CN115806558A - Synthesis of thienothiophene-bridged fluorine-containing triphenylene discotic liquid crystal semiconductor - Google Patents
Synthesis of thienothiophene-bridged fluorine-containing triphenylene discotic liquid crystal semiconductor Download PDFInfo
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- CN115806558A CN115806558A CN202111082933.6A CN202111082933A CN115806558A CN 115806558 A CN115806558 A CN 115806558A CN 202111082933 A CN202111082933 A CN 202111082933A CN 115806558 A CN115806558 A CN 115806558A
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- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 title claims abstract description 20
- 239000004065 semiconductor Substances 0.000 title claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 8
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 125000005580 triphenylene group Chemical group 0.000 title claims description 5
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000011737 fluorine Substances 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 claims abstract description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 229960001701 chloroform Drugs 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229920006395 saturated elastomer Chemical class 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- -1 triphenylene-2-yl Chemical group 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005442 molecular electronic Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention relates to synthesis of a synthetic discotic liquid crystal semiconductor for synthesizing a thienothiophene bridged fluorine-containing benzophenanthrene discotic liquid crystal semiconductor. Through the reaction of bithiophene and butyl lithium, and then with tetrafluorotetraalkoxytriphenylene, a bis (trifluorotetraalkoxy triphenylene-2-yl) thienothiophene derivative is obtained; it is characterized by having a structure shown in a general formula (I). Wherein in (I) R is-C n H 2n+1 And n represents an integer of 6 to 12 carbon atoms. The compounds of the general formula (I) self-assemble into a columnar liquid crystal mesophase in a wide temperature range and at room temperature.
Description
Technical Field
The invention relates to synthesis of 2, 5-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetraalkoxystriphenylen-2-yl) thieno [3,2-b ] thiophene discotic liquid crystal semiconductor.
Background
Discotic liquid crystal is a unique organic semiconductor material with remarkable conductivity and photoconduction performance, and the molecular structure of the discotic liquid crystal contains large-pi-bond conjugated polycyclic aromatic hydrocarbon and flexible alkyl chains. Due to its one-dimensional intermolecular columnar packing, it is capable of self-assembling into a columnar liquid crystalline phase, which provides a unique one-dimensional channel for charge carrier transport. Therefore, discotic liquid crystal semiconductors are expected to be applied to molecular electronics, optoelectronics, copying machines, solar cells, electroluminescent devices, and the like. Research on electron-rich discotic liquid crystal molecules has been extensive, and few reports have been made on electron-poor fluorine-containing discotic liquid crystal compounds due to difficulty in synthesis. The introduction of fluorine atoms on aromatic nuclei has important influence on the columnar phase stability of discotic liquid crystal molecules, and the types and migration rates of carriers. However, the properties of the fluorine-containing aromatic hydrocarbon are not very stable, and bithiophene is introduced into the fluorine atom-containing discotic liquid crystal compound, so that pi-pi orbitals among molecules are more effectively overlapped due to the expansion of S atom orbitals, and the interaction among molecules is enhanced, so that the properties of the discotic liquid crystal compound are enriched and adjustable.
Disclosure of Invention
Based on the above, the invention discloses a method for synthesizing 2,5-bis (1,3,4-trifluoro-6,7,10,11-tetraalkoxy triphenylene-2-yl) thieno [3,2-b ] thiophene discotic liquid crystal compound. 2, 5-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetraalkoxytriphenylene) thieno [3,2-b ] thiophene derivatives were obtained by reacting bithiophene with butyl lithium followed by reaction with 1,2,3, 4-tetrafluoro-6, 7,10, 11-tetraalkoxytriphenylene. The research shows that: the compound can form a stable columnar liquid crystal phase in a wider temperature range (including room temperature). The invention provides a synthetic method of a fluorine-containing arene-bithiophene triplet compound.
Synthesis of 2, 5-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetraalkoxystirenylen-2-yl) thieno [3,2-b ] thiophene discotic liquid crystal semiconductor, characterized by having a structure represented by the general formula (I):
a discotic liquid-crystal compound (I) according to claim 1, characterized in that said compound (I) wherein R is-C n H 2n+1 And n represents an integer of 6 to 12 carbon atoms.
A process for the synthesis of discotic liquid-crystalline semiconductors of 2, 5-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetraalkoxystriphenyl-2-yl) thieno [3,2-b ] thiophene of general formula (I) according to claim 1, which comprises the following steps:
the first step was to add bithiophene (a) to a 50 mL reaction tube, dissolve it with THF, and add it with a syringen-BuLi, then reacting for 3 h under the protection of argon and at-78 ℃, raising the temperature to room temperature and stirring for 4 h, and in the second step, raising the temperature to 50 ℃, adding 1,2,3, 4-tetrafluoro-6, 7,10, 11-tetraalkoxy triphenylene to react with the BuLi, raising the temperature to 70 ℃ and reacting for 12 h. The third step is extraction with dichloromethane and saturated brine, and the organic phase is anhydrous MgSO 4 Dried, filtered, spin-dried, purified by silica gel column chromatography [ eluent: v Trichloromethane ：V Petroleum ether = 1 : 1]. Finally recrystallizing with petroleum ether and toluene to obtain yellow solid (I), wherein R is-C n H 2n+1 And n represents an integer of 6 to 12 carbon atoms.
Drawings
FIG. 1R obtained in example 1 is C 10 H 21 Nuclear magnetic hydrogen spectrum of the intermediate a of (1).
FIG. 2 the R obtained in example 1 is C 10 H 21 Nuclear magnetic hydrogen spectrum of the general formula (I).
FIG. 3 the R obtained in example 1 is C 10 H 21 Nuclear magnetic fluorine spectrum of the general formula (I).
FIG. 4 the R obtained in example 1 is C 10 H 21 DSC profile of the general formula (I).
FIG. 5R obtained in example 1 is C 10 H 21 The polarizing weave pattern of the general formula (I).
Detailed Description
The following examples are given to illustrate the invention in detail, it being emphasized that the examples given below are only illustrative of the invention and are not intended to limit the scope of the invention. In the practical implementation, the skilled person in the art may still be able to make modifications or adaptations to the invention based on the above disclosure, without substantial changes.
Example 1.
The compound provided in this example is a preparation of a compound of formula (I)Wherein R is-C 10 H 21， The preparation reaction is as follows:
dodithiophene (25.28 mg,0.18 mmol) was weighed into a 50 mL reaction tube, THF (30 mL) was added under argon to completely dissolve it, the solution was cooled at-78 ℃ for 10 minutes, and a 10 mL syringe was used to add the solution under stirringnBuLi (0.29 mL,0.72 mmol) was reacted for 2 hours, then the reaction tube was taken out from the low temperature environment and returned to room temperature, after which the temperature was raised to 50 ℃ and a 1,2,3, 4-tetrafluoro-6, 7,10, 11-tetraplexy triphenylene (0.50 g,0.54 mmol) compound was added and reacted at 70 ℃ for 12 hours. Extracting with chloroform and saturated salt solution, separating organic phase with MgSO 4 Drying, filtering, vacuum evaporating solvent to obtain crude product, and purifying by column chromatography to obtain solid Trichloromethane : V Petroleum ether = 1 : 1]Recrystallization from toluene and petroleum ether gave yellow crystals (I) (88 mg, 25%).
Nuclear magnetic Hydrogen Spectroscopy 1H NMR (CDCl) 3 , TMS, 400 MHz) δ 8.45 (s, 2H, ArH), 8.40 (s, 2H,ArH), 7.88 (s, 2H, ArH), 7.74 (d, J = 6.6 Hz, 4H,ArH), 4.23 (s, 16H, OCH 2 ), 1.96 (s, 16H, CH 2 ), 1.54 (s, 12H, CH 2 ), 1.33( m, 100H, CH 2 ), 0.93 – 0.85 (m, 24H,CH 3 )。
Claims (5)
- Synthesis of 2, 5-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetraalkoxystriphenyl-2-yl) thieno [3,2-b ] thiophene discotic liquid crystal semiconductors, characterized by having the structure represented by the general formula (I):
a discotic liquid-crystal compound (I) according to claim 1, characterized in that said compound (I) wherein R is-C n H 2n+1 N tableThe number of carbon atoms is an integer of 6 to 12. - 2. A method for synthesizing a discotic liquid-crystal semiconductor of 2, 5-bis (1, 3, 4-trifluoro-6, 7,10, 11-tetraalkoxystirenylidene-2-yl) thieno [3,2-b ] thiophene in the general formula (I) shown in claim 1, which comprises the following steps:
the first step was to add bithiophene (a) to a 50 mL reaction tube, dissolve it with THF, and add itnBuLi, then reacting for 3 h under the protection of argon and-78 ℃, raising the temperature to room temperature and stirring for 4 h, and in the second step, raising the temperature to 50 ℃, adding 1,2,3, 4-tetrafluoro-6, 7,10, 11-tetraalkoxy triphenylene to react with the BuLi, raising the temperature to 70 ℃ and reacting for 12 h. - 3. The third step is to extract with chloroform and saturated salt solution, and the organic phase is anhydrous MgSO 4 Dried, filtered, concentrated and purified by silica gel column chromatography [ eluent: v Trichloromethane ：V Petroleum ether =1:1]。
- 4. Finally recrystallizing with petroleum ether and toluene to obtain yellow solid (I), wherein R is-C n H 2n+1 And n represents an integer of 6 to 12 carbon atoms.
- 5. Use of a bis (trifluorotetraalkoxystirenylene-2-yl) thienothiophene discotic liquid crystal material of the general formula (I) according to claim 1.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19907063A1 (en) * | 1999-02-19 | 2000-08-24 | Clariant Gmbh | New fluorinated thiophene derivatives useful as components of liquid crystal mixtures for use in switching and display devices |
| US20090169921A1 (en) * | 2008-01-02 | 2009-07-02 | Chien-Hong Cheng | Synthesis of triphenylene and pyrene based aromatics and their application in oleds |
| KR20120129733A (en) * | 2011-05-20 | 2012-11-28 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
| CN104387398A (en) * | 2014-10-14 | 2015-03-04 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compounds, and preparation method and application thereof |
| CN111362783A (en) * | 2018-12-26 | 2020-07-03 | 四川师范大学 | Tetratetrafluoro tetraalkoxy benzophenanthrene discotic liquid crystal compound and preparation method thereof |
| CN112409374A (en) * | 2020-11-20 | 2021-02-26 | 四川师范大学 | Preparation method of rigid core direct-connected graphene-like benzophenanthrene discotic liquid crystal and mesomorphism |
| CN112409323A (en) * | 2020-11-20 | 2021-02-26 | 四川师范大学 | Preparation method and mesomorphism of graphene-like conjugated heterocyclic benzophenanthrene discotic liquid crystal |
-
2021
- 2021-09-15 CN CN202111082933.6A patent/CN115806558A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19907063A1 (en) * | 1999-02-19 | 2000-08-24 | Clariant Gmbh | New fluorinated thiophene derivatives useful as components of liquid crystal mixtures for use in switching and display devices |
| US20090169921A1 (en) * | 2008-01-02 | 2009-07-02 | Chien-Hong Cheng | Synthesis of triphenylene and pyrene based aromatics and their application in oleds |
| KR20120129733A (en) * | 2011-05-20 | 2012-11-28 | (주)씨에스엘쏠라 | Organic light compound and organic light device using the same |
| CN104387398A (en) * | 2014-10-14 | 2015-03-04 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compounds, and preparation method and application thereof |
| CN111362783A (en) * | 2018-12-26 | 2020-07-03 | 四川师范大学 | Tetratetrafluoro tetraalkoxy benzophenanthrene discotic liquid crystal compound and preparation method thereof |
| CN112409374A (en) * | 2020-11-20 | 2021-02-26 | 四川师范大学 | Preparation method of rigid core direct-connected graphene-like benzophenanthrene discotic liquid crystal and mesomorphism |
| CN112409323A (en) * | 2020-11-20 | 2021-02-26 | 四川师范大学 | Preparation method and mesomorphism of graphene-like conjugated heterocyclic benzophenanthrene discotic liquid crystal |
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