An organic room-temperature phosphorescent material based on tetrathioaryl derivatives, its preparation method and application

Abstract

This invention discloses an organic room-temperature phosphorescent material based on tetrasulfide aromatic hydrocarbon derivatives, its preparation method, and its applications. This organic room-temperature phosphorescent material uses room-temperature phosphorescent molecular compounds based on tetrasulfide aromatic hydrocarbon derivatives as assembly units. In solution, these compounds can self-assemble into stable nanoparticles, exhibiting excellent aggregation-induced phosphorescence, with a phosphorescence lifetime as long as 23.7 μs and a phosphorescence quantum yield as high as 52.6%. The organic room-temperature phosphorescent material provided by this invention solves the technical problems of short phosphorescence lifetime and low phosphorescence quantum yield in aqueous room-temperature phosphorescent materials.

Description

Technical Field

[0001] This invention relates to the field of luminescent materials technology, and in particular to an organic room temperature phosphorescent material based on tetrathioaromatic derivatives, its preparation method, and its application. Background Technology

[0002] Organic room temperature phosphorescence (RTP) materials have attracted widespread attention from researchers due to their advantages such as low toxicity, long lifetime, large Stokes shift, low cost and variety, and have potential application value in fields such as bioimaging, anti-counterfeiting, organic light-emitting diodes, chemical sensing and information encryption.

[0003] Over the past few decades, researchers both domestically and internationally have proposed design strategies such as H-aggregation, crystal engineering, covalent polymerization, and host-guest doping to achieve efficient room-temperature phosphorescence emission of organic molecules in the solid state. These strategies are mainly based on promoting intersystem crossing (ISC) processes by enhancing spin-orbit coupling (SOC) and suppressing non-radiative dissipation by confining organic phosphors in rigid microenvironments.

[0004] In recent years, aqueous ultralong phosphorescent phosphors (RTPs) have attracted significant attention due to their immense potential, particularly in applications such as bioimaging and aqueous encryption inks. However, the room-temperature phosphorescence emission of organic molecules in solution, especially in aqueous solutions, remains a major challenge due to the oxygen quenching effect and significant nonradiative transition processes in aqueous solutions. Researchers have reported a series of aqueous organic room-temperature phosphorescent systems constructed using strategies and methods such as forming organic nanoparticles, macrocyclic supramolecular assembly, in-situ encapsulation within assembled hydrogen-bonded organic frameworks (HOFs), and integrating phosphorescent molecules with supramolecular scaffolds, greatly advancing the development of aqueous RTP materials. However, the organic room-temperature phosphorescent systems constructed using these strategies all face limitations such as relatively short phosphorescence lifetimes and low phosphorescence quantum yields. Furthermore, current RTP materials are mainly organometallic compounds and crystalline organic compounds, which suffer from high cost, high cytotoxicity, and complex preparation processes. Therefore, exploring and developing new aqueous room-temperature phosphorescent materials with long phosphorescence lifetimes and high quantum yields is of great significance and presents both challenges and opportunities. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides an organic room-temperature phosphorescent material based on tetrasulfide aromatic hydrocarbon derivatives, its preparation method, and its applications. The organic room-temperature phosphorescent material of this invention uses room-temperature phosphorescent molecular compounds based on tetrasulfide aromatic hydrocarbon derivatives as assembly units, which can self-assemble into stable nano-assemblies in aqueous solution as organic room-temperature phosphorescent materials. The organic room-temperature phosphorescent material provided by this invention overcomes the technical problems of short phosphorescence lifetime and low phosphorescence quantum yield of room-temperature phosphorescent materials in aqueous phases.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] On the one hand, the present invention provides a room-temperature phosphorescent molecular compound based on a tetrathioarene derivative, the chemical structure of which is shown in formula (1) or formula (2):

[0008]

[0009] In equations (1) and (2), Z1 is R1 and R2 are each selected in isolation from any one of -COOMe, -F, -Cl, -Br, -CF3, -CH3, and -OCH3.

[0010] In another aspect, the present invention provides a method for preparing the above-mentioned room-temperature phosphorescent molecular compound based on tetrathioarene derivatives, comprising the following steps:

[0011] The tetrahydroxytetrasulfide aromatic derivative and Z1X were reacted in a solvent at 80–100 °C under the action of an alkali to obtain the room temperature phosphorescent molecular compound based on the tetrasulfide aromatic derivative; X is a halogen.

[0012] In the technical solution of the present invention, the halogen is selected from any one of Cl, Br, and I.

[0013] In the technical solution of the present invention, the structural formula of the tetrahydroxytetrathio aromatic hydrocarbon derivative is shown in formula (3):

[0014]

[0015] In formula (3), the hydroxyl group is para- or meta-substituted.

[0016] In the technical solution of the present invention, the tetrahydroxytetrasulfur aromatic derivative can be prepared by nucleophilic substitution reaction with Z1Br to obtain the room temperature phosphorescent molecular compound based on the tetrasulfur aromatic derivative.

[0017] In a preferred embodiment, the alkali is potassium carbonate and / or cesium carbonate;

[0018] Preferably, the molar ratio of the tetrahydroxytetrathioaryl derivative, the molar ratio of Z1Br to the molar ratio of the base is 1:(4-6):(4-8), and more preferably 1:4.5:6;

[0019] Preferably, the solvent is N,N-dimethylformamide (DMF) and / or acetonitrile;

[0020] Preferably, the reaction time is 12 to 24 hours;

[0021] Preferably, the reaction is carried out in an inert gas atmosphere;

[0022] In some specific embodiments, the preparation method further includes post-processing steps such as cooling and purification.

[0023] In a preferred embodiment, the preparation method of the tetrahydroxytetrathio aromatic derivative includes the following steps:

[0024] p-hydroxythiophenol / m-hydroxythiophenol was reacted with tetrafluoroterephthalonitrile in a solvent at 45-60°C under the action of an alkali to obtain the tetrahydroxytetrathio aromatic derivative.

[0025] Preferably, the alkali is potassium carbonate and / or cesium carbonate;

[0026] Preferably, the solvent is N,N-dimethylformamide (DMF) and / or acetonitrile;

[0027] Preferably, the ratio of the amount of tetrafluoroterephthalonitrile, the amount of p-hydroxythiophenol / m-hydroxythiophenol to the amount of base is 1:4 to 8:8 to 12.

[0028] Preferably, the reaction time is 6 to 10 hours;

[0029] Preferably, the reaction is carried out in an inert gas atmosphere;

[0030] In some specific embodiments, the preparation method further includes post-treatment of adding hydrochloric acid to quench the reaction and purification.

[0031] In another aspect, the present invention provides an organic room temperature phosphorescent material, wherein the organic room temperature phosphorescent material is a supramolecular nanoparticle formed by the self-assembly of the above-mentioned room temperature phosphorescent molecular compound based on tetrathioarene derivative.

[0032] In a preferred embodiment, the organic room-temperature phosphorescent material is a supramolecular nanoparticle formed by the self-assembly of the room-temperature phosphorescent molecular compound based on tetrathioaromatic derivatives via solvent precipitation.

[0033] In a preferred embodiment, the solvent precipitation method includes the following steps: adding a solution containing the room-temperature phosphorescent molecular compound based on tetrathioroic derivatives to a poor solvent, and obtaining the supramolecular nanoparticles by ultrasonic oscillation;

[0034] Preferably, the solvent in the solution containing the room-temperature phosphorescent molecular compound based on a tetrathioroic derivative is selected from at least one of tetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide, and N,N-dimethylformamide.

[0035] Preferably, the unsuitable solvent is water;

[0036] Preferably, the duration of the ultrasonic oscillation is 1 to 5 minutes;

[0037] In some specific embodiments, the supramolecular nanoparticles obtained by the above preparation method exhibit excellent aggregation-induced phosphorescence, with a phosphorescence lifetime of up to 23.7 μs and a phosphorescence quantum yield of up to 52.6%.

[0038] In another aspect, the present invention provides a light-harvesting system, wherein the light-harvesting system uses the above-mentioned room-temperature phosphorescent molecular compound based on tetrasulfide aromatic hydrocarbon derivatives as a light-harvesting antenna and energy donor, and a fluorescent dye as an energy acceptor, wherein the room-temperature phosphorescent molecular compound based on tetrasulfide aromatic hydrocarbon derivatives and the fluorescent dye are co-assembled in solution to form the light-harvesting system.

[0039] In a preferred embodiment, the fluorescent dye is copper phthalocyanine (II) (CuPc);

[0040] Preferably, the molar ratio of the room-temperature phosphorescent molecular compound based on tetrathioaromatic derivatives to the fluorescent dye in the solution is 50 to 2000:1.

[0041] In another aspect, the present invention provides a method for preparing the above-mentioned light-harvesting system, comprising the following steps:

[0042] A solution containing the above-mentioned room-temperature phosphorescent molecular compound based on tetrathioroline derivatives and fluorescent dye is added to a poor solvent, and the light-harvesting system is obtained by ultrasonic oscillation.

[0043] In a preferred embodiment, the solvent of the solution is a hydrophilic organic solvent selected from at least one of tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide (DMF), and acetonitrile;

[0044] Preferably, the unsuitable solvent is water;

[0045] Preferably, the duration of the ultrasonic oscillation is 1 to 5 minutes.

[0046] In another aspect, the present invention provides the application of the above-mentioned light-harvesting system in the fields of bioimaging, photocatalysis and luminescent materials.

[0047] The above technical solution has the following advantages or beneficial effects:

[0048] This invention provides an organic room-temperature phosphorescent material based on tetrasulfide aromatic hydrocarbon derivatives. This organic room-temperature phosphorescent material uses room-temperature phosphorescent molecular compounds based on tetrasulfide aromatic hydrocarbon derivatives as assembly units. It can self-assemble into stable nanoparticles in an aqueous solution, exhibiting long phosphorescence lifetime and high phosphorescence quantum yield.

[0049] Compared with the prior art, the present invention has the following advantages:

[0050] (1) The synthesis process of the room temperature phosphorescent molecular compound based on tetrathioroic derivatives in this invention is simple, the reaction conditions are mild, the reaction yield is high, and the post-processing is convenient, making it suitable for large-scale preparation.

[0051] (2) The room temperature phosphorescent molecular compound based on tetrathioroic derivatives in this invention can form stable supramolecular nanoassemblies in a variety of organic solvents or aqueous solutions. In particular, it can be assembled into supramolecular nanoparticles with good water dispersibility in aqueous solution. These nanoparticles have excellent aggregation-induced room temperature phosphorescence performance, with a phosphorescence lifetime of 23.7 μs and a phosphorescence quantum yield of up to 52.6%.

[0052] (3) The light-harvesting system prepared by the present invention using room temperature phosphorescent molecular compounds based on tetrathioroic derivatives can be constructed in the aqueous phase, and has the advantages of low cost, green and environmentally friendly, and suitable for application in biological systems.

[0053] (4) The light-harvesting system provided by the present invention can still transfer energy well even at a high donor / acceptor ratio. A single acceptor can receive up to hundreds or even thousands of times the energy transferred by the donors. At the same time, it has a high energy transfer capability, with the best energy transfer efficiency reaching 76%. Attached Figure Description

[0054] Figure 1 The images show the phosphorescence spectrum (a) and phosphorescence intensity trend (b) of pTHBT-Cl in a mixed solution of tetrahydrofuran and water with a water content (volume percentage) of 0-95% in Example 7 of this invention.

[0055] Figure 2 The images show the phosphorescence spectrum (a) and phosphorescence intensity trend (b) of pTHBT-Me in a mixed solution of tetrahydrofuran and water with a water content (volume percentage) of 0-95% in Example 7 of this invention.

[0056] Figure 3The images show the phosphorescence spectrum (a) and phosphorescence intensity trend (b) of mTHBT-Cl in a mixed solution of tetrahydrofuran and water with a water content (volume percentage) of 0-95% in Example 7 of this invention.

[0057] Figure 4 The images show the phosphorescence spectrum (a) and phosphorescence intensity variation trend (b) of mTHBT-Me in a mixed solution of tetrahydrofuran and water with a water content (volume percentage) of 0-95% in Example 7 of this invention.

[0058] Figure 5 This is a fluorescence spectrum test result of the light-harvesting system with different energy donor / acceptor concentration ratios prepared in Example 9 of the present invention.

[0059] Figure 6 This is a fluorescence spectrum test result of the light-harvesting system with different energy donor / acceptor concentration ratios prepared in Example 10 of the present invention.

[0060] Figure 7 This is a fluorescence spectrum test result of the light-harvesting system with different energy donor / acceptor concentration ratios prepared in Example 11 of the present invention.

[0061] Figure 8 This is a fluorescence spectrum test result of the light-harvesting system with different energy donor / acceptor concentration ratios prepared in Example 12 of the present invention. Detailed Implementation

[0062] The following embodiments are merely some, not all, of the embodiments of the present invention. Therefore, the detailed descriptions of the embodiments provided below are not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0063] In this invention, unless otherwise specified, all equipment and raw materials are commercially available or commonly used in the industry. The methods described in the following embodiments are conventional methods in the art, unless otherwise specified.

[0064] Example 1: Tetrahydroxytetrathioaryl derivative pTHBT-OH

[0065] This embodiment provides a tetrahydroxytetrathio aromatic derivative pTHBT-OH, the preparation process of which is shown below:

[0066]

[0067] The specific steps are as follows:

[0068] In a 250 mL double-necked flask equipped with a magnetic stir bar, tetrafluoroterephthalonitrile (1.0 g, 5.0 mmol), p-hydroxythiophenol (3.78 g, 30.0 mmol), K2CO3 (8.28 g, 60.0 mmol), and ultra-dry DMF (50 mL) were added sequentially; the reaction was carried out in a metal bath at 45 °C for 6 h under nitrogen protection, and the reaction progress was monitored by TLC during the reaction.

[0069] After the reaction was completed, 50 mL of hydrochloric acid solution (6 M) was added to the reaction system to quench the reaction, and a reddish-yellow solid was obtained. The solid product was filtered and washed with a large amount of water. After vacuum drying, the target product pTHBT-OH was obtained with a yield of 90%.

[0070] The NMR spectrum of pTHBT-OH prepared in this embodiment is as follows: 1 H NMR (400MHz, d) 6 -acetone, δ): 6.81 (d, J = 8.7Hz, ArH, 8H), 7.20 (d, J = 8.6Hz, ArH, 8H), 8.78 (s, ArOH, 4H). 13 C NMR (100MHz, d) 6 -acetone, δ):157.8,146.7,133.1,128.0,123.5,116.6,114.5.

[0071] Example 2: Tetrahydroxytetrathioaromatic derivative mTHBT-OH

[0072] This embodiment provides a tetrahydroxytetrathio aromatic derivative mTHBT-OH, the preparation process of which is shown below:

[0073]

[0074] The specific steps are as follows:

[0075] In a 250 mL double-necked flask equipped with a magnetic stirrer, tetrafluoroterephthalonitrile (1.0 g, 5.0 mmol), m-hydroxythiophenol (3.78 g, 30.0 mmol), K2CO3 (8.28 g, 60.0 mmol), and ultra-dry DMF (50 mL) were added sequentially; the reaction was carried out in a metal bath at 45 °C for 6 h under nitrogen protection, and the reaction progress was monitored by TLC during the reaction.

[0076] After the reaction was completed, 50 mL of 6 M hydrochloric acid solution was added to the reaction system to quench the reaction, and a red solid was obtained. The solid product was filtered, washed with a large amount of water, and dried. After vacuum drying, the target product mTHBT-OH was obtained with a yield of 86%.

[0077] The NMR spectrum of mTHBT-OH prepared in this embodiment is as follows:1 H NMR (400MHz, d) 6 -DMSO, δ): 6.54 (d, J = 7.8 Hz, ArH, 8H), 6.62-6.64 (m, ArH, 8H), 7.11 (t, J = 7.9 Hz, ArOH, 4H), 9.70 (s, ArOH, 4H). 13 C NMR (100MHz, d) 6 -DMSO, δ): 158.1, 145.2, 135.2, 130.6, 129.1, 118.7, 115.0, 114.5.

[0078] Example 3: Room temperature phosphorescent molecular compound pTHBT-Cl based on tetrathioarneside derivatives

[0079] This embodiment provides a room-temperature phosphorescent molecular compound pTHBT-Cl based on a tetrathioroic derivative, the preparation process of which is shown below:

[0080]

[0081] The specific steps are as follows:

[0082] In a 250 mL double-necked flask equipped with a magnetic stir bar, pTHBT-OH (0.63 g, 1.0 mmol), 3,5-dichlorobenzyl bromide (1.09 g, 4.5 mmol), K2CO3 (0.83 g, 6.0 mmol), and ultra-dry DMF (30 mL) were added sequentially; the reaction was carried out overnight in a metal bath at 80 °C under nitrogen protection, and the reaction progress was monitored by TLC during the process.

[0083] After the reaction was completed, 200 mL of water was added to the reaction system to precipitate the product. The product was filtered and washed with a large amount of water. The crude solid product was purified by silica gel rapid column chromatography to obtain a white solid pTHBT-Cl with a yield of 93%.

[0084] The NMR spectrum of pTHBT-Cl prepared in this embodiment is as follows: 1 H NMR (400MHz, CDCl3, δ): 4.95 (s, ArCH2O, 8H), 6.81-6.85 (m, ArH, 8H), 7.22-7.23 (m, ArH, 4H), 7.24-7.26 (m, ArH, 12H), 7.30-7.31 (m, ArH, 4H). 13 C NMR (100MHz, CDCl3, δ): 157.5, 147.0, 139.7, 135.3, 133.8, 128.3, 127.4, 125.5, 115.9, 114.5, 68.6.

[0085] The high-resolution mass spectrometer (HRMS-ESI) of pTHBT-Cl prepared in this embodiment: C 60 H 37 N₂O₄Cl₈S₄([M+H)₂) + ); Calculated value of molecular ion peak: m / z 1256.9139, measured value: m / z 1256.9142.

[0086] Example 4: Room-temperature phosphorescent molecular compound pTHBT-Me based on tetrathioarneside derivatives

[0087] This embodiment provides a room-temperature phosphorescent molecular compound pTHBT-Me based on a tetrathioroic derivative, the preparation process of which is shown below:

[0088]

[0089] In a 250 mL double-necked flask equipped with a magnetic stirrer, pTHBT-OH (0.63 g, 1.0 mmol), dimethyl 5-(bromomethyl)isophthalate (1.30 g, 4.5 mmol), K2CO3 (0.83 g, 6.0 mmol), and ultra-dry DMF (30 mL) were added sequentially; the reaction was carried out overnight in a metal bath at 80 °C under nitrogen protection, and the reaction progress was monitored by TLC during the reaction.

[0090] After the reaction was completed, 200 mL of water was added to the reaction system to precipitate the product. The product was filtered, washed with a large amount of water, and dried. The crude product was purified by silica gel rapid column chromatography to obtain a white solid pTHBT-Me with a yield of 95%.

[0091] The NMR spectrum of pTHBT-Me prepared in this embodiment is as follows: 1 H NMR (400MHz, CDCl3, δ): 3.94 (s, ArCH2OCH3, 24H), 5.07 (s, ArCH2O, 8H), 6.87-6.90 (m, A rH,8H),7.23-7.26(m,ArH,8H),8.21(d,J=1.6Hz,ArH,8H),8.58(t,J=1.5Hz,ArH,4H). 13 C NMR (100MHz, CDCl3, δ): 170.2, 162.9, 151.1, 143.5, 137.2, 137.0, 135.4, 134.0, 132.5, 130.7, 121.3, 73.4, 57.7.

[0092] The high-resolution mass spectrometer (HRMS-ESI) of pTHBT-Me prepared in this embodiment: C 76 H 61N2O 20 S4([M+H)) + ); Calculated value of molecular ion peak: m / z 1449.2695, measured value: m / z 1449.2687.

[0093] Example 5: Room-temperature phosphorescent molecular compound mTHBT-Cl based on tetrathioarneside derivatives

[0094] This embodiment provides a room-temperature phosphorescent molecular compound mTHBT-Cl based on tetrathioroic hydrocarbon derivatives, the preparation process of which is shown below:

[0095]

[0096] In a 250 mL double-necked flask equipped with a magnetic stir bar, mTHBT-OH (0.63 g, 1.0 mmol), 3,5-dichlorobenzyl bromide (1.09 g, 4.5 mmol), K2CO3 (0.83 g, 6.0 mmol), and ultra-dry DMF (30 mL) were added sequentially; the reaction was carried out overnight in a metal bath at 80 °C under nitrogen protection, and the reaction progress was monitored by TLC during the reaction.

[0097] After the reaction was completed, 200 mL of water was added to the reaction system to precipitate the product. The product was filtered, washed with plenty of water, and dried. The crude product was purified by silica gel rapid column chromatography to obtain a white solid mTHBT-Cl with a yield of 92%.

[0098] The NMR spectrum of mTHBT-Cl prepared in this embodiment is as follows: 1 H NMR (400MHz, CDCl3, δ): 4.87 (s, ArCH2O, 8H), 6.77-6.81 (m, ArH, 12H), 7.14-7.18 (m, ArH, 4H), 7.23 (d, J = 1.9Hz, ArH, 8H), 7.30-7.30 (t, J = 1.9Hz, ArH, 4H). 13 C NMR (100MHz, CDCl3, δ): 171.2, 158.7, 146.5, 139.7, 135.3, 130.6, 129.2, 128.3, 125.5, 123.5, 117.1, 114.6, 114.2, 68.5.

[0099] The high-resolution mass spectrometer (HRMS-ESI) of mTHBT-Cl prepared in this embodiment: C 60 H 37 N₂O₄Cl₈S₄([M+H)₂) + ); Calculated value of molecular ion peak: m / z 1256.9139, measured value: m / z 1256.9131.

[0100] Example 6: Room-temperature phosphorescent molecular compound mTHBT-Me based on tetrathioarneside derivatives

[0101] This embodiment provides a room-temperature phosphorescent molecular compound mTHBT-Me based on a tetrathioroic derivative, the preparation process of which is shown below:

[0102]

[0103] In a 250 mL double-necked flask equipped with a magnetic stir bar, mTHBT-OH (0.63 g, 1.0 mmol), dimethyl 5-(bromomethyl)isophthalate (1.30 g, 4.5 mmol), K2CO3 (0.83 g, 6.0 mmol), and ultra-dry DMF (30 mL) were added sequentially; the reaction was carried out overnight in a metal bath at 80 °C under nitrogen protection, and the reaction progress was monitored by TLC during the reaction.

[0104] After the reaction was completed, 200 mL of water was added to the reaction system to precipitate the product. The product was filtered, washed with a large amount of water, and dried. The crude product was purified by silica gel rapid column chromatography to obtain a white solid mTHBT-Me with a yield of 93%.

[0105] The NMR spectrum of mTHBT-Me prepared in this embodiment is as follows: 1 H NMR (400MHz, CDCl3, δ): 3.87 (s, ArCH2OCH3, 24H), 5.10 (s, ArCH2O, 8H), 6.81-6.89 (m, A rH,12H),7.17-7.21(m,ArH,4H),8.10(d,J=1.5Hz,ArH,8H),8.30(t,J=1.5Hz,ArH,4H). 13 C NMR (100MHz, CDCl3, δ): 165.5, 159.1, 145.6, 138.9, 136.1, 132.5, 131.0, 130.7, 130.2, 129.3, 121.8, 115.1, 114.9, 114.3, 68.5, 53.0.

[0106] The high-resolution mass spectrometer (HRMS-ESI) of mTHBT-Me prepared in this embodiment: C 76 H 61 N2O 20 S4([M+H)) + The calculated value of the molecular ion peak is m / z 1449.2695, and the measured value is m / z 1449.2689.

[0107] Example 7

[0108] This embodiment tested the phosphorescence intensity of the room-temperature phosphorescent molecular compounds based on tetrathioarene derivatives prepared in Examples 3-6 in both dissolved and aggregated states. Taking compound pTHBT-Cl as an example, the test process is as follows:

[0109] Take a 100mL volumetric flask and prepare a solution with a concentration of 10... -3 A tetrahydrofuran solution of compound pTHBT-Cl at a concentration of 1 mol / L;

[0110] Take 11 10 mL sample vials, numbered 0 to 10, and add 0.5 mL of tetrahydrofuran solution of the above compound pTHBT-Cl to each sample vial using a pipette;

[0111] Add 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, and 0.5 mL of tetrahydrofuran to test tubes labeled 0-9, respectively; then add 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, and 9.5 mL of deionized water to test tubes labeled 1-10, respectively, to obtain water concentrations of 5 × 10⁻⁶. -5 A solution of compound pTHBT-Cl in mol / L was prepared; the prepared solution was sonicated in an ultrasonic instrument for 60 seconds and then subjected to phosphorescence spectroscopy.

[0112] Figure 1-4 The figures show the phosphorescence spectra and phosphorescence enhancement trends of compounds pTHBT-Cl, pTHBT-Me, mTHBT-Cl, and mTHBT-Me in their dissolved and aggregated states, respectively. It can be seen from the figures that the compounds pTHBT-Cl, pTHBT-Me, mTHBT-Cl, and mTHBT-Me synthesized in this invention exhibit aggregation-induced phosphorescence. Among them, pTHBT-Cl shows higher luminescence efficiency in its aggregated state (a tetrahydrofuran-water mixed solution with 95% water content, where water content refers to volume percentage, the same applies below) compared to its dissolved state (…). The luminescence efficiency of pTHBT-Me in the aggregated state (95% water content tetrahydrofuran-water mixed solution) was increased by 62 times compared to that in the dissolved state (tetrahydrofuran solution). The luminescence efficiency of mTHBT-Cl in the aggregated state (95% water content tetrahydrofuran-water mixed solution) was increased by 27.6 times compared to that in the dissolved state (tetrahydrofuran solution). The luminescence efficiency of mTHBT-Me in the aggregated state (95% water content tetrahydrofuran-water mixed solution) was increased by 40.6 times compared to that in the dissolved state (tetrahydrofuran solution).

[0113] Table 1 shows the photophysical properties of compounds pTHBT-Cl, pTHBT-Me, mTHBT-Cl, and mTHBT-Me in their dissolved state (tetrahydrofuran solution) and aggregated state (tetrahydrofuran-water mixed solution with 95% water content). The table shows that in the dissolved state, compounds pTHBT-Cl, pTHBT-Me, mTHBT-Cl, and mTHBT-Me exhibit very poor luminescence properties, with the phosphorescence lifetime (τ) being particularly low. p The highest value was 29 ns (mTHBT-Cl), and the phosphorescence quantum yield (Φ) was... PL The highest phosphorescence efficiency was only 4.29% (mTHBT-Me). However, in the aggregated state, the luminescence efficiency of all four compounds was significantly improved. Among them, the phosphorescence quantum yield of compound mTHBT-Me increased from 4.29% in the dissolved state to 52.63%, and the phosphorescence lifetime also increased from 13.4 ns to 23.7 μs. In addition, the system also exhibited a significant positional isomerization effect. The meta-substituted compounds (mTHBT-Cl and mTHBT-Me) showed varying degrees of improvement in phosphorescence lifetime and phosphorescence quantum yield compared with the para-substituted compounds (pTHBT-Cl and pTHBT-Me).

[0114] Table 1

[0115]

[0116] Example 8: Preparation of supramolecular nanoparticles

[0117] In this embodiment, nanoparticles were prepared from the above compounds pTHBT-Cl, pTHBT-Me, mTHBT-Cl, and mTHBT-Me via solvent precipitation. Taking compound pTHBT-Cl as an example, the preparation process is as follows:

[0118] Step 1, prepare a solution with a concentration of 1×10 -3 5 mL of tetrahydrofuran solution of compound pTHBT-Cl (mol / L);

[0119] Step 2: Take 5 sample vials with a volume of 5 mL each, and label them 1 to 5;

[0120] Step 3: Use a pipette to transfer 0.5 mL of the tetrahydrofuran solution of compound pTHBT-Cl into 5 sample vials, and place the sample vials in a vacuum drying oven to allow the solvent to evaporate completely.

[0121] Step 4: Add 0.5 mL, 1.0 mL, 1.5 mL, 2.0 mL, and 2.5 mL of tetrahydrofuran to bottles 1 through 5 respectively to dissolve the compound;

[0122] Step 5: Take five more 10mL sample vials (numbered 6-10) and add 9.5mL, 9.0mL, 8.5mL, 8.0mL, and 7.5mL of deionized water, respectively. Add a small magnetic stir bar to each of vials 6-10 and turn on the stirrer. Use a disposable syringe to slowly drop the tetrahydrofuran solution of compound pTHBT-Cl from vials 1-5 into the high-speed stirred sample vials 6-10. After the drop is complete, sonicate each of sample vials 6-10 for 1 minute to obtain uniformly dispersed supramolecular nanoparticles.

[0123] The concentration of the nanoparticle dispersion prepared in this embodiment is 5 × 10⁻⁶. -5 mo1 / L.

[0124] Example 9: Preparation of a light-harvesting system

[0125] In this embodiment, the above-mentioned compound pTHBT-Cl is used as the optical harvesting antenna and energy donor (D), and copper phthalocyanine (II) (CuPc) is used as the energy acceptor (A) to prepare a light-harvesting system. The process is as follows:

[0126] Step 1, prepare a solution with a concentration of 1×10 -3 5 mL of tetrahydrofuran solution of compound pTHBT-Cl (mol / L);

[0127] Step 2: Prepare tetrahydrofuran solutions of copper phthalocyanine (II) at different concentrations;

[0128] Step 3: Mix the trace donor compound pTHBT-Cl solution with the trace copper phthalocyanine (II) acceptor solution at different final concentration ratios (D / A = 50 / 1, 100 / 1, 500 / 1, 1000 / 1, 1500 / 1, 2000 / 1, molar concentration ratio) (sample vials are labeled 1 to 6), and then place the sample vials labeled 1 to 6 in a vacuum drying oven to allow the solvent to evaporate completely;

[0129] Step 4: Add 1.0 mL of tetrahydrofuran to each of bottles 1 to 6 using a pipette to dissolve the mixture;

[0130] Step 5: Add the above mixed solution dropwise to 4.0 mL of deionized water; sonicate for 5 min with continuous shaking, and obtain aqueous solutions of nanoassemblies with different energy donor / acceptor concentration ratios (D / A) through co-assembly, wherein the concentration of the donor compound pTHBT-Cl is 5 × 10⁻⁶. -5 mo1 / L;

[0131] The fluorescence of the aqueous solution of the nano-assemblies prepared in this embodiment was measured using a fluorescence spectrophotometer with an excitation wavelength of 365 nm. The test results are shown in [Figure number missing]. Figure 5The energy transfer efficiency and antenna efficiency were calculated based on the spectral data, and the results are shown in Table 2. The system with an energy donor / acceptor concentration ratio of D / A = 50 / 1 can achieve an energy transfer efficiency of 70.7% and an antenna efficiency of 40.2%.

[0132] Table 2

[0133]

[0134] Example 10: Preparation of a light-harvesting system

[0135] In this embodiment, the above-mentioned compound pTHBT-Me is used as the optical harvesting antenna and energy donor (D), and copper phthalocyanine (II) (CuPc) is used as the energy acceptor (A) to prepare a light-harvesting system. The process is as follows:

[0136] Step 1, prepare a solution with a concentration of 1×10 -3 5 mL of tetrahydrofuran solution of compound pTHBT-Me at mol / L;

[0137] Step 2: Prepare tetrahydrofuran solutions of copper phthalocyanine (II) at different concentrations;

[0138] Step 3: Mix the trace donor compound pTHBT-Me solution (D) and the trace copper phthalocyanine (II) (CuPc) acceptor solution (A) at different final concentration ratios (D / A = 50 / 1, 100 / 1, 500 / 1, 1000 / 1, 1500 / 1, 2000 / 1, molar concentration ratio) (labeled 1 to 6), and then place the sample vials labeled 1 to 6 into a vacuum drying oven to allow the solvent to evaporate completely;

[0139] Step 4: Add 1.0 mL of tetrahydrofuran to each of bottles 1 to 6 using a pipette to dissolve the mixture;

[0140] Step 5: Add the above mixed solution dropwise to 4.0 mL of deionized water; sonicate for 5 min with continuous shaking, and obtain aqueous solutions of nanoassemblies with different energy donor / acceptor concentration ratios (D / A) through co-assembly, wherein the concentration of the donor compound pTHBT-Me is 5 × 10⁻⁶. -5 mo1 / L.

[0141] The fluorescence of the nanoparticle aqueous solution prepared in this embodiment was measured using a fluorescence spectrophotometer with an excitation wavelength of 365 nm. The test results are shown in [Figure number missing]. Figure 6 The energy transfer efficiency and antenna efficiency were calculated based on the spectral data, and the results are shown in Table 3. Table 3 shows that the system with an energy donor / acceptor concentration ratio of D / A = 50 / 1 achieves an energy transfer efficiency of 75.1% and an antenna effect of 42.9%.

[0142] Table 3

[0143]

[0144] Example 11 Preparation of a light-harvesting system

[0145] In this embodiment, the above-mentioned compound mTHBT-Cl is used as the optical harvesting antenna and energy donor (D), and copper phthalocyanine (II) (CuPc) is used as the energy acceptor (A) to prepare a light-harvesting system. The process is as follows:

[0146] Step 1, prepare a solution with a concentration of 1×10 -3 5 mL of a tetrahydrofuran solution of compound mTHBT-Cl at a concentration of 1 mol / L;

[0147] Step 2: Prepare tetrahydrofuran solutions of copper phthalocyanine (II) at different concentrations;

[0148] Step 3: Mix trace amounts of donor compound mTHBT-Cl solution (D) and trace amounts of copper phthalocyanine (II) (CuPc) acceptor solution (A) at different final concentration ratios (D / A = 50 / 1, 100 / 1, 500 / 1, 1000 / 1, 1500 / 1, 2000 / 1, molar concentration ratios) (labeled 1 to 6), and then place sample vials labeled 1 to 6 into a vacuum drying oven to allow the solvent to evaporate completely;

[0149] Step 4: Add 1.0 mL of tetrahydrofuran to each of bottles 1 to 6 using a pipette to dissolve the mixture;

[0150] Step 5: Add the above mixed solution dropwise to 4.0 mL of deionized water; sonicate for 5 min with continuous shaking, and obtain aqueous solutions of nanoassemblies with different energy donor / acceptor concentration ratios (D / A) through co-assembly, wherein the concentration of the donor compound mTHBT-Cl is 5 × 10⁻⁶. -5 mo1 / L.

[0151] The fluorescence of the aqueous solution of the nano-assemblies prepared in this embodiment was measured using a fluorescence spectrophotometer with an excitation wavelength of 365 nm. The test results are shown in [Figure number missing]. Figure 7 The energy transfer efficiency and antenna efficiency were calculated based on the spectral data, and the results are shown in Table 4. Table 4 shows that the system with an energy donor / acceptor concentration ratio of D / A = 50 / 1 achieves an energy transfer efficiency of 74.4% and an antenna effect of 52.5%.

[0152] Table 4

[0153]

[0154] Example 12 Preparation of a light-harvesting system

[0155] In this embodiment, the above-mentioned compound mTHBT-Me is used as the optical harvesting antenna and energy donor (D), and copper phthalocyanine (II) (CuPc) is used as the energy acceptor (A) to prepare a light-harvesting system. The process is as follows:

[0156] Step 1, prepare a solution with a concentration of 1×10 -3 5 mL of a tetrahydrofuran solution of the compound mTHBT-Me at a concentration of 1 mol / L;

[0157] Step 2: Prepare tetrahydrofuran solutions of copper phthalocyanine (II) at different concentrations;

[0158] Step 3: Mix trace amounts of donor compound mTHBT-Me solution (D) and trace amounts of copper phthalocyanine (II) (CuPc) acceptor solution (A) at different final concentration ratios (D / A = 50 / 1, 100 / 1, 500 / 1, 1000 / 1, 1500 / 1, 2000 / 1, molar concentration ratios) (labeled 1 to 6), and then place sample vials labeled 1 to 6 into a vacuum drying oven to allow the solvent to evaporate completely;

[0159] Step 4: Add 1.0 mL of tetrahydrofuran to each of bottles 1 to 6 using a pipette to dissolve the mixture;

[0160] Step 5: Add the above mixed solution dropwise to 4.0 mL of deionized water; sonicate for 5 min with continuous shaking, and obtain aqueous solutions of nanoassemblies with different energy donor / acceptor concentration ratios (D / A) through co-assembly, wherein the concentration of the donor compound mTHBT-Me is 5 × 10⁻⁶. -5 mo1 / L.

[0161] The fluorescence of the nanoparticle aqueous solution prepared in this embodiment was measured using a fluorescence spectrophotometer with an excitation wavelength of 365 nm. The test results are shown in [Figure number missing]. Figure 8 The energy transfer efficiency and antenna efficiency were calculated based on the spectral data, and the results are shown in Table 5. Table 5 shows that the system with an energy donor / acceptor concentration ratio of D / A = 50 / 1 achieves an energy transfer efficiency of 76.1% and an antenna effect of 51.4%.

[0162] Table 5

[0163]

[0164] As can be seen from the above examples, the room-temperature phosphorescent dendritic molecular compounds based on tetrathioaryl derivatives prepared in this invention are not only simple to synthesize and have high yields, but also can form nano-assemblies with good water dispersibility and stability in aqueous solutions. The supramolecular nanoparticles constructed through self-assembly exhibit excellent aggregation-induced phosphorescence properties. In addition, these dendritic phosphorescent molecules can also serve as excellent light-harvesting systems for constructing multi-color (from green to yellow or red) luminescent systems.

[0165] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A room-temperature phosphorescent molecular compound based on a tetrathioaryl derivative, characterized in that, The chemical structure is shown in formula (1) or formula (2): Equation (1) Equation (2) In equations (1) and (2), Z1 is R1 and R2 are each selected in isolation from any one of -COOMe, -F, -Cl, and -Br.

2. The method for preparing the room-temperature phosphorescent molecular compound based on tetrathioaryl derivatives according to claim 1, characterized in that, Includes the following steps: A tetrahydroxytetrathio aromatic derivative and Z1X were reacted in a solvent at 80-100°C under the action of an alkali to obtain the room-temperature phosphorescent molecular compound based on the tetrathio aromatic derivative; X is a halogen. The structural formula of the tetrahydroxytetrathio aromatic hydrocarbon derivative is shown in formula (3): Equation (3) In formula (3), the hydroxyl group is para- or meta-substituted.

3. The preparation method according to claim 2, characterized in that, The halogen is selected from any one of Cl, Br, and I.

4. The preparation method according to claim 2, characterized in that, The alkali is potassium carbonate and / or cesium carbonate.

5. The preparation method according to claim 3, characterized in that, The ratio of the amount of the tetrahydroxytetrathio aromatic derivative, the amount of Z1Br, and the amount of the base is 1:(4~6):(4~8).

6. The preparation method according to claim 5, characterized in that, The ratio of the amount of the tetrahydroxytetrathio aromatic derivative, the amount of Z1Br, and the amount of the base is 1:4.5:

6.

7. The preparation method according to claim 2, characterized in that, The solvent is N,N-dimethylformamide and / or acetonitrile.

8. The preparation method according to claim 2, characterized in that, The reaction time is 12 to 24 hours.

9. The preparation method according to claim 2, characterized in that, The reaction is carried out in an inert gas atmosphere.

10. The preparation method according to claim 2, characterized in that, The preparation method of the tetrahydroxytetrathio aromatic derivative includes the following steps: reacting p-hydroxythiophenol / m-hydroxythiophenol with tetrafluoroterephthalonitrile in a solvent at 45-60°C under the action of an alkali to obtain the tetrahydroxytetrathio aromatic derivative.

11. The preparation method according to claim 10, characterized in that, The alkali is potassium carbonate and / or cesium carbonate.

12. The preparation method according to claim 10, characterized in that, The solvent is N,N-dimethylformamide and / or acetonitrile.

13. The preparation method according to claim 10, characterized in that, The ratio of the amount of tetrafluoroterephthalonitrile, the amount of p-hydroxythiophenol / m-hydroxythiophenol, and the amount of base is 1:4~8:8~12.

14. The preparation method according to claim 10, characterized in that, The reaction time is 6 to 10 hours.

15. The preparation method according to claim 10, characterized in that, The reaction is carried out in an inert gas atmosphere.

16. An organic room-temperature phosphorescent material prepared from the room-temperature phosphorescent molecular compound based on tetrathioaryl derivatives as described in claim 1, characterized in that, The organic room-temperature phosphorescent material is a supramolecular nanoparticle formed by the self-assembly of a room-temperature phosphorescent molecular compound based on a tetrathioaromatic derivative.

17. The organic room-temperature phosphorescent material according to claim 16, characterized in that, The organic room-temperature phosphorescent material is a supramolecular nanoparticle formed by the self-assembly of the room-temperature phosphorescent molecular compound based on tetrathioaromatic derivatives through solvent precipitation.

18. The organic room-temperature phosphorescent material according to claim 17, characterized in that, The solvent precipitation method includes the following steps: adding a solution containing the room-temperature phosphorescent molecular compound based on tetrathioroic derivatives to a poor solvent, and obtaining the supramolecular nanoparticles by ultrasonic oscillation.

19. The organic room-temperature phosphorescent material according to claim 18, characterized in that, The solvent in the solution containing the room-temperature phosphorescent molecular compound based on a tetrathioroic derivative is selected from at least one of tetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide, and N,N-dimethylformamide.

20. The organic room-temperature phosphorescent material according to claim 18, characterized in that, The unsuitable solvent is water.

21. The organic room-temperature phosphorescent material according to claim 18, characterized in that, The duration of the ultrasonic oscillation is 1 to 5 minutes.

22. A light-harvesting system prepared from a room-temperature phosphorescent molecular compound based on a tetrathioaryl derivative as described in claim 1, characterized in that, The light-harvesting system uses the room-temperature phosphorescent molecular compound based on tetrasulfide aromatic hydrocarbon derivatives as the light-harvesting antenna and energy donor, and the fluorescent dye as the energy acceptor. The room-temperature phosphorescent molecular compound based on tetrasulfide aromatic hydrocarbon derivatives and the fluorescent dye are co-assembled in solution to form the light-harvesting system.

23. The light-harvesting system according to claim 22, characterized in that, The fluorescent dye is copper phthalocyanine (II).

24. The light-harvesting system according to claim 22, characterized in that, The molar ratio of the room-temperature phosphorescent molecular compound based on tetrathioaromatic derivatives and the fluorescent dye in the solution is 50~2000:

1.

25. A method for preparing the light-harvesting system according to any one of claims 22-24, characterized in that, Includes the following steps: A solution containing the above-mentioned room-temperature phosphorescent molecular compound based on tetrathioroline derivatives and fluorescent dye is added to a poor solvent, and the light-harvesting system is obtained by ultrasonic oscillation.

26. The preparation method according to claim 25, characterized in that, The solvent of the solution is a hydrophilic organic solvent selected from at least one of tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, and acetonitrile.

27. The preparation method according to claim 25, characterized in that, The unsuitable solvent is water.

28. The preparation method according to claim 25, characterized in that, The duration of the ultrasonic oscillation is 1 to 5 minutes.

29. The application of the light-harvesting system according to any one of claims 22-24 in the fields of bioimaging, photocatalysis and luminescent materials, wherein the application is not for the purpose of diagnosing or treating diseases.

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