CN115385796A - Benzophenanthrene charge transfer compound and synthesis method thereof - Google Patents
Benzophenanthrene charge transfer compound and synthesis method thereof Download PDFInfo
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- 238000012546 transfer Methods 0.000 title claims abstract description 52
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 title abstract description 12
- VHQGURIJMFPBKS-UHFFFAOYSA-N 2,4,7-trinitrofluoren-9-one Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C2=C1 VHQGURIJMFPBKS-UHFFFAOYSA-N 0.000 claims abstract description 13
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 230000015572 biosynthetic process Effects 0.000 claims description 23
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
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- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
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- 239000000376 reactant Substances 0.000 claims description 4
- XYJBIADAEAEWNG-UHFFFAOYSA-N 1,2-dipentoxybenzene Chemical compound CCCCCOC1=CC=CC=C1OCCCCC XYJBIADAEAEWNG-UHFFFAOYSA-N 0.000 claims description 3
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 claims description 3
- XTKHESQIKTWMCD-UHFFFAOYSA-N 1-pentoxy-4-(4-pentoxyphenyl)benzene Chemical group C1=CC(OCCCCC)=CC=C1C1=CC=C(OCCCCC)C=C1 XTKHESQIKTWMCD-UHFFFAOYSA-N 0.000 claims description 3
- HSUMWUWQWBCAQE-UHFFFAOYSA-N 2-iodo-4-(3-iodo-4-pentoxyphenyl)-1-pentoxybenzene Chemical group CCCCCOC(C=CC(C(C=C1)=CC(I)=C1OCCCCC)=C1)=C1I HSUMWUWQWBCAQE-UHFFFAOYSA-N 0.000 claims description 3
- KWAGLBKKEHBCIK-UHFFFAOYSA-N 5-(3-hydroxy-4-pentoxyphenyl)-2-pentoxyphenol Chemical group CCCCCOC(C=CC(C(C=C1)=CC(O)=C1OCCCCC)=C1)=C1O KWAGLBKKEHBCIK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 3
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
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- 230000002194 synthesizing effect Effects 0.000 claims description 3
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims 1
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- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
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- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/45—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/21—Acetic acid esters of hydroxy compounds with more than three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
- C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
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Abstract
The invention relates to a benzophenanthrene charge transfer complex and a synthesis method thereof, and is characterized in that the benzophenanthrene charge transfer complex is formed by compounding 3, 6-diethyl-2, 7,10, 11-tetrapentyloxyphenyl phenanthrene and 2,4, 7-trinitro-9-fluorenone. The complex has a complex self-assembly structure with body-centered cubic phase (BCCphase), frank-KasperA15 phase, double helix phase (DGphase) and columnar phase and the like. The charge transfer compound can form complex phase state transition by simple molecules, and can change the phase state structure by adjusting the temperature, so that the charge transfer efficiency is changed, and the charge transfer compound has potential application value in charge transfer materials in photoelectric devices such as organic thin film transistors, organic light emitting diodes and organic solar cells.
Description
Technical Field
The invention relates to a benzophenanthrene charge transfer compound and a synthesis method thereof, belonging to the field of liquid crystal materials and charge transfer materials.
Background
As an important branch of supramolecular self-assembly systems, discotic liquid crystals were discovered in 1979 by indian scientist s. The benzophenanthrene-based discotic liquid crystal generally consists of a rigid portion and a flexible portion. As a specific molecular self-assembly material, the material can spontaneously form ordered aggregates through hydrogen bonds, electrostatic force, pi-pi stacking action and synergistic action thereof, and the self-assembly structure of the material can be accurately regulated and controlled by adjusting parameters such as the length and the type of a flexible chain.
The interaction in the supermolecule system with a complex self-assembly structure mostly shows additive and synergistic performance, and has certain directionality and selectivity, and the total binding force can be not less than that of chemical bonds. Molecular self-recognition is the manifestation of this weak interaction binding, which is the key to the formation of highly ordered molecular assemblies. At the same time, most supramolecular systems have the ability to be internally tuned for error correction, which is generally not achieved by purely covalent systems, and thus molecular self-assembly plays a very important role and position in supramolecular systems. The thermodynamic factors and the kinetic path for promoting the material to form self-assembly enable the material to have potential application prospects in the fields of molecular electronics, catalysts, drug delivery, biological materials and the like. Moreover, the special topological property of the complex self-assembly structure can even expand the research into the research field of topological insulators and even topological photonic crystals.
At present, the benzophenanthrene charge transfer complex liquid crystal has relatively few types or single phase structure at home and abroad, and a relatively complex preparation process is mostly adopted, so that the benzophenanthrene discotic liquid crystal material with excellent performance and a complex self-assembly structure and a simple, convenient and efficient preparation method thereof are obtained, and the urgent need for the development of the field is met.
Disclosure of Invention
The invention aims to provide a charge transfer compound with a complex self-assembly structure of benzophenanthrene and a synthesis method thereof, which can be used as a charge transport material in photoelectric devices such as organic thin film transistors, organic light emitting diodes and organic solar cells.
In order to achieve the purpose, the invention adopts the following technical scheme:
a benzophenanthrene charge transfer complex characterized by the chemical structure shown in figure 9:
the benzophenanthrene charge transfer complex is characterized in that 3, 6-diethoxy-2, 7,10, 11-Tetrapentyloxyphenylphenanthrene (TPE) is used as a Donor (Donor) for forming a charge transfer complex, 2,4, 7-trinitro-9-fluorenone (TNF) is used as an Acceptor (Acceptor) for forming the charge transfer complex, and the molar ratio of the two is 4:1 to 1:4.
the method for synthesizing the benzophenanthrene charge transfer complex comprises the following steps:
the first step is as follows: synthesis of 4,4' -dipentyloxybiphenyl
Under the protection of nitrogen, 4' -dihydroxy biphenyl, potassium carbonate, potassium iodide and hexadecyl trimethyl ammonium bromide are added into ethanol/acetone solvent in sequence. Heating to 60 ℃, stirring for 1 hour, adding bromo-n-pentane, heating to 80 ℃, reacting for 24 hours, pouring the product into ice water, repeatedly washing, filtering and recrystallizing to obtain white flake solid.
The second step is that: synthesis of 3,3 '-diiodo-4, 4' -dipentyloxybiphenyl
Glacial acetic acid, iodine, iodic acid and the first-step product are added into a mixed solution of deionized water and trichloromethane under the protection of nitrogen, concentrated sulfuric acid is added, the temperature is raised to 85 ℃, and after 24-hour reaction, white crystals can be obtained through extraction, drying, filtering, vacuum drying and recrystallization.
The third step: synthesis of 3,3 '-dihydroxy-4, 4' -dipentyloxybiphenyl
Under the protection of nitrogen, polyethylene glycol, deionized water, potassium hydroxide and the white crystal obtained in the second step are added into a three-neck flask, and the mixture is fully stirred for 30 minutes. Slowly adding cuprous iodide, heating to 140 deg.C, reacting for 36 hr, stopping heating, and acidifying the reactant with hydrochloric acid when the temperature is reduced to room temperature. Then white needle crystal can be obtained by extraction, drying, column chromatography and recrystallization.
The fourth step: synthesis of 3,3 '-diisopropyl-4, 4' -dipentyloxybiphenyl
Under the protection of nitrogen, the product of the third step, potassium carbonate, potassium iodide, cetyltrimethylammonium bromide and alcohol/acetone (75 ml/75 ml) solvent were added to a 100ml three-neck flask, the temperature was raised to 85 ℃, and the reaction was carried out for 24 hours. Then filtering, circularly steaming, drying, carrying out column chromatography and recrystallizing in sequence to obtain white solid powder.
The fifth step: synthesis of 3, 6-dihydroxy-2, 7,10, 11-tetrapentyloxyphenyl phenanthrene
And (3) adding the product obtained in the fourth step and 1, 2-dipentyloxybenzene into dichloromethane in a nitrogen environment, stirring for 30 minutes, slowly adding anhydrous ferric chloride, and reacting for 24 hours at room temperature. The obtained reactant is purified by column chromatography to obtain a white solid.
And a sixth step: synthesis of the donor (D), 3, 6-diethoxy-2, 7,10,11 Tetrapentyloxyphenylphenanthrene (TPE), of the charge transfer complex according to claim 2:
and (3) adding the white solid obtained in the fifth step, glacial acetic acid and 4-dimethylaminopyridine into dichloromethane in a nitrogen protection environment, heating to 45 ℃, uniformly stirring for 10-15 minutes, adding dicyclohexylcarbodiimide, reacting for 24 hours, and performing column chromatography and recrystallization to obtain a white product TPE.
The seventh step: synthesis of acceptor (A), 2,4, 7-trinitro-9-fluorenone (TNF) of charge transfer complex according to claim 3
Adding 9-fluorenone into deionized water, fully stirring, heating to 80 ℃, and dropwise adding a mixture of concentrated sulfuric acid and concentrated nitric acid. After 2 hours of reaction, heating was stopped, the reaction was cooled to room temperature and quenched by adding deionized water thereto. And then washing, drying and recrystallizing the product to obtain the faint yellow needle-shaped crystal TNF.
Eighth step: synthesis of a charge transfer complex according to claim 1
Mixing the hot saturated trichloromethane solution of TPE obtained in the sixth step with the hot saturated trichloromethane solution of TNF obtained in the seventh step according to a certain molar ratio, standing for a period of time to generate black precipitates, filtering out the precipitates, and washing with a small amount of trichloromethane to obtain a final product.
Compared with the prior art, the invention has the beneficial effects that:
the charge transfer compound with the complex self-assembly behavior, which is synthesized based on the benzophenanthrene derivative, is easy to obtain raw materials and simple in synthesis method. Simple acquisition of complex self-assembly structures such as a body-centered cubic phase (BCC phase), a Frank-Kasper A15 phase, a double helix phase (DG phase) and a columnar phase can be realized through temperature regulation. Therefore, the charge transmission efficiency of the material is changed, and the material has potential application value in charge transmission materials in photoelectric devices such as organic thin film transistors, organic light emitting diodes and organic solar cells.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a nuclear magnetic hydrogen spectrum of 3, 6-diethoxy-2, 7,10,11 Tetrapentyloxyphenyl Phenanthrene (TPE) prepared in example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of 2,4,7-trinitro-9-fluorenone (TNF) prepared in example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of a charge transfer complex of 3,6-diethoxy-2,7,10,11 tetrapentyloxyphenazine and 2,4,7-trinitro-9-fluorenone prepared in example 1;
FIG. 4 is a DSC plot of the charge transfer complex prepared in example 1;
FIG. 5 is an X-ray diffraction pattern of the charge transfer complex during temperature ramp of example 2;
FIG. 6 is a polarization weave pattern during temperature rise of the charge transfer complex in example 2;
FIG. 7 is an X-ray diffraction pattern of the charge transfer complex of example 3 during temperature reduction;
FIG. 8 is a schematic diagram of a polarizing structure of the charge transfer complex of example 3 during cooling.
FIG. 9 is a diagram of a benzophenanthrene charge transfer complex of the general formula (I).
FIG. 10 is a reaction mechanism diagram for the synthesis of 3, 6-diethoxy-2, 7,10, 11-tetrapentyloxyphenazine based on a charge transfer complex of 3, 6-diethoxy-2, 7,10,11 tetrapentyloxyphenazine and 2,4, 7-trinitro-9-fluorenone.
FIG. 11 is charge transfer complex CTC TPE-TNF The composite graph of (1).
FIG. 12 is a diagram showing the reaction mechanism of 2,4,7-trinitro-9-fluorenone (TNF).
FIG. 13 is CTC TPE-TNF Transition temperature diagram between phases during temperature rise.
Fig. 14 is a graph of transition temperatures between phases of the charge transfer complex during temperature reduction in example 3.
Detailed Description
The present invention will be further described with reference to the following examples.
The following examples are only for illustrating the technical solution of the present invention and are not intended to limit the scope of the present invention.
The symbols and meanings referred to in the following examples are as follows:
Cr-BCC represents the transition temperature from the crystalline state to the body-centered cubic phase;
BCC-A15 represents the transition temperature from the body centered cubic phase to the Frank-Kasper A15 phase;
A15-DG represents the transition temperature from Frank-Kasper A15 phase to the double helix phase;
DG-BCC represents the transition temperature from the double helix phase to the body centered cubic phase;
CP denotes clearing point;
Iso-BCC denotes the transition temperature of the system from anisotropic to body-centered cubic phase;
BCC-A15 represents the transition temperature from the body centered cubic phase to the Frank-Kasper A15 phase;
A15-A15+ Colh represents the transition temperature from the Frank-Kasper A15 phase to the Frank-Kasper A15 phase in which the hexagonal columnar phase coexists;
cr represents a crystallization temperature.
The invention will be further illustrated by the following examples
Example 1
The synthesis scheme of a charge transfer complex based on 3,6-diethoxy-2,7,10,11 tetrapentyloxyphenazine and 2,4,7-trinitro-9-fluorenone is shown in FIG. 12.
The reaction mechanism of 3, 6-diethoxy-2, 7,10,11 tetrapentyloxyphenyl phenanthrene is shown in FIG. 10:
(1) Synthesis of Compound 1 (4, 4' -dipentyloxybiphenyl)
4,4' -dihydroxybiphenyl (97.8 g), potassium carbonate (240 g), potassium iodide (9.7 g), cetyltrimethylammonium bromide (9.7 g), ethanol/acetone (300 ml/100 ml) solvent were added to a 1000ml three-necked flask under nitrogen protection. After heating to 60 ℃, stirring for 1 hour, adding bromo-n-pentane (225.6 g), heating to 80 ℃, reacting for 24 hours, pouring the product into ice water for repeated washing, then filtering, and recrystallizing to obtain white flake solid 1 (yield 97%).
(2) Synthesis of Compound 2 (3, 3 '-diiodo-4, 4' -dipentyloxybiphenyl)
Deionized water (30 ml), chloroform (70 ml), glacial acetic acid (100 g), iodine (21 g), iodic acid (8.87 g) and compound 1 (32.6 g) were charged into a 500ml three-necked flask under nitrogen protection, followed by concentrated sulfuric acid (3.8 g). Then the temperature is raised to 85 ℃, the reaction is carried out for 24 hours, and white crystals 2 (yield 94.6%) can be obtained after extraction, drying, filtration, evaporation, vacuum drying and recrystallization.
(3) Synthesis of Compound 3 (3, 3 '-bishydroxy-4, 4' -dipentyloxybiphenyl)
Polyethylene glycol 400 (240 ml), deionized water (60 ml), potassium hydroxide (130 g) and compound 2 (28.9 g) were charged into a 500ml three-necked flask under nitrogen protection, and stirred for 30 minutes. Cuprous iodide (9 g) was added slowly, then the temperature was raised to 140 ℃, after 36 hours of reaction, heating was stopped, and when the temperature was lowered to room temperature, the reaction mass was acidified with hydrochloric acid. Then extracting, drying, column chromatography and recrystallizing to obtain white needle crystal 3 (yield is 50%)
(4) Synthesis of Compound 4 (3, 3 '-diisopropyl-4, 4' -dipentyloxybiphenyl)
Compound 3 (6 g), K2CO3 (13.5 g), KI (1.08 g) and cetyltrimethylammonium bromide, ethanol/acetone (75 ml/75 ml) solvent were added to a 100ml three-necked flask under nitrogen protection, the temperature was raised to 85 ℃ and reacted for 24 hours. Then filtering, circularly steaming, drying, column chromatography and recrystallizing in sequence to obtain a white flaky solid 4 (yield is 80%)
(5) Synthesis of Compound 5 (3, 6-Dimethylbenzene-2, 7,10,11 Tetrapentyloxyphenylphenanthrene)
Compound 4 (13.3 g), 1, 2-dipentyloxybenzene (11.3 g) and methylene chloride (160 ml) were charged into a 100ml three-necked flask under nitrogen atmosphere, stirred for 30 minutes, then anhydrous ferric chloride was slowly added thereto, and the mixture was reacted at room temperature for 24 hours. The white solid obtained was then purified by column chromatography 5 (yield 60%).
(6) Synthesis of Compound 6 (3, 6-diethoxy-2, 7,10, 11-tetrapentyloxyphenyl phenanthrene)
Under the protection of nitrogen, compound 5 (0.5 g), dichloromethane (30 ml), glacial acetic acid (0.5 ml) and DMAP (18.28) were charged into a 50ml three-necked flask, heated to 45 ℃ and stirred for 10-15 minutes, then DCC was added and reacted for 24 hours. Then, the white product 6 can be obtained by column chromatography and recrystallization (yield is 65 percent).
Nuclear magnetic hydrogen spectrum 1 H-NMRδ H (400MHz,CDCl 3 ):8.03(s,2H,),7.84(s,4H),4.22(m,8H),2.39(m,6H),1.91(m,8H,),1.49(m,16H),1.00(t,12H)。
The reaction mechanism of 2,4,7-trinitro-9-fluorenone (TNF) is shown in FIG. 12.
Deionized water (20 ml) and 9-fluorenone (18 g) were added to a 500ml three-necked flask, stirred, heated to 80 ℃, and a mixture of concentrated sulfuric acid and concentrated nitric acid (concentrated sulfuric acid to 96% by mass and 95% by mass of concentrated nitric acid in a volume ratio of 1. After 2 hours of reaction the heating was stopped, the reaction was cooled to room temperature and quenched by adding 200ml of water thereto. After this time, the product was washed with water, dried and recrystallized to give a yellow solid (yield 85%).
Nuclear magnetic hydrogen spectrum 1 H-NMRδ H (400MHz，CDCl 3 ):9.04(s,1H),8.84(s,1H),8.68(s,1H),8.57(d,1H),8.39(d,1H)。
FIG. 11 is charge transfer complex CTC TPE-TNF A composite drawing of (2).
The hot solution of compound 6 saturated in chloroform was mixed with the hot solution of TNF saturated in chloroform at the same molar ratio, after which the color of the solution turned red. After a period of rest, a red precipitate appeared which was filtered off and washed with a small amount of CHCl 3.
Nuclear magnetic hydrogen spectrum 1 H-NMRδ H (400MHz,CDCl 3 ):8.90(s,1H),8.60(s,1H),8.47(s,1H),8.43(d,1H),8.16(d,1H),7.91(s,2H),7.71(s,4H),4.24(m,8H),2.38(m,6H),1.95(m,8H),1.53(m,16H),0.97(t,12H)。
FIG. 1 shows nuclear magnetic hydrogen spectra of 3, 6-diethoxy-2, 7,10, 11-Tetrapentyloxyphenyl Phenanthrene (TPE) prepared in this example;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 2,4,7-trinitro-9-fluorenone (TNF) prepared in this example;
FIG. 3 is a nuclear magnetic hydrogen spectrum of a charge transfer complex of 3,6-diethoxy-2,7,10,11-tetrapentyloxyphenaphenanthrene and 2,4,7-trinitro-9-fluorenone prepared in this example;
FIG. 4 is a DSC chart of the charge transfer complex prepared in this example.
Example 2
In this example, the liquid crystal properties of the molecules synthesized in example 1 during the temperature rise were observed and studied, and the phase change of the charge transfer complex was analyzed by combining a differential scanning calorimeter and a polarizing microscope with a temperature rise rate of 10 ℃/min.
FIG. 13 is CTC in example 2 TPE-TNF Transition temperature between phases during temperature rise.
X-ray diffraction data:
at 25 ℃ and 75 ℃ appear
The series of diffraction peaks, whose d-values can be indexed to the (110), (200), (310) (321) (400) planes of the BCC lattice,
at 90 deg.C, appear
The series of diffraction peaks) whose d-values can be indexed to the (110), (200), (210), (211), (310), (400), (411), (420), (510), (520) facets of the Frank-Kasper a15 phase,
at 108 ℃, appear
The d values of the series of diffraction peaks can be indexed as the (211), (220), (400), (431), (440), (541) planes of the DG phase,
at 165 deg.C, a single diffraction peak appears in the small angle region
Can be indexed to the (110) plane of the BCC phase,
FIG. 5 shows an X-ray diffraction pattern of CTCTPE-TNF during temperature rise;
FIG. 6 shows the polarization weave pattern of CTCTPE-TNF during the temperature rise.
Example 3
In this example, the liquid crystal properties of the molecules synthesized in example 1 during the cooling process were observed and studied, and the phase change of the charge transfer complex was analyzed by combining a differential scanning calorimeter, a polarization microscope and one-dimensional X-ray diffraction at a cooling rate of 10 ℃/min.
Fig. 14 shows the transition temperature between the phases of the charge transfer complex in example 3 during the temperature reduction process.
X-ray diffraction data:
at 104 deg.C, appear
The d values of the diffraction peaks in the group can be indexed to the (200), (210), (211) planes of the Frank-Kasper A15 phase,
at 89 deg.C, appear
The d values of the diffraction peaks in the group can be indexed as (200), (210) and (211) planes of the Frank-Kasper A15 phase,
three additional derived peaks
The d values of which can be indexed to the (100), (210) and (300) planes of the hexagonal lattice,
at 41 deg.C, small angle region appears
Three diffraction peaks whose d-value ratios are indexable as (200), (210), (220) planes of the Frank-Kasper A15 phase,
four additional diffraction peaks
The ratio of the d values of which can be indexed to the (100), (110), (200) and (300) planes of the hexagonal lattice,
at 32 deg.C, small angle region appears
Three diffraction peaks having d-value ratios of (210), (220), (310) planes indexable to Frank-Kasper A15 phase,
four additional diffraction peaks
The ratio of the d values of which can be indexed to the (100), (110), (210) and (300) planes of the hexagonal lattice,
FIG. 7 shows an X-ray diffraction diagram of the charge transfer complex during cooling;
fig. 8 shows the polarization weave pattern of the charge transfer compound during the cooling process.
Claims (5)
1. A benzophenanthrene charge transfer complex and a synthesis method thereof are characterized in that the benzophenanthrene charge transfer complex has a 3, 6-diethoxy-2, 7,10, 11-tetrapentyloxyphenyl phenanthrene structure based on the synthesis of the charge transfer complex of 3, 6-diethoxy-2, 7,10, 11-trinitro-9-fluorenone.
2. The benzophenanthrene charge transfer complex and the synthesis method thereof according to claim 1, wherein 3, 6-diethoxy-2, 7,10, 11-Tetrapentyloxyphenyl Phenanthrene (TPE) is used as a Donor (Donor) for forming the charge transfer complex, 2,4, 7-trinitro-9-fluorenone (TNF) is used as a receptor (Acceptor) for forming the charge transfer complex, and the molar ratio of the two is 4.
3. The method for synthesizing benzophenanthrene charge transfer complex and the method for synthesizing the same as claimed in claim 1, comprising the following steps:
the first step is as follows: synthesis of 4,4' -dipentyloxybiphenyl
Under the protection of nitrogen, 4' -dihydroxy biphenyl, potassium carbonate, potassium iodide and hexadecyl trimethyl ammonium bromide are added into ethanol/acetone solvent in sequence. Heating to 60 ℃, stirring for 1 hour, adding bromo-n-pentane, heating to 80 ℃, reacting for 24 hours, pouring the product into ice water, repeatedly washing, filtering and recrystallizing to obtain white flake solid.
The second step is that: synthesis of 3,3 '-diiodo-4, 4' -dipentyloxybiphenyl
Adding glacial acetic acid, iodine, iodic acid and the product of the first step into a mixed solution of deionized water and trichloromethane under the protection of nitrogen, then adding concentrated sulfuric acid, heating to 85 ℃, reacting for 24 hours, extracting, drying, filtering, drying in vacuum, and recrystallizing to obtain white crystals.
The third step: synthesis of 3,3 '-dihydroxy-4, 4' -dipentyloxybiphenyl
Under the protection of nitrogen, polyethylene glycol, deionized water, potassium hydroxide and the white crystal obtained in the second step are added into a three-neck flask, and the mixture is fully stirred for 30 minutes. Slowly adding cuprous iodide, heating to 140 ℃, reacting for 36 hours, stopping heating, and acidifying the reactant with hydrochloric acid when the temperature is reduced to room temperature. Then white needle crystal can be obtained by extraction, drying, column chromatography and recrystallization.
The fourth step: synthesis of 3,3 '-diisopropyl-4, 4' -dipentyloxybiphenyl
Under the protection of nitrogen, adding the product of the third step, potassium carbonate, potassium iodide, hexadecyl trimethyl ammonium bromide and an ethanol/acetone solvent into a three-neck flask, heating to 85 ℃, and reacting for 24 hours. Then filtering, circularly steaming, drying, carrying out column chromatography and recrystallizing in sequence to obtain white solid powder.
The fifth step: synthesis of 3, 6-dihydroxy-2, 7,10,11 tetrapentyloxyphenyl phenanthrene
Adding the product obtained in the fourth step and 1, 2-dipentyloxybenzene into dichloromethane under a nitrogen environment, stirring for 30 minutes, slowly adding anhydrous ferric chloride, and reacting for 24 hours at room temperature. The obtained reactant is purified by column chromatography to obtain a white solid.
And a sixth step: synthesis of the donor (D) of the charge transfer complex according to claim 2, namely 3, 6-diethoxy-2, 7,10,11 Tetrapentyloxyphenyl Phenanthrene (TPE):
and (3) adding the white solid obtained in the fifth step, glacial acetic acid and 4-dimethylaminopyridine into dichloromethane in a nitrogen protection environment, heating to 45 ℃, uniformly stirring for 10-15 minutes, adding dicyclohexylcarbodiimide, reacting for 24 hours, and performing column chromatography and recrystallization to obtain a white product TPE.
The seventh step: synthesis of acceptor (A), 2,4, 7-trinitro-9-fluorenone (TNF) of charge transfer complex according to claim 3
Adding 9-fluorenone into deionized water, fully stirring, heating to 80 ℃, and dropwise adding a mixture of concentrated sulfuric acid and concentrated nitric acid. After 2 hours of reaction heating was stopped, the reaction was cooled to room temperature and quenched by adding deionized water thereto. And then washing, drying and recrystallizing the product to obtain the faint yellow needle-shaped crystal TNF.
Eighth step: synthesis of a charge transfer complex according to claim 1
Mixing the hot saturated trichloromethane solution of TPE obtained in the sixth step and the hot saturated trichloromethane solution of TNF obtained in the seventh step according to a certain molar ratio, standing for a period of time to generate black precipitates, filtering out the precipitates, and washing with a small amount of trichloromethane to obtain a final product.
4. The benzophenanthrene charge transfer complex and the synthesis method thereof according to claim 1, characterized by having liquid crystal properties of a complex self-assembled structure, wherein the complex self-assembled structure is one or more of body centered cubic phase (BCC phase), frank-Kasper a15 phase, double helix phase (DG phase), and columnar phase.
5. The benzophenanthrene charge transfer complex and the synthesis method thereof according to claim 1 have potential applications in the fields of thermal switches and topological insulators.
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