7.46(s,ArH,2H),7.77(s,ArH,1H),7.81(s,ArH,2H),7.86(s,ArH,2H),7.88(s,ArH,4H). 13 C NMR (100MHz, CDCl3, δ): 165.9, 151.9, 141.5, 139.5, 138.7, 132.1 (q, J = 33.6Hz), 131.7 (q, J = 33.6Hz), 127.3, 127. 3,126.4,123.1(q,J=272.7Hz),122.3(quint,J=3.6Hz),122.0(quint,J=3.6Hz),121.7,109.4,73.6,69.9,52.5.

[0054] Example 2

[0055]

[0056] In a 100mL single-mouth bottle equipped with a stirring magnet, dendrimer G-1 (1.73g, 2.0mmol), 10MKOH aq. (1.0mL, 10.0mmol) and THF-H2O (3:1, v / v, 60mL) were added in sequence, and the reaction system was heated under reflux overnight under nitrogen protection, and TLC was used to track the reaction progress. After the reaction was completed, 2M hydrochloric acid solution was added for acidification three times in a row (pH test paper was close to 1-2). At this time, some precipitation appeared in the solution, and most of the tetrahydrofuran was removed in vacuo, filtered, and the solid was washed three times with distilled water. After vacuum drying, a white powder solid G-2 was obtained with a yield of 98%. 1 H NMR(400MHz,acetone-d6,δ):5.46(s,ArCH2O,2H),5.52(s,ArCH2O,4H),7.60(s, ArH,2H),7.93(s,ArH,1H),8.02(s,ArH,2H),8.05(s,ArH,2H),8.21(s,ArH,4H). 13 C NMR (100MHz, acetone-d6, δ): 166.8, 153.0, 142.4, 142.1, 141.4, 132.2 (q, J = 33.3Hz), 132.0 ( q, J = 33.2Hz), 128.9 ( d, J = 3.3Hz), 128.5 (d, J=4.5Hz), 127.6, 124.4 (q, J=272.2Hz), 124.3 (q, J=272.2Hz), 122.6 (quint, J=3.7Hz), 122.3 (quint, J=3.7Hz), 110.2, 74.0, 70.3.

[0057] Example 3

[0058]

[0059] In a 250mL single-mouth bottle equipped with a stirring magnet, G-1 (1.73g, 2.0mmol) and 100mL ultra-dry tetrahydrofuran THF were added in sequence, and LiAlH4 (0.09g, 2.4mmol) was slowly added under ice bath conditions. After the addition, the ice bath was removed, and a reflux condenser was installed. The mixture was heated to reflux for 1h in a metal bath at 100°C, and the reaction was monitored by TLC plates during the reaction. After the reaction was completed, about 0.1mL H2O, 0.2mL 15% NaOH solution and 0.3mL H2O were added in sequence under ice bath conditions. A white solid appeared in the solution, which was filtered and washed three times with tetrahydrofuran (3x 50mL). The filtrate was added with anhydrous sodium sulfate and dried for 1h. After filtering, the organic solvent was removed under reduced pressure to obtain a white solid G-3 with a yield of 95%. 1 H NMR(400MHz,CDCl3,δ):4.67(s,ArCH2OH,2H),5.15(s,ArCH2O,2H),5.22(s,ArCH2O,4H), 6.76(s,ArH,2H),7.76(s,ArH,1H),7.82(s,ArH,2H),7.85(s,ArH,2H),7.87(s,ArH,4H). 13 C NMR (100MHz, CDCl3, δ): 152.3, 139.9, 139.1, 137.9, 137.0, 132.2 (q, J = 33.6Hz), 131.6 (q, J = 33.5Hz), 127.4 (d, J = 3.0Hz), 1 27.2 (d, J = 2.9Hz), 123.1 (q, J = 272.6Hz), 122.2 (quint, J = 3.8Hz), 121.8 (quint, J = 3.7Hz), 121.8, 106.7, 73.6, 69.9, 64.9.

[0060] Example 4

[0061]

[0062] In a 250mL single-mouth bottle equipped with a stirring magnet, G-3 (1.67g, 2.0mmol) and ultra-dry DCM (50mL) were added, and PBr3 (0.3mL, 3.0mmol) was slowly added with a 1mL glass syringe under ice bath conditions. The ice bath was removed after 10min. Under nitrogen protection, the reaction system was reacted in a metal bath at 40°C for 2 hours. TLC monitored the reaction process. After the reaction was complete, 10mL of NaHCO3 saturated aqueous solution was slowly added under ice bath conditions to quench the reaction. Then 100mL of DCM was added to extract three times, the organic phases were combined, and anhydrous sodium sulfate was added to dry. Filter and remove the solvent under reduced pressure to obtain a crude product. The obtained crude product was purified by rapid silica gel column chromatography (eluent: petroleum ether) to obtain a white powder solid G-4 with a yield of 92%. 1 H NMR(400MHz,CDCl3,δ):4.44(s,ArCH2Br,2H),5.14(s,ArCH2O,2H),5.22(s,ArC H2O,4H),6.78(s,ArH,2H),7.76(s,ArH,1H),7.80(s,ArH,2H),7.86(s,ArH,6H). 13 C NMR (100MHz, CDCl3, δ): 152.2, 139.7, 138.8, 137.9, 134.7, 132.1 (q, J = 33.5Hz), 131.7 (q, J = 33.4Hz), 127.4 (d, J = 3.4Hz ), 127.2 (d, J = 2.8Hz), 123.1 (q, J = 272.2Hz), 122.2 (quint, J = 3.7Hz), 121.9 (quint, J = 3.7Hz), 109.2, 73.7, 70.0, 33.1.

[0063] Example 5

[0064]

[0065] In a 250mL single-mouth bottle equipped with a stirring magnet, dendrimer G-4 (2.188g, 2.438mmol), TMSCN (0.484g, 4.876mmol), K2CO3 (0.673g, 4.876mmol) and acetonitrile (50mL) were added in sequence. The reaction system was reacted in a metal bath at 80°C overnight under nitrogen protection, and TLC was used to track the reaction progress. After the reaction was completed, the reaction solvent was removed. Then 200mL of dichloromethane and 50mL of water were added to extract the product. The aqueous phase was extracted twice with dichloromethane, the organic phases were combined, and 50mL of saturated brine was added to wash once. The organic phase was dried with anhydrous sodium sulfate, filtered, and the solvent was spin-dried to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain a white solid G-5 with a yield of 90%.1 H NMR(400MHz,CDCl3,δ):3.74(s,ArCH2CN,2H),5.15(s,ArCH2O,2H),5.22(s,ArC H2O,4H),6.71(s,ArH,2H),7.77(s,ArH,1H),7.80(s,ArH,2H),7.87(s,ArH,6H). 13 C NMR (100MHz, CDCl3, δ): 152.6, 139.6, 138.7, 137.6, 132.2 (q, J = 33.6Hz), 131.7 (q, J = 33.4Hz), 127.4, 127.4 (d, J = 3.1Hz), 127. 2(d,J=3.8Hz),126.7,123.1(q,J=269.6Hz),122.3(quint,J=3.6Hz),121.9(quint,J=3.4Hz),117.3,108.1,73.7,70.0,23.8.

[0066] Example 6

[0067]

[0068] In a 250mL single-mouth bottle equipped with a stirring magnet, G-1 (1.73g, 2.0mmol), hydrazine hydrate (0.2mL, 4.0mmol) and MeOH-THF (v / v=1:1, 30mL) were added. The reaction system was heated to reflux in a metal bath at 85℃ under nitrogen protection for 12h, and the reaction progress was monitored by TLC during this period. After the reaction was completed, all solvents were removed under reduced pressure to obtain a crude product. The crude product was precipitated with methanol twice, filtered, and vacuum dried to obtain a white powder solid G-6 with a yield of 95%. 1 H NMR(400MHz,DMSO-d6,δ):4.67(bs,ArCONHNH2,2H),5.25(s,ArCH2O,2H),5.40(s,ArCH2O,4H), 7.47(s,ArH,2H),7.95(s,ArH,3H),8.05(s,ArH,2H),8.16(s,ArH,4H),9.84(s,ArCONHNH2,1H). 13CNMR(100MHz,DMSO-d6,δ):164.9,151.6,141.0,140.2,139.2,130.4(q,J=32.9Hz),130.2(q,J=32.9Hz),129.3,128.2(d,J=2.2Hz), 127.4 (d, J = 2.9Hz), 123.2 (q, J = 272.7Hz), 123.1 (q, J = 272.6Hz), 121.6 (quint, J = 3.7Hz), 121.3 (quint, J = 3.7Hz), 106.8, 72.6, 69.0.

[0069] Example 7

[0070]

[0071] In a 250mL double-necked bottle equipped with a stirring magnet, dendrimer G-4 (1.885g, 2.1mmol), methyl 3,5-dihydroxybenzoate (0.168g, 1.0mmol), potassium carbonate (0.414g, 3.0mmol) and ultra-dry DMF (50mL) were added in sequence. The reaction system was reacted in a metal bath at 80°C under nitrogen protection for 12 hours, during which the reaction progress was tracked by TLC. After the reaction was completed, 200mL of water was added to the reaction system to precipitate the product, which was filtered and washed with a large amount of water. The crude product was purified by silica gel column chromatography to obtain white solid G-7 with a yield of 89%. 1 H NMR (400MHz, CDCl3, δ): 3.93 (s, COOCH3, 3H), 5.02 (s, ArCH2O, 4H), 5.17 (s, ArCH2O, 4H), 5.23 (s, ArCH2O, 8H), 6.73 (t, J = 2.4Hz ,ArH,1H),6.81(s,ArH,2H),7.30(d,J=2.3Hz,ArH,2H),7.77(s,ArH,2H),7.82(s,ArH,4H),7.85(s,ArH,4H),7.86(s,ArH,8H). 13C NMR (100MHz, CDCl3, δ):166.6,159.5,152.4,139.8,139.0,137.6,133.4,13 2.3,132.1(q,J=33.5Hz),131.7(q,J=33.4Hz),127.4(d,J=2.7Hz),127.2(d ,J=2.9Hz),123.2(q,J=181.9Hz),123.1(q,J=181.9Hz),122.2(quint,J=2. 4Hz), 121.9 (quint, J = 2.5Hz), 108.3, 107.6, 107.3, 73.7, 70.0, 69.9, 52.5.

[0072] Example 8

[0073]

[0074] In a 250mL double-necked bottle equipped with a stirring magnet, add dendrimer G-5 (1.26g, 1.494mmol), 2-pyrenealdehyde (0.344g, 1.494mmol), potassium tert-butoxide (0.335g, 2.988mmol) and ultra-dry ethanol (40mL) in sequence. The reaction system was reacted at room temperature overnight under nitrogen protection, and TLC was used to track the reaction progress. After the reaction, a yellow precipitate was formed. After filtering, the solid was washed several times with frozen ethanol and dried under vacuum to obtain an orange solid compound G-8 with a yield of 95%. 1 H NMR(400MHz,CDCl3,δ):5.19(s,ArCH2O,2H),5.29(s,ArCH2O,4H),7.17(s,ArH ,2H),7.81(s,ArH,1H),7.84(s,ArH,2H),7.88(s,ArH,2H),7.91(s,ArH,4H),8 .06(t,J=7.7Hz,ArH,1H),8.08-8.17(m,ArH,3H),8.21(d,J=2.8Hz,ArH,2H),8 .24-8.27(m,ArH,3H),8.50(s,ArCH=C(CN)Ar,1H),8.63(d,J=8.1Hz,ArH,1H). 13C NMR (100MHz, CDCl3, δ): 152.6, 140.8, 139.6, 138.8, 138.7, 133.1, 132.2 (q, J = 33.5Hz) ,131.7(q,J=33.4Hz),131.4,131.3,130.6,129.9,129.1,129.0,127.4,127.4,127.3,1 27.3,127.2,126.5,126.2,126.1,125.0,124.7,124.5,123.1(q,J=273.0Hz),122.3,12 2.3(quint,J=3.7Hz),122.0(quint,J=4.0Hz),121.8,118.1,113.7,106.5,73.7,70.1.

[0075] Example 9

[0076]

[0077] In a 250mL single-mouth bottle equipped with a stirring magnet, G-6 (0.86g, 1.0mmol), 9-anthracenecarboxaldehyde (0.21g, 1.0mmol) and THF-EtOH (v / v=2:1, 30mL) were added, and then 2 drops of acetic acid were added as a catalyst. The reaction system was heated to reflux in a metal bath at 100°C for 12h under nitrogen protection and light protection, and the reaction progress was monitored by TLC during this period. After the reaction was completed, all solvents were removed under reduced pressure to obtain a crude product. The crude product was precipitated twice with methanol, filtered, and vacuum dried to obtain a yellow powder solid G-9 with a yield of 90%. 1 H NMR(400MHz,acetone-d6,δ):5.11(s,ArCH2O,2H),5.38(s,ArCH2O,4H),7.41-7.42(m,ArH,4H),7.75(s ,ArH,2H),7.95-8.03(m,ArH,12H),8.50(s,ArCHN,1H),8.70(d,J=8.6Hz,ArH,2H),9.70(s,ArCONH,1H). 13C NMR (100MHz, CDCl3, δ): 163.1, 152.1, 147.5, 141.1, 140.3, 140.2, 131.3, 131.3 (q, J = 33.2Hz), 131.1 (q, J = 33.2Hz), 130.1, 129.8, 129.7, 128. 9,127.7,127.3,126.9,125.3,125.1,124.9,123.4(q,J=272.1Hz),121.7(quint,J=3.7Hz),121.4(quint,J=3.8Hz),119.4,107.7,72.8,69.4.

[0078] Effect example 1:

[0079] 12 mg of dendrimer was weighed in a sample bottle with a diameter of 1 cm and a volume of 5 mL, 0.2 mL of solvent was added, and the solution was heated in a water bath at 100°C until the dendrimer was completely dissolved. The hot solution was then slowly cooled to room temperature and left to stand for 1 hour before observing its state: 1) If the system does not flow, a stable gel is formed, indicated by "G"; 2) If only a partial colloid is formed, it is indicated by "PG"; 3) If a precipitate is formed, it is indicated by "P"; 4) If the system is still a clear solution (>60 mg / mL), it is indicated by "S". If the dendrimer is insoluble in the solvent when heating is started, it is indicated by "I". The minimum gel concentration is the minimum mass of dendrimer required to form a stable gel at 25°C. The results are shown in Table 1.

[0080] Table 1 Gelation properties of dendrimer gel factors G-1, G-7, G-8 and G-9

[0081] Entry Solvents G-1 G-7 G-8 G-9 1 1,2-Dichloroethane S S G(33) G(20) 2 <![CDATA[CCl4]]> G(80) S PG P 3 Acetonitrile S S PG G(9.1) 4 Nitromethane S S P G(7.7) 5 2-Methoxyethanol G(26.7) PG I G(20) 6 2-Ethoxyethanol G(80) S I G(20) 7 Benzylalcohol G(16) PG I P 8 n-Butanol G(7.6) G(20) I P 9 n-Pentanol G(9.7) G(22) I G(33.3) 10 n-Hexanol G(9.7) G(33) I P 11 1-Octanol G(9.7) G(30) I G(14.3) 12 1-Decanol G(6.2) G(30) I P 13 Anisole:Hexane(1:1,v / v) S S G(30) G(33.3) 14 Anisole:Hexane(1:2,v / v) S S G(33) G(20) 15 <![CDATA[Pyridine:H2O(4:1,v / v)]]> G(3.2) P I P

[0082] Effect Example 2:

[0083] Aggregation-induced emission properties of compounds G-8 and G-9

[0084] Take a 100mL volumetric flask and prepare 10% G-8 -3 Take 11 10mL sample bottles, numbered 0 to 10, and add 0.5mL of 10 mol / L tetrahydrofuran solution into each sample bottle using a pipette. -3mol / L tetrahydrofuran solution of compound G-8, add tetrahydrofuran 9.5mL, 8.5mL, 7.5mL, 6.5mL, 5.5mL, 5.5mL, 3.5mL, 2.5mL, 1.5mL, 0.5mL to the test tubes numbered 0 to 9 in sequence, and then add distilled water 1.0mL, 2.0mL, 3.0mL, 4.0mL, 5.0mL, 6.0mL, 7.0mL, 8.0mL, 9.0mL, 9.5mL to the test tubes numbered 1 to 10 in sequence, so that 5×10 of compound G-8 with different water contents are obtained. -5 mol / L solution. The prepared solution was ultrasonicated in an ultrasonicator for 60 seconds and then the fluorescence spectrum test was performed immediately. The fluorescence spectra and fluorescence enhancement trend diagrams of compounds G-8 and G-9 in the dissolved state and the aggregated state are shown in Figure 1 , Figure 2 .

[0085] It can be seen from the results of the above specific implementation methods that the peripheral trifluoromethyl functionalized dendrimer gelator prepared in the present invention is not only simple to synthesize and has a high yield, but also has very excellent gelling properties, a wide range of gelling solvents, and a low gelling concentration. It is a very excellent type of organic gelator.

[0086] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A type of peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gel factor, characterized by: Its chemical structural formula is any one of the following I, II, III and IV: Wherein, X is independently selected from COOC n H 2n+1 , COOH, CONHNH2, CONHCH2CH2Br, CH2OH, CH2Br or CH2CN, where n is an integer greater than or equal to 1; Each R is independently selected from 1-pyrenyl, 9-anthryl, 9-phenanthrenyl, 3-perylenyl, 1-naphthyl, 2-naphthyl or 2-benzothiazole.

2. The polybenzyl ether dendrimer gelator based on peripheral trifluoromethyl functionalization according to claim 1, characterized in that: X is independently selected from COOCH3, COOH, CONHNH2, CH2OH, CH2Br or CH2CN; R is independently selected from 1-pyrene or 9-anthracenyl.

3. An organic gel material, characterized in that: It comprises the polybenzyl ether dendrimer gel factor based on peripheral trifluoromethyl functionalization as described in claim 1.

4. A method for preparing an organogel material as claimed in claim 3, characterized in that: The polybenzyl ether dendrimer gel factor is heated and dissolved in a solvent, and then cooled and allowed to stand to obtain an organic gel material.

5. The method for preparing an organogel material according to claim 4, characterized in that: The solvent is selected from any one of 1,2-dichloroethane, carbon tetrachloride, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, benzyl alcohol, n-butanol, n-pentanol, n-hexanol, n-octanol, 1-decyl alcohol, acetonitrile and nitromethane.

6. The method for preparing an organogel material according to claim 4, characterized in that: The solvent is selected from a mixed solution of anisole and n-hexane, or a mixed solution of pyridine and water.

7. The method for preparing an organogel material according to claim 4, characterized in that: The minimum gelling concentration of the polybenzyl ether dendrimer gel factor is 3.2 mg / mL.

8. The use of the polybenzyl ether dendrimer gel factor based on peripheral trifluoromethyl functionalization according to claim 1, characterized in that: The polybenzyl ether dendrimer gel factor can be used as an assembly unit to prepare functional supramolecular gel or supramolecular self-assembly system.

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