CN111875636A - 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 method and a 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 communication 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: y.xie, z.li, "triangle," adapting interests and new aspects ", Chem,2018,4, 943; liuming Li, Wuqi, Shihui Fang, Anzhoufu, Huang Wei, research progress of organic/metal organic electroluminescent materials, chemical bulletin, 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 breakage monitoring are difficult to realize, and 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 body pulse, heartbeat 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 oxidized benzothiophene-based flexible organic triboluminescent material, 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 respectively and independently selected from any one of hydrogen atoms, alkyl, halogen, alkoxy, nitro, amino, aldehyde groups, 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 atoms, alkyl, halogen, alkoxy, nitro, amino, aldehyde, 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) Cl2Heating reflux is carried out under catalysis, and the flexible organic tribo-luminescent material based on the oxidized benzothiophene is obtained through a Suzuki reaction.
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 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 triboluminescent material is characterized in that: 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 is 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 and flexible stress-responsive luminescent films prepared by coating the amorphous powders on a polymer film substrate
Detailed Description
The invention will now be further described with reference to the following examples and 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 respectively and 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 atoms, alkyl, halogen, alkoxy, amino, aldehyde, cyano and phenyl.
The method for synthesizing the oxidized benzothiophene-based flexible organic triboluminescent material [ general formula (1) ] comprises the following steps:
(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) Cl2Heating and refluxing to obtain the target product under catalysis.
A method for synthesizing a flexible organic friction luminescent material based on oxidized benzothiophene (2) is realized by the following steps of directly carrying out coupling reaction on an aromatic compound containing bromine or iodine and a nitrogen-hydrogen-containing aromatic ring or aromatic heterocyclic compound: 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, 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 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 added2O and 5mLH2SO4Iodine (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 a nitrogen atmosphere, 3' -diiododibenzothiophenesulfone (1.22g, 2.60mmol) was added thereto, 50mL of toluene was added thereto and dissolved, phenanthroline (51.12mg, 0.28mmol), cuprous iodide (45.02mg,0.24mmol) and potassium hydroxide (0.53g,9.45mmol) were added thereto, and the mixture was heated to 110 ℃ and stirred for reaction for 16 hours. After the reaction is finished, the toluene in the reaction solution is removed through rotary evaporation, 50ml of dichloromethane is added for dissolution, and then the reaction solution is poured into a separating funnel and washed 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 in 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' -iododibenzothiophene sulfone (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 silica gel column chromatography, wherein the eluent is a mixed solution of dichloromethane and methanol at a volume ratio of 30: 1. 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 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 and the like.
Claims (10)
1. 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.
2. The oxidized benzothiophene-based flexible organic triboluminescent material according to claim 1, characterized in that: the electron donor group D is selected from any one of the following molecules:
3. the oxidized benzothiophene-based flexible organic triboluminescent material according to claim 2, characterized in that: 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 respectively and independently selected from any one of hydrogen atoms, alkyl, halogen, alkoxy, nitro, amino, aldehyde groups, cyano and phenyl.
4. The oxidized benzothiophene-based flexible organic triboluminescent material according to claim 1, characterized in that: the electron acceptor group A is selected from any one of the following molecules:
5. the oxidized benzothiophene-based flexible organic triboluminescent material according to claim 4, characterized in that: 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 atoms, alkyl, halogen, alkoxy, nitro, amino, aldehyde, cyano and phenyl.
6. The method for synthesizing the oxidized benzothiophene-based flexible organic triboluminescent material according to any one of claims 1 to 5, wherein: 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) Cl2Heating reflux is carried out under catalysis, and the flexible organic tribo-luminescent material based on the oxidized benzothiophene is obtained through a Suzuki reaction.
7. The method for synthesizing the oxidized benzothiophene-based flexible organic triboluminescent material according to any one of claims 1 to 5, wherein: 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.
8. The method for synthesizing the oxidized benzothiophene-based flexible organic triboluminescent material according to any one of claims 1 to 5, wherein: 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.
9. The use method of the oxidized benzothiophene-based flexible organic triboluminescent material according to any one of claims 1 to 5, 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.
10. The use method of the oxidized benzothiophene-based flexible organic triboluminescent material according to any one of claims 1 to 5, characterized in that: the prepared flexible film is used for monitoring physiological signals of human body pulse, heartbeat and the like.
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| CN202010779659.7A CN111875636B (en) | 2020-08-05 | 2020-08-05 | Flexible organic friction luminescent material based on oxidized benzothiophene and preparation and use methods thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108299514A (en) * | 2018-04-02 | 2018-07-20 | 江西师范大学 | The complex of iridium luminescent material of the sulfuryl containing dibenzothiophenes and its application |
| JP2019073489A (en) * | 2017-10-19 | 2019-05-16 | Dic株式会社 | Organic electroluminescence element and material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2019073489A (en) * | 2017-10-19 | 2019-05-16 | Dic株式会社 | Organic electroluminescence element and material |
| CN108299514A (en) * | 2018-04-02 | 2018-07-20 | 江西师范大学 | The complex of iridium luminescent material of the sulfuryl containing dibenzothiophenes and its application |
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