Graphene nanoribbon and preparation method thereof

Abstract

The present invention can provide a graphene nanoribbon having at least one structural unit represented by the following general formula by a method with a small number of steps and suppressed side reactions. In the formula, the dashed lines are the same or different and represent the absence of a bond or a single bond; *1 represents a bonding point; when the dashed line bonded to *2 is a single bond, *2 represents a bonding point; R 3a , R 3b , R 3c and R 3d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 3a With R 3b , and R 3c With R 3d At least one group of them may be bonded to each other to form a ring.

Description

Technical Field

[0001] The invention relates to a graphene nanoribbon and a preparation method thereof. Background Art

[0002] Graphene nanoribbons (GNRs) are expected to be used in semiconductors, solar cells, transparent electrodes, high-speed transistors, organic EL elements, etc. due to their high hole mobility, semiconductor properties, transparency, mechanical strength, flexibility, etc.

[0003] As a method for synthesizing GNR, there are two synthesis methods that are roughly divided into a top-down method and a bottom-up method. In particular, the charm of the latter is that it is possible to precisely control the edge structure and width and synthesize a large number of GNRs. However, GNRs with shorter lengths lack solubility, so it is not possible to use a method in which a shorter GNR is synthesized as an intermediate and further reacted. Therefore, a method is required to synthesize a longer GNR by initiating a polymerization reaction with a highly soluble matrix compound with a smaller number of steps.

[0004] In general, nanographene is synthesized by using a coupling reaction of aromatic ring components and a Diels-Alder reaction, and finally converting to graphene by a dehydrogenation cyclization reaction (for example, see Non-Patent Document 1). The same method is also used in the synthesis of GNRs.

[0005] In addition, in recent years, a method for reacting a polycyclic aromatic compound having a K block and a silole skeleton in the presence of a palladium compound and o-tetrachlorobenzoquinone, and a method for reacting a polycyclic aromatic compound having a K block with a polycyclic aromatic compound having a silole skeleton have been known (for example, refer to Patent Document 1).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2017 / 131190

[0009] Non-patent literature

[0010] Non-patent document 1: Nat. Chem. 2014, 6, 126 Summary of the invention

[0011] Technical Problems to be Solved by the Invention

[0012] However, the method of the above-mentioned Non-Patent Document 1 is a multi-step reaction, so the yield is low, and since side reactions may occur, it is not a highly versatile method.

[0013] Therefore, an object of the present invention is to provide GNR by a method with a small number of steps and suppressed side reactions.

[0014] Technical means to solve technical problems

[0015] The inventors of the present invention have conducted intensive research to solve the above technical problems, and as a result, have found that a GNR having a specific structure can be synthesized by a method in which a specific initiator and a specific silole compound are reacted in the presence of a palladium compound and o-tetrachlorobenzoquinone and, if necessary, a silver compound, the number of steps being small and the side reactions being suppressed. The inventors of the present invention have further conducted research based on the above findings and have completed the present invention. That is, the present invention includes the following configurations.

[0016] Item 1. A graphene nanoribbon having at least one structural unit represented by the following general formula (1),

[0017] [Chemical formula 1]

[0018]

[0019] Wherein, the dashed lines are the same or different and indicate the absence of a bond or a single bond; *1 indicates a bonding point; when the dashed line bonded to *2 is a single bond, *2 indicates a bonding point; R 3a , R 3b , R 3c and R 3d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 3a With R 3b and / or R 3c With R 3d They may be bonded to each other to form a ring.

[0020] Item 2. The graphene nanoribbon according to Item 1, which has at least one structural unit represented by the following general formula (3),

[0021] [Chemical formula 2]

[0022]

[0023] Wherein, the dashed lines are the same or different and indicate the absence of a bond or a single bond; *5 indicates a bonding point; when the dashed line bonded to *6 is a single bond, *6 indicates a bonding point; R 5a , R 5b , R 5c and R 5d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 5a With R 5b and / or R5c With R 5d They may be bonded to each other to form a ring.

[0024] Item 3. The graphene nanoribbon according to Item 1 or 2, further comprising at least one structural unit represented by the following general formula (2),

[0025] [Chemical formula 3]

[0026]

[0027] Wherein, the dashed lines are the same or different and indicate the absence of a bond or a single bond; *3 indicates a bonding point; when the dashed line bonded to *4 is a single bond, *4 indicates a bonding point; R 4a , R 4b , R 4c and R 4d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 4a With R 4b and / or R 4c With R 4d optionally bonded to each other to form a ring; wherein R 4a With R 3a Different, R 4b With R 3b Different, R 4c With R 3c Different and R 4d With R 3d different.

[0028] Item 4. The graphene nanoribbon according to any one of Items 1 to 3, further comprising at least one structural unit of the structural unit represented by the following general formula (11), the structural unit represented by the following general formula (12), and the structural unit represented by the following general formula (13),

[0029] [Chemical formula 4]

[0030]

[0031] Wherein, the dashed line is the same as the dashed line; *1 represents a bonding point; when the dashed line bonded to *2 is a single bond, *2 represents a bonding point; R 1a , R 1b , R 1c , R 1d , R 2a and R 2bare the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a boronic acid or its ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; a1 and a2 are the same or different and represent a carbon atom or a nitrogen atom; R 1c With R 1d optionally bonded to each other to form a ring,

[0032] [Chemical formula 5]

[0033]

[0034] In the formula, *7 represents the bonding point,

[0035] [Chemical formula 6]

[0036]

[0037] In the formula, *8 represents a bonding point; a3 represents an oxygen atom or a sulfur atom.

[0038] Item 5. The graphene nanoribbon according to Item 4, which is represented by the following general formula (4), general formula (14) or general formula (15),

[0039] [Chemical formula 7]

[0040]

[0041] In the formula, the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , the dotted lines a1 and a2, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d They are optionally bonded to each other to form a ring; n represents an integer greater than 0,

[0042] [Chemical formula 8]

[0043]

[0044] In the formula, R 3a , R 3b , R 3c , R 3d and n and R 3a , R 3b , R 3c , R 3d and n are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d optionally bonded to each other to form a ring,

[0045] [Chemical formula 9]

[0046]

[0047] In the formula, R 3a , R 3b , R 3c , R 3d , n and a3 and said R 3a , R 3b , R 3c , R 3d , n and a3 are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d They may be bonded to each other to form a ring.

[0048] Item 6. The graphene nanoribbon according to Item 4 or 5, which is represented by the following general formula (4A), the following general formula (14A) or the following general formula (15A),

[0049] [Chemical formula 10]

[0050]

[0051] In the formula, the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 and the dotted line, R 1a , R 1b, R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 are the same; R 4a , R 4b , R 4c and R 4d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4a With R 4b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4c With R 4d optionally bonded to each other to form a ring; wherein R 4a With R 3a Different, R 4b With R 3b Different, R 4c With R 3c Different and R 4d With R 3d different; n and m are the same or different and represent an integer greater than 0,

[0052] [Chemical formula 11]

[0053]

[0054] In the formula, R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , n and m and the R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , n and m are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4a With R 4b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4c With R 4d optionally bonded to each other to form a ring,

[0055] [Chemical formula 12]

[0056]

[0057] In the formula, R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , n, m and a3 and the R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , n, m and a3 are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4a With R 4b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4c With R 4d They may be bonded to each other to form a ring.

[0058] Item 7. The graphene nanoribbon according to any one of Items 4 to 6, which is represented by the following general formula (4A1), the following general formula (14A1), or the following general formula (15A1),

[0059] [Chemical formula 13]

[0060]

[0061] R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R3c , R 3d , a1 and a2 and the R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 are the same; R 5a , R 5b , R 5c and R 5d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5a With R 5b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5c With R 5d are optionally bonded to each other to form a ring; n and m are the same or different and represent an integer greater than 0,

[0062] [Chemical formula 14]

[0063]

[0064] In the formula, R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , n and m and the R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , n and m are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5a With R5b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5c With R 5d optionally bonded to each other to form a ring,

[0065] [Chemical formula 15]

[0066]

[0067] In the formula, R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , n, m and a3 and the R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , n, m and a3 are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5a With R 5b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5c With R 5d They may be bonded to each other to form a ring.

[0068] Item 8. A method for preparing a graphene nanoribbon according to any one of Items 1 to 7, comprising:

[0069] (1) a first polymerization step of reacting an acetylene compound represented by the following general formula (5A), an aromatic compound containing a K region represented by the following general formula (5B), dibenzocyclooctadiyn, benzothiophene or benzofuran, and a silole compound represented by the following general formula (6) in the presence of a palladium compound and o-tetrachlorobenzoquinone;

[0070] [Chemical formula 16]

[0071]

[0072] In the formula, R 1a and R 1bare the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a hydrocarbon boronic acid or its ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; k1 and k2 are the same or different and represent an integer of 1 to 3; when k1 and k2 are integers greater than 2, each R 1a and / or R 1b Optional same or different,

[0073] [Chemical formula 17]

[0074]

[0075] In the formula, R 1a , R 1b , R 1c , R 1d , R 2a and R 2b are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a boronic acid or its ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; a1 and a2 are the same or different and represent a carbon atom or a nitrogen atom;

[0076] [Chemical formula 18]

[0077]

[0078] In the formula, R 3a , R 3b , R 3c and R 3d With the R 3a , R 3b , R 3c and R 3d Same; R 6a and R 6b are the same or different and represent a hydrogen atom or an alkyl group.

[0079] Item 9. The preparation method according to Item 8, wherein the first polymerization step is performed in the presence of a silver compound.

[0080] Item 10. The preparation method according to Item 9, wherein the silver compound contains AgSbF6 or AgBF4.

[0081] Item 11. The preparation method according to Item 9 or 10, wherein the amount of the silver compound used is 0.5 to 5.0 mol relative to 1 mol of the silole compound.

[0082] Item 12. The production method according to any one of Items 8 to 11, wherein the amount of the palladium compound used is 0.1 to 3.0 mol relative to 1 mol of the silole compound.

[0083] Item 13. A silole compound represented by the following general formula (6):

[0084] [Chemical formula 21]

[0085]

[0086] In the formula, R 3a , R 3b , R 3c and R 3d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; wherein R 3a , R 3b , R 3c and R 3d Not all hydrogen atoms; R 3a With R 3b and / or R 3c With R 3d Optionally bond to each other to form a ring; R 6a and R 6b are the same or different and represent a hydrogen atom or an alkyl group.

[0087] Item 14. A method for preparing the silole compound according to Item 13, comprising:

[0088] a step of reacting a halogen-containing silole compound represented by the following general formula (8) with a Grignard reagent represented by the following general formula (9) or a boronic acid compound represented by the following general formula (10),

[0089] [Chemical formula 22]

[0090]

[0091] In the formula, R 3c , R 3d , R 6a and R 6b With the R 3c , R 3d , R 6a and R 6b Same; X 1 and X 2 are the same or different and represent a hydrogen atom or a halogen atom; X 1 With X 2 optionally bonded to form a ring containing a halogen atom; wherein X 1 and X 2 Not all hydrogen atoms.

[0092] General formula (9):

[0093] R 7 MgX3 (9)

[0094] In the formula, R 7 represents an alkyl group; X 3 represents a halogen atom,

[0095] [Chemical formula 23]

[0096]

[0097] In the formula, R 8 represents a monovalent aromatic hydrocarbon group; R 9 and R 10 are the same or different and represent a hydrogen atom or an alkyl group; R 9 With R 10 They may be bonded to each other to form a ring together with the adjacent -OBO-.

[0098] Item 15. A halogen-containing silole compound represented by the following general formula (8):

[0099] [Chemical formula 24]

[0100]

[0101] In the formula, R 3c and R 3d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 3c With R 3d Optionally bond to each other to form a ring; R 6a and R 6b are the same or different and represent a hydrogen atom or an alkyl group; X 1 and X 2 are the same or different and represent a hydrogen atom or a halogen atom; X 1 With X 2 optionally bonded to form a ring containing a halogen atom; wherein X 1 and X 2 Not all hydrogen atoms.

[0102] Effects of the Invention

[0103] According to the present invention, GNR can be provided by a method with a small number of steps and suppressed side reactions. The GNR can be obtained by reacting a specific initiator with a specific silole compound in the presence of a palladium compound and o-tetrachlorobenzoquinone and, if necessary, a silver compound, and by repeating the reaction multiple times, a block copolymer GNR can be synthesized. DETAILED DESCRIPTION

[0104] In this specification, "comprising" is a concept including any one of "comprising", "consisting essentially of", and "consisting only of". In addition, in this specification, when "A to B" is used to express a numerical range, it means A or more and B or less.

[0105] 1. Graphene Nanoribbons

[0106] The graphene nanoribbon of the present invention is a polymer having at least one structural unit represented by the following general formula (1).

[0107] [Chemical formula 29]

[0108]

[0109] In the formula, the dashed lines are the same or different and represent the absence of bonding or a single bond. *1 represents the bonding point; when the dashed line bonded to *2 is a single bond, *2 represents the bonding point. R 3a , R 3b , R 3c and R 3d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group. 3a With R 3b and / or R 3c With R 3d They may be bonded to each other to form a ring.

[0110] In the general formula (1), R 3a , R 3b , R 3c and R 3d Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0111] In the general formula (1), R 3a , R 3b , R 3c and R 3d The alkyl group represented is, for example, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 15, more preferably 1 to 13), and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0112] When the alkyl group is substituted, the substituent is not particularly limited, and examples thereof include the halogen atoms described above. When the alkyl group is substituted, the number of substituents is not particularly limited, and may be, for example, 1 to 3.

[0113] In the general formula (1), R 3a , R 3b , R 3c and R 3d The cycloalkyl group represented is preferably a cycloalkyl group having 3 to 20 (preferably 4 to 15, more preferably 5 to 13) carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

[0114] When the cycloalkyl group is substituted, the substituent is not particularly limited, and examples thereof include the halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms (e.g., methyl, ethyl, n-propyl, etc.). When substituted with a substituent, the number of substituents is not particularly limited, and can be, for example, 1 to 3.

[0115] In the general formula (1), R 3a , R 3b , R 3c and R 3d The (poly)ether group represented by means of is an ether group or a polyether group. 11c (R 11c represents the above-mentioned alkyl) and the like. 11c Preferably, an ether group having an alkyl group having 1 to 4 carbon atoms is used. Examples of the polyether group include -(OR 11a ) k -OR 11b (R 11a and R 11b are the same or different and represent an alkyl group; k represents an integer from 1 to 20). These repeating units OR 11a It may contain not only the same repeating unit but also two or more different repeating units. 11a and R 11b A polyether group having an alkyl group having 1 to 4 carbon atoms.

[0116] R 11a and R 11b All are alkyl groups, and the above-mentioned alkyl groups can be cited. When having a substituent, the above-mentioned types and numbers can also be cited. In addition, k is preferably an integer of 1 to 20, more preferably an integer of 1 to 15, and even more preferably an integer of 1 to 5.

[0117] Examples of the polyether group include -(OC2H5)2OCH3, -(OC2H5)3OCH3, -(OC2H5)4OCH3, -(OC2H5) 11 OCH3, -(OC2H5) 12 OCH3, -(OC2H5) 13 OCH3, etc.

[0118] When the polyether group is used, the water solubility of the obtained graphene nanoribbon can be further improved.

[0119] In the general formula (1), R 3a , R 3b , R 3c and R 3d The ester group represented by can be exemplified by -COOR 11d (R 11d represents the above-mentioned alkyl) and the like. It is preferable to use a group having as R 11d An ester group of an alkyl group having 1 to 4 carbon atoms.

[0120] In the general formula (1), R 3a , R 3b , R 3c and R 3d The monovalent aromatic hydrocarbon group represented is a monovalent group having an aromatic hydrocarbon ring, and is a group formed by removing a hydrogen atom bonded to a carbon atom constituting the aromatic hydrocarbon ring. In addition, at least one hydrogen atom bonded to a carbon constituting the aromatic hydrocarbon ring may be substituted with a substituent.

[0121] As the monovalent aromatic hydrocarbon ring, there are not only benzene rings, but also rings formed by condensing a plurality of benzene rings (benzene condensed rings), rings formed by condensing a benzene ring with other aromatic hydrocarbon rings, and the like (hereinafter, a ring formed by condensing a plurality of benzene rings and a ring formed by condensing a benzene ring with other rings are sometimes referred to as "condensed hydrocarbon rings"). As the condensed hydrocarbon ring, for example, there are pentalene rings, indene rings, naphthalene rings, dihydronaphthalene rings, anthracene rings, tetracene rings, pentacene rings, pyrene rings, perylene rings, triphenylene rings, azulene rings, heptalene rings, biphenylene rings, indacene rings, acenaphthylene rings, fluorene rings, phenalene rings, phenanthrene rings, and the like.

[0122] When the monovalent aromatic hydrocarbon group is substituted, the substituent is not particularly limited, and examples thereof include the halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms (e.g., methyl, ethyl, n-propyl, etc.), etc. When substituted with a substituent, the number of substituents is not particularly limited, and for example, 1 to 3 may be used.

[0123] In the general formula (1), R 3a , R 3b, R 3c and R 3d The monovalent heterocyclic group is a monovalent group having a heterocyclic ring, and is a group formed by removing a hydrogen atom bonded to a carbon atom constituting the heterocyclic ring. In addition, at least one hydrogen atom bonded to a carbon atom constituting the heterocyclic ring may be substituted with a substituent.

[0124] As the above-mentioned heterocycle, for example, a heterocycle (specifically, an aromatic heterocycle or an aliphatic heterocycle, particularly an aromatic heterocycle) having at least one atom selected from a nitrogen atom, an oxygen atom, a boron atom, a phosphorus atom, a silicon atom and a sulfur atom can be listed. As a specific example of the heterocycle, a furan ring, a thiophene ring, a pyrrole ring, a thiol ring, a borole ring, a phosphole ring, an oxazole ring, a dioxole ring, a thiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, an aromatic heterocycle such as a pyrazine ring, etc. can be listed. In addition, it can also be a condensed heterocycle of these heterocycles themselves or a condensed heterocycle of these heterocycles and a benzene ring, the above-mentioned condensed hydrocarbon ring, etc. (thienothiophene ring, quinoline ring, benzodioxole ring, etc.).

[0125] When the monovalent heterocyclic group is substituted, the substituent is not particularly limited, and examples thereof include the halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms (e.g., methyl, ethyl, n-propyl, etc.), but are not limited thereto, and any substituent may be used. When substituted with a substituent, the number of substituents is not particularly limited, and may be, for example, 1 to 3.

[0126] In the general formula (1), R 3a With R 3b , R 3c With R 3d At least one group of the above may be bonded to each other to form a ring. Examples of the ring formed in this case include the above-mentioned alicyclic ring (cycloalkyl), aromatic hydrocarbon ring, and heterocyclic ring.

[0127] For the general formula (1), preferably R 3a , R 3b , R 3c and R 3d are all hydrogen atoms, or three are hydrogen atoms and one is an alkyl group or a polyether group, or R 3a With R 3b and / or R 3c With R 3d They are bonded to each other to form a ring.

[0128] In addition, in the general formula (1), the dashed lines are the same or different and indicate the absence of a bond or a single bond. *1 indicates a bonding point. When the dashed line bonded to *2 is a single bond, *2 indicates a bonding point. When the dashed line connected to the bonding point *2 in the general formula (1) is a single bond, it indicates an armchair-type graphene nanoribbon, and when there is no dashed line bonded to *2 in the general formula (1), it indicates a Fjord-type graphene nanoribbon.

[0129] The above-mentioned graphene nanoribbon of the present invention is a polymer having at least one structural unit represented by the above-mentioned general formula (1), but considering the compound used as an initiator in the preparation method described later, it is preferred that at least one end is at least one structural unit represented by the following general formula (11), the following general formula (12) and the following general formula (13).

[0130] [Chemical formula 30]

[0131]

[0132] Wherein, the dashed line is the same as the dashed line; *1 represents a bonding point; when the dashed line bonded to *2 is a single bond, *2 represents a bonding point; R 1a , R 1b , R 1c , R 1d , R 2a and R 2b are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a boronic acid or its ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; a1 and a2 are the same or different and represent a carbon atom or a nitrogen atom; R 1c With R 1d They may be bonded to each other to form a ring.

[0133] [Chemical formula 31]

[0134]

[0135] In the formula, *7 represents the bonding point.

[0136] [Chemical formula 32]

[0137]

[0138] In the formula, *8 represents a bonding point; a3 represents an oxygen atom or a sulfur atom.

[0139] That is, the graphene nanoribbon of the present invention is preferably a polymer represented by the following general formula (4), the following general formula (14), or the following general formula (15).

[0140] [Chemical formula 33]

[0141]

[0142] In the formula, the dotted line, R 1a , R 1b , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 and the dotted line, R 1a , R 1b , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d They may be bonded to each other to form a ring; and n represents an integer of 0 or greater.

[0143] [Chemical formula 34]

[0144]

[0145] In the formula, R 3a , R 3b , R 3c , R 3d and n and R 3a , R 3b , R 3c , R 3d and n are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d They may be bonded to each other to form a ring.

[0146] [Chemical formula 35]

[0147]

[0148] In the formula, R 3a , R 3b , R 3c , R 3d , n and a3 and said R 3a , R 3b , R 3c , R 3d , n and a3 are the same; R bonded to the same benzene ring3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d They may be bonded to each other to form a ring.

[0149] In the general formulas (4) and (11), R 1a , R 1b , R 1c , R 1d , R 2a and R 2b The halogen atoms, alkyl groups, (poly)ether groups, ester groups, monovalent aromatic hydrocarbon groups and monovalent heterocyclic groups represented by the present invention may be the halogen atoms, alkyl groups, (poly)ether groups, ester groups, monovalent aromatic hydrocarbon groups and monovalent heterocyclic groups mentioned above. The types and numbers of the substituents are also the same as those mentioned above.

[0150] In the general formulas (4) and (11), R 1a , R 1b , R 1c , R 1d , R 2a and R 2b Examples of the boronic acid or ester group thereof include a boryl group and a pinacolate boryl group.

[0151] For general formulas (4) and (11), from the perspective of raw material availability, water solubility, etc., R 1a , R 1b , R 1c , R 1d , R 2a and R 2b Preferred are hydrogen atoms, alkyl groups, polyether groups, etc. When it is an alkyl group, it is more preferably a branched alkyl group, further preferably isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, etc., and particularly preferably is tert-butyl.

[0152] In the general formulas (4) and (11), R 1c With R 1d They may be bonded to each other to form a ring. Examples of the ring formed in this case include the above-mentioned alicyclic ring (cycloalkyl group), aromatic hydrocarbon ring, and heterocyclic ring.

[0153] In the general formulae (4) and (11), from the viewpoint of availability and the like, a1 and a2 are preferably carbon atoms among carbon atoms and nitrogen atoms.

[0154] In the graphene nanoribbon of the present invention, the number of repeating units (i.e., n) is an integer greater than 0, and is not particularly limited. It can be appropriately selected according to the desired properties, and is preferably 10 to 1000, and more preferably 10 to 500. In addition, for example, it can also be set to an oligomer having a repeating unit number (i.e., n) of 1 to 99, preferably an oligomer having a repeating unit number of 2 to 49, more preferably an oligomer having a repeating unit number of 2 to 19, and further preferably an oligomer having a repeating unit number of 3 to 9. The number of repeating units of the graphene nanoribbon of the present invention is calculated from the number average molecular weight measured by gel permeation chromatography and converted to polystyrene.

[0155] In general formulae (4) and (11), the dashed lines are the same or different and indicate the absence of a bond or a single bond; *1 indicates a bonding point; when the dashed line bonded to *2 is a single bond, *2 indicates a bonding point. When the dashed line connected to the bonding point *2 in general formula (11) is a single bond, it indicates an armchair graphene nanoribbon; when the dashed line does not exist in general formula (11), it indicates a Fjord graphene nanoribbon.

[0156] As another specific embodiment of the graphene nanoribbon of the present invention, R in the general formula (1) can be prepared 3a With R 3b They are bonded to each other to form a ring and have at least one structural unit represented by the following general formula (3).

[0157] [Chemical formula 36]

[0158]

[0159] Wherein, the dashed lines are the same or different and indicate the absence of a bond or a single bond; *5 indicates a bonding point; when the dashed line bonded to *6 is a single bond, *6 indicates a bonding point; R 5a , R 5b , R 5c and R 5d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 5a With R 5b and / or R 5c With R 5d They may be bonded to each other to form a ring.

[0160] In the general formula (3), R 5a , R 5b , R 5c and R 5dThe halogen atoms, alkyl groups, cycloalkyl groups, (poly)ether groups, ester groups, aromatic hydrocarbon groups and heterocyclic groups represented by the present invention may be the halogen atoms, alkyl groups, cycloalkyl groups, (poly)ether groups, ester groups, aromatic hydrocarbon groups and heterocyclic groups mentioned above. The types and quantities of the substituents, preferred specific examples and the like are also the same as those mentioned above.

[0161] In addition, in the general formula (3), R 5a With R 5b and / or R 5c With R 5d They may be bonded to each other to form a ring. Examples of the ring formed in this case include the above-mentioned alicyclic ring (cycloalkyl group), aromatic hydrocarbon ring, and heterocyclic ring.

[0162] In addition, in the general formula (3), the dashed lines are the same or different and indicate the absence of a bond or a single bond; *5 indicates a bonding point; when the dashed line bonded to *6 is a single bond, *6 indicates a bonding point. When the dashed line connected to the bonding point *6 in the general formula (3) is a single bond, it indicates an armchair graphene nanoribbon, and when there is no dashed line in the general formula (3), it indicates a Fjord graphene nanoribbon.

[0163] The graphene nanoribbons of the present invention satisfying the above conditions include not only homopolymers but also block copolymers. The block copolymer preferably has at least one structural unit represented by the general formula (1) and at least one structural unit represented by the following general formula (2).

[0164] [Chemical formula 37]

[0165]

[0166] Wherein, the dashed lines are the same or different and indicate the absence of a bond or a single bond; *3 indicates a bonding point; when the dashed line bonded to *4 is a single bond, *4 indicates a bonding point; R 4a , R 4b , R 4c and R 4d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a (poly)ether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 4a With R 4b and / or R 4c With R 4d optionally bonded to each other to form a ring; wherein R 4a With R 3a Different, R 4b With R 3b Different, R 4c With R 3c Different and R 4d With R 3d different.

[0167] In the general formula (2), R 4a , R 4b , R 4c and R 4d The halogen atoms, alkyl groups, cycloalkyl groups, (poly)ether groups, ester groups, aromatic hydrocarbon groups and heterocyclic groups represented by the present invention may be the halogen atoms, alkyl groups, cycloalkyl groups, (poly)ether groups, ester groups, aromatic hydrocarbon groups and heterocyclic groups mentioned above. The types and quantities of the substituents, preferred specific examples and the like are also the same as those mentioned above.

[0168] In addition, in the general formula (2), R 4a With R 4b and / or R 4c With R 4d They may be bonded to each other to form a ring. Examples of the ring formed in this case include the above-mentioned alicyclic ring (cycloalkyl group), aromatic hydrocarbon ring, and heterocyclic ring.

[0169] In addition, in the general formula (2), the dashed lines are the same or different and indicate the absence of a bond or a single bond; *3 indicates a bonding point; when the dashed line bonded to *4 is a single bond, *4 indicates a bonding point. When the dashed line connected to the bonding point *4 in the general formula (2) is a single bond, it indicates an armchair graphene nanoribbon, and when there is no dashed line bonded to *4 in the general formula (2), it indicates a Fjord graphene nanoribbon.

[0170] In the above-mentioned graphene nanoribbons of the present invention, the graphene nanoribbons as block copolymers are polymers having at least one structural unit represented by the above-mentioned general formula (1) and at least one structural unit represented by the general formula (2), but considering the compound used as an initiator in the preparation method described later, it is preferred that at least one end has at least one structural unit among the structural units represented by the above-mentioned general formulas (11), (12) and (13).

[0171] That is, in the graphene nanoribbon of the present invention, the graphene nanoribbon as the block copolymer is preferably a graphene nanoribbon represented by the following general formula (4A), the following general formula (14A), or the following general formula (15A).

[0172] [Chemical formula 38]

[0173]

[0174] In the formula, the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d, R 4a , R 4b , R 4c , R 4d , a1, a2 and n and the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , a1, a2 and n are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4a With R 4b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4c With R 4d They may be bonded to each other to form a ring; m represents an integer of 0 or greater.

[0175] [Chemical formula 39]

[0176]

[0177] In the formula, R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , n and m and the R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , n and m are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4a With R 4bOptionally bonded to each other to form a ring; R bonded to the same benzene ring 4c With R 4d They may be bonded to each other to form a ring.

[0178] [Chemical formula 40]

[0179]

[0180] In the formula, R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , a3, n and m and the R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , a3, n and m are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4a With R 4b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4c With R 4d They may be bonded to each other to form a ring.

[0181] In the general formulae (4A), (14A) and (15A), the number of repeating units (i.e., n and m) is an integer greater than 0, and is not particularly limited. It can be appropriately selected according to the desired properties, and for example, it is preferably 10 to 1000, and more preferably 10 to 500. In addition, for example, it can be set to an oligomer having a repeating unit number (i.e., n and m) of 1 to 99, preferably an oligomer having a repeating unit number of 2 to 49, more preferably an oligomer having a repeating unit number of 2 to 19, and further preferably an oligomer having a repeating unit number of 3 to 9. The repeating unit numbers n and m of the graphene nanoribbon of the present invention are calculated from the number average molecular weight measured by gel permeation chromatography and converted to polystyrene.

[0182] As a specific embodiment of the graphene nanoribbon of the present invention, R 4d With R 3d The polymer is formed by copolymerization of graphene nanoribbons with different groups and different substituents. 4aWith R 3a , R 4b With R 3b , R 4c With R 3c The same applies to the case where different groups are used. The graphene nanoribbons can form vesicles and micelles, for example, because they can simultaneously exhibit lipid solubility and water solubility, and can be used as water-soluble carbon materials.

[0183] In addition, the graphene nanoribbon of the present invention having at least one structural unit represented by the above general formula (3) can also be made into a polymer having at least one structural unit represented by the above general formula (1) and at least one structural unit represented by the general formula (3) (however, in this case, the structural unit represented by the general formula (3) is not the same as the structural unit represented by the general formula (1)). In this case, considering the compound used as an initiator in the preparation method described later, it is preferred that at least one terminal has at least one structural unit among the structural units represented by the above general formulas (11), (12) and (13).

[0184] That is, the graphene nanoribbon of the present invention can be a graphene nanoribbon represented by the following general formula (4A1), general formula (14A1) or general formula (15A1).

[0185] [Chemical formula 41]

[0186]

[0187] In the formula, the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , a1, a2, n and m and the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , a1, a2, n and m are the same; R bonded to the same benzene ring3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5a With R 5b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5c With R 5d They may be bonded to each other to form a ring.

[0188] [Chemical formula 42]

[0189]

[0190] In the formula, R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , n and m and the R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , n and m are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5a With R 5b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5c With R 5d They may be bonded to each other to form a ring.

[0191] [Chemical formula 43]

[0192]

[0193] In the formula, R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , a3, n and m and the R 3a , R 3b , R3c , R 3d , R 5a , R 5b , R 5c , R 5d , a3, n and m are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5a With R 5b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5c With R 5d They may be bonded to each other to form a ring.

[0194] The above-mentioned graphene nanoribbon having at least one structural unit represented by the above-mentioned general formula (1) and at least one structural unit represented by the general formula (3) is a graphene nanoribbon whose width changes midway in the molecule. For the properties (metallicity or semiconductor) of the graphene nanoribbon, since it can be changed according to its width or peripheral structure, it is possible to make a graphene nanoribbon that exhibits both semiconductor properties and metallic properties. By replacing transistors with graphene nanoribbon blocks having semiconductor properties in this block copolymer, and replacing metal nanowires of electronic circuits with graphene nanoribbon blocks having metallic properties in this block copolymer, transistors composed of graphene nanoribbons can be expected.

[0195] In the graphene nanoribbon of the present invention, the number average molecular weight is not particularly limited and can be appropriately selected according to the desired properties. From the perspective of solubility, for example, it is preferably 10,000 or more, more preferably 15,000 to 300,000, further preferably 20,000 to 200,000, and particularly preferably 30,000 to 150,000. In addition, for example, when a low molecular weight oligomer is prepared, the number average molecular weight of the graphene nanoribbon of the present invention can be set to, for example, 500 to 5,000. The number average molecular weight of the graphene nanoribbon of the present invention is measured by gel permeation chromatography and converted to polystyrene.

[0196] The polydispersity index (PDI) of the graphene nanoribbons of the present invention is determined by connecting two polystyrene gel columns (TOSOH TSKgel Multipore H XL The amount was calculated by size exclusion chromatography (SEC) using a 4-M SEC column (7.8 mm×300 mm) and eluting with a tetrahydrofuran (THF) eluent containing 0.1% tetrabutylammonium bromide (TBAB) at 40°C and a liquid feeding rate of 1.0 mL / min.

[0197] Graphene nano ribbon of the present invention has said structure, and width depends on the length of the substrate used in the preparation method described later. In addition, the length of graphene nano ribbon of the present invention depends on the degree of polymerization (number of repeating units) of graphene nano ribbon of the present invention. In addition, the length of substrate refers to the length of the compound represented by general formula (5A), general formula (5B), general formula (6), general formula (7) and general formula (7A) described later, dibenzocyclooctadiyne, benzothiophene, benzofuran etc. Therefore, the width of graphene nano ribbon can be controlled by changing the kind of substrate, and the length of graphene nano ribbon can be controlled by changing reaction conditions.

[0198] The width of the graphene nanoribbon of the present invention is preferably 0.1 to 2.0 nm, more preferably 0.5 to 1.5 nm.

[0199] In addition, the length of the graphene nanoribbon of the present invention is preferably more than 10nm, more preferably 20 to 500nm, further preferably 50 to 400nm, and particularly preferably 100 to 300nm. In addition, for example, when the graphene nanoribbon of the present invention is made into a low molecular weight oligomer, the length of the graphene nanoribbon of the present invention can be appropriately selected according to the required characteristics. For example, as long as a silver compound is used on the basis of palladium compounds and o-tetrachlorobenzoquinone in the preparation method described later, it is easy to generate a graphene nanoribbon with a longer length, and when only palladium compounds and o-tetrachlorobenzoquinone are used without using silver compounds, it is easy to generate a graphene nanoribbon with a shorter length. In addition, a long graphene nanoribbon can be expected to be used in semiconductors, solar cells, etc., and even a short graphene nanoribbon can be expected to be used in organic EL elements, etc.

[0200] The above-mentioned graphene nanoribbon of the present invention has high solubility in organic solvents such as chloroform, dichloromethane, tetrahydrofuran (THF), ethyl acetate, and therefore has excellent film-forming properties. In addition, various charge transport materials such as OLED (organic laser display), OFET (organic field effect transistor), and organic thin film solar cells can be expected. It is particularly expected to contribute to the establishment of high-efficiency electron donor molecule groups and high-efficiency electron acceptor molecule groups for organic thin film solar cells.

[0201] 2. Preparation method of graphene nanoribbons

[0202] The graphene nanoribbon of the present invention can be synthesized, for example, by a preparation method having the following first polymerization step:

[0203] (1) A first polymerization step in which an acetylene compound represented by the following general formula (5A), an aromatic compound containing a K region represented by the following general formula (5B), dibenzocyclooctadiyne, benzothiophene or benzofuran and a silole compound represented by the following general formula (6) are reacted in the presence of a palladium compound and o-tetrachlorobenzoquinone.

[0204] [Chemical formula 44]

[0205]

[0206] In the formula, R 1a and R 1b With the R 1a and R 1b k1 and k2 are the same or different and represent an integer from 1 to 3; when k1 and k2 are integers greater than 2, each R 1a and / or R 1b Optional same or different.

[0207] [Chemical formula 45]

[0208]

[0209] In the formula, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , a1 and a2 and the R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , a1 and a2 are the same.

[0210] [Chemical formula 46]

[0211]

[0212] In the formula, R 3a , R 3b , R 3c and R 3d With the R 3a , R 3b , R 3c and R 3d Same; R 6a and R 6b are the same or different and represent a hydrogen atom or an alkyl group.

[0213] In addition, when the graphene nanoribbon of the present invention is made into a block copolymer, the following second polymerization step may be further included after the first polymerization step:

[0214] (2) A second polymerization step of reacting the K-block-containing polymer obtained in step (1) with a silole compound represented by the following general formula (7) in the presence of a palladium compound and o-chlorobenzoquinone.

[0215] [Chemical formula 47]

[0216]

[0217] In the formula, R 4a , R 4b , R 4c , R 4d , R 6a and R 6b With the R 4a , R 4b , R 4c , R 4d , R 6a and R 6b same.

[0218] (2-1) Matrix

[0219] Alkyne compounds

[0220] In the production method of the present invention, examples of the alkyne compound that can be used as a substrate include alkyne compounds represented by the following general formula (5A).

[0221] [Chemical formula 48]

[0222]

[0223] In the formula, R 1a , R 1b , k1 and k2 and the R 1a , R 1b , k1 and k2 are the same.

[0224] In the general formula (5A), from the viewpoint of availability, R 1a and R 1b All are hydrogen atoms.

[0225] In the general formula (5A), k1 and k2 are integers of 1 to 3, and from the viewpoint of availability, k1 and k2 are preferably both 1. 1a and / or R 1b When it is a group other than a hydrogen atom, the substitution position is not particularly limited, but is preferably the para position or the meta position, and more preferably the para position.

[0226] Examples of the alkyne compound include the following alkyne compounds.

[0227] [Chemical formula 49]

[0228]

[0229] In the formula, tBu represents a tert-butyl group; Bpin represents a pinacol boronate group.

[0230] Aromatic compounds containing K region

[0231] In the production method of the present invention, examples of the K-containing aromatic compound that can be used as a substrate include the K-containing aromatic compound represented by the following general formula (5B).

[0232] [Chemical formula 50]

[0233]

[0234] In the formula, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , a1 and a2 and the R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , a1 and a2 are the same.

[0235] In general formula (5B), from the perspective of accessibility, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b Preferred are a hydrogen atom, an alkyl group, and the like.

[0236] In the general formula (5B), a1 and a2 are preferably carbon atoms from the viewpoint of availability and the like.

[0237] Examples of the aromatic compound in the K-containing region include the following aromatic compounds.

[0238] [Chemical formula 51]

[0239]

[0240] In the formula, tBu represents a tert-butyl group; Ph represents a phenyl group.

[0241] Other matrices

[0242] Furthermore, as a substrate (initiator), in addition to the compounds represented by the above-mentioned general formulae (5A) and (5B), dibenzocyclooctadiyne, benzothiophene, and benzofuran can also be used.

[0243] Silole compounds

[0244] In the production method of the present invention, examples of the silole compound that can be used as a substrate in the first polymerization step include silole compounds represented by the following general formula (6).

[0245] [Chemical formula 52]

[0246]

[0247] In the formula, R 3a , R 3b , R 3c and R 3d With the R 3a , R 3b , R 3c and R 3d Same; R 6a and R 6b are the same or different and represent a hydrogen atom or an alkyl group.

[0248] In the production method of the present invention, examples of the silole compound that can be used as a substrate in the second polymerization step include silole compounds represented by the following general formula (7).

[0249] [Chemical formula 53]

[0250]

[0251] In the formula, R 4a , R 4b , R 4c , R 4d , R 6a and R 6b With the R 4a , R 4b , R 4c , R 4d , R 6a and R 6b same.

[0252] The silole compound may be: 3a With R 3b are bonded to each other to form a ring, or in the general formula (7) R 4a With R 4b A silole compound represented by the following general formula (7A) which is bonded to each other to form a ring.

[0253] [Chemical formula 54]

[0254]

[0255] In the formula, R 5a , R 5b , R 5c , R 5d , R 6a and R 6b With the R 5a , R 5b , R 5c , R 5d , R 6a and R 6b same.

[0256] In the general formula (6), R 3a , R 3b , R 3c and R 3d The above groups can be used. 3a , R 3b , R 3c and R 3d When all of R are hydrogen atoms, the thermal durability of the graphene nanoribbon derived from the silole compound can be improved, and the self-aggregation property can be improved because the interaction between molecules becomes stronger. In this regard, when R in the general formula (7) 4a , R 4b , R 4c and R 4d When all of them are hydrogen atoms, R 5a , R 5b , R 5c and R 5d The same is true when both are hydrogen atoms.

[0257] In the general formulae (6), (7) and (7A), R 6a and R 6b The alkyl group represented by the above-mentioned alkyl group may be the alkyl group described above. The type and number of the substituents are also the same as described above.

[0258] Examples of the silole compound that satisfies the above-mentioned conditions and can be used in the first polymerization step and the second polymerization step include the following silole compounds.

[0259] [Chemical formula 55]

[0260]

[0261] In the formula, n-Bu represents n-butyl; n-octyl represents n-octyl.

[0262] Among them, the following compounds are easily obtained as solids (crystals) at room temperature (eg, 25° C.), and are therefore preferred from the viewpoint of easiness in improving the purity by an industrial method such as crystallization.

[0263] [Chemical formula 56]

[0264] and

[0265] Furthermore, from the viewpoint of easily improving the solvent solubility of the obtained graphene nanoribbon, the following compounds are preferred.

[0266] [Chemical formula 57]

[0267]

[0268] In the above general formula (6), R 3a and / or R 3b The compound containing an alkyl group can be synthesized, for example, by a preparation method having the following steps:

[0269] A step of reacting a halogen-containing silole compound represented by the following general formula (8) with a Grignard reagent represented by the following general formula (9) or a boronic acid compound represented by the following general formula (10).

[0270] [Chemical formula 58]

[0271]

[0272] In the formula, R 3c , R 3d , R 6a and R 6b With the R 3c , R 3d , R 6a and R 6b Same; X 1 and X 2 are the same or different and represent a hydrogen atom or a halogen atom; X 1 and X 2 optionally bonded to form a ring containing a halogen atom; wherein X 1 and X 2 Not all hydrogen atoms.

[0273] R 7 MgX 3 (9)

[0274] In the formula, R 7 represents an alkyl group or a monovalent aromatic hydrocarbon group; X 3 represents a halogen atom.

[0275] [Chemical formula 59]

[0276]

[0277] In the formula, R 8 represents an alkyl group or a monovalent aromatic hydrocarbon group; R 9 and R 10 are the same or different and represent a hydrogen atom or an alkyl group; R 9 and R 10 They may be bonded to each other to form a ring together with the adjacent -OBO-.

[0278] In the general formula (8), as X 1 and X 2 Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

[0279] In addition, in the general formula (8), X 1 and X 2 The halogen atoms may be bonded to each other to form a ring containing a halogen atom. Examples of the ring formed in this case include a ring formed by substituting at least one of the halogen atoms on the above-mentioned aromatic hydrocarbon ring and heterocyclic ring.

[0280] The halogen-containing silole compound represented by the general formula (8) can be prepared, for example, by the method described in the examples described below. In addition, from the perspective of industrial availability, the halogen atom in the halogen-containing silole compound represented by the general formula (8) is preferably a chlorine atom. Specifically, for example, the following compounds can be listed.

[0281] [Chemical formula 60]

[0282]

[0283] In the formula, n-octyl represents n-octyl.

[0284] In the general formula (9), R 7 The alkyl group and the monovalent aromatic hydrocarbon group represented by the above-mentioned group can be the same as those described above. The types and numbers of the substituents are also the same as those described above.

[0285] In the general formula (9), as X 3 As the halogen atom represented by the moiety, the above-mentioned halogen atoms can be used.

[0286] Examples of the Grignard reagent satisfying the above conditions include alkyl magnesium halides such as methylmagnesium chloride, methylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, n-hexylmagnesium chloride, n-hexylmagnesium bromide, n-octylmagnesium chloride, n-octylmagnesium bromide, 2-ethylhexylmagnesium chloride, and 2-ethylhexylmagnesium bromide; and phenylmagnesium chloride, phenylmagnesium bromide, 4-n-butylphenylmagnesium chloride, 4-n-butylphenylmagnesium bromide, 4-n-octylphenylmagnesium chloride, and 4-n-octylphenylmagnesium bromide.

[0287] When the halogen-containing silole compound represented by the general formula (8) is reacted with the Grignard reagent represented by the general formula (9), the reaction can be carried out with reference to the conditions described in, for example, JACS 2002, 124, 13856.

[0288] In the general formula (10), R 8 The alkyl group and the monovalent aromatic hydrocarbon group represented may be the above-mentioned alkyl group and the monovalent aromatic hydrocarbon group. The type and number of the substituents are also the same as above.

[0289] In the general formula (10), R 9 and R 10 The alkyl group represented by the above-mentioned alkyl group may be the alkyl group described above. The type and number of the substituents are also the same as described above.

[0290] In addition, when R in the general formula (10) 9 and R 10 When both are alkyl groups, the two may be bonded to each other to form a ring together with the adjacent -OBO-. In this case, examples of the boronic acid compound include the following compounds.

[0291] [Chemical formula 61]

[0292]

[0293] In the formula, R 8 With the R 8 same.

[0294] Among these compounds, R 9 and R 10 All are hydrogen atoms.

[0295] Examples of the boronic acid compound satisfying the above conditions include the following compounds.

[0296] [Chemical formula 62]

[0297]

[0298] In the formula, n-Bu represents n-butyl; n-Octyl represents n-octyl.

[0299] When the halogen-containing silole compound represented by the general formula (8) is reacted with the boronic acid compound represented by the general formula (10), the reaction can be carried out with reference to the conditions described in, for example, JACS 2005, 127, 4685.

[0300] In addition, the above shows that R is introduced into the general formula (6). 3a and / or R 3b An example of a method for preparing a compound having an alkyl group of 4a and / or R 4b In the general formula (7A), a compound having an alkyl group of 5a and / or R 5b Compounds containing an alkyl group can also be synthesized in the same manner.

[0301] In the preparation method of the present invention, from the perspective of easily obtaining graphene nanoribbons with higher molecular weight, the amount of the compound (alkyne compound, aromatic compound containing K region, dibenzocyclooctadiyne, benzothiophene, benzofuran or polymer containing K region) reacting with the silole compound in the first polymerization step and the second polymerization step is preferably 0.0005 to 0.5 mol relative to 1 mol of the silole compound, more preferably 0.0005 to 0.1 mol, further preferably 0.001 to 0.05 mol, and particularly preferably 0.002 to 0.03 mol. Furthermore, when the amount of the compound (alkyne compound, aromatic compound containing K region, dibenzocyclooctadiyne, benzothiophene, benzofuran or polymer containing K region) to be reacted with the silole compound is set to 0.01 to 0.5 mol, preferably 0.02 to 0.5 mol, more preferably 0.05 to 0.5 mol, and further preferably 0.1 to 0.5 mol relative to 1 mol of the silole compound, it is also possible to easily obtain a low molecular weight, i.e., a graphene nanoribbon oligomer. That is, a graphene nanoribbon having a desired molecular weight can be designed according to the desired performance and application.

[0302] (2-2) Palladium compounds

[0303] In the preparation method of the present invention, a palladium compound is used as a catalyst. In addition, when the palladium compound is not used, the polymerization reaction hardly proceeds, and it is difficult to obtain the graphene nanoribbon of the present invention.

[0304] As palladium compounds, known palladium compounds as catalysts for synthesis of polymer compounds etc. can be listed, and from the perspective of being easy to obtain graphene nanoribbons with higher molecular weight, divalent palladium compounds are preferably used. As palladium compounds that can be used, for example, Pd(OH)2, Pd(OCOCH3)2, Pd(OCOCF3)2, Pd(acac)2, PdCl2, PdBr2, PdI2, Pd(NO3)2, Pd(CH3CN)4(SbF6)2, etc. can be listed. In addition, acac represents acetylacetonate. In the present invention, from the perspective of using weakly cationic palladium compounds to prevent the matrix silole skeleton from being easily destroyed and to easily obtain graphene nanoribbons with higher molecular weight, Pd(OH)2, Pd(OCOCH3)2, Pd(OCOCF3)2, PdBr2, PdI2, Pd(CH3CN)4(SbF6)2, etc. are preferred, Pd(OCOCH3)2, Pd(OCOCF3)2, PdBr2, PdI2, Pd(CH3CN)4(SbF6)2, etc. are more preferred, and Pd(OCOCF3)2 is further preferred.

[0305] The amount of the palladium compound can be appropriately selected according to the type of substrate. From the perspective of easily obtaining graphene nanoribbons with a higher molecular weight, for example, the amount of the palladium compound is preferably 0.1 to 3.0 mol, more preferably 0.2 to 2.0 mol, and further preferably 0.5 to 1.5 mol relative to 1 mol of the silole compound as the substrate.

[0306] (2-3) o-Tetrachlorobenzoquinone

[0307] In the preparation method of the present invention, o-tetrachlorobenzoquinone is used as an oxidant. In addition, when o-tetrachlorobenzoquinone is not used, polymerization reaction is hardly carried out, and the graphene nanoribbon of the present invention cannot be obtained. In addition, when other oxidants (p-tetrachlorobenzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 3,5-di-tert-butyl-1,2-benzoquinone, CuCl2, etc.) are used to replace o-tetrachlorobenzoquinone, polymerization reaction is also hardly carried out, and the graphene nanoribbon of the present invention cannot be obtained.

[0308] The amount of o-tetrachlorobenzoquinone used can be appropriately selected according to the type of substrate. From the perspective of easily obtaining graphene nanoribbons with a higher molecular weight, for example, the amount of o-tetrachlorobenzoquinone used is preferably 0.5 to 5.0 mol, more preferably 1.0 to 3.0 mol, and further preferably 1.5 to 2.5 mol relative to 1 mol of the thiole compound as the substrate.

[0309] (2-4) Silver compounds

[0310] In the preparation method of the present invention, it is preferably carried out in the presence of a silver compound. By using a silver compound, it is easy to obtain graphene nanoribbons with a higher molecular weight.

[0311] There is no particular limitation on the silver compound, and examples thereof include organic silver compounds such as silver acetate, silver pivalate (AgOPiv), silver trifluoromethanesulfonate (AgOTf), and silver benzoate (AgOCOPh); inorganic silver compounds such as silver nitrate, silver fluoride, silver chloride, silver bromide, silver iodide, silver sulfate, silver oxide, silver sulfide, silver tetrafluoroborate (AgBF4), silver hexafluorophosphate (AgPF6), and silver hexafluoroantimonate (AgSbF6), etc. From the perspective of easily obtaining graphene nanoribbons with higher molecular weight, inorganic silver compounds are preferred, and silver tetrafluoroborate (AgBF4), silver hexafluorophosphate (AgPF6), and silver hexafluoroantimonate (AgSbF6) are more preferred, and silver tetrafluoroborate (AgBF4), silver hexafluoroantimonate (AgSbF6), etc. are further preferred, and silver hexafluoroantimonate (AgSbF6) is particularly preferred. These silver compounds can be used alone or in combination of two or more.

[0312] The amount of the silver compound can be appropriately selected according to the type of the substrate. From the perspective of easily obtaining a graphene nanoribbon with a higher molecular weight, for example, the amount of the silver compound is preferably 0.5 to 5.0 moles, more preferably 1.0 to 3.0 moles, and even more preferably 1.5 to 2.5 moles relative to 1 mole of the silole compound as the substrate. In addition, when using a plurality of silver compounds, it is preferred to adjust the total amount in the above range.

[0313] (2-5) Others

[0314] In the preparation method of the present invention, it is preferably carried out in a solvent. As a solvent, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane can be listed; aliphatic halogenated hydrocarbons such as dichloromethane, dichloroethane (DCE), chloroform (CHCl3), carbon tetrachloride, and trichloroethylene (TCE); aromatic halogenated hydrocarbons such as bromobenzene (PhBr), 1,3,5-tribromobenzene (PhBr3), etc. These solvents can be used alone or in combination of two or more. In the present invention, among these solvents, from the perspective of easily obtaining graphene nanoribbons with higher molecular weight, aliphatic halogenated hydrocarbons, aromatic halogenated hydrocarbons, etc. are preferred, and dichloroethane (DCE), chloroform (CHCl3), trichloroethylene (TCE), bromobenzene (PhBr), 1,3,5-tribromobenzene (PhBr3), etc. are more preferred, and dichloroethane (DCE), trichloroethylene (TCE), 1,3,5-tribromobenzene (PhBr3), etc. are further preferred, and dichloroethane (DCE), trichloroethylene (TCE), 1,3,5-tribromobenzene (PhBr3), etc. are particularly preferred, and dichloroethane (DCE) is particularly preferred.

[0315] In the production method of the present invention, in addition to the above-mentioned components, additives may be appropriately used within a range that does not impair the effects of the present invention.

[0316] The preparation method of the present invention is preferably carried out under anhydrous conditions and in an inert gas atmosphere (nitrogen, argon, etc.), and the reaction temperature is usually preferably about 40 to 110° C., more preferably about 50 to 100° C., and further preferably 60 to 90° C. The reaction time can be set to a time sufficient for the polymerization reaction, and is usually preferably 10 minutes to 72 hours, and more preferably 1 to 48 hours.

[0317] After the reaction is completed, the target graphene nanoribbon can be obtained through conventional separation and purification steps (removal of metals by silica gel column chromatography, separation or separation and purification of polymers by gel permeation chromatography (GPC), etc.).

[0318] 3. Preparation method of armchair graphene nanoribbons

[0319] According to the above-mentioned preparation method, a Fjord-type graphene nanoribbon having at least one structural unit represented by the following general formula (1-2) can generally be obtained.

[0320] [Chemical formula 63]

[0321]

[0322] In the formula, * represents the bonding point; R 3a , R 3b , R 3c and R 3d With the R 3a , R 3b , R 3c and R 3d By subjecting the Fjord-type graphene nanoribbon to a ring contraction reaction, an armchair-type graphene nanoribbon having at least one structural unit represented by the following general formula (1-1) can be obtained.

[0323] [Chemical formula 64]

[0324]

[0325] In the formula, * represents the bonding point; R 3a , R 3b , R 3c and R 3d With the R 3a , R 3b , R 3c and R 3d same.

[0326] More specifically, armchair graphene nanoribbons represented by the following general formula (4-1) can be obtained by subjecting the Fjord-type graphene nanoribbons represented by the following general formula (4-2) obtained by the above-mentioned production method of the present invention to a ring contraction reaction.

[0327] [Chemical formula 65]

[0328]

[0329] In the formula, the dotted line indicates the absence of a bond or a single bond; R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1, a2 and n and the R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1, a2 and n are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d They may be bonded to each other to form a ring.

[0330] [Chemical formula 66]

[0331]

[0332] In the formula, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1, a2 and n and the R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b, R 3c , R 3d , a1, a2 and n are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d They may be bonded to each other to form a ring.

[0333] In the armchair-type graphene nanoribbons obtained by the above method, the armchair-type graphene nanoribbons which are block copolymers are polymers having at least one structural unit represented by the above general formula (1-1) and at least one structural unit represented by the following general formula (2-1), but considering the compound used as an initiator in the above preparation method, it is preferred that at least one end has a structural unit represented by the above general formula (11).

[0334] [Chemical formula 67]

[0335]

[0336] In the formula, * represents the bonding point; R 4a , R 4b , R 4c and R 4d With the R 4a , R 4b , R 4c and R 4d same.

[0337] That is, among the armchair graphene nanoribbons of the present invention, the armchair graphene nanoribbon that is a block copolymer is preferably an armchair graphene nanoribbon represented by the following general formula (4-1A).

[0338] [Chemical formula 68]

[0339]

[0340] In the formula, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , a1, a2, n and m and the R 1a , R 1b , R 1c , R1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , a1, a2, n and m are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4a With R 4b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4c With R 4d They may be bonded to each other to form a ring.

[0341] As a specific embodiment of the armchair graphene nanoribbon of the present invention, R 4d With R 3d The polymer is formed by copolymerization of graphene nanoribbons with different groups and different substituents. 4a With R 3a , R 4b With R 3b , R 4c With R 3c The armchair graphene nanoribbons can be used as water-soluble carbon materials because they can form vesicles and micelles, for example, because they can simultaneously exhibit lipid solubility and water solubility.

[0342] In addition, the graphene nanoribbon of the present invention having at least one structural unit represented by the following general formula (3-1) can also be made into a polymer having at least one structural unit represented by the above general formula (1-1) and at least one structural unit represented by the general formula (3-1) (however, in this case, the structural unit represented by the general formula (3-1) is different from the structural unit represented by the general formula (1-1)). In this case, considering the compound used as an initiator in the above-mentioned preparation method, it is preferred that at least one terminal has a structural unit represented by the above-mentioned general formula (11).

[0343] [Chemical formula 69]

[0344]

[0345] In the formula, * represents the bonding point; R 5a , R 5b , R5c and R 5d With the R 5a , R 5b , R 5c and R 5d same.

[0346] That is, the armchair graphene nanoribbon of the present invention can be made into an armchair graphene nanoribbon represented by the following general formula (4-1B).

[0347] [Chemical formula 70]

[0348]

[0349] In the formula, the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , a1, a2, n and m and the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , a1, a2, n and m are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5a With R 5b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5c With R 5d They may be bonded to each other to form a ring.

[0350] The armchair graphene nanoribbon having at least one structural unit represented by the general formula (1-1) and at least one structural unit represented by the general formula (3-1) is an armchair graphene nanoribbon whose width changes in the middle of the molecule. Since the properties (metallic or semiconducting) of the graphene nanoribbon can be changed according to its width or peripheral structure, it is also possible to make an armchair graphene nanoribbon that exhibits both semiconductor and metallic properties. By replacing transistors with graphene nanoribbon blocks having semiconductor properties in the present block copolymer and replacing metal nanowires of electronic circuits with graphene nanoribbon blocks having metallic properties in the present block copolymer, transistors composed of graphene nanoribbons can be expected.

[0351] The ring contraction reaction is not particularly limited. As the ring contraction reaction, it can be a common oxidation reaction, or it can be a Scholl reaction (dehydrogenation cyclization reaction). In addition, it is not limited to an oxidation reaction, and it can also be a reductive reaction. At this time, an oxidation reaction using antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride, cupric chloride, ferric chloride (FeCl ), boron trifluoride, phosphorus pentoxide, manganese dioxide, selenium oxide, iodine, etc. can be implemented, and a reductive reaction using potassium can also be induced. In the present invention, it is preferred to use FeCl Scholl reaction or a reductive reaction using potassium.

[0352] The solvent used in this step may be a non-polar solvent or a polar solvent. Examples thereof include alkanes such as hexane, heptane, and octane; halogenated alkanes such as dichloromethane, chloroform, carbon tetrachloride, and ethylene chloride; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and pentamethylbenzene; halogenated benzenes such as chlorobenzene and bromobenzene; ethers such as diethyl ether and anisole; methyl nitrate; dimethyl sulfoxide; nitromethane, etc. The above solvents may be used alone or in combination of two or more.

[0353] The reaction temperature of the ring contraction reaction is usually selected from the range of 0°C to the boiling point of the solvent. In addition, the reaction pressure of the ring contraction reaction is usually selected from the range of normal pressure. Furthermore, the reaction time of the ring contraction reaction is usually selected from the range of 1 to 96 hours.

[0354] The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon atmosphere, a nitrogen atmosphere, etc. Alternatively, it may be an air atmosphere.

[0355] After the reaction is completed, the target graphene nanoribbon can be obtained through conventional separation and purification steps (removal of metals by silica gel column chromatography, separation or separation and purification of polymers by gel permeation chromatography (GPC), etc.).

[0356] Example

[0357] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples in any way.

[0358] Unless otherwise specified, all materials including dry solvents were purchased and used without purification. Dimethylchlorosilane was distilled immediately before use. Unless otherwise specified, all reactions were performed using standard vacuum line techniques and oven-dried glassware under nitrogen atmosphere using dry solvents. All post-processing and purification steps were performed in air using reagent grade solvents.

[0359] Thin layer chromatography (TLC) was performed using E. Merck silica gel 60F 254 Pre-coated plate (0.25mm) was used, and the developed chromatogram was analyzed using a UV lamp (254nm). Open column chromatography was implemented using KANTO silica gel 60N (spherical, neutral, 40-100μm). Biotage Metal Scavenger Si-TMT was used as a metal scavenger. Preparative thin layer chromatography (PTLC) was implemented on the basis of TLC plates prepared using Wako-gel (registered trademark) B5-F silica coated plates (0.75mm), and the developed chromatogram was analyzed using UV lamps (254nm and 365nm). Separation and recycling gel permeation chromatography (GPC) was performed using a JAIGEL-3H and 5H chromatographic columns connected in series with a flow rate of 3.5ml / min and CHCl3 as an eluent, and an LC-9210II NEXT instrument (Japan Analytical Industry Co., Ltd) connected in series with UV and RI detectors. The molecular weight of the synthesized polymer (GNR) was determined by using two polystyrene gel columns (TOSOHTSKgel Multipore H XL -M SEC column 7.8mm × 300mm) on a Shimadzu Prominence 2000 instrument and using tetrahydrofuran (THF) containing 0.1% by mass of tetrabutylammonium bromide (TBAB) as the eluent at a flow rate of 1.0mL / min. Molecular weight calibration curves were obtained using standard polystyrene (TOSOH TSKgel polystyrene standards). High-resolution mass spectrometry (HRMS) was measured by using 3-nitrobenzyl alcohol (NBA) as a matrix and using a JEOL JMS-700 (Fast Atom Bombardment Mass Spectrometry, FAB-MS). Nuclear magnetic resonance (NMR) spectra were measured using a JEOL ECS-600 ( 1 H600MHz, 13 C 150MHz) spectrometer.1 H NMR chemical shifts are expressed in parts per million (ppm) relative to tetramethylsilane (δ 0.00 ppm) or CD2Cl2 (δ 5.32 ppm). 13 C NMR chemical shifts are expressed in parts per million (ppm) relative to CDCl3 (δ 77.0 ppm) or C2D2Cl4 (δ 73.78 ppm). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, dd = doublet of doublets, ddd = doublet of doublet of doublets, t = triplet, td = triplet of doublets, q = quartet, m = multiplet), bond constant (Hz), and integration.

[0360] Synthesis Example 1: Synthesis of 3-chloro-3-ethylundecane

[0361] [Chemical formula 71]

[0362]

[0363] In the formula, Et represents ethyl and THF represents tetrahydrofuran.

[0364] Magnesium crumbs (5.8 g, 240 mmol) were added to a 200 mL two-necked round-bottom flask with a magnetic stirrer, and the reaction vessel was heated with a heat gun under reduced pressure while stirring for 10 minutes. After the flask was cooled to room temperature, n-octyl bromide (37.1 mL, 225 mmol) and THF (100 mL) were added. 1,2-dibromoethane (2 drops, for activation of magnesium crumbs) was added to the reaction mixture, and the reaction mixture was stirred at 40°C for 1 hour to prepare the corresponding Grignard reagent. 3-Pentanone (Compound S1; 16.0 mL, 150 mmol) and THF (100 mL) were added to another 300 mL two-necked round-bottom flask with a magnetic stirrer. The prepared Grignard reagent solution was added dropwise to the ketone solution while vigorously stirring at 0°C. Then, the reaction mixture was stirred at 40°C for 14 hours. After confirming the progress of the reaction by TLC, water is used to quench the obtained reaction mixture.Use saturated NH4Cl aqueous solution and water to wash the organic layer, use Na2SO4 to dry, and filter, concentrate under reduced pressure to obtain 3-ethyl-3-hydroxy undecane (compound S2) as a crude product. Add concentrated hydrochloric acid (35mL) to a 200mL round-bottom flask equipped with a magnetic stirrer and compound S2 as a crude product. After stirring the reaction mixture for 1 hour at room temperature, diethyl ether (100mL) is used to extract 3 times. Use brine to wash the combined organic layer, then use Na2SO4 to dry. After filtering, remove the solvent under reduced pressure. By purification based on flash column chromatography (eluent: hexane) on silica gel, 3-chloro-3-ethyl undecane (compound S3; 17.0g) is obtained.

[0365] Synthesis Example 2: Synthesis of APEX Monomer M

[0366] [Chemical formula 72]

[0367]

[0368] In the formula, Et represents ethyl. B2pin2 represents bis(pinacol)diboron. dba represents dibenzylideneacetone. Ph represents phenyl. AcOK represents potassium acetate. Bpin represents pinacolboryl. DME represents 1,2-dimethoxyethane. n-BuLi represents n-butyllithium. THF represents tetrahydrofuran. Me represents methyl. t-Bu represents tert-butyl. C7H5F3 represents trifluorotoluene.

[0369] Under a nitrogen atmosphere, 2-naphthol (compound S4; 12.0 g, 83.2 mmol), 3-chloro-3-ethylundecane (compound S3; 27.3 g, 124.9 mmol) and CH2Cl2 (120 mL) were added to a 200 mL double-necked round-bottom flask with a magnetic stirrer. Then, AlCl3 (11.0 g, 83.2 mmol) was added at room temperature. After the mixture was stirred at 40°C for 6 hours, the reaction was quenched with methanol (30 mL). The organic layer was washed with water, dried with Na2SO4, filtered, and concentrated under reduced pressure to obtain a crude product. Purification based on open column chromatography on silica gel (eluent: CH2Cl2 / hexane = 4:1) gave 6-(3-ethyl-3-undecyl)-2-naphthol (compound S5) (13.0 g, 48%) as a colorless oil.

[0370] Under nitrogen atmosphere, compound S5 (8.00 g, 24.5 mmol) and CH2Cl2 (120 mL) were added to a 200 mL double-mouthed round-bottom flask with a magnetic stirrer. Then, triethylamine (6.83 mL, 49.0 mmol) was added at 0°C. After the mixture was stirred for 0.5 hours at this temperature, (CF3SO2)2O (4.53 mL, 26.9 mmol) was added. After further stirring at 0°C for 2 hours, the reaction was quenched with water. The reaction mixture was extracted 3 times with CH2Cl2 (50 mL). The combined organic layer was washed with brine and then dried with Na2SO4. After filtering, the solvent was removed under reduced pressure to obtain a crude product. Purification by open column chromatography on silica gel (eluent: CH 2 Cl 2 / hexane=4:1) gave 6-(3-ethyl-3-undecyl)-2-naphthyl trifluoromethanesulfonate (Compound S6) (6.12 g) as a colorless oil.

[0371] Under nitrogen atmosphere, compound S6 (5.00 g, 10.9 mmol), bis(pinacolato)diboron (B2pin2; 4.15 g, 16.4 mmol), tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct (Pd2(dba)3-CHCl3; 1.13 g, 1.09 mmol, 10 mol%), triphenylphosphine (PPh3; 3.63 mL, 2.18 mmol, 20 mol%) and potassium acetate (KOAc; 3.21 g, 32.7 mmol) were added to 1,4-dioxane (125 mL) in a 200 mL two-necked round-bottom flask with a magnetic stirrer. The reaction mixture was stirred at 100°C for 4 hours and then quenched with water. The reaction mixture was extracted three times with CH2Cl2 (40 mL). The combined organic layer was washed with brine and then dried with Na2SO4. After filtration, the solvent was removed under reduced pressure to obtain a crude product. Purification was performed by flash column chromatography on silica gel (eluent: hexane / CH2Cl2=4:1) to obtain 2-(6-(3-ethyl-3-undecyl)-2-naphthyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (compound S7) (4.11 g, 84%) as a colorless oil.

[0372] Under nitrogen atmosphere, compound S7 (3.15 g, 7.21 mmol), 1-bromo-2-iodobenzene (1.70 g, 6.01 mmol), bis(triphenylphosphine)palladium(2)dichloride (PdCl2(PPh3)2; 84 mg, 0.12 mmol, 20 mol%) and K2CO3 (2.08 g, 15.0 mmol) were added to 1,2-dimethoxyethane (30 mL) and water (15 mL) in a 200 mL two-necked round-bottom flask with a magnetic stirrer. After stirring the reaction mixture at 80°C for 5 hours, 1,2-dimethoxyethane was evaporated. Water (40.0 mL) and diethyl ether (20.0 mL) were added, and the organic layer was separated. The aqueous layer was extracted three times with diethyl ether (20 mL). The combined organic layer was washed with brine and then dried with Na2SO4. After filtration, the solvent was removed under reduced pressure to obtain a crude product. Purification by flash column chromatography on silica gel (eluent: hexane) gave 2-(2-bromophenyl)-6-(3-ethyl-3-undecyl)naphthalene (Compound S8) (2.50 g, 74%) as a colorless oil.

[0373] Under nitrogen atmosphere, compound S8 (2.50 g, 5.37 mmol) and tetrahydrofuran (THF; 100 mL) were added to a 200 mL double-necked round-bottom flask with a magnetic stirrer. Then, n-butyl lithium (n-BuLi; 1.6 M in n-hexane, 5.03 mL, 8.06 mmol) was added dropwise at -78°C. After the mixture was stirred at this temperature for 15 minutes, distilled dimethylsilyl chloride (0.97 mL, 8.06 mmol) was added at -78°C. After the reaction mixture was stirred at room temperature for 24 hours, it was quenched with water. The reaction mixture was extracted with diethyl ether. The combined organic layer was washed with brine and then dried with Na2SO4. After filtering, the solvent was removed under reduced pressure to obtain a crude product. Purification by flash column chromatography on silica gel (eluent: hexane) gave (2-(6-(3-ethyl-3-undecyl)-2-naphthyl)phenyl)dimethylsilane (Compound S9) (2.12 g, 88%) as a colorless oil.

[0374] Under nitrogen atmosphere, compound S9 (1.3 g, 2.90 mmol) and (trifluoromethyl)benzene (50 mL) were added to a 200 mL two-necked round-bottom flask with a magnetic stirrer. Then, 2-(tert-butylperoxy)-2-methylpropane (1.61 mL, 8.77 mmol) was added at room temperature. The reaction mixture was stirred at 130°C for 36 hours. After cooling to room temperature, the reaction mixture was concentrated and then purified by silica gel column chromatography (eluent: hexane / CH2Cl2=19:1) to obtain 3-(3-ethyl-3-undecyl)-11,11-dimethyl-11H-benzo[b]naphtho[2,1-d]silole (Compound M) (0.72 g, 55%) as a colorless oil.

[0375] 3-(3-ethyl-3-undecyl)-11,11-dimethyl-11H-benzo[b]naphtho[2,1-d]silole (Compound M):

[0376] 1 H-NMR (600MHz, CDCl3) δ7.95 (d, J = 8.4Hz, 1H), 7.87-7.90 (m, 2H), 7.78-7.80 (m, 1H), 7.68-7.72 (m, 2H), 7.51-7.55 (m, 1H), 7.44-7.47 ( m,1H),7.28-7.30(m,1H),1.76-1.78(m,2H),1.35-1.37(m,2H),1.08-1.23(m,12H),0.79-0.85(m,9H),0.65-0.70(m,3H),0.55(s,6H).

[0377] HRMS(FAB+)m / z calcd for C 32 H 43 Si[M+H] + :443.3129, found 443.3126.

[0378] Synthesis Example 3: Synthesis of APEX Monomer M"

[0379] [Chemical formula 73]

[0380]

[0381] In the formula, Ts represents a tosyl group. DMF represents dimethylformamide. n-BuLi represents n-butyllithium. THF represents tetrahydrofuran. i-Pr represents an isopropyl group. Ph represents a phenyl group. DME represents 1,2-dimethoxyethane. Me represents a methyl group. t-Bu represents a tert-butyl group. C7H5F3 represents trifluorotoluene.

[0382] Under nitrogen atmosphere, 2-(2-(2-methoxyethoxy)ethoxy)ethyl 4-methylbenzenesulfonate (compound S11; 13.9 g, 101 mmol), 6-bromo-2-naphthol (compound S10; 7.50 g, 33.6 mmol), K2CO3 (13.9 g, 101 mmol) and dimethylformamide (DMF; 150 mL) were added to a 200 mL two-necked round-bottom flask with a magnetic stirrer. After stirring the mixture at 100°C for 14 hours, the reaction was quenched with water (30 mL). The reaction mixture was extracted three times with ethyl acetate (EtOAc; 100 mL). The combined organic layers were washed with brine and then dried with Na2SO4. After filtration, the solvent was removed under reduced pressure to obtain a crude product. Purification by open column chromatography on silica gel (eluent: ethyl acetate / hexane = 2:1) gave 2-bromo-6-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)naphthalene (Compound S12) (11.5 g, 93%) as a colorless oil.

[0383] Under nitrogen atmosphere, compound S12 (5.00 g, 13.5 mmol) and tetrahydrofuran (THF; 135 mL) were added to a 200 mL double-necked round-bottom flask with a magnetic stirrer. Then, n-butyl lithium (n-BuLi; 1.6 M in n-hexane, 9.34 mL, 14.9 mmol) was added dropwise at -78°C. After the mixture was stirred at this temperature for 10 minutes, triisopropyl borate (B(Oi-Pr)3; 1.94 mL, 16.3 mmol) was added at -78°C. After the reaction mixture was stirred at room temperature overnight, it was quenched with 1N HCl. The reaction mixture was extracted with ethyl acetate. The combined organic layer was washed with brine and then dried with Na2SO4. After filtration, the solvent was removed under reduced pressure to obtain a crude product. Purification by flash column chromatography on silica gel (eluent: ethyl acetate / hexane = 2:1) gave (6-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)naphthalen-2-yl)boronic acid (Compound S13) (4.5 g, 99%) as a colorless oil.

[0384] Under nitrogen atmosphere, compound S13 (4.50 g, 13.5 mmol), 1-bromo-2-iodobenzene (2.31 mL, 16.4 mmol), bis(triphenylphosphine)palladium dichloride (2) (PdCl2(PPh3)2; 210 mg, 0.29 mmol, 20 mol%) and K2CO3 (4.14 g, 29.9 mmol) were added to 1,2-dimethoxyethane (150 mL) and water (20 mL) in a 200 mL two-necked round-bottom flask with a magnetic stirrer. After stirring the reaction mixture at 80°C for 5 hours, 1,2-dimethoxyethane was evaporated. Water (40 mL) and ethyl acetate (50 mL) were added, and the organic layer was separated. The aqueous layer was extracted three times with ethyl acetate (50 mL). The combined organic layer was washed with brine and then dried with Na2SO4. After filtration, the solvent was removed under reduced pressure to obtain a crude product. Purification by flash column chromatography on silica gel (eluent: ethyl acetate) gave 2-(2-bromophenyl)-6-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)naphthalene (Compound S14) (4.6 g) as a colorless oil.

[0385] Under nitrogen atmosphere, compound S14 (5.0 g, 11.2 mmol) and tetrahydrofuran (THF; 100 mL) were added to a 200 mL double-necked round-bottom flask with a magnetic stirrer. Then, n-butyl lithium (n-BuLi; 1.6 M in n-hexane, 10.1 mL, 10.7 mmol) was added dropwise at -78°C. After the mixture was stirred at this temperature for 15 minutes, distilled dimethylsilyl chloride (1.79 mL, 16.1 mmol) was added at -78°C. After the reaction mixture was stirred at room temperature for 24 hours, it was quenched with water. The reaction mixture was extracted with diethyl ether. The combined organic layer was washed with brine and then dried with Na2SO4. After filtering, the solvent was removed under reduced pressure to obtain a crude product. Extraction by flash column chromatography on silica gel (eluent: hexane) gave (2-(6-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)naphthalen-2-yl)phenyl)dimethylsilane (Compound S15) (3.00 g, 63%) as a colorless oil.

[0386] Under nitrogen atmosphere, compound S15 (0.1 g, 0.22 mmol) and (trifluoromethyl)benzene (5.0 mL) were added to a 200 mL two-necked round-bottom flask containing a magnetic stirrer. Then, 2-(tert-butylperoxy)-2-methylpropane (0.12 mL, 0.67 mmol) was added at room temperature. The reaction mixture was stirred at 130°C for 36 hours. After cooling to room temperature, the reaction mixture was concentrated and then purified by column chromatography on silica gel (eluent: hexane) to obtain 3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-11,11-dimethyl-11H-benzo[b]naphtho[2,1-d]silole (Compound M") (40 mg, 40%) as a colorless oil.

[0387] 3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-11,11-dimethyl-11H-benzo[b]naphtho[2,1-d]silole (Compound M"):

[0388] 1H-NMR (600MHz, CD2Cl2) δ7.91(d,J=9.0Hz,1H),7.80-7.84(m,4H),7.75(d,J=9.0Hz,1H),7.65(d,J=7.8Hz,1H),7.42(t,1H),7.26(t,1H ),7.21-7.19(m,2H),4.23(t,J=4.8Hz,2H),3.87(m,2H),3.69(m,2H),3.62(m,2H),3.58(m,2H),3.49(m,2H),3.37(s,3H),0.56(s,6H).

[0389] HRMS(FAB+)m / z calcd for C 25 H 30 O4Si[M] + :422.1913,found422.1915.

[0390] Synthesis Example 4: Synthesis of APEX Monomer M''

[0391] [Chemical formula 74]

[0392]

[0393] In the formula, Et represents an ethyl group. Bpin represents a pinacol boroyl group. Ph represents a phenyl group. n-BuLi represents n-butyl lithium. THF represents tetrahydrofuran. Me represents a methyl group. i-Pr represents an isopropyl group.

[0394] Under nitrogen atmosphere, 1-bromonaphthalen-1-ol (4.00 g, 17.9 mmol) and dichloromethane (170 mL) were added to a 300 mL double-necked round-bottom flask with a magnetic stirrer. Then, triethylamine (5.0 mL, 36 mmol) was added dropwise at 0°C. Then, triethylamine (6.83 mL, 49.0 mmol) was added at 0°C. After stirring the mixture at this temperature for 0.5 hours, (CF3SO2)2O (3.32 mL, 19.7 mmol) was added. After further stirring at 0°C for 2 hours, the reaction was quenched with water. The reaction mixture was extracted 3 times with CH2Cl2 (50 mL). The combined organic layer was washed with brine and then dried with Na2SO4. After filtering, the solvent was removed under reduced pressure to obtain a crude product. Purification by open column chromatography on silica gel (eluent: CH 2 Cl 2 / hexane=4:1) gave 1-bromo-2-naphthyl trifluoromethanesulfonate (Compound S16) (6.0 g) as a white solid.

[0395] Under nitrogen atmosphere, compound S16 (2.50 g, 7.04 mmol), compound S7 (3.00 g, 67.04 mmol), triphenylphosphine (PPh3; 1.65 mg, 1.41 mmol, 20 mol%), K2CO3 (0.97 g, 7.04 mmol), and 1,4-dioxane (70 mL) were added to a 200 mL double-necked round-bottom flask with a magnetic stirrer. After stirring the reaction mixture at 80°C for 12 hours, 1,4-dioxane was evaporated. Water (40.0 mL) and diethyl ether (20.0 mL) were added, and the organic layer was separated. The aqueous layer was extracted three times with diethyl ether (20 mL). The combined organic layer was washed with brine and then dried with Na2SO4. After filtration, the solvent was removed under reduced pressure to obtain a crude product. Purification by flash column chromatography on silica gel (eluent: hexane) gave 1-bromo-6′-(3-ethyl-3-undecyl)2,2′-binaphthyl (Compound S17) (2.10 g, 57%) as a colorless oil.

[0396] Under nitrogen atmosphere, compound S17 (2.00 g, 3.88 mmol) and tetrahydrofuran (THF; 40 mL) were added to a 200 mL double-necked round-bottom flask with a magnetic stirrer. Then, n-butyl lithium (n-BuLi; 1.6 M in n-hexane, 3.64 mL, 5.82 mmol) was added dropwise at -78°C. After the mixture was stirred at this temperature for 15 minutes, distilled dimethylsilyl chloride (0.65 mL, 5.82 mmol) was added at -78°C. After the reaction mixture was stirred at room temperature for 24 hours, it was quenched with water. The reaction mixture was extracted with diethyl ether. The combined organic layer was washed with brine and then dried with Na2SO4. After filtering, the solvent was removed under reduced pressure to obtain a crude product. Purification by flash column chromatography on silica gel (eluent: hexane) gave (6′-(3-(3-ethyl-3-undecyl)-(2,2′-binaphthyl)dimethylsilane (Compound S18) (1.5 g) as a colorless oil.

[0397] Under nitrogen atmosphere, compound S18 (0.50 g, 1.01 mmol), tris(triphenylphosphine)rhodium chloride (RhCl(PPh3); 46 mg, 5 mol%), 3,3-dimethyl-1-butene (0.65 mL, 75.05 mmol), and 1,4-dioxane (2 mL) were added to a 30 mL two-necked round-bottom flask with a magnetic stirrer. After stirring the reaction mixture at 110°C for 12 hours, 1,2-dioxane was evaporated. Water (40.0 mL) and diethyl ether (20.0 mL) were added, and the organic layer was separated. The aqueous layer was extracted three times with diethyl ether (20 mL). The combined organic layers were washed with brine and dried with Na2SO4. After filtration, the solvent was removed under reduced pressure to obtain a crude product. Purification by flash column chromatography on silica gel (eluent: hexane) gave 3-(3-ethyl-3-undecyl)-13,13-dimethyl-13H-dinaphtho[1,2,-b:2',3',-d]silole (Compound M'") (0.31 g, 62%) as a colorless oil.

[0398] 1 H-NMR (600MHz, CDCl3) δ10.58(s,1H),10.48-10.46(m,2H),10.30(d,J=8.4Hz,1H),10.23-10.21(m,2H),10.16(d, J=9Hz,1H),10.02(s,1H),9.88-9.87(m,3H),4.13-3.90(m,4H),3.58-3.52(m,2H),3.28-2.98(m,9H),2.33(s,6H).

[0399] HRMS(FAB+)m / z calcd for C 35 H 44 Si[M] + :492.3212,found492.3209.

[0400] Synthesis Example 5: Synthesis of halogen-containing silole compound S23

[0401] [Chemical formula 75]

[0402]

[0403] In the formula, Tf represents trifluoromethanesulfonyl group and Me represents methyl group. n Bu represents n-butyl. t Bu represents tert-butyl. Ph represents phenyl. dppp represents 1,3-bis(diphenylphosphino)propane. dba represents dibenzylideneacetone. THF represents tetrahydrofuran.

[0404] Under nitrogen atmosphere, 1-bromo-2-naphthol (compound S19; 13.4 g, 60 mmol) and CH2Cl2 (120 mL) were added to a 300 mL double-necked round-bottom flask with a magnetic stirrer. Then, pyridine (9.7 mL, 120 mmol) was added at 0°C. After stirring the mixture at this temperature for 10 minutes, trifluoromethanesulfonic anhydride (Tf2O; 10.0 mL, 60 mmol) was added. After further stirring at 0°C for 2 hours. The reaction was quenched with water. The reaction mixture was extracted three times with ethyl acetate (50 mL). The combined organic layers were washed with brine and then dried with Na2SO4. After filtering, the solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by chromatography on silica gel (eluent: hexane) to obtain 1-bromo-2-naphthyl trifluoromethanesulfonate (compound S20) (21.2 g, >99%) as a brown oil.

[0405] Under nitrogen atmosphere, magnesium crumbs (2.7 g, 109 mmol) were added to a 100 mL two-necked round-bottom flask with a magnetic stirrer, and the reaction vessel was heated with a heat gun under reduced pressure while stirring for 10 minutes. After the flask was cooled to room temperature, 1-bromo-4-chlorobenzene (15.7 g, 82 mmol) and diethyl ether (Et2O; 54 mL) were added. The reaction mixture was stirred at room temperature for 30 minutes to prepare the corresponding Grignard reagent. Compound S20 (19.4 g, 55 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3; 1.0 g, 1 mmol), 1,3-bis(diphenylphosphino)propane (dppp; 0.84 g, 2 mmol), LiBr (4.7 g, 55 mmol) and Et2O (27 mL) were added to another 100 mL two-necked round-bottom flask with a magnetic stirrer. The Grignard reagent prepared separately in the above manner was added dropwise to the reaction mixture while stirring at 0°C. After the addition, the reaction mixture was warmed to room temperature and stirred at room temperature for 14 hours, then quenched with 1M HCl and extracted three times with ethyl acetate (50 mL). The combined organic layer was washed with brine and then dried with Na2SO4. After filtering, the solvent was removed under reduced pressure to obtain a crude product. The crude product was recrystallized from ethyl acetate to obtain 1-bromo-2-(4-chlorophenyl)naphthalene (compound S21) (13.79 g, 80%) as pale yellow crystals.

[0406] Under nitrogen atmosphere, compound S21 (3.2 g, 10 mmol) and tetrahydrofuran (THF; 50 mL) were added to a 100 mL two-necked round-bottom flask with a magnetic stirrer. After the reaction mixture was cooled to -78°C, n-butyllithium (n-BuLi; 1.6 M in n-hexane, 7.0 mL, 11 mmol) was added dropwise to the reaction mixture while stirring at -78°C. After the reaction mixture was stirred at the same temperature for 30 minutes, dimethylsilyl chloride (1.4 mL, 20 mmol) was added at -78°C and stirred at the same temperature for 1 hour. After stirring, the temperature was raised to room temperature, stirred at room temperature for 14 hours, then quenched with cold water, and extracted three times with diethyl ether (Et2O; 50 mL). The combined organic layer was washed with brine and then dried with Na2SO4. After filtration, the solvent was removed under reduced pressure to obtain a crude product. The crude product was recrystallized using hexane to obtain (2-(4-chlorophenyl)-1-dimethylsilylnaphthalene (Compound S22) (2.38 g, 80%) as pale yellow crystals.

[0407] Under nitrogen atmosphere, compound S22 (1.0 g, 3.4 mmol), tris(triphenylphosphine)rhodium chloride (I) (RhCl(PPh3)3; 62 mg, 0.07 mmol), 3,3-dimethyl-1-butene (2.2 mL, 16.8 mmol) and toluene (3.4 mL) were added to a 20 mL round-bottom flask with a magnetic stirrer. The reaction mixture was heated and stirred at reflux (bath temperature 130°C) for 4 hours. After cooling to room temperature, the solvent was removed under reduced pressure to obtain a crude product. The crude product was purified by chromatography on silica gel (eluent: hexane) to obtain 9-chloro-11,11-dimethyl-11H-benzo[b]naphtho[2,1-d]silole (compound S23) (450 mg, 45%) as colorless crystals.

[0408] 1 H-NMR (400MHz, CDCl3) δ7.92(d,J=5.4Hz,2H),7.89-7.84(m,1H),7.84-7.81(m,1H),7.79(d,J=8.4Hz,1 H),7.61(d,J=2.0Hz,1H),7.55-7.49(m,1H),7.49-7.44(m,1H),7.42(dd,J8.4,2.0Hz,1H),0.59(s,6H).

[0409] 13C-NMR (100MHz, CDCl3) δ146.3,145.7,141.6,136.8,136.6,133.5,133.0,132.5,-2.8,-3.0.

[0410] HRMS(FAB+)m / z calcd for C 18 H 15 ClSi[M+] + :294.0632,found 294.0659.

[0411] Synthesis Example 6: Synthesis of APEX Monomer M3

[0412] [Chemical formula 76]

[0413]

[0414] In the formula, n-octyl represents n-octyl, acac represents acetylacetonato, and THF represents tetrahydrofuran.

[0415] Under nitrogen atmosphere, compound S23 (147 mg, 0.5 mmol), tris(acetylacetonato)iron(III) (Fe(acac)3; 9 mg, 0.03 mmol), tetrahydrofuran (THF; 3.0 mL) and N-methyl-2-pyrrolidone (NMP; 0.2 mL) were added to a 20 mL round-bottom flask with a magnetic stirrer. n-Octylmagnesium bromide (1.0 M in THF, 0.6 mL, 0.6 mmol) was added to the reaction mixture at 0°C. The mixture was then warmed to room temperature and stirred at room temperature for 14 hours, then quenched with water and extracted three times with ethyl acetate (5 mL). The combined organic layers were washed with brine and dried over Na2SO4. After filtration, the solvent was removed under reduced pressure to obtain a crude product. The obtained crude product was purified by chromatography on silica gel (eluent: hexane) to obtain (11,11-dimethyl-9-octyl-11H-benzo[b]naphtho[2,1-d]silole (Compound M3) (64 mg, 34%) as colorless crystals.

[0416] 1H-NMR (400MHz, CDCl3) δ7.96(d,J=7.9Hz,1H),7.91(d,J=7.9Hz,1H),7.84(t,J=7.9Hz,2H),7.80(d,J=7.9Hz,1H),7.56-7.49(m,2H) ,7.43(t,J=7.9Hz,1H),7.32-7.27(m,1H),2.66(t,J=7.9Hz,2H),1.66(quin,J=7.9Hz,2H),1.46-1.24(t,J=6.8Hz,3H),0.58(s,6H).

[0417] 13 C-NMR (100MHz, CDCl3) δ146.9,145.7,142.2,139.2,136.8,136.6,132.85,132.81,130.8,130.3,1 28.9,128.3,126.5,125.1,120.8,119.7,36.0,31.9,31.7,29.5(2C),29.3,22.7,14.1,-2.7(2C).

[0418] HRMS(FAB+)m / z calcd for C 26 H 32 Si[M+] + :372.2273, found 372.2285.

[0419] Synthesis Example 7: Synthesis of APEX Monomer M4

[0420] [Chemical formula 77]

[0421]

[0422] In the formula, n-Bu represents a normal butyl group, Ac represents an acetyl group, and SPhos represents a compound represented by the following formula (2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl).

[0423] [Chemical formula 78]

[0424]

[0425] In the formula, Cy represents a cyclohexyl group.

[0426] Under nitrogen atmosphere, compound S23 (147 mg, 0.5 mmol), n-butylphenylboronic acid (133 mg, 0.75 mmol), palladium acetate (Pd(OAc)2; 6 mg, 0.025 mmol), 2-dicyclohexylphosphine-2',6'dimethoxybiphenyl (SPhos; 21 mg, 0.05 mmol), K3PO4 (318 mg, 1.5 mmol) and toluene (1 mL) were added to a 20 mL round-bottom flask with a magnetic stirrer. The reaction mixture was heated to 100°C and stirred at the same temperature for 18 hours, then quenched with water and extracted three times with ethyl acetate (5 mL). The combined organic layer was washed with brine and then dried with Na2SO4. After filtration, the solvent was removed under reduced pressure to obtain a crude product. The obtained crude product was purified by chromatography on silica gel (eluent: hexane) to obtain 9-(4-butylphenyl)-11,11-dimethyl-11H-benzo[b]naphtho[2,1-d]silole (Compound M4) (128 mg, 65%) as colorless crystals.

[0427] 1 H-NMR (400MHz, CDCl3) δ8.03-7.91(m,3H),7.91-7.83(m,3H),7.69(dd,J=7 .9,1.8Hz,1H),7.59(d,J=8.2Hz,2H),7.59(d,J=8.2Hz,2H),7.55-7.49(m,1 H),7.48-7.42(m,1H),7.28(d,J=8.2Hz,2H),2.66(t,J=7.5,2H),1.66(qui n,J=7.5Hz,2H),1.41(sex,J=7.5Hz,2H),0.96(t,J=7.5Hz,3H),0.62(s,6H)

[0428] 13 C-NMR (100MHz, CDCl3) δ146.9,146.5,142.1,140.2,139.8,138.5,137.1,136.8,133.0,131.3,131.0, 128.95,128.91,128.86(2C),128.4,126.9,126.7,125.4,121.3,119.8,35.3,33.7,22.4,14.0,-2.75.

[0429] HRMS(FAB+)m / z calcd for C 28 H 28 Si[M+] +:392.1960, found 392.1960.

[0430] Example 1: APEX polymerization based on initiator I' (Part 1)

[0431] [Chemical formula 90]

[0432]

[0433] In the formula, n-octyl represents n-octyl.

[0434] Under nitrogen atmosphere, monomer M3 (25.0 mg, 67.8 μmol, 1.00 equiv), Pd(OCOCF3)2 (22.5 mg, 67.8 μmol, 1.00 equiv), AgSbF6 (46.6 mg, 135 μmol, 2.00 equiv) and o-tetrachlorobenzoquinone (33.3 mg, 135 μmol, 2.00 equiv) were added to a 5 mL Schlenk tube with a magnetic stirrer. A solution of initiator I' (0.12 mg, 6.78 μmol, 0.01 equiv) in 1,2-dichloroethane (0.1 mL) was added to the reaction mixture, followed by 1,2-dichloroethane (0.57 mL). After the mixture was stirred at 80°C for 21.5 hours, the reaction mixture was cooled to room temperature and passed through a short pad of silica gel, and then passed through a metal capture agent while being washed with CH2Cl2. The solvent was removed under reduced pressure to obtain a crude product. The crude polymer was analyzed by size exclusion chromatography (SEC) using a 0.1% by mass solution of tetrabutylammonium bromide (TBAB) in tetrahydrofuran as an eluent, and it was confirmed that Mn = 1.9 × 10 4 Fjord-type graphene nanoribbon GNR14.

[0435] Example 2: APEX polymerization based on initiator I' (Part 2)

[0436] [Chemical formula 91]

[0437]

[0438] In the formula, n-Bu represents n-butyl.

[0439] The reaction was carried out in the same manner as in Example 1 except that 0.067 mmol (26 mg) of monomer M4 was used instead of monomer M3 to obtain a crude product. The crude product was analyzed by size exclusion chromatography (SEC) under the same conditions as those described in Example 1, and it was confirmed that Mn = 1.5 × 10 4 Fjord-type graphene nanoribbon GNR15.

[0440] Examples 3-14: APEX polymerization based on various initiators

[0441] The crude product was obtained by the same reaction as in Example 1 except that 6.78 μmol (0.01 equivalent) of the initiator shown in Tables 1 to 2 was used instead of the initiator I'. The crude product was analyzed by size exclusion chromatography (SEC) under the same conditions as those described in Example 1 to confirm the Mn of the obtained GNR. The Mn is shown in Tables 1 to 2.

[0442] In addition, in Tables 1 and 2, R is the following group.

[0443] [Chemical formula 92]

[0444]

[0445] In the formula, Et represents an ethyl group; nOctyl represents an n-octyl group. In addition, in Table 1, OMe represents a methoxy group, CO2Me represents a methoxycarbonyl group, and Bpin represents a pinacol boroyl group. Furthermore, in Table 2, tBu represents a tert-butyl group.

[0446] [Table 1]

[0447]

[0448] [Table 2]

[0449]

[0450] Example 15: APEX polymerization based on initiator I''

[0451] [Chemical formula 93]

[0452]

[0453] Under nitrogen atmosphere, 2,7-bis((2,5,8,11,14,17,20,23,26,29,32,35-dodeca-triacontane-37-yl)oxy)phenanthrene (initiator I"'; 34.3 mg, 26.5 μmol, 0.20 equiv), benzonaphthosilole (monomer M5; 34.5 mg, 132 μmol, 1.00 equiv), Pd(OCOCF3)2 (44.0 mg, 132 μmol, 1.00 equiv), AgSbF6 (91.0 mg, 2 65μmol, 2.00 equivalents) and o-tetrachlorobenzoquinone (65.1mg, 265μmol, 2.00 equivalents). 1,2-Dichloroethane (1.3mL) was added to the reaction mixture. After stirring the mixture at 80°C for 21.5 hours, the reaction mixture was cooled to room temperature and passed through a short silica gel column, and then passed through a metal capture agent while washing with CH2Cl2. The solvent was removed under reduced pressure to obtain a crude product. Fjord-type graphene nanoribbon GNR16 was obtained as a black powder by purification based on gel permeation chromatography (GPC).

Claims

1. A graphene nanoribbon having at least one structural unit represented by the following general formula (1), In formula (1), the dashed line indicates the absence of a bond; *1 indicates a bonding point; R 3a , R 3b , R 3c and R 3d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an ether group or a polyether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 3a With R 3b and / or R 3c With R 3d They may be bonded to each other to form a ring.

2. The graphene nanoribbon according to claim 1, comprising at least one structural unit represented by the following general formula (3): In formula (3), the dashed line indicates the absence of a bond; *5 indicates the bonding point; R 5a , R 5b , R 5c and R 5d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an ether group or a polyether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 5a With R 5b and / or R 5c With R 5d They may be bonded to each other to form a ring.

3. The graphene nanoribbon according to claim 1 or 2, further comprising at least one structural unit represented by the following general formula (2): In formula (2), the dashed line indicates the absence of a bond; *3 indicates the bonding point; R 4a , R 4b , R 4c and R 4d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an ether group or a polyether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 4a With R 4b and / or R 4c With R 4d are optionally bonded to each other to form a ring; wherein, R 4a With R 3a Different, R 4b With R 3b Different, R 4c With R 3c Different, and R 4d With R 3d different.

4. A graphene nanoribbon comprising at least one structural unit represented by the following general formula (1), and at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (11), a structural unit represented by the following general formula (12), and a structural unit represented by the following general formula (13), In formula (1), the dashed lines are the same or different and represent the absence of a bond or a single bond; *1 represents a bonding point; when the dashed line bonded to *2 is a single bond, *2 represents a bonding point; R 3a , R 3b , R 3c and R 3d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an ether group or a polyether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R 3a With R 3b and / or R 3c With R 3d optionally bonded to each other to form a ring, In formula (11), the dashed line is the same as the dashed line; *1 represents a bonding point; when the dashed line bonded to *2 is a single bond, *2 represents a bonding point; R 1a , R 1b , R 1c , R 1d , R 2a and R 2b are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an ether group or a polyether group, an ester group, a boronic acid or an ester group thereof, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; a1 and a2 are the same or different and represent a carbon atom or a nitrogen atom; R 1c With R 1d optionally bonded to each other to form a ring, In formula (12), *7 represents the bonding point, In formula (13), *8 represents a bonding point; a3 represents an oxygen atom or a sulfur atom.

5. The graphene nanoribbon according to claim 4, which is represented by the following general formula (4), the following general formula (14) or the following general formula (15), In formula (4), the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 and the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d They are optionally bonded to each other to form a ring; n represents an integer greater than 0, In formula (14), R 3a , R 3b , R 3c , R 3d and n and R 3a , R 3b , R 3c , R 3d and n are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d optionally bonded to each other to form a ring, In formula (15), R 3a , R 3b , R 3c , R 3d , n and a3 and said R 3a , R 3b , R 3c , R 3d , n and a3 are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d They may be bonded to each other to form a ring.

6. The graphene nanoribbon according to claim 4, which is represented by the following general formula (4A), the following general formula (14A) or the following general formula (15A), In formula (4A), the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 and the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 are the same; R 4a , R 4b , R 4c and R 4d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an ether group or a polyether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4a With R 4b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4c With R 4d are optionally bonded to each other to form a ring; wherein, R 4a With R 3a Different, R 4b With R 3b Different, R 4c With R 3c Different, and R 4d With R 3d different; n and m are the same or different and represent an integer greater than 0, In formula (14A), R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , n and m and the R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , n and m are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4a With R 4b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4c With R 4d optionally bonded to each other to form a ring, In formula (15A), R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , n, m and a3 and the R 3a , R 3b , R 3c , R 3d , R 4a , R 4b , R 4c , R 4d , n, m and a3 are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4a With R 4b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 4c With R 4d They may be bonded to each other to form a ring.

7. The graphene nanoribbon according to any one of claims 4 to 6, which is represented by the following general formula (4A1), the following general formula (14A1) or the following general formula (15A1), In formula (4A1), the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 and the dotted line, R 1a , R 1b , R 1c , R 1d , R 2a , R 2b , R 3a , R 3b , R 3c , R 3d , a1 and a2 are the same; R 5a , R 5b , R 5c and R 5d are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an ether group or a polyether group, an ester group, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5a With R 5b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5c With R 5d are optionally bonded to each other to form a ring; n and m are the same or different and represent an integer greater than 0, In formula (14A1), R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , n and m and the R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , n and m are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5a With R 5b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5c With R 5d optionally bonded to each other to form a ring, In formula (15A1), R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , n, m and a3 and the R 3a , R 3b , R 3c , R 3d , R 5a , R 5b , R 5c , R 5d , n, m and a3 are the same; R bonded to the same benzene ring 3a With R 3b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 3c With R 3d Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5a With R 5b Optionally bonded to each other to form a ring; R bonded to the same benzene ring 5c With R 5d They may be bonded to each other to form a ring.

8. A method for preparing a graphene nanoribbon according to any one of claims 1 to 7, wherein: The preparation method has the following features: (1) a first polymerization step of reacting an alkyne compound represented by the following general formula (5A), an aromatic compound containing a K region represented by the following general formula (5B), dibenzocyclooctadiyne, benzothiophene or benzofuran, and a silole compound represented by the following general formula (6) in the presence of a palladium compound and o-tetrachlorobenzoquinone; In formula (5A), R 1a and R 1b are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an ether group or a polyether group, an ester group, a hydrocarbon boronic acid or an ester group thereof, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; k1 and k2 are the same or different and represent an integer of 1 to 3; when k1 and k2 are integers greater than 2, each R 1a and / or R 1b Optional same or different, In formula (5B), R 1a , R 1b , R 1c , R 1d , R 2a and R 2b are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an ether group or a polyether group, an ester group, a boronic acid or an ester group thereof, a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group; a1 and a2 are the same or different and represent a carbon atom or a nitrogen atom, In formula (6), R 3a , R 3b , R 3c and R 3d With the R 3a , R 3b , R 3c and R 3d Same; R 6a and R 6b are the same or different and represent a hydrogen atom or an alkyl group.

9. The preparation method according to claim 8, wherein: The first polymerization step is performed in the presence of a silver compound.

10. The preparation method according to claim 9, wherein: The silver compound contains AgSbF6 or AgBF4.

11. The preparation method according to claim 9, wherein: The amount of the silver compound used is 0.5 to 5.0 moles relative to 1 mole of the silole compound.

12. The preparation method according to any one of claims 8 to 11, wherein The amount of the palladium compound used is 0.1 to 3.0 moles relative to 1 mole of the silole compound.

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