Organic room-temperature phosphorescent material based on tetrasulfide aromatic hydrocarbon derivative as well as preparation method and application of organic room-temperature phosphorescent material

Abstract

The invention discloses an organic room-temperature phosphorescent material based on a tetrasulfide aromatic hydrocarbon derivative as well as a preparation method and application of the organic room-temperature phosphorescent material. The organic room-temperature phosphorescent material takes a room-temperature phosphorescent molecular compound based on a tetrasulfide aromatic hydrocarbon derivative as an assembly element, and can be self-assembled into stable nanoparticles in a solution to serve as the organic room-temperature phosphorescent material, an excellent aggregation-induced phosphorescence phenomenon is shown, the phosphorescence life is as long as 23.7 microseconds, and the phosphorescence quantum yield is as high as 52.6%. The organic room-temperature phosphorescent material provided by the invention solves the technical problems of short phosphorescent life, low phosphorescent quantum yield and the like of a room-temperature phosphorescent material in a water phase.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and in particular to an organic room temperature phosphorescent material based on tetrathioarene derivatives, and a preparation method and application thereof. Background Art

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

[0003] In the past few decades, researchers at home and abroad 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. The above strategies are mainly based on promoting the intersystem crossing (ISC) process by enhancing spin-orbit coupling (SOC) and suppressing the non-radiative dissipation of organic phosphors by confining them in a rigid microenvironment.

[0004] In recent years, aqueous ultralong RTP materials have attracted great attention due to their great potential, especially in applications such as bioimaging and aqueous encrypted inks. However, due to the quenching effect of oxygen in the aqueous phase and the significant non-radiative transition process, the room temperature phosphorescence emission of organic molecules in solution, especially in aqueous solution, still faces great challenges. Researchers have successively reported the construction of a series of aqueous organic room temperature phosphorescence systems by forming organic nanoparticles, macrocyclic supramolecular assembly, in situ encapsulation in assembled hydrogen-bonded organic frameworks (HOFs), and integrating phosphorescent molecules with supramolecular scaffolds, which has greatly promoted the development of aqueous RTP materials. However, the organic room temperature phosphorescence systems constructed by the above strategies all face limitations such as relatively short phosphorescence lifetime and low phosphorescence quantum yield. In addition, the current RTP materials are mainly organometallic compounds and crystalline organic compounds, which have the problems of high cost, high cytotoxicity and complex preparation process. Therefore, it is of great significance and challenge to explore and develop new aqueous room temperature phosphorescence materials with long phosphorescence lifetime and high quantum yield. Summary of the invention

[0005] In view of the above technical problems, the present invention provides an organic room temperature phosphorescent material based on tetrathioarene derivatives and a preparation method and application thereof. The organic room temperature phosphorescent material in the present invention uses a room temperature phosphorescent molecular compound based on tetrathioarene derivatives as an assembly unit, which can self-assemble into a stable nano-assembly in an aqueous solution as an organic room temperature phosphorescent material. The organic room temperature phosphorescent material provided by the present invention overcomes the technical problems of short phosphorescence lifetime and low phosphorescence quantum yield of room temperature phosphorescent materials in aqueous phase.

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

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

[0008]

[0009] In formula (1) and formula (2), Z1 is R1 and R2 are each independently selected 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] A tetrahydroxytetrathioarene derivative and Z1X are reacted in a solvent at 80-100° C. under the action of a base to obtain the room temperature phosphorescent molecular compound based on the tetrathioarene 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 tetrahydroxytetrathioarene derivative is shown in formula (3):

[0014]

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

[0016] In the technical solution of the present invention, the tetrahydroxytetrathioarene derivative can undergo a nucleophilic substitution reaction with Z1Br to prepare the room temperature phosphorescent molecular compound based on the tetrathioarene derivative.

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

[0018] Preferably, the ratio of the amount of the tetrahydroxytetrathioarene derivative, the amount of Z1Br and the amount of the base is 1:(4-6):(4-8), 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 certain specific embodiments, the preparation method further comprises post-treatments of cooling and purification.

[0023] As a preferred embodiment, the method for preparing the tetrahydroxytetrathioarene derivative comprises the following steps:

[0024] reacting p-hydroxythiophenol / m-hydroxythiophenol with tetrafluoroterephthalonitrile in a solvent at 45-60° C. under the action of a base to obtain the tetrahydroxytetrathioarene derivative;

[0025] Preferably, the base 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 and the amount of base is 1:4-8:8-12;

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

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

[0030] In certain specific embodiments, the preparation method further comprises 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 self-assembly of the above-mentioned room temperature phosphorescent molecular compound based on tetrathioarene derivatives.

[0032] As a preferred embodiment, the organic room temperature phosphorescent material is a supramolecular nanoparticle formed by self-assembly of the above-mentioned room temperature phosphorescent molecular compound based on tetrathioarene derivatives through a solvent precipitation method.

[0033] As a preferred embodiment, the solvent precipitation method comprises the following steps: adding a solution containing the room temperature phosphorescent molecular compound based on tetrathioarene derivatives into 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 tetrathioarene derivatives is at least one selected from tetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide and N,N-dimethylformamide;

[0035] Preferably, the poor solvent is water;

[0036] Preferably, the ultrasonic oscillation time 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] On the other hand, the present invention provides a light harvesting system, which uses the above-mentioned room temperature phosphorescent molecular compound based on tetrathioarene derivatives as a light collection antenna and energy donor, and a fluorescent dye as an energy acceptor. The room temperature phosphorescent molecular compound based on tetrathioarene derivatives and the fluorescent dye are co-assembled in a solution to form a light harvesting system.

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

[0040] Preferably, the molar concentration ratio of the room temperature phosphorescent molecular compound based on tetrathioarene derivatives and 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 light harvesting system, comprising the following steps:

[0042] The solution containing the room temperature phosphorescent molecular compound based on tetrathioarene derivatives and fluorescent dye is added into a poor solvent, and the light harvesting system is obtained by ultrasonic oscillation.

[0043] As 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 poor solvent is water;

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

[0046] In another aspect, the present invention provides applications of the light harvesting system in the fields of biological imaging, photocatalysis and luminescent materials.

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

[0048] The invention provides an organic room temperature phosphorescent material based on tetrathioarene derivatives. The organic room temperature phosphorescent material uses room temperature phosphorescent molecular compounds based on tetrathioarene derivatives as assembly units, can self-assemble into stable nanoparticles in an aqueous solution, has a long phosphorescence lifetime and a 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 tetrathioarene derivatives in the present invention is simple, the reaction conditions are mild, the reaction yield is high, the post-treatment is convenient, and it is suitable for mass production;

[0051] (2) The room temperature phosphorescent molecular compound based on tetrathioarene derivatives in the present invention can form a stable supramolecular nanoassembly in a variety of organic solvents or aqueous solutions, and can be assembled into supramolecular nanoparticles with good water dispersibility in aqueous phase. The nanoparticles have excellent aggregation-induced room temperature phosphorescence performance, 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 room temperature phosphorescent molecular compound based on tetrathioarene derivatives of the present invention can be constructed in an aqueous phase, and has the advantages of low cost, green environmental protection, and being suitable for application in biological systems;

[0053] (4) The light-harvesting system provided by the present invention can still transfer energy well at a higher donor / acceptor ratio. A unit acceptor can receive energy transferred by hundreds or even thousands of times the amount of the donor, while having high-efficiency energy transfer capabilities, with the best energy transfer efficiency reaching 76%. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 It is a phosphorescence spectrum diagram (a) and a phosphorescence intensity variation trend diagram (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 the present invention.

[0055] Figure 2 It is a phosphorescence spectrum diagram (a) and a phosphorescence intensity variation trend diagram (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 the present invention.

[0056] Figure 3It is a phosphorescence spectrum diagram (a) and a phosphorescence intensity variation trend diagram (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 the present invention.

[0057] Figure 4 It is a phosphorescence spectrum diagram (a) and a phosphorescence intensity variation trend diagram (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 the present invention.

[0058] Figure 5 It is a graph showing the fluorescence spectrum test results 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 graph showing the fluorescence spectrum test results 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 graph showing the fluorescence spectrum test results 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 graph showing the fluorescence spectrum test results of the light harvesting system with different energy donor / acceptor concentration ratios prepared in Example 12 of the present invention. DETAILED DESCRIPTION

[0062] The following embodiments are only some embodiments of the present invention, rather than all embodiments. Therefore, the detailed description in the embodiments of the present invention provided below is not intended to limit the scope of the present invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative work belong to the protection scope of the present invention.

[0063] In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in the industry. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

[0064] Example 1 Tetrahydroxytetrathioarene derivative pTHBT-OH

[0065] This embodiment provides a tetrahydroxytetrathioarene derivative pTHBT-OH, and its preparation process is as follows:

[0066]

[0067] The specific steps are:

[0068] In a 250 mL double-necked bottle equipped with a stirring magnet, 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 in sequence; the mixture was reacted in a metal bath at 45 °C under nitrogen protection for 6 h, 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 red-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 example: 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 Tetrahydroxytetrathioarene derivative mTHBT-OH

[0072] This embodiment provides a tetrahydroxytetrathioarene derivative mTHBT-OH, and its preparation process is as follows:

[0073]

[0074] The specific steps are:

[0075] In a 250 mL double-necked bottle equipped with a stirring magnet, tetrafluoroterephthalonitrile (1.0 g, 5.0 mmol), m-hydroxybenzenethiol (3.78 g, 30.0 mmol), K2CO3 (8.28 g, 60.0 mmol) and ultra-dry DMF (50 mL) were added in sequence; the mixture was reacted in a metal bath at 45 °C under nitrogen protection for 6 h, 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 example: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 tetrathioarene derivatives

[0079] This embodiment provides a room temperature phosphorescent molecular compound pTHBT-Cl based on tetrathioarene derivatives, and its preparation process is as follows:

[0080]

[0081] The specific steps are:

[0082] In a 250 mL double-necked bottle equipped with a stirring magnet, 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 in sequence; the mixture was reacted in a metal bath at 80 °C overnight under nitrogen protection, and the reaction progress was monitored by TLC during the reaction.

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

[0084] The NMR spectrum of pTHBT-Cl prepared in this example: 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] High resolution mass spectrum (HRMS-ESI) of pTHBT-Cl prepared in this example: 60 H 37 N2O4Cl8S4([M+H] + ); calculated molecular ion peak value: m / z 1256.9139, measured value: m / z 1256.9142.

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

[0087] This embodiment provides a room temperature phosphorescent molecular compound pTHBT-Me based on tetrathioarene derivatives, and its preparation process is as follows:

[0088]

[0089] In a 250 mL double-necked bottle equipped with a stirring magnet, 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 in sequence; the mixture was reacted in a metal bath at 80 °C overnight under nitrogen protection, and the reaction progress was monitored by TLC;

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

[0091] The NMR spectrum of pTHBT-Me prepared in this example: 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] High resolution mass spectrum (HRMS-ESI) of pTHBT-Me prepared in this example: 76 H 61N2O 20 S4([M+H] + ); calculated molecular ion peak value: m / z 1449.2695, measured value: m / z 1449.2687.

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

[0094] This embodiment provides a room temperature phosphorescent molecular compound mTHBT-Cl based on tetrathioarene derivatives, and its preparation process is as follows:

[0095]

[0096] In a 250 mL double-necked bottle equipped with a stirring magnet, 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 in sequence; the mixture was reacted in a metal bath at 80 °C overnight 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, which was filtered, and the solid crude product was washed with a large amount of water and dried. The obtained crude product was purified by silica gel flash column chromatography to obtain white solid mTHBT-Cl with a yield of 92%.

[0098] The NMR spectrum of mTHBT-Cl prepared in this example: 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] High resolution mass spectrum (HRMS-ESI) of mTHBT-Cl prepared in this example: 60 H 37 N2O4Cl8S4([M+H] + ); calculated molecular ion peak value: m / z 1256.9139, measured value: m / z 1256.9131.

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

[0101] This embodiment provides a room temperature phosphorescent molecular compound mTHBT-Me based on tetrathioarene derivatives, and its preparation process is as follows:

[0102]

[0103] In a 250 mL double-necked bottle equipped with a stirring magnet, mTHBT-OH (0.63 g, 1.0 mmol), 5-(bromomethyl) dimethyl isophthalate (1.30 g, 4.5 mmol), K2CO3 (0.83 g, 6.0 mmol) and ultra-dry DMF (30 mL) were added in sequence; the mixture was reacted 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, which was filtered, and the solid crude product was washed with a large amount of water and dried. The crude product was purified by silica gel flash column chromatography to obtain white solid mTHBT-Me with a yield of 93%.

[0105] The NMR spectrum of mTHBT-Me prepared in this example: 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] High resolution mass spectrum (HRMS-ESI) of mTHBT-Me prepared in this example: 76 H 61 N2O 20 S4([M+H] + ), molecular ion peak calculated value: m / z 1449.2695, measured value: m / z 1449.2689.

[0107] Example 7

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

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

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

[0111] Tetrahydrofuran 9.5mL, 8.5mL, 7.5mL, 6.5mL, 5.5mL, 5.5mL, 3.5mL, 2.5mL, 1.5mL, and 0.5mL were added to the test tubes labeled 0 to 9, respectively; then deionized water 1.0mL, 2.0mL, 3.0mL, 4.0mL, 5.0mL, 6.0mL, 7.0mL, 8.0mL, 9.0mL, and 9.5mL were added to the test tubes labeled 1 to 10, respectively, to obtain water contents of different concentrations of 5×10 -5 mol / L solution of the compound pTHBT-Cl; the prepared solution was sonicated in an ultrasonic instrument for 60 seconds and then subjected to phosphorescence spectrum testing.

[0112] Figure 1-4 The phosphorescence spectra and phosphorescence enhancement trend diagrams of the compounds pTHBT-Cl, pTHBT-Me, mTHBT-Cl and mTHBT-Me in the dissolved state and the aggregated state are shown respectively. It can be seen from the figures that the compounds pTHBT-Cl, pTHBT-Me, mTHBT-Cl and mTHBT-Me synthesized by the present invention have the characteristics of aggregation-induced phosphorescence, among which the luminescence efficiency of pTHBT-Cl in the aggregated state (tetrahydrofuran-water mixed solution with a water content of 95%, the water content refers to the volume percentage, the same applies below) is higher than that in the dissolved state ( The luminescence efficiency of pTHBT-Me in the aggregated state (a mixed solution of tetrahydrofuran-water with a water content of 95%) was increased by 62 times compared with that in the dissolved state (tetrahydrofuran solution). The luminescence efficiency of mTHBT-Cl in the aggregated state (a mixed solution of tetrahydrofuran-water with a water content of 95%) was increased by 27.6 times compared with that in the dissolved state (tetrahydrofuran solution). The luminescence efficiency of mTHBT-Me in the aggregated state (a mixed solution of tetrahydrofuran-water with a water content of 95%) was increased by 40.6 times compared with that in the dissolved state (tetrahydrofuran solution).

[0113] Table 1 shows the test results of the photophysical properties of the compounds pTHBT-Cl, pTHBT-Me, mTHBT-Cl and mTHBT-Me in the dissolved state (tetrahydrofuran solution) and the aggregated state (tetrahydrofuran-water mixed solution with a water content of 95%). It can be seen from the table that in the dissolved state, the luminescence properties of the compounds pTHBT-Cl, pTHBT-Me, mTHBT-Cl and mTHBT-Me are very poor, among which the phosphorescence lifetime (τ p ) is up to 29ns (mTHBT-Cl), and the phosphorescence quantum yield (Φ PL ) is only 4.29% (mTHBT-Me) at most. However, in the aggregated state, the luminescence efficiency of the four compounds has been qualitatively improved. The phosphorescence quantum yield of the compound mTHBT-Me has increased from 4.29% in the dissolved state to 52.63%, and the phosphorescence lifetime has also increased from 13.4ns to 23.7μs. In addition, the system also shows an obvious positional isomerization effect. The phosphorescence lifetime and phosphorescence quantum yield of the meta-substituted compounds (mTHBT-Cl and mTHBT-Me) are improved to varying degrees 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 example, the above compounds pTHBT-Cl, pTHBT-Me, mTHBT-Cl and mTHBT-Me are prepared into nanoparticles by solvent precipitation method. Taking the compound pTHBT-Cl as an example, the preparation process is as follows:

[0118] Step 1: prepare a concentration of 1×10 -3 5 mL of tetrahydrofuran solution of the compound pTHBT-Cl at mol / L;

[0119] Step 2, take 5 sample bottles with a volume of 5 mL, numbered 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 bottles, and place the sample bottles in a vacuum drying oven to completely evaporate the solvent;

[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 to 5 respectively to dissolve the compound;

[0122] Step 5, take another 5 10mL sample bottles (labeled 6 to 10), add 9.5mL, 9.0mL, 8.5mL, 8.0mL and 7.5mL of deionized water respectively; add a small stirring magnet to bottles 6 to 10 respectively and start stirring; use a disposable syringe to slowly drop the tetrahydrofuran solution of compound pTHBT-Cl in bottles 1 to 5 into the high-speed stirring sample bottles 6 to 10; after the dropwise addition is completed, the sample bottles 6 to 10 are ultrasonicated for 1 minute to obtain uniformly dispersed supramolecular nanoparticles.

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

[0124] Example 9 Preparation of light harvesting system

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

[0126] Step 1: prepare a concentration of 1×10 -3 5 mL of tetrahydrofuran solution of the compound pTHBT-Cl at mol / L;

[0127] Step 2, preparing tetrahydrofuran solutions of copper (II) phthalocyanine with different concentrations;

[0128] Step 3, mixing a trace amount of donor compound pTHBT-Cl solution and a trace amount of copper phthalocyanine (II) acceptor solution according to different final concentration ratios (D / A=50 / 1, 100 / 1, 500 / 1, 1000 / 1, 1500 / 1, 2000 / 1, molar concentration ratio) (sample bottles are numbered 1 to 6), and then placing sample bottles numbered 1 to 6 in a vacuum drying oven to completely evaporate the solvent;

[0129] Step 4, add 1.0 mL of tetrahydrofuran to bottles 1 to 6 respectively using a pipette to dissolve the mixture;

[0130] Step 5, the mixed solution was added dropwise to 4.0 mL of deionized water; ultrasonic oscillation was performed for 5 min, and shaking was continued during the process, and aqueous solutions of nanoassemblies with different energy donor / acceptor concentration ratios (D / A) were obtained by co-assembly, wherein the concentration of the donor compound pTHBT-Cl was 5×10 -5 mo1 / L;

[0131] The fluorescence of the aqueous solution of the nanoassembly prepared in this example was measured using a fluorescence spectrophotometer with an excitation wavelength of 365 nm. The test results are shown in Figure 5The energy transfer efficiency and antenna efficiency were calculated based on the spectrum data, and the results are shown in Table 2. The energy transfer efficiency of the system with the energy donor / acceptor concentration ratio D / A=50 / 1 can reach 70.7%, and the antenna efficiency (Antennaeffect) can reach 40.2.

[0132] Table 2

[0133]

[0134] Example 10 Preparation of light harvesting system

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

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

[0137] Step 2, preparing tetrahydrofuran solutions of copper (II) phthalocyanine with different concentrations;

[0138] Step 3, mixing a trace amount of donor compound pTHBT-Me solution (D) and a trace amount of copper (II) phthalocyanine (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) (numbered 1 to 6), and then placing the sample bottles numbered 1 to 6 in a vacuum drying oven to completely evaporate the solvent;

[0139] Step 4, add 1.0 mL of tetrahydrofuran to bottles 1 to 6 respectively using a pipette to dissolve the mixture;

[0140] Step 5, the mixed solution was added dropwise to 4.0 mL of deionized water; ultrasonic oscillation was performed for 5 min, and shaking was continued during the process, and aqueous solutions of nanoassemblies with different energy donor / acceptor concentration ratios (D / A) were obtained by co-assembly, wherein the concentration of the donor compound pTHBT-Me was 5×10 -5 mo1 / L.

[0141] The fluorescence of the nanoparticle aqueous solution prepared in this example was measured using a fluorescence spectrophotometer with an excitation wavelength of 365 nm. The test results are shown in Figure 6 The energy transfer efficiency and antenna efficiency were calculated based on the spectrum data, and the results are shown in Table 3. As can be seen from Table 3, the energy transfer efficiency of the system with the energy donor / acceptor concentration ratio D / A=50 / 1 can reach 75.1%, and the antenna effect can reach 42.9.

[0142] Table 3

[0143]

[0144] Example 11 Preparation of light harvesting system

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

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

[0147] Step 2, preparing tetrahydrofuran solutions of copper (II) phthalocyanine with different concentrations;

[0148] Step 3, mixing a trace amount of donor compound mTHBT-Cl solution (D) and a trace amount of copper (II) phthalocyanine (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) (numbered 1 to 6), and then placing the sample bottles numbered 1 to 6 in a vacuum drying oven to completely evaporate the solvent;

[0149] Step 4, add 1.0 mL of tetrahydrofuran to bottles 1 to 6 respectively using a pipette to dissolve the mixture;

[0150] Step 5, the mixed solution was added dropwise to 4.0 mL of deionized water; ultrasonic oscillation was performed for 5 min, and shaking was continued during the process, and aqueous solutions of nanoassemblies with different energy donor / acceptor concentration ratios (D / A) were obtained by co-assembly, wherein the concentration of the donor compound mTHBT-Cl was 5×10 -5 mo1 / L.

[0151] The fluorescence of the aqueous solution of the nanoassembly prepared in this example was measured using a fluorescence spectrophotometer with an excitation wavelength of 365 nm. The test results are shown in Figure 7 The energy transfer efficiency and antenna efficiency are calculated based on the spectrum data, and the results are shown in Table 4. As can be seen from Table 4, the energy transfer efficiency of the system with the energy donor / acceptor concentration ratio D / A=50 / 1 can reach 74.4%, and the antenna effect can reach 52.5.

[0152] Table 4

[0153]

[0154] Example 12 Preparation of light harvesting system

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

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

[0157] Step 2, preparing tetrahydrofuran solutions of copper (II) phthalocyanine with different concentrations;

[0158] Step 3, mixing a trace amount of donor compound mTHBT-Me solution (D) and a trace amount of copper (II) phthalocyanine (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) (numbered 1 to 6), and then placing the sample bottles numbered 1 to 6 in a vacuum drying oven to completely evaporate the solvent;

[0159] Step 4, add 1.0 mL of tetrahydrofuran to bottles 1 to 6 respectively using a pipette to dissolve the mixture;

[0160] Step 5, the mixed solution was added dropwise to 4.0 mL of deionized water; ultrasonic oscillation was performed for 5 min, and shaking was continued during the process, and aqueous solutions of nanoassemblies with different energy donor / acceptor concentration ratios (D / A) were obtained by co-assembly, wherein the concentration of the donor compound mTHBT-Me was 5×10 -5 mo1 / L.

[0161] The fluorescence of the nanoparticle aqueous solution prepared in this example was measured using a fluorescence spectrophotometer with an excitation wavelength of 365 nm. The test results are shown in Figure 8 The energy transfer efficiency and antenna efficiency are calculated based on the spectrum data, and the results are shown in Table 5. As can be seen from Table 5, the energy transfer efficiency of the system with the energy donor / acceptor concentration ratio D / A=50 / 1 can reach 76.1%, and the antenna effect can reach 51.4.

[0162] Table 5

[0163]

[0164] As can be seen from the above examples, the room temperature phosphorescent dendrimer compound based on tetrathioarene derivatives prepared in the present invention is not only simple to synthesize and has a high yield, but also can form a nanoassembly with good water dispersibility and stability in an aqueous solution, and the supramolecular nanoparticles constructed by self-assembly have excellent aggregation-induced phosphorescence properties. In addition, the dendrimer phosphorescent molecule can also be used as an excellent light-harvesting system to construct a multi-color (from green to yellow or red) luminescent system.

[0165] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A room temperature phosphorescent molecular compound based on tetrathioarene derivatives, characterized in that: The chemical structure is shown in formula (1) or formula (2): In formula (1) and formula (2), Z1 is R1 and R2 are each independently selected from any one of -COOMe, -F, -Cl, -Br, -CF3, -CH3 and -OCH3.

2. The method for preparing a room temperature phosphorescent molecular compound based on tetrathioarene derivatives according to claim 1, characterized in that: The following steps are involved: A tetrahydroxytetrathioarene derivative and Z1X are reacted in a solvent at 80-100° C. under the action of a base to obtain the room temperature phosphorescent molecular compound based on the tetrathioarene derivative; X is a halogen.

3. The preparation method according to claim 2, characterized in that: The halogen is selected from any one of Cl, Br, and I; Preferably, the structural formula of the tetrahydroxytetrathioarene derivative is as shown in formula (3): In formula (3), the hydroxyl group is substituted at the para or meta position; Preferably, the preparation method of the tetrahydroxytetrathioarene derivative comprises the following steps: reacting p-hydroxythiophenol / m-hydroxythiophenol with tetrafluoroterephthalonitrile in a solvent at 45-60° C. under the action of a base to obtain the tetrahydroxytetrathioarene derivative; Preferably, the base is potassium carbonate and / or cesium carbonate; Preferably, the solvent is N,N-dimethylformamide and / or acetonitrile; Preferably, 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; Preferably, the reaction time is 6 to 10 hours; Preferably, the reaction is carried out in an inert gas atmosphere.

4. The preparation method according to claim 2, characterized in that: The base is potassium carbonate and / or cesium carbonate; Preferably, the ratio of the amount of the tetrahydroxytetrathioarene derivative, the amount of Z1Br and the amount of the base is 1:(4-6):(4-8), more preferably 1:4.5:6; Preferably, the solvent is N,N-dimethylformamide and / or acetonitrile; Preferably, the reaction time is 12 to 24 hours; Preferably, the reaction is carried out in an inert gas atmosphere.

5. An organic room temperature phosphorescent material prepared from the room temperature phosphorescent molecular compound based on tetrathioarene derivatives according to claim 1, characterized in that: The organic room temperature phosphorescent material is a supramolecular nanoparticle formed by self-assembly of the room temperature phosphorescent molecular compound based on tetrathioarene derivatives.

6. The organic room temperature phosphorescent material according to claim 5, characterized in that: The organic room temperature phosphorescent material is a supramolecular nanoparticle formed by self-assembly of the room temperature phosphorescent molecular compound based on tetrathioarene derivatives through a solvent precipitation method; Preferably, the solvent precipitation method comprises the following steps: adding a solution containing the room temperature phosphorescent molecular compound based on tetrathioarene derivatives into a poor solvent, and obtaining the supramolecular nanoparticles by ultrasonic oscillation; Preferably, the solvent in the solution containing the room temperature phosphorescent molecular compound based on tetrathioarene derivatives is at least one selected from tetrahydrofuran, acetonitrile, 1,4-dioxane, dimethyl sulfoxide and N,N-dimethylformamide; Preferably, the poor solvent is water; Preferably, the ultrasonic oscillation time is 1 to 5 minutes.

7. A light harvesting system prepared from the room temperature phosphorescent molecular compound based on tetrathioarene derivatives according to claim 1, characterized in that: The light-harvesting system uses the room temperature phosphorescent molecular compound based on tetrathioarene derivatives as a light-collecting antenna and energy donor, and uses a fluorescent dye as an energy acceptor. The room temperature phosphorescent molecular compound based on tetrathioarene derivatives and the fluorescent dye form a light-harvesting system by co-assembling in a solution.

8. The light harvesting system according to claim 7, characterized in that The fluorescent dye is copper (II) phthalocyanine; Preferably, the molar concentration ratio of the room temperature phosphorescent molecular compound based on tetrathioarene derivatives and the fluorescent dye in the solution is 50 to 2000:

1.

9. The method for preparing the light harvesting system according to claim 7 or 8, characterized in that: The following steps are involved: Adding a solution containing the room temperature phosphorescent molecular compound based on tetrathioarene derivatives and a fluorescent dye into a poor solvent, and obtaining the light harvesting system by ultrasonic oscillation; Preferably, 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; Preferably, the poor solvent is water; Preferably, the ultrasonic oscillation time is 1 to 5 minutes.

10. Use of the light harvesting system according to claim 7 or 8 in the fields of biological imaging, photocatalysis and luminescent materials.

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