Pure organic long-afterglow material of o-benzoyl sulfimide derivative as well as preparation and application of pure organic long-afterglow material

Abstract

The invention discloses an o-benzoyl sulfimide derivative pure organic long-afterglow material as well as a preparation method and application of the o-benzoyl sulfimide derivative pure organic long-afterglow material. The preparation method of the material comprises the following step: carrying out one-step reaction on o-benzoyl sulfonyl imide and corresponding halogenated hydrocarbon or acyl chloride to synthesize the N-site modified long afterglow material of the o-benzoyl sulfonyl imide. The invention has the following characteristics: (1) the raw materials are cheap and easily available, and the synthesis process is mature; (2) the material is long in afterglow life and high in quantum efficiency; and (3) the material has low cytotoxicity and good biocompatibility, and has great potential in the fields of long afterglow display and drug anti-counterfeiting.

Description

Technical Field

[0001] The invention belongs to the field of pure organic long afterglow materials, and in particular relates to pure organic long afterglow materials of o-benzoylsulfonyl imide derivatives and preparation and application thereof. Background Art

[0002] Room temperature phosphorescent materials have attracted extensive attention due to their superior properties such as long life, large Stokes shift, and high exciton utilization. Room temperature phosphorescent materials have been widely used in the fields of bio-imaging, organic light-emitting diodes, chemical sensing, etc. Room temperature phosphorescent materials mainly include metal coordination phosphorescent materials and pure organic room temperature phosphorescent materials. Metal coordination phosphorescent materials contain heavy metal atoms, which can promote intersystem crossing and have high phosphorescence quantum efficiency. However, the lifetime of metal coordination phosphorescent materials is only at the microsecond level and expensive heavy metals are required to prepare such materials, which limits the application scope of room temperature phosphorescent material systems. The lifetime of pure organic room temperature phosphorescent materials reaches the microsecond or second level. When the ultraviolet light is turned off, the room temperature phosphorescent light is visible to the naked eye. It is applied in the field of bio-imaging or chemical sensing to eliminate background fluorescence interference, improve resolution, and do not require high-end precision instruments for monitoring. However, it is difficult to achieve room temperature phosphorescent light in pure organic materials due to weak spin-orbit coupling and the fact that triplet excitons do not emit light due to transition prohibition (from triplet to singlet). At present, a series of outstanding strategies have been proposed to achieve pure organic room temperature phosphorescence, such as crystal-induced phosphorescence, host-guest doping, H-aggregation, formation of polymers or carbon quantum dots, etc. Aromatic carbonyl groups are often introduced into pure organic small molecule structures due to their own electron flipping, which makes spin-orbit forbidden to spin-orbit allowed, and promotes spin-orbit coupling, thereby promoting intersystem crossing, so that pure organic compounds are endowed with room temperature phosphorescence properties. Analysis of the single crystal data of reported carbon-based room temperature phosphorescent materials shows that carbonyl plays an important role in it. On the one hand, carbonyl groups provide hydrogen bonding sites and form multiple hydrogen bonding interactions with neighboring molecules, which is conducive to limiting the non-radiative transition of triplet excitons. At the same time, they form crystals and isolate quenchers such as water vapor and oxygen in the air. On the other hand, carbonyl groups are closely stacked with π-conjugated phosphorescent chromophores to form strong intermolecular electronic coupling, promote intermolecular charge exchange, and at the same time, regulate the molecular energy level and transition probability, etc., greatly promote intersystem crossing, thereby promoting the generation of phosphorescence or increasing the phosphorescence quantum yield. It is worth noting that the carbonyl and amino groups combine to form an amide functional group, which can form strong hydrogen bonds between the functional groups, which is also the key to the room temperature phosphorescence of some proteins. In addition, aromatic sulfone groups are often introduced into pure organic small molecule structures to improve the phosphorescence quantum efficiency. How to determine which functional group, aromatic carbonyl or aromatic sulfone, plays a decisive role in improving the room temperature phosphorescence performance is a huge challenge.

[0003] Since the discovery of o-benzoylsulfonyl imide and its derivatives, this system has always attracted great attention and is often used as a food sweetener. However, so far, there has been little research on its room temperature phosphorescence properties. In fact, due to the two intermolecular electronic coupling interactions between its molecules, n-π* and π-π*, they tend to form a tighter intermolecular stacking in the crystal. o-benzoylsulfonyl imide and its derivatives are a promising ultra-long phosphorescent luminescent material. Summary of the invention

[0004] One of the purposes of the present invention is to provide a class of pure organic long afterglow materials of o-benzoylsulfonyl imide derivatives.

[0005] Another object of the present invention is to provide a molecular structure design and preparation method of the pure organic long afterglow material of the o-benzoylsulfonyl imide derivative.

[0006] Another object of the present invention is to provide the application of the pure organic long afterglow material of o-benzoylsulfonyl imide derivative in long afterglow display and drug anti-counterfeiting.

[0007] In order to enrich the pure organic long afterglow material system and meet its practical application in drug anti-counterfeiting, the present invention designs and prepares a series of pure organic long afterglow materials. The purpose of the present invention is achieved by the following methods:

[0008] The pure organic long afterglow material of o-benzoylsulfonyl imide derivative has the structural formula of any of the following:

[0009]

[0010] Among them, any two groups of X1, X2, and X3 are -H, and the other group is -H, -F, -Cl, -Br, -NH2, -OC n H 2n+1 , -CF3, -CN, such as: X1=H, X2=H, X3=Cl.

[0011] The photophysical properties of the pure organic long afterglow material of the o-benzoylsulfonyl imide derivative are as follows: the luminescence lifetime of the material in the aggregated state is as long as 0.635s, and the phosphorescence quantum efficiency is as high as 15%.

[0012] The preparation method of the pure organic long afterglow material of o-benzoylsulfonyl imide derivative is as follows: o-benzoylsulfonyl imide is used as a raw material, and reacted with a corresponding halogenated hydrocarbon or acyl chloride in one step to synthesize the long afterglow material modified at the N position of o-benzoylsulfonyl imide.

[0013] Furthermore, the halogenated hydrocarbon is 3-bromopropane, and the acyl chloride is 4-chlorobenzoyl chloride.

[0014] The general formula for the preparation process of the above materials is as follows:

[0015]

[0016] The present invention characterizes the structure of the long afterglow material by nuclear magnetic resonance (NMR) and single crystal X-ray diffraction, and studies in detail the photophysical properties of this series of long afterglow materials in solution state and aggregated state by measuring ultraviolet absorption spectrum, fluorescence emission spectrum and phosphorescence lifetime. By changing different groups, changing the dipole moment of the molecules and regulating the stacking mode of the molecules, rational regulation of the photophysical properties is achieved.

[0017] The o-benzoylsulfonyl imide derivative pure organic long afterglow material has long room temperature phosphorescence lifetime, low preparation cost, low toxicity and good biocompatibility, and can be used for long afterglow display and drug anti-counterfeiting.

[0018] Compared with the prior art, the present invention has the following beneficial effects: (1) the raw materials are cheap and readily available, and the synthesis process is mature; (2) the material has a long afterglow lifetime and high quantum efficiency; (3) the pure organic long afterglow material of o-benzoylsulfonyl imide derivative has low cytotoxicity and good biocompatibility, and has great potential in the field of long afterglow display and drug anti-counterfeiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is the phosphorescence spectrum of HBID and MBID materials.

[0020] Figure 2 This is the room temperature phosphorescence lifetime diagram of HBID and MBID materials.

[0021] Figure 3 It is a schematic diagram of HBID realizing long persistence display.

[0022] Figure 4 This is a schematic diagram of MBID to achieve drug anti-counterfeiting. DETAILED DESCRIPTION

[0023] Example 1

[0024] Synthesis of long afterglow material HBID derived from o-benzoylsulfonyl imide

[0025] o-Benzoylsulfonyl imide (1.0 g, 4.88 mmol) was reacted with an aqueous solution of potassium carbonate (0.337 g, 2.44 mol) for 2 hours to obtain sodium o-benzoylsulfonyl imide. Sodium o-benzoylsulfonyl imide was mixed with iodomethane (1 mL, 5 mmol) in an N,N-dimethylformamide solution (10 ml), stirred at 120 ° C for 10 hours, and then the reaction mixture was poured into 80 mL of water, extracted with ethyl acetate three times (20 mL each time), the organic layers were combined, washed with brine three times (30 mL each time), dried, and concentrated. The crude product was purified by column chromatography (petroleum ether / dichloromethane = 8 / 1). The structural characterization is as follows: H NMR spectrum 1 H NMR (600MHz, Chloroform-d) δ8.06 (d, J = 7.5Hz, 1H), 7.93 (d, J = 7.6Hz, 1H), 7.88-7.81 (m, 2H), 3.26 (s, 3H).

[0026] The structural formula of the long afterglow material HBID derived from o-benzoylsulfonyl imide obtained in this embodiment is as follows:

[0027]

[0028] Example 2

[0029] Synthesis of long-lasting glow material MBID derived from o-benzoylsulfonyl imide

[0030] Mix o-benzoylsulfonyl imide (1.0 g, 4.88 mmol) and p-methoxybenzyl bromide (1 mL, 5 mmol) in DMF (10 mL), stir at 120 ° C for 10 h, then pour the reaction mixture into 80 mL of water, extract with ethyl acetate three times (20 mL each time), combine the organic layers, wash with brine three times (30 mL each time), dry and concentrate. The crude product is purified by column chromatography (petroleum ether / dichloromethane = 4 / 1). The structural characterization is as follows: H NMR spectrum 1 H NMR(600MHz,Chloroform-d)δ8.04(d,J=7.6Hz,1H),7.92(d,J=7.6Hz,1H),7.83(dtd,J=24 .0,7.5,1.0Hz,2H),7.45(d,J=8.7Hz,2H),6.88(d,J=8.7Hz,2H),4.85(s,2H),3.79(s,3H).

[0031] The structural formula of the long afterglow material MBID derived from o-benzoylsulfonyl imide obtained in this example is as follows:

[0032]

[0033] Example 3

[0034] Application of o-benzoylsulfonyl imide derivatives in long afterglow display.

[0035] 1) Weigh 100 mg of the long afterglow material crystal HBID synthesized in Example 1, add an appropriate amount of aloe vera gel, and grind with quartz agate for 30 minutes to form viscous microcrystals;

[0036] 2) placing a screen printing frame printed with a "water grass" pattern on a glass plate, applying the microcrystals ground in step 1) evenly on the pattern, and separating the screen frame and the glass plate after partial drying and hardening, thereby preparing a "water grass" pattern printed with HBID;

[0037] 3) Irradiate the pattern printed in step 2) with ultraviolet light, and a blue "water grass" pattern can be observed. When the 365nm ultraviolet light is turned off, a green "water grass" pattern appears. The pattern can be observed by the naked eye for 3 seconds, achieving a long afterglow display. Figure 3 shown.

[0038] Example 4

[0039] Application of o-benzoylsulfonyl imide derivatives in drug anti-counterfeiting

[0040] 1) Weigh 100 mg of the long afterglow material crystal MBID synthesized in Example 2, add an appropriate amount of aloe vera gel, and grind with quartz agate for 30 minutes to form viscous microcrystals;

[0041] 2) placing a screen printing frame printed with the letters "R", "WTO" and the numbers "20230712" on the hydrotalcite chewable tablet, and evenly applying the microcrystalline material ground in step 1) on the pattern, and after partial drying and hardening, separating the screen frame from the tablet, thereby preparing tablets on which the letters "R", "WTO" and the numbers "20230712" are printed respectively by MBID;

[0042] 3) The pattern printed in step 2) is irradiated with an ultraviolet lamp, and blue letters "R", "WTO" and numbers "20230712" can be observed. When the 365nm ultraviolet lamp is turned off, green letters "R", "WTO" and numbers "20230712" appear, and the pattern can be observed by naked eyes for 3s. Therefore, o-benzoylsulfonyl imide derivatives can be used for drug anti-counterfeiting.

Claims

1. A pure organic long afterglow material of o-benzoylsulfonyl imide derivative, characterized in that: Its structural formula is any of the following: Among them, any two groups of X1, X2, and X3 are -H, and the other group is -H, -F, -Cl, -Br, -NH2, -OC n H 2n+1 , -CF3, -CN.

2. The pure organic long afterglow material of o-benzoylsulfonyl imide derivative according to claim 1, characterized in that: The luminescence lifetime of the material in the aggregated state is 0.635s, and the phosphorescence quantum efficiency is 15%.

3. The method for preparing the pure organic long afterglow material of o-benzoylsulfonyl imide derivative according to claim 1 or 2, characterized in that: The N-position modified long afterglow material of o-benzoylsulfonyl imide is synthesized by reacting o-benzoylsulfonyl imide with corresponding halogenated hydrocarbon or acyl chloride in one step.

4. The method for preparing the pure organic long afterglow material of o-benzoylsulfonyl imide derivative according to claim 3, characterized in that: The halogenated hydrocarbon is 3-bromopropane, and the acyl chloride is 4-chlorobenzoyl chloride.

5. Use of the pure organic long afterglow material of o-benzoylsulfonyl imide derivative as claimed in claim 1 or 2 in long afterglow display.

6. Use of the pure organic long afterglow material of o-benzoylsulfonyl imide derivative as claimed in claim 1 or 2 in drug anti-counterfeiting.

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