WO2017131190A1

WO2017131190A1 - Polymer and method for producing same

Info

Publication number: WO2017131190A1
Application number: PCT/JP2017/003037
Authority: WO
Inventors: 健一郎伊丹; 英人伊藤; 裕太矢野; 雄平宮内; 伸彦三苫
Original assignee: 国立大学法人名古屋大学
Priority date: 2016-01-28
Filing date: 2017-01-27
Publication date: 2017-08-03
Also published as: JP6664710B2; JPWO2017131190A1

Abstract

Provided is a polymer which contains a polycyclic aromatic compound as a repeating unit and in which the polycyclic aromatic compound contained as a repeating unit is bonded to an adjacent polycyclic aromatic compound that is a repeating unit in such a way as to share one bond that constitutes a benzene ring in the polycyclic aromatic compound. The polymer is obtained through (co)polymerization of a polycyclic aromatic compound having a K region and a silole skeleton as a raw material or a polycyclic aromatic compound having a K region and a polycyclic aromatic compound having a silole skeleton as raw materials, is obtained using a method which has fewer steps and in which secondary reactions are suppressed, and can constitute a GNR in which the width and length are controlled. The repeating unit is preferably a repeating unit represented by general formula (1) [In the formula, * denotes the repeating unit site. m denotes an integer of 1 or higher. A denotes an aromatic ring having a K region. In cases where m is 2 or higher, the plurality of A moieties may be the same as, or different from, each other. R¹ and R³ each denote a hydrogen atom. R² and R⁴ may be the same as, or different from, each other, and each denote a branched chain alkyl group or a group represented by general formula (2) (In the formula, *, m, A, R¹ and R³ are as described above. R^2a denotes a branched chain alkyl group. At least one combination of R¹ and R^2a, R¹ and A, and R³ and A may bond to each other to form a ring.) At least one combination of R¹ and R², R³ and R⁴, R¹ and A, and R³ and A may bond to each other to form a ring.]

Description

Polymer and production method thereof

The present invention relates to a polymer and a method for producing the same.

Graphene nanoribbon (GNR) has high hole mobility, semiconducting properties, transparency, mechanical strength, flexibility, etc., so it can be used for semiconductors, solar cells, transparent electrodes, high-speed transistors, organic EL devices, etc. The application of is expected.

Since the physical properties of GNR depend on its width, length, and edge structure, precise synthesis with controlled width, length, and edge structure on the order of nm is indispensable for the development of the desired properties. is there. There are roughly two types of GNR synthesis methods: top-down method and bottom-up method. In particular, the latter is attractive in that GNR can be synthesized in large quantities by precisely controlling the edge structure and width. However, since GNR with a short length has poor solubility, it is not possible to employ a method in which a short GNR is synthesized and then used as an intermediate for further reaction. Therefore, a method for synthesizing a long GNR by causing a polymerization reaction from a highly soluble substrate compound with a short number of steps is required.

As a general synthesis of nano graphene, the coupling reaction of aromatic ring components and the Diels-Alder reaction are used, and finally graphene is formed by a dehydrocyclization reaction (see, for example, Non-Patent Document 1). A similar method is even adopted in the synthesis of GNR.

However, since the method of Non-Patent Document 1 is a multistage reaction, the yield is low, and a side reaction occurs, so that it is not necessarily a highly versatile method.

Therefore, an object of the present invention is to provide a method for synthesizing a polymer constituting GNR having a controlled width and length by a method with few steps and suppressing side reactions.

As a result of intensive studies to solve the above problems, the present inventors have found that a polycyclic aromatic compound having a K region and a silole skeleton in the presence of a silver compound and o-chloranil and, if necessary, a palladium compound. It was found that by reacting, a polymer constituting a GNR having a controlled width, length and edge structure can be synthesized in one step without causing side reactions. In this reaction, when a polycyclic aromatic compound having a K region and a polycyclic aromatic compound having a silole skeleton are used as a substrate, a polymer constituting GNR can be synthesized in the same manner. This polymer is a polymer in which a polycyclic aromatic structure having a plurality of K regions is used as a repeating unit, and the K regions of the repeating unit are condensed. Based on such knowledge, the present inventors have further studied and completed the present invention. That is, the present invention includes the following configurations.

Item 1. A polycyclic aromatic compound as a repeating unit, and the polycyclic aromatic compound as the repeating unit is used as an adjacent repeating unit so as to share one bond constituting the benzene ring in the polycyclic aromatic compound. A polymer bound to a polycyclic aromatic compound.

Item 2. Item 2. The polycyclic aromatic compound having a K region and a silole skeleton, or the (co) polymerization using a polycyclic aromatic compound having a K region and a polycyclic aromatic compound having a silole skeleton as raw materials. polymer.

Item 3. General formula (1):

[In formula, * shows a repeating site | part. m represents an integer of 1 or more. A represents an aromatic ring having a K region. When m is an integer of 2 or more, the plurality of A may be the same or different. R ¹ and R ³ represent a hydrogen atom. R ² and R ⁴ are the same or different and are a branched alkyl group, or general formula (2):

(In the formula, *, m, A, R ¹ and R ³ are the same as above. R ^2a represents a branched alkyl group. At least ^one of R ¹ and R ^2a , R ¹ and A, and R ³ and A One may be bonded to each other to form a ring.)
The group represented by these is shown. At least ^one of R ¹ and R ² , R ³ and R ⁴ , R ¹ and A, and R ³ and A may be bonded to each other to form a ring. ]
The polymer of claim |

item

1 or 2 which has a repeating unit represented by these.

Item 4. The repeating unit is represented by the general formulas (1A) to (1F):

[Wherein, *, R ^2a and R ^4a are the same as defined above. Y is the same or different and represents CH or N. R ^2b and R ^4b are the same or different and represent a branched alkyl group. ]
Item 4. The polymer according to any one of Items 1 to 3, which is a repeating unit represented by any one of:

Item 5. Item 5. The polymer according to any one of Items 1 to 4, wherein the number average molecular weight is 10,000 or more.

Item 6. Item 6. A graphene nanoribbon comprising the polymer according to any one of Items 1 to 5.

Item 7. Item 7. The graphene nanoribbon according to Item 6, having a width of 0.5 to 10.0 nm and a length of 10 nm or more.

Item 8. Item 6. The method for producing a polymer according to any one of Items 1 to 5,
(1) a step of reacting a polycyclic aromatic compound having a K region and a silole skeleton in the presence of a palladium compound and o-chloranil; or (2) a polycycle having a K region in the presence of a palladium compound and o-chloranil. A production method comprising a step of reacting an aromatic compound with a polycyclic aromatic compound having a silole skeleton.

Item 9. In the step (1), the polycyclic aromatic compound having a K region and a silole skeleton is represented by the general formula (3A) or (3B):

[Wherein, A is the same or different and represents an aromatic ring having a K region. R ¹ and R ³ represent a hydrogen atom. R ^2a and R ^4a are the same or different and represent a branched alkyl group. At least ^one of R ¹ and R ^2a , R ³ and R ^4a , R ¹ and A, and R ³ and A may be bonded to each other to form a ring. R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. ]
Item 9. The production method according to Item 8, which is a compound represented by:

Item 10. In the step (2), the polycyclic aromatic compound having a K region is represented by the general formula (4):

[Wherein, A is the same or different and represents an aromatic ring having a K region. R ¹ and R ³ represent a hydrogen atom. R ² and R ⁴ are the same or different, and are a branched alkyl group, or general formula (4A):

(In the formula, A, R ¹ and R ³ are the same as defined above. R ^2a represents a branched alkyl group. At least one of R ¹ and R ^2a , R ¹ and A, and R ³ and A And may be linked to form a ring.)
The group represented by these is shown. At least ^one of R ¹ and R ² , R ³ and R ⁴ , R ¹ and A, and R ³ and A may be bonded to each other to form a ring. ]
Item 10. The production method according to Item 8 or 9, which is a compound represented by:

Item 11. In the step (2), the polycyclic aromatic compound having a silole skeleton is represented by the general formula (5):

[Wherein, B are the same or different and each represents an aromatic ring having a silole skeleton. R ¹ and R ³ represent a hydrogen atom. R ^2a and R ^4a are the same or different and represent a branched alkyl group. At least ^one of R ¹ and R ^2a , R ³ and R ^4a , R ¹ and B, and R ³ and B may be bonded to each other to form a ring. R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. ]
Item 11. The production method according to any one of Items 8 to 10, which is a compound represented by:

Item 12. Item 12. The production method according to any one of Items 8 to 11, wherein the steps (1) and (2) are performed in the presence of a silver compound.

Item 13. The silver compound contains AgSbF ₆ or AgBF _4, method according to claim 12.

Item 14. The amount of the silver compound used is based on 1 mol of the polycyclic aromatic compound having the K region and a silole skeleton, the polycyclic aromatic compound having the K region, or the polycyclic aromatic compound having the silole skeleton. Item 14. The production method according to Item 12 or 13, which is 0.5 to 5.0 mol.

Item 15. The amount of the palladium compound used is 1 mol of the polycyclic aromatic compound having the K region and a silole skeleton, the polycyclic aromatic compound having the K region, or the polycyclic aromatic compound having the silole skeleton. Item 15. The production method according to any one of Items 8 to 14, which is 0.07 to 5.0 mol.

Item 16. Item 8. A laminate in which the graphene nanoribbon according to item 6 or 7 is disposed on a conductive material.

Item 17. Item 17. The laminate according to Item 16, wherein the conductive material is graphene.

According to the present invention, the polycyclic aromatic compound is a repeating unit, and the polycyclic aromatic compound as the repeating unit shares one bond constituting the benzene ring in the polycyclic aromatic compound, Since a polymer bonded to a polycyclic aromatic compound as an adjacent repeating unit can be provided, a graphene nanoribbon having a controlled width and length can be produced. According to the present invention, by reacting a polycyclic aromatic compound having a K region and a silole skeleton in the presence of a silver compound and o-chloranil and, if necessary, a palladium compound, side reactions can be carried out in only one step. Without generation, it is possible to synthesize a polymer constituting a GNR with a controlled width, length and edge structure. In this reaction, when a polycyclic aromatic compound having a K region and a polycyclic aromatic compound having a silole skeleton are used as a substrate, a polymer constituting GNR can be synthesized in the same manner.

2 is a graph showing the results of ¹ H-NMR in Test Example 1. 2 is a UV / Vis absorption and fluorescence spectrum of Test Example 1. 4 is a graph showing the results of FT-ATR-IR analysis of Test Example 1. 4 is a Raman spectrum of Test Example 1. 4 is a graph showing the results of ¹ H-NMR in Test Example 2. 4 is a UV / Vis absorption and fluorescence spectrum of Test Example 2. It is the UV / Vis absorption and fluorescence spectrum of pyrene in THF solution. 6 is a graph showing the results of FT-ATR-IR analysis in Test Example 2. 4 is a Raman spectrum of Test Example 2. 6 is a graph showing the results of HPLC analysis of Test Example 3. 6 is a UV / Vis absorption and fluorescence spectrum of Test Example 3. 2 is an IR spectrum of the polymer obtained in Example 12. 2 is a UV / Vis absorption spectrum of the polymer obtained in Example 12. 4 is an IR spectrum of the polymer obtained in Example 13. 2 is a UV / Vis absorption spectrum and a fluorescence spectrum of the polymer obtained in Example 13. 6 is an AFM image of a polymer whose arrangement was observed in Test Example 4. FIG. 6 is a measurement result of DC resistivity of a graphene field effect transistor before and after dropping a GNR solution in Test Example 5. FIG.

1. Polymer The polymer of the present invention has a polycyclic aromatic structure as a repeating unit, and the polycyclic aromatic compound as the repeating unit shares one bond constituting the benzene ring in the polycyclic aromatic compound. Thus, it is a polymer bonded to a polycyclic aromatic compound as an adjacent repeating unit. Such a polymer of the present invention is a (co) polymerization using a polycyclic aromatic compound having a K region and a silole skeleton, or a polycyclic aromatic compound having a K region and a polycyclic aromatic compound having a silole skeleton as raw materials. It can be obtained by (polymerization or copolymerization). The K region means a convex portion at the end of the armchair that the polycyclic aromatic compound has as follows. That is, the polymer of this invention is comprised by the convex parts of a polycyclic aromatic compound condensing.

In such a polymer of the present invention, since the K regions of the repeating units are bonded so as to share one bond constituting the benzene ring, the following structure is formed at the position where the repeating units are bonded to each other. Have

[In the formula, a site indicated by a dotted line means a condensation site between repeating units. * Means a bond. Adjacent * s may combine with each other to form a ring. ]
Such a repeating unit possessed by such a polymer is a polymer obtained by condensing a repeating unit with a polycyclic aromatic structure having a phenanthrene skeleton, but only if the polycyclic aromatic structure having a phenanthrene skeleton is used. In addition, a structure in which an aromatic ring or a heteroaromatic ring is condensed to phenanthrene is also included. As such a repeating unit, for example, the general formula (1):

(In the formula, *, m, A, R ¹ and R ³ are the same as above. R ^2a represents a branched alkyl group. At least ^one of R ¹ and R ^2a , R ¹ and A, and R ³ and A One may be bonded to each other to form a ring.)
The group represented by these is shown. At least ^one of R ¹ and R ² , R ³ and R ⁴ , R ¹ and A, and R ³ and A may be bonded to each other to form a ring. ]
The repeating unit represented by these is mentioned.

That is, R ² in the general formula (1) includes R ^2a (branched alkyl group) and a group represented by the general formula (2). R 2 in the general formula (1) ^{Examples of} ⁴ include R ^4a (branched alkyl group) and a group represented by the general formula (2).

In the polymer of the present invention, two bonds extending from the ring A in the above repeating unit are combined with two benzene rings in the adjacent repeating unit to form a benzene ring. That is, the polymer of the present invention has the general formula (6):

[Wherein, m, A, R ¹ , R ² , R ³ and R ⁴ are the same as defined above. The dotted line means that a similar structure follows. ]
It has the structure represented by these.

In general formulas (1), (2) and (6), m is an integer of 1 or more. Depending on the number of m, the width of the graphene nanoribbon made of the resulting polymer varies. That is, by adjusting m, the width of the graphene nanoribbon made of the resulting polymer can be adjusted. From the viewpoint of ease of synthesis of the polymer of the present invention and the ability to increase the molecular weight (the number of repetitions can be increased), m is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. .

In the general formulas (1), (2), and (6), A is an aromatic ring having a K region (that is, an armchair end portion or a convex portion). A may be bonded to at least one of R ¹ and R ³ to form a ring.In this case, A is bonded to at least one of R ¹ and R ³ so as to have a K region. It is preferable to form.

As such a ring A, for example,

[Wherein, R ² and R ⁴ are the same as defined above. Y is the same or different and represents CH or N. ]
Etc.

R ¹ and R ³ are hydrogen atoms. R ¹ and / or R ³ may combine with A to form a ring. Examples of the ring formed at this time include a benzene ring and a naphthalene ring.

The branched chain alkyl group represented by R ² and R ⁴ may be appropriately selected depending on the type of the substrate, but the following repeating units (1A), (1C), (1E), (1F), etc. From the viewpoint of solubility, R ^2a of the repeating unit (1D) described later is represented by the general formula (7):

[Wherein, R ⁷ are the same or different and each represents a C 1-4 alkyl group. R ⁸ represents a C6-10 alkyl group. ]
The group represented by these is preferable.

Examples of R ⁷ in the general formula (7) include C1-4 alkyl groups such as a methyl group, an ethyl group, and an n-propyl group. These alkyl groups are preferably selected in accordance with the distance between the repeating units in consideration of the steric environment. For example, when the ring A is a benzene ring, that is, when the repeating unit has a structure having a pyrene skeleton, R ⁷ must be an ethyl group from the viewpoint of easily obtaining a higher molecular weight polymer. Is preferred.

Examples of R ⁸ in the general formula (7) include C7-10 alkyl groups such as an n-heptyl group, an n-octyl group, and an n-nonyl group. These alkyl groups can be appropriately selected in consideration of the solubility of the solvent used.

Therefore, examples of the branched alkyl group represented by R ² and R ⁴ include, for example, general formulas (7A) to (7C):

[Wherein R ⁷ is the same as defined above. ]
The group represented by general formula (7B) is more preferable.

In addition, R ^4a of the repeating unit (1D) described later is represented by the general formula (8):

[Wherein R ⁷ is the same or different and represents a C 1-8 alkyl group. ]
The group represented by these is preferable.

Examples of R ⁹ in the general formula (8) include C1-8 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. These alkyl groups are preferably selected in accordance with the distance between the repeating units in consideration of the steric environment. For example, with respect to R ^4a of the repeating unit (1D) described later, it is preferable that all of R ⁹ is n-pentyl from the viewpoint of easily obtaining a higher molecular weight polymer.

When R ² and R ⁴ are a group represented by the general formula (2), the branched alkyl group described above is preferable as the branched alkyl group represented by R ^2a .

R ¹ and R ² , R ³ and R ⁴ may be bonded to each other to form a ring. R ¹ and R ^2a may be bonded to each other to form a ring. As the ring formed at this time, for example,

[Wherein, R ^2a is the same as defined above. ]
Etc.

As repeating units satisfying the above conditions, for example, general formulas (1A) to (1F):

[Wherein, *, Y, R ^2a and R ^4a are the same as defined above. R ^2b and R ^4b are the same or different and represent a branched alkyl group. ]
The repeating unit represented by these is mentioned. Among these, from the viewpoint of easily obtaining a higher molecular weight polymer, the repeating unit represented by the general formula (1A) is preferable.

For this reason, the polymers of the present invention have the general formulas (6A) to (6F):

[Wherein, Y, R ^2a and R ^4a are the same as defined above. ]
It is preferable to have a structure represented by

In the polymer of the present invention, the number of repeating units (that is, the degree of polymerization) is not particularly limited and can be appropriately selected according to the required characteristics. For example, 10 to 1000 is preferable, and 30 to 500 is more preferable. The number of repeating units of the polymer of the present invention is calculated from the number average molecular weight measured in terms of polystyrene by gel permeation chromatography.

In the polymer of the present invention, the number average molecular weight is not particularly limited and can be appropriately selected according to necessary characteristics. For example, it is preferably 10,000 or more, more preferably 15000 to 300000, further preferably 20000 to 200000, 30000 ˜180,000 is particularly preferred. The number average molecular weight of the polymer of the present invention is measured in terms of polystyrene by gel permeation chromatography.

The width of the polymer of the present invention is preferably 0.5 to 2.0 nm, more preferably 0.7 to 1.5 nm. The width of the polymer means the width of the polycyclic aromatic skeleton portion that is the main skeleton, and is measured by observation with an atomic force microscope. When a compound represented by the following general formula (3A1), (4A), (5A) or the like is used as a substrate, a polymer having a width of about 0.7 nm is easily generated. When a compound represented by (3B), (5B) or the like is used, a polymer having a width of about 1.2 nm is likely to be produced. When a compound represented by the following general formula (4B) or the like is used as a substrate, A polymer with a width of about 1.5 nm is likely to be produced.

2. Polymer production method The polymer of the present invention described above is, for example,
(1) a step of reacting a polycyclic aromatic compound having a K region and a silole skeleton in the presence of a palladium compound and o-chloranil; or (2) a polycycle having a K region in the presence of a palladium compound and o-chloranil. It can be synthesized by a production method comprising a step of reacting an aromatic compound with a polycyclic aromatic compound having a silole skeleton.

By adopting such a method, in the step (1), a regioselective and continuous one-step π between the K region and the silole skeleton in the polycyclic aromatic compound having the K region and the silole skeleton. Extended polymerization (hereinafter also referred to as “APEX polymerization”) proceeds. In the step (2), regioselective and continuous APEX polymerization is performed between the K region in the polycyclic aromatic compound having a K region and the silole skeleton in the polycyclic aromatic compound having a silole skeleton. proceed. This polymerization reaction proceeds because the silole skeleton functions as a π-extended reagent. For this reason, the polymer of the present invention can be precisely synthesized by a reaction of only one step, and the number of processes can be greatly reduced.

(2-1) Polycyclic aromatic compound having a substrate K region and a silole skeleton In the production method of the present invention, a polycyclic aromatic compound having a K region and a silole skeleton that can be used as a substrate includes K at one end. There is no particular limitation as long as it is a polycyclic aromatic compound having a region and having a silole skeleton at the opposite end. For example, the general formula (3A) or (3B):

[Wherein, A, R ¹ , R ^2a and R ³ are the same as defined above. R ^4a represents a branched alkyl group. At least ^one of R ¹ and R ^2a , R ³ and R ^4a , R ¹ and A, and R ³ and A may be bonded to each other to form a ring. R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or an alkyl group. ]
The compound represented by these is preferable.

As the branched alkyl group represented by R ^4a , the above-described branched alkyl group is preferable.

Examples of the alkyl group represented by R ⁵ and R ⁶ include C1-4 alkyl groups such as a methyl group, an ethyl group, and an n-propyl group.

When at least one of R ¹ and R ^2a , R ³ and R ^4a , R ¹ and A, and R ³ and A are bonded to each other to form a ring, examples of the ring formed include those described above.

Examples of polycyclic aromatic compounds having a K region and a silole skeleton that satisfy the above conditions include, for example, general formulas (3A1), (3A2), and (3B1):

[Wherein, R ^2a , R ^4a , R ⁵ and R ⁶ are the same as defined above. ]
The compound represented by these is mentioned. Specifically, as a polycyclic aromatic compound having a K region and a silole skeleton, for example,

Etc. Among these, the compound represented by the general formula (3A1) is preferable from the viewpoint of easily obtaining a higher molecular weight polymer.

Polycyclic aromatic compound having a K region In the production method of the present invention, the polycyclic aromatic compound having a K region that can be used as a substrate is particularly a polycyclic aromatic compound having a K region at both ends. Not limited. For example, general formula (4):

[Wherein, A, R ¹ , R ² , R ³ and R ⁴ are the same as defined above. At least ^one of R ¹ and R ² , R ³ and R ⁴ , R ¹ and A, and R ³ and A may be bonded to each other to form a ring. ]
The compound represented by these is mentioned.

When at least one of R ¹ and R ² , R ³ and R ⁴ , R ¹ and A, and R ³ and A are bonded to each other to form a ring, examples of the ring formed include those described above.

Examples of polycyclic aromatic compounds having a K region that satisfy the above conditions include, for example, general formulas (4A) to (4B):

[Wherein, Y, R ^2a and R ^4a are the same as defined above. ]
The compound represented by these is mentioned. Specifically, as a polycyclic aromatic compound having a K region, for example,

Etc.

Polycyclic aromatic compound having a silole skeleton In the production method of the present invention, the polycyclic aromatic compound having a silole skeleton that can be used as a substrate is a polycyclic aromatic compound having a silole skeleton at both ends. Not limited. For example, general formula (5):

[Wherein, R ¹ , R ^2a , R ³ , R ^4a , R ⁵ and R ⁶ are the same as defined above. B is the same or different and represents an aromatic ring having a silole skeleton. At least ^one of R ¹ and R ^2a , R ³ and R ^4a , R ¹ and B, and R ³ and B may be bonded to each other to form a ring. ]
The compound represented by these is preferable.

In the general formula (5), B is an aromatic ring having a silole skeleton. As such a ring B, for example,

[Wherein, R ⁵ and R ⁶ are the same as defined above. ]
Etc.

R ¹ and / or R ³ may combine with B to form a ring. R ¹ and R ^2a , R ³ and R ^4a may be bonded to each other to form a ring. Examples of the ring formed at this time include a benzene ring and a naphthalene ring.

Examples of the polycyclic aromatic compound having a silole skeleton that satisfies the above conditions include, for example, general formulas (5A) to (5B):

[Wherein, R ^2a , R ^4a , R ⁵ and R ⁶ are the same as defined above. ]
The compound represented by these is mentioned. Specifically, as a polycyclic aromatic compound having a silole skeleton, for example,

Etc.

In the production method of the present invention, when step (2) is employed, that is, when a polycyclic aromatic compound having a K region is reacted with a polycyclic aromatic compound having a silole skeleton, a polycyclic having a silole skeleton The amount of the aromatic compound used is preferably from 0.2 to 3.0 mol, more preferably from 0.3 to 2.0 mol, more preferably from 0.5 mol to 1 mol of the polycyclic aromatic compound having a K region, from the viewpoint of easily obtaining a higher molecular weight polymer. More preferred is ˜1.5 mol.

(2-2) Palladium Compound In the production method of the present invention, a palladium compound is used as a catalyst. When no palladium compound is used, the polymerization reaction hardly proceeds and it is difficult to obtain the polymer of the present invention.

Examples of the palladium compound include a known palladium compound as a catalyst for synthesis of a polymer compound and the like, and a divalent palladium compound is preferable from the viewpoint of easily obtaining a higher molecular weight polymer. Examples of palladium compounds that can be used include Pd (OH) ₂ , Pd (OCOCH ₃ ) ₂ , Pd (OCOCF ₃ ) ₂ , Pd (acac) ₂ , PdCl ₂ , PdBr ₂ , PdI ₂ , Pd (NO ₃ ) ₂ , Pd (CH ₃ CN) ₄ (SbF ₆ ) _{2 and the} like. Acac means acetylacetonate. In the present invention, by using a weak cationic palladium compound, it is difficult to collapse the silole skeleton of the substrate, and from the viewpoint of easily obtaining a higher molecular weight polymer, Pd (OH) ₂ , Pd (OCOCH ₃ ) ₂ , Pd (OCOCF ₃ ) ₂ , PdBr ₂ , PdI ₂ , Pd (CH ₃ CN) ₄ (SbF ₆ ) ₂ etc. are preferred, Pd (OCOCH ₃ ) ₂ , Pd (OCOCF ₃ ) ₂ , PdBr ₂ , PdI ₂ , Pd ( CH ₃ CN) ₄ (SbF ₆ ) ₂ is more preferable, and Pd (OCOCF ₃ ) ₂ is more preferable.

The amount of the palladium compound can be appropriately selected depending on the type of the substrate, and from the viewpoint of easily obtaining a higher molecular weight polymer, for example, the polycyclic aromatic compound having the K region as a substrate and a silole skeleton, 0.07 to 5.0 mol is preferable, 0.15 to 4.0 mol is more preferable, and 0.3 to 3.0 mol is more preferable with respect to 1 mol of the polycyclic aromatic compound having the K region or the polycyclic aromatic compound having the silole skeleton. 0.6 to 2.0 mol is particularly preferable.

(2-3) o-chloranil In the production method of the present invention, o-chloranil is used as an oxidizing agent. When o-chloranil is not used, the polymerization reaction hardly proceeds and the polymer of the present invention cannot be obtained. Instead of o-chloranil, other oxidizing agents (p-chloranil, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 3,5-di-t-butyl-1,2- Similarly, when benzoquinone, CuCl ₂ or the like is used, the polymerization reaction hardly proceeds and the polymer of the present invention cannot be obtained.

The amount of o-chloranil used can be appropriately selected depending on the type of substrate. From the viewpoint of easily obtaining a higher molecular weight polymer, for example, a polycyclic aromatic compound having the K region as a substrate and a silole skeleton. The polycyclic aromatic compound having the K region or the polycyclic aromatic compound having the silole skeleton is preferably 0.5 to 5.0 mol, more preferably 1.0 to 3.0 mol, and even more preferably 1.5 to 2.5 mol. preferable.

(2-4) Silver Compound In the production method of the present invention, steps (1) and (2) are preferably performed in the presence of a silver compound. By using a silver compound, it is easy to obtain a higher molecular weight polymer.

The silver compound is not particularly limited, and is an organic silver compound such as silver acetate, silver pivalate (AgOPiv), silver trifluoromethanesulfonate (AgOTf), silver benzoate (AgOCOPh); silver nitrate, silver fluoride, silver chloride, Inorganic silver such as silver bromide, silver iodide, silver sulfate, silver oxide, silver sulfide, silver tetrafluoroborate (AgBF ₄ ), silver hexafluorophosphate (AgPF ₆ ), silver hexafluoroantimonate (AgSbF ₆ ) Inorganic silver compounds are preferred from the viewpoint of easily obtaining higher molecular weight polymers, such as silver tetrafluoroborate (AgBF ₄ ), silver hexafluorophosphate (AgPF ₆ ), silver hexafluoroantimonate (AgSbF ₆ ) and the like are more preferable, silver tetrafluoroborate (AgBF ₄ ), silver hexafluoroantimonate (AgSbF ₆ ) and the like are more preferable, and silver hexafluoroantimonate (AgSbF ₆ ) is particularly preferable. . These silver compounds can be used alone or in combination of two or more.

The amount of silver compound used can be appropriately selected depending on the type of substrate, and from the viewpoint of easily obtaining a higher molecular weight polymer, for example, a polycyclic aromatic compound having the K region as a substrate and a silole skeleton, 0.5 to 5.0 mol is preferable, 1.0 to 3.0 mol is more preferable, and 1.5 to 2.5 mol is more preferable with respect to 1 mol of the polycyclic aromatic compound having the K region or the polycyclic aromatic compound having the silole skeleton. . In addition, when using a some silver compound, it is preferable to adjust so that a total usage-amount will be in the said range.

(2-5) Others In the production method of the present invention, steps (1) and (2) are preferably performed in a solvent. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane (DCE), chloroform (CHCl ₃ ), carbon tetrachloride, and trichloroethylene (TCE); And aromatic halogenated hydrocarbons such as bromobenzene (PhBr) and 1,3,5-tribromobenzene (PhBr ₃ ). These can be used alone or in combination of two or more. Among these, in the present invention, aliphatic halogenated hydrocarbons, aromatic halogenated hydrocarbons, and the like are preferable from the viewpoint of easily obtaining a higher molecular weight polymer. Dichloroethane (DCE), chloroform (CHCl ₃ ), trichloroethylene (TCE) are preferable. ), Bromobenzene (PhBr), 1,3,5-tribromobenzene (PhBr ₃ ) and the like are more preferable, such as dichloroethane (DCE), trichloroethylene (TCE), 1,3,5-tribromobenzene (PhBr ₃ ), etc. Are more preferred, and dichloroethane (DCE) is particularly preferred.

In the production method of the present invention, in addition to the above components, additives can be appropriately used as long as the effects of the present invention are not impaired.

The production method of the present invention is preferably carried out under anhydrous conditions and under an inert gas atmosphere (nitrogen gas, argon gas, etc.), and the reaction temperature is usually preferably about 40 to 110 ° C., and preferably about 50 to 100 ° C. More preferred is 60 to 90 ° C. The reaction time can be a time during which the polymerization reaction proceeds sufficiently, and is usually preferably 10 minutes to 72 hours, more preferably 1 to 48 hours.

After completion of the reaction, the target polymer can be obtained through normal isolation and purification steps (metal removal by silica gel column chromatography, polymer separation or fractionation by gel permeation chromatography (GPC), etc.).

3. Graphene nanoribbon The graphene nanoribbon (GNR) of the present invention comprises the above-described polymer of the present invention. As described above, the polymer of the present invention is a polycyclic aromatic compound having a K region and a silole skeleton in the step (1), and has a K region in the step (2). APEX polymerization proceeds between the K region in the ring aromatic compound and the silole skeleton in the polycyclic aromatic compound having a silole skeleton.

For this reason, the width of the GNR of the present invention depends on the length of the substrate used in the production method. The length of the GNR of the present invention depends on the degree of polymerization (the number of repeating units) of the polymer of the present invention. Note that the length of the substrate, the general formula (3A), the length from R ² to R ⁴ in (3B) and from R ^2a in (5) to R ^4a length, the general formula (4) means. For this reason, the width of GNR can be controlled by changing the type of substrate, and the length of GNR can be controlled by changing the reaction conditions. Since the GNR of the present invention is a GNR having a uniform width and length, it is possible to synthesize a large amount of GNRs having a uniform width and length. As described above, according to the present invention, since the width and length of the GNR can be precisely controlled, fine adjustment of electronic physical properties and the like are also possible.

The width of the GNR of the present invention is preferably 0.5 to 10.0 nm, more preferably 0.6 to 2.0 nm, and even more preferably 0.7 to 1.5 nm. The GNR width means the distance between the central portion of the GNR and the central portion of the adjacent GNR, and is measured by observation with an atomic force microscope.

Further, the length of the GNR of the present invention is preferably 10 nm or more, more preferably 20 to 500 nm, further preferably 50 to 400 nm, and particularly preferably 100 to 300 nm. For example, in the production method of the present invention, if a silver compound is used in addition to a palladium compound and o-chloranil, a longer GNR is likely to be generated, and a silver compound other than a palladium compound and o-chloranil is not used. A GNR having a shorter length is likely to be generated. A long GNR composed of a polymer with a high degree of polymerization is expected to be applied to semiconductors, solar cells, etc., but even a short GNR composed of a polymer with a low degree of polymerization is suitable for organic EL devices, etc. Is expected to be applied.

Such a GNR of the present invention is excellent in film formability because of its high solubility in organic solvents such as chloroform, dichloromethane, tetrahydrofuran (THF) and ethyl acetate. Perylene bisimide oligomers are known to exhibit the highest power generation efficiency (conversion efficiency of about 8%) among molecules other than fullerenes as acceptor molecules for organic dye solar cells (Nat. Commun. 2015, Therefore, it is expected to be used as various charge transport materials for OLED, OFET, organic thin-film solar cells, etc. In particular, it is expected to lead to the creation of high-efficiency electron donor molecule groups and high-efficiency electron acceptor molecule groups for organic thin-film solar cells.

Also, the GNR of the present invention can increase the resistivity of the conductive material. For example, by placing GNR on graphene as a conductive material, the resistivity (especially direct current resistivity) of graphene can be increased. For this reason, it can be expected that a graphene field effect transistor having a desired resistivity can be obtained by using the GNR of the present invention.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

¹ H NMR (600 MHz, 400 MHz) and ¹³ C NMR (151 MHz) spectra were recorded in CDCl _{3 on} a JEOL ECA-600 spectrometer. ¹ H NMR chemical shift (δ) is expressed in relative parts per million (ppm) of tetramethylsilane (δ 0.00 ppm). Mass spectra were obtained with JEOL JMS-700. The HPLC chart indicates that the higher the molecular weight of the polymer, the more the peak on the left side. All reactions were performed using a dry solvent under an argon (Ar) gas atmosphere in a flame-dried glass container using standard vacuum line techniques.

[Synthesis Example 1: Synthesis of Compound 2]

First, diethyl ketone (compound 1; 1.06 mL, 10 mmol) and Grignard reagent (1.5 equivalents, 15 mmol) synthesized from 1-bromooctane and Mg are stirred in THF at -20 ° C, and then stirred at room temperature. It was made to react. The reaction was stopped by adding water to the reaction solution, extracted with diethyl ether, and the solvent was distilled off. The corresponding alcohol was then isolated by chromatography using hexane as a developing solvent (69%).

Next, the obtained alcohol (3-ethyl-undecan-3-ol) was reacted by vigorously stirring in concentrated hydrochloric acid for 1 hour. The reaction was stopped by adding water to the reaction solution, extracted with diethyl ether, and the solvent was distilled off. Thereafter, Compound 2 (3-chloro-3-ethylundecane) was isolated by chromatography using hexane as a developing solvent, and it was confirmed by ¹ H-NMR that the target compound was obtained (99%).
¹ H-NMR (400 MHz, CDCl ₃ ): 0.88 (t, 9H), 0.96 (t, 4H), 1.26 (s, 14H).

[Synthesis Example 2: Synthesis of Compound 11]

Fluorene (166 mg, 1 mmol) and Compound 2 (2.5 mmol) obtained in Synthesis Example 1 were allowed to react with AlCl ₃ (2.0 mmol) in CH ₃ NO ₂ at 40 ° C. for 24 hours. Crafts alkylation reaction was performed. The reaction was stopped by adding methanol to the reaction solution, the organic phase was washed with water, and then the solvent was distilled off. Compound 11 was isolated by chromatography using hexane as a developing solvent, and it was confirmed by ¹ H-NMR and FAB-MS that the desired compound was obtained (50%).
¹ H-NMR (400 MHz, CDCl ₃ ) 0.86-0.88 (m, 18), 1.06-1.32 (m, 36H), 3.85 (s, 2H), 7.31-7.39 (m, 2H), 7.41-7.45 (m , 2H), 7.66 (d, 2H). MS (FAB): m / z (%) = 530 [M ⁺ ] (100).

[Synthesis Example 3: Synthesis of Compound 7]

After reacting compound 11 (120 mg, 0.22 mmol) obtained in Synthesis Example 2 with n-butyllithium (n-BuLi; 1.0 equivalent) in THF at 0 ° C. for 3 minutes to cause a lithiation reaction , Paraformaldehyde ((CH ₂ O) n; 1.1 eq) was reacted in THF at 100 ° C. for 20 minutes. The reaction was stopped by adding a saturated aqueous NaHCO ₃ solution to the reaction solution, extracted with diethyl ether, and the solvent was distilled off. Further, P ₂ O ₅ (5.0 equivalents) was reacted with toluene in the toluene at room temperature for 1 hour to perform pinacol rearrangement. The reaction was stopped by adding a saturated aqueous NaHCO ₃ solution to the reaction solution, extracted with diethyl ether, and the solvent was distilled off. Upon completion of the reaction, the corresponding compound 7 was isolated by chromatography using hexane as a developing solvent, and it was confirmed by ¹ H-NMR and FAB-MS that the desired compound was obtained (60 mg, 47%, 2 step ).
¹ H-NMR (400 MHz, CDCl ₃ ): 0.81-0.83 (m, 18H), 1.23-126 (m, 36H), 7.53-7.96 (m, 2H), 8.23-8.25 (m, 2H), 8.55- 8.57 (m, 2H), 8.83-8.85 (m, 2H). MS (FAB): m / z (%) = 542 [M ^{· +} ] (100).

[Synthesis Example 4: Synthesis of Compound 8]

It is obtained after reacting compound 7 obtained in Synthesis Example 3 with t-butyllithium (t-BuLi; 4.0 equivalents) in TMEDA (4.0 equivalents) at 60 ° C. for 3 hours to cause a lithiation reaction. The compound and dimethyldichlorosilane (Me ₂ SiCl ₂ ; 2.0 equivalents) were stirred in THF at −78 ° C. and then reacted at room temperature for 24 hours. The reaction was stopped by adding a saturated aqueous NaHCO ₃ solution to the reaction solution, extracted with diethyl ether, and the solvent was distilled off. The reaction was completed and the corresponding compound 8 was isolated by chromatography using hexane as a developing solvent, and it was confirmed by ¹ H-NMR and FAB-MS that the target compound 8 was obtained (35%).
¹ H-NMR (600 MHz, CDCl ₃ ) 0.53 (s, 6H), 0.80-0.85 (m, 18H), 1.20-1.24 (m, 36H), 7.63-7.65 (m, 2H), 7.70 (s, 2H ), 7.84-7.85 (m, 2H). MS (FAB): m / z (%) = 599 [M + H ^{· +} ] (100).

[Example 1]
For compound 8 obtained in Synthesis Example 4, using Pd (CH ₃ CN) ₄ (SbF ₆ ) ₂ (5 mol%) and o-chloranil (2.0 equivalents) in dichloroethane (DCE) at 80 ° C. The reaction was allowed for 2 hours, 4 hours or 12 hours. After removing the metal using chromatography, the molecular weight was measured by HPLC. The results are shown in Table 1. When APEX polymerization was attempted under standard reaction conditions, dimers and trimers were detected with a matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (MALDI-TOF-MS) (YN-049). Next, when the reaction time was lengthened and all o-chloranil was consumed, 14-mer and 16-mer were also detected (YN-050). While the reaction mixture was stirred for 12 hours, all of the monomer was not consumed, suggesting that it is preferable to add more catalyst.

[Example 2]
Next, the same treatment as in Example 1 was performed except that the reaction time was 12 hours, and the amount of Pd (CH ₃ CN) ₄ (SbF ₆ ) ₂ used was a predetermined amount of 5 mol% to 1.0 equivalent. . The 5 mol% sample is YN-050 of Example 1. The results are shown in Table 2. As the amount of the catalyst used was increased to 10 mol%, 20 mol%, and 50 mol%, the monomer was completely consumed, and a polymer having a higher molecular weight was detected (YN-054, 055, 057). When the amount of the catalyst used was 1.0 equivalent, the number average molecular weight of the polymer of 1% or more was 25000 or more (YN-057). From these results, it can be understood that 1.0 equivalent of the catalyst is most effective.

[Example 3]
Next, the same treatment as in Example 2 was performed except that the amount of Pd (CH ₃ CN) ₄ (SbF ₆ ) ₂ used was 50 mol% and the reaction time was 6 hours or 12 hours. The sample for 12 hours is YN-055 of Example 2. The results are shown in Table 3. As a result, since no significant difference was observed, it can be understood that the product is not decomposed or oxidized during the reaction.

[Example 4]
Next, the amount of Pd (CH ₃ CN) ₄ (SbF ₆ ) ₂ used was 1.0 equivalent, and DCE was added so that the concentration of compound 8 obtained in Synthesis Example 4 was a predetermined concentration of 50 mM to 0.5 M. Except for this, the same treatment as in Example 2 was performed. The 50 mM sample is YN-057 of Example 2. The results are shown in Table 4. As the concentration of the substrate increases, a polymer with a higher molecular weight was detected by HPLC, but it can be understood that 0.1M is the most effective from the viewpoint of solubility.

[Example 5]
Next, the same treatment as in Example 4 was performed, except that various solvents were added so that the concentration of Compound 8 obtained in Synthesis Example 4 was 0.1M. The DCE sample is YN-060 of Example 4. The results are shown in Table 5. As a result, it can be understood that DCE is most effective.

[Example 6]
Next, the same treatment as in Example 4 was performed, except that DCE was added so that the concentration of Compound 8 obtained in Synthesis Example 4 was 0.1 M, and the heating conditions were variously changed. The sample at 80 ° C. and 12 hours is YN-060 of Example 4. The results are shown in Table 6. As a result, it can be understood that 80 ° C. and 12 hours are the most effective.

[Example 7]
Next, DCE was added so that the concentration of Compound 8 obtained in Synthesis Example 4 was 0.1 M, and the same treatment as in Example 4 was performed except that various oxidizing agents were used instead of o-chloranil. It was. The o-chloranil sample is YN-060 of Example 4. The results are shown in Table 7. As a result, when an oxidizing agent other than o-chloranil is used, the polymerization reaction does not proceed sufficiently and the polymer of the present invention cannot be obtained.

[Example 8]
Next, DCE was added so that the concentration of Compound 8 obtained in Synthesis Example 4 was 0.1 M, and the same treatment as in Example 4 was performed except that various palladium compounds and various silver compounds were used. . A sample of Pd (CH ₃ CN) ₄ (SbF ₆ ) ₂ and none is YN-060 of Example 4. The results are shown in Table 8.

[Example 9]
Next, the same treatment as in Example 8 was performed, except that PdCl ₂ was used as the palladium compound, AgSbF ₆ was used as the silver compound, and the usage amounts of the palladium compound and the silver compound were variously changed. The 1eq. And 2eq. Samples are YN-092 of Example 8. The results are shown in Table 9. As a result, it can be understood that 1 equivalent of the palladium compound and 2 equivalents of the silver compound are the most effective.

[Example 10]
Next, the same treatment as in Example 8 was performed except that AgSbF ₆ was used as the silver compound and various compounds were used as the palladium compound. A sample of PdCl ₂ is YN-092 of Example 8. The results are shown in Table 10. As a result, it can be understood that Pd (OCOCF ₃ ) ₂ is the most effective palladium compound.

[Example 11]
Next, the same treatment as in Example 10 was performed except that Pd (OCOCF ₃ ) ₂ was used as the palladium compound and the amount of the silver compound used was variously changed. The 2.0 eq. Sample is YN-104 of Example 10. The results are shown in Table 11.

From the above, it can be understood that the most preferable conditions for polymerization are the following conditions.

[Test Example 1]
In the same manner as in YN-060 of Example 4 (Table 4), the polymer of the present invention was obtained using 75 mg (1.3 mmol) of the substrate. Thereafter, when isolated by GPC, a polymer having a number average molecular weight of about 30,000, a polymer of 5 to 16 mer, a tetramer, a trimer and a dimer were obtained, and the silole skeleton disappeared in all.

In addition, as a result of APEX polymerization, from the result of ¹ H-NMR, the peak of the compound below the tetramer is significantly broadened, and the ¹ H signal transitions from 8.00 ppm to 9.80 ppm. Suggests existence. For this reason, in all the above-mentioned examples, it is suggested that APEX polymerization proceeds to obtain the polymer of the present invention. The results are shown in Table 12 and FIG.

Table 13 and FIG. 2 show the UV / Vis absorption and fluorescence spectra in the THF solution for the above Entry IV 1 (dimer), 3 (tetramer) and 5 (molecular weight of about 30000). In FIG. 2, a solid line is an absorption spectrum and a broken line is a fluorescence spectrum. All entries were measurable because they had sufficient solubility in organic solvents such as THF, dichloromethane, and chloroform. The main absorption bands of

Entry

3 and 5 were red-shifted compared to

Entry

1 and 2. The UV / Vis absorption spectra of

Entry

1 and 2 had almost the same characteristics. The band gaps of

Entry

1, 2, 3, and 5 mean the onset of the UV / Vis absorption spectrum, and are 4.5, 3.9, 3.7, and 3.2 eV, respectively. These results mean that the band gap decreases as the conjugate length increases. Furthermore, from the fluorescence spectra of

Entry

1, 2, 3, and 5, the maximum fluorescence wavelengths in the THF solution were 486, 497, 493, and 506 nm, respectively.

In addition, FT-ATR-IR analysis of each entry was performed. As a result, in each entry, a peak was observed at a position of 865 cm ⁻¹ of the aromatic CH bond in the concave site indicating APEX polymerization. The results are shown in FIG.

Next, from the result of Raman spectrum at 532 nm of Entry 5, although not clear due to fluorescence, D band (disorder band) at 1352 cm ^-1 and G band (graphite band) at 1524 cm ^-1 ). This result is consistent with GNR literature values. The results are shown in FIG.

These measurement results mean that GNR can be synthesized by APEX polymerization.

[Test Example 2]
In the same manner as in YN-111 of Example 11 (Table 11), the polymer of the present invention was obtained using 75 mg (1.3 mmol) of the substrate. Then, when isolated by GPC, a polymer having a number average molecular weight of about 1000000, a polymer having a number average molecular weight of about 150,000, a trimer, and a dimer were obtained, and the silole skeleton disappeared in all.

In addition, as a result of APEX polymerization, from the ¹ H-NMR result, the peak at 9.80 ppm is extremely broad, suggesting the presence of a concave site. For this reason, in all the above-mentioned examples, it is suggested that APEX polymerization proceeds to obtain the polymer of the present invention. The results are shown in Table 14 and FIG.

Table 15 and FIG. 6A show the UV / Vis absorption and fluorescence spectra in the THF solution for each entry obtained above. In FIG. 6A, the upper diagram is the absorption spectrum, and the lower diagram is the fluorescence spectrum. For reference, the optical spectrum of pyrene in a THF solution is shown in FIG. 6B. All entries were measurable because they had sufficient solubility in organic solvents such as THF, dichloromethane, and chloroform. The main absorption bands of Entry 1 (molecular weight 1000000 or more) and 2 (molecular weight 150,000) were shifted red compared to Entry 3 (trimmer). The UV / Vis absorption spectra of

Entry

1 and 2 had almost the same characteristics. The band gaps of

Entry

1, 2, 3, and 4 mean the onset of the UV / Vis absorption spectrum, and are 2.5, 2.8, 3.2, and 3.9 eV, respectively. These results mean that the band gap decreases as the conjugate length increases. Furthermore, from the fluorescence spectrum of each entry, the maximum fluorescence wavelengths in the THF solution were 451, 440, 416, and 431 nm, respectively.

In addition, FT-ATR-IR analysis of each entry was performed. As a result, in each entry, a peak was observed at the position of 865 cm ⁻¹ of the aromatic CH bond in the concave site indicating APEX polymerization. The results are shown in FIG.

Then, chromatic results of the Raman spectrum at 532nm of Entry 1, although not clear for fluorescent, D band at 1352cm ^-1 (disorder band), the G band (graphite band) to the position of 1524Cm ^-1 Was. This result is consistent with GNR literature values. The results are shown in FIG.

[Test Example 3]
In the same manner as YN-111 in Example 11 (Table 11), a polymer of the present invention was obtained using 150 mg (2.6 mmol) of the substrate. After that, when isolated by GPC, a polymer having a number average molecular weight of about 150,000, a polymer having a number average molecular weight of about 60000-70000, a polymer having a number average molecular weight of about 50000, a trimer, and a dimer are obtained. It disappeared.

In addition, as a result of APEX polymerization, from the ¹ H-NMR result, the peak at 9.80 ppm is extremely broad, suggesting the presence of a concave site. For this reason, in all the above-mentioned examples, it is suggested that APEX polymerization proceeds to obtain the polymer of the present invention. The results are shown in Table 16 and FIG.

Table 17 and FIG. 10 show the UV / Vis absorption and fluorescence spectra in the THF solution for each entry obtained above. In FIG. 10, the upper diagram is the absorption spectrum, and the lower diagram is the fluorescence spectrum. All entries were measurable because they had sufficient solubility in organic solvents such as THF, dichloromethane, and chloroform. The main absorption bands of Entry 1 (molecular weight of about 150,000) and 2 (molecular weight of about 60000-70000) were shifted in red compared to Entry 4 (trimmer). The UV / Vis absorption spectra of

Entry

1 and 2 had almost the same characteristics. The band gaps of

Entry

1, 2, 3, 4, and 5 mean the onset of the UV / Vis absorption spectrum, and are 2.5, 2.8, 3.2, 3.9, and 3.9 eV, respectively. These results mean that the band gap decreases as the conjugate length increases. Furthermore, from the fluorescence spectrum of each entry, the maximum maximum fluorescence wavelengths in the THF solution were 473, 473, 443, 442 and 430 nm, respectively.

In addition, FT-ATR-IR analysis of each entry was performed. As a result, in each entry, a peak was observed at the position of 865 cm ⁻¹ of the aromatic CH bond in the concave site indicating APEX polymerization.

Then, chromatic results of the Raman spectrum at 532nm of Entry 1, although not clear for fluorescent, D band at 1352cm ^-1 (disorder band), the G band (graphite band) to the position of 1524Cm ^-1 Was. This result is consistent with GNR literature values.

[Synthesis Example 5: Synthesis of Compound 10]

A reductive amination reaction was performed on compound 9 (12 mL, 59 mmol) by allowing ammonium acetate (NH ₄ OAc; 519 mmol) and NaBH ₃ CN (35 mmol) to act in methanol at room temperature for 54 hours. The reaction was stopped by adding concentrated hydrochloric acid to the reaction solution, and the solvent was distilled off. The crude product was dispersed in water and adjusted to pH = 10 using 1M aqueous NaOH. Chloroform was added to this solution for extraction, and then the solvent was distilled off to isolate the target compound 10. It was confirmed by ¹ H-NMR that the target compound was obtained (96%).
¹ H-NMR (400 MHz, CDCl ₃ ) 0.98 (s, 6H), 1.30-1.32 (m, 16H), 2.65 (s, 2H), 3.24 (m, 1H).

[Synthesis Example 6: Synthesis of Compound 12]

Bromination reaction was carried out by allowing Br ₂ (28 mmol) and I ₂ (6 mmol) to act on compound 11 (5.0 g, 13 mmol) in sulfuric acid at 85 ° C. for 24 hours. After the reaction, the reaction solution was cooled to room temperature, and the generated precipitate was collected by filtration. The precipitate was washed with water and dried to obtain the target compound 12 (96%, Crude). Since this compound is insoluble in any organic solvent, the compound was not identified and purified.

[Synthesis Example 7: Synthesis of Compound 13]

Compound 10 (39 mmol) obtained in Synthesis Example 5 was reacted at 150 ° C. for 4 hours in NMP with respect to Compound 12 (6.9 g, 12 mmol) obtained in Synthesis Example 6. The reaction solution cooled to room temperature was added to dilute hydrochloric acid to precipitate the product, which was collected by filtration. The precipitate was washed with water and dried to obtain a crude product of target compound 13. Thereafter, the target compound was isolated by chromatography and recrystallization, and it was confirmed by ¹ H-NMR and FAB-MS that the target compound 13 was obtained (39%).
^{1 H-NMR (400MHz, CDCl} 3): 0.83 (t, 12H), 1.25-1.27 (m, 16H), 1.84-186 (m, 2H), 1.87 (m, 4H), 2.24 (m, 4H), 5.18 (m, 2H), 8.61-8.63 (m, 6H). MS (FAB): m / z (%) = 854 [M ^{• +} ] (100), 699 [M-alkyl ^{• +} ] (43).

[Synthesis Example 8: Synthesis of Compound 14]

The compound 13 (0.015 mmol) obtained in Synthesis Example 7 was reacted with t-butyllithium (t-BuLi; 4.0 equivalents) in tetramethylethylenediamine (TMEDA; 4.0 equivalents) at 60 ° C. for 3 hours, followed by lithiation. After causing the reaction, the obtained compound and dimethylchlorosilane (Me ₂ SiHCl; 2.2 equivalents) were stirred in diethyl ether at −78 ° C. and then reacted at room temperature for 24 hours. The reaction was stopped by adding a saturated aqueous NaHCO ₃ solution to the reaction solution, extracted with diethyl ether, and the solvent was distilled off. Upon completion of the reaction, the corresponding compound 14 was purified by PTLC, and it was confirmed by FAB-MS that the target compound 14 was obtained (30%).
MS (FAB): m / z (%) = 813 [M ⁺ ] (100).

[Synthesis Example 9: Synthesis of Compound 15]

Reaction of compound 14 (30 mg; 0.04 mmol) obtained in Synthesis Example 8 with chlorotris (triphenylphosphine) rhodium (RhCl (PPh ₃ ) ₃ ; 5 mol%) in 1,4-dioxane at 135 ° C. for 3 hours I let you. The reaction was stopped by distilling off the solvent, and purification was performed by PTLC. It was confirmed by FAB-MS that the target compound 15 was obtained (30%).
m / z (%) = 810 [M ^{· +} ] (100).

[Example 12]

Next, using a commercially available compound 16 (2 mg, 0.004 mmol) as a substrate, compound 15 (3 mg, 0.004 mmol) obtained in Synthesis Example 9, and using 2.0 equivalents of Pd (OCOCF ₃ ) ₂ as a palladium compound, a silver compound As in Example 11, except that 4.0 equivalent of AgSbF ₆ was used and 4.0 equivalent of o-chloranil was used. The results are shown in Table 18.

From the above, the reaction proceeded not only in homopolymerization but also in copolymerization, and the polymer of the present invention could be obtained. FIG. 11 shows the IR spectrum of the obtained polymer. As a result, the presence of a carbonyl group and a concave site was suggested, suggesting that the polymer of the present invention was obtained. Moreover, the UV / Vis absorption spectrum of the obtained polymer is shown in FIG. As a result, it is suggested that an absorption band is present at a position of 200 to 600 nm.

[Synthesis Example 10: Synthesis of Compound 16]

Compound 10 (16 mmol) obtained in Synthesis Example 5 was reacted with Compound 11 (3.2 g, 8 mmol) in imidazole at 150 ° C. for 4 hours. The reaction solution cooled to room temperature was added to dilute hydrochloric acid to precipitate the product, which was collected by filtration. The precipitate was washed with water and dried to obtain a crude product of target compound 16. Thereafter, the target compound was isolated by chromatography using dichloromethane as a developing solvent, and it was confirmed by ¹ H NMR, ¹³ C NMR and FAB-MS that target compound 16 was obtained (96%).
¹ H NMR (400MHz, CDCl ₃ ) δ0.83 (t, 12H), 1.23-1.35 (m, 24H), 1.83-1.85 (m, 4H), 2.21-2.27 (m, 4H), 5.18-5.19 (m , 2H), 8.61-8.68 (m, 8H). 13 C NMR (150 MHz, CDCl 3) δ164.54, 134.24, 131.72, 120.96, 129.45, 126.22, 122.86, 54.83, 32.39, 31.86, 26.78, 22.68, 14.16 HRMS (FAB) m / z calcd for C ₄₆ H ₅₄ N ₂ O ₄ ⁺ [M] ⁺ : 698.4038, found 698.4042.

[Synthesis Example 11: Synthesis of Compound 17]

Bromination reaction was carried out by allowing Br ₂ (257 mmol) to act on the compound 16 (0.6 g, 0.9 mmol) obtained in Synthesis Example 10 in dichloromethane at room temperature for 2 days. The reaction was stopped by adding a saturated aqueous sodium thiosulfate solution to the reaction solution, followed by extraction with dichloromethane and evaporation of the solvent to obtain a crude product of the target compound 17. Thereafter, the target compound was isolated by chromatography using dichloromethane as a developing solvent, and it was confirmed by ¹ H NMR, ¹³ C NMR and FAB-MS that target compound 17 was obtained (96%).
¹ H NMR (400MHz, CDCl ₃ ) δ0.84 (t, 12H), 1.22-1.30 (m, 24H), 1.82-1.84 (m, 4H), 2.21-2.27 (m, 4H), 5.18-5.19 (m , 2H), 8.69 (d, J = 7.6 Hz, 2H), 8.92 (d, J = 7.6 Hz, 2H), 9.49-9.51 (m, 2H). ¹³ C NMR (150 MHz, CDCl ₃ ) δ164.27 , 163.79, 163.13, 162.59, 138.58, 137.91, 133.11, 132.98, 132.83, 132.63, 130.62, 130.50, 129.86, 129.39, 128.56, 128.20, 128.10, 127.30, 126.98, 123.88, 123.46, 123.15, 122.75, 551.628 , 55.08, 54.90, 32.45, 31.84, 26.70, 22.69, 14.18. HRMS (FAB) m / z calcd for C ₄₆ H ₅₂ N ₂ O ₄ Br ₂ ⁺ [M] ⁺ : 854.2293, found 854.2291.

[Synthesis Example 12: Synthesis of Compound 18]

Trimethylsilylacetylene (4.0 mmol), Pd (Ph ₃ ) ₄ (10 mol%) and CuI (10 mol%) were mixed in THF / diisopropylamine mixed solvent with respect to compound 17 (0.4 g, 0.4 mmol) obtained in Synthesis Example 11. And reacted at 60 ° C. for 20 hours. The reaction was stopped by adding water to the reaction solution cooled to room temperature, extracted with dichloromethane, and the solvent was distilled off to obtain a crude product of target compound 18. Thereafter, the target compound was isolated by chromatography using dichloromethane as a developing solvent, and it was confirmed by ¹ H-NMR, ¹³ C-NMR and FAB-MS that the target compound 18 was obtained (90%).
¹ H NMR (400MHz, CDCl ₃ ) δ0.37 (s, 18H), 0.84 (t, 12H), 1.24-1.33 (m, 24H), 1.80-1.84 (m, 4H), 2.21-2.28 (m, 4H ), 5.18 (m, 2H), 8.14 (d, J = 7.6 Hz, 2H), 8.81 (d, J = 7.6 Hz, 2H), 10.18-10.26 (m, 2H). ¹³ C NMR (150 MHz, CDCl ₃ ) δ164.90, 164.64, 163.82, 163.55, 139.42, 139.12, 138.44, 137.22, 134.53, 124.36, 131.47, 130.60, 128.43, 128.42, 128.00, 127.96, 127.79, 127.79, 124.34, 123.61, 123.03, 122.45, 120.78, 120.20 , 107.06, 106.76, 106.39, 106.33, 55.36, 32.89, 32.36, 27.26, 23.20, 14.67, 0.23, 0.09.HRMS (FAB) m / z calcd for C ₅₆ H ₇₀ N ₂ O ₄ Si ₂ ⁺ [M] ⁺ : 890.4874, found 890.4871.

[Synthesis Example 13: Synthesis of Compound 19]

Deprotection was carried out by reacting Compound 18 (0.15 g, 0.1 mmol) obtained in Synthesis Example 12 with tetrabutylammonium fluoride (TBAF; 3.1 eq) in dichloromethane at 0 ° C. for 15 minutes. The obtained compound was reacted with PtCl ₂ (30 mol%) and 1M aqueous hydrogen chloride solution (20 mol%) in a toluene solvent at 90 ° C. for 12 hours. The reaction solution cooled to room temperature was evaporated to obtain a crude product of target compound 19. Then, the target compound was isolated by chromatography using a mixed solvent of chloroform / hexane 1: 1, and the target compound 19 was confirmed by ¹ H NMR, ¹³ C NMR, and FAB-MS. (12%).
¹ H NMR (400MHz, CDCl ₃ ) δ0.84 (t, 12H), 1.24-1.31 (m, 24H), 1.88-1.94 (m, 4H), 2.33-2.36 (m, 4H), 5.31 (brs, 2H ), 8.77 (s, 4H) , 9.46 (s, 4H). 13 C NMR (150MHz, CDCl 3) δ164.78, 131.67, 129.38, 128.95, 128.88, 122.81, 122.80, 120.04, 55.33, 32.73 32.74, 27.03, 22.82, 14.25. HRMS (FAB) m / z calcd for C ₅₀ H ₅₄ N ₂ O ₄ ⁺ [M] ⁺ : 746.4083, found 746.4081.

[Example 13]

For compound 19 (20 mg, 0.027 mmol) obtained in Synthesis Example 13, compound 20 (7.1 mg, 0.0027 mmol), 2.0 equivalents of Pd (OCOCF ₃ ) ₂ as a palladium compound, and 4.0 g of AgSbF ₆ as a silver compound are used. The reaction was carried out in dichloroethane at 80 ° C. for 12 hours using 4.0 equivalents of o-chloranil. After removing the metal using chromatography and a metal scavenger, the molecular weight was measured by HPLC. The results are shown in Table 19. As a result, the reaction proceeded also in the case of copolymerization, and the polymer of the present invention could be obtained. The IR spectrum of the obtained polymer is shown in FIG. Moreover, the UV / Vis absorption spectrum and fluorescence spectrum of the obtained polymer are shown in FIG. As a result, it is suggested that it has an absorption band at a position of 350 to 550 nm, and an emission band at a position of 450 to 700 nm.

[Test Example 4: Graphene nanoribbon array]
The polymer obtained in Entry 2 of Test Example 2 (GNR; Mn = 1555032, Mw / Mn = 1.20, ca. 300mer, width about 0.7 nm, length about 135 nm) was arranged on graphene. The polymer width means the width of the pyrene skeleton in the polymer obtained in Test Example 2. Specifically, graphene was peeled off with an adhesive tape on a silicon substrate with a thermal oxide film, and 20 μL of a GNR solution was dropped. The solution is 0.002 mg of GNR dissolved in 1 mL of 1,2,4-trichlorobenzene. The substrate on which the solution was dropped was heated in air at 100 ° C. for 10 minutes to dry the droplets.

The surface of the graphene sample onto which the GNR solution was dropped was observed with an atomic force microscope (AFM). The surface was observed by tapping mode using Dimension FastScan AFM (manufactured by Bruker). The obtained phase image is shown in FIG. From FIG. 15, the GNR was selectively oriented on the graphene, and the ribbon width was about 4 nm. The ribbon width means the distance between the center portion of the ribbon and the center portion of the adjacent ribbon.

[Test Example 5: Measurement of DC resistivity]
A gold electrode with a thickness of 60 nm was attached by fine processing to graphene exfoliated into a silicon substrate with a thermal oxide film, and processed into a field effect transistor. On this graphene, the polymer obtained in Entry 2 of Test Example 2 (GNR; Mn = 155032, Mw / Mn = 1.20, ca. 300mer, width of about 0.7 nm, length of about 135 nm) was added dropwise and dried. The direct current resistivity of the produced GNR-graphene composite was measured. Specifically, a probe is attached to the sample electrode and the substrate using an SP-0 type prober (manufactured by ESS Tech), a 10 mV voltage is applied between the source and drain, and the gate voltage is swept from -40 V to 40 V. The change in resistivity was measured. A 4200-SCS type semiconductor parameter analyzer (manufactured by Keithley Instruments) was used for voltage application and DC resistance measurement. FIG. 16 shows the measurement results of the DC resistivity of the graphene field effect transistor before and after dropping the GNR solution.

FIG. 16 shows that the graphene field effect transistor has an increased DC resistance by orienting the GNR on the graphene. Furthermore, the resistivity of graphene before GNR alignment was 8 kΩ at the charge neutral point, but 10 kΩ after GNR alignment, and the electrical resistivity increased by 1.25 times. From this, it was found that a material having an increased electrical resistivity can be obtained by orienting GNR molecules on the graphene surface.

Claims

A polycyclic aromatic compound as a repeating unit, and the polycyclic aromatic compound as the repeating unit is used as an adjacent repeating unit so as to share one bond constituting the benzene ring in the polycyclic aromatic compound. A polymer bound to a polycyclic aromatic compound.
The polycyclic aromatic compound having a K region and a silole skeleton, or the (cyclic) polymerization using a polycyclic aromatic compound having a K region and a polycyclic aromatic compound having a silole skeleton as raw materials. Polymer.
General formula (1):

[In formula, * shows a repeating site | part. m represents an integer of 1 or more. A represents an aromatic ring having a K region. When m is an integer of 2 or more, the plurality of A may be the same or different. R 1 and R 3 represent a hydrogen atom. R 2 and R 4 are the same or different and are a branched alkyl group, or general formula (2):

(In the formula, *, m, A, R 1 and R 3 are the same as above. R 2a represents a branched alkyl group. At least one of R 1 and R 2a , R 1 and A, and R 3 and A One may be bonded to each other to form a ring.)
The group represented by these is shown. At least one of R 1 and R 2 , R 3 and R 4 , R 1 and A, and R 3 and A may be bonded to each other to form a ring. ]
The polymer of Claim 1 or 2 which has a repeating unit represented by these.
The repeating unit is represented by the general formulas (1A) to (1F):

[Wherein, *, R 2a and R 4a are the same as defined above. Y is the same or different and represents CH or N. R 2b and R 4b are the same or different and represent a branched alkyl group. ]
The polymer according to any one of claims 1 to 3, which is a repeating unit represented by any of the above:
The polymer according to any one of claims 1 to 4, having a number average molecular weight of 10,000 or more.
A graphene nanoribbon comprising the polymer according to any one of claims 1 to 5.
The graphene nanoribbon according to claim 6, having a width of 0.5 to 10.0 nm and a length of 10 nm or more.
A method for producing the polymer according to any one of claims 1 to 5,
(1) a step of reacting a polycyclic aromatic compound having a K region and a silole skeleton in the presence of a palladium compound and o-chloranil; or (2) a polycycle having a K region in the presence of a palladium compound and o-chloranil. A production method comprising a step of reacting an aromatic compound with a polycyclic aromatic compound having a silole skeleton.
In the step (1), the polycyclic aromatic compound having a K region and a silole skeleton is represented by the general formula (3A) or (3B):

[Wherein, A is the same or different and represents an aromatic ring having a K region. R 1 and R 3 represent a hydrogen atom. R 2a and R 4a are the same or different and represent a branched alkyl group. At least one of R 1 and R 2a , R 3 and R 4a , R 1 and A, and R 3 and A may be bonded to each other to form a ring. R 5 and R 6 are the same or different and each represents a hydrogen atom or an alkyl group. ]
The manufacturing method of Claim 8 which is a compound represented by these.
In the step (2), the polycyclic aromatic compound having a K region is represented by the general formula (4):

[Wherein, A is the same or different and represents an aromatic ring having a K region. R 1 and R 3 represent a hydrogen atom. R 2 and R 4 are the same or different, and are a branched alkyl group, or general formula (4A):

(In the formula, A, R 1 and R 3 are the same as defined above. R 2a represents a branched alkyl group. At least one of R 1 and R 2a , R 1 and A, and R 3 and A And may be linked to form a ring.)
The group represented by these is shown. At least one of R 1 and R 2 , R 3 and R 4 , R 1 and A, and R 3 and A may be bonded to each other to form a ring. ]
The manufacturing method of Claim 8 or 9 which is a compound represented by these.
In the step (2), the polycyclic aromatic compound having a silole skeleton is represented by the general formula (5):

[Wherein, B are the same or different and each represents an aromatic ring having a silole skeleton. R 1 and R 3 represent a hydrogen atom. R 2a and R 4a are the same or different and represent a branched alkyl group. At least one of R 1 and R 2a , R 3 and R 4a , R 1 and B, and R 3 and B may be bonded to each other to form a ring. R 5 and R 6 are the same or different and each represents a hydrogen atom or an alkyl group. ]
The production method according to any one of claims 8 to 10, which is a compound represented by the formula:
The production method according to any one of claims 8 to 11, wherein the steps (1) and (2) are carried out in the presence of a silver compound.
The silver compound contains AgSbF 6 or AgBF 4, The method according to claim 12.
The amount of the silver compound used is based on 1 mol of the polycyclic aromatic compound having the K region and a silole skeleton, the polycyclic aromatic compound having the K region, or the polycyclic aromatic compound having the silole skeleton. The production method according to claim 12 or 13, wherein the amount is 0.5 to 5.0 mol.
The amount of the palladium compound used is 1 mol of the polycyclic aromatic compound having the K region and a silole skeleton, the polycyclic aromatic compound having the K region, or the polycyclic aromatic compound having the silole skeleton. The production method according to any one of claims 8 to 14, wherein the amount is 0.07 to 5.0 mol.
A laminate in which the graphene nanoribbon according to claim 6 or 7 is disposed on a conductive material.
The laminate according to claim 16, wherein the conductive material is graphene.