An all-organic room temperature phosphorescent material

Abstract

The application discloses a kind of all-organic room temperature phosphorescence (RTP) materials, with polyhydroxy polymer cyclodextrin as host molecule, phosphorescence guest is obtained by screening a large number of samples, four kinds of effective organic small molecules.The host molecule and the guest molecule are uniformly mixed, and the RTP material can be prepared after drying.This preparation method combines the unique structural advantages of cyclodextrin and the simple and easy characteristics of organic phosphorescence guest, and through the strong intermolecular hydrogen bond between polyhydroxy polymer cyclodextrin, the vibration and rotation of phosphorescence molecules are limited, and the RTP material with long afterglow and long-term stability in air, non-toxic and environmental protection is prepared.

Description

Technical Field

[0001] This invention relates to room temperature phosphorescent materials, specifically to an all-organic room temperature phosphorescent material. Background Technology

[0002] Fluorescent materials utilize the radiative transition from a singlet excited state to the ground state, typically with a short lifetime of only a few nanoseconds. Phosphorescent materials, on the other hand, utilize the radiative transition from an exciton to the triplet excited state, with a photoluminescence lifetime on the order of seconds visible to the naked eye. This process is usually slow and cannot compete with ultrafast non-radiative processes. Long-lifetime phosphorescent materials can eliminate the interference of short-lifetime fluorescence, making them suitable for advanced anti-counterfeiting and encryption applications. At room temperature, the triplet excited state of phosphorescence is easily deactivated through non-radiative processes such as vibration. Therefore, most organic phosphorescent emission phenomena can only be observed at low temperatures or inert atmospheres. With the deepening research on luminescent materials, all-organic room-temperature phosphorescence has attracted widespread attention from researchers due to its unique optical properties, such as large Stokes shift, multicolored emission, low toxicity, and long-lifetime emission, showing broad application prospects in various optoelectronic, sensing, organic light-emitting diode (OLED), bioimaging, information encryption, and advanced security and anti-counterfeiting fields.

[0003] Because the triplet energy generated by organic molecule excitation is easily lost through thermal vibration and collision processes or exposure to quenchers (such as oxygen), promoting intersystem crossover (ISC) processes to fill the excited triplet state and suppressing nonradiative relaxation processes to isolate quenching factors are crucial in the construction of all-organic room-temperature phosphorescent materials. Based on this, several methods have been developed to realize organic room-temperature phosphorescent materials: introducing heavy atoms and heteroatoms, embedding organic phosphors into polymer matrices, crystallization, host-guest interactions, H aggregation, and forming hydrogen bond networks. Most RTP materials are composed of rare earth elements or organometallic complexes, which are costly, highly toxic, and environmentally unfriendly. Furthermore, the introduction of heavy atoms and heteroatoms reduces the thermal stability of the material and leads to a shortened lifespan. In addition, embedding into polymer matrices complicates the preparation process, making it difficult to control biotoxicity; the harsh growth conditions and uncontrollable growth process of crystals greatly limit the development and commercial application of room-temperature phosphorescent materials (RTPs). Therefore, developing all-organic RTPs is a significant challenge.

[0004] Small molecules and polyhydroxy cyclodextrins form supramolecular assemblies through host-guest interactions and intermolecular hydrogen bonding. As novel RTP materials, they can overcome the shortcomings of traditional low-temperature phosphorescent materials and inorganic and organometallic complexes containing noble metals, showing great application potential. By utilizing host-guest interactions, phosphorescent groups are embedded as guests into the host molecule (macrocyclic cavity), forming a hydrogen bond network with the host material or suppressing the vibration and rotation of phosphorescent groups through host-guest interactions, thereby improving phosphorescence lifetime.

[0005] Host-guest interactions typically utilize cyclodextrins as the host molecule, which are macrocyclic molecules linked by α-1,4 glycosidic bonds. Their structure resembles a truncated pyramid, with a hydrophobic internal cavity and a hydrophilic external surface. Based on the number of glucose units they contain, they can be classified as α-CD, β-CD, and γ-CD, exhibiting good biocompatibility and degradability. Traditional guest molecules require design and optimization, and their preparation methods are complex and their synthetic steps cumbersome.

[0006] Xiang Ma's research group developed amorphous metal-free organometallic compounds with high-efficiency RTP emission by modifying different phosphors onto β-CD. (Amorphous Metal-Free Room-Temperature Phosphorescent SmallMolecules with Multicolor Photoluminescence via a Host-Guest and Dual-Emission Strategy[J]. J.Am.Chem.Soc.2018,140,1916-1923). This non-crystalline metal-free compound with RTP emission is reported for the first time, but it introduces heavy atoms, shortens the lifetime, and the preparation of the phosphor requires design and synthesis, which is cumbersome.

[0007] Xiang Ma's research group further prepared heavy-atom-free, all-organic phosphorescent small-molecule RTP materials by modifying heavy-atom-free luminescent groups onto β-CD (Heavy-atom-free amorphous materials with facile preparation and effiffifficient room-temperature phosphorescence emission [J]. Chem. Commun., 2019, 55, 5355-5358). The materials prepared by this method have high stability and long lifetime, but the fabrication process is still cumbersome and requires multi-step design and synthesis.

[0008] The above methods for preparing room-temperature phosphorescent materials all have the following drawbacks:

[0009] (1) The preparation method is cumbersome and complicated, with many synthesis steps and a long reaction time, making it difficult to produce on a large scale.

[0010] (2) Since the triplet excited state is easily deactivated through non-radiative processes such as vibration, the RTP material prepared cannot exist stably in the air for a long time, which limits its application.

[0011] The phosphorescent guest used in this invention does not require design and synthesis. It is simple, readily available and inexpensive. Through screening a large number of samples, this invention fixes non-phosphorescent fluorescent organic small molecules into cyclodextrin to obtain RTP materials that exhibit both phosphorescence and a long afterglow time. These materials can remain stable in air for 30 days and the long afterglow of phosphorescence can still be observed. Summary of the Invention

[0012] This invention addresses the shortcomings of existing room-temperature phosphorescent materials by providing an all-organic room-temperature phosphorescent material. Using polyhydroxy polymeric cyclodextrin as the host molecule, and through screening a large number of samples, four types of effective small organic molecules were obtained as phosphorescent guests. These are then uniformly mixed and dried to prepare the RTP material. This preparation method combines the unique structural advantages of cyclodextrin with the readily available organic phosphorescent guests. By utilizing the strong intermolecular hydrogen bonds between polyhydroxy polymeric cyclodextrins (CDs), the vibration and rotation of phosphorescent molecules are restricted, resulting in an RTP material that exhibits both long afterglow and long-term stability in air, is non-toxic, and environmentally friendly. It can remain stable in air for 30 days, and the long afterglow of phosphorescence can still be observed.

[0013] The present invention relates to an all-organic room-temperature phosphorescent material, which uses polyhydroxy polymeric cyclodextrin as the main molecule and effectively combines it with organic phosphorescent guest molecules through host-guest interactions and hydrogen bonding interactions. This results in an RTP material that exhibits both phosphorescence and a long afterglow time, and can remain stable in air for a long period of time. It can remain stable in air for 30 days and the long afterglow of phosphorescence can still be observed.

[0014] The polyhydroxy polymeric cyclodextrin used in this invention is a type of macrocyclic host compound with a special structure. Its internal cavity is hydrophobic, while its external surface is hydrophilic. It is specifically prepared by the following method:

[0015] A certain amount of cyclodextrin (CDs) and sodium hydroxide (NaOH) are dissolved in a certain amount of water, ultrasonically mixed, stirred for a certain time, and then a certain amount of epichlorohydrin is added. Stirring is continued at room temperature. The reaction liquid is washed with acetone until a white solid is obtained and the supernatant is colorless and transparent, which yields polyhydroxy polymerized cyclodextrin.

[0016] The organic phosphorescent guest molecules include benzene-based phosphorescent guest molecules, biphenyl-based phosphorescent guest molecules, naphthalene-cyclic phosphorescent guest molecules, and phenanthrene-cyclic phosphorescent guest molecules. These organic phosphorescent guest molecules are four categories identified through screening a large number of samples. They are essentially fluorescent molecules, but can be excited to exhibit phosphorescent properties under confined conditions.

[0017] The general structural formulas of the organic phosphorescent guest molecules obtained by screening in this invention are shown below:

[0018]

[0019]

[0020] This invention relates to an all-organic room-temperature phosphorescent material, which uses polyhydroxy polymeric cyclodextrins (CDs) as the host molecule. The supramolecular polymer and an organic phosphorescent guest are ultrasonically mixed until homogeneous, followed by drying to prepare the RTP material. This preparation method combines the unique structural advantages of cyclodextrins with the readily available nature of the guest molecule, eliminating the need for designing and synthesizing guest molecules and cumbersome post-processing. Through the strong intermolecular hydrogen bonds between the polyhydroxy polymeric cyclodextrins (CDs), a room-temperature RTP material with both long afterglow and high stability is prepared, making it environmentally friendly. The prepared material can remain stable in air for 30 days, and the long afterglow of phosphorescence can still be observed.

[0021] Specifically, the steps include the following:

[0022] Step 1: Synthesis of Polyhydroxy Polycyclodextrin

[0023] A certain amount of cyclodextrin (CDs) and sodium hydroxide (NaOH) are dissolved in a certain amount of water, ultrasonically mixed, stirred for a certain time, and then a certain amount of epichlorohydrin is added. Stirring is continued at room temperature. The reaction liquid is washed with acetone until a white solid is obtained and the supernatant is colorless and transparent, which yields polyhydroxy polymerized cyclodextrin.

[0024] When synthesizing polyhydroxy cyclodextrins, the reaction time can range from 6 to 12 hours, and the reactant concentration, reactant ratio, and stirring speed can be adjusted within a certain range according to the required material properties.

[0025] Step 2: Preparation of all-organic room temperature phosphorescent materials

[0026] Take the polyhydroxy polymeric cyclodextrin obtained in step 1, add a certain amount of neutral phosphate buffer (pH 7.4), and sonicate to dissolve it to obtain a polyhydroxy polymeric cyclodextrin solution; add a well dispersed organic phosphorescent guest molecule solution to the polyhydroxy polymeric cyclodextrin solution, and sonicate to mix evenly; pour the resulting mixture into a petri dish, and then place it in an oven to dry, and obtain a solid supramolecular assembly, i.e., the room temperature phosphorescent material.

[0027] The cyclopaste is selected from one or more of α-CD, β-CD, and γ-CD.

[0028] The phosphoric acid solution that dissolves the polymeric cyclodextrin can be replaced with other buffer solutions (such as citric acid buffer solution) or water.

[0029] In this invention, the mass fraction of sodium hydroxide added is preferably 10-33%, more preferably 10-20%. This proportion is based on the total mass of sodium hydroxide as a percentage of the raw materials.

[0030] In this invention, the mass fraction of epichlorohydrin added is preferably 10-33%, more preferably 12-20%. This proportion is based on the total mass of epichlorohydrin as a percentage of the raw materials.

[0031] In this invention, after adding epichlorohydrin, the stirring speed for synthesizing polyhydroxy polymeric cyclodextrin is preferably 300 r / min to 400 r / min; the stirring time is preferably 8-10 h.

[0032] In this invention, the drying temperature is preferably 130-200℃, more preferably 140-180℃; the drying time is preferably 15-25 min.

[0033] Further, 0.3 g of polyhydroxy polymeric cyclodextrin was dissolved in 1 mL of phosphate buffer solution and sonicated until completely dissolved; 200-800 μL of organic phosphorescent guest solution was added to the above solution and sonicated until homogeneous.

[0034] In this invention, the mass fraction of the organic phosphorescent guest in the liquid assembly is preferably 0.06-0.6%, and the condition varies with the mass fraction of the host molecule.

[0035] Further optimization is preferred, with the mass ratio of polyhydroxy polymeric cyclodextrin to organophosphorescent guest being 1000:1.

[0036] The content of organic phosphorescent guest molecules can be adjusted within a certain range according to the required performance of the material.

[0037] This invention utilizes self-prepared polyhydroxy polymerized cyclodextrin, which is readily available, inexpensive, requires few synthesis steps, and has simple post-processing. Compared to commonly used organometallic complexes, this invention employs a fully organic system, using screened fluorescent small molecules as organic phosphorescent guest molecules. These molecules exhibit good composite effects with the host material and can be obtained directly without design synthesis or post-processing, thus reducing costs. Blending the polymer with the organic phosphorescent guest yields supramolecular assemblies, which are non-toxic, environmentally friendly, and can be used to regulate the luminescence of solid-state materials. They are stable in air for extended periods, greatly advancing the research progress of phosphorescent materials. The purpose of this invention is to prepare polyhydroxy polymerized cyclodextrin, screen a sufficient number of organic small molecules with high luminescence efficiency, and utilize the host-guest interactions and hydrogen bonding interactions between the two to co-assemble RTP materials with highly efficient organic room-temperature phosphorescence emission, applicable to multiple fields.

[0038] This invention provides a novel room-temperature phosphorescent material with long afterglow and good stability. The cyclodextrin used in this invention is a type of macrocyclic host compound with a unique structure; its internal cavity is hydrophobic, while its external surface is hydrophilic. The guest molecules are four types of organic phosphorescent guest molecules identified through extensive sample screening. These are essentially fluorescent molecules, but can be excited to exhibit phosphorescent properties under confined conditions. This invention effectively combines host-guest interactions and hydrogen bonding interactions to obtain an RTP material that exhibits both phosphorescence and a long afterglow time, and can remain stable in air for an extended period. The prepared material can remain stable in air for 30 days, and the long afterglow of phosphorescence can still be observed. Attached Figure Description

[0039] Figure 1 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-m-aminobenzoic acid.

[0040] Figure 2 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-m-aminobenzoic acid.

[0041] Figure 3 Phosphorescence spectrum of polyhydroxy polymerized β-CD-terephthalic acid solid supramolecular assembly.

[0042] Figure 4 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-terephthalic acid.

[0043] Figure 5 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-2-aminoisophthalic acid.

[0044] Figure 6 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-2-aminoisophthalic acid.

[0045] Figure 7 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-3,4-dihydroxybenzoic acid.

[0046] Figure 8 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-3,4-dihydroxybenzoic acid.

[0047] Figure 9 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-biphenyl-4-carboxylic acid.

[0048] Figure 10 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-biphenyl-4-carboxylic acid.

[0049] Figure 11 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-benzidine.

[0050] Figure 12 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-benzidine.

[0051] Figure 13 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-3,3'-dihydroxybenzidine.

[0052] Figure 14 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-3,3'-dihydroxybenzidine.

[0053] Figure 15 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-3,3',5,5'-tetramethylbenzidine.

[0054] Figure 16 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-3,3',5,5'-tetramethylbenzidine.

[0055] Figure 17 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-2,2'-dihydroxybiphenyl.

[0056] Figure 18 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-2,2'-dihydroxybiphenyl.

[0057] Figure 19 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-4,4'-diaminoterphenyl.

[0058] Figure 20Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-4,4'-diaminoterphenyl.

[0059] Figure 21 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-1,5-naphthalenedisulfonic acid.

[0060] Figure 22 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-1,5-naphthalenedisulfonic acid.

[0061] Figure 23 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-2-naphthalenesulfonic acid.

[0062] Figure 24 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-2-naphthalenesulfonic acid.

[0063] Figure 25 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-1,4,5,8-naphthenic acid.

[0064] Figure 26 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-1,4,5,8-naphthotracarboxylic acid.

[0065] Figure 27 Phosphorescence spectrum of solid supramolecular assembly of polyhydroxy polymerized β-CD-naphthalene-1,3,6-trisulfonic acid.

[0066] Figure 28 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-naphthalene-1,3,6-trisulfonic acid.

[0067] Figure 29 Phosphorescence spectrum of polyhydroxy polymerized β-CD-9-aminophenanthrene solid supramolecular assembly.

[0068] Figure 30 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-9-aminophenanthrene.

[0069] Figure 31 Phosphorescence spectrum of solid supramolecular assemblies of polyhydroxy polymerized β-CD-9-phenanthroline boric acid.

[0070] Figure 32 Long afterglow image of a solid supramolecular assembly of polyhydroxy polymerized β-CD-9-phenanthroline.

[0071] * Figure 2 , 4Some images in series 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, and 32 have unclear white text. This is a feature that appears when the images are exported and cannot be deleted. It can be ignored. Detailed Implementation

[0072] The following examples illustrate the content of this invention, including the synthesis of polyhydroxy polymeric cyclodextrin and the phosphorescence spectroscopy testing of the supramolecular assembly of polyhydroxy polymeric cyclodextrin-organic phosphorescent guest. However, the scope of protection of this invention is not limited to the following examples.

[0073] 1.1 Examples 1-5 illustrate the preparation method of polyhydroxy polymeric cyclodextrin α-CD.

[0074] Example 1: Preparation of polyhydroxy polymeric cyclodextrin α-CD

[0075] 1. Dissolve 2g of α-CD and 4.2g of sodium hydroxide (NaOH) in 5mL of water and stir at room temperature for 30 minutes.

[0076] 2. Add 1 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 500 r / min for 12 h at room temperature.

[0077] Example 2: Preparation of polyhydroxy polymeric cyclodextrin α-CD

[0078] 1. Dissolve 2g of α-CD and 2.1g of sodium hydroxide (NaOH) in 5mL of water and stir at room temperature for 30 minutes.

[0079] 2. Add 1 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 400 r / min for 10 h at room temperature.

[0080] Example 3: Preparation of polyhydroxy polymeric cyclodextrin α-CD

[0081] 1. Dissolve 2g of α-CD and 1.4g of sodium hydroxide (NaOH) in 5mL of water and stir at room temperature for 30 minutes.

[0082] 2. Add 1 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 400 r / min for 10 h at room temperature.

[0083] Example 4: Preparation of polyhydroxy polymeric cyclodextrin α-CD

[0084] 1. Dissolve 2g of α-CD and 1.4g of sodium hydroxide (NaOH) in 5mL of water and stir at room temperature for 30 minutes.

[0085] 2. Add 1.2 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 300 r / min for 10 h at room temperature.

[0086] Example 5: Preparation of polyhydroxy polymeric cyclodextrin α-CD

[0087] 1. Dissolve 2g of α-CD and 1.4g of sodium hydroxide (NaOH) in 5mL of water and stir at room temperature for 30 minutes.

[0088] 2. Add 1.3 ml of epichlorohydrin to the above reaction solution, stir and mix thoroughly, and stir at 300 r / min for 8 h at room temperature. 1.2 Examples 6-10 illustrate the preparation method of polyhydroxy polymerized cyclodextrin β-CD.

[0089] Example 6: Preparation of polyhydroxy polymeric cyclodextrin β-CD

[0090] 1. Dissolve 5g of β-CD and 8.5g of sodium hydroxide (NaOH) in 10mL of water and stir at room temperature for 30 minutes.

[0091] 2. Add 2 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 400 r / min for 12 h at room temperature.

[0092] Example 7: Preparation of polyhydroxy polymeric cyclodextrin β-CD

[0093] 1. Dissolve 5g of β-CD and 4.2g of sodium hydroxide (NaOH) in 10mL of water and stir at room temperature for 30 minutes.

[0094] 2. Add 2 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 400 r / min for 10 h at room temperature.

[0095] Example 8: Preparation of polyhydroxy polymeric cyclodextrin β-CD

[0096] 1. Dissolve 5g of β-CD and 2.2g of sodium hydroxide (NaOH) in 10mL of water and stir at room temperature for 30 minutes.

[0097] 2. Add 2.4 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 300 r / min for 10 h at room temperature.

[0098] Example 9: Preparation of polyhydroxy polymeric cyclodextrin β-CD

[0099] 1. Dissolve 5g of β-CD and 2.2g of sodium hydroxide (NaOH) in 10mL of water and stir at room temperature for 30 minutes.

[0100] 2. Add 2.8 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 400 r / min for 9 h at room temperature.

[0101] Example 10: Preparation of polyhydroxy polymeric cyclodextrin β-CD

[0102] 1. Dissolve 5g of β-CD and 2.2g of sodium hydroxide (NaOH) in 10mL of water and stir at room temperature for 30 minutes.

[0103] 2. Add 3.4 ml of epichlorohydrin to the above reaction solution, stir and mix thoroughly, and stir at 400 r / min for 8 h at room temperature. 1.3 Examples 11-15 illustrate the preparation method of polyhydroxy polymerized cyclodextrin γ-CD.

[0104] Example 11: Preparation of Polyhydroxy Polymerized γ-CD

[0105] 1. Dissolve 2g of γ-CD and 3.9g of sodium hydroxide (NaOH) in 5mL of water and stir at room temperature for 30 minutes.

[0106] 2. Add 0.8 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 400 r / min for 10 h at room temperature.

[0107] Example 12: Preparation of Polyhydroxy Polymerized γ-CD

[0108] 1. Dissolve 2g of γ-CD and 2.2g of sodium hydroxide (NaOH) in 5mL of water and stir at room temperature for 30 minutes.

[0109] 2. Add 0.8 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 400 r / min for 10 h at room temperature.

[0110] Example 13: Preparation of Polyhydroxy Polymerized γ-CD

[0111] 1. Dissolve 2g of γ-CD and 1.1g of sodium hydroxide (NaOH) in 5mL of water and stir at room temperature for 30 minutes.

[0112] 2. Add 1.0 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 300 r / min for 8 h at room temperature.

[0113] Example 14: Preparation of Polyhydroxy Polymerized γ-CD

[0114] 1. Dissolve 2g of γ-CD and 1.1g of sodium hydroxide (NaOH) in 5mL of water and stir at room temperature for 30 minutes.

[0115] 2. Add 1.1 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 400 r / min for 8 h at room temperature.

[0116] Example 15: Preparation of Polyhydroxy Polymerized γ-CD

[0117] 1. Dissolve 2g of γ-CD and 1.1g of sodium hydroxide (NaOH) in 5mL of water and stir at room temperature for 30 minutes.

[0118] 2. Add 1.2 ml of epichlorohydrin to the above reaction solution, stir and mix thoroughly, and stir at 400 r / min for 8 h at room temperature. 1.4 Examples 16-18 illustrate the preparation method of polyhydroxy polymerized (β+γ)-CD.

[0119] Example 16: Preparation of polyhydroxy polymer (β+γ)-CD

[0120] 1. Dissolve 2.5g β-CD, 2.85g γ-CD and 2.3g sodium hydroxide (NaOH) in 10mL of water and stir at room temperature for 30 minutes.

[0121] 2. Add 2.6 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 300 r / min for 10 h at room temperature.

[0122] Example 17: Preparation of polyhydroxy polymer (β+γ)-CD

[0123] 1. Dissolve 2.5g β-CD, 2.85g γ-CD and 2.3g sodium hydroxide (NaOH) in 10mL of water and stir at room temperature for 30 minutes.

[0124] 2. Add 3 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 400 r / min for 8 h at room temperature.

[0125] Example 18: Preparation of polyhydroxy polymer (β+γ)-CD

[0126] 1. Dissolve 2.5g β-CD, 2.85g γ-CD and 2.3g sodium hydroxide (NaOH) in 10mL of water and stir at room temperature for 30 minutes.

[0127] 2. Add 3.4 ml of epichlorohydrin to the above reaction solution, stir and mix evenly, and stir at 400 r / min for 8 h at room temperature.

[0128] In this invention, the mass fraction of sodium hydroxide added is preferably 10-33%, more preferably 10-20%.

[0129] In this invention, the mass fraction of epichlorohydrin added is preferably 10-33%, more preferably 12-20%.

[0130] In this invention, after adding epichlorohydrin, the stirring speed for synthesizing polyhydroxy polymeric cyclodextrin is preferably 300 r / min to 400 r / min; the stirring time is preferably 8-10 h.

[0131] 2.1 Examples 19-22 illustrate the preparation method of polyhydroxy polymerized α-CD-organic phosphorescent guest assemblies.

[0132] Example 19: Preparation of a solution of polyhydroxy polymerized α-CD-organophosphorescent guest assembly

[0133] (1) Dissolve 0.3g of polyhydroxy polymer α-CD in 1mL of phosphate buffer solution and sonicate until completely dissolved.

[0134] (2) Add 200 μL of organic phosphorescent guest solution to the above solution and mix thoroughly by ultrasonication.

[0135] Example 20: Preparation of a solution of a polyhydroxy polymerized α-CD-organophosphorescent guest assembly

[0136] (1) Dissolve 0.3g of polyhydroxy polymer α-CD in 1mL of phosphate buffer solution and sonicate until completely dissolved.

[0137] (2) Add 400 μL of organic phosphorescent guest solution to the above solution and mix thoroughly by ultrasonication.

[0138] Example 21: Preparation of a solution of a polyhydroxy polymerized α-CD-organophosphorescent guest assembly

[0139] (1) Dissolve 0.3g of polyhydroxy polymer α-CD in 1mL of phosphate buffer solution and sonicate until completely dissolved.

[0140] (2) Add 600uL of organic phosphorescent guest solution to the above solution and mix thoroughly by ultrasonication.

[0141] Example 22: Preparation of a solution of polyhydroxy polymerized α-CD-organophosphorescent guest assembly

[0142] (1) Dissolve 0.3g of polyhydroxy polymer α-CD in 1mL of phosphate buffer solution and sonicate until completely dissolved.

[0143] (2) Add 800 μL of organic phosphorescent guest solution to the above solution and mix thoroughly by ultrasonication.

[0144] 2.2 Examples 23-26 illustrate the preparation method of polyhydroxy polymerized β-CD-organophosphorescent guest assembly solutions.

[0145] Examples 23-26:

[0146] Using β-CD instead of α-CD, polyhydroxy polymers were prepared in the same manner as in Examples 19-22. Examples 27-30 illustrate the preparation method of polyhydroxy polymerized γ-CD-organic phosphorescent guest assembly solutions.

[0147] Examples 27-30:

[0148] Except for using polyhydroxy polymerized γ-CD instead of polyhydroxy polymerized α-CD, the same method as in Examples 19-22 was used to prepare 2.4 Examples 31-34 to illustrate the preparation method of polyhydroxy polymerized (β+γ)-CD-organic phosphorescent guest assembly solutions. Examples 31-34:

[0149] The polyhydroxy polymer (β+γ)-CD was used instead of the polyhydroxy polymer α-CD, and the same method as in Examples 19-22 was used to prepare the product.

[0150] In this invention, the mass fraction of organic phosphorescent guests in the four types of polyhydroxy polymer-organic phosphorescent guest liquid assemblies is preferably 0.06-0.6%, and the condition varies with the mass fraction of the host molecules.

[0151] 3.1 Examples 35-37 illustrate the preparation method of polyhydroxy polymerized cyclodextrin-organophosphorescent guest supramolecular solid-state assemblies. Example 35: Preparation method of polyhydroxy polymerized cyclodextrin-organophosphorescent guest solid-state assemblies.

[0152] The solution of polyhydroxy polymerized cyclodextrin-organic phosphorescent guest assembly was transferred to a petri dish, placed in an oven, and dried at 100°C for 30 min to obtain the RTP material.

[0153] Example 36: Preparation method of solid-state assembly of polyhydroxy polymerized cyclodextrin-organic phosphorescent guest.

[0154] The solution of polyhydroxy polymerized cyclodextrin-organic phosphorescent guest assembly was transferred to a petri dish and placed in an oven to dry at 150°C for 25 min to obtain the RTP material.

[0155] Example 37: Preparation method of solid-state assembly of polyhydroxy polymerized cyclodextrin-organophosphorescent guest.

[0156] The solution of polyhydroxy polymerized cyclodextrin-organic phosphorescent guest assembly was transferred to a petri dish and placed in an oven to dry at 200°C for 15 min to obtain the RTP material.

[0157] In this invention, the drying temperature is preferably 130-200℃, more preferably 140-180℃; the drying time is preferably 15-25 min. 4. Phosphorescence Spectrum Testing of Room Temperature Phosphorescent Materials

[0158] Taking the polyhydroxy polymerized β-CD-organic phosphorescent guest molecule as an example, the following examples use a phosphorescence spectrometer to perform spectral testing on the obtained assembly.

[0159] Example 38:

[0160] Example 38 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-m-aminobenzoic acid.

[0161] Figure 1 The figure shows the phosphorescence spectrum of the polyhydroxy polymerized β-CD-m-aminobenzoic acid solid supramolecular assembly prepared according to the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 426 nm.

[0162] Figure 2 The image shows the long afterglow of the polyhydroxy polymerized β-CD-m-aminobenzoic acid solid supramolecular assembly prepared according to the above synthesis method. The long afterglow time is about 3 s.

[0163] Example 39:

[0164] Example 39 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-terephthalic acid.

[0165] Figure 3 The figure shows the phosphorescence spectrum of the polyhydroxy polymer β-CD-terephthalic acid solid supramolecular assembly prepared by the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 430 nm.

[0166] Figure 4 The image shows the long afterglow of the polyhydroxy polymerized β-CD-terephthalic acid solid supramolecular assembly prepared according to the above synthesis method. The long afterglow time is about 2 s.

[0167] Example 40:

[0168] Example 40 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-2-aminoisophthalic acid.

[0169] Figure 5 The figure shows the phosphorescence spectrum of the polyhydroxy polymerized β-CD-2-aminoisophthalic acid solid supramolecular assembly prepared according to the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 485 nm.

[0170] Figure 6 The image shows the long afterglow of the solid supramolecular assembly of polyhydroxy polymerized β-CD-2-aminoisophthalic acid prepared by the above synthesis method. The long afterglow time is about 2 s.

[0171] Example 41:

[0172] Example 41 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-3,4-dihydroxybenzoic acid.

[0173] Figure 7 The figure shows the phosphorescence spectrum of the solid supramolecular assembly of polyhydroxy polymerized β-CD-3,4-dihydroxybenzoic acid prepared by the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 512 nm.

[0174] Figure 8 The image shows the long afterglow of the solid supramolecular assembly of polyhydroxy polymerized β-CD-3,4-dihydroxybenzoic acid prepared by the above synthesis method. The long afterglow time is about 5 s.

[0175] Example 42:

[0176] Example 42 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-biphenyl-4-carboxylic acid.

[0177] Figure 9 The figure shows the phosphorescence spectrum of the polyhydroxy polymer β-CD-biphenyl-4-carboxylic acid solid supramolecular assembly prepared by the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 457 nm and 488 nm.

[0178] Figure 10 The image shows the long afterglow of the solid supramolecular assembly of polyhydroxy polymerized β-CD-biphenyl-4-carboxylic acid prepared by the above synthesis method. The long afterglow time is about 5 s.

[0179] Example 43:

[0180] Example 43 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-benzidine.

[0181] Figure 11 The figure shows the phosphorescence spectrum of the polyhydroxy polymerized β-CD-benzidine solid supramolecular assembly prepared according to the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 530 nm.

[0182] Figure 12 The image shows the long afterglow of the polyhydroxy polymerized β-CD-benzidine solid supramolecular assembly prepared according to the above synthesis method. The long afterglow time is about 5 s.

[0183] Example 44:

[0184] Example 44 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-3,3'-dihydroxybenzidine.

[0185] Figure 13The figure shows the phosphorescence spectrum of the polyhydroxy polymer β-CD-3,3'-dihydroxybenzidine solid supramolecular assembly prepared according to the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 560 nm.

[0186] Figure 14 The image shows the long afterglow of the solid supramolecular assembly of polyhydroxy polymerized β-CD-3,3'-dihydroxybenzidine prepared according to the above synthesis method. The long afterglow time is about 2 s.

[0187] Example 45:

[0188] Example 45 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-3,3',5,5'-tetramethylbenzidine.

[0189] Figure 15 The figure shows the phosphorescence spectrum of the solid supramolecular assembly of polyhydroxy polymer β-CD-3,3',5,5'-tetramethylbenzidine prepared according to the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 530 nm.

[0190] Figure 16 The image shows the long afterglow of the solid supramolecular assembly of polyhydroxy polymerized β-CD-3,3',5,5'-tetramethylbenzidine prepared according to the above synthesis method. The long afterglow time is about 4 s.

[0191] Example 46:

[0192] Example 46 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-2,2'-dihydroxybiphenyl.

[0193] Figure 17 The figure shows the phosphorescence spectrum of the polyhydroxy polymer β-CD-2,2'-dihydroxybiphenyl solid supramolecular assembly prepared according to the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 500 nm.

[0194] Figure 18 The image shows the long afterglow of the polyhydroxy polymer β-CD-2,2'-dihydroxybiphenyl solid supramolecular assembly prepared by the above synthesis method. The long afterglow time is about 4 s.

[0195] Example 47:

[0196] Example 46 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-4,4'-diaminoterphenyl.

[0197] Figure 19 The figure shows the phosphorescence spectrum of the polyhydroxy polymer β-CD-4,4'-diaminoterphenyl solid supramolecular assembly prepared by the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 570 nm.

[0198] Figure 20 The image shows the long afterglow of the polyhydroxy polymerized β-CD-4,4'-diaminoterphenyl solid supramolecular assembly prepared according to the above synthesis method. The long afterglow time is about 3 s.

[0199] Example 48:

[0200] Example 48 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-2-naphthalenesulfonic acid.

[0201] Figure 21 The figure shows the phosphorescence spectrum of the polyhydroxy polymerized β-CD-1,5-naphthalene disulfonic acid solid supramolecular assembly prepared according to the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelengths are 497 nm and 524 nm.

[0202] Figure 22 The image shows the long afterglow of the solid supramolecular assembly of polyhydroxy polymerized β-CD-1,5-naphthalenedisulfonic acid prepared by the above synthesis method. The long afterglow time is about 5 s.

[0203] Example 49:

[0204] Example 49 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-1,5-naphthalenedisulfonic acid.

[0205] Figure 23 The figure shows the phosphorescence spectrum of the polyhydroxy polymer β-CD-2-naphthalenesulfonic acid solid supramolecular assembly prepared according to the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 520 nm.

[0206] Figure 24 The image shows the long afterglow of the polyhydroxy polymerized β-CD-2-naphthalenesulfonic acid solid supramolecular assembly prepared according to the above synthesis method. The long afterglow time is about 4 s.

[0207] Example 50:

[0208] Example 50 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-1,4,5,8-naphthalenetetracarboxylic acid.

[0209] Figure 25 The figure shows the phosphorescence spectrum of the polyhydroxy polymer β-CD-1,4,5,8-naphthalenetetracarboxylic acid solid supramolecular assembly prepared according to the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 530 nm.

[0210] Figure 26 The image shows the long afterglow of the solid supramolecular assembly of polyhydroxy polymerized β-CD-1,,4,5,8-naphthalenetetracarboxylic acid prepared by the above synthesis method. The long afterglow time is about 3 s.

[0211] Example 51:

[0212] Example 51 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-naphthalene-1,3,6-trisulfonic acid.

[0213] Figure 27 The figure shows the phosphorescence spectrum of the polyhydroxy polymerized β-CD-naphthalene-1,3,6-trisulfonic acid solid supramolecular assembly prepared according to the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 550 nm.

[0214] Figure 28 The image shows the long afterglow of the polyhydroxy polymerized β-CD-naphthalene-1,3,6-trisulfonic acid solid supramolecular assembly prepared according to the above synthesis method. The long afterglow time is about 7 s.

[0215] Example 52:

[0216] Example 52 demonstrates the phosphorescence spectrum of a polyhydroxy polymerized β-CD-9-aminophenanthrene solid supramolecular assembly.

[0217] Figure 29 The figure shows the phosphorescence spectrum of the polyhydroxy polymer β-CD-9-aminophenanthrene solid supramolecular assembly prepared by the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelength is 438 nm.

[0218] Figure 30 The image shows the long afterglow of the polyhydroxy polymer β-CD-9-aminophenanthrene solid supramolecular assembly prepared according to the above synthesis method. The long afterglow time is about 9 s.

[0219] Example 53:

[0220] Example 53 demonstrates the phosphorescence spectrum of a solid supramolecular assembly of polyhydroxy polymerized β-CD-9-phenanthroline.

[0221] Figure 31 The figure shows the phosphorescence spectrum of the polyhydroxy polymer β-CD-9-phenanthroline solid supramolecular assembly prepared by the above synthesis method. As can be seen from the figure, its phosphorescence emission wavelengths are 490 nm and 520 nm.

[0222] Figure 32 The image shows the long afterglow of the polyhydroxy polymerized β-CD-9-phenanthroline solid supramolecular assembly prepared according to the above synthesis method. The long afterglow time is about 3 s.

[0223] This invention utilizes a prepared polyhydroxy polymeric cyclodextrin, whose raw materials are readily available, inexpensive, and involve few synthesis steps and simple post-processing. It uses screened small organic molecules as phosphorescent guest molecules, which can be directly purchased without requiring design, synthesis, or post-processing, thus reducing costs and experimental time. The polymer is blended with the organic phosphorescent guest and dried to obtain a supramolecular assembly, which is non-toxic and environmentally friendly. The entire preparation strategy is extremely simple, and the resulting material can be used to control the luminescence of solid-state materials. It is stable in air for extended periods, and this discovery greatly advances the research progress of phosphorescent materials, enabling large-scale industrial production and broad applications.

[0224] The above is a detailed description of feasible embodiments of the present invention. However, these embodiments are not intended to limit the patent scope of the present invention. All equivalent implementations or modifications that do not depart from the technical essence of the present invention should be included in the patent scope of the present invention.

Claims

1. An all-organic room-temperature phosphorescent material, characterized in that: Using polyhydroxy polymeric cyclodextrin as the main molecule, and by utilizing host-guest interactions and hydrogen bonding interactions to effectively combine with organic phosphorescent guest molecules, an all-organic room temperature phosphorescent material that can remain stable in air for 30 days and still exhibit a long afterglow phenomenon of phosphorescence was obtained. The all-organic room-temperature phosphorescent material was prepared through the following steps: Step 1: Synthesis of Polyhydroxy Polycyclodextrin Dissolve cyclodextrin and sodium hydroxide in water, mix thoroughly by ultrasonication, stir for a certain period of time, then add epichlorohydrin and continue stirring at room temperature; take the reaction liquid and wash with acetone until a white solid is obtained and the supernatant is colorless and transparent, thus obtaining polyhydroxy polymerized cyclodextrin. Step 2: Preparation of all-organic room temperature phosphorescent materials Take the polyhydroxy polymeric cyclodextrin obtained in step 1, add neutral phosphate buffer, and sonicate to dissolve to obtain a polyhydroxy polymeric cyclodextrin solution; add a well dispersed organic phosphorescent guest molecule solution to the polyhydroxy polymeric cyclodextrin solution, and sonicate to mix evenly; pour the resulting mixture into a petri dish, and then place it in an oven to dry to obtain a solid supramolecular assembly, i.e., the room temperature phosphorescent material. The organic phosphorescent guest molecules are selected from benzene-based phosphorescent guest molecules, biphenyl-based phosphorescent guest molecules, naphthalene-cyclic phosphorescent guest molecules, and phenanthrene-cyclic phosphorescent guest molecules.

2. The all-organic room-temperature phosphorescent material according to claim 1, characterized in that: The general structural formula of the organic phosphorescent guest molecule is shown below: ； ； 。 3. The all-organic room-temperature phosphorescent material according to claim 1, characterized in that: The cyclopaste is selected from one or more of α-CD, β-CD, and γ-CD.

4. The all-organic room-temperature phosphorescent material according to claim 1, characterized in that: In step 2, 0.3g of polyhydroxy polymeric cyclodextrin is dissolved in 1mL of neutral phosphate buffer solution and sonicated until completely dissolved; 200-800uL of organic phosphorescent guest molecule solution is added to the above solution and sonicated to mix evenly; the resulting mixture is poured into a petri dish and then placed in an oven to dry, thereby obtaining a solid supramolecular assembly, i.e., the room temperature phosphorescent material.

5. The all-organic room-temperature phosphorescent material according to claim 4, characterized in that: The mass fraction of organic phosphorescent guest molecules in the organic phosphorescent guest molecule solution is 0.06-0.6%.

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