A raloxifene derivative with room temperature phosphorescence characteristics and its application

Abstract

The present invention provides a raloxifene derivative with room temperature phosphorescence characteristics and an application thereof. The invention originality finds that the raloxifene derivative has room temperature phosphorescence characteristics, has the advantages of easy raw material availability, simple synthesis, easy crystallization, fluorescence-room temperature phosphorescence dual emission in a crystalline state and a powder state, and a long phosphorescence emission wavelength, and the like. Meanwhile, the room temperature phosphorescence characteristics can be easily regulated by changing a substituent group. The raloxifene derivative with room temperature phosphorescence characteristics can be used as a luminescent material, and has medicinal value, and can be used for long afterglow in vivo imaging and integrated diagnosis and treatment of diseases.

Description

Technical Field

[0001] The invention relates to the field of luminescent materials, and in particular to a raloxifene derivative with room temperature phosphorescence characteristics and application thereof. Background Art

[0002] Room temperature phosphorescent (RTP) materials have a wide range of application values ​​in the fields of organic light-emitting diodes (OLEDs), chemical sensors, bio-imaging, anti-counterfeiting, information encryption, etc. In recent years, stimuli-responsive room temperature phosphorescent materials can respond to external stimuli, such as mechanical force, heat, light, electric field, chemical substances, etc., and their room temperature phosphorescent (RTP) behavior (including quantum yield, luminescent color and lifetime) can show dynamic changes under external stimuli. Due to their special properties, stimuli-responsive room temperature phosphorescent materials have received more and more attention, especially in the fields of anti-riot, sensors, data storage, etc., which greatly broadens the application range of RTP materials.

[0003] Traditional room temperature phosphorescent materials mainly focus on inorganic and organometallic systems, which often have some inherent problems, such as high cost, difficult preparation, poor stability, and strong biological toxicity. In contrast, pure organic small molecule RTP materials have the characteristics of low cost, easy preparation, high stability, high biocompatibility, and easier structure adjustment. At present, the design strategy of pure organic small molecule RTP materials mainly includes the following two aspects: 1. Promote the intersystem crossing pathway between singlet and triplet states. Specific methods include introducing atoms or groups with lone pairs of electrons in aromatic systems, introducing heavy atoms such as halogens, and constructing donor-acceptor structures; 2. Inhibit or reduce triplet non-radiative transitions and quenching. Specific methods include crystallization, host-guest interactions, and construction of supramolecular frameworks. However, for most pure organic molecules, the transition from the triplet excited state to the ground state during phosphorescence is spin-forbidden, and it is extremely complicated to simultaneously control triplet excitons and stimulus response sites, which leads to great difficulties in developing pure organic small molecule RTP materials. Summary of the invention

[0004] The purpose of the present invention is to provide a raloxifene derivative having room temperature phosphorescence properties and its application, to creatively discover that the raloxifene derivative has room temperature phosphorescence properties, and to apply the raloxifene derivative to the related fields of luminescent materials.

[0005] In order to solve the development difficulties of pure organic small molecule RTP materials in the prior art, the applicant searched for suitable materials from a variety of pure organic small molecules based on the structural characteristics of RTP materials, and after a lot of research, investigation and experiments, discovered raloxifene derivatives that can be used for RTP materials.

[0006] I believe that technicians in the medical field must be familiar with raloxifene. Raloxifene is a second-generation selective estrogen receptor modulator (SERM). Many animal studies and clinical trials in the past have shown that raloxifene can specifically bind to estrogen receptors, behave as an estrogen agonist in the bone and cardiovascular systems, and behave as an estrogen antagonist in the uterus and breast systems. It can be used to prevent and treat osteoporosis in postmenopausal women and improve menopausal symptoms in postmenopausal women. Therefore, raloxifene is often used as a gynecological drug.

[0007] In the past, people only paid attention to the application of raloxifene and its derivatives in the field of biomedicine, but ignored its photoluminescent properties as organic small molecules, including fluorescence, room temperature phosphorescence, stimulus response performance, etc. From the perspective of molecular structure, atoms and groups with lone pairs of electrons in the raloxifene molecule, such as sulfur, hydroxyl, carbonyl, and alkoxy, are directly connected to the aromatic system, which may have a higher intersystem crossing efficiency. At the same time, there are multiple adjustable sites on the molecular skeleton, and the luminescent properties can be further improved by changing the substituents. In addition, the raloxifene and its derivatives reported are all powders, which are very easy to crystallize. These characteristics suggest that raloxifene and its derivatives are very likely to have properties such as room temperature phosphorescence, so the applicant uses raloxifene as the basic structure to explore its performance in luminescent materials. Moreover, there is no precedent for a pure organic room temperature phosphorescence system developed based on small molecule drugs. If the medicinal value and photoluminescent properties of small molecules can be taken into account, such a new organic room temperature phosphorescence system will have great application and research value in the fields of biological detection, treatment, pathological pharmacology, etc.

[0008] In the first aspect, the present invention proposes the use of a raloxifene derivative having room temperature phosphorescence characteristics as a room temperature phosphorescent material, and its structure is shown in formula (I):

[0009]

[0010] In Formula I, R1, R2, and R3 include but are not limited to hydrogen, C1-C 30 Alkyl, C1-C 30 Alkoxy, hydroxyl, C1-C 30 The group selected by R1, R2 and R3 may be the same or different.

[0011] Preferably, when R2 and R3 are CH3O, R1 is CH3CH2O, CH3O, OH, CH3, H, OCOCH3, COOCH3, COOH, CN, F, Cl, Br. The reason why these substituents are selected in this scheme is that these substituents are relatively small, which is conducive to the formation of a tighter stacking of molecules during the crystallization process, and is conducive to the formation of a stable triplet state, thereby increasing the lifetime of phosphorescent emission. Second, substituents containing oxygen, nitrogen and halogen are conducive to promoting intersystem crossing and enhancing phosphorescent emission.

[0012] Further preferably, when R2 and R3 are CH3O, R1 is OCOCH3, COOCH3, CN, or F. The reason for this arrangement is that the electron-withdrawing substituents are conducive to enhancing the intramolecular charge transfer effect, reducing the energy gap between the singlet state and the triplet state, thereby further promoting intersystem crossing and enhancing phosphorescence emission, and the introduction of these substituents is conducive to forming compact aggregates during the crystallization process, further stabilizing the triplet state, and improving the lifetime of phosphorescence emission.

[0013] Preferably, R1, R2, and R3 are all C1-C 12 Ester group, C1-C 30 The ester group is represented by OOR, R is C1-C 12 Carbon chain, the structure is shown in formula (II):

[0014]

[0015] Preferably, R1, R2, and R3 are all OCOCH3.

[0016] Specifically, the raloxifene derivative with room temperature phosphorescence characteristics is used as a room temperature phosphorescent material. The raloxifene derivative with room temperature phosphorescence characteristics has room temperature phosphorescence characteristics, multiple stimulus responsiveness, long afterglow imaging performance and medicinal value. It is applied to the fields of information encryption, in vivo imaging and integrated diagnosis and treatment.

[0017] In a second aspect, the present invention provides a method for preparing a raloxifene derivative having room temperature phosphorescence characteristics, wherein the raloxifene derivative having room temperature phosphorescence characteristics is used as a room temperature phosphorescence material, comprising the following steps:

[0018] Under the protection of inert gas, (4-(acetyloxy)phenyl)(6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)methanone is added to pyridine hydrohalide and heated to obtain (4-hydroxyphenyl)(6-hydroxy-2-(4-hydroxyphenyl)benzo[b]thiophen-3-yl)methanone;

[0019] Under the protection of inert gas, (4-hydroxyphenyl)(6-hydroxy-2-(4-hydroxyphenyl)benzo[b]thiophene-3-yl)methanone is dissolved in an organic carbon chain acid anhydride and refluxed to obtain a raloxifene derivative having room temperature phosphorescence characteristics. The chemical structural formula of the raloxifene derivative having room temperature phosphorescence characteristics is shown in formula (II):

[0020]

[0021] Specifically, the preparation formula of the preparation method is as follows:

[0022]

[0023] The halogen X in the pyridine hydrohalide is Cl, Br, or I.

[0024] In some embodiments, the raw material (4-(acetoxy)phenyl)(6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)methanone is added to the pyridine hydrohalide and heated at 150-250° C. for 2-6 hours. Preferably, the pyridine hydrohalide is pyridine hydrochloride, and the heating temperature is 180-200° C., and the heating time is 3-4 hours.

[0025] In some embodiments, the ratio of the starting material (4-(acetoxy)phenyl)(6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)methanone to pyridine hydrohalide is 1:5.0 to 1:15.0.

[0026] In some embodiments, (4-hydroxyphenyl)(6-hydroxy-2-(4-hydroxyphenyl)benzo[b]thiophen-3-yl)methanone is dissolved in an organic carbon chain acid anhydride and refluxed at 130-300° C. for 2-5 hours.

[0027] In some embodiments, the ratio of (4-hydroxyphenyl)(6-hydroxy-2-(4-hydroxyphenyl)benzo[b]thiophen-3-yl)methanone to the organic carbon chain acid anhydride is 1:30 to 1:80.

[0028] In some embodiments, the inert gas is nitrogen.

[0029] In a third aspect, the present invention provides a method for preparing a raloxifene derivative having room temperature phosphorescence characteristics, wherein the raloxifene derivative having room temperature phosphorescence characteristics is used as a room temperature phosphorescence material, comprising the following steps:

[0030] Under the protection of inert gas and ice bath, 6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene is added to ultra-dry dichloromethane solvent, and then the acyl chloride is slowly added and the catalyst anhydrous aluminum chloride is added in batches. The mixture is slowly restored to room temperature and stirred for 1-3 hours to obtain a raloxifene derivative having room temperature phosphorescence characteristics, wherein the chemical structural formula of the raloxifene derivative having room temperature phosphorescence characteristics is shown in formula (III):

[0031]

[0032] This scheme adopts Friedel-Crafts acylation method to prepare raloxifene derivatives with room temperature phosphorescence characteristics. The preparation formula of this preparation method is as follows:

[0033]

[0034] In some embodiments, R1 is CH3CH2O, CH3O, CH3, H, OCOCH3, COOCH3, CN, F, Cl, Br.

[0035] In some embodiments, the raw material 6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene is added to ultra-dry dichloromethane, the acyl chloride is slowly added in an ice-water bath, and then the catalyst anhydrous aluminum chloride is added in batches, and the mixture is slowly returned to room temperature and stirred for 1-3 hours.

[0036] In some embodiments, the ratio of the raw material 6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene to anhydrous dichloromethane is 1:80.0 to 1:100.0.

[0037] In some embodiments, the ratio of the raw material 6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene to the corresponding acid chloride is 1:1.2 to 1:1.8.

[0038] In some embodiments, the ratio of the raw materials 6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene and anhydrous aluminum chloride is 1:1.5 to 1:2.5.

[0039] In some embodiments, the inert gas is nitrogen.

[0040] Correspondingly, according to the different substituents of R1, the raloxifene derivatives with room temperature phosphorescence characteristics shown in the chemical formula (III) have the following structures A01 to A10:

[0041]

[0042] Compared with the prior art, this technical solution has the following characteristics and beneficial effects:

[0043] (1) The applicant has innovatively discovered that the organic small molecule drug raloxifene derivatives have room temperature phosphorescence properties, and based on this discovery has developed a series of raloxifene derivatives with room temperature phosphorescence properties, which have the advantages of easy availability of raw materials, simple synthesis, easy crystallization, dual emission of fluorescence and room temperature phosphorescence in the crystalline powder state, and a long phosphorescence emission wavelength. At the same time, their room temperature phosphorescence properties can be easily controlled by changing the substituents.

[0044] (2) The raloxifene derivative with room temperature phosphorescence provided by the present invention has the characteristics of mechanical force stimulation response, temperature stimulation response, organic solvent stimulation response, etc. in the crystalline powder state, and can be used for information encryption.

[0045] (3) The raloxifene derivatives provided by the present invention can be used as room temperature phosphorescent materials to function as luminescent materials. At the same time, they have medicinal value and can be used for long afterglow in vivo imaging and integrated diagnosis and treatment of diseases. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figures 1 to 5 They correspond respectively to the photoluminescence spectrum (left), room temperature phosphorescence emission spectrum (middle), and room temperature phosphorescence lifetime decay curve (right) of the crystalline powders of compounds A01 to A13 in Examples 1 to 5 of the present invention.

[0047] Figures 6 to 8 They respectively correspond to the schematic diagrams of the multi-stimulus response performance of the A10-Ⅰ and A10-Ⅱ crystal powders in Example 6 of the present invention, including the photoluminescence spectrum (left), CIE color coordinates (middle), and powder X-ray diffraction (PXRD) diagram.

[0048] Fig. 9 It is an example diagram of the application of the A10-Ⅰ crystal powder in Example 7 of the present scheme, including a schematic diagram of the crystal transformation conditions between A10-Ⅰ and A10-Ⅱ (left), and an example diagram of the information encryption effect achieved by the A10-Ⅰ crystal powder through multiple stimulation responses (middle and right). DETAILED DESCRIPTION

[0049] The following will be combined with the accompanying drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field belong to the scope of protection of the present invention.

[0050] Those skilled in the art should understand that, in the disclosure of the present invention, the orientation or position relationship indicated by the terms "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc. are based on the orientation or position relationship shown in the drawings, which are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation. Therefore, the above terms should not be understood as limiting the present invention.

[0051] It is to be understood that the term "one" should be understood as "at least one" or "one or more", that is, in one embodiment, the number of an element may be one, while in another embodiment, the number of the element may be multiple, and the term "one" should not be understood as a limitation on the quantity.

[0052] Embodiment 1

[0053] (4-(Ethoxy)phenyl)(6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)methanone, the structure of which is shown in Formula A01:

[0054]

[0055] Preparation method: First, add the raw material 6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene to 80.0-90.0 equivalents of ultra-dry dichloromethane solvent under nitrogen protection and ice bath conditions. Slowly add 1.2-1.3 equivalents of p-ethoxybenzoyl chloride and then add 1.5-2.0 equivalents of anhydrous aluminum chloride in batches. After slowly returning to room temperature and stirring for 1-3 hours, add a mixed solution of ice water and dilute hydrochloric acid to quench the reaction; extract with dichloromethane and water, take the organic layer and repeat three times. Combine the dried organic layers, use ethyl acetate / petroleum ether = 1:10→1:5 eluent to separate and purify on a silica gel column to obtain the target product A01, with a yield of 55%. The purified product is dissolved in a dichloromethane solution, and then evaporated at room temperature to obtain a crystalline powder with room temperature phosphorescence characteristics. The synthesis steps of compounds A02-A09 are the same as those of Example 1, except that the p-ethoxybenzoyl chloride in the raw material is replaced with the corresponding product, such as p-methoxybenzoyl chloride, p-cyanobenzoyl chloride, p-fluorobenzoyl chloride, etc. The purified product is dissolved in a dichloromethane solution and then volatilized at room temperature to obtain a crystalline powder having room temperature phosphorescence properties.

[0056] The structural characteristics of the structural formula A01 are as follows: 1H NMR (400MHz, CDCl3) δ (TMS, ppm): 7.77 (1H, d, J 8.9), 7.52 (1H, d, J 8.9), 7.37–7.33 (2H, m), 7.32 (1H, d, J 2.3), 6.95 (1H, dd, J 8.9, 2.4), 6.77–6.73 (4H, dd), 4.02 (2H, q, J 7.0), 3.88 (1H, s), 3.75 (1H, s), 1.39 (3H, t, J 7.0). The room temperature phosphorescence properties of the structures A01-A03 are shown in the attached table. Figures 1 to 3 .like Figure 1 As shown, it can be seen that in the photoluminescence spectrum, the normalized intensity of the A01 and A02 structures in the wavelength range of 450-460nm is as high as 1a.u., and the normalized intensity of the A03 structure in the wavelength range of 470-480nm is also as high as 1a.u.; in the room temperature phosphorescence emission spectrum, the normalized intensity of the A02 and A03 structures in the wavelength range of 590-600nm is as high as 1a.u., and the normalized intensity of the A01 structure in the wavelength range of 610-620nm is as high as 1a.u.; in the room temperature phosphorescence lifetime decay curve, the A01 structure decays completely in about 40ms, the decay time of the A02 structure can reach 60ms, and the decay time of the A03 structure can be as high as 80ms. It can be seen that the structures A01-A03 of this scheme all have good room temperature phosphorescence properties and can be used to prepare room temperature phosphorescent luminescent materials.

[0057] like Figure 2 As shown, it can be seen that in the photoluminescence spectrum, the normalized intensity of the A04 structure in the wavelength range of 460-470nm is as high as 1a.u., the normalized intensity of the A05 structure in the wavelength range of 550-560nm is also as high as 1a.u., and the normalized intensity of the A06 structure in the wavelength range of 590-600nm is also as high as 1a.u.; in the room temperature phosphorescence emission spectrum, the normalized intensities of the A04 and A05 structures in the wavelength range of 550-560nm are as high as 1a.u., and the normalized intensity of the A06 structure in the wavelength range of 620-630nm is as high as 1a.u.; in the room temperature phosphorescence lifetime decay curve, the A05 structure decays completely in about 100ms, and the decay time of the A06 and A04 structures can be as high as 120ms. It can be seen that the structures A04-A06 of this scheme all have good room temperature phosphorescence properties and can be used to prepare room temperature phosphorescent luminescent materials.

[0058] like Figure 3As shown, it can be seen that in the photoluminescence spectrum, the normalized intensity of the A07 formula in the wavelength range of 450-460nm and the wavelength range of 600-610nm is as high as 1a.u., and the normalized intensity of the A08 and A09 formulas in the wavelength range of 470-480nm is also as high as 1a.u.; in the room temperature phosphorescence emission spectrum, the normalized intensity of the A07 formula in the wavelength range of 580-590nm is as high as 1a.u., and the normalized intensity of the A08 and A09 formulas in the wavelength range of 590-600nm is as high as 1a.u.; in the room temperature phosphorescence lifetime decay curve, the A09 formula decays completely in about 60ms, the A08 formula decays completely in about 100ms, and the decay time of the A07 formula can even exceed 140ms. It can be seen that the formulas A07-A09 of this scheme all have good room temperature phosphorescence properties and can be used to prepare room temperature phosphorescent luminescent materials.

[0059] Embodiment 2

[0060] (4-(acetyloxy)phenyl)(6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)methanone, the structure of which is shown in Formula A10:

[0061]

[0062] The synthesis steps are the same as those in Example 1, except that the p-ethoxybenzoyl chloride in the raw material is replaced with p-acetoxybenzoyl chloride. The purified product is dissolved in a dichloromethane solution, and the speed of solvent evaporation is adjusted to obtain two crystals with room temperature phosphorescence properties, A10-Ⅰ and A10-Ⅱ. The space groups are both P 21 / n, and the unit cell parameters of A10-Ⅰ are α=90°,β=107.463(4)°,γ=90°. The unit cell parameters of A10-Ⅱ are α=90°,β=98.769(9)°,γ=90°. The structural characterization parameters are:

[0063] 1 H NMR (400MHz, CDCl3) δ (TMS, ppm): 7.80 (2H,d,J 8.7), 7.59 (1H,d,J 8.9), 7.32 (1H,d,J 2.2), 7.30 (2H,d,J 8.8), 7.00 (2H,d,J 8.8),6.98(1H,dd,J 8.8,2.3),6.75(2H,d,J 8.8),3.89(3H,s),3.75(3H,s),2.27(3H,s).

[0064] The room temperature phosphorescence performance of the A10 structure is characterized as follows Figure 4 As shown, it can be seen that in the photoluminescence spectrum, the normalized intensity of the A10-I structure in the wavelength range of 590-600nm is as high as 1a.u., and the normalized intensity of the A10-II structure in the wavelength range of 470-480nm is as high as 1a.u.; in the room temperature phosphorescence emission spectrum, the normalized intensities of the A10-I structure and the A10-II structure in the wavelength range of 560-570nm are as high as 1a.u.; in the room temperature phosphorescence lifetime decay curve, the decay time of the A10-I structure and the A10-II structure can exceed 100ms. It can be seen that the structure A10 of this scheme has good room temperature phosphorescence properties and can be used to prepare room temperature phosphorescent luminescent materials.

[0065] Embodiment 3

[0066] (4-(acetoxy)phenyl)(6-acetoxy-2-(4-acetoxyphenyl)benzo[b]thiophen-3-yl)methanone, the structure of which is shown in Formula A11:

[0067]

[0068] Under nitrogen protection, the raw material A10 is added to 8 to 10 times the equivalent of pyridine hydrochloride, heated at 180-200°C for 3-4 hours, and extracted with ethyl acetate and water after cooling to room temperature, and the organic layer is taken and repeated three times. The concentrated organic layers are combined to obtain the crude intermediate product (4-hydroxyphenyl) (6-hydroxy-2-(4-hydroxyphenyl)benzo[b]thiophene-3-yl)methanone. Under nitrogen protection, the above intermediate product is dissolved in 50 to 60 times the equivalent of acetic anhydride and refluxed at 130-150°C for 3-4 hours. After cooling to room temperature, the excess acetic anhydride is first removed by rotary evaporation, and then extracted with dichloromethane and water, and the organic layer is taken and repeated three times. The dried organic layers are combined and separated and purified by silica gel column using dichloromethane / petroleum ether = 1:10→1:2 eluent to obtain the target product A11 with a yield of 85%. The purified product is dissolved in a dichloromethane solution and then evaporated at room temperature to obtain a crystalline powder with room temperature phosphorescence properties. The structural characterization is as follows: 1 H NMR(400MHz, CDCl3)δ(TMS,ppm):7.82–7.76(2H,m),7.69(1H,d,J 8.8),7.64(1H,d,J 2.1),7.44–7.38(2H,m),7.12(1H,dd,J8.8,2.2),7.07–7.01(2H,m),7.01–6.96(2H,m),2.35(3H,s),2.28(3H,s),2.27(3H,s).

[0069] Embodiment 4

[0070] (4-(Carboxy)phenyl)(6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)methanone, whose structure is shown in Formula A12.

[0071]

[0072] The crystalline powder of compound A05 was put into 30% sodium hydroxide aqueous solution and stirred at 60-80°C for 12 hours. Dilute hydrochloric acid was added for acidification, and the pH value of the system was adjusted to 1-3 and then filtered. The filter residue obtained was the target product A12 with a yield of 95%. The product was dissolved in dichloromethane solution and then volatilized at room temperature to obtain a crystalline powder with room temperature phosphorescence characteristics. Its structural characterization is as follows:

[0073] 1 H NMR(400MHz,DMSO)δ(TMS,ppm):13.33(1H,s),7.88(2H,d,J 8.0),7.76(2H,d,J 8.0),7.70(1H,s),7.54(1H,d,J 8.9),7.27(2H,d,J 8.3),7.06(1H,d,J 8.8),6.84(2H,d,J 8.3),3.86(3H,s),3.69(3H,s).

[0074] Embodiment 5

[0075] (4-(Hydroxy)phenyl)(6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)methanone, the structure of which is shown in Formula A13:

[0076]

[0077] Compound A10 was placed in a mixed solution of ethanol and water (ethanol: water = 7:3, v / v), 5 equivalents of anhydrous sodium acetate were added, and refluxed at 90-100°C for 9-12 hours. After cooling to room temperature, it was extracted with ethyl acetate and water, and the organic layer was taken and repeated three times. The organic layers were combined and dried, and the target product A13 was obtained after separation and purification on a silica gel column using ethyl acetate / petroleum ether = 1:10→1:5 eluent, with a yield of 95%. The purified product was dissolved in a dichloromethane solution, and then volatilized at room temperature to obtain a crystalline powder with room temperature phosphorescence characteristics. The structural formula of A13 is as follows:

[0078] 1H NMR(400MHz,CD3OD)δ(TMS,ppm):7.63(2H,d,J 8.8),7.46–7.40(2H,m),7.33–7.26(2H,m),6.96(1H,dt,J 9.0,2.2),6.82–6.74(2H,m),6.70–6.62(2H,m),3.86(3H,d,J2.7),3.72(3H,d,J 2.9).

[0079] The room temperature phosphorescence properties of the A11 structure, the A12 structure and the A13 structure are characterized as follows: Figure 5 As shown, it can be seen that in the photoluminescence spectrum, the normalized intensity of the A11 structure in the wavelength range of 470-480nm is as high as 1a.u., the normalized intensity of the A12 structure in the wavelength range of 500-510nm is also as high as 1a.u., and the normalized intensity of the A13 structure in the wavelength range of 620-630nm is also as high as 1a.u.; in the room temperature phosphorescence emission spectrum, the normalized intensity of the A11 structure in the wavelength range of 580-590nm is as high as 1a.u., the A12 structure The normalized intensity of the A12 and A13 formulas in the wavelength range of 590-600nm is as high as 1a.u., and the normalized intensity of the A13 formula in the wavelength range of 630-640nm is as high as 1a.u.; in the room temperature phosphorescence lifetime decay curve, the A12 and A13 formulas decay completely in about 10ms, and the decay time of the A11 formula can exceed 80ms. It can be seen that the A11-A13 formulas of this scheme have good room temperature phosphorescence properties and can be used to prepare room temperature phosphorescent materials.

[0080] Embodiment 6

[0081] The A10 structure was subjected to multiple stimulus tests such as mechanical force, organic solvent vapor, and temperature to test its responsiveness.

[0082] Mechanical force response:

[0083] Add the crystal powder of compound A10-I into the mortar and use the pestle to evenly grind the crystal powder of compound A10-I. During the grinding process, the luminescent color of the crystal powder of compound A10-I gradually changes from the original orange-yellow to blue. Figure 6 As shown in the figure, the gradual disappearance of the rigid structure of the crystal leads to the continuous weakening of the room temperature phosphorescence emission, which is the reason for the change in luminescence color. In addition, in the CIE color coordinate diagram, the luminescence color of the powder changes linearly from the original orange-yellow (color coordinates: 0.41, 0.38) to blue (color coordinates: 0.20, 0.22), and the correlation coefficient of the fitting line (R 2 ) is 0.99.

[0084] Organic solvent vapor response:

[0085] First, place the fully ground A10-Ⅰ crystal powder in an open container, and then place the open container in a sealed container containing sufficient liquid dichloromethane. The A10-Ⅰ powder does not come into direct contact with the liquid dichloromethane. Let it stand at room temperature for 0.5 to 1.0 hours to allow the A10-Ⅰ powder to fully contact with the dichloromethane vapor before taking it out. Figure 7 As shown, after fumigation with dichloromethane vapor, the luminescent color of the A10-Ⅰ powder changes from blue after grinding to blue-green (color coordinates: 0.21, 0.28), and the directional crystal transformation of A10-Ⅰ to A10-Ⅱ is the reason for the change in luminescent color.

[0086] Temperature Response:

[0087] First, the fully ground A10-Ⅰ crystal powder is placed in an open container, and then the open container is placed in a forced air oven, and after heat treatment at 130-135°C for 0.5-1.0 hour, it is taken out and cooled to room temperature. Figure 8 As shown, the luminescence color of the A10-Ⅰ powder after heat treatment changes from blue after grinding back to orange-yellow (color coordinates: 0.33, 0.29). The recovery of the room temperature phosphorescence emission caused by the recovery of the crystal rigid structure is the reason for the change in luminescence color.

[0088] First, place the A10-II crystal powder in an open container, and then place the open container in a forced air oven for heat treatment at 130-135°C for 0.5-1.0 hour. Figure 8 As shown, the luminescent color of the A10-Ⅱ powder after heat treatment changes from blue after grinding back to orange-yellow (color coordinates: 0.39, 0.35), and the directional crystal transformation of A10-Ⅱ to A10-Ⅰ is the reason for the change in luminescent color.

[0089] Embodiment 7

[0090] Application of compound A10 in information encryption

[0091] (1) Spread an appropriate amount of A10-Ⅰ crystal powder in a glass dish, and use a glass rod to repeatedly write the letter 'p' in the dish until the letter 'p' emitting blue light can be clearly observed under a 365nm ultraviolet lamp. Place the glass dish in a forced air oven, heat treat it at 130-135℃ for 0.5-1.0 hours, then take it out and cool it to room temperature. Fig. 9 As shown, after heat treatment, the blue luminescence of the letter 'p' disappears under ultraviolet light.

[0092] (2) As attached Fig. 9 As shown in the figure, first use the crystal powder of A10-Ⅰ and the fully ground A10-Ⅰ powder to lay flat in a glass dish to form the Arabic numeral '8'. Fig. 9The white box shows the crystal powder of A10-Ⅰ, and the gray box shows the fully ground A10-Ⅱ powder. Under the 365nm ultraviolet light, the blue and orange-yellow colors of light show the number '8'. After turning off the ultraviolet light, a digital camera can be used to capture the orange-yellow room temperature afterglow in the shape of the number '9'. Place the glass dish in a sealed container containing sufficient liquid dichloromethane, and the powder in the dish is not in direct contact with the liquid dichloromethane. Let it stand at room temperature for 0.5 to 1.0 hours, so that the powder in the dish is fully in contact with the dichloromethane vapor, and then take it out. Under the fluorescent light, the color of the powder in the dish is almost the same as before fumigation. However, under the 365nm ultraviolet light, the blue-green and orange-yellow colors of light show the number '8'. After turning off the ultraviolet light, a digital camera can still capture the orange-yellow room temperature afterglow in the shape of the number '9'. The glass dish was then placed in a blast oven and heat treated at 130-135°C for 0.5-1.0 hours, then taken out and cooled to room temperature. Under a fluorescent lamp, the color of the powder in the dish still did not change significantly. The difference was that under a 365nm ultraviolet lamp, the number '8' was only displayed in an orange-yellow luminous color. After turning off the ultraviolet lamp, a digital camera could be used to capture the orange-yellow room temperature afterglow in the shape of the number '8'.

[0093] Therefore, digital information encryption is achieved based on the stimulus response properties of compound A10.

[0094] The present invention is not limited to the above-mentioned optimal implementation mode. Anyone can derive other various forms of products under the inspiration of the present invention. However, no matter what changes are made in the shape or structure, all technical solutions that are the same or similar to those of the present application fall within the protection scope of the present invention.

Claims

1. Use of a raloxifene derivative having room temperature phosphorescence characteristics in the preparation of a room temperature phosphorescent material, characterized in that: The structure of the raloxifene derivative having room temperature phosphorescence characteristics is shown in the following formula (I): In formula (I), R1, R2, and R3 are selected from hydrogen, C1-C 30 Alkyl, C1-C 30 Alkoxy, hydroxyl, C1-C 30 An ester group, carboxyl group, cyano group, nitro group, halogen group, or amino group.

2. The use of the raloxifene derivative having room temperature phosphorescence characteristics according to claim 1 in the preparation of room temperature phosphorescent materials, characterized in that: When R2 and R3 are CH3O, R1 is one of CH3CH2O, CH3O, OH, CH3, H, OCOCH3, COOCH3, COOH, CN, F, Cl, and Br.

3. Use of the raloxifene derivative having room temperature phosphorescence characteristics according to claim 1 in the preparation of room temperature phosphorescent materials, characterized in that: R1, R2, and R3 are all OCOCH 3。 4. Use of a raloxifene derivative having room temperature phosphorescence characteristics in the preparation of a room temperature phosphorescent material, characterized in that: R is C1-C 29 Carbon chain, the structure is shown in formula (II):

5. Use of a raloxifene derivative having room temperature phosphorescence characteristics in the preparation of a room temperature phosphorescent material, characterized in that: R1 is one of CH3CH2O, CH3O, CH3, H, OCOCH3, COOCH3, CN, F, Cl, and Br. In this case, the structure is as shown in formula (III):

6. A method for preparing a raloxifene derivative having room temperature phosphorescence characteristics, characterized in that: The following steps are involved: Under the protection of inert gas, (4-(acetyloxy)phenyl)(6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)methanone is added to pyridine hydrohalide and heated to obtain (4-hydroxyphenyl)(6-hydroxy-2-(4-hydroxyphenyl)benzo[b]thiophen-3-yl)methanone; Under the protection of inert gas, (4-hydroxyphenyl)(6-hydroxy-2-(4-hydroxyphenyl)benzo[b]thiophene-3-yl)methanone is dissolved in an organic carbon chain acid anhydride, and refluxed to obtain a raloxifene derivative having room temperature phosphorescence characteristics. The chemical structural formula of the raloxifene derivative having room temperature phosphorescence characteristics is shown in formula (II), wherein R is C1-C 29 Carbon chain:

7. A method for preparing a raloxifene derivative having room temperature phosphorescence characteristics, comprising the following steps: Under the protection of inert gas and ice bath conditions, 6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene is added to an ultra-dry dichloromethane solvent, and then the acyl chloride is slowly added and then the catalyst anhydrous aluminum chloride is added in batches, and the mixture is slowly restored to room temperature and stirred for 1-3 hours to obtain a raloxifene derivative having room temperature phosphorescence characteristics, wherein the chemical structural formula of the raloxifene derivative having room temperature phosphorescence characteristics is shown in formula (III), wherein R1 is one of CH3CH2O, CH3O, CH3, H, OCOCH3, COOCH3, CN, F, Cl, and Br:

Images