Protonated product of pyridine derivative as well as compound, preparation method and application of protonated product

Abstract

The invention provides a protonated product of a pyridine derivative, a compound of the protonated product, a preparation method and application, and belongs to the technical field of photoelectric materials. Phosphorescence enhancement is realized through protonation of pyridine and derivatives thereof, the protonation product of pyridine and derivatives thereof is further doped with a polymer to prepare a phosphorescent compound film, and the polymer and the protonation product of pyridine and derivatives thereof are utilized to form a hydrogen bond, so that the phosphorescent compound film is obtained. A rigid structure formed through hydrogen-bond interaction limits the non-radiative relaxation of the compound and improves the room-temperature phosphorescence performance. The preparation method is simple, the raw materials are easy to obtain, low in cost and environmentally friendly, and the prepared phosphorescent compound has excellent phosphorescent performance, has the foldable cutting characteristic and can be applied to the aspects of flexible display, colorful phosphorescent object construction, information encryption, anti-counterfeiting and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of optoelectronic materials, and in particular to a protonated product of a pyridine derivative and a composite thereof, a preparation method and application thereof. Background Art

[0002] Organic room temperature phosphorescence (RTP) has a wide range of applications in bio-imaging, information encryption, organic light-emitting diodes, sensors, and many other fields. Lifespan and efficiency are two key factors of organic RTP materials. Long lifespan is an indispensable basic characteristic of RTP materials, and high phosphorescence efficiency is an important prerequisite to ensure that it emits bright light and has application prospects.

[0003] So far, reported methods for achieving long-lifetime and high-efficiency organic RTP include the introduction of carbonyls or heavy atoms, crystal engineering, charge transfer states, polymerization, matrix curing, host-guest complexation or self-assembly. However, current strategies are all focused on promoting intersystem crossing (ISC) from the excited state to the triplet state and suppressing the non-radiative decay from the excited state to the ground state. However, ISC is only one of the three competing deactivation processes of singlet excitons. The non-radiative decay through internal conversion (IC) and the radiative decay through fluorescence emission to the ground state are equally important.

[0004] Suppressing IC is also an effective way to increase the quantum yield of ISC (Φisc) and promote phosphorescence. However, the interaction between spins, electronic dynamics and nuclear dynamics make the excited state deactivation route complicated, making IC suppression lack directionality. In addition, phosphorescent moieties, such as benzoic acid and carbazole, are key parts in improving the efficiency of phosphorescent materials. However, the complexity of molecular excited states makes the design of universal phosphorescent moieties difficult to put into practice. Therefore, it is of great significance to synthesize a simple and universal strategy to enhance phosphorescence and obtain a class of phosphorescent moieties, which will surely have great scientific research value and market value. Summary of the invention

[0005] The purpose of the present invention is to provide a protonated product of a pyridine derivative and a composite thereof, a preparation method and an application thereof. In view of the difficulty of synthesizing existing phosphorescent compounds, a composite phosphorescent material with high synthesis yield, low cost, low pollution and high performance is developed, and phosphorescence enhancement is achieved.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] In a first aspect, the present invention provides a protonated product of a pyridine derivative, obtained by protonating pyridine and its derivatives, including: one of R / S-MeBINOL-PSSA, R / S-ClPPH, PPH, ClPPH, BrPPH, OMPPH, SPH, OPH, p-OMPH, ARH, QH, IQH, BrQH, and PhenH;

[0008] The structure of the protonated product of pyridine and its derivatives is shown in formula (II):

[0009]

[0010] In a second aspect, the present invention further provides a method for preparing a protonated product of a pyridine derivative, when the pyridine derivative is 4-phenylpyridine (PP), 4-(4-chlorophenyl)pyridine (ClPP), 4-(4-bromophenyl)pyridine (BrPP), 4-(4-methoxyphenyl)pyridine (OMPP), 4-(2-thienyl)pyridine (SP), 4-(2-furyl)pyridine (OP), 4-methoxypyridine (p-OMP), acridine (AR), quinoline (Q), isoquinoline (IQ), 6-bromoisoquinoline (BrQ), 1,10-phenanthroline (Phen), the method comprises the following steps:

[0011] Under ice bath conditions, hydrochloric acid is added to the ethanol solutions of various pyridine derivatives. After the solution becomes clear, the solvent is removed by rotary evaporation. The obtained solid is dissolved in a small amount of ethanol, and ether is gradually added dropwise. After the white solid is precipitated, it is filtered to obtain the protonated product of the pyridine derivative.

[0012] When the pyridine derivative is R / S-MeBINOL, the method comprises the following steps:

[0013] R / S-MeBINOL was prepared using R / S-6,6'-dibromo-1,1'-bis-2-naphthol as raw material. Poly(4-styrenesulfonic acid) solution was added to the ethanol solution of R / S-MeBINOL under ice bath conditions, and the solution turned yellow. The solvent was removed by rotary evaporation, and the obtained solid was dissolved in ethanol. Ether was gradually added dropwise, and yellow solid was precipitated and filtered to obtain R / S-MeBINOL-PSSA.

[0014] When the pyridine derivative is R / S-ClPP, the method comprises the following steps:

[0015] Mix 4-(4-chlorophenyl)pyridine (ClPP) and R / S-chiral camphorsulfonic acid (R / S-CSA) and add tetrahydrofuran. The solution becomes clear and is sonicated in an ultrasonic spectrometer for 1 to 30 minutes. Then n-hexane is added and sonicated for 1 to 30 minutes. The mixture is allowed to stand and filtered to obtain a white solid R / S-ClPPH.

[0016] In the third aspect, the present invention also provides a phosphorescent complex prepared from a protonated product of a pyridine derivative and a polymer. The phosphorescent complex is prepared by doping a polymer with the protonated product of pyridine and its derivatives to form hydrogen bonds. The rigid structure formed by the hydrogen bonding action is used to limit the non-radiative relaxation of the protonated product to improve the room temperature phosphorescence performance.

[0017] Preferably, the structure of the phosphorescent complex is as shown in formula (I):

[0018]

[0019] Preferably, the polymer includes one of polyvinyl alcohol, polymethyl methacrylate, polystyrene, polyacrylonitrile, polyimide and polyvinyl chloride.

[0020] In a fourth aspect, the present invention further provides a method for preparing a phosphorescent composite from a protonated product of a pyridine derivative and a polymer, comprising the following steps:

[0021] (1) Preparation of protonated products of pyridine derivatives;

[0022] (2) Preparation of phosphorescent complex: heat and dissolve the polymer in a first solvent to obtain a polymer solution, dissolve the protonated product of the pyridine derivative prepared in step (1) in a second solvent to obtain a protonated product solution of the pyridine derivative, mix the polymer solution and the protonated product solution of the pyridine derivative evenly, and evaporate to obtain the phosphorescent complex.

[0023] Preferably, in step (2), the concentration of the polymer solution is 40-60 mg / mL; the concentration of the protonated product solution of the pyridine derivative is 0.4-0.6 mg / mL; and the volume ratio of the polymer solution to the protonated product solution of the pyridine derivative is 1:100.

[0024] Preferably, in step (2), the first solvent is DMF or water, and the second solvent is DMF or ethanol.

[0025] In a fifth aspect, the present invention also provides a phosphorescent composite prepared from a protonated product of a pyridine derivative and a polymer for use in anti-counterfeiting encryption, flexible display or construction of colorful phosphorescent objects.

[0026] The beneficial effects of the present invention compared with the prior art are:

[0027] (1) The present invention achieves phosphorescence enhancement by protonating pyridine and its derivatives, and then further doping the protonated products of pyridine and its derivatives with a polymer to prepare a type of phosphorescent composite film, using the polymer and the protonated products of pyridine and its derivatives to form hydrogen bonds, and the rigid structure formed by the hydrogen bonding action limits the non-radiative relaxation of the compound to improve the room temperature phosphorescence performance.

[0028] (2) The preparation method of the present invention is simple, the raw materials are easily available and low in cost, and it is green and environmentally friendly. The prepared phosphorescent composite has excellent phosphorescent properties and is foldable and cuttable, and can be applied to flexible display, construction of colorful phosphorescent objects, information encryption, anti-counterfeiting and other aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0030] Figure 1 This is the preparation process of the protonated product R-MeBINOL-PSSA of the pyridine derivative in Example 1;

[0031] Figure 2 This is the preparation process of the protonated product R-ClPPH of the pyridine derivative in Example 2;

[0032] Figure 3 The preparation process of synthesizing the phosphorescent composite R-MeBINOL-PSSA@PMMA based on the protonated product R-MeBINOL-PSSA of the pyridine derivative in Example 5;

[0033] Figure 4 The preparation process of synthesizing the phosphorescent composite R-MeBINOL-PSSA@PVA based on the protonated product R-MeBINOL-PSSA of the pyridine derivative in Example 6;

[0034] Figure 5 The preparation process of synthesizing the phosphorescent complex R-ClPPH@PVA based on the protonated product R-ClPPH of the pyridine derivative in Example 7;

[0035] Figure 6 The preparation process of synthesizing the phosphorescent composite PPH@PVA based on the protonated product PPH of the pyridine derivative in Example 7;

[0036] Figure 7The preparation process of synthesizing the phosphorescent complex ClPPH@PVA based on the protonated product ClPPH of the pyridine derivative in Example 7;

[0037] Figure 8 This is the preparation process of synthesizing the phosphorescent complex BrPPH@PVA based on the protonated product BrPPH of the pyridine derivative in Example 7;

[0038] Fig. 9 The preparation process of synthesizing the phosphorescent complex OMPPH@PVA based on the protonated product OMPPH of the pyridine derivative in Example 7;

[0039] Fig.10 This is the preparation process of synthesizing the phosphorescent composite SPH@PVA based on the protonated product SPH of pyridine derivatives in Example 7;

[0040] Fig.11 The preparation process of synthesizing the phosphorescent complex OPH@PVA based on the protonated product OPH of the pyridine derivative in Example 7;

[0041] Fig.12 This is the preparation process of Example 7 for synthesizing the phosphorescent complex p-OMPH@PVA based on the protonated product p-OMPH of the pyridine derivative;

[0042] Fig.13 The preparation process of synthesizing the phosphorescent complex ARH@PVA based on the protonated product ARH of the pyridine derivative in Example 7;

[0043] Fig.14 This is the preparation process of synthesizing the phosphorescent complex IQH@PVA based on the protonated product IQH of the pyridine derivative in Example 7;

[0044] Fig.15 This is the preparation process of synthesizing the phosphorescent complex QH@PVA based on the protonated product QH of the pyridine derivative in Example 7;

[0045] Fig.16 This is the preparation process of synthesizing the phosphorescent complex BrQH@PVA based on the protonated product BrQH of the pyridine derivative in Example 7;

[0046] Fig.17 This is the preparation process of synthesizing the phosphorescent complex PhenH@PVA based on the protonated product PhenH of the pyridine derivative in Example 7;

[0047] Fig.18 This is the NMR spectrum of the protonated product R-ClPPH of the pyridine derivative of Example 7 in Experimental Example 1;

[0048] Fig.19Circularly polarized luminescence spectra of six composite phosphorescent thin film materials, R / S-MeBINOL-PSSA@PMMA, R / S-MeBINOL-PSSA@PVA, and R / S-ClPPH@PVA, prepared in Examples 5, 6, and 7 in Experimental Example 1;

[0049] Fig. 20 This is a luminescent image of the composite phosphorescent film material R-ClPPH@PVA prepared based on R-ClPPH in Experimental Example 1 after being folded into a bow tie;

[0050] Fig.21 The luminescent images of the composite phosphorescent thin film materials R-MeBINOL-PSSA@PMMA and R-MeBINOL-PSSA@PVA prepared based on R-MeBINOL-PSSA in Example 5 and Example 6 of Experimental Example 1 after engraving and cutting;

[0051] Fig. 22 The relevant photophysical data of the composite phosphorescent materials prepared in Examples 5-7;

[0052] Fig.23 This is the preparation process of 4-(2-thienyl)pyridine (SP) and 4-(2-furyl)pyridine (OP) in Example 8. DETAILED DESCRIPTION

[0053] 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.

[0054] 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.

[0055] 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.

[0056] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0057] The present invention provides a method for preparing a protonated product of a pyridine derivative, which mainly includes the following steps:

[0058] When the raw materials are 4-phenylpyridine (PP), 4-(4-chlorophenyl)pyridine (ClPP), 4-(4-bromophenyl)pyridine (BrPP), 4-(4-methoxyphenyl)pyridine (OMPP), 4-(2-thienyl)pyridine (SP), 4-(2-furyl)pyridine (OP), 4-methoxypyridine (p-OMP), acridine (AR), quinoline (Q), isoquinoline (IQ), 6-bromoisoquinoline (BrQ), 1,10-phenanthroline (Phen), the preparation method is as follows:

[0059] (1) Dissolve the pyridine derivative in ethanol under ice bath conditions, and add hydrochloric acid to the solution until it gradually becomes clear;

[0060] (2) removing the solvent by rotary evaporation to obtain a solid;

[0061] (3) The obtained solid was dissolved in ethanol, and ether was gradually added dropwise to precipitate a white solid, which was filtered to obtain the protonated product of the pyridine derivative.

[0062] When the raw material is R / S-MeBINOL, the preparation method is as follows:

[0063] (1) R / S-MeBINOL was prepared using R / S-6,6'-dibromo-1,1'-bis-2-naphthol as raw material;

[0064] (2) Add poly(4-styrene sulfonic acid) solution to the ethanol solution of R / S-MeBINOL under ice bath conditions, and the solution turns yellow;

[0065] The solvent was removed by rotary evaporation, and the resulting solid was dissolved in ethanol;

[0066] (3) Diethyl ether was gradually added dropwise, and a yellow solid was precipitated and filtered to obtain the protonated product R / S-MeBINOL-PSSA.

[0067] When the raw material is R / S-ClPP, the preparation method is as follows:

[0068] (1) 4-(4-chlorophenyl)pyridine (ClPP) and R / S-chiral camphorsulfonic acid (R / S-CSA) were mixed and added to tetrahydrofuran (THF), and the solution was observed to become clear;

[0069] (2) Ultrasonication for 1 to 30 minutes until white solid precipitates, then add n-hexane, and continue ultrasonication for 1 to 30 minutes. When more white solid precipitates, continue ultrasonication to obtain a nanostructure suspension;

[0070] (3) After standing for half an hour, a large amount of solid precipitation was observed, which was collected by filtration to obtain a white solid, which was the protonated product R / S-ClPPH.

[0071] Among them, the protonated products of the pyridine derivatives include R / S-MeBINOL-PSSA, R / S-ClPPH, PPH, ClPPH, BrPPH, OMPPH, SPH, OPH, p-OMPH, ARH, QH, IQH, BrQH, PhenH, etc., and the corresponding structures are shown in formula (II):

[0072]

[0073] Furthermore, the present invention provides a method for preparing a phosphorescent composite, which mainly comprises the following steps:

[0074] (1) Preparation of protonated products of pyridine derivatives;

[0075] (2) Preparation of phosphorescent complex: heat and dissolve the polymer in a first solvent to obtain a polymer solution, dissolve the protonated product of the pyridine derivative prepared in step (1) in a second solvent to obtain a protonated product solution of the pyridine derivative, mix the polymer solution and the protonated product solution of the pyridine derivative evenly, and evaporate to obtain the phosphorescent complex.

[0076] Example 1

[0077] In Example 1 of the present invention, a protonated product of a pyridine derivative, R-MeBINOL-PSSA, is synthesized, and the specific steps are as follows:

[0078] (1) Preparation of protonated product R-MeBINOL-PSSA of pyridine derivative:

[0079] according to Figure 1 R-MeBINOL-PSSA was prepared by the following preparation method:

[0080] A. In a 50mL round-bottom flask, add R-6,6'-dibromo-1,1'-bis-2-naphthol (1.0g, 2.3mmol) and potassium iodide (1.1g, 6.8mmol) in sequence. Add 60mL of acetonitrile to the reaction system, heat the reaction system to 75°C and stir for 10 hours. After the reaction is completed, cool the reaction system to room temperature, filter to obtain a white solid, wash the white solid with water (20mL*3) to obtain a white solid, and then wash the obtained white solid with acetone (20mL*3) to finally obtain the target product as a white solid R-MeBINBr (1.0g, yield 97%).

[0081] B. In a 50mL round-bottom flask, add R-MeBINBr (1.0g, 2.2mmol), pyridine-4-borate hydrochloride (1.0g, 6.5mmol), tetrakis(triphenylphosphine)palladium (0.12g, 0.1mmol) and sodium carbonate (0.7g, 6.6mmol) in sequence. Under nitrogen protection, add a mixed solvent of 50mL 1,4-dioxane and 50mL water (ratio of 5:1) to the reaction system, heat the reaction system to 85°C and stir for 24 hours. After the reaction is completed, cool the reaction system to room temperature and remove the solvent by rotary evaporation. Extract the mixture with dichloromethane and water. Dry the organic phase with anhydrous sodium sulfate and remove the solvent by rotary evaporation again. Finally, separate and purify by column chromatography (eluent composition: petroleum ether / ethyl acetate = 10 / 1, v / v), and the obtained white solid is the target product R-MeBINOL (0.81g, yield 79%).

[0082] C. Synthesis of R-MeBINOL-PSSA

[0083] In a 50mL round-bottom flask, add R-MeBINOL (0.5g, 1.1mmol). Add 10mL of ethanol to the reaction bottle, add poly(4-styrenesulfonic acid) solution dropwise under ice-water bath conditions, and the solution gradually turns yellow. Remove the solvent by rotary evaporation to obtain a yellow solid, dissolve the yellow solid in ethanol, and then add it dropwise into ether (eluent composition: ethanol / ether = 1:10, v / v), a yellow solid precipitates, and filter to obtain a yellow solid. The target product is finally obtained as a yellow solid R-MeBINOL-PSSA (0.56g, yield 95%).

[0084] A transparent composite phosphorescent thin film material S-MeBINOL-PSSA based on the protonated product of pyridine derivatives was prepared using S-6,6'-dibromo-1,1'-bis-2-naphthol as raw material.

[0085] Example 2

[0086] In Example 2 of the present invention, a protonated product of a pyridine derivative, R-ClPPH, is synthesized, and the specific steps are as follows:

[0087] according to Figure 2 As shown in the process, 4-chlorophenylpyridine (0.5 g, 2.6 mmol) and R-chiral camphorsulfonic acid (R-CSA, 0.6 g, 2.6 mmol) were added to a 20 mL centrifuge tube. 10 mL of tetrahydrofuran (THF) was added, and the solution became clear. A white solid was precipitated by ultrasonication in an ultrasonic spectrometer for 10 minutes, and then 10 mL of n-hexane was added to precipitate more white solid. The ultrasonication was continued for 10 minutes to obtain a nanostructured suspension. After standing for half an hour, a large amount of solid precipitated, which was collected by filtration to obtain a white solid R-ClPPH (0.56 g, yield 93%).

[0088] A protonated product of a pyridine derivative, S-ClPPH, was prepared using S-CSA as the starting material.

[0089] Example 3

[0090] In Example 3 of the present invention, the protonated product PPH of the pyridine derivative is synthesized, and the specific steps are as follows:

[0091] In a 50mL round-bottom flask, add phenylpyridine (PP) (0.5g, 3.2mmol). Add 10mL of ethanol to the reaction bottle, add hydrochloric acid solution dropwise under ice-water bath conditions, and the solution gradually becomes clear. Remove the solvent by rotary evaporation to obtain a white solid, dissolve the white solid in a small amount of ethanol, and then add it dropwise to ether (eluent composition: ethanol / ether = 1:10, v / v). A white solid precipitates and is filtered to obtain a yellow solid. The target product is finally obtained as a white solid PPH (0.58g, yield 96%).

[0092] Example 4

[0093] Example 4 of the present invention refers to the preparation method of Example 3, and uses 4-(4-chlorophenyl)pyridine (ClPP), 4-(4-bromophenyl)pyridine (BrPP), 4-(4-methoxyphenyl)pyridine (OMPP), 4-(2-thienyl)pyridine (SP), 4-(2-furyl)pyridine (OP), 4-methoxypyridine (p-OMP), acridine (AR), quinoline (Q), isoquinoline (IQ), 6-bromoisoquinoline (BrQ), and 1,10-phenanthroline (Phen) as raw materials to prepare ClPPH, BrPPH, OMPPH, SPH, OPH, p-OMPH, ARH, QH, IQH, BrQH, and PhenH.

[0094] Example 5

[0095] In Example 5 of the present invention, based on the protonated product R-MeBINOL-PSSA of the pyridine derivative prepared in Example 1, the phosphorescent composite R-MeBINOL-PSSA@PMMA was synthesized, and the specific steps were as follows:

[0096] Heat polymethyl methacrylate (PMMA) in DMF solution until completely dissolved and prepare a 40 mg / mL solution. Dissolve 0.4 mg R-MeBINOL-PSSA in 10 μL DMF solvent to prepare a 40 mg / mL solution, then drip it into 1 mL PMMA DMF solution. After fully mixing, drip the mixed solution onto a quartz plate or glass plate, evaporate the solvent, and obtain a transparent composite phosphorescent film material R-MeBINOL-PSSA@PMMA. The preparation route and luminescent effect of the composite phosphorescent film material are shown in the figure. Figure 3 shown.

[0097] Example 6

[0098] In Example 6 of the present invention, based on the protonated product R-MeBINOL-PSSA of the pyridine derivative prepared in Example 1, the phosphorescent composite R-MeBINOL-PSSA@PVA was synthesized, and the specific steps were as follows:

[0099] Heat polyvinyl alcohol (PVA) in an aqueous solution until it is completely dissolved and prepare a 40 mg / mL PVA solution. Take 0.4 mg of the R-MeBINOL-PSSA prepared in Example 1, dissolve it in 10 μL of ethanol solvent, prepare a 40 mg / mL solution, and then drop it into 1 mL of PVA aqueous solution. After fully mixing, drop the mixed solution on a quartz plate or glass plate, evaporate the solvent, and obtain a transparent composite phosphorescent film material R-MeBINOL-PSSA@PVA. The preparation route and luminescent effect of the composite phosphorescent film material are shown in Figure 4 shown.

[0100] Example 7

[0101] Example 7 of the present invention adopts the method of Example 6 to synthesize phosphorescent composites S / R-ClPPH@PVA, PPH@PVA, ClPPH@PVA, BrPPH@PVA, OMPPH@PVA, SPH@PVA, OPH@PVA, p-OMPH@PVA, ARH@PVA, QH@PVA, IQH@PVA, BrQH@PVA, and PhenH with the protonated products of pyridine derivatives S / R-ClPPH, PPH, ClPPH, BrPPH, OMPPH@PVA, PPH@PVA, p-OMPH@PVA, ARH@PVA, QH@PVA, IQH@PVA, BrQH@PVA, and PhenH@PVA, respectively. The preparation routes and luminescent effects of each composite phosphorescent film material are as follows: Figure 5-17 shown.

[0102] Example 8

[0103] The present invention synthesizes 4-(2-thienyl)pyridine (SP) and 4-(2-furyl)pyridine (OP), and the specific steps are as follows:

[0104] according to Fig.23 The preparation method shown is used to prepare SP and OP:

[0105] In a 250mL round-bottom flask, 4-bromopyridine hydrochloride (1.0g, 5.1mmol), 2-thiopheneboronic acid (1g, 7.6mmol), tetrakis(triphenylphosphine)palladium (0.28g, 0.25mmol) and sodium carbonate (1.6g, 15.3mmol) were added in sequence. Under nitrogen protection, 60mL of a mixed solvent of DMF and water (ratio of 3:1) was added to the reaction system, and then heated to 90°C and stirred for 12 hours. After the reaction, the reaction system was cooled to room temperature and the solvent was removed by vacuum distillation. The mixture was extracted with dichloromethane and water. The organic phase after extraction was dried over anhydrous sodium sulfate and the solvent was removed by vacuum distillation again. Finally, it was separated and purified by column chromatography (eluent composition: petroleum ether / ethyl acetate = 20 / 1, v / v), and the obtained white solid was the target product SP (0.71g, yield 87%).

[0106] In a 250mL round-bottom flask, 4-bromopyridine hydrochloride (1.0g, 5.1mmol), 2-furanboronic acid (0.85g, 7.6mmol), tetrakis(triphenylphosphine)palladium (0.28g, 0.25mmol) and sodium carbonate (1.6g, 15.3mmol) were added in sequence. Under nitrogen protection, 60mL of a mixed solvent of DMF and water (ratio of 3:1) was added to the reaction system, and then heated to 90°C and stirred for 12 hours. After the reaction, the reaction system was cooled to room temperature and the solvent was removed by vacuum distillation. The mixture was extracted with dichloromethane and water. The organic phase after extraction was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum distillation again. Finally, it was separated and purified by column chromatography (eluent composition: petroleum ether / ethyl acetate = 20 / 1, v / v), and the obtained white solid was the target product OP (0.65g, yield 89%).

[0107] Test Example 1

[0108] Experimental Example 1 of the present invention characterizes the composite phosphorescent thin film materials prepared in Examples 1 to 3, and the specific steps are as follows:

[0109] (1) Take the composite phosphorescent film material prepared based on R-ClPPH in Example 3 and detect its NMR (see Fig.18 ), and detect the circularly polarized emission spectra of the six composite phosphorescent film materials prepared in Examples 1 to 3 (see Fig.19 ).

[0110] Depend on Fig.18 It can be seen that the compound R / S-ClPPH obtained by the method for preparing the protonated product of pyridine derivative provided by the present invention has a high purity. Fig.19 It can be seen that the phosphorescent composites R / S-MeBINOL-PSSA@PVA, R / S-MeBINOL-PSSA@PMMA, and S / R-ClPPH@PVA prepared by doping the prepared compounds with polymers PVA and PMMA have their chiral properties and realize circularly polarized organic room temperature phosphorescence.

[0111] (2) The composite phosphorescent film material prepared in Example 3 was folded into a bowknot and its phosphorescence was tested. The results are shown in FIG. Fig. 20 .

[0112] Depend on Fig. 20 It can be seen that the composite phosphorescent thin film material prepared in Example 3 of the present invention can continuously display a butterfly under the irradiation of a 254nm ultraviolet lamp and for 0.3s after the ultraviolet lamp is turned off.

[0113] (3) Example 1 and Example 2 Two different luminescent composite phosphorescent film materials prepared based on R-MeBINOL-PSSA were spliced ​​into multi-color flowers and the number "0816" by engraving, cutting, folding, etc. to prepare a variety of different 3D patterns. Fig.21 .

[0114] Fig.21 It is shown that the composite phosphorescent film material of the present invention has the characteristics of foldability, multi-color and flexibility, and can be used for the construction of flexible 3D phosphorescent objects and information encryption.

[0115] Test Example 2

[0116] Experimental Example 2 of the present invention detected the relevant photophysical data of the composite phosphorescent materials prepared in Examples 1 to 15, and the results are shown in Fig. 22 .

[0117] Depend on Fig. 22 It can be seen that these two different polymers can be used to further restrict the protonation of pyridine derivatives so as to significantly increase the phosphorescence lifetime or quantum yield.

[0118] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details in the above embodiments. Those skilled in the art will appreciate that, without departing from the spirit and scope of the present invention, a variety of equivalent replacements, modifications or improvements may be made to the technical solution of the present invention and its embodiments, which all fall within the scope of the present invention. It should also be noted that, in the absence of contradictions, the various specific technical features described in the above specific embodiments may be combined in any suitable manner to avoid unnecessary duplication. In addition, any combination of the various embodiments of the present invention may also be performed, and as long as they do not violate the concept of the present invention, they shall also be regarded as the contents disclosed by the present invention.

Claims

1. A protonated product of a pyridine derivative, obtained by protonating pyridine and its derivatives, characterized in that: include: One of R / S-MeBINOL-PSSA, R / S-ClPPH, PPH, ClPPH, BrPPH, OMPPH, SPH, OPH, p-OMPH, ARH, QH, IQH, BrQH, PhenH; The structure of the protonated product of pyridine and its derivatives is shown in formula (II):

2. The method for preparing a protonated product of a pyridine derivative according to claim 1, characterized in that: When the pyridine derivative is PP, ClPP, BrPP, OMPP, SP, OP, p-OMP, AR, Q, IQ, BrQ, or Phen, the method comprises the following steps: Under ice bath conditions, hydrochloric acid was added to the ethanol solutions of various pyridine derivatives. After the solution became clear, the solvent was removed by rotary evaporation. The obtained solid was dissolved in a small amount of ethanol, and ether was gradually added dropwise. After the white solid precipitated, it was filtered to obtain the protonated product of the pyridine derivative.

3. The method for preparing a protonated product of a pyridine derivative according to claim 1, characterized in that: When the pyridine derivative is R / S-MeBINOL, the method comprises the following steps: R / S-MeBINOL was prepared using R / S-6,6'-dibromo-1,1'-bis-2-naphthol as raw material. In an ice bath, a poly(4-styrenesulfonic acid) solution was added to the ethanol solution of R / S-MeBINOL, and the solution turned yellow. The solvent was removed by rotary evaporation, and the obtained solid was dissolved in ethanol. Ether was gradually added dropwise, and a yellow solid was precipitated and filtered to obtain R / S-MeBINOL-PSSA.

4. The method for preparing a protonated product of a pyridine derivative according to claim 1, characterized in that: When the pyridine derivative is R / S-ClPP, the method comprises the following steps: Mix 4-(4-chlorophenyl)pyridine and R / S-chiral camphorsulfonic acid and add tetrahydrofuran. The solution becomes clear. Ultrasonicate for 1 to 30 minutes in an ultrasonic spectrometer, then add n-hexane and continue ultrasonicating for 1 to 30 minutes. Let stand and collect by filtration to obtain a white solid R / S-ClPPH.

5. A phosphorescent composite prepared from a protonated product of a pyridine derivative and a polymer, characterized in that: The phosphorescent composite is prepared by doping a polymer on the basis of the protonated product of the pyridine derivative described in claim 1 to form hydrogen bonds, and the rigid structure formed by the hydrogen bonds is used to limit the non-radiative relaxation of the protonated product to improve the room temperature phosphorescent performance.

6. The phosphorescent composite prepared from the protonated product of the pyridine derivative and a polymer according to claim 5, characterized in that: The structure of the phosphorescent composite is shown in formula (I):

7. The phosphorescent composite prepared from the protonated product of the pyridine derivative and a polymer according to claim 5, characterized in that: The polymer includes one of polyvinyl alcohol, polymethyl methacrylate, polystyrene, polyacrylonitrile, polyimide and polyvinyl chloride.

8. A method for preparing a phosphorescent composite from a protonated product of a pyridine derivative and a polymer, characterized in that: The steps include: (1) Preparation of protonated products of pyridine derivatives; (2) Preparation of phosphorescent complex: heat and dissolve the polymer in a first solvent to obtain a polymer solution, dissolve the protonated product of the pyridine derivative prepared in step (1) in a second solvent to obtain a protonated product solution of the pyridine derivative, mix the polymer solution and the protonated product solution of the pyridine derivative evenly, and evaporate to obtain the phosphorescent complex.

9. The method for preparing a phosphorescent composite from a protonated product of a pyridine derivative and a polymer according to claim 8, characterized in that: In step (2), the concentration of the polymer solution is 40-60 mg / mL; the concentration of the protonated product solution of the pyridine derivative is 0.4-0.6 mg / mL; the volume ratio of the polymer solution to the protonated product solution of the pyridine derivative is 1:100; the first solvent is DMF or water, and the second solvent is DMF or ethanol.

10. Use of a phosphorescent complex prepared from a protonated product of a pyridine derivative and a polymer as described in any one of claims 5 to 7 or a phosphorescent complex prepared from a protonated product of a pyridine derivative and a polymer as described in any one of claims 8 to 9 in anti-counterfeiting encryption, flexible display or construction of colorful phosphorescent objects.

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