CN111875636B - Flexible organic friction luminescent material based on oxidized benzothiophene and preparation and use methods thereof - Google Patents
Flexible organic friction luminescent material based on oxidized benzothiophene and preparation and use methods thereof Download PDFInfo
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Abstract
The invention relates to a flexible organic friction luminescent material based on oxidized benzothiophene and a preparation and use method thereof, wherein the general structural formula of the flexible organic friction luminescent material is D-X-A, wherein D is an electron donor group with a twisted configuration, A is an electron acceptor group with a twisted configuration, X is oxidized benzothiophene, and D, X, A is connected through covalent bonds. The material synthesized by the invention has amorphous frictional luminescence performance, is extremely sensitive to external force stimulation and crack induction of the substrate material, and is accompanied with a fluorescent signal which is easy to detect. The material synthesis method is simple, the luminous quantum efficiency is high, the frictional luminescence performance is good, the stress response type flexible device can be prepared, and the method is applied to the fields of novel flexible stress sensors, high-precision damage monitoring of materials, micro-damage detection of precision instruments and aerospace and aviation equipment and the like.
Description
Technical Field
The invention belongs to a flexible organic friction luminescent material and preparation and use methods thereof, and relates to a flexible organic friction luminescent material based on oxidized benzothiophene and preparation and use methods thereof. The flexible organic friction luminescent material has good friction luminescent performance and higher fluorescence quantum efficiency under an amorphous state, can be prepared into a stress response type flexible photoelectric device, and is applied to the fields of high-precision damage monitoring of materials, micro-damage detection of precision instruments and the like.
Background
Triboluminescence is also called mechanoluminescence, which refers to a process in which a solid material converts mechanical energy into light energy and releases the light energy to the outside under the action of external force (friction, stretching, extrusion, collision, etc.), and is disclosed in the following documents: N.C. Eddingsaas, K.S. Suslick, "Light from Sound of Crystal series" Nature,2006,444,163. Compared with the traditional luminescent material, the friction luminescent material has unique excitation mode (only excited by mechanical energy without an external power supply or light source), has obvious responsiveness to external stress stimulation, and also has important potential application value in the fields of novel light sources, biological imaging, trademark anti-counterfeiting, information encryption, stress sensing, material damage monitoring and the like, see documents: xie, Z.Li, "Triboluminescence," recording interest and new aspects ", chem,2018,4,943; liu Mingli, wu Qi, shi Huifang, an Zhongfu, huang Wei, "development of organic/metal-organic electroluminescent materials", journal of chemistry, 2018,76,246.
The triboluminescent materials may be classified into inorganic triboluminescent materials and organic triboluminescent materials according to their compositions. The inorganic friction luminescent material has strong luminous brightness and high force response sensitivity, but the noble metal elements participate in the inorganic friction luminescent material to cause the price to be high and the toxicity to be high, and the luminescence of most of the materials is limited in a red area, so that the development of the inorganic friction luminescent material is limited. Compared with inorganic friction luminescent materials, the organic friction luminescent materials have obvious advantages in the aspects of luminescent wavelength adjustment, molecular modifiability, flexible device preparation, cost and the like, and therefore have wider market prospects and application spaces.
At present, the triboluminescence phenomenon of organic materials can only occur in a non-centrosymmetric crystalline state, the materials are difficult to prepare into films, flexible photoelectric devices are difficult to prepare, non-planar (non-planar under common application conditions) stress sensing and material damage monitoring are difficult to realize, and the flexible development and practical application of the organic triboluminescence materials are severely restricted. Therefore, how to overcome the 'crystalline dependence' of triboluminescence, obtain amorphous triboluminescence, and realize flexible design of organic triboluminescence materials and devices is a key problem faced by the development of the materials.
The amorphous organic friction luminescent material is extremely sensitive to external force stimulation and crack induction of a substrate material, is accompanied by a fluorescent signal easy to detect, and has wide application prospects in the fields of research and development of novel flexible stress sensors, high-precision damage monitoring of materials and the like. In addition, the material can also be widely applied to micro-damage detection and organism internal stress detection of precision instruments and space flight and aviation equipment. For example, the coating based on the material can be coated on the wings of an airplane, and the stress distribution of the wings can be accurately analyzed through the light intensity on the surfaces of the wings in a wind tunnel experiment; the flexible film based on the material can be used for monitoring abnormal jitter signals of precise aerospace equipment, monitoring physiological signals of human pulse, heartbeat and the like, and the like.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a flexible organic friction luminescent material based on oxidized benzothiophene and a preparation and use method thereof, and the regulation and control of the luminescent color and the amorphous friction luminescent performance of the material are realized by changing the molecular donor/acceptor structure and regulating the interaction between molecules.
Another objective is to provide a method for synthesizing the said oxidized benzothiophene-based flexible organic triboluminescent materials, which has simple process, high yield, easy purification, and can adjust the triboluminescent properties (luminescence wavelength, brightness, lifetime) of the final product by introducing different functional groups.
The third purpose is to combine the amorphous friction luminescence property of the flexible organic friction luminescence material based on the oxidized benzothiophene and apply the material to the fields of high-precision damage monitoring of materials and the like.
Technical scheme
A flexible organic friction luminescent material based on oxidized benzothiophene is characterized by having a structural general formula as follows:
wherein D is an electron donor group with a twisted configuration, A is an electron acceptor group with a twisted configuration, and the electron donor group D, the oxidized benzothiophene and the electron acceptor group A are connected through covalent bonds.
The electron donor group D is selected from any one of the following molecules:
r1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14 and R15 in the structure of the electron donor group D are the same or different and are independently selected from any one of hydrogen atom, alkyl, halogen, alkoxy, nitro, amino, aldehyde group, cyano and phenyl.
The electron acceptor group A is selected from any one of the following molecules:
r1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 in the structure of the electron acceptor group A are the same or different and are respectively and independently selected from any one of hydrogen atom, alkyl, halogen, alkoxy, nitro, amino, aldehyde group, cyano and phenyl.
The method for synthesizing the oxidized benzothiophene-based flexible organic friction luminescent material is characterized by comprising the following steps of: mixing aromatic compound containing boric acid ester or boric acid group and aromatic ring or aromatic heterocyclic compound containing bromine or iodine at molar ratio of 0.3: 1 to 4: 1, adding potassium carbonate as base in tetrahydrofuran solution, and adding ferrocene palladium chloride [ Pd (dppf) Cl ] to obtain solution 2 Heating reflux is carried out under catalysis, and the flexible organic tribo-luminescent material based on the oxidized benzothiophene is obtained through a Suzuki reaction.
A synthetic method of the oxidized benzothiophene-based flexible organic friction luminescent material is characterized by comprising the following steps: mixing an aromatic compound containing bromine or iodine directly with a nitrogen-hydrogen containing aromatic ring or an aromatic heterocyclic compound at a molar ratio of 1: 0.8-1: 3, heating and refluxing in a toluene solution by taking potassium carbonate or potassium hydroxide as a base under the catalysis of cuprous iodide and phenanthroline, and carrying out a Ullmann reaction to obtain the benzothiophene oxide-based flexible organic triboluminescent material.
The method for synthesizing the oxidized benzothiophene-based flexible organic friction luminescent material is characterized by comprising the following steps of: mixing an aromatic compound containing benzaldehyde with an aromatic ring or an aromatic heterocyclic compound containing phosphite ester at one end or two ends at a molar ratio of 0.3: 1 to 4: 1, and carrying out Wittig reaction in a tetrahydrofuran solution under the action of potassium tert-butoxide to obtain the oxidized benzothiophene-based flexible organic triboluminescent material.
The use method of the oxidized benzothiophene-based flexible organic triboluminescent material is characterized in that: the stress response type flexible device is prepared and applied to the fields of high-precision damage monitoring of materials and micro-damage detection of precision instruments and aerospace and aviation equipment.
The use method of the oxidized benzothiophene-based flexible organic friction luminescent material is characterized by comprising the following steps: the prepared flexible film is used for monitoring physiological signals of human body pulse, heartbeat and the like.
Advantageous effects
The invention provides a flexible organic friction luminescent material based on oxidized benzothiophene and a preparation and use method thereof, wherein the structural general formula of the flexible organic friction luminescent material is D-X-A, wherein D is an electron donor group with a twisted configuration, A is an electron acceptor group with a twisted configuration, X is oxidized benzothiophene, and D, X, A are connected through covalent bonds.
The development of organic friction luminescence from crystal particles which are difficult to apply to amorphous coatings and flexible films can be realized, a foundation is laid for the preparation and research of curved surface stress sensing devices and film flexible stress sensing devices, the organic friction luminescence material is promoted to be widely applied in the fields of intelligent anti-counterfeiting, stress sensing, biomedicine, material damage monitoring, molecular machines and the like, and the organic friction luminescence material has important research value and scientific significance for the development of intelligent flexible organic photoelectric materials and devices for sensing external stimulation.
The synthetic method has simple process and easy purification, the synthesized luminescent material has larger molecular dipole moment and distorted configuration, the orderliness of the material in an amorphous state can be improved by virtue of intermolecular interaction, the amorphous state triboluminescence is realized, and the triboluminescence wavelength, brightness, service life and other properties of a final product can be adjusted by introducing different functional groups. In addition, the flexible organic friction luminescent material based on the oxidized benzothiophene can be prepared into a stress response type flexible photoelectric device, and is applied to the field of stress sensing, such as high-precision damage monitoring of materials, micro-damage detection of precision instruments and aerospace and aviation equipment, and the like.
Drawings
FIG. 1 shows fluorescence spectra of flexible organic friction luminescent materials M1 and M2 provided by the invention
FIG. 2 shows the triboluminescence spectra of the flexible organic triboluminescent materials M1 and M2 provided by the present invention
FIG. 3 is a fluorescent photograph of amorphous powders of materials M1 and M2 provided by the present invention and a flexible stress-responsive luminescent film coated on a polymer film substrate
Detailed Description
The invention will now be further described with reference to the following examples, and the accompanying drawings:
the invention relates to a flexible organic friction luminescent material based on oxidized benzothiophene, which has a molecular structure shown in a general formula (1):
in the general formula (1), D is an electron donor group with a distorted configuration, A is an electron acceptor group with a distorted configuration, and D, oxidized benzothiophene and A are connected through covalent bonds.
Preferably, the electron donor D described in the general formula (1) may be selected from any one of the following molecules:
r1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14 and R15 are independently selected from any one of hydrogen atom, alkyl, halogen, alkoxy, amino, aldehyde group, cyano and phenyl.
Preferably, the electron acceptor a described in the general formula (1) may be selected from any one of the following molecules:
r1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are independently selected from any one of hydrogen atom, alkyl, halogen, alkoxy, amino, aldehyde group, cyano and phenyl.
The several synthesis methods of the oxidized benzothiophene-based flexible organic triboluminescent material [ general formula (1) ]:
(1) Carrying out Suzuki reaction on an aromatic compound containing boric acid ester or boric acid group and an aromatic ring or aromatic heterocyclic compound containing bromine or iodine to obtain a target product; (2) Directly reacting bromine or iodine-containing aromatic compound with nitrogen-hydrogen-containing aromatic ring or aromatic heterocyclic compound Ullmann to obtain target product; (3) An aromatic compound containing benzaldehyde is reacted with an aromatic ring or aromatic heterocyclic compound containing phosphite ester at one end or both ends to obtain a target product through Wittig reaction.
A synthetic method of a flexible organic friction luminescent material (1) comprises the following steps of carrying out coupling reaction on an aromatic compound containing a boric acid ester or boric acid group and an aromatic ring or aromatic heterocyclic compound containing bromine or iodine: providing aromatic compound containing bromine or iodine and aromatic ring or aromatic heterocyclic compound containing boric acid or boric acid ester in tetrahydrofuran solution, taking potassium carbonate as alkali, and adding ferrocene palladium chloride [ Pd (dppf) Cl 2 Heating and refluxing under catalysis to obtain the target product.
A method for synthesizing a flexible organic friction luminescent material based on oxidized benzothiophene (2) is characterized in that the coupling reaction of bromine or iodine-containing aromatic compounds and nitrogen-hydrogen-containing aromatic rings or aromatic heterocyclic compounds is realized by the following steps: providing an aromatic compound containing bromine or iodine and a nitrogen-hydrogen-containing aromatic ring or aromatic heterocyclic compound, heating and refluxing in a toluene solution by taking potassium carbonate or potassium hydroxide as alkali under the catalysis of cuprous iodide and phenanthroline to obtain a target product.
A method for synthesizing a flexible organic friction luminescent material based on oxidized benzothiophene (3) the reaction of an aromatic compound containing benzaldehyde and an aromatic ring or an aromatic heterocyclic compound containing phosphite ester at one end or two ends is realized by the following steps: provides aromatic compound containing benzaldehyde and aromatic ring or aromatic heterocyclic compound containing phosphite ester in tetrahydrofuran solution, and through Wittig reaction under the action of potassium tert-butoxide to obtain the target product.
The flexible organic friction luminescent material [ general formula (1) ] based on the oxidized benzothiophene can be prepared into a stress response type friction luminescent device, and is applied to the field of stress sensing, such as high-precision damage monitoring of materials, micro-damage detection of precision instruments and aerospace and aviation equipment, and the like.
The synthetic method has simple process and easy purification, and the synthesized luminescent material has larger molecular dipole moment and distorted configuration, can improve the orderliness of the material in an amorphous state by virtue of intermolecular interaction, realizes amorphous state triboluminescence, and can adjust the triboluminescence wavelength, brightness, service life and other properties of a final product by introducing different functional groups. In addition, the flexible organic friction luminescent material based on the oxidized benzothiophene can be prepared into a stress response type flexible photoelectric device, and is applied to the fields of high-precision damage monitoring of materials, micro-damage detection of precision instruments and aerospace and aviation equipment and the like.
The present invention is further illustrated by the following specific examples, but the present invention is not limited to these specific examples.
Example 1:
(1) Synthesis of intermediate [ 3,3' -diiododibenzothiophene sulfone ]
Dibenzothiophene sulfone (5.00g, 23.12mmol) was dissolved in 50mL of acetic acid, and 5mL of H was added 2 O and 5mL H 2 SO 4 Iodine (7.04g, 27.75mmol) and periodic acid (6.32g, 27.75mmol) were added with stirring. And raising the temperature until the solvent flows back, stirring and refluxing for 16 hours, then cooling the reaction solution, pouring the reaction solution into water, performing suction filtration, and evaporating the filtrate by using a rotary evaporator. Purifying by silica gel column chromatography, wherein the eluent is a mixed solution of dichloromethane and n-hexane with a volume ratio of 1:1. 7.30g of pure product are obtained, yield 67.5%.
(2) Synthesis of intermediate [ 3-diphenylamino-3' -iododibenzothiophene sulfone ]
Diphenylamine (0.40g, 2.36mmol) was charged into a 250mL dry three-necked flask under nitrogen, 3,3' -diiododibenzothiophene sulfone (1.22g, 2.60mmol) was added, 50mL toluene was added to dissolve, phenanthroline (51.12mg, 0.28mmol), cuprous iodide (45.02mg, 0.24mmol) and potassium hydroxide (0.53g, 9.45mmol) were added, the temperature was raised to 110 ℃, and the reaction was stirred for 16h. After the reaction, toluene was removed from the reaction solution by rotary evaporation, 50ml of dichloromethane was added and dissolved, and then the reaction solution was poured into a separatory funnel and washed with water for 2 to 3 times. Drying the organic layer with anhydrous sodium sulfate, filtering, spin-drying the filtrate in a rotary evaporator, and purifying by silica gel column chromatography, wherein the eluent is a mixed solution of dichloromethane and n-hexane with a volume ratio of 3:2. 0.71g of a yellow solid is obtained in 59.0% yield.
(3) Synthesis of target product [ 3-diphenylamino-3' -diphenylphosphinyl dibenzothiophene sulfone ] (M1)
3-Diphenylamino-3' -iododibenzothiophenesulfone (0.60g, 1.18mmol) was dissolved in toluene, and 3mL of triethylamine was added. Diphenylphosphine (0.48g, 2.36mmol) was added. And raising the temperature until the solvent flows back, adding 0.05g of palladium tetratriphenylphosphine as a catalyst, stirring and refluxing for 36 hours, then cooling the reaction solution, performing suction filtration, and evaporating the filtrate by using a rotary evaporator. Purifying by using a silica gel column chromatography method, wherein the eluent is a mixed solution of dichloromethane and methanol with a volume ratio of 30. 0.43g of pure product is obtained, yield 62.6%.
Example 2:
(1) Synthesis of intermediate [ 3-carbazolyl-3' -iodo-dibenzothiophene sulfone ]
Referring to step (2) in example 1, 3-carbazolyl-3' -iododibenzothiophenone was synthesized using carbazole instead of diphenylamine. (yield 55.2%)
(2) Synthesis of target product [ 3-carbazolyl-3' -diphenylphosphinyl dibenzothiophene sulfone ] (M2)
Referring to step (3) in example 1, 3-carbazolyl-3 ' -diphenylphosphinyl dibenzothiophene sulfone was synthesized using 3-carbazolyl-3 ' -iododibenzothiophene sulfone instead of 3-diphenylamino-3 ' -iododibenzothiophene sulfone. (yield 60.8%)
In conclusion, the material synthesized by the invention has amorphous frictional luminescence performance, is extremely sensitive to external force stimulation and crack induction of the substrate material, and is accompanied with a fluorescent signal which is easy to detect. The material synthesis method is simple, the luminous quantum efficiency is high, the triboluminescence performance is good, the stress response type flexible device can be prepared, and the method is applied to the fields of novel flexible stress sensors, high-precision damage monitoring of materials and the like.
Claims (4)
2. The method for synthesizing the oxidized benzothiophene-based flexible organic triboluminescent material M1 according to claim 1, characterized by comprising the following steps:
step 1: synthesizing an intermediate 3,3' -diiododibenzothiophene sulfone,
5.00g of dibenzothiophene sulfone was dissolved in 50mL of acetic acid, and 5mL of H was added 2 O and 5mL H 2 SO 4 Adding 7.04g of iodine and 6.32g of periodic acid under stirring; raising the temperature until the solvent flows back, stirring and flowing back for 16 hours, cooling the reaction liquid, pouring the reaction liquid into water, performing suction filtration, and evaporating the filtrate by using a rotary evaporator; purifying by silica gel column chromatography, wherein the eluent is a mixed solution of dichloromethane and n-hexane with a volume ratio of 1:1; 7.30g of pure product is obtained, and the yield is 67.5%;
step 2: synthesizing an intermediate 3-diphenylamino-3' -iodo-dibenzothiophene sulfone,
adding 0.40g of diphenylamine into a 250mL dry three-necked bottle under the atmosphere of nitrogen, adding 1.22g of 3,3' -diiododibenzothiophene sulfone, adding 50mL of toluene for dissolution, adding 51.12mg of phenanthroline, 45.02mg of cuprous iodide and 0.53g of potassium hydroxide, heating to 110 ℃, and stirring for reaction for 16 hours; after the reaction is finished, removing toluene from the reaction solution through rotary evaporation, adding 50ml of dichloromethane for dissolution, then pouring the reaction solution into a separating funnel, and washing for 2-3 times; drying the organic layer with anhydrous sodium sulfate, filtering, spin-drying the filtrate in a rotary evaporator, and purifying by silica gel column chromatography, wherein the eluent is a mixed solution of dichloromethane and n-hexane with a volume ratio of 3:2; 0.71g of yellow solid is obtained, and the yield is 59.0%;
and step 3: synthesizing a target product 3-diphenylamino-3' -diphenyl phosphinyl dibenzothiophene sulfone,
dissolving 0.60g of 3-diphenylamino-3' -iododibenzothiophene sulfone in toluene, adding 3mL of triethylamine, and adding 0.48g of diphenylphosphine; raising the temperature until the solvent flows back, adding 0.05g of palladium tetratriphenylphosphine as a catalyst, stirring and refluxing for 36 hours, then cooling the reaction solution, performing suction filtration, and evaporating the filtrate by using a rotary evaporator; purifying by a silica gel column chromatography method, wherein the eluent is a mixed solution of dichloromethane and methanol with a volume ratio of 30; 0.43g of pure product is obtained, yield 62.6%.
3. The method for synthesizing the oxidized benzothiophene-based flexible organic triboluminescent material M2 according to claim 1, characterized by comprising the following steps:
step 1: synthesizing an intermediate 3-carbazolyl-3' -iodo-dibenzothiophene sulfone,
adding 0.40g of carbazole into a 250mL dry three-necked bottle in a nitrogen atmosphere, adding 1.22g of 3,3' -diiodo dibenzothiophene sulfone, adding 50mL of toluene for dissolving, adding 51.12mg of phenanthroline, 45.02mg of cuprous iodide and 0.53g of potassium hydroxide, heating to 110 ℃, and stirring for reacting for 16 hours; after the reaction is finished, removing toluene from the reaction solution through rotary evaporation, adding 50ml of dichloromethane for dissolution, then pouring the reaction solution into a separating funnel, and washing for 2-3 times; drying the organic layer with anhydrous sodium sulfate, filtering, spin-drying the filtrate in a rotary evaporator, and purifying by silica gel column chromatography, wherein the eluent is a mixed solution of dichloromethane and n-hexane with a volume ratio of 3:2; synthesizing 3-carbazolyl-3' -iodo-dibenzothiophene sulfone with a yield of 55.2%;
and 2, step: synthesizing a target product 3-carbazolyl-3' -diphenyl phosphinyl dibenzothiophene sulfone,
dissolving 0.60g of 3-carbazolyl-3' -iodo-dibenzothiophene sulfone in toluene, adding 3mL of triethylamine, and adding 0.48g of diphenylphosphine; raising the temperature until the solvent flows back, adding 0.05g of palladium tetratriphenylphosphine as a catalyst, stirring and refluxing for 36 hours, then cooling the reaction solution, performing suction filtration, and evaporating the filtrate by using a rotary evaporator; purifying by a silica gel column chromatography method, wherein the eluent is a mixed solution of dichloromethane and methanol with a volume ratio of 30; 3-carbazolyl-3' -diphenyl phosphinyl dibenzothiophene sulfone is synthesized with a yield of 60.8%.
4. Use of the oxidized benzothiophene-based flexible organic triboluminescent material according to claim 1, characterized in that: the method is used for preparing stress response type flexible devices, and is applied to the fields of high-precision damage monitoring of materials and micro-damage detection of precision instruments and aerospace and aviation equipment.
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CN104745176A (en) * | 2015-03-19 | 2015-07-01 | 武汉大学 | Aggregation-induced emissive blue-ray molecule by construction of dibenzothiophene sulfone unit as well as preparation method and application of aggregation-induced emissive blue-ray molecule |
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CN102775398A (en) * | 2012-07-25 | 2012-11-14 | 烟台万润精细化工股份有限公司 | Novel bipolar material and application thereof |
CN104745176A (en) * | 2015-03-19 | 2015-07-01 | 武汉大学 | Aggregation-induced emissive blue-ray molecule by construction of dibenzothiophene sulfone unit as well as preparation method and application of aggregation-induced emissive blue-ray molecule |
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