Organic room-temperature phosphorescent material and preparation method thereof
By using a combination of single aromatic ring and double aromatic ring organic compounds in organic room temperature phosphorescent materials, the problem of long and difficult screening of materials in the prior art is solved, rapid screening and efficient preparation are achieved, and the performance of materials is improved and Application potential.
Patent Information
- Application Number
- CN202411548099.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-31
- Publication Date
- 2025-02-11
AI Technical Summary
The lack of effective strategies in the prior art to screen suitable host materials and guest materials leads to an increase in time and difficulty in building a host-guest doped room temperature phosphorescence system.
An organic room temperature phosphorescent material is provided, including mono-aromatic ring organic compounds as host materials and bi-aromatic ring organic compounds as guest materials, and achieves rapid screening and efficient preparation through specific molar ratios and structural design.
The rapid screening and simplification of the construction of a doped room temperature phosphorescence system for host and guest doped is achieved, reducing the cost of raw materials and the difficulty of preparation, while improving the phosphorescence lifetime and photoluminescence quantum yield.
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Abstract
Description
Technical Field
[0001] The present application relates to the technical field of luminescent materials, and in particular to an organic room temperature phosphorescent material and a preparation method thereof. Background Art
[0002] Room temperature phosphorescence (RTP) materials have attracted widespread attention due to their long phosphorescence lifetime and large Stokes shift. Compared with inorganic materials and metal complex room temperature phosphorescent materials, pure organic room temperature phosphorescent materials have the advantages of easy availability of raw materials, low price, easy processing, and low biological toxicity, and are expected to be widely used in many fields. However, the construction of pure organic room temperature phosphorescent materials is not easy. Pure organic molecules generally have a small spin-orbit coupling (SOC), and it is difficult to obtain a sufficient number of excited triplet molecules through the intersystem crossing (ISC) process. In addition, the excited triplet state is easily quenched by vibration, high temperature or oxygen molecules. Therefore, the phosphorescence emission of pure organic compounds is usually observed under low temperature or inert gas conditions.
[0003] At present, host-guest doping is a simple and efficient method for preparing pure organic room-temperature phosphorescent materials. By physically mixing matching host materials and guest materials, the energy conversion process between the two will promote the appearance of room-temperature phosphorescence emission.
[0004] However, the process of screening matching host and guest materials lacks an effective and complete strategy, which increases the time and difficulty of screening and constructing host-guest doped room temperature phosphorescent systems. Summary of the invention
[0005] The purpose of the present application is to provide an organic room temperature phosphorescent material and a preparation method thereof, so as to provide a strategy for rapidly screening host materials and guest materials suitable as host-guest doped room temperature phosphorescent systems, thereby shortening the time for screening and constructing host-guest doped room temperature phosphorescent systems, and reducing the difficulty of screening and constructing host-guest doped room temperature phosphorescent systems.
[0006] An embodiment of the present application provides an organic room temperature phosphorescent material, which includes: a host material, the host material includes a single aromatic ring organic compound, the single aromatic ring organic compound includes one aromatic ring or multiple aromatic rings that are not directly connected to each other; a guest material, the guest material includes a double aromatic ring organic compound, the double aromatic ring organic compound includes at least two aromatic rings, the at least two aromatic rings include two directly connected aromatic rings, and the other aromatic rings except the two directly connected aromatic rings in the at least two aromatic rings are connected to the two directly connected aromatic rings at intervals.
[0007] The main material is a mixture of one or more single aromatic ring organic compounds represented by general formula (I-1) to (I-3):
[0008]
[0009] Wherein, in the general formula (I-1), R1 is selected from -COOCH3 or -COOH, and R2, R3, R4, R5 and R6 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH; in the general formula (I-2), R1, R2, R3, R4 and R5 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH in the general formula (I-2) is ≥1; in the general formula (I-3), R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 Each is independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH.
[0010] The guest material is a mixture of one or more of the diaromatic organic compounds represented by the general formula (II-1) to (II-8):
[0011]
[0012]
[0013] In the general formula (II-1), R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10Each of the following is independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH in the general formula (II-1) is ≥ 1; in the general formula (II-2) and the general formula (II-3), R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH in the general formula (II-2) is ≥ 1, the number of -COOCH3 or -COOH in the general formula (II-3) is ≥1; in the general formulas (II-4) to (II-6), R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH contained in each of the general formulas (II-4) to (II-6) is ≥1; in the general formula (II-7), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH; in the general formula (II-8), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 Each is independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH.
[0014] Wherein, the molar ratio of the host material to the guest material in the organic room temperature phosphorescent material is 10000:1 to 100:1.
[0015] Among them, organic room temperature phosphorescent materials exhibit blue-green to yellow-green afterglow emission after being irradiated with ultraviolet light at room temperature.
[0016] Among them, the phosphorescence lifetime of the organic room temperature phosphorescent material is 13.89 to 1008.9 ms.
[0017] The photoluminescence quantum yield of the organic room temperature phosphorescent material is 4.0% to 35.0%.
[0018] An embodiment of the present application also provides a method for preparing an organic room temperature phosphorescent material. The method for preparing an organic room temperature phosphorescent material is used to prepare any of the above-mentioned organic room temperature phosphorescent materials. The method comprises: dissolving a host material and a guest material in a solvent respectively and then mixing them, and then removing the solvent to obtain the organic room temperature phosphorescent material.
[0019] The method comprises: weighing the host material and the guest material respectively; dissolving the weighed host material and guest material respectively in a solvent to prepare a host material solution and a guest material solution; and adding the guest material solution dropwise into the host material solution under stirring to obtain a mixed solution, wherein the molar ratio of the host material to the guest material in the mixed solution is controlled to be between 10000:1 and 100:1.
[0020] Wherein, the solvent is dichloromethane and / or methanol.
[0021] The present application provides an organic room temperature phosphorescent material and a preparation method thereof. The organic room temperature phosphorescent material includes a host material and a guest material, wherein the host material includes a single aromatic ring organic compound, the single aromatic ring organic compound includes one aromatic ring or multiple aromatic rings that are not directly connected to each other, and the guest material includes a double aromatic ring organic compound, the double aromatic ring organic compound includes at least two aromatic rings, the at least two aromatic rings include two directly connected aromatic rings, and the other aromatic rings in the at least two aromatic rings are connected to the two directly connected aromatic rings at intervals, thereby providing a method for efficiently screening host materials and guest materials in a pure organic two-component room temperature phosphorescent system, and can achieve the preparation of host-guest doped room temperature phosphorescent materials. The raw materials are easy to obtain, the preparation method is simple and convenient, the phosphorescence life is long, and good applications can be obtained in anti-counterfeiting, information encryption and biological imaging. The method of screening the host and the guest is intuitive and effective, the raw materials of the prepared room temperature phosphorescent material are cheap and easy to obtain, the preparation method is simple and convenient, and it can be used to quickly select materials suitable as the host and guest of the doped room temperature phosphorescent system. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The technical solution and other beneficial effects of the present application will be made apparent by describing in detail the specific implementation methods of the present application in conjunction with the accompanying drawings.
[0023] Figure 1 is a phosphorescence emission spectrum of an organic room temperature phosphorescent material prepared by the method for preparing an organic room temperature phosphorescent material provided in Example 1 of the present application;
[0024] Figure 2is a phosphorescence lifetime decay curve of an organic room temperature phosphorescent material prepared by the method for preparing an organic room temperature phosphorescent material provided in Example 1 of the present application;
[0025] Figure 3 is a phosphorescence emission spectrum of an organic room temperature phosphorescent material prepared by the method for preparing an organic room temperature phosphorescent material provided in Example 2 of the present application;
[0026] Figure 4 is a phosphorescence lifetime decay curve of an organic room temperature phosphorescent material prepared by the method for preparing an organic room temperature phosphorescent material provided in Example 2 of the present application;
[0027] Figure 5 is a phosphorescence emission spectrum of an organic room temperature phosphorescent material prepared by the method for preparing an organic room temperature phosphorescent material provided in Example 3 of the present application;
[0028] Figure 6 is a phosphorescence lifetime decay curve of an organic room temperature phosphorescent material prepared by the method for preparing an organic room temperature phosphorescent material provided in Example 3 of the present application;
[0029] Figure 7 is a phosphorescence emission spectrum of an organic room temperature phosphorescent material prepared by the method for preparing an organic room temperature phosphorescent material provided in Example 4 of the present application;
[0030] Figure 8 This is a phosphorescence lifetime decay curve of the organic room temperature phosphorescent material prepared by the preparation method of the organic room temperature phosphorescent material provided in Example 4 of the present application. DETAILED DESCRIPTION
[0031] The present application is further described in detail below in conjunction with the accompanying drawings and examples. It is particularly noted that the following examples are only used to illustrate the present application, but are not intended to limit the scope of the present application. Similarly, the following examples are only some embodiments of the present application rather than all embodiments, and all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of this application.
[0032] In the following description of the present application, reference is made to “some embodiments”, which describe a subset of all possible embodiments, but it can be understood that “some embodiments” may be the same subset or different subsets of all possible embodiments and may be combined with each other without conflict.
[0033] In the following description of the present application, the terms "first\second\third" involved are merely used to distinguish similar objects and do not represent a specific ordering of the objects. It can be understood that "first\second\third" can be interchanged with a specific order or sequence where permitted, so that the embodiments of the present application described here can be implemented in an order other than that illustrated or described here.
[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein are only for the purpose of describing the embodiments of this application and are not intended to limit this application.
[0035] The following is a detailed description with reference to specific embodiments. It should be noted that the serial numbers of the following embodiments are not intended to limit the preferred order of the embodiments.
[0036] The embodiment of the present application provides an organic room temperature phosphorescent material, which includes a host material and a guest material. Among them, the host material includes a single aromatic ring organic compound, and the single aromatic ring organic compound includes one aromatic ring or multiple aromatic rings that are not directly connected to each other. The guest material includes a double aromatic ring organic compound, and the double aromatic ring organic compound includes at least two aromatic rings, and the at least two aromatic rings include two aromatic rings that are directly connected, and the other aromatic rings in the at least two aromatic rings except the two aromatic rings that are directly connected are spaced from the two aromatic rings that are directly connected.
[0037] In this embodiment, the above-mentioned organic room temperature phosphorescent material can be a pure organic room temperature phosphorescent material, the main material included in the above-mentioned organic room temperature phosphorescent material can be selected from one or more mixtures of a series of single aromatic ring organic compounds, and the guest material included in the above-mentioned organic room temperature phosphorescent material can be selected from one or more mixtures of a series of double aromatic ring organic compounds.
[0038] Furthermore, it should be noted that the inventors of the present application have discovered in their long-term research and development that there are impurities in isophthalic acid and dimethyl isophthalate that induce room temperature phosphorescence, and the impurity structure is a biphenyl-like compound. Further, inspired by the impurity structure, the inventors of the present application have selected a series of single aromatic ring organic compounds (e.g., single aromatic ring organic compounds shown in the following formulas (I-1) to (I-17)) and a series of double aromatic ring organic compounds (e.g., double aromatic ring organic compounds shown in the following formulas (II-1) to (II-28)), so as to quickly select materials suitable for use as host and guest materials of the doped room temperature phosphorescent system from a series of single aromatic ring organic compounds and a series of double aromatic ring organic compounds, and the method of screening host and guest materials in this way is intuitive and effective, the raw materials of the prepared room temperature phosphorescent material are cheap and easy to obtain, the preparation method is simple and convenient, and the phosphorescence life is long.
[0039] In some embodiments, in the above-mentioned organic room temperature phosphorescent material, the host material may be a mixture of one or more of the monoaromatic ring organic compounds represented by the following general formulas (I-1) to (I-3):
[0040]
[0041] Wherein, in the above general formula (I-1), R1 is selected from -COOCH3 or -COOH, and R2, R3, R4, R5 and R6 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH.
[0042] In the above general formula (I-2), R1, R2, R3, R4 and R5 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH in the general formula (I-2) is ≥1.
[0043] In the above general formula (I-3), R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 Each is independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH.
[0044] In some embodiments, in the above organic room temperature phosphorescent material, the guest material may be a mixture of one or more of the following biaromatic ring organic compounds represented by the following general formulas (II-1) to (II-8):
[0045]
[0046] In the above general formula (II-1), R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 They are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH in the above general formula (II-1) is ≥1.
[0047] In the above general formula (II-2) and the above general formula (II-3), R1, R2, R3, R4, R5, R6, R7, R8 and R9 are respectively and independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH in the above general formula (II-2) is ≥1, and the number of -COOCH3 or -COOH in the above general formula (II-3) is ≥1.
[0048] In the above general formulas (II-4) to (II-6), R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH contained in each of the above general formulas (II-4) to (II-6) is ≥1.
[0049] In the above general formula (II-7), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 Each is independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH.
[0050] In the above general formula (II-8), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 Each is independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH.
[0051] In some specific embodiments, in the above-mentioned organic room temperature phosphorescent material, the main material can be a single aromatic ring organic compound, for example, it can be any one of the single aromatic ring organic compounds shown in the above-mentioned general formulas (I-1) to (I-3), and the guest material can be a double aromatic ring organic compound, for example, it can be any one of the double aromatic ring organic compounds shown in the above-mentioned general formulas (II-1) to (II-8).
[0052] In some examples, in the above-mentioned organic room temperature phosphorescent material, the host material and the guest material can be dimethyl isophthalate (i.e., the monoaromatic ring organic compound represented by the general formula (I-1) when R1 and R3 contained therein are both -COOCH3, and R2, R4, R5 and R6 contained therein are all -H) and dimethyl 4,4'-biphenyl dicarboxylate (i.e., the general formula (II-1) when R9 and R 10They are all -COOCH3, and the bicyclic aromatic ring organic compounds represented by R1, R2, R3, R4, R5, R6, R7 and R8 contained therein are all -H), and both can be directly purchased from reagent companies.
[0053] In some examples, in the above-mentioned organic room temperature phosphorescent material, the main material and the guest material can be 3,5-pyridinedicarboxylic acid methyl ester (that is, the monoaromatic ring organic compound shown in the above-mentioned general formula (I-2) when R2 and R5 contained therein are both -COOCH3, and R1, R3 and R4 contained therein are all -H) and 2,2'-bipyridine-5,5'-dicarboxylic acid dimethyl ester (that is, the above-mentioned general formula (II-4) when R7 and R8 contained therein are both -COOCH3, and R1, R2, R3, R4, R5 and R6 contained therein are all -H) The double aromatic ring organic compound shown, and both can be directly purchased from reagent companies.
[0054] In some examples, in the above organic room temperature phosphorescent material, the host material and the guest material can be benzophenone (i.e., the above general formula (I-3) in which R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 are all -H) and 4-phenylbenzophenone (i.e., the general formula (II-7) wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 Both are diaromatic organic compounds as indicated by -H), and both can be purchased directly from reagent companies.
[0055] In some examples, in the above-mentioned organic room temperature phosphorescent material, the host material and the guest material can be respectively p-phenylenedimethyl ether (i.e., the monoaromatic ring organic compound shown in the above-mentioned general formula (I-1) when R1 and R4 contained therein are both -OCH3, and R2, R3, R5 and R6 contained therein are all -H) and 4,4'-dimethoxybiphenyl (i.e., the above-mentioned general formula (II-1) when R9 and R 10 All are -OCH3, and the bicyclic aromatic ring organic compounds represented by R1, R2, R3, R4, R5, R6, R7 and R8 contained therein are all -H), and both can be directly purchased from reagent companies.
[0056] In the above embodiment, in the above organic room temperature phosphorescent material, the molar ratio of the host material to the guest material may be 10000:1 to 100:1, for example, may be specifically 1000:1, or may be specifically 100:1.
[0057] In the above embodiment, the above organic room temperature phosphorescent material can present a blue-green to yellow-green afterglow emission after being irradiated with ultraviolet light at room temperature. The phosphorescence lifetime of the above organic room temperature phosphorescent material can be 13.89 to 1008.9 ms, for example, it can be specifically 810.5 ms, 1008.9 ms, 13.89 ms or 112.07 ms. The photoluminescence quantum yield of the above organic room temperature phosphorescent material is 4.0% to 35.0%, for example, it can be specifically 35.0%, 4.5%, 4.0% or 13.4%.
[0058] Furthermore, it can be understood that in this embodiment, by selecting different host materials and / or different guest materials to construct a host-guest doped room temperature phosphorescent system, the phosphorescence lifetime and / or photoluminescence quantum yield of the host-guest doped room temperature phosphorescent material (that is, the above-mentioned organic room temperature phosphorescent material) can be made adjustable, thereby obtaining a long phosphorescence lifetime (up to 1008.9 ms) and / or a high photoluminescence quantum yield (up to 13.4%).
[0059] As can be seen from the above, the organic room temperature phosphorescent material provided in this embodiment includes a host material and a guest material, wherein the host material includes a single aromatic ring organic compound, the single aromatic ring organic compound includes one aromatic ring or multiple aromatic rings that are not directly connected to each other, and the guest material includes a double aromatic ring organic compound, the double aromatic ring organic compound includes at least two aromatic rings, the at least two aromatic rings include two directly connected aromatic rings, and the other aromatic rings in the at least two aromatic rings are connected to the two directly connected aromatic rings at intervals, thereby providing a method for efficiently screening host materials and guest materials in a pure organic two-component room temperature phosphorescent system, and can achieve the preparation of host-guest doped room temperature phosphorescent materials. The raw materials are easy to obtain, the preparation method is simple and convenient, the phosphorescence lifetime is long, and it can be well applied in anti-counterfeiting, information encryption and biological imaging.
[0060] In order to better implement the organic room temperature phosphorescent material provided in the embodiment of the present application, the embodiment of the present application also provides a method for preparing the organic room temperature phosphorescent material, which can be applied to prepare the organic room temperature phosphorescent material provided in any of the above embodiments. In addition, the specific process of the method for preparing the organic room temperature phosphorescent material can be as follows:
[0061] The host material and the guest material are dissolved in a solvent respectively and then mixed, and then the solvent is removed to obtain an organic room temperature phosphorescent material.
[0062] Wherein, the host material includes a single aromatic ring organic compound, and the single aromatic ring organic compound includes one aromatic ring or multiple aromatic rings that are not directly connected to each other. The guest material includes a double aromatic ring organic compound, and the double aromatic ring organic compound includes at least two aromatic rings, wherein the at least two aromatic rings include two aromatic rings that are directly connected, and the other aromatic rings in the at least two aromatic rings are spaced apart from the two aromatic rings that are directly connected. In addition, during specific implementation, the screening method of the host material and the guest material can refer to the screening method of the host material and the guest material in the above-mentioned organic room temperature phosphorescent material embodiment, so it will not be repeated here.
[0063] The solvent may be an organic solvent, for example, dichloromethane and / or methanol.
[0064] In some embodiments, the above-mentioned dissolving the host material and the guest material in solvents and then mixing them may include:
[0065] Step S11. Weigh the host material and the guest material respectively.
[0066] Step S12: Dissolve the weighed host material and guest material in solvents to prepare host material solution and guest material solution respectively.
[0067] The concentration of the host material in the host material solution may be 10 mmol / L, and the concentration of the guest material in the guest material solution may be 0.1 mmol / L.
[0068] Step S13: Add the guest material solution dropwise into the host material solution under stirring to obtain a mixed solution.
[0069] Specifically, in the process of adding the guest material solution to the host material solution under stirring conditions to obtain a mixed solution, the molar ratio of the host material to the guest material in the mixed solution can be controlled at 10000:1 to 100:1, for example, can be specifically controlled at 1000:1, or can be specifically controlled at 100:1.
[0070] Accordingly, removing the above solvent to obtain an organic room temperature phosphorescent material may include:
[0071] Step S14: removing the solvent from the mixed solution to obtain an initial sample, and vacuum drying the initial sample to obtain a dried sample, wherein the dried sample is an organic room temperature phosphorescent material.
[0072] Furthermore, in the specific implementation, the host material and the guest material weighed in the above step S11 can be dissolved in 10 mL of dichloromethane, ultrasonically oscillated until completely dissolved, and prepared into a 10 mmol / L host material solution and a 0.1 mmol / L guest material solution. Then, a certain volume of 10 mmol / L host material solution and a certain volume of 0.1 mmol / L guest material solution can be taken respectively, and the molar ratio of the host material in the taken host material solution to the guest material in the taken guest material solution is 10000:1 to 100:1, and then the taken guest material solution is slowly added dropwise to the taken host material solution under vigorous stirring to prepare a mixed solution, so that the molar ratio of the host material and the guest material in the mixed solution can be controlled to be 10000:1 to 100:1. Afterwards, a rotary evaporator can be used to remove the solvent in the mixed solution to obtain an initial sample, and then the initial sample can be dried in a vacuum drying oven to obtain a uniformly mixed white powder (that is, the above-mentioned organic room temperature phosphorescent material).
[0073] For ease of understanding, the present application is further described in detail below through four specific embodiments (ie, Embodiment 1, Embodiment 2, Embodiment 3 and Embodiment 4).
[0074] Example 1
[0075] In Example 1, the host material and the guest material contained in the organic room temperature phosphorescent material are dimethyl isophthalate and dimethyl 4,4'-biphenyl dicarboxylate, respectively, and both can be directly purchased from a reagent company. Accordingly, the specific process of the preparation method of the organic room temperature phosphorescent material can be as follows:
[0076] Step S21. Weigh 19.4 mg of dimethyl isophthalate and 0.27 mg of dimethyl 4,4'-biphenyl dicarboxylate respectively, then dissolve the weighed 19.4 mg of dimethyl isophthalate and 0.27 mg of dimethyl 4,4'-biphenyl dicarboxylate in 10 mL of dichloromethane respectively, and oscillate ultrasonically until completely dissolved to prepare a 10 mmol / L host material solution and a 0.1 mmol / L guest material solution.
[0077] Step S22. Take 5 ml of the host material solution and 0.5 ml of the guest material solution respectively, and slowly add the taken guest material solution drop by drop into the taken host material solution under vigorous stirring to prepare a mixed solution, and the molar ratio of the host material to the guest material in the mixed solution is controlled at 1000:1.
[0078] Step S23: using a rotary evaporator to remove the solvent in the mixed solution, and drying in a vacuum drying oven to obtain a uniformly mixed white powder, which is the organic room temperature phosphorescent material A1.
[0079] Furthermore, the organic room temperature phosphorescent material A1 produces bright green phosphorescence under 305 nm light excitation. The delayed emission spectrum of the organic room temperature phosphorescent material A1 is shown in FIG. Figure 1 As shown in FIG. 1 , the maximum emission wavelength is 512 nm. The delayed emission lifetime decay curve of the organic room temperature phosphorescent material A1 is shown in FIG. Figure 2 As shown, the phosphorescence lifetime obtained by fitting is 810.5 ms. The photoluminescence quantum yield of the organic room temperature phosphorescent material A1 is 35.0%.
[0080] Example 2
[0081] In Example 2, the host material and the guest material contained in the organic room temperature phosphorescent material are 3,5-pyridinedicarboxylic acid methyl ester and 4,4'-biphenyldicarboxylic acid dimethyl ester, respectively, and both can be directly purchased from a reagent company. Accordingly, the specific process of the preparation method of the organic room temperature phosphorescent material can be as follows:
[0082] Step S31. Weigh 19.5 mg of 3,5-pyridinedicarboxylic acid methyl ester and 0.27 mg of 4,4'-biphenyldicarboxylic acid dimethyl ester respectively, then dissolve the weighed 19.5 mg of 3,5-pyridinedicarboxylic acid methyl ester and 0.27 mg of 4,4'-biphenyldicarboxylic acid dimethyl ester in 10 ml of dichloromethane respectively, and perform ultrasonic oscillation until completely dissolved to prepare a 10 mmol / L host material solution and a 0.1 mmol / L guest material solution.
[0083] Step S32. Take 5 ml of the host material solution and 5 ml of the guest material solution respectively, and slowly add the taken guest material solution drop by drop into the taken host material solution under vigorous stirring to prepare a mixed solution, and the molar ratio of the host material to the guest material in the mixed solution is controlled at 100:1.
[0084] Step S33. The solvent in the mixed solution is removed by a rotary evaporator, and a uniformly mixed white powder is obtained after drying in a vacuum drying oven, which is the organic room temperature phosphorescent material A2.
[0085] Furthermore, the organic room temperature phosphorescent material A2 produces bright green phosphorescence under 310 nm light excitation. The delayed emission spectrum of the organic room temperature phosphorescent material A2 is Figure 3 As shown in FIG. 1 , the maximum emission wavelength is 522 nm. The delayed emission lifetime decay curve of the organic room temperature phosphorescent material A2 is shown in FIG. Figure 4 As shown, the fitted phosphorescence lifetime is 1009.0 ms, and the photoluminescence quantum yield of the organic room temperature phosphorescent material A2 is 4.5%.
[0086] Example 3
[0087] In Example 3, the host material and guest material contained in the organic room temperature phosphorescent material are benzophenone and 4-phenylbenzophenone, respectively, and both can be directly purchased from a reagent company. Accordingly, the specific process of the preparation method of the organic room temperature phosphorescent material can be as follows:
[0088] Step S41. Weigh 19.4 mg of benzophenone and 0.26 mg of 4-phenylbenzophenone respectively, then dissolve the weighed 19.4 mg of benzophenone and 0.26 mg of 4-phenylbenzophenone in 10 ml of dichloromethane respectively, and oscillate ultrasonically until completely dissolved to prepare a 10 mmol / L host material solution and a 0.1 mmol / L guest material solution.
[0089] Step S42. Take 5 ml of the host material solution and 5 ml of the guest material solution respectively, and slowly add the taken guest material solution drop by drop into the taken host material solution under vigorous stirring to prepare a mixed solution, and the molar ratio of the host material to the guest material in the mixed solution is controlled at 100:1.
[0090] Step S43: using a rotary evaporator to remove the solvent in the mixed solution, and drying in a vacuum drying oven to obtain a uniformly mixed white powder, which is the organic room temperature phosphorescent material A3.
[0091] Furthermore, the organic room temperature phosphorescent material A3 produces bright green phosphorescence under 375 nm light excitation. The delayed emission spectrum of the organic room temperature phosphorescent material A3 is Figure 5 As shown in FIG. 1 , the maximum emission wavelength is 487 nm. The delayed emission lifetime decay curve of the organic room temperature phosphorescent material A3 is shown in FIG. Figure 6 As shown, the fitted phosphorescence lifetime is 13.89 ms, and the photoluminescence quantum yield of the organic room temperature phosphorescent material A3 is 4.0%.
[0092] Example 4
[0093] In Example 4, the host material and guest material contained in the organic room temperature phosphorescent material are p-phenylenedimethyl ether and 4,4'-dimethoxybiphenyl, respectively, and both can be directly purchased from a reagent company. Accordingly, the specific process of the preparation method of the organic room temperature phosphorescent material can be as follows:
[0094] Step S51. Weigh 13.8 mg of p-phenylenedimethyl ether and 0.21 mg of 4,4'-dimethoxybiphenyl respectively, then dissolve the weighed 13.8 mg of p-phenylenedimethyl ether and 0.21 mg of 4,4'-dimethoxybiphenyl respectively in 10 ml of dichloromethane, and oscillate ultrasonically until completely dissolved to prepare a 10 mmol / L host material solution and a 0.1 mmol / L guest material solution.
[0095] Step S52. Take 5 ml of the host material solution and 5 ml of the guest material solution respectively, and slowly add the taken guest material solution drop by drop into the taken host material solution under vigorous stirring to prepare a mixed solution, and the molar ratio of the host material to the guest material in the mixed solution is controlled at 100:1.
[0096] Step S53. The solvent in the mixed solution is removed by a rotary evaporator, and a uniformly mixed white powder is obtained after drying in a vacuum drying oven, which is the organic room temperature phosphorescent material A4.
[0097] Furthermore, the organic room temperature phosphorescent material A4 produces bright green phosphorescence under 316 nm light excitation. The delayed emission spectrum of the organic room temperature phosphorescent material A4 is Figure 7 As shown in FIG. 1 , the maximum emission wavelength is 482 nm. The delayed emission lifetime decay curve of the organic room temperature phosphorescent material A4 is shown in FIG. Figure 8 As shown, the fitted phosphorescence lifetime is 112.07 ms, and the photoluminescence quantum yield of the organic room temperature phosphorescent material A4 is 13.4%.
[0098] Combined with Example 1, Example 2, Example 3 and Example 4, and combined with Figures 1 to 8 , it can be explained that: the host-guest doped room temperature phosphorescent material prepared in the embodiment of the present application has a long afterglow from blue-green to yellow-green at room temperature that can be seen by the naked eye. In addition, according to the different host materials and guest materials selected, the phosphorescence lifetime of the host-guest doped room temperature phosphorescent material prepared in the embodiment of the present application is adjustable, and the phosphorescence lifetime can reach up to 1008.9ms. The photoluminescence quantum yield of the host-guest doped room temperature phosphorescent material prepared in the embodiment of the present application is adjustable, and the photoluminescence quantum yield can reach up to 35.0%.
[0099] As can be seen from the above, the preparation method of the organic room temperature phosphorescent material provided in this embodiment is obtained by dissolving the main material and the guest material in a solvent respectively, mixing them, and then removing the solvent to obtain the organic room temperature phosphorescent material, wherein the main material includes a single aromatic ring organic compound, the single aromatic ring organic compound includes one aromatic ring or multiple aromatic rings that are not directly connected to each other, and the guest material includes a double aromatic ring organic compound, the double aromatic ring organic compound includes at least two aromatic rings, the at least two aromatic rings include two directly connected aromatic rings, and the other aromatic rings in the at least two aromatic rings are connected to the two directly connected aromatic rings at intervals, thereby providing a method for efficiently screening the main material and the guest material in a pure organic two-component room temperature phosphorescent system, and can achieve the preparation of the host and guest doped room temperature phosphorescent material. The raw materials are easy to obtain, the preparation method is simple and convenient, the phosphorescence lifetime is long, and it can be well applied in anti-counterfeiting, information encryption and biological imaging.
[0100] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.
[0101] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application. The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application.
Claims
1. An organic room temperature phosphorescent material, characterized in that: include: A host material, wherein the host material comprises a single aromatic ring organic compound, wherein the single aromatic ring organic compound comprises one aromatic ring or a plurality of aromatic rings that are not directly connected to each other; A guest material, wherein the guest material includes a double aromatic ring organic compound, wherein the double aromatic ring organic compound includes at least two aromatic rings, wherein the at least two aromatic rings include two aromatic rings that are directly connected, and wherein the other aromatic rings among the at least two aromatic rings except the two aromatic rings that are directly connected are connected to the two aromatic rings that are directly connected at intervals.
2. The organic room temperature phosphorescent material according to claim 1, characterized in that: The main material is a mixture of one or more single aromatic ring organic compounds represented by general formula (I-1) to (I-3): Wherein, in the general formula (I-1), R1 is selected from -COOCH3 or -COOH, and R2, R3, R4, R5 and R6 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH; In the general formula (I-2), R1, R2, R3, R4 and R5 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH in the general formula (I-2) is ≥1; In the general formula (I-3), R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 Each is independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH.
3. The organic room temperature phosphorescent material according to claim 1, characterized in that: The guest material is a mixture of one or more of the diaromatic organic compounds represented by general formula (II-1) to (II-8): Wherein, in the general formula (II-1), R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 Each of -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 and -COOH is independently selected, and the number of -COOCH3 or -COOH in the general formula (II-1) is ≥1; In the general formula (II-2) and the general formula (II-3), R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH in the general formula (II-2) is ≥1, and the number of -COOCH3 or -COOH in the general formula (II-3) is ≥1; In the general formulae (II-4) to (II-6), R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH, and the number of -COOCH3 or -COOH contained in each of the general formulae (II-4) to (II-6) is ≥1; In the general formula (II-7), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 Each independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH; In the general formula (II-8), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 Each is independently selected from -H, -CH3, -NH3, -OH, -OCH3, -CO, -CN, -COOCH3 or -COOH.
4. The organic room temperature phosphorescent material according to claim 1, characterized in that: The molar ratio of the host material to the guest material in the organic room temperature phosphorescent material is 10000:1 to 100:
1.
5. The organic room temperature phosphorescent material according to claim 1, characterized in that: The organic room temperature phosphorescent material exhibits blue-green to yellow-green afterglow emission after being irradiated by ultraviolet light at room temperature.
6. The organic room temperature phosphorescent material according to claim 1, characterized in that: The phosphorescence lifetime of the organic room temperature phosphorescent material is 13.89 to 1008.9 ms.
7. The organic room temperature phosphorescent material according to claim 1, characterized in that: The photoluminescence quantum yield of the organic room temperature phosphorescent material is 4.0% to 35.0%.
8. A method for preparing an organic room temperature phosphorescent material, characterized in that: Applicable to preparing the organic room temperature phosphorescent material according to any one of claims 1 to 7, the method comprising: The host material and the guest material are respectively dissolved in a solvent and then mixed, and then the solvent is removed to obtain the organic room temperature phosphorescent material.
9. The preparation method according to claim 8, characterized in that: The step of dissolving the host material and the guest material in a solvent respectively and then mixing them comprises: Weigh the host material and the guest material respectively; Dissolving the weighed host material and the guest material in a solvent to prepare a host material solution and a guest material solution respectively; The guest material solution is added dropwise to the host material solution under stirring to obtain a mixed solution, and the molar ratio of the host material to the guest material in the mixed solution is controlled to be 10000:1 to 100:
1.
10. The preparation method according to claim 8, characterized in that: The solvent is dichloromethane and / or methanol.