Panchromatic organic phosphorescent material constructed by carbazole-benzoindole isomer and application of panchromatic organic phosphorescent material

Abstract

The invention discloses a panchromatic organic room temperature phosphorescence (RTP) material system constructed based on a molecular isomerization strategy, and a preparation method and application thereof. The positions of nitrogen atoms in a tricyclic fused aromatic skeleton are accurately regulated and controlled to construct structural isomers including benzoindole [g], [e] and [f] and carbazole, and red, yellow, green and blue panchromatic RTP emission is realized. The compound can be efficiently synthesized by a one-pot solvent-free mechanochemical method, is doped in polymers such as PVA (Polyvinyl Alcohol) to construct a stable phosphorescent composite material, and shows a phosphorescent life as long as 4.23 seconds, an efficient TSFRET effect and adaptability to various matrixes. Theoretical and crystallographic analysis reveals a regulation and control mechanism of a heterogeneous structure on luminescence performance. The method is suitable for the fields of anti-counterfeiting, underwater imaging, security identification and the like, and a new path for constructing the panchromatic phosphorescent material is provided.

Description

Technical Field

[0001] This invention relates to the field of organic photofunctional materials technology, specifically to a full-color organic room-temperature phosphorescent material based on carbazole and benzoindole structural isomers and its applications. Background Technology

[0002] Room-temperature phosphorescence (RTP) materials have attracted significant attention from the scientific and industrial communities in recent years due to their promising applications in anti-counterfeiting, optoelectronic displays, bio-imaging, information storage, and encryption. In particular, RTP materials based on purely organic molecules have become a cutting-edge research direction in organic light-emitting materials due to their advantages such as the absence of heavy metals, environmental friendliness, and tunable molecular structure.

[0003] Traditional organic RTP materials are typically designed using rigid frameworks, intermolecular hydrogen bonds, crystallization state restrictions, or the introduction of heavy atom effects to enhance intersystem crossing (ISC) processes. However, these strategies often have the following problems: (1) the material design lacks versatility and the emission color is difficult to control; (2) the emission wavelength is concentrated in the blue-green region, making it difficult to achieve full-color coverage of visible light; (3) the preparation process is complex, requiring the use of organic solvents, heavy metal catalysts, or multi-step synthesis routes, which is not conducive to green and large-scale development; (4) the stability and lifespan are poor in practical application environments such as flexible polymers, which limits practical applications.

[0004] In particular, how to achieve full-color RTP emission (red, yellow, green, and blue) from a single backbone through molecular structure regulation has remained a significant unsolved scientific and engineering problem in this field. Currently, there is still a lack of a material system that is structurally simple, precisely regulated, stable in performance, and universally adaptable, which can be widely applied to different polymer platforms to meet the needs of various application scenarios.

[0005] Therefore, there is an urgent need to develop a full-color organic RTP material system with adjustable structure, controllable color, excellent performance, and green synthesis potential, so as to promote the application of such materials in practical scenarios. Summary of the Invention

[0006] The purpose of this invention is to provide a full-color phosphorescent material system with simple structure, stable performance, tunable color, and long lifespan. By precisely controlling the position of nitrogen atoms in the molecular backbones of carbazole and benzoindole, molecular isomers are constructed, enabling them to exhibit visible light room-temperature phosphorescence emission behavior ranging from red, yellow, and green to blue in different polymer matrices. To achieve the above objective, this invention provides a full-color organic phosphorescent material system constructed from carbazole-benzoindole isomers, characterized by comprising a polymer matrix material and an organic light-emitting isomer dispersed therein, wherein the organic light-emitting isomer comprises: Carbazole derivatives, Class A g-configuration benzoindole (Bd[g]) derivatives, Class B, e-configuration benzoindole (Bd[e]) derivatives, Class C, One, two, or more of the following are class D derivatives of f-configuration benzoindole (Bd[f]).

[0007] Preferably, the carbazole derivative class A comprises any one of the following compounds, with the following structural formula:

[0008] Preferably, the g-configuration benzoindole (Bd[g]) derivative class B comprises any one of the following compounds, with the following structural formula:

[0009] Preferably, the e-configuration benzoindole (Bd[e]) derivative class C includes any one of the following compounds, with the following structural formula:

[0010] Preferably, the f-configuration benzoindole (Bd[f]) derivative class D comprises any one of the following compounds, with the following structural formula:

[0011] Preferably, the reaction formula for the carbazole derivative type A is:

[0012] Preferably, the reaction formula for the g-configuration benzoindole (Bd[g]) derivative type B is as follows:

[0013] Preferably, the reaction formula for the e-configuration benzoindole derivative C is:

[0014] Preferably, the reaction formula for the f-configuration benzoindole derivative type D is:

[0015] Preferably, the polymer matrix is ​​selected from one of polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, and polyvinyl butyral.

[0016] Preferably, the preparation method of the carbazole derivative type A is as follows: The substituted nitrobenzene was added to the reaction flask along with the substituted phenylboronic acid in a ratio of 1:2.4 molar equivalents, 4 molar equivalents of K2CO3, 0.1 molar equivalents of Pd(OAc)2, and 5 molar equivalents of PPh3. The mixture was refluxed in o-dichloroethane at 180°C for 48 hours under nitrogen atmosphere. After the reaction was cooled to room temperature, it was extracted with water and dichloromethane. The organic phase was purified on a silica gel column to obtain the carbazole derivative A. Preferably, the preparation method of the g-configuration benzoindole derivative type B is as follows: Compound 1-naphthylhydrazine hydrochloride was added to a ball mill jar with phenylacetone of different substituents at a molar ratio of 1:1.1. Then, oxalic acid and dimethylurea were added to the ball mill jar in a molar ratio of 1:3.5:1.5 to 1-naphthylhydrazine hydrochloride. Finally, acetic acid at a mass ratio of 0.1 μL / mg to 1-naphthylhydrazine hydrochloride was added as a catalyst. After the ball mill jar was sealed, it was fixed in a planetary ball mill and reacted at room temperature, in air atmosphere, and at 30 Hz for 3 h. After the reaction was completed, the reaction mixture was cooled to room temperature, and then the product was transferred to a round-bottom flask, dissolved in an organic solvent, and then the organic solvent was evaporated under reduced pressure. The product was then purified by silica gel column chromatography to obtain a white solid, which yielded the g-configuration benzoindole derivative type B. Preferably, the preparation method of the e-configuration benzoindole derivative C is as follows: Compound 2-naphthylhydrazine hydrochloride was added to a ball mill jar with phenylacetone of different substituents at a molar ratio of 1:1.1. Then, oxalic acid and dimethylurea were added to the ball mill jar in a molar ratio of 1:3.5:1.5 to 2-naphthylhydrazine hydrochloride. Finally, acetic acid was added as a catalyst at a mass ratio of 0.1 μL / mg to 2-naphthylhydrazine hydrochloride. After the ball mill jar was sealed, it was fixed in a planetary ball mill and reacted at room temperature, in air atmosphere, and at 30 Hz for 3 h. After the reaction was completed, the reaction mixture was cooled to room temperature, and then the product was transferred to a round-bottom flask, dissolved in an organic solvent, and then the organic solvent was evaporated under reduced pressure. The product was then purified by silica gel column chromatography to obtain a white solid, which yielded the C-type benzoindole derivative of the e-configuration. Preferably, the preparation method of the f-configuration benzoindole derivative type D is as follows: One equivalent of substituted N-(naphthyl-2-yl)acetamide, 0.025 equivalents of [{RuCl2(pcymene)}2] and 0.1 equivalents of AgSbF6 were purged three times in a reaction vessel under argon atmosphere. Then, 1.1 equivalents of substituted 1-propynyl-1-phenyl and 2.5 equivalents of pivalic acid were added in isopropanol solvent under argon atmosphere. The mixture was refluxed at 100°C for 12 hours. The reaction was cooled to room temperature and then extracted with water and dichloromethane. The organic phase was purified by silica gel column chromatography to obtain a pure white intermediate 1. Intermediate 1 was added to a reaction solvent obtained by mixing 17% hydrochloric acid and tetrahydrofuran at a volume ratio of 1:1, and reacted at 100 °C for 17 hours to obtain intermediate 2. Under argon atmosphere, 1.2 equivalents of bis(trifluoroacetoxy)iodine (PIFA) was dissolved in tetrahydrofuran and then added dropwise to a solution of 1 equivalent of intermediate 2. The resulting mixture was stirred at room temperature for 1 hour and then subjected to silica gel column chromatography to obtain f-type benzoindole derivative D.

[0017] This invention also provides a method for preparing a full-color organic phosphorescent material system constructed as described above using the carbazole-benzoindole isomer: When the polymer matrix is ​​polyvinyl alcohol, the preparation method corresponding to 1 mg of organic light-emitting isomer is as follows: A 1 mL tetrahydrofuran solution containing 1 mg of an organic light-emitting isomer was thoroughly mixed with a polyvinyl alcohol aqueous solution consisting of 100 mg of polyvinyl alcohol and 9 mL of water. The mixture was then dropped into a dye cartridge and baked at 60°C for 2-3 hours to obtain film A. The degree of polymerization of the polyvinyl alcohol was 17 and the alcohol solubility was 99%. When the polymer matrix is ​​polyvinylpyrrolidone, polymethyl methacrylate, or polyvinyl butyral, the preparation method corresponding to each 1 mg of organic luminescent isomer is as follows: One mL of dichloromethane solution containing 1 mg of the organic light-emitting isomer was thoroughly mixed with 4 mL of dichloromethane solution containing 100 mg of the polymer matrix. The well-mixed solution was then dropped into a dye cartridge and evaporated to dryness at room temperature to obtain films B, C, or D. Then, films A, B, C, or D are dried in a vacuum oven at 65°C for 12 hours to remove residual moisture.

[0018] This invention also provides an application of the full-color organic phosphorescent material system constructed as described above using the carbazole-benzoindole isomer, the application including the following methods: a) High-temperature anti-counterfeiting labels and information encryption; b) Underwater imaging and positioning markers; c) Emergency lighting or signage system; d) Motion tracking and visual response systems in biomimetic smart materials.

[0019] The beneficial effects of the technical solution provided by this invention are: Achieving full-color tunable phosphorescence emission: This invention constructs a family of structural isomers (including benzoindole [f], benzoindole [e], benzoindole [g], and carbazole) by precisely controlling the position of nitrogen atoms in the tricyclic aromatic skeletons of carbazole and benzoindole, achieving room-temperature phosphorescence emission in the full-color visible light region of red, yellow, green, and blue (RYGB), covering the entire visible light range, and breaking through the bottleneck of limited color control in traditional organic RTP materials.

[0020] The synthesis method is green and efficient: the isomer can be synthesized by solvent-free one-pot mechanochemical synthesis, which is efficient and fast, avoids the use of toxic organic solvents and metal catalysts, and has significant advantages such as simple process, low cost and environmental friendliness, making it suitable for green and large-scale production.

[0021] Excellent and stable luminescence performance: The obtained composite material can maintain stable RTP emission characteristics in a variety of polymer matrices. The phosphorescence lifetime of some systems can reach 4.23 seconds. It has high brightness, long lifetime, good reproducibility and environmental adaptability, making it suitable for applications in real complex environments.

[0022] With clear theoretical support and a well-defined structure-performance relationship, the study uses multi-dimensional theoretical and structural analysis, including density functional theory (DFT), TD-DFT, single-crystal structure, and inter-interaction region indication (IRI), to clearly reveal the key regulatory role of nitrogen atom sites in the isomer on the triplet behavior and emission energy level of the molecule, providing theoretical guidance for subsequent molecular design.

[0023] Highly adaptable and widely applicable: This phosphorescent material system is compatible with a variety of polymer matrices (such as PVA, PMMA, PVP, and PVB), exhibiting excellent film-forming and processability properties. It is suitable for multiple fields such as high-temperature anti-counterfeiting, underwater visual imaging, bioluminescent bionic control, and emergency signage, and has broad prospects for practical application and industrialization.

[0024] A general structural heterogeneity design strategy is proposed: This invention not only constructs a specific material system, but also proposes a general and scalable "structural heterogeneity regulation" strategy, providing a new idea and technical platform for constructing multicolor controllable organic functional phosphorescent materials. Attached Figure Description

[0025] Figure 1 A schematic diagram illustrating the realization of full-color organic room-temperature phosphorescence (RTP) emission using the molecular isomerization strategy provided in this embodiment of the invention; Figure 2 Phosphorescence emission patterns of four guest molecules, Ph-Cz, Ph-Bd[g], Ph-Bd[e], and Ph-Bd[f], and PVA doped materials provided in embodiments of the present invention; Figure 3Phosphorescence lifetime diagrams of four guest molecules, Ph-Cz, Ph-Bd[g], Ph-Bd[e], and Ph-Bd[f], and PVA doped materials provided in embodiments of the present invention; Figure 4 Phosphorescence CIE coordinate diagrams of four guest molecules, Ph-Cz, Ph-Bd[g], Ph-Bd[e], and Ph-Bd[f], and PVA doped materials provided in embodiments of the present invention; Figure 5 These are photographs of the phosphorescent material under ultraviolet light irradiation (365 nm) on and off states, as provided in embodiments of the present invention. The top image shows phosphorescent films prepared by doping four different guest molecules into a polyvinyl alcohol (PVA) matrix; the bottom image shows a PVA composite material formed by co-doping two adjacent guest molecules, achieving tunable afterglow emission color.

[0026] Figure 6 Phosphorescence high-temperature resistance diagrams of four guest molecules (Ph-Cz, Ph-Bd[g], Ph-Bd[e], Ph-Bd[f]) and PVP-doped materials provided in embodiments of the present invention; Figure 7 The following is an illustration of the illumination of emergency signs by phosphorescence on a Ph-Bd[g]-doped PVA matrix provided in this embodiment of the invention. Figure 8 Stability diagram of phosphorescence in seawater for Ph-Bd[g] and Ph-Bd[e] doped PVB matrices provided in embodiments of the present invention; Figure 9 Interaction region indication (IRI) diagram of guest compound Ph-Cz in PVA matrix provided for embodiments of the present invention; Figure 10 LUMO-HOMO diagrams of four guest molecules, Ph-Cz, Ph-Bd[g], Ph-Bd[e], and Ph-Bd[f], provided in the embodiments of the present invention; Figure 11 The DFT calculation diagrams of four guest molecules, Ph-Cz, Ph-Bd[g], Ph-Bd[e], and Ph-Bd[f], are provided in the embodiments of the present invention. Figure 12 Phosphorescence emission patterns of Ph-Cz doped in different polymer matrices provided in embodiments of the present invention; Figure 13 Phosphorescence emission patterns of Ph-Bd[g] doped in different polymer matrices provided in embodiments of the present invention; Figure 14 Phosphorescence emission patterns of Ph-Bd[e] doped in different polymer matrices provided in embodiments of the present invention; Figure 15FRET energy transfer afterglow emission spectra of the Bd[g]-FLS, Bd[g]-RHB, Bd[e]-FLS and Bd[e]-RHB systems provided in the embodiments of the present invention; Figure 16 A single-crystal image of the Ph-Cz guest molecule provided in an embodiment of the present invention; Figure 17 A single-crystal image of the Ph-Bd[g] guest molecule provided in an embodiment of the present invention; Figure 18 A single-crystal image of the Ph-Bd[e] guest molecule provided in an embodiment of the present invention; Figure 19 The proton nuclear magnetic resonance spectrum of the guest compound Ph-Cz provided in the embodiments of the present invention; Figure 20 The proton nuclear magnetic resonance spectrum of the guest compound Ph-Bd[g] provided in the embodiments of the present invention; Figure 21 The proton nuclear magnetic resonance spectrum of the guest compound Ph-Bd[e] provided in the embodiments of the present invention; Figure 22 The proton nuclear magnetic resonance spectrum of the guest compound Ph-Bd[f] provided in the embodiments of the present invention; Detailed Implementation To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. Of course, the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0027] Example 1 Preparation of carbazole derivatives (Class A) 2-Bromo-4-methyl-1-nitrobenzene (0.432 g, 2 mmol), phenylboronic acid (0.586 g, 4.8 mmol), K₂CO₃ (1.104 g, 8 mmol), palladium acetate (45 mg, 0.2 mmol), and PPh₃ (2.623 g, 10 mmol) were added to a 50 mL reaction flask. The mixture was refluxed at 180 °C in 15 mL of dichloroethane for 48 hours under nitrogen protection. After cooling to room temperature, the reaction was extracted with water and dichloromethane. The organic phase was purified by silica gel column chromatography using petroleum ether-ethyl acetate (5:1) as eluent to give the light brown product Ph-Cz, a carbazole derivative, class A compound 2.

[0028] Example 2 Preparation of g-configuration benzoindole (Bd[g]) derivatives (Class B) 1-Naphthylhydrazine hydrochloride (0.390 g, 2 mmol), 1-(p-tolyl)prop-1-one (0.326 g, 2.2 mmol), oxalic acid (0.64 g, 7 mmol), dimethylurea (0.28 g, 3 mmol), and 40 μL of acetic acid were added to a 15 mL ball mill jar. Two small steel balls with a diameter of 10 mm were then added to the jar. The jar was fixed to a ball mill, and the mill frequency was set to 30 Hz. The mixture was ground in air at room temperature for 3 hours. The product was cooled to room temperature, washed with water, and filtered to obtain a crude solid product. The crude product was purified by silica gel column chromatography using petroleum ether-ethyl acetate (5:1) as the eluent to obtain a light pink pure product, Ph-Bd[g], a g-configuration benzoindole (Bd[g]) derivative, class B compound 9.

[0029] Example 3 Preparation of e-configuration benzoindole (Bd[e]) derivatives (Class C) 2-Naphthylhydrazine hydrochloride (0.390 g, 2 mmol), 1-(p-tolyl)prop-1-one (0.326 g, 2.2 mmol), oxalic acid (0.64 g, 7 mmol), dimethylurea (0.28 g, 3 mmol), and 40 μL of acetic acid were added to a 15 mL ball mill jar. Two small steel balls with a diameter of 10 mm were then added to the jar. The jar was fixed to a ball mill, and the mill frequency was set to 30 Hz. The mixture was air-milled for 3 hours at room temperature. The product was cooled to room temperature, washed with water, and filtered to obtain a crude solid product. The crude product was purified by silica gel column chromatography using petroleum ether-ethyl acetate (5:1) as the eluent to obtain a light pink pure product, Ph-Bd[e], a class C compound 21 of the e-configuration benzoindole (Bd[e]) derivative.

[0030] Example 4 Preparation of f-configuration benzoindole (Bd[f]) derivatives, Class D N-(naphthyl-2-yl)acetamide (0.370 g, 2 mmol), [{RuCl2(pcymene)}2] (0.01 g, 5.0 mol%), and AgSbF6 (0.01 g, 20 mol%) were evacuated three times under an argon atmosphere in a 25 mL reaction flask. Then, under an argon atmosphere, 1-propynyl-1-phenyl (0.28 mL, 2.2 mmol), glutaric acid (0.5 mL, 5 mmol), and 10 mL of isopropanol were added, and the mixture was refluxed at 100 °C for 12 hours. After cooling to room temperature, the mixture was extracted with water and dichloromethane. The organic phase was purified by silica gel column chromatography using petroleum ether-ethyl acetate (3:1) as eluent to give a white intermediate 1. The reaction was then carried out at 100 °C for 17 hours. A 1:1 mixture of 17% hydrochloric acid and tetrahydrofuran was added to the reaction system, and intermediate 1 was converted to intermediate 2 in 91% yield. A solution of bis(trifluoroacetoxy)iodine (PIFA) (400 mg, 0.93 mmol) dissolved in tetrahydrofuran (3 mL) was slowly added dropwise (10 min) under argon protection until intermediate 2 (200 mg, 0.77 mmol) dissolved in tetrahydrofuran (3 mL). The resulting mixture was stirred at room temperature for 1 hour, filtered through a short silica gel filtration membrane, and concentrated under reduced pressure to give the benzopyridine [f] product. Using n-hexane-dichloromethane (4:1) as the eluent, a pale yellow solid product Ph-Bd [f] was given in 20% yield, which is a class D compound 33 of the f-configuration benzoindole (Bd [f]) ​​derivative.

[0031] Example 5 Ph-Cz and PVA doped materials provided in the embodiments of the present invention A tetrahydrofuran solution (1 ml) of Ph-Cz guest molecule (1 mg) was thoroughly mixed with an aqueous solution of polyvinyl alcohol (PVA) (containing 100 mg PVA1799 (degree of polymerization 17, alcohol solubility 99) and 9 ml of water). The well-mixed solution was then dropped into a dye cartridge and baked at 60 °C for 3 hours to prepare a Ph-Cz@PVA film.

[0032] The preparation method is the same as that used for Ph-Cz and PVA doped materials, except that Ph-Cz is replaced with Ph-Bd[g].

[0033] The preparation method is the same as that used for Ph-Cz and PVA doped materials, except that Ph-Cz is replaced with Ph-Bd[e].

[0034] The preparation method is the same as that used for Ph-Cz and PVA doped materials, except that Ph-Cz is replaced with Ph-Bd[f].

[0035] Example 6 Ph-Cz and PVB doped materials provided in the embodiments of the present invention A dichloromethane solution (1 ml) of guest molecule Ph-Cz (1 mg) was thoroughly mixed with a dichloromethane solution (4 ml) of polyvinylpyrrolidone (PVP) (100 mg). The well-mixed solution was then dropped into a dye ribbon and evaporated to dryness at room temperature to obtain a film. All films were then dried in a vacuum oven at 65°C for 12 hours to remove residual moisture to prepare Ph-Cz@PVP films.

[0036] The preparation method is the same as that used for Ph-Cz and PVA doped materials, except that Ph-Cz is replaced with Ph-Bd[g].

[0037] The preparation method is the same as that used for Ph-Cz and PVA doped materials, except that Ph-Cz is replaced with Ph-Bd[e].

[0038] The preparation method is the same as that used for Ph-Cz and PVA doped materials, except that Ph-Cz is replaced with Ph-Bd[f].

[0039] Example 7 Prepared using the same method as in Embodiment 6, except that PVP is replaced with PMMA.

[0040] Example 8 Prepared using the same method as in Embodiment 6, except that PVP is replaced with PVB.

[0041] Example 9 The PVA composite material formed by co-doping of two adjacent guest molecules provided in this invention achieves tunable afterglow emission color. A tetrahydrofuran solution (1 ml) of Ph-Cz guest molecule (1 mg) and Ph-Bd[g] guest molecule (1 mg) was thoroughly mixed with an aqueous solution of polyvinyl alcohol (PVA) (containing 100 mg PVA1799 (degree of polymerization 17, alcohol solubility 99) and 9 ml of water). The well-mixed solution was then dropped into a dye cartridge and baked at 60 °C for 3 hours to prepare a PVA film co-doped with two adjacent guest molecules.

[0042] This invention proposes a universal and scalable method for regulating full-color organic room-temperature phosphorescence (RTP) emission, based on a molecular isomerization strategy. Through rational molecular design and structural regulation of Cz with three benzoindole isomers (Bd[g], Bd[e], Bd[f]), and combined with guest-host complex and co-doping strategies using various polymer matrices such as PVA, PVP, and PVB, the following method was successfully implemented: Continuously tunable RTP emission covering the entire visible light region from blue to green to yellow to red (CIE coordinates allow for precise positioning and design); long-lived afterglow on the millisecond to second scale and programmable, multi-channel time / color dual-encrypted luminescence achieved through FRET energy transfer and co-doping with adjacent guest molecules; excellent thermal and environmental stability exhibited in different polymer matrices such as PVA, PVP, and PVB, among which the Ph-Bd[g] / Ph-Bd[e] mechanism, single-crystal structure ( Figure 16 –18), IRI Interaction Indicator Diagram ( Figure 9 ), HOMO–LUMO energy level distribution ( Figure 10 ) and DFT calculation results ( Figure 11 Together, these findings indicate that molecular isomerization-induced fine-tuning of energy levels, intermolecular interactions, and the rigid confinement effect in the polymer matrix effectively suppress nonradiative decay and enhance intersystem crossing (ISC) efficiency, thus achieving stable and efficient RTP emission without the involvement of heavy atoms. NMR characterization ( Figure 19 –22) This further confirmed the correctness of the chemical structure of each guest molecule, providing a solid basis for the reproducible and scalable preparation of the material system of this invention.

[0043] In summary, this invention offers significant advantages such as designable structure, simple preparation process, controllable cost, and excellent environmental and thermal stability. It not only provides a new and universal pathway for obtaining fully tunable organic RTP materials but also lays the foundation for their engineering applications in fields such as emergency signage lighting, information anti-counterfeiting and data encryption, time-resolved imaging and sensing, marine environmental monitoring, and underwater imaging. It should be understood that this invention is not limited to the specific embodiments shown in the specification and drawings. All equivalent substitutions and modifications made to the molecular skeleton, substituents, polymer matrix type, doping method and ratio, FRET donor-acceptor combination, etc., based on the core ideas of this invention (molecular isomerization + polymer confinement + energy transfer / co-doping strategy), should fall within the protection scope of this invention.

Claims

1. A full-color organic phosphorescent material system constructed from carbazole-benzoindole isomers, characterized in that, It includes a polymer matrix material and an organic light-emitting isomer dispersed therein, wherein the organic light-emitting isomer includes: Carbazole derivatives, Class A g-configuration benzoindole (Bd[g]) derivatives, Class B, e-configuration benzoindole (Bd[e]) derivatives, Class C, One, two, or more of the following are class D derivatives of f-configuration benzoindole (Bd[f]).

2. The full-color organic phosphorescent material system constructed from carbazole-benzoindole isomers according to claim 1, characterized in that, The carbazole derivative class A includes any one of the following compounds, with the following structural formulas: The g-configuration benzoindole (Bd[g]) derivatives of class B include any one of the following compounds, with the following structural formulas: The e-configuration benzoindole (Bd[e]) derivatives of class C include any one of the following compounds, with the following structural formulas: The f-configuration benzoindole (Bd[f]) derivatives of class D include any one of the following compounds, with the following structural formulas: 。 3. The full-color organic phosphorescent material system constructed from carbazole-benzoindole isomers according to claim 2, characterized in that, The reaction formula for the carbazole derivative type A is as follows: The reaction formula for the g-configuration benzoindole (Bd[g]) derivative type B is as follows: The reaction formula for the C-type benzoindole (Bd[e]) derivative is as follows: The reaction formula for the f-configuration benzoindole (Bd[f]) derivative D is as follows: 。 4. The full-color organic phosphorescent material system constructed from carbazole-benzoindole isomers according to claim 3, characterized in that, The polymer matrix is ​​selected from one of polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, and polyvinyl butyral.

5. The full-color organic phosphorescent material system constructed from the carbazole-benzoindole isomer according to claim 4, characterized in that, The preparation method of the carbazole derivative type A is as follows: The substituted nitrobenzene was reacted with substituted phenylboronic acid in a ratio of 1:2.4 molar equivalents, 4 molar equivalents of K2CO3, 0.1 molar equivalents of Pd(OAc)2 and 5 molar equivalents of PPh3 in a reaction flask. The reaction was carried out under nitrogen atmosphere and refluxed in o-dichloroethane solvent. After the reaction was cooled to room temperature, it was extracted with water and dichloromethane. The organic phase was purified on a silica gel column to obtain the carbazole derivative A. The preparation method of the g-configuration benzoindole derivative type B is as follows: Compound 1-naphthylhydrazine hydrochloride was added to a ball mill jar with phenylacetone of different substituents at a molar ratio of 1:1.

1. Then, oxalic acid and dimethylurea were added to the ball mill jar in a molar ratio of 1:3.5:1.5 to 1-naphthylhydrazine hydrochloride. Finally, acetic acid at a mass ratio of 0.1 μL / mg to 1-naphthylhydrazine hydrochloride was added as a catalyst. The ball mill jar was sealed and fixed in a planetary ball mill. The reaction was carried out at room temperature under an air atmosphere. After the reaction was completed, the reaction mixture was cooled to room temperature, and the product was transferred to a round-bottom flask, dissolved in an organic solvent, and then the organic solvent was evaporated under reduced pressure. The product was then purified by silica gel column chromatography to obtain a white solid, which yielded the g-configuration benzoindole derivative type B. The preparation method of the e-configuration benzoindole derivative C is as follows: Compound 2-naphthylhydrazine hydrochloride was added to a ball mill jar with phenylacetone of different substituents at a molar ratio of 1:1.

1. Then, oxalic acid and dimethylurea were added to the ball mill jar in a molar ratio of 1:3.5:1.5 to 2-naphthylhydrazine hydrochloride. Finally, acetic acid at a mass ratio of 0.1 μL / mg to 2-naphthylhydrazine hydrochloride was added as a catalyst. The ball mill jar was sealed and fixed in a planetary ball mill. The reaction was carried out at room temperature under an air atmosphere. After the reaction was completed, the reaction mixture was cooled to room temperature, and the product was transferred to a round-bottom flask, dissolved in an organic solvent, and then the organic solvent was evaporated under reduced pressure. The product was then purified by silica gel column chromatography to obtain a white solid, which yielded the C-type benzoindole derivative of the e-configuration. The preparation method of the f-configuration benzoindole derivative type D is as follows: One equivalent of substituted N-(naphthyl-2-yl)acetamide, 0.025 equivalents of [{RuCl2(pcymene)}2] and 0.1 equivalents of AgSbF6 were purged three times in a reaction vessel under argon atmosphere. Then, 1.1 equivalents of substituted 1-propynyl-1-phenyl and 2.5 equivalents of pivalic acid were added under argon atmosphere and refluxed in isopropanol solvent. The reaction was cooled to room temperature and then extracted with water and dichloromethane. The organic phase was purified by silica gel column chromatography to obtain a pure white intermediate 1. Intermediate 1 was added to a reaction solvent obtained by mixing 17% hydrochloric acid and tetrahydrofuran at a volume ratio of 1:1 to obtain intermediate 2. Under argon atmosphere, 1.2 equivalents of bis(trifluoroacetoxy)iodine (PIFA) was dissolved in tetrahydrofuran and then added dropwise to a solution of 1 equivalent of intermediate 2. The resulting mixture was stirred at room temperature and then subjected to silica gel column chromatography to obtain f-type benzoindole derivative D.

6. A method for preparing a full-color organic phosphorescent material system constructed from the carbazole-benzoindole isomer as described in claim 5, characterized in that, When the polymer matrix is ​​polyvinyl alcohol, the preparation method corresponding to 1 mg of organic light-emitting isomer is as follows: A 1 mL tetrahydrofuran solution containing 1 mg of an organic light-emitting isomer was thoroughly mixed with a polyvinyl alcohol aqueous solution consisting of 100 mg of polyvinyl alcohol and 9 mL of water. The mixture was then dropped into a dye tube and baked to obtain film A. The degree of polymerization of the polyvinyl alcohol was 17 and the alcohol solubility was 99. When the polymer matrix is ​​polyvinylpyrrolidone, polymethyl methacrylate, or polyvinyl butyral, the preparation method corresponding to each 1 mg of organic luminescent isomer is as follows: One mL of dichloromethane solution containing 1 mg of the organic light-emitting isomer was thoroughly mixed with 4 mL of dichloromethane solution containing 100 mg of the polymer matrix. The well-mixed solution was then dropped into a dye cartridge and evaporated to dryness at room temperature to obtain films B, C, or D. Then, films A, B, C, or D are dried in a vacuum oven to remove residual moisture.

7. An application of a full-color organic phosphorescent material system constructed from the carbazole-benzoindole isomer as described in any one of claims 1-6, wherein the application includes the following application methods: a) High-temperature anti-counterfeiting labels and information encryption; b) Underwater imaging and positioning markers; c) Emergency lighting or signage system; d) Motion tracking and visual response systems in biomimetic smart materials.

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