CN113429382B - 1,1' - ([ 2,2' -bithiophene ] -3,3' -diyl) bis (ethan-1-one) and preparation and application thereof - Google Patents
1,1' - ([ 2,2' -bithiophene ] -3,3' -diyl) bis (ethan-1-one) and preparation and application thereof Download PDFInfo
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- CN113429382B CN113429382B CN202110736900.2A CN202110736900A CN113429382B CN 113429382 B CN113429382 B CN 113429382B CN 202110736900 A CN202110736900 A CN 202110736900A CN 113429382 B CN113429382 B CN 113429382B
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Abstract
The invention belongs to the technical field of polymer material synthesis, and particularly relates to 1,1'- ([ 2,2' -dithiophene)]-3,3' -diyl) bis (eth-1-one) and preparation and application thereof. The 1,1'- ([ 2,2' -dithiophene)]-3,3' -diyl) bis (eth-1-one) has the structural formula:
. By adopting the method for controlling the conformational relaxation and conjugation of the molecular rotor, 1,1'- ([ 2,2' -bithiophene) is synthesized]-3,3' -diyl) bis (eth-1-one) molecular rotor and its main properties were studied systematically. Rotors of different torsion angles and degrees of conjugation produce different colors of luminescence. In addition, hydrogen bond stimulation can easily overcome the rotational energy barrier between the twisted and near-planar conformations. In the synthesis process, the separation of by-products has certain technical difficulties.
Description
Technical Field
The invention belongs to the technical field of polymer material synthesis, and particularly relates to 1,1' - ([ 2,2' -bithiophene ] -3,3' -diyl) bis (ethyl-1-ketone), and a preparation method and application thereof.
Background
The stimulus response type luminescent materials (SRLMs) have wide application prospects in the fields of displays, sensors, memories and the like, and the design of the SRLMs is a research hotspot all the time. SRLMs exhibit a change in luminescence behavior upon stimulation by appropriate chemical and physical factors (e.g., chemical substances, mechanical forces, light or magnetic radiation, etc.).
In 2018, mcCoy et al reported design methods [ d.e. McCoy, t. Feo, t.a. Harvey and r.o. Prum, nat. Commun., 2018, 9, 1 ] for constructing high-sensitivity switching machines SRLMs by controlling photophysical processes such as inter-system cross-over (ISC) processes. In the same year, yang et al constructed a delayed fluorescence-based SRLM [ Y. Yang, X. Fang, K. -Z. Wang and D. Yang, adv. Sci., 2018, 5, 1801187 ] by controlling the transition of the molecular stacking pattern between solid dimers.
In addition to the above modes, modulation of the conformation and conjugation of molecules is a common approach. In 2011, luo et al reported that mechanically discolored aluminate compounds with smaller twist angles and larger conjugated conformations had redder emission [ X. Luo, J. Li, C. Li, L. Heng, Y.Q. Dong, Z. Liu, Z. Bo and B.Z. Tang, adv. Mater., 2011, 23, 3261-3265 ].
Since the molecular rotor contains a single bond that can rotate, the conformation of the molecule and the degree of conjugation can be modulated by an external stimulus. The conformation relation between the ground state and the excited state of the biphenyl and the derivatives thereof with molecular rotor properties is that the vertical excited state (Franck-Condon state) is subjected to conformation relaxation to reach a planar excited state under the condition of no rotating potential barrier. This phenomenon means that modulation of the luminescence behavior of the rotor is easily achieved by altering the conformation and the degree of conjugation of the rotor under external stimuli. Therefore, designing SRLMs based on conformational relaxation of the excited state should be a good approach.
Disclosure of Invention
The invention provides 1,1' - ([ 2,2' -dithiophene ] -3,3' -diyl) bis (ethan-1-one) and a preparation method and application thereof.
The invention is realized by the following technical scheme: 1,1'- ([ 2,2' -dithiophene)]-3,3' -diyl) bis (ethan-1-one), said 1,1' - ([ 2,2' -dithiophene)]-3,3' -diyl) bis (eth-1-one) has the formula:
。
the preparation method of 1,1' - ([ 2,2' -dithiophene ] -3,3' -diyl) bis (ethan-1-one) comprises the following specific steps:
36mL of an n-hexane solution of n-butyllithium having a concentration of 2.5M 2 After the replacement, the solution was cooled to-78 ℃ and 300mL of anhydrous tetrahydrofuran was added; adding 30 mmol of 3,3 '-dibromo-2,2' -bithiophene 70 ml dropwise in 0.8-1.2 hours; after completion, the mixture was stirred at-78 ℃ for 2 hours, and then 95 mmol of N-methoxy-N-methylacetamide was added dropwise, the reaction solution was allowed to naturally warm to room temperature and reacted overnight; after the reaction is detected by liquid chromatography-mass spectrometry, water is added to quench the reaction, then 250 ml ethyl acetate is used for extraction, the ethyl acetate is used for extraction for 3 times under the same condition, the obtained organic phase is washed by 50 mL water and 50 mL saturated saline solution and Na 2 SO 4 Drying, filtering and concentrating to obtain a crude product; purifying the crude product by flash column chromatography, wherein the flash column chromatography is silica gel column, and eluting with 20% petroleum ether/ethyl acetate to obtain pale yellow solid 1,1'- ([ 2,2' -dithiophene)]3,3' -diyl) bis (ethan-1-one) in a yield of 42.7%; liquid chromatography-Mass Spectrometry (ESI) 250.9 (M + 1) + ； 1 H NMR (400 MHz, CD3OD) δ: 7.58 (d, J = 4.0, 2H), 7.56 (d, J = 4.0, 2H), 2.30 (s, 6H)。
The invention synthesizes 1,1' - ([ 2,2' -dithiophene ] -3,3' -diyl) bis (ethan-1-one) molecular rotor by adopting a method for controlling the conformational relaxation and conjugation of the molecular rotor, and systematically researches the main properties of the molecular rotor. Rotors of different torsion angles and degrees of conjugation produce different colors of illumination. In addition, hydrogen bond stimulation can easily overcome the rotational energy barrier between the twisted and near-planar conformations. In the synthesis process, the separation of byproducts has certain technical difficulty.
Drawings
FIG. 1 is a synthetic route diagram according to the present invention;
FIG. 2 shows HNMR-CDCL of the obtained compound 3 A drawing;
FIG. 3 is a LC-MS (liquid chromatography-mass spectrometry) chart of the obtained compound;
FIG. 4 is a photograph of the resulting polymer film 1,1' - ([ 2,2' -dithiophene ] -3,3' -diyl) bis (ethan-1-one) in response to water under UV-365 nm radiation.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In a 1L three-necked flask, a solution of N-butyllithium (36mL, 2.5M, 90mmol) in N-hexane was placed 2 After displacement, it was cooled to-78 ℃ and anhydrous tetrahydrofuran (300 mL) was added. A solution of 3,3 '-dibromo-2,2' -bithiophene (9.65 g,30 mmol) in THF (70 ml) was added dropwise over a period of 0.8-1.2 hours. The mixture was then stirred at-78 ℃ for a further 2 hours, followed by dropwise addition of N-methoxy-N-methylacetamide (9.8g, 95 mmol), after which the reaction solution was allowed to warm to room temperature naturally and reacted overnight. After the reaction is detected by liquid chromatography-mass spectrometry, water is added to quench the reaction, 250 ml ethyl acetate is used for extraction, the ethyl acetate is used for extraction for 3 times under the same condition, the obtained organic phase is sequentially washed by 50 mL water and 50 mL saturated saline solution, na is added to the organic phase, and the organic phase is washed by the sodium chloride solution and the sodium chloride solution 2 SO 4 Drying, filtering and concentrating to obtain a crude product; the crude product was purified by flash column chromatography on silica gel eluting with 20% EA/PE (petroleum ether/ethyl acetate) to give 1,1'- ([ 2,2' -bithiophene) as a pale yellow solid]-3,3' -diyl) bis (ethan-1-one) (3.2 g, 42.7%). The specific synthetic route is shown in figure 1. Detecting HNMR-CDCL of the obtained compound 3 The diagram is shown in fig. 2, and the diagram of LC-MS is shown in fig. 3. Liquid chromatography-Mass Spectrometry (ESI) 250.9 (M + 1) + 。 1 H NMR (400 MHz, CD3OD) δ: 7.58 (d, J = 4.0, 2H), 7.56 (d, J = 4.0, 2H), 2.30 (s, 6H)。
The invention synthesizes the bithiophene rotor derivative, and the rotors with different torsion angles and conjugation degrees generate different luminescent colors by applying a strategy of controlling conformational relaxation and conjugation of the molecular rotor. Hydrogen bond stimulation can easily overcome the rotational energy barrier between the twisted and near-planar conformations. The aldehyde group is introduced into one side of the bithiophene to serve as a hydrogen bond site, so that the luminous response of driving the rotor to rotate under the stimulation of the hydrogen bond is realized. 1,1' - ([ 2,2' -dithiophene ] -3,3' -diyl) bis (ethan-1-one) is sensitive to hydrogen bonding. To facilitate the application of the stimuli-responsive material, the bithiophene derivative is doped into a polyvinylpyrrolidone (PVP) matrix and a polymer film is formed by casting. We studied the response of polymer films to water stimuli. As shown in FIG. 4, the film exhibited blue fluorescence at 495 nm under UV-365 nm irradiation. When writing with water on the film, the fluorescent writing with an earth-yellow color clearly appears. After dropping water on the membrane, the fluorescence red-shifted from 495 nm to 498 nm, due to the formation of hydrogen bonds, the excited state is stabilized and controlled by the near-planar conformation. The dripped film was baked in an oven at 80 degrees celsius for 3 hours, and then the yellowish brown fluorescence disappeared and returned to the previous blue emission. The film has reversible response to water, and can be used for stimulus response behaviors of materials such as information encryption, environmental protection erasable and intelligent sensing.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (2)
1. 1,1'- ([ 2,2' -dithiophene)]-3,3' -diyl) bis (eth-1-one), characterized in that: the 1,1'- ([ 2,2' -dithiophene)]-3,3' -diyl) bis (eth-1-one) has the formula:
。
2. the application of 1,1'- ([ 2,2' -dithiophene ] -3,3 '-diyl) bis (ethan-1-one) in the stimulus response behavior of information encryption, environmental protection erasable and intelligent sensing materials as claimed in claim 1, wherein 1,1' - ([ 2,2 '-dithiophene ] -3,3' -diyl) bis (ethan-1-one) reacts reversibly to water, and the preparation steps are as follows:
36mL of an n-hexane solution of n-butyllithium having a concentration of 2.5M 2 After the replacement, the solution was cooled to-78 ℃ and 300mL of anhydrous tetrahydrofuran was added; adding 30 mmol of 3,3 '-dibromo-2,2' -bithiophene 70 ml drop by drop in 0.8-1.2 hours; after completion, the mixture was stirred for another 2 hours, and then 95 mmol of N-methoxy-N-methylacetamide was added dropwise, and the reaction solution was allowed to naturally warm to room temperature and reacted overnight; after the reaction is detected by liquid chromatography-mass spectrometry, water is added to quench the reaction, then 250 ml ethyl acetate is used for extraction, the ethyl acetate is used for extraction for 3 times under the same condition, the obtained organic phase is washed by 50 mL water and 50 mL saturated saline solution and Na 2 SO 4 Drying, filtering and concentrating to obtain a crude product; purifying the crude product by flash column chromatography, wherein the flash column chromatography is silica gel column, and eluting with 20% petroleum ether/ethyl acetate to obtain light yellow solid 1,1'- ([ 2,2' -dithiophene)]-3,3' -diyl) bis (ethan-1-one).
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Citations (4)
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|---|---|---|---|---|
| US3702253A (en) * | 1965-04-30 | 1972-11-07 | Firmenich & Cie | Flavor modified soluble coffee |
| US5602170A (en) * | 1992-02-19 | 1997-02-11 | Industrial Technology Research Institute | Medicinal thiophene compounds |
| JP2005220075A (en) * | 2004-02-05 | 2005-08-18 | Rikogaku Shinkokai | Method for producing heterocyclic compound, and catalytic system |
| CN110551098A (en) * | 2019-06-17 | 2019-12-10 | 湖北固润科技股份有限公司 | oxime ester photoinitiator containing five-membered aromatic heterocyclic structure and preparation and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702253A (en) * | 1965-04-30 | 1972-11-07 | Firmenich & Cie | Flavor modified soluble coffee |
| US5602170A (en) * | 1992-02-19 | 1997-02-11 | Industrial Technology Research Institute | Medicinal thiophene compounds |
| JP2005220075A (en) * | 2004-02-05 | 2005-08-18 | Rikogaku Shinkokai | Method for producing heterocyclic compound, and catalytic system |
| CN110551098A (en) * | 2019-06-17 | 2019-12-10 | 湖北固润科技股份有限公司 | oxime ester photoinitiator containing five-membered aromatic heterocyclic structure and preparation and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Stimuli-responsive luminescent bithiophene-dicarbaldehyde molecular rotors by hydrogen bonding;Stimuli-responsive luminescent bithiophene-dicarbaldehyde molecu;《Journal of Materials Chemistry C》;20201207;第8卷(第45期);第16100-16106页，尤其是摘要，第16101页Scheme 1，第16104页右栏最后一段 * |
| Synthesis and characterization of benzo- and naphtho[2,1-b:3,4-b’]dithiophene-containing oligomers for photovoltaic applications;Mirjam Lobert等;《Journal of Materials Chemistry C： Materials for Optical and Electronic Devices》;20141231;第2卷(第24期);第4879-4892页，尤其是第4880页右栏Scheme 2，第4888页右栏第一段 * |
| Synthesis of systems containing two orthocondensed thiophene rings into a seven-membered heterocycle;Meunier, P等;《Journal of Heterocyclic Chemistry》;19781231;第15卷(第4期);第593-599页，尤其是第593页 * |
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