Organic phosphorescent material based on dithiopyrrole derivative modified by carbazole derivative as well as preparation method and application of organic phosphorescent material

Abstract

The invention discloses an organic phosphorescent material based on a dithipyrrole derivative modified by a carbazole derivative as well as a preparation method and application of the organic phosphorescent material, belongs to the technical field of luminescent materials, and overcomes the defects that the existing pure organic phosphorescent material is low in luminous efficiency, short in service life and high in environmental sensitivity through molecular structure design. Meanwhile, the problems of toxicity and biological incompatibility of heavy metal materials are avoided. By introducing carbazole and derivative groups thereof, the optical performance and application value of the material are remarkably improved, and the material has a wide application prospect in the fields of biological imaging and phototherapy. Therefore, the method has important innovative significance and practical value in the fields of organic photoelectric materials and biomedical materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to an organic phosphorescent material based on a dithiapyrrole derivative modified by a carbazole derivative, and a preparation method and application thereof. Background Art

[0002] In the research of organic phosphorescent materials, traditional organic phosphorescent materials mainly rely on complexes containing heavy metals (such as platinum, ruthenium, etc.) to achieve efficient phosphorescence emission. These heavy metal complexes can effectively promote intersystem crossing (ISC) due to their strong spin-orbit coupling effect, thereby improving the efficiency of triplet excited state generation and achieving efficient phosphorescence emission. However, the disadvantages of this type of material include high cost, complex synthesis, high toxicity, and potential bio-incompatibility in biomedical applications.

[0003] In recent years, researchers have gradually turned to the development of pure organic phosphorescence (POP) materials that do not contain heavy metals. These materials avoid the toxicity and cost issues of heavy metals while striving to achieve long-life phosphorescence through molecular structure design. However, pure organic phosphorescent materials usually face the problems of low luminescence efficiency, short phosphorescence lifetime, and easy quenching by oxygen and heat at room temperature. These problems are mainly caused by the following reasons: (1) Weak spin-orbit coupling: In pure organic materials, due to the lack of heavy metal elements, the spin-orbit coupling effect is weak, resulting in low intersystem crossing (ISC) efficiency, thereby limiting the generation of triplet excited states and phosphorescence emission. (2) Poor stability of triplet excited states: The triplet excited states of pure organic materials are usually unstable and easily affected by intramolecular rotation or vibration, resulting in non-radiative transitions, thereby reducing phosphorescence efficiency and lifetime. (3) High environmental sensitivity: Pure organic phosphorescent materials are easily affected by environmental factors (such as oxygen, humidity, temperature, etc.) at room temperature, resulting in phosphorescence quenching. Therefore, it is difficult for such materials to maintain long-term phosphorescence emission in air or biological environments.

[0004] Heavy metal complex phosphorescent materials (such as platinum complexes) are usually composed of complexes containing heavy metal elements (such as platinum, ruthenium, iridium, etc.), and achieve efficient phosphorescence emission through the spin-orbit coupling effect. These materials have the following disadvantages: (1) High cost: Heavy metal elements are scarce and expensive, which increases the cost of materials. (2) Toxicity issues: Heavy metal elements may have potential biological toxicity, which limits their application in the biomedical field. (3) Complex synthesis: The synthesis of heavy metal complexes usually involves complex chemical reaction steps and high process difficulty. (4) Environmental impact: It may cause environmental or biocompatibility problems in organisms, affecting their application in biological imaging or phototherapy.

[0005] Pure organic phosphorescent materials attempt to improve their optical properties through delayed fluorescence (such as TADF) or phosphorescence emission through molecular design, such as by introducing structures such as alkynylbenzene (such as alkynylbenzene compounds). These materials have the following disadvantages: (1) Low luminescence efficiency: Due to the weak spin-orbit coupling effect, the efficiency of triplet excited state generation is low, and the optical performance is not as good as that of heavy metal complex materials. (2) Short phosphorescence lifetime: The triplet excited state in the material is not stable enough and is easily quenched by heat or intramolecular motion. (3) Environmental sensitivity: These materials are easily quenched by oxygen in the air or in organisms, resulting in a significant decrease in the intensity and lifetime of phosphorescence.

[0006] In summary, although the heavy metal complexes in the prior art have high luminescence efficiency, they have problems such as high cost, toxicity and poor biocompatibility in biomedical applications. Although pure organic phosphorescent materials avoid the toxicity problem of heavy metals, they still have major deficiencies in luminescence efficiency, life span and environmental stability. These problems are mainly due to the fact that the existing materials cannot take into account both efficient phosphorescent emission and environmental stability in structural design, and therefore are limited in practical applications. Summary of the invention

[0007] In view of the shortcomings of heavy metal complexes and pure organic phosphorescent materials in the prior art, the purpose of the present invention is to design and develop a new type of organic phosphorescent material, which has a room temperature phosphorescence effect and can simultaneously take into account efficient phosphorescent emission, long life and good environmental stability.

[0008] To achieve the above object, the present invention provides the following technical solutions:

[0009] One of the technical solutions of the present invention:

[0010] An organic phosphorescent material based on a dithiapyrrole derivative modified by a carbazole derivative, the structural formula of which is shown in Formula 1-2:

[0011]

[0012] Among them, R is a straight-chain alkyl group, a branched-chain alkyl group, a cyclic alkyl group or a benzene ring, and R contains or does not contain a halogen substituent; R1 is a straight-chain alkyl group, a branched-chain alkyl group, a cyclic alkyl group, an alkoxy group, an aryl group or hydrogen; X1 is sulfur (S), oxygen (O) or selenium; X2 is oxygen (O), sulfur (S) or selenium; Ar1 ​​is an aromatic ring; Ar2 is hydrogen or a heteroaromatic ring.

[0013] Further, R is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or a benzene ring, and R contains or does not contain a halogen substituent; R1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, alkoxy, aryl or hydrogen; X1 is sulfur (S), oxygen (O) or selenium; X2 is oxygen (O), sulfur (S) or selenium; Ar1 ​​is a benzene ring, pyridine, furan or thiophene; Ar2 is hydrogen, carbazole, indole, benzopyrrole, quinoline or quinazoline.

[0014] In the present invention, R and R1 may be the same or different, and when R1 is an alkoxy or aryl group, the non-polar nature of the alkyl chain enables it to have a stronger solvation effect with molecules in non-polar or low-polar solvents, making the overall molecule easier to be wrapped and dissolved by the solvent. The introduction of an aromatic ring can expand the π-conjugated system of the molecule, reduce the HOMO-LUMO energy level difference of the molecule, and make electronic transitions (such as π→π* transitions) more likely to occur, thereby improving luminous efficiency and red-shifted emission wavelength. X1 and X2 represent sulfur, oxygen and selenium, respectively. When the two are isovalent heteroatoms such as selenium, the electronic push-pull effect caused by different subversive properties can adjust the optical properties of the molecule. Ar1 is preferably a benzene ring, and Ar1 can also be other aromatic rings with 6π electrons (such as pyridine, furan, thiophene), which can improve the optical properties of organic phosphorescent materials. Ar2 is preferably carbazole. When it is other heterocyclic structures (such as indole, benzopyrrole, quinoline, quinazoline, etc.), the aromatic ring can regulate phosphorescence or delayed fluorescence properties by affecting the excited state characteristics of the molecule (such as the ratio of singlet to triplet or splitting energy). The rigid skeleton of the aromatic ring can reduce the non-radiative relaxation process of the molecule in the excited state (such as molecular vibration and rotation dissipation energy), thereby increasing the luminescence quantum yield. The electronic properties and optical properties of the compound can be further improved.

[0015] Furthermore, the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative is selected from the following structures:

[0016]

[0017] The present invention overcomes the shortcomings of low luminous efficiency, short life and high environmental sensitivity of existing pure organic phosphorescent materials through molecular structure design, while avoiding the toxicity and biocompatibility problems of heavy metal materials. The present invention significantly improves the optical properties and application value of the material by introducing carbazole and its derivative groups, especially in the fields of biological imaging and phototherapy. Therefore, the present invention has important innovative significance and practical value in the fields of organic optoelectronic materials and biomedical materials.

[0018] The organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative can show a phosphorescent lifetime of up to 7.84 ms under the condition of 77K.

[0019] The second technical solution of the present invention:

[0020] The present invention also provides a method for preparing the above-mentioned organic phosphorescent material based on dithiapyrrole derivatives modified by carbazole derivatives, selecting a compound raw material containing X1 and X2 heteroatoms, introducing a carbonyl group or a sulfonyl group into the aromatic ring skeleton through an acyl chlorination reaction, connecting the Ar1 and Ar2 groups to the core molecular structure through a Suzuki, Stille or Heck coupling reaction, and obtaining the organic phosphorescent material based on dithiapyrrole derivatives modified by carbazole derivatives after structural modification.

[0021] The core skeleton of the organic phosphorescent material based on dithiapyrrole derivatives modified by carbazole derivatives is dithiapyrrole (DTP), which is connected with the carbazole derivatives through Buchwald coupling reaction. The carbazole group includes carbazole (Cz), benz[g]indole (g) or benz[f]indole (f). The carbazole group is covalently connected to a specific site of the DTP core through a carbon-carbon bond or a carbon-nitrogen bond to enhance the stability of the molecular structure and the π-π stacking effect, thereby improving the photophysical properties.

[0022] In the above-mentioned method for preparing an organic phosphorescent material based on a dithiapyrrole derivative modified with a carbazole derivative, the palladium catalyst used includes tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) and a suitable ligand (such as tri-tert-butylphosphine tetrafluoroborate (( t Bu)3PHBF4)).

[0023] In the above-mentioned method for preparing the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative, the reaction temperature is controlled at 80-120° C. and the reaction time is 12-24 hours.

[0024] In the above-mentioned method for preparing the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative, the reaction is carried out under the protection of nitrogen.

[0025] In the above-mentioned method for preparing the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative, after the reaction is completed, it also includes the step of purifying the product by means of column chromatography, recrystallization and single crystal growth.

[0026] The third technical solution of the present invention:

[0027] The present invention provides a luminescent film, which is doped with the above-mentioned organic phosphorescent material based on dithiapyrrole derivatives modified by carbazole derivatives, the matrix is ​​polymethyl methacrylate (PMMA), and the doping concentration of the organic phosphorescent material based on dithiapyrrole derivatives modified by carbazole derivatives is 0.01-50wt.% (that is, the addition amount of the organic phosphorescent material based on dithiapyrrole derivatives modified by carbazole derivatives relative to the matrix is ​​0.01-50wt.%).

[0028] By adjusting the doping concentration of the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative, the molecular distance and the interaction strength can be regulated, and then the luminescent properties (such as the red shift of the spectrum and the phosphorescence lifetime) can be adjusted. The distance and interaction between the molecules of carbazole and its derivatives in the film can be regulated by the doping concentration, thereby controlling the red shift of the spectrum and the extension of the phosphorescence lifetime, so that the film exhibits excellent optical properties at both room temperature and low temperature (for example, the luminescent film of the present invention exhibits excellent phosphorescence properties under the conditions of 298K and 77K).

[0029] The luminescent film prepared by doping the organic phosphorescent material based on dithiapyrrole derivatives modified by carbazole derivatives in PMMA exhibited a phosphorescence lifetime as long as 11.93 ms at room temperature.

[0030] The fourth technical solution of the present invention:

[0031] The present invention provides another luminescent film, which is doped with the above-mentioned organic phosphorescent material based on dithiapyrrole derivatives modified by carbazole derivatives, the matrix is ​​4-bromobenzophenone (BP-Br), and the doping concentration of the organic phosphorescent material based on dithiapyrrole derivatives modified by carbazole derivatives is 0.01-50wt.% (that is, the addition amount of the organic phosphorescent material based on dithiapyrrole derivatives modified by carbazole derivatives relative to the matrix is ​​0.01-50wt.%).

[0032] Doping organic phosphorescent materials based on dithiapyrrole derivatives modified with carbazole derivatives into BP-Br can increase the triplet exciton concentration and enhance the delayed fluorescence efficiency, thereby improving the phosphorescence lifetime and delayed fluorescence efficiency.

[0033] The organic phosphorescent material based on dithiapyrrole derivatives modified with carbazole derivatives was doped into the luminescent film prepared in BP-Br and exhibited a phosphorescence lifetime of up to 9.59 ms at room temperature.

[0034] The fifth technical solution of the present invention:

[0035] The present invention also provides the use of the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative in the preparation of an optoelectronic device. The optoelectronic device includes an OLED display device or a light-emitting diode, and may also include other optoelectronic materials.

[0036] Technical solution six of the present invention:

[0037] The present invention also provides the use of the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative in in vivo imaging for non-therapeutic purposes.

[0038] The organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative has long life and high-efficiency near-infrared luminescence characteristics, and thus can be used for in vivo imaging for non-therapeutic purposes.

[0039] Technical solution seven of the present invention:

[0040] The present invention also provides the use of the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative in preparing a sensor. For example, the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative of the present invention can be used to prepare an optical sensor for detecting changes in a specific chemical environment.

[0041] Compared with the prior art, the present invention has the following advantages and technical effects:

[0042] The present invention introduces different carbazoles and their derivatives (carbazole (Cz), benzo[g]indole and benzo[f]indole) into the dithiopyrrole (DTP) skeleton through the Buchwald reaction (Suzuki, Stille or Heck coupling reaction), significantly improving the electron donor performance of the molecule, and enhancing the efficiency of intermolecular charge transfer and intersystem crossing (ISC). The DTP core skeleton retains its high electron density and rigid π-conjugated plane, and different molecular structures are formed by the introduction of different carbazoles and their derivatives to study their performance in the aggregated state. The introduction of carbazole and its derivative groups can enhance the non-covalent interactions between molecules, such as π-π stacking, CH···π interactions, etc., thereby improving the efficiency and life of phosphorescent emission.

[0043] The invention significantly improves the phosphorescence emission efficiency by introducing carbazole and its derivative groups and optimizing the film structure, thus overcoming the defect of low luminescence efficiency of existing pure organic phosphorescent materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0045] Figure 1 Schematic diagram of the synthesis process of the organic phosphorescent material of the present invention, X is a halogen atom (such as fluorine, chlorine, bromine, iodine);

[0046] Figure 2The molecular structures of DTP-Cz, DTP-g, and DTP-f;

[0047] Figure 3 The luminescence effect of 1wt% DTP-g doped PMMA film under different conditions;

[0048] Figure 4 For DTP 1 H NMR (500MHz, CDCl3) graph;

[0049] Figure 5 The MS (TOF MS ES+) pattern of DTP (m / z calculated value: 263.0802; experimental value: 263.0802);

[0050] Figure 6 For DTP-Br 1 H NMR (500MHz, CDCl3) graph;

[0051] Figure 7 For DTP-Br 13 C NMR (126MHz, CDCl3) graph;

[0052] Figure 8 The MS (TOF MS AP+) pattern of DTP-Br (m / z calculated value: 629.9596; experimental value: 629.9594);

[0053] Fig. 9 For DTP-Cz 1 H NMR (500 MHz, CD2Cl2) graph;

[0054] Fig.10 For DTP-Cz 13 C NMR (126 MHz, CD2Cl2) graph;

[0055] Fig.11 The MS (TOF MS AP+) pattern of DTP-Cz (m / z calculated value: 802.2562; experimental value: 802.2558);

[0056] Fig.12 The MS (TOF MS AP+) pattern of DTP-g (m / z calculated value: 802.2562; experimental value: 802.2571);

[0057] Fig.13 The MS (TOF MS AP+) pattern of DTP-f (m / z calculated value: 802.2562; experimental value: 802.2563);

[0058] Fig.14For DTP-Ph core 1 H NMR (400 MHz, CDCl3) graph;

[0059] Fig.15 For DTP-Ph core 13 C NMR (100 MHz, CDCl3) graph;

[0060] Fig.16 For DTP-Ph 1 H NMR (400 MHz, CDCl3) graph;

[0061] Fig.17 For DTP-Ph 13 C NMR (100 MHz, CDCl3) graph;

[0062] Fig.18 HRMS m / z pattern of DTP-Ph (m / z calculated value: 463.0701; experimental value: 463.0698.);

[0063] Fig.19 For DTT 1 H NMR (400 MHz, CDCl3) graph;

[0064] Fig. 20 For DTT 13 C NMR (100 MHz, CDCl3) graph;

[0065] Fig.21 128.32.HRMS m / z pattern of DTT (m / z calculated: 403.9999; found: 404.0009);

[0066] Fig. 22 is the photoluminescence quantum yield (PLQY) of DTP derivatives (i.e., DTP-Cz, DTP-g, and DTP-f) in different states at room temperature, wherein the black dots represent “black-MeTHF”, indicating the fluorescence quantum yield of DTP derivatives in 2-methyltetrahydrofuran; the blue dots represent “blue-Crystal”, indicating the fluorescence quantum yield of DTP derivatives in the crystal state; the pink dots represent “pink-PMMA”, indicating the fluorescence quantum yield of DTP derivatives in the thin film state doped in PMMA; the brown dots represent “brown-BP-Br”, indicating the fluorescence quantum yield of DTP derivatives in the solid state doped in BP-Br;

[0067] Fig.23is the solvation effect absorption spectrum of DTP-Cz, where “Tolu” represents toluene, “EA” represents ethyl acetate, “THF” represents tetrahydrofuran, “DMF” represents dimethylformamide, and “DMSO” represents dimethyl sulfoxide;

[0068] Fig.24 is the solvation effect emission spectrum of DTP-Cz, where “Tolu” represents toluene, “EA” represents ethyl acetate, “THF” represents tetrahydrofuran, “DMF” represents dimethylformamide, “DCM” represents dichloromethane, “DMSO” represents dimethyl sulfoxide, and “EtOH” represents anhydrous ethanol;

[0069] Fig.25 is the AIE curve emission spectrum of DTP-Cz, f w (vol%) represents the volume fraction of DTP-Cz in water, for example, "10" represents the volume fraction of DTP-Cz in water is 10%;

[0070] Fig.26 AIE curve emission spectrum of DTP-Cz - dot-line diagram;

[0071] Fig. 27 is the luminescence concentration dependence-emission spectrum of DTP-Cz doped PMMA, wherein "1:100" means that the DTP-Cz doping concentration is 1wt.%, "10:100" means that the DTP-Cz doping concentration is 10wt.%, and "100:100" means that the DTP-Cz doping concentration is 50wt.%;

[0072] Fig.28 The emission concentration dependence of DTP-Cz doped BP-Br - emission spectrum, where "0.1%" means that the DTP-Cz doping concentration is 0.1wt.%, and "1%" means that the DTP-Cz doping concentration is 1wt.%;

[0073] Fig.29 is the normalized steady-state PL spectra of DTP-Cz, DTP-g, and DTP-f at room temperature;

[0074] Fig.30 is the normalized phosphorescence spectra of DTP-Cz, DTP-g, and DTP-f at 77K;

[0075] Fig.31 Time-resolved decay curves of DTP-Cz, DTP-g, and DTP-f at 77K with a monitoring wavelength of 690nm;

[0076] Fig.32 is the normalized phosphorescence PL spectrum of DTP-g-doped PMMA film at room temperature;

[0077] Fig.33 The time-resolved decay curve of DTP-Cz doped PMMA film at room temperature at a wavelength of 690nm;

[0078] Fig.34 is the normalized PL spectrum of DTP-g doped BP-Br at room temperature;

[0079] Fig.35 The time-resolved decay curve of DTP derivative-doped BP-Br monitored at room temperature at a wavelength of 650 nm. DETAILED DESCRIPTION

[0080] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0081] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0082] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0083] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0084] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0085] Unless otherwise specified, the room temperature in the embodiments of the present invention is 25±2° C.; “%” in the embodiments of the present invention and the accompanying drawings refers to mass percentage.

[0086] All raw materials used in the examples of the present invention were purchased from commercial sources. For example, 3,3'-dibromo-2,2'-bithiophene, n-hexylamine, tris(dibenzylideneacetone)dipalladium (Pd2(dba)3), racemic 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (rac-BINAP) were purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; sodium tert-butoxide (NaO t Bu) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; tri-tert-butylphosphine tetrafluoroborate (( t Bu)3PHBF4) was purchased from Shanghai Bid Pharmaceutical Technology Co., Ltd.; 9H-carbazole (CAS No.: 86-74-8) was purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd.; 1H-benzo[g]indole (1H-benzo[g]indole, CAS No.: 233-34-1) was purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd.; 1H-benzo[f]indole (1H-benzo[f]indole, CAS No.: 268-58-6) was purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd.; DTT core (Dithieno[2,3-b:3′,2′-d]thiophene, CAS No.: 236-63-5) was purchased from Shanghai Bid Pharmaceutical Technology Co., Ltd.

[0087] The present invention introduces different carbazoles and their derivatives (carbazole (Cz), benzo[g]indole (g) and benzo[f]indole (f)) into a dithiopyrrole (DTP) skeleton through the Buchwald reaction. The introduction of these derivatives significantly improves the electron donor performance of the molecule, and enhances the efficiency of intermolecular charge transfer and intersystem crossing (ISC). In terms of chemical structure, the DTP core skeleton retains its high electron density and rigid π-conjugated plane. By introducing different carbazoles and their derivatives, different molecular structures are formed to study their performance in an aggregated state. The introduction of carbazole and its derivative groups can enhance non-covalent interactions between molecules, such as π-π stacking, CH···π interactions, etc., thereby improving the efficiency and life of phosphorescent emission.

[0088] Figure 1 Schematic diagram of the synthesis process of the organic phosphorescent material of the present invention, X is a halogen atom (such as fluorine, chlorine, bromine, iodine); Figure 2 The molecular structures of DTP-Cz, DTP-g and DTP-f.

[0089] Figure 3 The luminescence effect of 1wt% DTP-g doped PMMA film under different conditions. DTP and its derivatives are evenly distributed in the PMMA matrix to form a stable film structure. The higher the doping concentration, the stronger the intermolecular interaction, thus showing different optical behaviors, such as red shift and enhanced phosphorescence lifetime.

[0090] The crystal structure of DTP and its derivatives, intermolecular π-π stacking, halogen bonds, and various weak interactions (such as N···H, S···H, CH···π, and S···π interactions) can be observed through X-ray crystallography. These non-covalent interactions can stabilize the intermolecular stacking structure and are significantly enhanced at low temperatures, reducing the non-radiative relaxation of molecules, thereby extending the phosphorescence lifetime of organic phosphorescent materials. Among them, the N···H interaction is due to the weak electrostatic attraction between the lone pair of electrons of the nitrogen atom and the hydrogen atom; the S···H interaction comes from the polarization of the sulfur atom and the weak attraction of the hydrogen atom; the CH···π interaction is the weak electrostatic interaction between the hydrogen atom and the π electron cloud of the aromatic ring; the S···π interaction is the mutual attraction between the sulfur atom and the π electrons of the aromatic ring, and the π-π stacking plays a stabilizing role in the molecules through the overlap of the π electron clouds between the aromatic rings.

[0091] In the present invention, the principle of improving the phosphorescence emission efficiency is as follows: the present invention forms a stable triplet excited state and reduces the probability of non-radiative transition by introducing carbazole and its derivatives into the DTP skeleton. The strong electron donor performance of carbazole and its derivative groups enhances the charge transfer efficiency between molecules and promotes the intersystem crossing (ISC) process, thereby increasing the generation rate of the triplet excited state. This improvement makes up for the defect of weak spin-orbit coupling effect of traditional pure organic phosphorescent materials.

[0092] In the present invention, the principle of extending the phosphorescence lifetime is as follows: the present invention achieves effective regulation of phosphorescence emission by adjusting the doping concentration in the film and controlling the interaction strength between molecules, thereby significantly extending the luminescence lifetime of the material. In the PMMA matrix, carbazole and its derivatives stabilize the molecular structure through non-covalent interactions such as π-π stacking and CH···π interaction, reduce the non-radiative energy loss caused by intramolecular rotation and vibration, and thus extend the phosphorescence lifetime.

[0093] The present invention uses a PMMA matrix to wrap DTP-carbazole derivative molecules to form a stable film structure, thereby improving the environmental stability of the material, especially showing higher durability and reliability in practical applications such as biological imaging and phototherapy. The film structure formed by carbazole and its derivatives in the PMMA matrix has a strong intermolecular interaction, can effectively isolate oxygen and moisture in the environment, and reduce the occurrence of quenching reactions. This improvement makes the material have higher light stability and durability in the air or biological environment.

[0094] It should be pointed out that the matters not described in detail in the present invention are conventional operating means in the art and are not the focus of the present invention.

[0095] The technical solution of the present invention is further illustrated by the following embodiments.

[0096] Example 1 Preparation of DTP-Cz

[0097] In a dry 100 mL two-necked flask, 3,3'-dibromo-2,2'-bithiophene (2.50 g, 7.71 mmol), n-hexylamine (0.78 g, 7.71 mmol), Pd2(dba)3 (353.0 mg, 0.39 mmol), rac-BINAP (961.4 mg, 1.54 mmol) and NaO were added. t Bu (1.85 g, 1.28 mmol) was dissolved in 50 mL of toluene. The mixture was heated to 110 ° C and refluxed for 24 hours under a nitrogen atmosphere. After the reaction was completed, it was cooled to room temperature and the reaction product was washed with saturated brine. The organic phase was dried over anhydrous Na2SO4, and after the solvent was concentrated, the crude product was purified by column chromatography (CH2Cl2 / petroleum ether, volume ratio 1 / 9) to obtain 1.45 g of a white solid product 4-hexyl-4H-dithieno[3,2-b:2',3'-d]pyrrole (DTP, C 14 H 17 NS2), DTP 1 H NMR (500MHz, CDCl3) Figure 4 As shown, δ7.15 (d, J = 5.2 Hz, 2H), 7.03 (d, J = 5.2 Hz, 2H), 4.20 (t, J = 7.0 Hz, 2H), 1.88 (p, J = 7.1 Hz, 2H), 1.36-1.29 (m, 6H), 0.91 (t, 3H). MS of DTP (TOF MS ES+) (m / z calculated value: 263.0802; experimental value: 263.0802) is as follows Figure 5 As shown. The yield of DTP is 71.4%, and the synthetic route of DTP is as follows:

[0098]

[0099] In a dry 100 mL Schlenk tube, DTP (3.00 g, 11.39 mmol) was dissolved in 20 mL of dichloromethane (CH2Cl2, DCM) under nitrogen atmosphere to obtain a DTP solution;

[0100] In a dry 100mL two-necked flask, anhydrous aluminum chloride (AlCl3) (9.11g, 68.33mmol) and 4-bromobenzoyl chloride (10.00g, 45.56mmol) were added, dissolved in 40mL DCM, and stirred for 15 minutes under nitrogen protection at 0°C. Subsequently, the DTP solution was slowly added to the two-necked flask in 15 minutes by dropwise addition, and the mixture was refluxed at 40°C for 72 hours. After the reaction was completed, it was cooled to room temperature and the reaction product was quenched with ice water. The organic phase was dried over anhydrous Na2SO4, and after concentrating the solvent, the crude product was purified by column chromatography (CH2Cl2 / petroleum ether, volume ratio 1 / 1) to obtain 3.22g of red solid product DTP-Br (C 28 H 23 Br2NO2S2H, yield: 44.9%). 1 H NMR (500MHz, CDCl3) Figure 6 As shown, δ7.77 (d, J = 8.5 Hz, 4H), 7.69 (d, J = 8.4 Hz, 4H), 7.55 (s, 2H), 4.21 (t, J = 7.1 Hz, 2H), 1.84 (q, J = 7.1 Hz, 2H), 1.33-1.24 (m, 6H), 0.85 (t, 3H). 13 C NMR (126MHz, CDCl3) Figure 7 As shown, δ 187.80, 147.20, 143.07, 137.84, 137.60, 130.52, 122.03, 117.76, 99.63, 47.54, 31.34, 30.31, 26.71, 22.54, 14.02. MS (TOF MS AP+) of DTP-Br (m / z calculated value: 629.9596; experimental value: 629.9594) is shown in Figure 8 , the synthetic route of DTP-Br is as follows:

[0101]

[0102] In a dry 100 mL Schlenk tube, DTP-Br (1.00 g, 1.59 mmol), 9H-carbazole (0.79 g, 4.77 mmol), Pd2(dba)3 (72.7 mg, 79.44 μmol), ( t Bu)3PHBF4 (91.2mg, 317.75μmol) and NaO tBu (458.1 mg, 4.77 mmol) was dissolved in 20 mL of toluene and refluxed at 110° C. for 48 hours under nitrogen atmosphere. After the reaction was completed, the mixture was cooled to room temperature and the reaction product was washed with saturated brine. The organic layer was extracted three times with ethyl acetate, and the organic phases were combined and dried over anhydrous Na2SO4. After removing the solvent, the crude product was purified by column chromatography (CH2Cl2 / petroleum ether, volume ratio 1 / 1) to obtain 0.57 g of orange solid DTP-Cz (C 52 H 39 N3O2S2H, yield: 44.9%). 1 H NMR (500MHz, CD2Cl2) Fig. 9 As shown, δ8.18(d,J=5.1Hz,8H),7.82(d,J=8.1Hz,4H),7.76(s,2H),7.59(d,J=8.2Hz,4H),7.48(t,J=7.7Hz,4H), 7.35(t,J=7.4Hz,4H),4.33(t,J=7.0Hz,2H),1.93(p,2H),1.36-1.26(m,6H),0.84(t,J=6.9Hz,3H).DTP-Cz 13 CNMR (126MHz, CD2Cl2) Fig.10 As shown, δ187.49, 147.37, 143.48, 141.33, 140.36, 136.76, 130.85, 126.59, 126.21, 123.74, 121.58, 120.55, 120.39, 118.22, 109.79, 47.56, 31.34, 30.30, 26.64, 22.51, 13.77. The MS (TOF MS AP+) map of DTP-Cz (m / z calculated value: 802.2562; experimental value: 802.2558) is as shown Fig.11 As shown, the synthetic route of DTP-Cz is as follows:

[0103]

[0104] The molecules in the DTP-Cz crystal cell prepared in Example 1 are in the form of dimers and there are weak intermolecular interactions. Based on this, the luminescence properties can be adjusted by doping PMMA with different concentrations of DTP derivative molecules. The intermolecular forces can effectively limit the range of intramolecular motion and thus improve the luminescence efficiency, which is beneficial to the formation of phosphorescence.

[0105] Example 2 Preparation of DTP-g

[0106] In a dry 100 mL Schlenk reaction tube, DTP-Br (1.00 g, 1.59 mmol), 1H-benzo[g]indole (0.79 g, 4.77 mmol), Pd2(dba)3 (72.7 mg, 79.44 μmol), ( t Bu)3PHBF4 (91.2mg, 317.75μmol) and NaO t Bu (458.1 mg, 4.77 mmol) was then dissolved in 20 mL of toluene under a nitrogen atmosphere and refluxed at 110 ° C for 48 hours. After the reaction was completed, it was cooled to room temperature and the reaction product was washed with saturated brine. Subsequently, the organic layer was extracted three times with ethyl acetate, and the organic layers were combined and dried over anhydrous Na2SO4. After removing the solvent, the crude product was purified by column chromatography (CH2Cl2 / petroleum ether, 1:1, v / v) to obtain 0.29 g of the target product DTP-g (C 52 H 39 N3O2S2H), yellow-green solid (yield 22.8%). 1 H NMR (500 MHz, CD2Cl2) data are as follows: δ 8.12 (d, J = 8.0 Hz, 4H), 7.95 (d, J = 8.1 Hz, 2H), 7.78 (d, J = 8.5 Hz, 2H), 7.74 (s, 2H), 7.72 (d, J = 8.0 Hz, 4H), 7.61 (d, J = 8.6 Hz, 2H), 7.58 (d, J = 8.5 Hz, 2H), 7.3 9(t,J=7.5Hz,2H), 7.31(d,J=3.1Hz,2H), 7.27(t,J=7.7Hz,2H), 6.86(d,J=3.1Hz,2H), 4.3 2(t,J=7.1Hz,2H), 1.92(p,J=7.1Hz,2H), 1.35-1.25(m,6H), 0.82(t,J=7.0Hz,3H).DTP-g 13 C NMR (126 MHz, CD2Cl2) data are as follows: δ 187.47, 147.39, 145.19, 143.40, 137.66, 131.55, 130.44, 130.02, 129.38, 129.09, 127.02, 126.59, 124.96, 123.76, 122.34, 122.15, 121.68, 121.14, 120.82, 118.20, 105.04, 47.58, 31.33, 30.28, 26.67, 22.51, 13.73. The mass spectrum (TOF MS AP+) of DTP-g (m / z calculated value: 802.2562; experimental value: 802.2571) is as follows: Fig.12As shown, the synthetic route of DTP-g is as follows:

[0107]

[0108] Example 3 Preparation of DTP-f

[0109] In a dry 100 mL Schlenk reaction tube, DTP-Br (1.00 g, 1.59 mmol), 1H-benzo[f]indole (0.79 g, 4.77 mmol), Pd2(dba)3 (72.7 mg, 79.44 μmol), ( t Bu)3PHBF4 (91.2mg, 317.75μmol) and NaO t Bu (458.1 mg, 4.77 mmol) was then dissolved in 20 mL of toluene under a nitrogen atmosphere. The reaction mixture was refluxed at 110°C for 48 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and washed with saturated brine. Subsequently, the organic layer was extracted three times with ethyl acetate, and the organic layers were combined and dried over anhydrous Na2SO4. After removing the solvent, the crude product was purified by column chromatography (CH2Cl2 / petroleum ether, 1:1, v / v) to obtain 0.30 g of the target product DTP-f (C 52 H 39 N3O2S2H), a red solid (yield 23.6%). 1 H NMR (500MHz, CD2Cl2) is as follows: δ8.21(d,J=9.0Hz,4H), 8.15(d,J=8.5Hz,4H), 7.98( d,J=7.0Hz,2H), 7.93(d,J=7.2Hz,2H), 7.85(d,J=8.5Hz,4H), 7.74(s,2H), 7. 70(d,J=3.5Hz,2H), 7.44-7.37(m,4H), 6.92(d,J=4.4Hz,2H), 4.33(t,J=7.1H z, 2H), 1.92 (p, J = 7.0Hz, 2H), 1.36-1.25 (m, 6H), 0.85 (t, J = 7.0Hz, 3H). DTP-f 13CNMR (126 MHz, CD2Cl2) is as follows: δ 187.20, 147.29, 143.49, 143.34, 135.82, 135.35, 131.28, 131.08, 130.92, 130.67, 129.29, 128.04, 127.64, 124.35, 123.42, 123.04, 121.43, 118.83, 118.04, 106.28, 104.60, 47.54, 31.37, 30.31, 26.69, 22.55, 13.80. Fig.13 The MS (TOFMS AP+) image of DTP-f (m / z calculated value: 802.2562; experimental value: 802.2563) is shown. The synthetic route of DTP-f is as follows:

[0110]

[0111] Example 4 Preparation of DTP-Ph

[0112] In a dry 100 mL two-necked flask, 3,3'-dibromo-2,2'-bithiophene (3.0 g, 9.26 mmol), aniline (0.86 g, 9.26 mmol), Pd2(dba)3 (421.2 mg, 0.46 mmol), BINAP (1.15 g, 1.85 mmol) and NaO were added. t Bu (2.22 g, 23.15 mmol) was dissolved in 50 mL of toluene. The mixture was reacted at 110 ° C under nitrogen protection for 24 hours. After the reaction was completed, it was cooled to room temperature and the product was washed with saturated brine. The organic layer was dried over anhydrous Na2SO4, and after evaporating the solvent, the crude product was purified by column chromatography (CH2Cl2 / n-hexane, volume ratio 1 / 10) to obtain 1.92 g of white solid 4-phenyl-4H-dithieno[3,2-b:2',3'-d]pyrrole (DTP-Ph core (DTP-Ph core)), with a yield of 81.4%. DTP-Ph core 1 H NMR (400MHz, CDCl3) Fig.14 As shown, δ7.59 (d, 2H), 7.52 (t, 2H), 7.32 (t, 1H), 7.17 (s, 4H). 13 CNMR (100MHz,CDCl3) Fig.15 As shown, 143.97, 139.89, 129.77, 126.00, 123.45, 122.62, 116.93, 112.253. The synthetic route of DTP-Ph core is as follows:

[0113]

[0114] In a dry 100mL Schlenk tube, DTP-Ph core (0.40g, 1.57mmol) was dissolved in 20mL DCM and operated under nitrogen protection. In another dry 100mL two-necked flask, anhydrous aluminum chloride (1.04g, 7.83mmol) and benzoyl chloride (0.66g, 4.71mmol) were added, dissolved in 20mL DCM, and stirred for 15 minutes under nitrogen protection at 0°C. Subsequently, the solution of DTP-Ph core was slowly added dropwise to the flask over 15 minutes, and the mixture was heated at 40°C for 48 hours. After the reaction was completed, the mixture was cooled to room temperature and quenched with ice water. The organic layer of the reaction product was dried over anhydrous Na2SO4. After evaporation of the solvent, the crude product was purified by column chromatography (DCM / n-hexane, volume ratio 1 / 1) to obtain 243 mg of a yellow solid (4-phenyl-4H-dithieno[3,2-b:2',3'-d]pyrrole-2,6-diyl)bis(benzophenone) (DTP-Ph, C 28 H 17 NO2S2) (yield: 33.4%). DTP-Ph 1 H NMR (400MHz, CDCl3) Fig.16 As shown, δ7.88 (d, 4H), 7.69 (s, 2H), 7.61 (t, 2H), 7.56-7.50 (m, 8H), 7.43-7.39 (m, 1H). 13 CNMR (100MHz,CDCl3) Fig.17 As shown, the HRMS m / z pattern of DTP-Ph (m / z calculated value: 463.0701; experimental value: 463.0698.) Fig.18 As shown, the synthetic route of DTP-Ph is as follows:

[0115]

[0116] Example 5 Preparation of DTT

[0117] In a dry 100mL Schlenk tube, DTT core (0.30g, 1.53mmol) was dissolved in 25mL dichloromethane (CH2Cl2) and reacted under nitrogen protection. In another dry 100mL two-necked flask, anhydrous aluminum chloride (1.22g, 9.18mmol) and benzoyl chloride (0.86g, 6.11mmol) were added, dissolved in 25mL dichloromethane, and stirred for 15 minutes under nitrogen protection at 0°C. Subsequently, the DTT core solution was slowly added dropwise to the flask over 15 minutes, and the mixture was heated at 40°C for 48 hours. After the reaction was completed, the mixture was cooled to room temperature and quenched with ice water. The organic layer was dried over anhydrous Na2SO4, and the solvent was evaporated. The crude product was purified by column chromatography (CHCl3 / n-hexane, volume ratio 3 / 1) to obtain 197 mg of yellow solid dithieno[3,2-b:2',3'-d]thiophene-2,6-diylbis(benzophenone) (DTT, C 22 H 12 O2S3), yield: 31.8%. DTT 1 H NMR (400MHz, CDCl3) Fig.19 As shown, δ7.91 (d, 4H), 7.89 (s, 2H), 7.64 (t, 2H), 7.55 (t, 4H). 13 C NMR (100MHz,CDCl3) Fig. 20 As shown, 188.24, 146.25, 144.19, 137.60, 136.90, 132.63, 129.13, 128.67, 128.32. HRMS m / z diagram (m / z calculated value: 403.9999; experimental value: 404.0009) is as follows Fig.21 As shown, the synthetic route of DTT is as follows:

[0118]

[0119] The photoluminescence quantum yield (PLQY) of DTP derivatives (i.e. DTP-Cz, DTP-g, DTP-f) at room temperature in different states was tested. The specific test method is: the PLQY can be obtained by testing the samples in the following NMR tube using the Hamamatsu absolute PL quantum yield spectrometer. The results are shown in Fig. 22 It can be seen that the different PLQYs in different matrices reflect the environmental effect.

[0120] Preparation of DTP derivative MeTHF (2-methyltetrahydrofuran) solution: Dissolve the DTP derivative in MeTHF to prepare a concentration of 10 -3 Use a pipette to measure a certain volume of the stock solution and a certain volume of MeTHF to prepare a concentration of 10-5 The test sample of M. Add the MeTHF solution of DTP derivative into the NMR tube.

[0121] Preparation of DTP derivative doped PMMA film stock solution: Weigh a certain amount of DTP derivative and dissolve it in a certain volume of dichloromethane (DCM) to prepare a solution with a concentration of 1 mg / mL. Weigh a certain amount of PMMA and dissolve it in a certain volume of dichloromethane (DCM) to prepare a solution with a concentration of 100 mg / mL. Mix the two solutions in proportion to obtain DCM mixed solutions of DTP derivatives and PMMA in different mass ratios (for example, according to the volume ratio of DTP derivative solution: PMMA solution = 1:1, a DCM mixed solution of DTP derivative doped PMMA with a doping concentration of 1wt.% can be obtained. Similarly, doping solutions with different doping concentrations can be obtained (doping concentration is 0.01-50wt.%)). Add 50μL of DTP derivative doped PMMA film stock solution to the nuclear magnetic tube and heat it at 80℃ to completely volatilize the solvent DCM, and then the DTP derivative doped PMMA film can be obtained in the nuclear magnetic tube.

[0122] Preparation of DTP derivative doped BP-Br: Weigh 1 mg of DTP derivative and 100 mg of BP-Br, mix them, heat the mixed solid to 100°C and gradually cool it to obtain a DTP derivative doped BP-Br solid with a doping concentration of 1 wt.%, and add the final solid to the NMR tube. Similarly, solids with different doping concentrations (doping concentration of 0.01-50 wt.%) can be obtained.

[0123] Preparation of DTP derivative crystals: Dissolve the DTP derivative in DCM to form a saturated solution, filter and remove impurities, then slowly drop EA, and slowly evaporate the solvent at room temperature to precipitate crystals. Collect the crystals and add them to a NMR tube.

[0124] Test the solvation effect of DTP-Cz. The specific test method is: prepare a dilute solution of DTP derivatives with solvents of different polarities, and then use a UV spectrophotometer to test to obtain a spectrum. The absorption spectrum of the solvation effect of DTP-Cz can be found in Fig.23 , DTP-Cz solvation effect emission spectrum see Fig.24 It can be seen that the emission of DTP-Cz red-shifts with the increase of solvent polarity, which has typical TICT characteristics.

[0125] The AIE curve emission spectrum of DTP-Cz is shown in Fig.25 , AIE curve emission spectrum of DTP-Cz - dotted line diagram see Fig.26 , it can be seen that DTP-Cz is not an AIE molecule.

[0126] The emission spectrum of DTP-Cz doped PMMA was tested by mixing DTP-Cz DCM solution and PMMA DCM solution in different proportions and then dropping them on a glass sheet to obtain a DTP-Cz doped PMMA film. The emission spectrum was tested using Edinburgh FLS1000. The results are shown in Fig. 27 It can be seen that the luminescence red shifts with the increase of doping concentration.

[0127] The emission spectrum of DTP-Cz doped with BP-Br was tested by placing a mixed solid of DTP-Cz and BP-Br on a quartz glass with grooves, heating and melting it, and gradually cooling it to obtain a sample. The emission spectrum was tested using Edinburgh FLS1000. The results are shown in Fig.28 It can be seen that BP-Br is conducive to the formation of phosphorescence. With the increase of doping concentration, the fluorescence emission red-shifts, while the phosphorescence emission remains unchanged.

[0128] The normalized steady-state PL spectra of DTP-Cz, DTP-g, and DTP-f at room temperature were tested. The specific method was as follows: the crystals of DTP derivatives were used to test the solid emission spectra using Edinburgh FLS1000. The results are shown in Fig.29 , it can be seen that the crystal emission spectrum has an obvious red shift compared to the single-molecule spectrum of the solution, reflecting that the intermolecular interaction reflects the formation of dimers or ground-state-excited state complexes.

[0129] The normalized phosphorescence spectra of DTP-Cz, DTP-g and DTP-f at 77K were tested. The specific method was as follows: the crystals of DTP derivatives were used to test the solid low-temperature delayed emission spectra using Edinburgh FLS1000, with a delay time of 0.5 milliseconds. The results are shown in Fig.30 It can be seen that the generation of phosphorescence is enhanced in the low-temperature crystal state due to the restriction of molecular non-radiative transitions.

[0130] Test the time-resolved decay curves of DTP-Cz, DTP-g and DTP-f at 77K with a wavelength of 690nm. The specific method is: Use the crystal of DTP derivative to test the solid time-resolved decay curve using Edinburgh FLS1000. The results are shown in Fig.31 It can be seen that DTP-Cz with the best crystallinity has a longer phosphorescence lifetime. This is because the formation of crystals limits the non-radiative transition of molecules and effectively isolates the quenching of phosphorescence by oxygen.

[0131] The normalized phosphorescence PL spectrum of DTP-g doped PMMA film at room temperature is shown in Fig.32 It can be seen that the delayed fluorescence shows a concentration-dependent effect, and the emission red shifts as the concentration increases.

[0132] The time-resolved decay curve of DTP-Cz doped PMMA film at room temperature at a wavelength of 690nm was monitored. The specific method was as follows: the time-resolved decay curve of the film was tested using Edinburgh FLS1000 using DTP-Cz PMMA film. The results are shown in Fig.33 , it can be seen that it has room temperature phosphorescence effect.

[0133] The normalized PL spectrum of DTP-g doped BP-Br at room temperature is shown in Fig.34 It can be seen that DTP-g exhibits room temperature phosphorescence effect in BP-Br.

[0134] The time-resolved decay curves of BP-Br doped with different concentrations of DTP derivatives at a wavelength of 650nm were monitored at room temperature. The specific method was as follows: the mixed solid doped with DTP derivatives and BP-Br was placed in a nuclear magnetic resonance tube and the solid time-resolved decay curve was tested using Edinburgh FLS1000. The results are shown in Fig.35 It can be seen that DTP derivatives exhibit room temperature phosphorescence properties in BP-Br and the lifetime is about 10 milliseconds.

[0135] The above results show that the present invention tests the photophysical properties of organic phosphorescent materials at room temperature (298K) and low temperature (77K) respectively. The results show that these organic phosphorescent materials exhibit stable delayed fluorescence and phosphorescence in PMMA films, and the phosphorescence lifetime is significantly prolonged as the temperature decreases. At the same time, the delayed fluorescence intensity dependence under different excitation intensities is measured. The present invention has developed an organic phosphorescent material with efficient phosphorescent emission, long lifetime and excellent environmental stability by optimizing the DTP skeleton and introducing carbazole and its derivative groups. The organic phosphorescent material has broad application prospects in the fields of bioimaging, phototherapy and information storage, and significantly improves the performance and practicality of pure organic phosphorescent materials.

[0136] The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. An organic phosphorescent material based on a dithiapyrrole derivative modified with a carbazole derivative, characterized in that: The structural formula is shown in Formula 1-2: Among them, R is a straight-chain alkyl group, a branched-chain alkyl group, a cyclic alkyl group or a benzene ring, and R contains or does not contain a halogen substituent; R1 is a straight-chain alkyl group, a branched-chain alkyl group, a cyclic alkyl group, an alkoxy group, an aryl group or hydrogen; X1 is sulfur, oxygen or selenium; X2 is oxygen, sulfur or selenium; Ar1 ​​is an aromatic ring, and Ar1 contains or does not contain a halogen substituent; Ar2 is hydrogen or a heteroaromatic ring.

2. The organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative according to claim 1, characterized in that: R is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or a benzene ring, and R contains or does not contain a halogen substituent; R1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, alkoxy, aryl or hydrogen; X1 is sulfur, oxygen or selenium; X2 is oxygen, sulfur or selenium; Ar1 ​​is a benzene ring, pyridine, furan or thiophene, and Ar1 contains or does not contain a halogen substituent; Ar2 is hydrogen, carbazole, indole, benzopyrrole, quinoline or quinazoline.

3. The organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative according to claim 2, characterized in that: Select from the following structures:

4. A method for preparing an organic phosphorescent material based on a dithiapyrrole derivative modified with a carbazole derivative according to any one of claims 1 to 3, characterized in that: A compound raw material containing X1 and X2 heteroatoms is selected, a carbonyl group or a sulfyl group is introduced into the aromatic ring skeleton through an acyl chlorination reaction, and the Ar1 and Ar2 groups are connected to the core molecular structure through a Suzuki, Stille or Heck coupling reaction. After structural modification, the organic phosphorescent material based on the dithiapyrrole derivative modified with a carbazole derivative is obtained.

5. A luminescent film, characterized in that: The organic phosphorescent material doped with the dithiapyrrole derivative modified by carbazole derivatives according to any one of claims 1 to 3, wherein the matrix is ​​polymethyl methacrylate, and the doping concentration of the organic phosphorescent material based on the dithiapyrrole derivative modified by carbazole derivatives is 0.01-50wt.%.

6. A luminescent film, characterized in that: The organic phosphorescent material doped with the dithiapyrrole derivative modified with a carbazole derivative according to any one of claims 1 to 3, wherein the matrix is ​​4-bromobenzophenone, and the doping concentration of the organic phosphorescent material based on the dithiapyrrole derivative modified with a carbazole derivative is 0.01-50wt.%.

7. Use of the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative according to any one of claims 1 to 3 in the preparation of optoelectronic devices, characterized in that: The optoelectronic device includes an OLED display device or a light emitting diode.

8. Use of the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative according to any one of claims 1 to 3 in in vivo imaging for non-therapeutic purposes.

9. Use of the organic phosphorescent material based on the dithiapyrrole derivative modified by the carbazole derivative according to any one of claims 1 to 3 in the preparation of a sensor.

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