CN112479831B

CN112479831B - Metal organic framework material based on twisted hexabenzocoronene and preparation method and application thereof

Info

Publication number: CN112479831B
Application number: CN202011352552.0A
Authority: CN
Inventors: 陈龙; 邢国龙; 刘婧娟
Original assignee: Tianjin University
Current assignee: Tianjin University
Priority date: 2020-11-26
Filing date: 2020-11-26
Publication date: 2022-04-29
Anticipated expiration: 2040-11-26
Also published as: CN112479831A

Abstract

The invention discloses a twisted hexabenzocoronene-based metal organic framework material, a preparation method and application thereof, wherein the twisted hexabenzocoronene-based metal organic framework material is c-HBC-8OH-M-MOF for short and is shown in a formula (IV):

Description

Metal organic framework material based on twisted hexabenzocoronene and preparation method and application thereof

Technical Field

The invention belongs to the field of metal organic framework materials, and particularly relates to a metal organic framework material based on twisted hexabenzocoronene, and a preparation method and application thereof.

Background

Metal-organic frameworks (MOFs) are a class of inorganic-organic hybrid porous materials with a periodic network structure formed by connecting Metal nodes/clusters and organic ligands. The MOFs has wide application prospect in the fields of gas adsorption and separation, catalysis, biomedicine and the like. However, conventional MOFs generally have poor conductivity, which greatly limits the applications of MOFs materials in the fields of batteries, sensors, and the like.

Two-dimensional conjugated metal-organic frameworks (2D conjugated MOFs) are a class of two-dimensional materials emerging in recent years that are composed of pi-conjugated planar ligands and metal atoms and have excellent electrical conductivity. Compared with the traditional MOFs, pi-d connection in the plane of the two-dimensional conjugated metal organic framework material is more beneficial to the delocalization of charge carriers, so that more excellent conductivity is caused. Meanwhile, due to the inherent porosity of the material, the porous conductive MOFs show potential application in the fields of electrochemical catalysis, energy storage, chemical sensors and the like. So far, two-dimensional conjugated metal organic frameworks are mainly based on planar ligands with pi conjugation derived from benzene, triphenylene, coronene, tetraphenylnaphthalene, phthalocyanine and the like, and two-dimensional conjugated metal organic frameworks based on non-planar ligands are rarely reported. Therefore, the synthesis of the two-dimensional conjugated metal-organic framework based on the non-planar ligand has important significance for researching the structure-activity relationship of the conductive MOFs.

Hexabenzocoronene (HBC) is a large-pi conjugated polycyclic aromatic hydrocarbon with unique electronic structure and self-assembly performance, and has wide application in liquid crystal, field effect transistor and the like. The hexabenzocoronene can be classified into planar hexabenzocoronene (p-HBC) and twisted hexabenzocoronene (c-HBC). Unlike planar hexabenzocoronene, the non-planar structure imparts a unique electronic structure to the distorted hexabenzocoronene, with somewhat more efficient intermolecular charge transfer. Therefore, the integration of the hexabenzocoronene molecules with a twisted structure into a metal-organic framework is beneficial to the improvement of the conductivity, but how to construct the twisted hexabenzocoronene-based metal-organic framework material is still a great challenge.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a

hydroxyl monomer

2, 3, 6, 7, 14, 15, 18, 19-octahydroxyhexabenzocoronene for synthesizing a twisted hexabenzocoronene-based metal organic framework material.

The second purpose of the invention is to provide a preparation method of 2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene.

A third object of the present invention is to provide a twisted hexabenzocoronene-based metal organic framework material.

A fourth object of the present invention is to provide a method for preparing a twisted hexabenzocoronene-based metal organic framework material.

A fifth object of the present invention is to provide an application of the twisted hexabenzocoronene-based metal-organic framework material for preparing a battery or a sensor.

The technical scheme of the invention is summarized as follows:

2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene, the structure of which is shown in formula (III), and is abbreviated as: c-HBC-8 OH:

the preparation method of the 2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene comprises the following steps:

1) synthesis of 6, 13-bis (3, 4-dimethoxyphenyl) methylene) -6, 13-dihydropentacene I:

carrying out Suzuki coupling reaction on 6, 13-bis (dibromomethylene) -6, 13-dihydropentacene and 3, 4-dimethoxyphenylboronic acid in 80% tetrahydrofuran aqueous solution by volume under the alkaline condition provided by sodium carbonate and catalyzed by tetrakis (triphenylphosphine) palladium (0) to obtain 6, 13-bis (3, 4-dimethoxyphenyl) methylene) -6, 13-dihydropentacene I;

2) synthesis of 2, 3, 6, 7, 14, 15, 18, 19-octamethoxy hexabenzocoronene II:

irradiating 6, 13-bis (3, 4-dimethoxyphenyl) methylene) -6, 13-dihydropentacene I and iodine elementary substance in propylene oxide and anhydrous toluene by using a 365nm ultraviolet lamp to obtain 2, 3, 6, 7, 14, 15, 18, 19-octamethoxy hexabenzocoronene II;

3) synthesis of 2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene III:

reacting 2, 3, 6, 7, 14, 15, 18, 19-octamethoxy hexabenzocoronene II and boron tribromide in dichloromethane to obtain 2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene III;

the reaction formula is as follows:

a twisted hexabenzocoronene-based metal organic framework material, c-HBC-8OH-M-MOF for short, is shown in formula IV:

wherein M is Cu, Co, Ni or Fe.

A process for preparing the organic metal frame material based on twisted hexabenzocoronene includes such steps asThe following steps: 2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene III and a divalent metal ion M²⁺Placing the metal organic framework material in water or N, N-dimethylformamide aqueous solution with the mass concentration of 1% -25% to obtain a metal organic framework material IV based on the twisted hexabenzocoronene, which is referred to as c-HBC-8OH-M-MOF for short; the reaction formula is as follows:

and M is Cu, Co, Ni or Fe.

An application of a twisted hexabenzocoronene-based metal organic framework material in preparation of a battery or a sensor.

The invention has the advantages that:

the metal organic framework material c-HBC-8OH-M-MOF (M ═ Cu, Co, Ni, Fe and the like) provided by the invention is constructed based on a hydroxyl monomer of twisted hexabenzocoronene, and because of the introduction of the twisted hexabenzocoronene, the c-HBC-8OH-M-MOF (M ═ Cu, Co, Ni, Fe and the like) has good conductivity and can be used for preparing a battery or a sensor. In addition, the invention also provides a strategy for constructing the conductive metal organic framework material.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of a compound represented by formula III.

FIG. 2 is an infrared spectrum of the compound of formula III.

FIG. 3 is a high resolution mass spectrum of the compound of formula III.

FIG. 4 is a powder X-ray diffraction pattern of the metal-organic framework material of formula IV.

FIG. 5 is an infrared spectrum of the metal organic framework material of formula IV.

FIG. 6 is a current-voltage curve of the metal-organic framework material of formula IV.

Detailed Description

The present invention will be further described with reference to the following examples.

Example 1

placing 3.1 g of 6, 13-bis (dibromomethylene) -6, 13-dihydropentacene, 5.5 g of 3, 4-dimethoxyphenylboronic acid, 4.2 g of sodium carbonate and 0.6 g of tetrakis (triphenylphosphine) palladium (0) in a 500 ml two-neck round-bottom flask, adding 250 ml of 80% tetrahydrofuran aqueous solution, freezing and degassing the obtained mixed solution for three times, and heating and refluxing for 36 hours in an inert atmosphere (nitrogen filling); 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 ethyl acetate/dichloromethane/petroleum ether (the volume ratio is 1/1/1) as an eluent, and performing vacuum drying to obtain light yellow powder 6, 13-bis (3, 4-dimethoxyphenyl) methylene) -6, 13-dihydropentacene I3.4 g (the yield is 80%);

2) synthesis of 2, 3, 6, 7, 14, 15, 18, 19-octamethoxy hexabenzocoronene II:

placing 6, 13-bis (3, 4-dimethoxyphenyl) methylene) -6, 13-dihydropentacene I, 190 mg of elemental iodine and 3.6 ml of epoxypropane in a 100 ml quartz tube, adding 85 ml of anhydrous toluene, irradiating for 12 hours by using a 365nm ultraviolet lamp, after the reaction is completed, treating a reaction liquid by using a saturated sodium thiosulfate aqueous solution, removing a volatile organic solvent from a mixed liquid by reduced pressure rotary evaporation, filtering, washing a filter cake by using water, methanol and n-hexane for three times respectively, and drying in vacuum to obtain 115 mg of an orange

yellow solid

2, 3, 6, 7, 14, 15, 18, 19-octamethoxy hexabenzocoronene II (yield 91%);

3) synthesis of 2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene III:

under an inert atmosphere (nitrogen), 673 mg of 2, 3, 6, 7, 14, 15, 18, 19-octamethoxy hexabenzocoronene II is dissolved in 70 ml of anhydrous dichloromethane, the mixture is cooled for 10 minutes in an ice-water bath, 7 ml of 1M boron tribromide dichloromethane solution is added dropwise to react for 12 hours, deoxygenated water is added to quench the reaction, the reaction is filtered, the filter cake is washed with water and dried in vacuum, and 570 mg of dark

green solid

2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene III is obtained (yield is 98%); the reaction formula is as follows:

the nuclear magnetic hydrogen spectrum, infrared spectrum and high-resolution mass spectrogram of 2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene III (c-HBC-8OH for short) are shown in figures 1,2 and 3.

Example 2

A preparation method of a twisted hexabenzocoronene-based metal organic framework material comprises the following steps:

under nitrogen atmosphere, 36.5 mg of 2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene (c-HBC-8OH) III and 48.3 mg of copper nitrate trihydrate are placed in 5 ml of 8% by mass aqueous N, N-dimethylformamide, (0.4 ml of N, N-dimethylformamide and 4.6 ml of purified water), subjected to ultrasonic treatment for 10 minutes, reacted at 85 ℃ for 72 hours, cooled to room temperature, centrifuged, collected solid, rinsed with water three times and rinsed with acetone three times. The solid was collected and dried under vacuum at room temperature for 24 hours to give 38 mg (yield 90%) of black twisted hexabenzocoronene-based metal-organic framework material IV (c-HBC-8 OH-Cu-MOF).

The X-ray powder diffraction pattern and the infrared spectrum of c-HBC-8OH-Cu-MOF are shown in FIGS. 4 and 5.

The reaction formula is as follows:

and M is Cu.

The corresponding twisted hexabenzocoronene-based metal-organic framework materials c-HBC-8OH-Co MOF, c-HBC-8OH-Ni MOF, or c-HBC-8OH-Fe-MOF were prepared as in this example, substituting 49.8 mg of cobalt acetate tetrahydrate, 49.8 mg of nickel acetate tetrahydrate, or 39.8 mg of ferrous chloride tetrahydrate for 48.3 mg of copper nitrate trihydrate of this example.

c-HBC-8OH-Cu-MOF can be obtained by using water or an aqueous solution of N, N-dimethylformamide with a mass concentration of 1% -25% (e.g., 1%, 10%, 20% or 25%) instead of the aqueous solution of N, N-dimethylformamide with a mass concentration of 8% in the present example.

Example 3

The test of the conductivity of the twisted hexabenzocoronene-based metal-organic framework material comprises the following steps:

3 mg of c-HBC-8OH-Cu-MOF prepared in example 2 were pressed into a cylinder having a diameter of 3 mm and a thickness of 0.274 mm, and a current-voltage curve was measured in a voltage range of-5.0 to 5.0V. As shown in FIG. 6, the c-HBC-8OH-Cu-MOF prepared in example 2 exhibited good conductivity, which was as high as 0.04 Siemens per centimeter.

The calculation formula of the conductivity is as follows:

the experiment proves that the metal organic framework material based on the twisted hexabenzocoronene is applied to the fields of battery or sensor preparation and the like.

The implementation proves that the twisted hexabenzocoronene-based metal organic framework material c-HBC-8OH-Cu-MOF, c-HBC-8OH-Co-MOF, c-HBC-8OH-Ni-MOF and c-HBC-8OH-Fe-MOF has good conductivity and can be respectively applied to the fields of battery or sensor preparation and the like.

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

1. A twisted hexabenzocoronene-based metal organic framework material, c-HBC-8OH-M-MOF for short, is characterized by being shown in a formula (IV):

wherein M is Cu.

2. The method for preparing the twisted hexabenzocoronene-based metal-organic framework material according to claim 1, which is characterized by comprising the following steps: 2, 3, 6, 7, 14, 15, 18, 19-octahydroxy hexabenzocoronene (III) and a divalent metal ion M²⁺Placing the metal organic framework material in water or N, N-dimethylformamide water solution with the mass concentration of 1% -25% to obtain a metal organic framework material (IV) based on twisted hexabenzocoronene, namely c-HBC-8OH-M-MOF for short; the reaction formula is as follows:

and M is Cu.

3. Use of a twisted hexabenzocoronene-based metal-organic framework material according to claim 1 for the production of batteries or sensors.