CN115745875A - Light-operated organic electroluminescent material containing triphenylethylene group, and synthesis method and application thereof - Google Patents
Light-operated organic electroluminescent material containing triphenylethylene group, and synthesis method and application thereof Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title abstract description 9
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 19
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- 238000005166 mechanoluminescence Methods 0.000 claims abstract description 19
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 125000003545 alkoxy group Chemical group 0.000 claims description 3
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Abstract
Description
技术领域technical field
本发明属于有机力致发光材料及制备领域，及其在应力传感、信息加密、防伪等领域的应用，涉及一种含三苯乙烯基的具有光开关响应特性的光控有机力致发光材料及制备使用方法。该类材料对外力刺激下能直接发射出强烈荧光；在紫外光持续照射后，材料发生光致变色，同时力致发光性能消失；而材料经过可见光照射恢复到初始状态后，力致发光性能重现。材料合成方法简单、发光量子效率高、光致变色和摩擦发光性能佳，可制备成应力响应型器件，应用于新型应力传感器、材料的高精度破损监测等领域。The invention belongs to the field of organic mechanoluminescent materials and their preparation, and their application in the fields of stress sensing, information encryption, anti-counterfeiting, etc., and relates to a light-controlled organic mechanoluminescent material containing a tristyryl group and having an optical switch response characteristic and methods of preparation and use. This type of material can directly emit strong fluorescence under external stimulation; after continuous irradiation with ultraviolet light, the material undergoes photochromism, and the mechanoluminescent performance disappears; and after the material is restored to the original state after being irradiated with visible light, the mechanoluminescent performance resumes. now. The material synthesis method is simple, the luminous quantum efficiency is high, and the photochromic and triboluminescent properties are good. It can be prepared into a stress-responsive device, which can be used in new stress sensors, high-precision damage monitoring of materials and other fields.
背景技术Background technique
有机力致发光材料是一类在外力(刮擦、拉伸、挤压、碰撞等)作用下将机械能转化为光能的有机功能发光材料。基于其独特、节能的激发方式(仅以机械能激发，无需外加电源或光源)，有机力致发光材料对外界应力刺激具有明显的响应性，在生物成像、新型光源、信息加密、商标防伪、应力传感等领域也具有重要的应用价值，见文献：Y.Xie et al.“Triboluminescence:recalling interest and new aspects”,Chem,2018,4,943.。Organic mechanoluminescent materials are a class of organic functional luminescent materials that convert mechanical energy into light energy under the action of external forces (scratch, stretch, squeeze, collision, etc.). Based on its unique and energy-saving excitation method (excited only by mechanical energy, no external power supply or light source), organic mechanoluminescent materials have obvious responsiveness to external stress stimuli, and are widely used in biological imaging, new light sources, information encryption, trademark anti-counterfeiting, stress Sensing and other fields also have important application value, see literature: Y.Xie et al. "Triboluminescence: recalling interest and new aspects", Chem, 2018, 4, 943.
近年来，研究者通过合理的分子设计拓展了有机力致发光种类，使其不仅能产生荧光，还能产生延迟荧光、磷光、长余辉、荧光-磷光双发射等多种类型的发光。随着高亮度有机力致发光材料的逐渐丰富与发展，其在柔性传感器件、信息加密、材料破损监测及生物医学等领域逐渐展露出巨大的发展潜力和应用价值。然而，目前对有机力致发光性能的可控调节仍然是一个巨大的挑战，制约了有机力致发光材料的智能化发展和实际应用。因此，如何实现力致发光性能的可控调节，获得多响应型有机力致发光，实现有机力致发光材料和器件由功能化向智能化转变，是该类材料发展面临的关键问题。In recent years, researchers have expanded the types of organic mechanoluminescence through rational molecular design, so that it can not only produce fluorescence, but also produce various types of luminescence such as delayed fluorescence, phosphorescence, long afterglow, and fluorescence-phosphorescence dual emission. With the gradual enrichment and development of high-brightness organic electroluminescent materials, they have gradually shown great development potential and application value in the fields of flexible sensor devices, information encryption, material damage monitoring, and biomedicine. However, the controllable adjustment of organic electroluminescent properties is still a great challenge, which restricts the intelligent development and practical application of organic electroluminescent materials. Therefore, how to realize the controllable adjustment of the mechanoluminescent performance, obtain multi-responsive organic mechanoluminescence, and realize the transformation of organic mechanoluminescent materials and devices from functional to intelligent are the key issues facing the development of this type of materials.
光致变色材料，得益于其利用光作为外部刺激来精确控制材料光物理性质的优异特性，一直以来受到了科研工作者的广泛关注。一般情况下，光致变色分子在光照射下会发生可逆环化反应，形成一个双稳态的光致变色体系，其中包括螺吡喃、螺恶嗪、偶氮苯化合物和芳基乙烯基化合物等，见文献：Irie,M.et al.“Photochromism:memories andswitches introduction”.Chem.Rev.100,1683-1684(2000).。近年来，三芳基乙烯和三芳基乙烯衍生物由于具有优良的光致变色性能、良好的发光性能和简单的化学结构，被认为是很有前途的光响应发光材料，见文献：Ou D.et al.“Combined aggregation inducedemission(AIE),photochromism and photoresponsive wettability in simpledichloro-substituted triphenylethylene derivatives”.Chem.Sci.7,5302-5306(2016).。因此，将力致发光和光致变色特性结合在三芳基乙烯和三芳基乙烯衍生物中可能是实现具有光开关响应的光控力致发光的一种可能途径。Photochromic materials, benefiting from their excellent characteristics of using light as an external stimulus to precisely control the photophysical properties of materials, have been widely concerned by researchers. In general, photochromic molecules undergo reversible cyclization reactions under light irradiation to form a bistable photochromic system, including spiropyrans, spirooxazines, azobenzene compounds and aryl vinyl compounds etc., see literature: Irie, M. et al. "Photochromism: memories and switches introduction". Chem. Rev. 100, 1683-1684 (2000). In recent years, triarylethenes and triarylethene derivatives have been considered as promising light-responsive luminescent materials due to their excellent photochromic properties, good luminescent properties and simple chemical structures, see literature: Ou D.et al. "Combined aggregation induced emission (AIE), photochromism and photoresponsive wettability in simpledichloro-substituted triphenylethylene derivatives". Chem.Sci.7, 5302-5306(2016). Therefore, combining mechanoluminescent and photochromic properties in triarylethenes and triarylethene derivatives may be a possible route to realize light-controlled mechanoluminescence with photoswitching responses.
本发明提供一种含三苯乙烯基的光控有机力致发光材料，可实现有机力致发光的可控调节。该类材料具有光开关响应的光控力致发光特性：材料对外力刺激下能直接发射出强烈荧光；在紫外光持续照射后，材料发生光致变色，同时力致发光性能消失；而材料经过可见光照射恢复到初始状态后，力致发光性能重现。材料合成方法简单、发光量子效率高、光致变色和摩擦发光性能佳，可制备成应力响应型器件，应用于新型应力传感器、材料的高精度破损监测等领域，对有机力致发光材料的智能化发展具有重要的研究价值和科学意义。The invention provides a light-controlled organic electroluminescence material containing a triphenylethylene group, which can realize the controllable adjustment of organic electroluminescence. This type of material has photo-controlled mechanoluminescence characteristics of optical switch response: the material can directly emit strong fluorescence under external stimulation; after continuous irradiation with ultraviolet light, the material undergoes photochromism, and the mechanoluminescence performance disappears at the same time; After visible light irradiation returned to the initial state, the mechanoluminescence performance was reproduced. The material synthesis method is simple, the luminous quantum efficiency is high, the photochromic and triboluminescent properties are good, and it can be prepared into a stress-responsive device, which can be used in the fields of new stress sensors and high-precision damage monitoring of materials. It has important research value and scientific significance.
发明内容Contents of the invention
要解决的技术问题technical problem to be solved
为了避免现有技术的不足之处，本发明提出一种含三苯乙烯基的具有光开关响应特性的光控有机力致发光材料及制备使用方法。In order to avoid the deficiencies of the prior art, the present invention proposes a light-controlled organic electroluminescence material containing a tristyryl group and having an optical switch response characteristic and a preparation method thereof.
本发明的目的是提供一种具有光开关响应特性的光控有机力致发光材料，通过改变官能团结构，调节分子间相互作用，实现材料力致发光性能的定向调控。The object of the present invention is to provide a light-controlled organic mechanoluminescent material with photoswitching response characteristics, and realize directional control of the mechanoluminescent performance of the material by changing the structure of the functional group and adjusting the interaction between molecules.
本发明的另一个目的是提供一种所述的具有光开关响应特性的光控有机力致发光材料的合成方法，此方法工艺简单，产率高，易于纯化，并可通过引入不同官能团进而调节终产物的力致发光性能(发光波长、亮度、寿命)。Another object of the present invention is to provide a method for synthesizing the light-controlled organic electroluminescent material with photoswitching response characteristics. This method has simple process, high yield, easy purification, and can be adjusted by introducing different functional groups. Mechanoluminescent properties of the final product (luminescence wavelength, brightness, lifetime).
本发明的第三个目的是结合所述的光控有机力致发光材料的光开光响应力致发光性能，将这类材料应用于材料的高精度应力传感等领域。The third object of the present invention is to combine the photo-switching and photo-response mechanoluminescence performance of the photo-controlled organic mechanoluminescence material, and apply this kind of material to the fields of high-precision stress sensing of materials and the like.
技术方案Technical solutions
一种含三苯乙烯基的具有光开关响应特性的光控有机力致发光材料，其特征在于：在三苯乙烯的端位上接上芳香杂环化合物A，结构通式为：A light-controlled organic electroluminescent material containing triphenylethylene group with photoswitching response characteristics, characterized in that: an aromatic heterocyclic compound A is connected to the end of triphenylethylene, and the general structural formula is:
其中，A为芳香杂环化合物。Wherein, A is an aromatic heterocyclic compound.
所述芳香杂环化合物A包括但不限于如下分子中的任意一种：The aromatic heterocyclic compound A includes but is not limited to any one of the following molecules:
其中：R1、R2、R3、R4和R5为相同，或不同；各自独自地选自氢原子、烷基、卤素、烷氧基、氨基、醛基、氰基、羟基、羧基中的任意一种。Wherein: R1, R2, R3, R4 and R5 are the same or different; each independently selected from any one of hydrogen atom, alkyl, halogen, alkoxy, amino, aldehyde, cyano, hydroxyl, carboxyl .
一种所述含三苯乙烯基的具有光开关响应特性的光控有机力致发光材料的合成方法，其特征在于步骤如下：A method for synthesizing an optically controlled organic electroluminescent material containing a tristyryl group and having an optical switch response characteristic, characterized in that the steps are as follows:
步骤1：将含溴或碘的芳香杂环化合物与含硼酸或硼酸酯的三苯乙烯化合物在四氢呋喃溶液中，以碳酸钾为碱，通入氮气搅拌混合；Step 1: the aromatic heterocyclic compound containing bromine or iodine and the triphenylethylene compound containing boric acid or boric acid ester are mixed in tetrahydrofuran solution, using potassium carbonate as the base, and nitrogen gas is introduced to stir and mix;
所述含溴或碘的芳香杂环化合物与含硼酸或硼酸酯的三苯乙烯化合物的摩尔比为1.1:1；The molar ratio of the aromatic heterocyclic compound containing bromine or iodine to the triphenylethylene compound containing boric acid or borate ester is 1.1:1;
步骤2：加入四(三苯基膦)钯【Pd(PPh3)4】催化下，加热至85℃回流24小时，得到含三苯乙烯基的具有光开关响应特性的光控有机力致发光材料。Step 2: Add tetrakis(triphenylphosphine)palladium [Pd(PPh 3 ) 4 ] under catalysis, heat to 85°C and reflux for 24 hours to obtain photo-controlled organic mechanoluminescence containing tristyryl groups with photoswitching response characteristics Material.
所述步骤2加热回流后，将反应液冷却，抽滤，滤液用旋转蒸发仪蒸干。After the step 2 is heated to reflux, the reaction solution is cooled, filtered with suction, and the filtrate is evaporated to dryness with a rotary evaporator.
所述蒸干后的反应物采用硅胶柱层析的方法进行提纯。The evaporated reactant was purified by silica gel column chromatography.
一种所述含三苯乙烯基的具有光开关响应特性的光控有机力致发光材料，其特征在于作为发光材料应用于应力检测器件制备材料。The light-controlled organic electroluminescent material containing triphenylethenyl and having photoswitching response characteristics is characterized in that it is used as a luminescent material for the preparation of stress detection devices.
一种所述含三苯乙烯基的具有光开关响应特性的光控有机力致发光材料，其特征在于该材料应用于应力传感、防伪等领域。A light-controlled organic electroluminescent material containing a tristyryl group and having an optical switch response characteristic is characterized in that the material is used in the fields of stress sensing, anti-counterfeiting and the like.
有益效果Beneficial effect
本发明提出的一种含三苯乙烯基的具有光开关响应特性的光控有机力致发光材料及制备使用方法，含硼酸酯或硼酸基团的三苯乙烯衍生物与含溴或碘的芳香杂环化合物的偶联反应由以下方法实现：提供含溴或碘的芳香杂环化合物与含硼酸或硼酸酯的三苯乙烯化合物在四氢呋喃溶液中，以碳酸钾为碱，在四(三苯基膦)钯【Pd(PPh3)4】催化下，加热回流得到发光材料。本发明所合成的材料具有光控力致发光性能，即该类材料对外力刺激下能直接发射出强烈荧光；在紫外光持续照射后，材料发生光致变色，同时力致发光性能消失；而材料经过可见光照射恢复到初始状态后，力致发光性能重现。材料合成方法简单、发光量子效率高、光致变色和摩擦发光性能佳，可制备成应力响应型器件，应用于新型应力传感器、材料的高精度破损监测等领域。The present invention proposes a light-controlled organic electroluminescent material containing tristyryl groups with photoswitching response characteristics and its preparation and use method. The tristyryl derivatives containing borate or boric acid groups and the tristyryl derivatives containing bromine or iodine The coupling reaction of aromatic heterocyclic compound is realized by following method: provide the aromatic heterocyclic compound containing bromine or iodine and the triphenylethylene compound containing boric acid or boric acid ester in tetrahydrofuran solution, with potassium carbonate as base, in four (three Phenylphosphine) palladium [Pd(PPh 3 ) 4 ] catalyzed by heating to reflux to obtain a luminescent material. The material synthesized in the present invention has light-controlled mechanoluminescence performance, that is, this type of material can directly emit strong fluorescence under external stimulation; after continuous irradiation with ultraviolet light, the material undergoes photochromism, and at the same time the mechanoluminescence property disappears; and After the material was restored to its original state by visible light irradiation, the mechanoluminescence performance was reproduced. The material synthesis method is simple, the luminous quantum efficiency is high, and the photochromic and triboluminescent properties are good. It can be prepared into a stress-responsive device, which can be used in new stress sensors, high-precision damage monitoring of materials and other fields.
本发明的合成方法工艺简单，容易纯化，所合成的光控力致发光材料拥有较大的分子偶极矩和扭曲的构型，能凭借分子间相互作用提高材料在晶态下的规整排列，实现力致发光性能；芳香杂环化合物中杂原子的引入能有效地调节其芳香性和HOMO、LUMO电子云分布，有利于分子在紫外光辐射下容易进行可逆的关环反应，实现光致变色性能。此外，本发明提供的一种具有光开关响应特性的光控有机力致发光材料可制备成应力响应型器件，应用于材料的高精度应力传感及检测等领域。The synthesis method of the present invention has a simple process and is easy to purify. The synthesized light-controlled mechanoluminescent material has a large molecular dipole moment and a distorted configuration, and can improve the regular arrangement of the material in the crystalline state by virtue of intermolecular interactions. Achieve mechanoluminescent performance; the introduction of heteroatoms in aromatic heterocyclic compounds can effectively adjust its aromaticity and HOMO, LUMO electron cloud distribution, which is conducive to the easy reversible ring-closing reaction of molecules under ultraviolet radiation to achieve photochromism performance. In addition, an optically controlled organic mechanoluminescent material with optical switch response characteristics provided by the present invention can be prepared into a stress-responsive device, which can be applied to the fields of high-precision stress sensing and detection of materials.
附图说明Description of drawings
图1是本发明提供的光控有机力致发光材料实施例1的荧光光谱和力致发光光谱。Fig. 1 is the fluorescence spectrum and the mechanoluminescence spectrum of Example 1 of the light-controlled organic mechanoluminescent material provided by the present invention.
图2是本发明提供的光控有机力致发光材料实施例1在365nm紫外光照射前后的紫外-可见吸收谱。Fig. 2 is the ultraviolet-visible absorption spectrum of Example 1 of the photo-controlled organic mechanoluminescent material provided by the present invention before and after irradiation with 365nm ultraviolet light.
图3是本发明提供的材料实施例1的晶体在紫外光持续照射前后的荧光和力致发光照片。Fig. 3 is a photo of fluorescence and mechanoluminescence of the crystal of material example 1 provided by the present invention before and after continuous irradiation with ultraviolet light.
图4是本发明提供的材料实施例1通过熔铸法制备成应力响应型器件及其光控力致发光的照片。Fig. 4 is a photo of a stress-responsive device prepared by the material example 1 provided by the present invention by melting and casting and its light-controlled mechanoluminescence.
具体实施方式Detailed ways
现结合实施例、附图对本发明作进一步描述：Now in conjunction with embodiment, accompanying drawing, the present invention will be further described:
本发明所述一种含三苯乙烯基的具有光开关响应特性的光控有机力致发光材料，其分子结构如通式(1)所示：According to the present invention, a light-controlled organic mechanoluminescent material containing a triphenylethenyl group and having an optical switch response characteristic has a molecular structure as shown in the general formula (1):
通式(1)中，A为具有芳香杂环的功能基团，A和三苯乙烯基团之间通过共价键连接。In the general formula (1), A is a functional group having an aromatic heterocycle, and A is connected to the triphenylethylene group through a covalent bond.
优选地，对于通式(1)所述的芳香杂环基团A，可以选自如下分子中的任意一种：Preferably, for the aromatic heterocyclic group A described in general formula (1), it can be selected from any one of the following molecules:
所述R1、R2、R3、R4和R5各自独自地选自氢原子、烷基、卤素、烷氧基、氨基、醛基、氰基、羟基、羧基中的任意一种。The R1, R2, R3, R4 and R5 are each independently selected from any one of a hydrogen atom, an alkyl group, a halogen, an alkoxy group, an amino group, an aldehyde group, a cyano group, a hydroxyl group, and a carboxyl group.
所述的一种含三苯乙烯基的具有光开关响应特性的光控有机力致发光材料【通式(1)】的合成方法：将含硼酸酯或硼酸基团的三苯乙烯与含溴或碘的芳香杂环化合物通过Suzuki反应得到目标产物。The synthesis method of the light-controlled organic electroluminescent material [general formula (1)] containing triphenylethylene group with photoswitching response characteristics: combining triphenylethylene containing boric acid ester or boric acid group with Aromatic heterocyclic compounds of bromine or iodine can be obtained by Suzuki reaction.
含硼酸酯或硼酸基团的三苯乙烯衍生物与含溴或碘的芳香杂环化合物的偶联反应由以下方法实现：提供含溴或碘的芳香杂环化合物与含硼酸或硼酸酯的三苯乙烯化合物在四氢呋喃溶液中，以碳酸钾为碱，在四(三苯基膦)钯【Pd(PPh3)4】催化下，加热回流得到目标产物。The coupling reaction of the triphenylethylene derivative containing boronate or boric acid group and the aromatic heterocyclic compound containing bromine or iodine is realized by the following method: provide the aromatic heterocyclic compound containing bromine or iodine and boric acid or borate The triphenylethylene compound is heated to reflux in tetrahydrofuran solution with potassium carbonate as the base under the catalysis of tetrakis(triphenylphosphine)palladium [Pd(PPh 3 ) 4 ] to obtain the target product.
以下通过具体的实施例对本发明作进一步的阐述，但本发明并不限于此特定例子。The present invention will be further described through specific examples below, but the present invention is not limited to this specific example.
实施例1：Example 1:
目标产物【2-氟-5-(1,2,2-三苯乙烯基)吡啶】(TPF)的合成Synthesis of the target product 【2-fluoro-5-(1,2,2-tristyryl)pyridine】(TPF)
将2-氟吡啶-5-硼酸酯(0.95g，4.27mmol)和1-溴-1,2,2-三苯乙烯(1.30g，3.88mmol)溶于50mL四氢呋喃中，加入10mL碳酸钾(1.61g，11.63mmol)溶液，通入氮气，室温下搅拌30min。加入四三苯基膦钯0.05g作为催化剂，升高温度至溶剂回流，搅拌回流24小时后将反应液冷却，抽滤，滤液用旋转蒸发仪蒸干。用硅胶柱层析的方法进行提纯，淋洗液为体积比1:1的二氯甲烷和正己烷的混合溶液。得纯产物1.00g，产率73.4％。Dissolve 2-fluoropyridine-5-boronate (0.95 g, 4.27 mmol) and 1-bromo-1,2,2-triphenylethylene (1.30 g, 3.88 mmol) in 50 mL of tetrahydrofuran, and add 10 mL of potassium carbonate ( 1.61g, 11.63mmol) solution, blown with nitrogen, and stirred at room temperature for 30min. Add 0.05 g of tetrakistriphenylphosphine palladium as a catalyst, raise the temperature until the solvent refluxes, stir and reflux for 24 hours, then cool the reaction liquid, filter with suction, and evaporate the filtrate to dryness with a rotary evaporator. Purification was carried out by silica gel column chromatography, and the eluent was a mixed solution of dichloromethane and n-hexane with a volume ratio of 1:1. 1.00 g of pure product was obtained with a yield of 73.4%.
实施例2：Example 2:
目标产物【2-氯-5-(1,2,2-三苯乙烯基)吡啶】(TPCl)的合成Synthesis of the Target Product [2-Chloro-5-(1,2,2-tristyryl)pyridine](TPCl)
参照实施例1的合成步骤，利用2-氯吡啶-5-硼酸酯代替2-氟吡啶-5-硼酸酯合成2-氯-5-(1,2,2-三苯乙烯基)吡啶。(产率为68.7％)Referring to the synthesis steps of Example 1, 2-chloropyridine-5-boronate was used to replace 2-fluoropyridine-5-boronate to synthesize 2-chloro-5-(1,2,2-tristyryl)pyridine . (The yield is 68.7%)
实施例3：Example 3:
目标产物【2-氯-5-(1,2,2-三苯乙烯基)噻吩】(TSF)的合成Synthesis of the target product 【2-Chloro-5-(1,2,2-tristyryl)thiophene】(TSF)
参照实施例1的合成步骤，利用2-氟噻吩-5-硼酸酯代替2-氟吡啶-5-硼酸酯合成2-氟-5-(1,2,2-三苯乙烯基)噻吩。(产率为60.1％)Referring to the synthesis steps of Example 1, 2-fluorothiophene-5-boronate was used instead of 2-fluoropyridine-5-boronate to synthesize 2-fluoro-5-(1,2,2-tristyryl)thiophene . (The yield is 60.1%)
综上所述，本发明所合成的材料具有光控力致发光性能，即该类材料对外力刺激下能直接发射出强烈荧光；在紫外光持续照射后，材料发生光致变色，同时力致发光性能消失；而材料经过可见光照射恢复到初始状态后，力致发光性能重现。材料合成方法简单、发光量子效率高、光致变色和摩擦发光性能佳，可制备成应力响应型器件，应用于新型应力传感器、材料的高精度破损监测等领域。以上所述，本领域的普通技术人员可以根据本发明的技术方案和技术构思做出其它各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。To sum up, the material synthesized by the present invention has photo-controllable mechanoluminescence performance, that is, this type of material can directly emit strong fluorescence under external stimulation; after continuous irradiation with ultraviolet light, the material undergoes photochromism, and at the same time, the mechanoluminescence The luminescence property disappears; and the mechanoluminescent property reappears after the material is restored to its original state after being irradiated with visible light. The material synthesis method is simple, the luminous quantum efficiency is high, and the photochromic and triboluminescent properties are good. It can be prepared into a stress-responsive device, which can be used in new stress sensors, high-precision damage monitoring of materials and other fields. As mentioned above, those skilled in the art can make various other corresponding changes and deformations according to the technical solutions and technical concepts of the present invention, and all these changes and deformations should belong to the protection scope of the claims of the present invention.
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