CN112574019B - Covalent organic framework material based on twisted hexabenzocoronene and preparation method thereof - Google Patents
Covalent organic framework material based on twisted hexabenzocoronene and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a covalent organic framework material based on twisted hexabenzocoronene and a preparation method thereof, wherein the covalent organic framework material based on the twisted hexabenzocoronene, referred to as c-HBC-COF for short, is shown in a formula (III):
Description
Technical Field
The invention belongs to the field of high-molecular organic porous materials, and particularly relates to a covalent organic framework material c-HBC-COF based on twisted hexabenzocoronene and a preparation method thereof.
Background
Covalent Organic Frameworks (COFs) are a class of organic porous materials with regular channel structures that are covalently linked. The covalent organic framework material has light weight and excellent stability, so that the material has potential application prospect in the fields of gas storage and photoelectricity. At present, the method for constructing the covalent organic framework material mainly comprises a bottom-up method and a top-down method, and molecules with specific functions can be introduced into a polymer framework through reasonable design while the extension of a conjugated framework is kept, so that the functionalization of the covalent organic framework material is realized. At present, a plurality of donor-acceptor type covalent organic framework materials are successfully constructed by a bottom-up strategy, and have excellent performances in the aspects of photocatalytic hydrogen production, heterogeneous catalysis and the like. However, the covalent organic framework material is poor in conductivity due to the fact that the covalent organic framework material is composed of all light elements, and application of the material in the fields of photoelectric devices and the like is limited.
The hexabenzocoronene is a very representative nano graphene, can be divided into two categories of planar hexabenzocoronene and twisted hexabenzocoronene according to molecular peak planarity, and has wide application in the aspects of liquid crystals, field effect transistors and the like. Twisted hexabenzocoronene has more interesting electronic structure and carrier transport characteristics than planar hexabenzocoronene, and is therefore popular in optoelectronic devices. Thus, the introduction of twisted hexabenzocoronene into a covalent organic framework material may perhaps achieve a significant increase in the conductivity of the covalent organic framework material. There are no reports of covalent organic framework materials based on imine linkage of twisted hexabenzocoronene. How to design and construct covalent organic framework materials with high conductivity and high carrier mobility is still a difficult problem.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an aldehyde monomer II for synthesizing a covalent organic framework material based on twisted hexabenzocoronene, wherein the chemical name is as follows: 3,5,15, 22-tetraaldehyde hexabenzocoronene.
The second purpose of the invention is to provide a preparation method of 3,5,15, 22-tetraaldehyde hexabenzocoronene.
A third object of the present invention is to provide a covalent organic framework material based on twisted hexabenzocoronene.
The fourth purpose of the invention is to provide a preparation method of the covalent organic framework material based on the twisted hexabenzocoronene.
The technical scheme of the invention is summarized as follows:
the structure of the 3,5,15, 22-tetraaldehyde hexabenzocoronene is shown as a formula II, which is abbreviated as: c-HBC-CHO:
the preparation method of the 3,5,15, 22-tetraaldehyde hexabenzocoronene comprises the following steps:
1) synthesis of 4,4 ', 4 ", 4"' - (pentacene-6, 13-dimethylenebis (methanedimethylene)) tetraphenylcarbaldehyde I:
carrying out Suzuki coupling reaction on 6, 13-bis (dibromomethylene) -6, 13-dihydropentacene and 4-formylphenylboronic acid in a mixed solvent of tetrahydrofuran and water with a volume ratio of 4:1 under the alkaline condition provided by potassium carbonate and catalyzed by a palladium catalyst to obtain 4, 4' - (pentacene-6, 13-dimethylenebis (methanedimethylene)) tetraphenylcarbaldehyde I;
2) synthesis of 3,5,15, 22-tetraaldehyde hexabenzocoronene II:
4, 4' - (pentacene-6, 13-dimethylene bis (methane dimethylene)) tetraphenyl formaldehyde I and iodine elementary substance are irradiated by a 365nm ultraviolet lamp in a mixed solvent of propylene oxide and anhydrous toluene with the volume ratio of 1:30 to obtain 3,5,15, 22-tetraaldehyde hexabenzocoronene II; the reaction formula is as follows:
a covalent organic framework material based on twisted hexabenzocoronene, c-HBC-COF for short, is shown in formula III:
a preparation method of a covalent organic framework material based on twisted hexabenzocoronene comprises the following steps:
dispersing 3,5,15, 22-tetraaldehyde hexabenzocoronene (II) and p-phenylenediamine in a mixed solvent of o-dichlorobenzene and n-butanol with a volume ratio of 19:1 to obtain a dispersion, adding an acetic acid aqueous solution as a catalyst, uniformly mixing, and reacting under a reflux condition to obtain a covalent organic framework material III based on distorted hexabenzocoronene, namely c-HBC-COF, wherein the ratio of the 3,5,15, 22-tetraaldehyde hexabenzocoronene II to the mixed solvent is 249.5 mg: 10 mL;
the reaction formula is as follows:
the invention has the advantages that:
the covalent organic framework material based on the twisted hexabenzocoronene is constructed based on an aldehyde monomer of the twisted hexabenzocoronene, and experiments prove that the covalent organic framework material based on the twisted hexabenzocoronene can be used for storing gas, and in addition, the conductivity of c-HBC-COF is obviously improved after the c-HBC-COF is doped with an iodine simple substance, so that the covalent organic framework material can be used as an electrode material.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a compound represented by formula II.
FIG. 2 is an infrared spectrum of a compound of formula II.
Figure 3 is a powder X-ray diffraction pattern of the distorted hexabenzocoronene-based covalent organic framework material of formula III.
Figure 4 is an infrared spectrum of a twisted hexabenzocoronene-based covalent organic framework material of formula III.
Fig. 5 is a nitrogen adsorption-desorption curve of the twisted hexabenzocoronene-based covalent organic framework material shown in formula III under a 77K temperature condition.
Fig. 6 is a current-voltage curve of the twisted hexabenzocoronene-based covalent organic framework material of formula III before and after doping with iodine.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The preparation method of the 3,5,15, 22-tetraaldehyde hexabenzocoronene comprises the following steps:
1) synthesis of 4,4 ', 4 ", 4"' - (pentacene-6, 13-dimethylenebis (methanedimethylene)) tetraphenylcarbaldehyde I:
3.7 g of 6, 13-bis (dibromomethylene) -6, 13-dihydropentacene, 5.4 g of 4-formylphenylboronic acid, 5.1 g of potassium carbonate and 0.7 g of tetrakis (triphenylphosphine) palladium (0) were placed in a 250 ml two-neck round-bottom flask, 300 ml of a mixed solvent (240 ml of tetrahydrofuran and 60 ml of water) was added thereto, and the resulting mixture was degassed by freezing three times and then heated under reflux for 24 hours under an inert atmosphere. After the reaction was completed, it was cooled to room temperature, and the reaction solution was extracted three times with ethyl acetate, and then the combined organic layers were washed three times with water, dried over anhydrous magnesium sulfate for 30 minutes, filtered, and the filtrate was collected. Removing volatile organic solvent from the filtrate by reduced pressure rotary evaporation, performing column chromatography on the obtained crude product by using dichloromethane/ethyl acetate (the volume ratio is 15/1) as an eluent, and performing vacuum drying to obtain light yellow powder 4, 4' - (pentacene-6, 13-dimethylene bis (methane dimethylene)) tetraphenyl formaldehyde I3.4 g (the yield is 79%);
2) synthesis of 3,5,15, 22-tetraaldehyde hexabenzocoronene II:
72 mg of 4, 4' - (pentacene-6, 13-dimethylenebis (methanedimethylene)) tetraphenylcarbaldehyde I, 127 mg of elemental iodine and 2.4 ml of propylene oxide were placed in a 100 ml quartz tube, 72 ml of anhydrous toluene (volume ratio of propylene oxide to anhydrous toluene was 1:30) was added, and irradiated with an ultraviolet lamp at a wavelength of 365nm for 12 hours. After the reaction is completed, treating the reaction solution with a saturated sodium thiosulfate solution, carrying out reduced pressure rotary evaporation on the mixed solution to remove a volatile organic solvent, filtering, washing a filter cake with water, ethanol and n-hexane for three times respectively, and carrying out vacuum drying to obtain an orange solid 3,5,15, 22-tetraaldehyde hexabenzocoronene II 71 mg (yield 100%); the reaction formula is as follows:
the nuclear magnetic hydrogen spectrum and infrared spectrogram of 3,5,15, 22-tetraaldehyde hexabenzocoronene II are shown in attached figures 1 and 2.
Example 2
A preparation method of a covalent organic framework material based on twisted hexabenzocoronene comprises the following steps:
249.5mg of 3,5,15, 22-tetraaldehyde hexabenzocoronene (II) and 75.7 mg of p-phenylenediamine were placed in a 50 ml Schlenk tube, 9.5 ml of o-dichlorobenzene and 0.5 ml of n-butanol were added, 1.0 ml of 6M aqueous acetic acid was added as a catalyst, and the resulting mixture was subjected to freeze degassing three times, then closed with a Teflon valve at 77 Kelvin, and then placed in an oven at 120 ℃ for reaction for 72 hours. After the reaction was complete, it was cooled to room temperature, filtered, and the filter cake was rinsed three times with tetrahydrofuran, N-dimethylacetamide, and acetone, respectively, and the solid was collected and dried under vacuum to give 270.6 mg of an orange-colored covalent organic framework material c-HBC-COF III (90.2% yield).
The reaction formula is as follows:
an X-ray powder diffraction pattern and infrared spectrum of covalent organic framework material c-HBC-COF based on twisted hexabenzocoronene are shown in figures 3 and 4.
The adsorption capacity of the c-HBC-COF to nitrogen under the temperature condition of 77K can reach 400cm3The experiment is shown in fig. 5, which shows that the covalent organic framework material can be used as a storage for gas.
In addition, the conductivity of the c-HBC-COF is obviously improved after the c-HBC-COF is doped with iodine (the mass ratio is 1: 0.64), and the current-voltage curve is shown in figure 6, so that the c-HBC-COF can be used as an electrode material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other modifications, simplifications or simple modifications without departing from the design principle and construction strategy of the present invention are included in the protection scope of the present invention.
Claims (4)
1.3,5,15, 22-tetraaldehyde hexabenzocoronene, the structure of which is shown in formula (II) and is abbreviated as follows: c-HBC-CHO:
2. a process for the preparation of 3,5,15, 22-tetraaldehyde hexabenzocoronene as claimed in claim 1, characterized by comprising the steps of:
1) synthesis of 4,4 ', 4 ", 4"' - (pentacene-6, 13-dimethylenebis (methanedimethylene)) tetraphenylcarbaldehyde (I):
carrying out Suzuki coupling reaction on 6, 13-bis (dibromomethylene) -6, 13-dihydropentacene and 4-formylphenylboronic acid in a mixed solvent of tetrahydrofuran and water under the alkaline condition provided by potassium carbonate and catalyzed by a palladium catalyst to obtain 4, 4' - (pentacene-6, 13-dimethylene bis (methane dimethylene)) tetraphenyl formaldehyde (I);
2) synthesis of 3,5,15, 22-tetraaldehyde hexabenzocoronene (II):
4, 4' - (pentacene-6, 13-dimethylene bis (methane dimethylene)) tetraphenyl formaldehyde (I) and iodine elementary substance are irradiated by an ultraviolet lamp with 365nm in a mixed solvent of propylene oxide and anhydrous toluene to obtain 3,5,15, 22-tetraaldehyde hexabenzocoronene (II); the reaction formula is as follows:
3. a covalent organic framework material based on twisted hexabenzocoronene, c-HBC-COF for short, which is characterized by being shown in a formula (III):
4. a process for the preparation of a covalent organic framework material based on contorted hexabenzocoronene, according to claim 3, characterized by comprising the following steps: dispersing 3,5,15, 22-tetraaldehyde hexabenzocoronene (II) and p-phenylenediamine in a mixed solvent of o-dichlorobenzene and n-butanol with a volume ratio of 19:1 to obtain a dispersion, adding an acetic acid aqueous solution as a catalyst, uniformly mixing, and reacting under a reflux condition to obtain a covalent organic framework material (III) based on distorted hexabenzocoronene, namely c-HBC-COF, wherein the ratio of the 3,5,15, 22-tetraaldehyde hexabenzocoronene (II) to the mixed solvent is 249.5 mg: 10 mL;
the reaction formula is as follows:
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| CN114349771B (en) * | 2021-12-09 | 2023-03-31 | 上海师范大学 | Hexabenzocoronene-based non-fullerene acceptor material and preparation and application thereof |
| CN114709557B (en) * | 2022-04-13 | 2023-10-27 | 南京工业大学 | Design synthesis of covalent organic framework material of post-modified carborane and application of covalent organic framework material in lithium-sulfur battery diaphragm |
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| WO2010060160A1 (en) * | 2008-11-28 | 2010-06-03 | The University Of Melbourne | Novel compounds, derivatives thereof and their use in heterojunction devices |
| CN108276574A (en) * | 2018-03-27 | 2018-07-13 | 台州学院 | A kind of cyclohexanediamine Quito hole covalent organic framework compound and preparation method thereof |
| CN109762180A (en) * | 2019-03-06 | 2019-05-17 | 云南大学 | Using triphenylphosphine as covalent organic frame of skeleton and its preparation method and application |
| CN111909389A (en) * | 2020-08-06 | 2020-11-10 | 山东师范大学 | Covalent organic framework material and preparation method and application thereof |
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| WO2010060160A1 (en) * | 2008-11-28 | 2010-06-03 | The University Of Melbourne | Novel compounds, derivatives thereof and their use in heterojunction devices |
| CN108276574A (en) * | 2018-03-27 | 2018-07-13 | 台州学院 | A kind of cyclohexanediamine Quito hole covalent organic framework compound and preparation method thereof |
| CN109762180A (en) * | 2019-03-06 | 2019-05-17 | 云南大学 | Using triphenylphosphine as covalent organic frame of skeleton and its preparation method and application |
| CN111909389A (en) * | 2020-08-06 | 2020-11-10 | 山东师范大学 | Covalent organic framework material and preparation method and application thereof |
Non-Patent Citations (1)
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