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

Abstract

The application relates to the field of supramolecular chemistry, and discloses a peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gelator, a preparation method and application thereof. The peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gelator is shown in the following formula, can form stable supramolecular organic gels or supramolecular self-assembly systems in various organic solvents or mixed solvents through the synergistic effect of multiple pi-pi interactions between peripheral aromatic rings and F...H weak hydrogen bonds, has a minimum gelation concentration CGC of 3.2 mg / mL, and is easy to be functionally modified, for example, a gel with an aggregation-induced emission performance is prepared by introducing 1-pyrene or 9-anthracene functional groups. The preparation method of the gelator is efficient, high-yield and high-purity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of supramolecular chemistry, and particularly relates to a kind of peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gelator, and the functional supramolecular organic gel with aggregation-induced emission enhancement performance further functionalized by the gelator. BACKGROUND

[0002] Unlike traditional covalent bond polymer gel, supramolecular gel is formed by non-covalent interaction of low molecular weight gelator molecules self-assembly into three-dimensional network with various nanostructures, so as to make the solvent immobilization. Due to the unique multi-level self-assembly structure and structural diversity, supramolecular gel has gradually developed into a kind of intelligent / functional soft material with broad application prospect. Small molecules capable of forming supramolecular gel, its structure and type cover from the simplest alkane to sugar, oligopeptide and urea, nucleotide, steroid compounds, metal complexes and complex dendrimers. At present, developing new supramolecular gelator, expanding the application field of supramolecular gel and clarifying its gelation mechanism are still the research difficulties and hotspots in the field of supramolecular gel.

[0003] Dendrimer is a kind of monodisperse macromolecule with regular and exquisite three-dimensional structure. Because of its unique properties such as molecular volume, shape and function can be accurately designed and controlled at molecular level, it has become one of the ideal molecules for constructing nanoscale soft material. Dendrimer gel, as a kind of special supramolecular gel, has the dual advantages of polymer gel and small molecule gel. At present, there are some typical hydrogen bond and van der Waals force provided by amide group and long chain alkyl group and other typical gelation elements to construct dendrimer gel system, but compared with small molecule gel, the report of dendrimer gel is still less, so it is of great significance to develop and develop a new type of dendrimer gelator with excellent gelation performance.

[0004] As an important class of fluorine-containing organic functional groups, trifluoromethyl (CF3) has strong electron-withdrawing inductive effect and stable carbon-fluorine bond. Introducing trifluoromethyl into organic molecules can significantly change the physicochemical properties (such as acidity, dipole moment, solubility, lipophilicity, conformation, pKa and membrane permeability) of the molecules, metabolic stability and bioavailability. At present, organic compounds containing trifluoromethyl are widely used in functional materials, agricultural chemicals, pharmaceuticals and other industries, and have attracted great interest of 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 atom is conducive to forming multiple F…H weak hydrogen bond interactions. Therefore, it is of great significance to modify the trifluoromethyl functional group to the periphery of poly(benzyl ether)-type dendrimers, and use the multiple supramolecular interactions of trifluoromethyl and the multiple bonding effect of dendrimers to construct a new gel system with excellent gelation performance and special functions. SUMMARY

[0005] The purpose of the present application is to provide a new type of dendrimer gelator with excellent gelation performance, simple and efficient synthesis and easy post-functionalization, which can form stable supramolecular organic gels in various organic solvents or mixed solvents, and can be easily post-functionalized to prepare functional organic gel systems.

[0006] To achieve the above purpose, in a first aspect, the present application provides a kind of poly(benzyl ether)-type dendrimer gelator functionalized by trifluoromethyl on the periphery, and its chemical structural formula is any one of the following I, II, III and IV:

[0007]

[0008] In formula (I) and (IV), X is independently selected from COOC

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

[0010] Preferably, X is 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-phenanthryl, 3-perylenyl, 1-naphthyl, 2-naphthyl or 2-benzothiazole.

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

[0013] In a second aspect, the present application provides a preparation method of a peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gelator of the 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 application, the reaction of step (1) is an etherification reaction of 3,5-bis(trifluoromethyl)benzyl bromide and 3,4,5-trihydroxybenzoic acid methyl ester by using nucleophilic substitution reaction, the reaction reagent used is selected from potassium carbonate and cesium carbonate, preferably potassium carbonate; the solvent used is selected from acetone, acetonitrile and DMF, preferably DMF. The molar ratio of the raw materials 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 the molar ratio of the raw materials is 1:3.1:4.5.

[0033] In the technical scheme of the present application, the reaction of step (2) is a hydrolysis reaction of dendrimer G-1 in the presence of an inorganic base and a solvent, 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 substance molar ratio of the dendrimer methyl ester to potassium hydroxide is 1:5-10, preferably 1:5.

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

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

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

[0037] In the technical scheme of the present application, the reaction of step (6) is a hydrazine reaction of dendrimer G-1 in the presence of hydrazine hydrate, 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 substance molar ratio of the dendrimer methyl ester to hydrazine hydrate is 1:1-3, preferably 1:2.

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

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

[0040] In the technical scheme of the present application, the reaction of step (9) is an imination reaction in the presence of an acetic acid catalyst, the solvent is selected from one or a mixture of tetrahydrofuran and ethanol, and preferably is a mixture of tetrahydrofuran and ethanol (2:1, v / v). The molar ratio of the raw materials of dendrimer G-6 and 9-anthracene formaldehyde is 1:1-1.5, and preferably is 1:1.

[0041] The preparation method of the peripheral trifluoromethyl functionalized polybenzyl ether type dendrimer gelator provided by the present application has mild reaction conditions, the post-treatment of the crude product is simple and easy to operate, and the reaction yield is high. In addition, such gelators can form stable supramolecular organic gels in various organic solvents or mixed solvents, have a wide gelation solvent and a low gelation concentration. It is worth mentioning that the gelators contain various reactive functional groups, which provide convenience for the preparation of functional supramolecular soft material by conveniently and quickly introducing functional groups.

[0042] In a third aspect, the present application provides an organic gel material comprising the polybenzyl ether type dendrimer gelator shown in formula I, II, III and IV.

[0043] In a fourth aspect, the present application provides a preparation method of the organic gel material containing the polybenzyl ether dendrimer gelator with the structure shown in formula I, II, III and IV, which comprises dissolving the peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gelator in a solvent at 100℃, and then standing after cooling, and obtaining the gel material by the bottle inversion method. The solvent comprises a single organic gel-forming solvent or a mixed solvent, the single organic gel-forming solvent is any one of 1,2-dichloroethane, carbon tetrachloride, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, benzyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, n-octyl alcohol, 1-oleyl alcohol, acetonitrile and nitromethane, and the mixed solvent is any one of a mixed solution of anisole and n-hexane or a mixed solution of pyridine and water. The minimum gel-forming concentration of the dendrimer gelator is 3.2 mg / mL.

[0044] The peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gelator provided by the present application is mainly used as a gel-forming (assembly) unit to prepare a functional supramolecular gel or a supramolecular self-assembly system, such as the functional gel system with enhanced aggregation-induced emission prepared in the example of the present application. The compounds G-8 and G-9 synthesized by the present application have the property of aggregation-induced emission, wherein the light emission efficiency of G-8 in the aggregated state is 14.3 times higher than that in the dissolved state, and the light emission efficiency of G-9 in the aggregated state is 8.5 times higher than that in the dissolved state.

[0045] The present application has the following advantages:

[0046] 1. The present application provides a dendrimer gelator with a novel structure, excellent gel-forming performance, simple and efficient synthesis and easy post-functionalization. The dendrimer gelator can form a stable supramolecular organic gel or a supramolecular self-assembly system in various organic solvents or mixed solvents through the synergistic effect of multiple π-π interactions between the peripheral aromatic rings and F…H weak hydrogen bonds, and the minimum gel-forming concentration CGC is 3.2 mg / mL.

[0047] 2. The core of the gelator has various reactive functional groups, which is easy to be post-functionalized. For example, the functional gel system prepared by the compounds G-8 and G-9 synthesized by the present application has the property of aggregation-induced emission, wherein the light emission efficiency of G-8 in the aggregated state is 14.3 times higher than that in the dissolved state, and the light emission efficiency of G-9 in the aggregated state is 8.5 times higher than that in the dissolved state. BRIEF DESCRIPTION OF DRAWINGS

[0048] Figure 1 Fig. 1 is a fluorescence spectrum (a) and a fluorescence intensity trend chart (b) of the compound G-8 prepared by the present application in a mixed solution of tetrahydrofuran and water with a water volume content of 0-90%;

[0049] Figure 2The fluorescence spectrum (a) and the fluorescence intensity trend graph (b) of the compound G-9 prepared in the application 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 scheme and advantages of the application more clear, the application will be further described in detail below in combination with examples. It should be understood that the specific examples described herein are only used to explain the application and not to limit the application. In order to better illustrate the application, the following examples are further illustrated by examples.

[0051] Example 1

[0052]

[0053] In a 250 mL double-mouth flask equipped with a magnetic stirrer, 3,4,5-trihydroxybenzoic acid methyl ester (1.84 g, 10 mmol), 3,5-bis(trifluoromethyl)benzyl bromide (9.52 g, 31 mmol), K2CO3(6.21 g, 45 mmol) and super dry DMF (50 mL) were added in sequence. The reaction system was reacted in a metal bath at 80°C under nitrogen protection for 12 h, and the reaction progress was tracked by TLC during the reaction. After the reaction was completed, 200 mL of water was added to the reaction system to precipitate the product, and the solid crude product was washed with a large amount of water. The obtained crude product was dissolved in 30 mL of THF, and then added dropwise into 200 mL of rapidly stirred methanol solvent, during which a large amount of solid precipitated, which was filtered, washed with methanol for several times, and dried under vacuum to obtain white solid G-1 with a yield of 96%. 1 H NMR (400 MHz, 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 (100 MHz, CDCl3, δ): 165.9, 151.9, 141.5, 139.5, 138.7, 132.1 (q, J = 33.6 Hz), 131.7 (q, J = 33.6 Hz), 127.3, 127.3, 126.4, 123.1 (q, J = 272.7 Hz), 122.3 (quint, J = 3.6 Hz), 122.0 (quint, J = 3.6 Hz), 121.7, 109.4, 73.6, 69.9, 52.5.

[0054] Example 2

[0055]

[0056] In a 100 mL single necked flask with a magnetic stir bar, dendrimer G-1 (1.73 g, 2.0 mmol), 10 M KOH aq. (1.0 mL, 10.0 mmol) and THF-H2O (3:1, v / v, 60 mL) were added sequentially. The reaction was heated to reflux overnight under a nitrogen atmosphere. The reaction progress was monitored by TLC. After the reaction was completed, the solution was acidified with 2 M HCl solution three times in succession (pH paper was close to 1-2). A portion of the precipitate appeared in the solution. Most of the THF was removed under vacuum. The solid was filtered and washed with distilled water three times. The white powder G-2 was obtained after drying under vacuum. The yield was 98%. 1 H NMR (400 MHz, acetone-d6, δ): 5.46 (s, ArCH20, 2H), 5.52 (s, ArCH20, 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 (100 MHz, acetone-d6, δ): 166.8, 153.0, 142.4, 142.1, 141.4, 132.2 (q, J = 33.3 Hz), 132.0 (q, J = 33.2 Hz), 128.9 (d, J = 3.3 Hz), 128.5 (d, J = 4.5 Hz), 127.6, 124.4 (q, J = 272.2 Hz), 124.3 (q, J = 272.2 Hz), 122.6 (quint, J = 3.7 Hz), 122.3 (quint, J = 3.7 Hz), 110.2, 74.0, 70.3.

[0057] Example 3

[0058]

[0059] In a 250 mL single necked flask equipped with a magnetic stir bar, G-1 (1.73 g, 2.0 mmol) and 100 mL of dry THF were added successively. LiAlH4(0.09 g, 2.4 mmol) was added slowly under ice bath condition. After the addition was completed, the ice bath was removed and a reflux condenser was attached. The reaction mixture was heated at 100 °C for 1 h. The reaction was monitored by TLC. After the reaction was completed, about 0.1 mL of H2O, 0.2 mL of 15% NaOH solution and 0.3 mL of H2O were added successively under ice bath condition. A white solid appeared in the solution. The solid was filtered and washed with THF (3 x 50 mL). The filtrate was dried over anhydrous Na2SO4for 1 h. After filtration, the organic solvent was removed under reduced pressure to give G-3 as a white solid in 95% yield. 1 H NMR (400 MHz, CDC13, 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 (100 MHz, CDC13, δ): 152.3, 139.9, 139.1, 137.9, 137.0, 132.2 (q, J = 33.6 Hz), 131.6 (q, J = 33.5 Hz), 127.4 (d, J = 3.0 Hz), 127.2 (d, J = 2.9 Hz), 123.1 (q, J = 272.6 Hz), 122.2 (quint, J = 3.8 Hz), 121.8 (quint, J = 3.7 Hz), 121.8, 106.7, 73.6, 69.9, 64.9.

[0060] Example 4

[0061]

[0062] In a 250 mL single neck flask with a magnetic stirrer, G-3 (1.67 g, 2.0 mmol) and super dry DCM (50 mL) were added, and PBr3(0.3 mL, 3.0 mmol) was slowly added with a 1 mL glass syringe under ice bath condition, 10 min later the ice bath was removed. The reaction was carried out at 40 °C in a metal bath for 2 h under nitrogen protection. The reaction process was monitored by TLC. After the reaction was completed, 10 mL of saturated aqueous NaHCO3solution was slowly added under ice bath condition to quench the reaction. Then 100 mL of DCM was added to extract three times, the organic phase was combined and dried with anhydrous sodium sulfate. Filtration, removal of solvent under reduced pressure to obtain the crude product. The obtained crude product was purified by flash silica gel column chromatography (eluent: petroleum ether) to obtain white powder solid G-4 with a yield of 92%. 1 H NMR (400 MHz, CDC13, δ): 4.44 (s, ArCH2Br, 2H), 5.14 (s, ArCH2O, 2H), 5.22 (s, ArCH2O, 4H), 6.78 (s, ArH, 2H), 7.76 (s, ArH, 1H), 7.80 (s, ArH, 2H), 7.86 (s, ArH, 6H). 13 C NMR (100 MHz, CDC13, δ): 152.2, 139.7, 138.8, 137.9, 134.7, 132.1 (q, J = 33.5 Hz), 131.7 (q, J = 33.4 Hz), 127.4 (d, J = 3.4 Hz), 127.2 (d, J = 2.8 Hz), 123.1 (q, J = 272.2 Hz), 122.2 (quint, J = 3.7 Hz), 121.9 (quint, J = 3.7 Hz), 109.2, 73.7, 70.0, 33.1.

[0063] Example 5

[0064]

[0065] In a 250 mL single neck flask with a magnetic stirrer, G-4 (2.188 g, 2.438 mmol), TMSCN (0.484 g, 4.876 mmol), K2CO3(0.673 g, 4.876 mmol) and acetonitrile (50 mL) were added in turn. The reaction was carried out at 80 °C in a metal bath overnight under nitrogen protection, and the reaction progress was tracked by TLC during the reaction. After the reaction was completed, the reaction solvent was removed. Then 200 mL of dichloromethane and 50 mL of water were added to extract the product, the aqueous phase was extracted with dichloromethane twice, the organic phase was combined and washed once with 50 mL of saturated brine, the organic phase was dried with anhydrous sodium sulfate, filtered and the solvent was rotary evaporated to obtain the crude product, which was purified by silica gel column chromatography to obtain white solid G-5 with a yield of 90%.1 H NMR (400 MHz, CDC13, δ): 3.74 (s, ArCH2CN, 2H), 5.15 (s, ArCH20, 2H), 5.22 (s, ArCH20, 4H), 6.71 (s, ArH, 2H), 7.77 (s, ArH, 1H), 7.80 (s, ArH, 2H), 7.87 (s, ArH, 6H). 13 C NMR (100 MHz, CDC13, δ): 152.6, 139.6, 138.7, 137.6, 132.2 (q, J = 33.6 Hz), 131.7 (q, J = 33.4 Hz), 127.4, 127.4 (d, J = 3.1 Hz), 127.2 (d, J = 3.8 Hz), 126.7, 123.1 (q, J = 269.6 Hz), 122.3 (quint, J = 3.6 Hz), 121.9 (quint, J = 3.4 Hz), 117.3, 108.1, 73.7, 70.0, 23.8.

[0066] Example 6

[0067]

[0068] In a 250 mL single necked flask equipped with a magnetic stir bar, G-1 (1.73 g, 2.0 mmol), hydrazine hydrate (0.2 mL, 4.0 mmol) and MeOH-THF (v / v = 1:1, 30 mL) were added. The reaction mixture was heated under reflux at 85 °C in a metal bath under nitrogen protection for 12 h, during which TLC was used to monitor the progress of the reaction. After the reaction was completed, all the solvents were removed under reduced pressure to obtain the crude product. The obtained crude product was precipitated with methanol twice, suction filtered and dried under vacuum to obtain white powder solid G-6 with a yield of 95%. 1 H NMR (400 MHz, DMSO-d6, δ): 4.67 (bs, ArCONHNH2, 2H), 5.25 (s, ArCH20, 2H), 5.40 (s, ArCH20, 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 (100 MHz, DMSO-d6, δ): 164.9, 151.6, 141.0, 140.2, 139.2, 130.4 (q, J = 32.9 Hz), 130.2 (q, J = 32.9 Hz), 129.3, 128.2 (d, J = 2.2 Hz), 127.4 (d, J = 2.9 Hz), 123.2 (q, J = 272.7 Hz), 123.1 (q, J = 272.6 Hz), 121.6 (quint, J = 3.7 Hz), 121.3 (quint, J = 3.7 Hz), 106.8, 72.6, 69.0.

[0069] Example 7

[0070]

[0071] Into a 250 mL two-necked flask equipped with a magnetic stir bar, dendron G-4 (1.885 g, 2.1 mmol), methyl 3,5-dihydroxybenzoate (0.168 g, 1.0 mmol), potassium carbonate (0.414 g, 3.0 mmol) and super dry DMF (50 mL) were added successively. The reaction mixture was heated at 80 °C in a metal bath under nitrogen for 12 h, during which the reaction progress was monitored by TLC. After the reaction was completed, the product was precipitated by adding 200 mL of water into the reaction mixture and filtered. The crude product was washed with copious amount of water. The crude product was purified by silica gel column chromatography to give G-7 as a white solid in 89% yield. 1 H NMR (400 MHz, CDC13, δ): 3.93 (s, COOCH3, 3H), 5.02 (s, ArCH20, 4H), 5.17 (s, ArCH20, 4H), 5.23 (s, ArCH20, 8H), 6.73 (t, J = 2.4 Hz, ArH, IH), 6.81 (s, ArH, 2H), 7.30 (d, J = 2.3 Hz, ArH, 2H), 7.77 (s, ArH, 2H), 7.82 (s, ArH, 4H), 7.85 (s, ArH, 4H), 7.86 (s, ArH, 8H). 13C NMR (100 MHz, CDC13, δ): 166.6, 159.5, 152.4, 139.8, 139.0, 137.6, 133.4, 132.3, 132.1 (q, J = 33.5 Hz), 131.7 (q, J = 33.4 Hz), 127.4 (d, J = 2.7 Hz), 127.2 (d, J = 2.9 Hz), 123.2 (q, J = 181.9 Hz), 123.1 (q, J = 181.9 Hz), 122.2 (quint, J = 2.4 Hz), 121.9 (quint, J = 2.5 Hz), 108.3, 107.6, 107.3, 73.7, 70.0, 69.9, 52.5.

[0072] Example 8

[0073]

[0074] In a 250 mL flask with a magnetic stirrer, dendrimer G-5 (1.26 g, 1.494 mmol), 2-pyrene aldehyde (0.344 g, 1.494 mmol), potassium tert-butoxide (0.335 g, 2.988 mmol) and super dry ethanol (40 mL) were added in sequence. The reaction system was reacted at room temperature overnight under nitrogen protection, and the reaction progress was tracked by TLC during the reaction. After the reaction was completed, a yellow precipitate was formed. The solid was washed with chilled ethanol for several times and dried under vacuum to obtain orange solid compound G-8 with a yield of 95%. 1 H NMR (400 MHz, CDC13, δ): 5.19 (s, ArCH20, 2H), 5.29 (s, ArCH20, 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 = 7.7 Hz, ArH, 1H), 8.08-8.17 (m, ArH, 3H), 8.21 (d, J = 2.8 Hz, ArH, 2H), 8.24-8.27 (m, ArH, 3H), 8.50 (s, ArCH=C(CN)Ar, 1H), 8.63 (d, J = 8.1 Hz, ArH, 1H). 13C NMR (100 MHz, CDC13, δ): 152.6, 140.8, 139.6, 138.8, 138.7, 133.1, 132.2 (q, J = 33.5 Hz), 131.7 (q, J = 33.4 Hz), 131.4, 131.3, 130.6, 129.9, 129.1, 129.0, 127.4, 127.4, 127.3, 127.3, 127.2, 126.5, 126.2, 126.1, 125.0, 124.7, 124.5, 123.1 (q, J = 273.0 Hz), 122.3, 122.3 (quint, J = 3.7 Hz), 122.0 (quint, J = 4.0 Hz), 121.8, 118.1, 113.7, 106.5, 73.7, 70.1.

[0075] Example 9

[0076]

[0077] In a 250 mL single necked flask equipped with a magnetic stir bar, G-6 (0.86 g, 1.0 mmol), 9-anthraldehyde (0.21 g, 1.0 mmol) and THF-EtOH (v / v = 2:1, 30 mL) were added, followed by 2 drops of acetic acid as catalyst. The reaction system was heated under reflux at 100 °C in a metal bath under nitrogen protection and light protection for 12 h, and the reaction progress was monitored by TLC during the reaction. After the reaction was completed, all the solvents were removed under reduced pressure to obtain the crude product. The obtained crude product was precipitated with methanol twice, suction filtered, and dried in vacuum to obtain yellow powder solid G-9 with a yield of 90%. 1 H NMR (400 MHz, acetone-d6, δ): 5.11 (s, ArCH20, 2H), 5.38 (s, ArCH20, 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 = 8.6 Hz, ArH, 2H), 9.70 (s, ArCONH, 1H). 13C NMR (100 MHz, CDC13, δ): 163.1, 152.1, 147.5, 141.1, 140.3, 140.2, 131.3, 131.3 (q, J = 33.2 Hz), 131.1 (q, J = 33.2 Hz), 130.1, 129.8, 129.7, 128.9, 127.7, 127.3, 126.9, 125.3, 125.1, 124.9, 123.4 (q, J = 272.1 Hz), 121.7 (quint, J = 3.7 Hz), 121.4 (quint, J = 3.8 Hz), 119.4, 107.7, 72.8, 69.4.

[0078] Example 1

[0079] In a 1 cm diameter, 5 mL volume sample bottle, 12 mg dendrimer was weighed, 0.2 mL solvent was added, and the sample was heated in a 100°C water bath until the dendrimer was completely dissolved. The hot solution was then allowed to cool slowly to room temperature, and the sample was observed after standing for 1 h: 1) if the system did not flow when the sample bottle was inverted, a stable gel had formed, indicated by "G"; 2) if only a partial gel had formed, indicated by "PG"; 3) if a precipitate had formed, indicated by "P"; 4) if the system was still a clear solution (> 60 mg / mL), indicated by "S". If the dendrimer was not soluble in the solvent at the start of heating, indicated by "I". The minimum gel concentration was 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 dendrimers 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 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 Pyridine:H2O (4:1, v / v) G(3.2) P I P

[0082] Example 2

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

[0084] A 100 mL volumetric flask was prepared with 10 mL of a 10 -3 mL sample bottles, labeled 0-10, were prepared by adding 0.5 mL of the 10 -3mol / L of compound G-8 in tetrahydrofuran, 9.5 mL, 8.5 mL, 7.5 mL, 6.5 mL, 5.5 mL, 5.5 mL, 3.5 mL, 2.5 mL, 1.5 mL, 0.5 mL of tetrahydrofuran were added into the test tubes with the labels 0-9, respectively, then 1.0 mL, 2.0 mL, 3.0 mL, 4.0 mL, 5.0 mL, 6.0 mL, 7.0 mL, 8.0 mL, 9.0 mL, 9.5 mL of distilled water were added into the test tubes with the labels 1-10, respectively, so that 5×10 -5 mol / L solutions of compound G-8 with different water contents were obtained. The prepared solutions were subjected to ultrasonic treatment for 60 s in an ultrasonic instrument, and then were subjected to fluorescence spectrum test. The fluorescence spectrum graphs and fluorescence enhancement trend graphs of compound 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 above specific embodiment results that the peripheral trifluoromethyl functionalized dendrimer gelator prepared in the present application has simple synthesis, high yield, excellent gelation performance, wide gelation solvent and low gelation concentration, and is a very excellent organic gelator.

[0086] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept scope of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the present application, and all fall within the protection scope of the present application.

Claims

1. A peripheral trifluoromethyl functionalized polybenzyl ether dendrimeric gelator, characterized in that: having any one of the following chemical structures I, G-8, and IV: wherein each X is independently selected from COOC n H 2n+1 , COOH, CONHNH2, CONHCH2CH2Br, CH2OH, CH2Br, or CH2CN, and n is an integer greater than or equal to 1.

2. The peripheral trifluoromethyl functionalized poly(benzyl ether)-type dendrimer gelator according to claim 1, wherein, X is each independently selected from COOCH3, COOH, CONHNH2, CH2OH, CH2Br or CH2CN.

3. Use of the peripheral trifluoromethyl functionalized polybenzyl ether dendrimer gelator of claim 1, characterized in that, The polybenzyl ether dendrimer gelator can be used as an assembling unit to prepare functional supramolecular gel or supramolecular self-assembly system.

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