CN112409325A - Synthesis and luminescence of bis-benzophenanthrene thiophene discotic liquid crystal compound - Google Patents
Synthesis and luminescence of bis-benzophenanthrene thiophene discotic liquid crystal compound Download PDFInfo
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Abstract
The invention relates to a bis-benzophenanthrene thiophene discotic liquid crystal compound and a previous step reactant thereof, namely 2, 7-bis (3 ', 4,4', 5-tetra (alkoxy) - [1,1' -biphenyl)]Synthesis and optical Properties of (E) -2-yl) -9H-thiophene. It is characterized by having a general formula (I) and a general formula (II). Wherein R is1Is C8~C16The compounds of the general formula (I) and the general formula (II) can self-assemble into a hexagonal columnar liquid crystal intermediate phase in a wide temperature range, and the compounds of the general formula (I) are gels of various polar/non-polar organic solvents. The invention also provides a preparation method of the bis-benzophenanthrene thiophene discotic liquid crystal compound, and the synthetic route is simple and fastThe compound in the general formula (I) can be prepared in FeCl through the compound in the general formula (II)3Intramolecular oxidation of a closed ring is achieved, and the compound in the general formula (I) and the compound in the general formula (II) before and after oxidation of the closed ring have liquid crystallinity.
Description
Technical Field
The invention relates to a synthesis and luminescence of a bis-benzophenanthrene thiophene discotic liquid crystal compound and a 2,3,7, 8-tetra (3, 4-bis (alkoxy) -phenyl) dibenzo-9H-thiophene discotic liquid crystal compound.
Background
The discotic liquid crystal can form a nano-microstructure material through self-assembly, and is a material with a nano-microstructure
The planar disc-shaped molecules conjugated by bonds can be self-assembled into a columnar structure, particularly a hexagonal columnar phase, due to columnar accumulation among one-dimensional molecules; thus, it can be used as a one-dimensional charge carrier system and can be applied in the fields of molecular electronics, photonics, photoconductivity, photovoltaics, and electroluminescent devices, and discotic liquid crystals are considered as promising organic semiconductors. However, the columnar internal accumulation of the polymer liquid crystal mesophase may also affect the parameters of the charge carrier flow efficiency due to topological defects, thermal fluctuations, molecular diffusion, etc., and the improvement of these properties requires that the desired molecular ordering mode be achieved by various methods such as a very stable sensor material, a suitable temperature, an ideal operating environment, etc., so that the reaction is conveniently processed, thereby improving the charge transfer performance. In thiophene and thiophene condensed aromatic hydrocarbon, the molecular orbits can be more effectively overlapped due to the expansion of S atom empty orbits, so that the intermolecular interaction is enhanced, and the carrier migration rate is correspondingly improved; it can be enhanced by connecting it to polycyclic aromatic hydrocarbon
The p-type character of the conjugated system even induces or enhances the optoelectronic properties of the system; the organic semiconductor material containing thiophene has outstanding application prospect in field effect transistors, organic solar cells, dye-sensitized solar cells and organic light-emitting diodes by combining the good stability and processability of thiophene compounds.
Disclosure of Invention
Based on the design, the bis-benzophenanthrene thiophene discotic liquid crystal compound and the 2,3,7, 8-tetra (3, 4-bis (alkoxy) -phenyl) dibenzo-9H-thiophene discotic liquid crystal compound are synthesized, and the compounds are mainly obtained by Suzuki coupling in the aspect of synthesis; the method mainly comprises the steps of carrying out Suzuki coupling on 2,3,7, 8-tetrabromodibenzothiophene and 2- (3, 4-bis (alkoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane to obtain a target compound, and carrying out ring closing on 2, 7-bis (3 ', 4,4', 5-tetra (alkoxy) - [1,1' -biphenyl ] -2-yl) -9H-thiophene to obtain a target compound, namely bis-benzophenanthrene thiophene; in addition, the bis-benzophenanthrene thiophene compound has gel property.
In addition, it is also necessary to provide methods for preparing bis-benzophenanthrofuran discotic liquid crystal compounds and 2, 7-bis (3 ', 4,4', 5-tetra (alkoxy) - [1,1' -biphenyl ] -2-yl) -9H-thiophene compounds.
A bis-benzophenanthrofuran discotic liquid crystal compound characterized by having a structure represented by general formula (I):
a2, 7-bis (3 ', 4,4', 5-tetra (alkoxy) - [1,1' -biphenyl ] -2-yl) -9H-thiophene discotic liquid crystal compound characterized by having a structure represented by the general formula (II):
wherein R is CnH2n+1And n represents an integer of 8 to 16 carbon atoms.
A discotic liquid-crystalline compound of the general formula (ii) 2, 7-bis (3 ', 4,4', 5-tetrakis (alkoxy) - [1,1' -biphenyl ] -2-yl) -9H-thiophene according to claim 2, characterized by comprising the following steps.
The method comprises the following steps: preparation of intermediate c 4-bromo-1, 2-bis (alkoxy) benzene:
dissolving the compound shown in the formula a in a 250ml round-bottom flask by adding NaOH aqueous solution with a molar ratio of 1:1, reacting in ice water bath for 3h by using a constant-pressure dropping funnel, cooling to room temperature, adding NaCl to saturate, extracting with diethyl ether, and extracting with anhydrous MgSO4Drying, filtering and concentrating to obtain yellow liquid b. Weighing the compounds b, K2CO31-bromoalkane and zinc powder in a molar ratio of 1:5: 2.1: 2 and a small amount of KI, DMF as solvent at 90oReacting for 24h under C, stopping the reaction, adding HCl solution to adjust the pH to be neutral, and filtering to remove K2CO3Concentrating by rotary evaporation, and performing silica gel column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2) to obtain a white solid c; wherein R is-CnH2n+1And n represents an integer of 8 to 16 carbon atoms.
Step two: synthesis of intermediate 2- (3, 4-bis (alkoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane (d):
weighing 4-bromo-1, 2-di (alkoxy) benzene (c), pinacol diboron, potassium acetate and PdCl2(dppf) was added to a 50mL reaction tube at a molar ratio of 1: 2: 4: 0.08, then 25mL of 1, 4-dioxane was added, and the reaction was stirred at 90 ℃ for 24h under argon. Cooled to room temperature, extracted with DCM and the organic phase over anhydrous MgSO4Drying, filtering, spin-drying, and silica gel column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2) to give a white solid d, wherein R is CnH2n+1，n represents an integer of 8 to 16 carbon atoms.
Synthesis of 2, 7-bis (3 ', 4,4', 5-tetrakis (alkoxy) - [1,1' -biphenyl ] -2-yl) -9H-thiophene Compound (II):
wherein R is CnH2n+1，n represents an integer of 8 to 16 carbon atoms;
weighing dibenzothiophene (1.0 g, 5.4 mmol) and dissolving in 40 ml of dry trichloromethane, slowly dropwise adding Br2 (6.19 g, 37.9 mmol), heating and refluxing for 24h, adding NaHSO3 solution to absorb excessive bromine water, and directly filtering to obtain a white solid e; weighing a compound d, e, K with a molar ratio of 5:1:50:0.22CO3And Pd (PPh)3)4，Adding a mixed solvent H into a 50mL reaction tube2O (3 ml)/THF (10 ml), under argon protection, at 70 deg.C for 48 h, cool to room temperature, add CH2Cl2Extracting, and collecting organic phase with anhydrous MgSO4Drying, filtration, spin-drying, and recrystallization from silica gel column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2) with ethyl acetate and ethanol gave white solid (II).
Preparation of bis-benzophenanthrene thiophene discotic liquid crystal compound (I):
wherein R is CnH2n+1，n represents an integer of 8 to 16 carbon atoms;
in a 100ml round-bottomed flask with compound (II): FeCl3 Weighing at a molar ratio of 1: 6, adding dichloromethane (50 ml) and nitromethane (3ml), reacting at room temperature, tracking the reaction at a point every 15min, adding methanol to stop the reaction after the reaction is finished, extracting with dichloromethane, and MgSO4Drying, filtration, spin-drying, and recrystallization from ethyl acetate by alumina column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2) gave solid (i).
The compound is obtained by performing ring closure after Suzuki coupling on 2,3,7, 8-tetrabromodibenzothiophene and 2- (3, 4-bis (alkoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane, a plurality of aryl groups are connected together in a fusion mode, and under the regulation action of a plurality of peripheral alkoxy flexible chains, a series of compounds before and after ring closure can be self-assembled into a stable hexagonal columnar liquid crystal intermediate phase in a wider temperature range and at room temperature, so that the compound has a good application value in the aspect of liquid crystal materials.
Drawings
FIG. 1R obtained in example 1 is C12H25Nuclear magnetic hydrogen spectrum of intermediate c.
FIG. 2R obtained in example 2 is C12H25Nuclear magnetic hydrogen spectrum of intermediate d.
FIG. 3R obtained in example 3 is C12H25Nuclear magnetic hydrogen spectrum of the general formula (II).
FIG. 4R obtained in example 4 is C12H25Nuclear magnetic hydrogen spectrum of general formula (I).
FIG. 5R obtained in example 3 is C12H25DSC profile of the general formula (II).
FIG. 6R obtained in example 4 is C12H25DSC profile of the general formula (I).
FIG. 7 the R obtained in example 3 is C12H25A polarizing weave pattern of the general formula (II).
FIG. 8R obtained in example 4 is C12H25A polarized light weave pattern of the general formula (I).
FIG. 9 shows that R is C in example 312H25XRD pattern of general formula (II).
FIG. 10 shows that R is C in example 412H25XRD pattern of general formula (I).
FIG. 11 shows that R is C in example 312H25Ultraviolet absorption spectrum of the general formula (II).
FIG. 12 shows that R is C in example 412H25Ultraviolet absorption spectrum of the general formula (I).
FIG. 13 shows that R is C in example 312H25Fluorescence emission spectrum of the solution (THF) of the general formula (II).
FIG. 14 shows that R is C in example 412H25Fluorescence emission spectrum of the solution (THF) of the general formula (I).
FIG. 15 shows that R is C in example 312H25A thin film fluorescence emission spectrum of formula (II).
FIG. 16 shows that R is C in example 412H25A thin film fluorescence emission spectrum of formula (I).
FIG. 17 is a photograph of an inverted gel in which R is C obtained in example 414H29The compound of the general formula (I) forms gel in organic solvent of ethyl acetate, hexane, cyclohexane, dichloromethane, tetrahydrofuran and toluene in sequence.
FIG. 18 is a diagram illustrating the structural formulae of the general formula (I) and the general formula (II) in the abstract.
Detailed Description
The following examples are given by way of illustration of the present invention, it being emphasized that the examples given below are given by way of illustration only 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.
The synthesis methods used in the following embodiments are all prior art:
T. Yasuda, T. Shimizu, F. Liu, G. Ungar, T. Kato, J. Am. Chem. Soc. 2011, 133, 13437–13444.
example 1:
the compound provided in this example is the preparation of intermediates b, C, which are compounds of formula (II) wherein R is C12H25，The preparation reaction is as follows:
dissolving NaOH (6.54 g and 0.16 mol) in distilled water (100 ml), transferring the solution into a 1000 ml round-bottom flask, adding 5-bromosalicylaldehyde (30 g and 0.15 mol), heating the solution to be clear, measuring 18 ml of 30% hydrogen peroxide by using a constant pressure dropping funnel under the condition of ice water bath, slowly dropping the hydrogen peroxide into the round-bottom flask, and reacting for 3 hours; cooling to room temperature, saturating with sodium chloride solution, extracting with diethyl ether (2X 100 ml), mixing the diethyl ether extracts, and adding anhydrous MgSO4Dried, filtered and concentrated to give b as a yellow oily liquid (28.1 g, 90.2% yield);
weighing compound b (5.0 g, 26.46 mmol), K2CO3(14.603 g, 0.106 mol), 1-bromododecane (19.78 g, 0.0794 mol) and 40 ml of butanone, a small amount of KI, at 90oReacting for 24 hours under C, filtering to remove K2CO3Concentration by rotary evaporation and chromatography on silica gel (petrol ether) gave pure white solid c (10.69 g, 76.9% yield);
nuclear magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz) , δ : 6.98(d, J = 7.2 Hz, 2H, ArH) , 6.73 (d, J = 8.8 Hz, 1H, ArH) , 3.93-3.97(m, 4H, OCH2), 1.77-1.83(m, 4H, CH2) , 1.43-1.47(m, 4H, CH2) , 1.28-1.33(m, 32H, CH2) , 0.88(t, J = 5.6 Hz , 6H, CH3)。
Example 2:
synthesis of intermediate 2- (3, 4-bis (dodecyloxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane (d) wherein R is C12H25，The preparation reaction is as follows:
weighing 4-bromo-1, 2-di (dodecyloxy) benzene (2g,3.81mmol), pinacol diboron (1.93g,7.62mmol), potassium acetate (1.49g,15.22mmol) and PdCl2(dppf) (0.25g,0.304mmol) was added to a 50mL reaction tube, and 1, 4-dioxahexa-zine was added theretoThe reaction was stirred at 90 ℃ for 24h under argon atmosphere with a ring of 25 ml. Cooled to room temperature, extracted with DCM and the organic phase over anhydrous MgSO4Drying, filtering, spin-drying, silica gel column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2) afforded d (2g, 92% yield) as a white solid;
nuclear magnetic hydrogen spectrum1H NMR (CDCl3, TMS, 400 MHz). δ: 7.38 (d, J = 8 Hz, 1 H, ArH), 7.29 (s, 1H, ArH), 6.87 (d, J = 8 Hz, 1 H, ArH), 4.04-3.99 (m, 4H, OCH2), 1.85-1.78 (m, 4H, CH2), 1.48-1.40 (m, 4H, CH2), 1.33 (s, 32H, CH2), 1.26 (s, 12H, CH3), 0.88 (t, J = 7.2 Hz, 6H, CH3)。
Example 3:
this example provides the preparation of a compound of formula (II) wherein R is C12H25The preparation reaction is as follows:
dibenzothiophene (1.0 g, 5.4 mmol) was dissolved in 40 ml of dry chloroform, and Br was slowly added dropwise2(6.19 g, 37.9 mmol), heated to reflux for 24h, NaHSO was added3The solution absorbed excess bromine water and was directly filtered to give e as a white solid (3.14 g, 86.3% yield); compound d (572.9 mg, 1mmol), e (100 mg, 0.2 mmol), and potassium carbonate (1.38 g,0.1 mmol) were weighed into a 50mL reaction tube and Pd (PPh) was added in a vacuum glove box3)4(46.27 mg, 0.04 mmol), injecting the mixture of 3mL of secondary water and 10mL of tetrahydrofuran which are subjected to scavenging oxygen into a reaction tube by using a syringe, stirring and reacting at 70 ℃ for 48 h under the protection of argon, extracting and separating by using distilled water and dichloromethane, drying by using anhydrous magnesium sulfate, filtering, distilling under reduced pressure, separating and purifying by silica gel column chromatography [ eluent is V (dichloromethane) = V (petroleum ether) =1:2 ]]To give a white solid II (384 mg, 97%);
nuclear magnetic hydrogen spectrum1H NMR(CDCl3, TMS, 400 MHz), δ:8.16 (s, 2H, ArH), 7.88 (s,2H, ArH), 6.78-6.86 (m, 8H, ArH), 6.69 (s, 4H, ArH),3.97 (t , J =8 Hz , 8H , OCH2), 3.72 (t, J = 8 Hz, 8H, OCH2), 1.80-1.83 (m, 8H, CH2), 1.63-1.70(m, 8H, CH2), 1.27-1.48(m, 144H, CH2), 0.86-0.89 (m, 24H, CH3)。
Example 4:
the compounds provided in this example are of formula (I) wherein R is C12H25，The preparation reaction is as follows:
in a 100ml round-bottomed flask with compound (II): FeCl3 Weighing in a molar ratio of =1: 6 (100 mg:66.1 mg), adding dichloromethane (50 ml) and nitromethane (5ml), reacting at room temperature, performing plate tracking reaction every 15min, adding methanol to terminate the reaction, extracting with dichloromethane, and MgSO 24Drying, filtration, spin-drying, and recrystallization from ethyl acetate by column chromatography on silica gel (eluent: V dichloromethane: V petroleum ether =1: 2) to give orange-yellow solid (I) (50 mg, 50% yield);
nuclear magnetic hydrogen spectrum1H NMR (CDCl3, TMS, 400 MHz), δ:9.09 (s, 2H, ArH), 8.71 (s, 2H, ArH), 8.22 (s, 2H, ArH), 7.89(s, 2H, ArH), 7.73 (s, 2H, ArH), 7.71(s, 2H, ArH), 4.41(t, J =6 Hz, 4H, OCH2), 4.24 (t, J = 8 Hz, 12H, OCH2), 1.98-2.03 (m ,16H, CH2), 1.67-1.70 (m, 16H, CH2), 1.25-1.45 (m, 128H, CH2), 0.84-0.89 (m, 24H, CH3)。
Claims (7)
1. A bis-benzophenanthrothiophene discotic liquid crystal compound is characterized by having a structure shown in a general formula (I):
2. 2,3,7, 8-tetrakis (3, 4-bis (alkoxy) -phenyl) dibenzo-9H-thiophene characterized by having the structure shown in formula (ii):
3. the bis-benzophenanthrene thiophene discotic liquid crystal compound (I) according to claim 1 and the 2,3,7, 8-tetrakis (3, 4-bis (alkoxy) -phenyl) dibenzo-9H-thiophene according to claim 2 (II), characterized in that R is-CnH2n+1And n represents an integer of 8 to 16 carbon atoms.
4. 2,3,7, 8-tetrakis (3, 4-bis (alkoxy) -phenyl) dibenzo-9H-thiophene of general formula (ii) according to claim 2, prepared by a process comprising:
the method comprises the following steps: preparation of intermediate c 4-bromo-1, 2-bis (alkoxy) benzene:
dissolving NaOH (6.54 g, 0.16 mol) in distilled water (100 ml) by taking a compound shown as a formula 5-bromosalicylaldehyde (a) as a raw material, transferring the solution into a 1000 ml round-bottom flask, adding a (30 g, 0.15 mol) into the flask, heating the solution to be dissolved and clear, measuring 18 ml of 30% hydrogen peroxide by using a constant-pressure dropping funnel under an ice water bath, slowly dropping the hydrogen peroxide into the round-bottom flask, and reacting for 3 hours; cooling to room temperature, saturating with sodium chloride solution, extracting with diethyl ether (2X 100 ml), mixing the diethyl ether extracts, and adding anhydrous MgSO4Drying, filtering and concentrating to obtain yellow oily liquid b for later use; weighing compound b (5.0 g, 26.46 mmol), K2CO3(14.603 g, 0.106 mol), 1-bromoalkane (0.0794 mol)And 40 ml of butanone, a small amount of KI at 90oReacting for 24 hours under C, filtering to remove K2CO3Concentrating by rotary evaporation, and performing silica gel column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2) to obtain a white solid c; r is-CnH2n+1N represents an integer of 8 to 16 carbon atoms;
step two: synthesis of intermediate 2- (3, 4-bis (alkoxy) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane (d):
weighing 4-bromo-1, 2-di (alkoxy) benzene (c), pinacol diboron, potassium acetate and PdCl2(dppf) added into a 50mL reaction tube according to the molar ratio of 1: 2: 4: 0.08, then added with 25mL of 1, 4-dioxane, and stirred and reacted for 24 hours at 90 ℃ under the protection of argon; cooled to room temperature, extracted with DCM and the organic phase over anhydrous MgSO4Drying, filtering, spin-drying, and performing silica gel column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2) to obtain a white solid d; r is-CnH2n+1N represents an integer of 8 to 16 carbon atoms;
step three: synthesis of 2, 7-bis (3 ', 4,4', 5-tetrakis (alkoxy) - [1,1' -biphenyl ] -2-yl) -9H-thiophene according to general formula (ii) shown in claim 2:
dibenzothiophene (1.0 g, 5.4 mmol) was weighed out and dissolved in 40 ml of dry chloroform, and Br was slowly added dropwise2 (6.19 g, 37.9 mmol), heated to reflux for 24h, NaHSO was added3Absorbing excessive bromine water by the solution, and directly filtering to obtain a white solid e; weighing a compound d, e, K with a molar ratio of 5:1:50:0.22CO3And Pd (PPh)3)4，In a 50mL reaction tube, weighing and adding a mixed solvent H2O（3 ml）THF (10 ml), under argon, at 70 ℃ for 48 h, cold to room temperature, with CH2Cl2Extracting, and collecting organic phase with anhydrous MgSO4Drying, filtration, spin-drying, and recrystallization from silica gel column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2) with ethyl acetate and ethanol gave white solid (II).
5. A discotic liquid crystal compound of bis-benzophenanthrothiophene of general formula (I) as defined in claim 1, which is prepared by:
in a 100ml round-bottomed flask with compound (II): FeCl3 Weighing at a molar ratio of 1: 6, adding dichloromethane (50 ml) and nitromethane (3ml), reacting at room temperature, tracking the reaction at a point every 15min, adding methanol to stop the reaction after the reaction is finished, extracting with dichloromethane, and MgSO4Drying, filtration, spin-drying, and recrystallization from ethyl acetate by alumina column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2) gave solid (i).
6. Use of the bis-benzophenanthrene thiophene discotic liquid crystal compound in the general formula (I) in claim 1 and the 2,3,7, 8-tetra (3, 4-bis (alkoxy) -phenyl) dibenzo-9H-thiophene discotic liquid crystal compound in the general formula (II) in claim 2 as organic liquid crystal semiconductor materials and organic luminescent materials.
7. Use of the bis-benzophenanthrene thiophene discotic liquid crystal compound of the general formula (I) according to claim 1 as an organic gelator.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113621386A (en) * | 2021-09-06 | 2021-11-09 | 国信宝威(北京)科技有限公司 | Discotic liquid crystal compound and application thereof |
| CN113621386B (en) * | 2021-09-06 | 2023-05-26 | 国信宝威(北京)科技有限公司 | Discotic liquid crystal compound and application thereof |
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