KR101153721B1 - Edge-functionalized two-dimensional graphene nanoribbons and method for manufacturing the same - Google Patents

Abstract

The present invention relates to novel two-dimensional graphene nanoribbons and a method for producing the same.
In detail, the present invention provides a graphene nanoribbon functionally controlled by combining a high-quality graphene material using an organic synthetic method and a functional organic substituent at an edge of the graphene, and a method of manufacturing the same. Graphene nanoribbons prepared according to the present invention are characterized by having a two-dimensional structure of 20 to 80 nm in length, about 2.5 nm in width, and about 0.16 to 0.17 nm in thickness.

Description

Edge-functionalized two-dimensional graphene nanoribbons and method for manufacturing the same

The present invention relates to graphene nanoribbons prepared by an organic synthetic method from bromobenzene and a method for producing the same.

A single layer that is separated by separating a single layer from graphite is called graphene. Graphene is essentially a plate-like carbon compound in which carbon atoms are bonded to one another. Graphene, which is a layer of graphite, is a single flat sheet made of sp2-carbon bonds and has a honeycomb shape. Graphene has various inherent characteristics such as excellent charge mobility, low sheet resistance and mechanical properties, and thermal and chemical stability compared to other materials. Recently, many application-related studies using the physical, chemical, and mechanical intrinsic properties of graphene have been reported. In particular, it has a charge mobility of more than 100 times that of silicon, and is a very excellent conductor. It is evaluated to be able to flow. Therefore, by utilizing these characteristics, it has technical and industrial application values in various fields such as electrode materials for displays and solar cells, charge transfer channel materials for next-generation semiconductor devices, and additives for conductive polymer films.

Graphene has good electrical, thermal and mechanical performance, making it suitable for applications in supercapacitors, room temperature ballistic field effect transistors, super sensitive sensors, micromechanical resonators, composite functional materials and nonlinear optical materials. The prospect is very large.

Graphene nanoribbons, which have promising electronic applications due to their semiconducting properties, are mostly obtained through direct peeling from graphite or oxidation of graphite. The material obtained by such a process has a fundamental problem that it is difficult to obtain a material having a size or a uniform size suitable for the purpose of use, and to make the structure of two-dimensional ends or corners uniform or to deform to suit the purpose.

Below is a brief look at the graphene manufacturing method developed to date.

1. Peeling directly from graphite:

1) Mechanical Peeling Method

It is a mechanical exfoliation method that peels one layer from graphite using a scotch tape or the like. Good quality graphene is needed for basic research, but it is too inefficient to commercialize it (Science, 2004, 306, 666).

2) Use a suitable solvent

The graphene can be stripped from the graphite using a suitable solvent without any special intercalation or oxidation-reduction. Solvent-Graphene Interfacial Interaction Energy A graphene dispersion solution can be obtained by finding a solvent that is well suited to the graphene-Graphene interaction energy (Nature Nanotech. 2008, 3, 563).

3) Heating expansion / insertion method

The expanded graphite is heated to 1000 ° C. to form a multilayered graphite flake, and molecules such as Oleum (f-sulphuric acid / SO ₂ ) and tetrabutyl ammonium hydroxide are used. It was sandwiched between graphene layers and placed in a solution containing DSPE-mPEG (1,2-Distearoyl-Snglycero-3- Phosphoethanolamine-N- [methoxy (polyethyleneglycol) -500]) and sonicated to prepare a graphene dispersion solution. can do.

4) Oxidation / Reduction Method of Graphite

Graphene is oxidized to form graphite oxide, the graphite oxide is stripped off, and then reduced to prepare graphene. Graphite oxide is mainly in the form of epoxy due to the internal double bonds compete with oxygen, and the edges have various functional groups including hydroxy, carboxyl group and other carbonyl groups. Such graphite oxide may be peeled into a single layer by ultrasonication or the like by increasing water solubility, and may be reduced by a reducing agent such as hydrazine to obtain graphene.

2. Epitaxial growth method:

It is a method of depositing and growing various metal-carbides (Si-C, Ru-C, Ni-C, etc.). In the Si-C crystal pyrolysis method, when Si-C single crystal is heated, SiC on the surface is decomposed to remove Si, and a graphene sheet is generated by the remaining carbon (C). At this time, methane and hydrogen gas are used at high temperature.

3. Organic Synthesis Method

It is produced by organic synthesis from a low molecular organic compound, or a method of polymerizing a precursor by synthesizing a precursor. Coupling reactions between aryl-aryl carbon atoms developed to date use a catalyst such as palladium (Mullen, J. Am. Chem. Soc., 2008, 130, 4216). The production of graphene-type compounds by an organic synthetic method is still in its infancy in the world, but it is difficult to synthesize a large-capacity, large-area graphene due to the difficult polymerization conditions and low polymerization frequency.

In order to solve the above problems, the present invention provides a monomolecular graphene nanoribbon using an organic synthesis method, more specifically, a graphene having high dispersibility in a solvent by fixing organic functional groups at both ends or corners of graphene, and having controlled structure and function. An object of the present invention is to provide a pen nanoribbon and a method of manufacturing the same.

In order to achieve the above object, the present inventors have conducted numerous studies. As a result, surprisingly inexpensive bromobenzene is used as a starting material to prepare graphene, and in particular, by replacing organic functional groups at both ends or corners of graphene, The organic functionalized two-dimensional graphene nanoribbons with high dispersibility in the solvent, control of structure and function, and quality can be prepared. The edge organofunctionalized graphene of the present invention greatly improves dispersibility in a solvent, and thus, the graphene has a surprising effect of compensating for the disadvantages of the conventional graphene having a problem of dispersibility in a solvent. .

In addition, the graphene nanoribbons prepared by the manufacturing method of the present invention are graphene nanoribbons having a width of 10 nm or less, specifically, a width of 2.5 nm. Conventionally, the graphene nanoribbons have a width of 10 nm or less. It is known to exhibit semiconductor properties in that the graphene nanoribbons of the present invention provide materials with very good semiconductor properties.

The present invention provides a high-quality graphene nanoribbon or a method for producing the same using an organic chemical synthesis method, in particular, by dispersing an organic functional group at the edge of the graphene nanoribbon, easy dispersibility, and can control the function and structure, To provide a two-dimensional graphene nanoribbons of the formula (1).

In addition, the present invention comprises the steps of designing and manufacturing a building block (building block) of the benzene ring derivative; Introducing functional organic substituents at both ends or corners of the benzene ring precursor using an organic chemical synthesis method; And preparing a graphene nanoribbon represented by the following Chemical Formula 1 according to a polymerization reaction and a dehydrogenation reaction.

[Formula 1]

로부터 선택되고, R⁵는 (C1-C4)알킬이고, a는 1 내지 4이고, b는 1 내지 4이며; R²는 B[OCH₂C(Me)₂]₂ 또는 아릴이고; R³는 수소원자 또는 요오드원자이고; n은 2 내지 20이다.]
[In Formula 1, R ¹ is a hydrogen atom, (C1-C8) alkyl, (C1-C10) alkoxy, di (C1-C4) alkylamino (C1-C4) alkoxy and

Is selected from R ⁵ is (C 1 -C 4) alkyl, a is 1-4, b is 1-4; R ² is B [OCH ₂ C (Me) ₂ ] ₂ or aryl; R ³ is a hydrogen atom or an iodine atom; n is 2 to 20.]

Hereinafter, the present invention will be described in detail.

The present invention can be carried out by the production method of the two aspects in order to manufacture the two-dimensional graphene nanoribbons of the formula (1).

The starting material is hexabromobenzene, which is commercially available and inexpensive to reduce material costs. Dichlorotetrabromobenzene (dichlorotetrabromobenzene) for the production of graphene nanoribbon using the organic synthesis method compared with the conventional production of the starting material, the present invention can reduce the material cost by using hexabromobenzene Manufacturing process.

The present invention in the preparation of the two-dimensional graphene nanoribbons of the formula (1), as a first aspect,

(a) reacting hexabromobenzene, Grignard reagent, and iodine (I ₂ ) at room temperature to obtain a compound of formula 4;

(b) adding a catalyst and a compound of formula 5 to the compound of formula 4 of step (a) and polymerizing to obtain a compound of formula 6; And

(c) dehydrogenating the compound of Chemical Formula 6 to prepare a compound of Chemical Formula 2;

It provides a method for producing a two-dimensional graphene nanoribbons comprising a.

[Formula 2]

[Formula 4]

[Chemical Formula 5]

[Formula 6]

로부터 선택되고, R⁵는 (C1-C4)알킬이고, a는 1 내지 4이고, b는 1 내지 4이며; n은 2 내지 20이다.
In Chemical Formulas 2, 4, and 6, R ¹ represents a hydrogen atom, (C 1 -C 8) alkyl, (C 1 -C 10) alkoxy, di (C 1 -C 4) alkylamino (C 1 -C 4) alkoxy and

Is selected from R ⁵ is (C 1 -C 4) alkyl, a is 1-4, b is 1-4; n is 2 to 20.

The present invention in the preparation of the two-dimensional graphene nanoribbons of the formula (1), as a second aspect,

(a ′) reacting hexabromobenzene, Grignard reagent, and iodine (I ₂ ) at room temperature to obtain a compound of formula 4;

(b ') adding a catalyst and a compound of formula 5 to the compound of formula 4 of step (a') and polymerizing to obtain a compound of formula 6;

(c ′) adding a bromo (C6-C30) aryl or phenylbromic acid to the compound of Formula 6 of step (b ′) to obtain a compound of Formula 7; And

(d ′) preparing a compound of Formula 3 by dehydrogenation of the compound of Formula 7 of step (c ′);

It provides a method for producing a two-dimensional graphene nanoribbons comprising a.

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

로부터 선택되고, R⁵는 (C1-C4)알킬이고, a는 1 내지 4이고, b는 1 내지 4이며; R⁶는 B[OCH₂C(Me)₂]₂ 또는 아릴이고 ; R⁷는 수소원자 또는 요오드원자이고; n은 2 내지 20이다.
In Chemical Formulas 3, 4, 6 and 7, R ¹ represents a hydrogen atom, (C 1 -C 8) alkyl, (C 1 -C 10) alkoxy, di (C 1 -C 4) alkylamino (C 1 -C 4) alkoxy and

Is selected from R ⁵ is (C 1 -C 4) alkyl, a is 1-4, b is 1-4; R ⁶ is B [OCH ₂ C (Me) ₂ ] ₂ or aryl; R ⁷ is a hydrogen atom or an iodine atom; n is 2 to 20.

Steps (a) and (a ′) of the first and second aspects of the present invention are performed by dissolving hexabromobenzene in an organic solvent such as tetrahydrofuran, ether, benzene and the like selected from argon, helium and nitrogen. Under the inert gas atmosphere of at least one species, the reaction is carried out by adding a Grignard reagent containing the same substituent as R ¹ of Formula 1, and further adding iodine (I ₂ ) to the diiodo represented by Formula 4 above. Yield a diaryltetraarylbenzene compound.

The present invention is to produce a diiodotetraarylbenzene of the formula (4) as an intermediate, the graphene nanoribbons are very effective in having physical properties for the semiconductor properties, that is, the width of the graphene nanoribbon is prepared to less than 10 nm The graphene nanoribbons prepared by the present invention in more detail are the intermediates that play a key role in providing the graphene nanoribbons having a width of 2.5 nm.

The Grignard reagent may be R ¹¹ -phenyl-MgBr or a mixture of R ¹¹ -phenyl-Br and Mg, wherein R ¹¹ is selected from a hydrogen atom, (C 1 -C 8) alkyl and (C 1 -C 4) alkoxy It is chosen. Preferably R ¹¹ is selected from hydrogen atom, methyl, ethyl, n-propyl, n-butyl, tert-butyl, methoxy, ethoxy and propoxy.

Steps (a) and (a ′) of the first and second aspects may be better understood through Scheme 1 below, which illustrates the embodiment of the present invention.

Scheme 1

In addition, the present invention is in the case of (a) and (a ') in the case that the ring group of R ¹ of Formula 4 is alkoxy or derivatives of 2 or more carbon atoms, in order to obtain even higher yields in the corner portion R in Formula 4 By adding tribromoborane and reacting the substituent of ¹ with methoxy, methoxy can be substituted with hydroxy (-OH) groups, which is very simple in reaction and can be obtained in high yield. There is this. Diiodoarylbenzene substituted with hydroxy groups can produce longer chains very simply and effectively by addition of a halide and base containing the desired organic substituent. This provides a very effective intermediate for producing heterofunctionalized graphene at the edge portion of the graphene nanoribbon. Scheme 2 is shown by way of example for better understanding.

Scheme 2

Steps (b) and (b ') of the first and second aspects of the present invention dissolve the compound of formula 4 obtained from the steps (a) and (a') in an organic solvent such as toluene and Suzuki-coupling reaction with the addition of the compound of formula 5 [1,4-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene] It is possible to produce a compound of Formula 6, which is a graphene precursor.

The compound of Formula 5 may reduce material costs because it is easy to purchase commercially and the price is low.

In the steps (b) and (b '), it is preferable to further add a catalyst, and the catalyst is a mixture of a palladium-based catalyst, a phase-transfer catalyst and a base compound, which is effective for carrying out the reaction more efficiently. The palladium-based catalyst is not limited unless it affects the effect of producing the compound of Formula 6 from Formula 4, specifically, Pd ₂ dba ₃ CHCl ₃ , Pd (OAc) ₂ , (dppf) PdCl ₂ , (PPh ₃ ) ₂ PdCl ₂ , (DPEphos) PdCl ₂ , Pd (CH ₃ CN) ₂ Cl ₂ , Pd (PhCN) ₂ Cl ₂ , Pd (PPh ₃ ) ₄ and PdCl ₂ may be used Preferably, Pd (PPh ₃ ) ₄ is used to improve the yield. The phase-transfer catalyst is not limited unless it affects the effect of producing the compound of Formula 6 or 7 from Formula 4, but specifically 15-crown-5, 18-crown-6, tetrabutylammonium hydro At least one selected from gensulfate, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium chloride, methyltridecylammonium chloride, methyltrioctylammonium chloride (Aliquat 336) and methyltributylammonium chloride It may be used, preferably using methyl trioctyl ammonium chloride (Aliquat 336) there is an advantage that can improve the yield more. The base compound may be one or more selected from K ₂ CO ₃ , Na ₂ CO ₃ , NaHCO ₃ , KHCO ₃ and CaCO ₃ .

The present invention is effective in producing graphene nanoribbons having a length of 20 to 80 nm by using the catalyst, and a very improved manufacturing process compared to the graphene nanoribbons obtained by the organic synthesis method up to 10 nm in length. Technology.

Preferably, steps (b) and (b ') of the first and second aspects of the present invention are subjected to reflux reaction.

는 B(OH)₂ 또는 (C6-C30)아릴로 치환할 수 있고, 아이오다이드(iodide)는 수소원자로 더 치환할 수도 있다.Step (c ′) of the second aspect of the present invention is to replace the compound of formula 6 by adding bromo (C6-C30) aryl or phenylbromic acid, so that the substituents at the left and right ends

May be substituted with B (OH) ₂ or (C6-C30) aryl, and iodide may be further substituted with a hydrogen atom.

Step (b) of the first aspect of the present invention and steps (b ') and (c') of the second aspect can be better understood by the following Scheme 3. Scheme 3 below illustrates an embodiment of the present invention.

Scheme 3

Step (c) and step (d) of the second aspect of the present invention may prepare a graphene material according to the dehydrogenation reaction of the compound of Formula 6 or the compound of Formula 7, respectively. The present invention provides a method for dehydrogenation using FeCl ₃ and nitromethane, although not particularly limited, if graphene can be formed by dehydrogenation as a raw material that can be used for the dehydrogenation reaction. The step of preparing the graphene by the dehydrogenation reaction can be better understood by the following Scheme 4, the following scheme 4 shows an embodiment of the present invention.

Scheme 4

Formula 2 to Formula 7 of the present invention more preferably R ¹ is a hydrogen atom, methyl, ethyl, n-propyl, n-butyl, tert-butyl, ethoxy, n-propoxy, n-butoxy, tert -Butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, n-octyloxy, dimethylaminomethoxy, diethylaminomethoxy, dimethylaminoethoxy, diethylaminoethoxy and 2- (2 -(2-methoxyethoxy) ethoxy) ethoxy; R ⁶ is B [OCH ₂ C (Me) ₂ ] ₂ or phenyl; R ⁷ is an iodine atom or a hydrogen atom; As for n, it is more preferable that it is 8-20.

All reaction processes of the first and second aspects of the invention are carried out under one or more inert gas atmospheres selected from argon, helium and nitrogen.

The present invention provides a compound represented by the following Chemical Formula 1 prepared by the method for preparing the two-dimensional graphene nanoribbons of the first and second aspects.

[Formula 1]

로부터 선택되고, R⁵는 (C1-C4)알킬이고, a는 1 내지 4이고, b는 1 내지 4이며; R²는 B[OCH₂C(Me)₂]₂ 또는 아릴이며; R³는 수소원자 또는 요오드원자이며; n은 2 내지 20이다.In Formula 1, R ¹ is a hydrogen atom, (C1-C8) alkyl, (C1-C10) alkoxy, di (C1-C4) alkylamino (C1-C4) alkoxy and

Is selected from R ⁵ is (C 1 -C 4) alkyl, a is 1-4, b is 1-4; R ² is B [OCH ₂ C (Me) ₂ ] ₂ or aryl; R ³ is a hydrogen atom or an iodine atom; n is 2 to 20.

More preferably, in Formula 1, R ¹ represents a hydrogen atom, methyl, ethyl, n-propyl, n-butyl, tert-butyl, ethoxy, n-propoxy, n-butoxy, tert-butoxy, n- Pentyloxy, neopentyloxy, n-hexyloxy, n-octyloxy, dimethylaminomethoxy, diethylaminomethoxy, dimethylaminoethoxy, diethylaminoethoxy and 2- (2- (2-methoxy Ethoxy) ethoxy) ethoxy; R ² is B [OCH ₂ C (Me) ₂ ] ₂ or phenyl; R ³ is a hydrogen atom or an iodine atom; n is a two-dimensional graphene nanoribbons, characterized in that 8 to 16.

The two-dimensional graphene nanoribbons of the present invention has a horizontal length of 20 to 80 nm, a vertical length of about 2.5 nm, and a thickness of about 0.16 to 0.17 nm in a two-dimensional structure. Compared to graphene nanoribbons, the most important factor is that the graphene width should be 10 nm or less in order to have semiconductor characteristics. The present invention is a graphene nanoribbon having a width of 2.5 nm, and has excellent semiconductor characteristics. It is expected to exhibit excellent transistor characteristics.

In addition, the edge organic functionalized two-dimensional graphene nanoribbons of the present invention has a very excellent dispersibility to the solvent as shown in FIG. Considering that the conventional graphene has a limited dispersion due to low dispersion in solvents, it is expected that the graphene may be applied to various fields of electronic devices such as semiconductor fields requiring semiconductor characteristics of graphene in addition to transistor fields. The organic solvent having excellent dispersibility with respect to the edge organic functionalized two-dimensional graphene nanoribbons of the present invention is dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), pyridin, At least one selected from acetone, tetrahydrofuran (THF), dioxane, hexamethylphosphoride (HMPA), dichloromethane, chloroform, toluene, benzene, dichlorobenzene and tetrachloroethane can be used.

In the present invention, dichlorotetrabromobenzene was prepared separately and selected as a starting material. However, in the present invention, it is easy to purchase commercially and inexpensive, so that the material cost can be reduced. By producing an amide arylbenzene, economic effects such as process costs can be obtained, and the present invention can control the length of the graphene nanoribbons by using a Pd catalyst, and has a much longer length than the conventional graphene nanoribbons. Improved graphene nanoribbons can be prepared, and by introducing methoxy groups into the edge portions of the graphene nanoribbons, graphene nanoribbons having long chain functional groups can be produced in high yield.

In addition, the graphene nanoribbons of the present invention provides a graphene nanoribbon having a length of 20-80 nm and a width of 2.5 nm, thereby providing a core material for producing devices such as transistors having excellent semiconductor properties and excellent electrical properties. Can be provided.

1 shows the ¹ H-NMR spectrum of Polymer 2c of Example 10. FIG.
2 shows the ¹³ C-NMR spectrum of polymer 2c of Example 10. FIG.
FIG. 3 shows Matrix-Assisted Laser Desorption Ionization (MALDI-TOF) spectra of polymers 2c (A), 2d (B), and 2g (C) of Examples 10-12.
4 shows the Raman spectrum of 3 g of graphene of Example 13. FIG.
Laser wavelength: 514 nm; Laser power: 3 mW; Laser spot size: 5 μm
FIG. 5 shows a scanning tunnel microscope (STM) image of 3 g of graphene of Example 13. FIG.
FIG. 6 shows a scanning tunnel microscope (STM) image of 3 g of graphene of Example 13. FIG.
7 is a sample in which 3 g of graphene of Example 13 was dispersed in a THF solvent.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.

Example 1 Preparation of 1a

Hexabromobenzene (551 mg, 1 mmol) and tetrahydrofuran (15 mL) were placed in a round bottom flask and filled with argon. 3M phenylmagnesium bromide (4 mL, 12 mmol) was slowly added dropwise using a syringe and stirred for 24 hours at room temperature under an argon atmosphere. Iodine (1.523 g, 6 mmol) was added to the reaction solution in tetrahydrofuran (5 mL) and stirred at room temperature for 2 hours. The remaining iodine was removed from the reaction solution with 1 N sodium sulfite (10 mL). Distilled water (25 mL) and diethyl ether (10 mL) were added, divided into two layers, and the resulting solid was filtered and dried in vacuo. (342 mg, yield: 54%).

1 H NMR (300 MHz, CDCl 3) δ 7.21-7.11 (m, 12H), 7.06-7.03 (m, 8H)

Example 2 Preparation of 1b

Hexabromobenzene (551 mg, 1 mmol) and tetrahydrofuran (15 mL) were placed in a round bottom flask and filled with argon. 1 M tolymagnesium bromide (12 mL, 12 mmol) was slowly added dropwise using a syringe and stirred for 12 hours at room temperature under an argon atmosphere. Iodine (1.523 g, 6 mmol) was added to the reaction solution in tetrahydrofuran (5 mL) and stirred at room temperature for 2 hours. The remaining iodine was removed from the reaction solution with 1 N sodium sulfite (10 mL). Distilled water (25 mL) and diethyl ether (10 mL) were added, divided into two layers, and the resulting solid was filtered and dried in vacuo. (180 mg, yield: 46%)

1 H NMR (300 MHz, CDCl 3) 6.98 (d, 8H, J = 8.1 Hz), 6.91 (d, 8H, J = 8.0 Hz), 2.25 (s, 12H)

Example 3 Preparation of 1c

 Magnesium (1.458 g, 60 mmol) and tetrahydrofuran (40 mL) were placed in a round bottom flask and filled with argon, and 1-bromo-4-butylbenzene (7.057 mL, 40 mmol) was slowly added dropwise using a syringe. And it stirred for 2 hours at room temperature under argon atmosphere. Hexabromobenzene (2.206 g, 4 mmol) and tetrahydrofuran (20 mL) were placed in a round bottom flask, filled with argon, and then mixed with magnesium and 1-bromo-4-butylbenzene solution using a dropping channel. Dropped slowly and stirred for 15 hours at room temperature under argon atmosphere. Iodine (6.091 g, 24 mmol) was dissolved in tetrahydrofuran (10 mL) and the mixture was stirred at room temperature for 2 hours. The remaining iodine was removed with 2N sodium bisulfite (20 mL) in the reaction solution. Distilled water (70 mL) and diethyl ether (50 mL) were added, divided into two layers, and the resulting solid was filtered and dried in vacuo. (1.221 g, yield: 46%)

1 H NMR (300 MHz, CDCl 3) δ 6.95 (d, 8H, J = 8.3 Hz), 6.70 (d, 8H, J = 8.2 Hz), 2.49 (t, 8H, J = 7.5 Hz), 1.54-1.43 (m, 8H), 1.25-1.18 (m, 8H), 0.87 (t, 12H, J = 7.3 Hz)

Example 4 Preparation of 1d

 Magnesium (1.337 g, 55 mmol) and tetrahydrofuran (50 mL) were placed in a round bottom flask and filled with argon, and then 1-bromo-4-tert-butylbutylbenzene (8.525 mL, 50 mmol) was removed using a syringe. Dropped slowly and stirred for 2 hours at room temperature under argon atmosphere. Hexabromobenzene (2.757 g, 5 mmol) and tetrahydrofuran (20 mL) were placed in a round bottom flask, filled with argon, and then mixed with magnesium and 1-bromo-4-butylbenzene solution using a dropping channel. Dropped slowly and stirred for 15 hours at room temperature under argon atmosphere. Iodine (6.091 g, 24 mmol) was added to the reaction solution in tetrahydrofuran (10 mL) and stirred at room temperature for 2 hours. The remaining iodine was removed from the reaction solution with 1 N sodium sulfite (20 mL). Distilled water (70 mL) and diethyl ether (50 mL) were added, divided into two layers, and the resulting solid was filtered and dried in vacuo (2.558 g, yield: 52%).

1 H NMR (300 MHz, CDCl 3) δ 7.12 (d, 8H, J = 7.4 Hz), 6.92 (d, 8H, J = 7.6 Hz), 1.20 (s, 36H)

Example 5 Preparation of 1e

Hexabromobenzene (2.206 g, 4 mmol) and tetrahydrofuran (20 mL) were placed in a round bottom flask and filled with argon. 0.5M 4-methoxyphenylmagnesium bromide (80 mL, 40 mmol) was slowly added dropwise using a dropping channel and stirred for 17 hours at room temperature under an argon atmosphere. Iodine (6.091 g, 24 mmol) was added to the reaction solution in tetrahydrofuran (10 mL) and stirred at room temperature for 2 hours. The remaining iodine was removed from the reaction solution with 1 N sodium sulfite (20 mL). Distilled water (50 mL) and diethyl ether (30 mL) were added, divided into two layers, and the resulting solid was filtered and dried in vacuo. (1.8 g, yield: 60%)

1 H NMR (300 MHz, CDCl 3) δ 6.93 (d, 8H, J = 8.7 Hz), 6.71 (d, 8H, J = 8.7 Hz), 3.74 (s, 12H)

Example 6 Preparation of 1f

2,3,5,6-tetra- (4'-methoxy) phenyl-1,4-diiodobenzene (754 mg, 1 mmol) and dichloromethane (5 mL) were added and nitrogen was added at -78 ° C. Filled. 1M of boron tribromide (4 mL, 4 mmol) was slowly added to the reaction solution, the temperature was gradually raised, and the mixture was stirred at room temperature for 6 hours. Ice water (10 mL) was added to the reaction solution, 2N sodium bisulfite (10 mL) and ethyl acetate (10 mL) were added thereto, followed by stirring at room temperature for 10 minutes. The resulting solid was filtered and dried in vacuo (653 mg, yield: 94%).

1 H NMR (300 MHz, DMSO-d6) δ 6.74 (d, 4H, J = 8.5 Hz), 6.48 (d, 4H, J = 8.5 Hz)

Example 7 Preparation of 1 g

2,3,5,6-tetra- (4'-hydroxy) phenyl-1,4-diiodobenzene (362 mg, 0.518 mmol), potassium hydroxide (465 mg, 8.294 mmol), iodooctane (0.754 mL, 4.147 mmol) and dimethyl sulfoxide (5 mL) were added to a round bottom flask and stirred for 48 hours at room temperature under a nitrogen atmosphere. The resulting solid was filtered and dissolved in dichloromethane and washed with brine, and the obtained organic layer was dried over anhydrous magnesium sulfate, filtered and the solvent was evaporated off, and then the compound was separated by column chromatography (392 mg, Yield: 66%)

1 H NMR (300 MHz, CDCl 3) δ 6.91 (d, 8H, J = 8.7 Hz), 6.69 (d, 8H, J = 8.7 Hz), 3.86 (t, 8H, J = 6.6 Hz), 1.75-1.70 (m, 8H), 1.43-1.27 (m, 40H), 0.90-0.85 (m, 12H)

Example 8 Preparation of 1h

2,3,5,6-tetra- (4'-hydroxy) phenyl-1,4-diiodobenzene (350 mg, 0.5 mmol), potassium hydroxide (830 mg, 6 mmol), [2- [2- (2-methoxyethoxy) ethoxy] ethoxy] -p-tolylsulfonate (954 mg, 3.0 mmol) and dimethyl sulfoxide (5 mL) were added to a round bottom flask and stirred at room temperature for 96 hours. It was. Distilled water (20 mL) was added to the reaction solution, and the mixture was extracted with dichloromethane. The organic layer obtained was dried over anhydrous magnesium sulfate, filtered and the solvent was evaporated to remove the residue, and then the compound was separated by column chromatography (412 mg, yield: 64%).

1 H NMR (300 MHz, CDCl 3) δ 6.90 (d, 8H, J = 8.5 Hz), 6.70 (d, 8H, J = 8.5 Hz), 4.05 (t, 8H, J = 4.4 Hz), 3.82 (t, 8H, J = 4.4 Hz), 3.74-3.63 (m, 24H), 3.56-3.53 (m, 8H) 3.37 (s, 12H)

Example 9 Preparation of 1i

2,3,5,6-tetra- (4'-hydroxy) phenyl-1,4-diiodobenzene (350 mg, 0.5 mmol), potassium carbonate (608 mg, 4.4 mmol), 2- (diethyl Amino) ethyl chloride hydrochloride (378 mg, 2.2 mmol) and acetone (20 mL) were added to a round bottom flask and stirred for 96 hours under reflux conditions. The reaction solution was filtered, washed with distilled water and dried in vacuo. (320 mg, yield: 76%)

1 H NMR (300 MHz, MeOH) δ 6.67 (d, 8H, J = 6.7 Hz), 6.43 (d, 2H, J = 6.8 Hz), 3.84 (bs, 16H), 3.68 (q, 16H, J = 7.2 Hz) , 1.36 (t, 24H, J = 7.2 Hz)

Example 10 Preparation of 2c

2,3,5,6-tetra- (4'-normal-butyl) phenyl-1,4-diiodobenzene (134 mg, 0.156 mmol), 1,4-benzenediboronic acid bispinacol ester (52 mg, 0.156 mmol), tetrakis triphenylphosphine palladium (9 mg, 0.0078 mmol), aliquat 336 (1.3 mg, 0.0031 mmol), 2M K2CO3 (4.2 mL, 8.426 mmol), toluene (12 mL) After filling with argon at −78 ° C., the mixture was stirred for 72 hours under reflux conditions. Bromobenzene (32 mg, 0.203 mmol) dissolved in toluene (2 mL) was added to the reaction solution, which was then stirred for 24 hours under reflux conditions. The reaction solution was poured into a mixed solution of methanol (300 mL) / conc. Hydrochloric acid (25), stirred at room temperature for 4 hours, and filtered. The filtered solid was stirred with acetone (100 mL) at 60 ℃ for 1 hour and then filtered. The filtered solid was stirred with reflux conditions with tetrahydrofuran (100 mL) for 2 hours and then filtered. The filtered solution was concentrated, methanol (30 mL) was added and the resulting solid was filtered. (59 mg, yield: 55%)

FIG. 1 shows ¹ H (A) and ¹³ C-NMR (B) spectra of 2c, and FIG. 2 shows Matrix-Assisted Laser Desorption Ionization (MALDI-TOF) spectra (A) of 2c.

1 H NMR (300 MHz, CDCl 3) δ 6.64-6.62 (m, 10H), 6.42-6.39 (m, 8H), 6.07 (bs, 2H), 2.40 (bs, 8H), 1.46-1.41 (m, 8H), 1.25 -1.16 (m, 8H), 0.87-0.82 (m, 12H)

Example 11 Preparation of 2d

2,3,5,6-tetra- (4'-tert-butyl) phenyl-1,4-diiodobenzene (430 mg, 0.5 mmol), 1,4-benzenediboronic acid bispinacol Ester (165 mg, 0.5 mmol), tetrakis triphenylphosphine palladium (29 mg, 0.025 mmol), aliquat 336 (4 mg, 0.01 mmol), 2M K2CO3 (13.5 mL, 27 mmol), toluene (40 mL) Charged with argon at -78 ℃ and stirred for 6 days under reflux conditions. A solution of bromobenzene (102 mg, 0.65 mmol) dissolved in toluene (2 mL) was added to the reaction solution, followed by stirring for 24 hours under reflux conditions. The reaction solution was poured into a mixed solution of methanol (500 mL) / conc. Hydrochloric acid (60), stirred at room temperature for 4 hours, and filtered. The filtered solid was stirred with acetone (100 mL) at room temperature for 2 hours and then filtered. The filtered solid was stirred with reflux conditions with tetrahydrofuran (100 mL) for 2 hours and then filtered. The filtered solution was concentrated, methanol (20 mL) was added and the resulting solid was filtered. (234 mg, yield: 69%)

2 shows the MALDI-TOF spectrum of 2d.

1 H NMR (300 MHz, CDCl 3) δ 6.98-6.96 (m, 4H), 6.71-6.68 (m, 4H), 6.45-6.43 (m, 4H), 6.32-6.30 (m, 4H), 6.13 (bs, 4H) , 1.16 (s, 36)

Example 12 Preparation of 2g

2,3,5,6-tetra- (4'-octyloxy) phenyl-1,4-diiodobenzene (110 mg, 0.0958 mmol), 1,4-benzenediboronic acid bispinacol ester ( 32 mg, 0.0958 mmol), tetrakis triphenylphosphine palladium (6 mg, 0.0048 mmol), aliquat 336 (1 mg, 0.0019 mmol), 2M K2CO3 (2.6 mL, 5.178 mmol), toluene (5 mL) was added- After filling with argon at 78 ° C., the mixture was stirred for 6 days under reflux conditions. A solution of bromobenzene (20 mg, 0.125 mmol) dissolved in toluene (1 mL) was added to the reaction solution, followed by stirring for 24 hours under reflux conditions. The reaction solution was poured into a mixed solution of methanol (200 mL) / conc. Hydrochloric acid (20), stirred at room temperature for 4 hours, and filtered. The filtered solid was stirred with acetone (100 mL) at room temperature for 1 hour and then filtered. The filtered solid was stirred with reflux conditions with tetrahydrofuran (100 mL) for 2 hours and then filtered. The filtered solution was concentrated, methanol (20 mL) was added and the resulting solid was filtered. (72mg, yield: 77%)

2 shows the MALDI-TOF spectrum of 2g.

1 H NMR (300 MHz, CDCl 3) δ 6.59-6.34 (m, 16H), 6.10 (bs, 4H), 3.78 (bs, 8H), 1.69 (bs, 8H), 1.39-1.27 (m, 40H), 0.88-0.84 (m, 12H)

Example 13 Preparation of 3 g

Polymer (23 mg) and dichloromethane (200 mL) were added and filled with argon. Ferric chloride (260 mg, 1.61 mmol) was dissolved in nitromethane (0.7 mL) and stirred at room temperature for 24 hours. After distillation under reduced pressure to remove the solvent, the reaction solution was poured into a mixed solution of methanol (200 mL) / conc. Hydrochloric acid (60 mL), stirred at room temperature for 24 hours, and filtered. The filtered solid was stirred together with acetone (200 mL) under reflux conditions for 72 hours and then filtered. The filtered solid was dissolved in tetrahydrofuran (20 mL), methanol (40 mL) was added thereto, and the produced solid was filtered. (6 mg, yield: 26%)

FIG. 3 shows Raman spectra of graphene prepared from Example 13 (Laser wavelength: 514 nm; Laser power: 3 mW; Laser spot size: 5 um). 4 and 5 show scanning tunneling microscope (STM) images of graphene prepared from Example 13. FIG.

1 H NMR (300 MHz, THF) δ 2.04 (s, 32H), 1.49-0.86 (m, 32H)

Claims (10)

New two-dimensional graphene nanoribbons represented by the formula (1).
[Formula 1]

[In Formula 1, R ¹ is a hydrogen atom, (C1-C8) alkyl, (C1-C10) alkoxy, di (C1-C4) alkylamino (C1-C4) alkoxy and

Is selected from R ⁵ is (C 1 -C 4) alkyl, a is 1-4, b is 1-4; R ² is

, And aryl; R ³ is selected from hydrogen atom, iodine atom and aryl; n is 2 to 20.]
The method of claim 1,
R ¹ is hydrogen atom, methyl, ethyl, n-propyl, n-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, n-butoxy, tert-butoxy, n-pentyloxy, neo Pentyloxy, n-hexyloxy, n-octyloxy, dimethylaminomethoxy, diethylaminomethoxy, dimethylaminoethoxy, diethylaminoethoxy and 2- (2- (2-methoxyethoxy) Oxy) ethoxy; R ² is

, And phenyl; R ³ is selected from a hydrogen atom and an iodine atom; 2 is a two-dimensional graphene nanoribbon, characterized in that 8 to 16.
(a) reacting hexabromobenzene, Grignard reagent, and iodine (I ₂ ) at room temperature to obtain a compound of formula 4;
(b) adding a palladium-based catalyst, a phase-transfer catalyst, a mixture of a base compound, and a compound of formula 5 to the compound of formula 4 in step (a) to polymerize to obtain a compound of formula 6; And
(c) dehydrogenating the compound of Chemical Formula 6 in step (b) to prepare a compound of Chemical Formula 2;
Method for producing a two-dimensional graphene nanoribbons comprising a.
(2)

[Chemical Formula 4]

[Chemical Formula 5]

[Formula 6]

[In Formulas 2 and 4 to 6, R ¹ is a hydrogen atom, (C1-C8) alkyl, (C1-C10) alkoxy, di (C1-C4) alkylamino (C1-C4) alkoxy and

Is selected from R ⁵ is (C 1 -C 4) alkyl, a is 1-4, b is 1-4; n is 2 to 20.]
(a) reacting hexabromobenzene, Grignard reagent, and iodine (I ₂ ) at room temperature to obtain a compound of formula 4;
(b) adding a palladium-based catalyst, a phase-transfer catalyst, a mixture of a base compound, and a compound of formula 5 to the compound of formula 4 in step (a) to polymerize to obtain a compound of formula 6;
(c) adding bromo (C6-C30) aryl or phenylbromic acid to the compound of Formula 6 in step (b) to obtain a compound of Formula 7; And
(d) dehydrogenating the compound of Formula 7 to prepare a compound of Formula 3;
Method for producing a two-dimensional graphene nanoribbons comprising a.
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[In Formulas 3, 4, 6, and 7, R ¹ is a hydrogen atom, (C1-C8) alkyl, (C1-C10) alkoxy, di (C1-C4) alkylamino (C1-C4) alkoxy and

Is selected from R ⁵ is (C 1 -C 4) alkyl, a is 1-4, b is 1-4; R ⁶ is aryl; R ⁷ is selected from a hydrogen atom and an iodine atom; n is 2 to 20.]
delete The method according to claim 3 or 4,
The palladium-based catalyst is Pd ₂ (di-benzylidene-acetone) ₃ CHCl ₃ , Pd (OAc) ₂ , ((di-phenyl-phosphanyl) -ferrocene) PdCl ₂ , (PPh ₃ ) ₂ PdCl ₂ , (di-phenyl -phosphino-phenyl-
ether) PdCl ₂ , Pd (CH ₃ CN) ₂ Cl ₂ , Pd (PhCN) ₂ Cl ₂ , Pd (PPh ₃ ) ₄ and the production of two-dimensional graphene nanoribbons characterized in that at least one selected from PdCl ₂ Way.
The method according to claim 3 or 4,
The phase-transfer catalyst is 15-crown-5, 18-crown-6, tetrabutylammonium hydrogensulfate, tetrabutylammonium bromide, tetrabutylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium chloride, methyltridecylammonium chloride , Methyltrioctylammonium chloride (Aliquat 336) and methyltributylammonium chloride is a method for producing a two-dimensional graphene nanoribbon, characterized in that at least one.
The method according to claim 3 or 4,
The base compound is a method for producing two-dimensional graphene nanoribbon, characterized in that at least one selected from K ₂ CO ₃ , Na ₂ CO ₃ , NaHCO ₃ , KHCO ₃ and CaCO ₃ .
The method according to any one of claims 3 and 4,
The Grignard reagent of step (a) is R ¹¹ -phenyl-MgBr, or a mixture of R ¹¹ -phenyl-Br and Mg, wherein R ¹¹ is a hydrogen atom, (C 1 -C 8) alkyl and (C 1 -C 4) alkoxy Method for producing a two-dimensional graphene nanoribbon, characterized in that selected from.
The method according to any one of claims 3 and 4,
R ¹ is hydrogen atom, methyl, ethyl, n-propyl, n-butyl, tert-butyl, ethoxy, n-propoxy, n-butoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, n-octyloxy, dimethylaminomethoxy, diethylaminomethoxy, dimethylaminoethoxy, diethylaminoethoxy and 2- (2- (2-methoxyethoxy) ethoxy) Selected from oxy; R ⁶ is phenyl; R ⁷ is an iodine atom or a hydrogen atom; n is a method for producing a two-dimensional graphene nanoribbon, characterized in that 8 to 16.

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