Compound, composition, conductive additive, electrode, and laminate

Abstract

To provide a compound excellent in conductivity, a composition, an electroconductive aid, an electrode, and a laminate.SOLUTION: The invention provides a compound represented by formula (1) defined by Z1-αa-βb-γc-δd-εe-Z2, and specifically, a compound represented by formula (7) in the figure, for example.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound, a composition, a conductive additive, an electrode, and a laminate. Specifically, the present invention relates to a compound, a composition, a conductive additive, an electrode, and a laminate having excellent electrical conductivity. [Background technology]

[0002] Patent Document 1 discloses a conductive oligomer having a specific molecular structure. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2020 / 262443 Summary of the Invention [Problem to be solved by the invention]

[0004] However, it has been found that conventional techniques such as that of Patent Document 1 have room for further improvement in terms of electrical conductivity.

[0005] An object of the present invention is to provide a compound, a composition, a conductive assistant, an electrode, and a laminate that are excellent in electrical conductivity. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that a compound having a specific structure in which multiple types of units are linked has excellent electrical conductivity, and have completed the present invention. According to the present invention, the following compounds and the like can be provided. A compound represented by the following formula (1): Z 1 -α a -β b -γ c -δ d -ε e -Z 2 (1) [In formula (1), α is a unit represented by the following formula (1α), and a is an integer of 1 to 10. When a is 2 or more, two or more units α are the same as each other. β is a unit represented by the following formula (1β), and b is an integer of 1 to 10. When b is 2 or more, two or more units β are the same as each other. γ is a unit represented by the following formula (1γ), and c is an integer of 1 to 10. When c is 2 or more, two or more units γ are the same as each other. δ is a unit represented by the following formula (1δ), and d is an integer of 0 to 10. When d is 2 or more, two or more units δ are the same as each other. ε is a unit represented by the following formula (1ε), and e is an integer of 0 to 10. When e is 2 or more, two or more units ε are the same. The structure of unit α is different from the structure of unit β. The structure of unit β is different from the structure of unit γ. The structure of the unit γ is different from that of the unit δ. The structure of the unit δ is different from the structure of the unit ε. Z 1 and Z 2 are each independently, Y 1 , Y 2 R 1 or CR 2 R 3 R 4 is. Y 1 represents H (hydrogen atom), F (fluorine atom), Cl (chlorine atom), Br (bromine atom), I (iodine atom), or a substituted or unsubstituted aryl group having 6 to 22 ring carbon atoms; Y 1 If there are two Y 1 are the same or different from each other. Y 2 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), SO3 (S is sulfur atom, O is oxygen atom), SO2 (S is sulfur atom, O is oxygen atom), or PO3 (P is phosphorus atom, O is oxygen atom), and Y 2 If there are two Y 2are the same or different from each other. R 1 ~R 4 are each independently H (hydrogen atom), a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 ring carbon atoms. R 1 If there are two R 1 are the same or different from each other. R 2 If there are two R 2 are the same or different from each other. R 3 If there are two R 3 are the same or different from each other. R 4 If there are two R 4 are the same or different from each other.] [ka] [In formula (1α), Q 1 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 1 is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 1 are identical to each other. R 11 ~R 14 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. f is an integer of 1 to 3. If f is 2 or more, two or more R 13 are the same or different from each other, and two or more R 14 are the same or different from each other.] [ka] [In formula (1β), Q 2is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 2 is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 2 are identical to each other. R 21 ~R 24 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. g is an integer of 1 to 3. If g is 2 or more, two or more R 23 are the same or different from each other, and two or more R 24 are the same or different from each other.] [ka] [In formula (1γ), Q 3 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 3 is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 3 are identical to each other. R 31 ~R 34 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. h is an integer of 1 to 3. If h is 2 or more, two or more R 33 are the same or different from each other, and two or more R 34 are the same or different from each other.] [ka] [In formula (1δ), Q 4 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 4is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 4 are identical to each other. R 41 ~R 44 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. i is an integer from 1 to 3. If i is 2 or more, two or more R 43 are the same or different from each other, and two or more R 44 are the same or different from each other.] [ka] [In formula (1ε), Q 5 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 5 is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 5 are identical to each other. R 51 ~R 54 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. j is an integer of 1 to 3. If j is 2 or more, two or more R 53 are the same or different from each other, and two or more R 54 are the same or different from each other.] [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a compound, a composition, a conductive additive, an electrode, and a laminate having excellent electrical conductivity. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram conceptually illustrating planarization inhibition and crystallization inhibition in a conventional conductive oligomer (for comparison). DETAILED DESCRIPTION OF THE INVENTION

[0009] The compound, composition, conductive additive, electrode, and laminate of the present invention will be described in detail below.

[0010] In this specification, "x to y" represents a numerical range of "greater than or equal to x and less than or equal to y." The upper and lower limits of the numerical ranges can be arbitrarily combined. Any combination of two or more of the following embodiments is also an embodiment of the present invention.

[0011] In this specification, in a chemical structural formula, a hydrogen atom, i.e., a protium atom, a deuterium atom, or a tritium atom is assumed to be bonded to a possible bonding position that is not explicitly marked with a symbol such as "R" or "D" representing a deuterium atom.

[0012] In this specification, the number of ring carbon atoms refers to the number of carbon atoms among the atoms constituting the ring itself of a compound having a structure in which atoms are bonded in a ring (for example, a monocyclic compound, a fused ring compound, a bridged compound, a carbocyclic compound, and a heterocyclic compound). When the ring is substituted with a substituent, the carbon atoms contained in the substituent are not included in the number of ring carbon atoms. The same applies to the "number of ring carbon atoms" described below unless otherwise specified. For example, a benzene ring has 6 ring carbon atoms, and a naphthalene ring has 10 ring carbon atoms.

[0013] In the present specification, the "number of carbon atoms XX to YY" in the expression "substituted or unsubstituted ZZ group having carbon atoms XX to YY" refers to the number of carbon atoms when the ZZ group is unsubstituted, and does not include the number of carbon atoms of the substituent when the ZZ group is substituted. The number of carbon atoms is selected as an integer. The same applies when the number of carbon atoms is the number of ring carbon atoms. A "substituted ZZ group" means a group in which one or more hydrogen atoms of an "unsubstituted ZZ group" have been replaced with a substituent. An "unsubstituted ZZ group" means that a hydrogen atom in the ZZ group is not replaced with a substituent. The hydrogen atom in the "unsubstituted ZZ group" is a protium atom, a deuterium atom, or a tritium atom.

[0014] 1.Compound A compound according to one aspect of the present invention is represented by the following formula (1). Z 1 -α a -β b -γ c -δ d -ε e -Z 2 (1) [In formula (1), α is a unit represented by the following formula (1α), and a is an integer of 1 to 10. When a is 2 or more, two or more units α are the same as each other. β is a unit represented by the following formula (1β), and b is an integer of 1 to 10. When b is 2 or more, two or more units β are the same as each other. γ is a unit represented by the following formula (1γ), and c is an integer of 1 to 10. When c is 2 or more, two or more units γ are the same as each other. δ is a unit represented by the following formula (1δ), and d is an integer of 0 to 10. When d is 2 or more, two or more units δ are the same as each other. ε is a unit represented by the following formula (1ε), and e is an integer of 0 to 10. When e is 2 or more, two or more units ε are the same. The structure of unit α is different from the structure of unit β. The structure of unit β is different from the structure of unit γ. The structure of the unit γ is different from that of the unit δ. The structure of the unit δ is different from the structure of the unit ε. Z 1 and Z 2 are each independently, Y 1 , Y 2 R 1 or CR 2 R 3 R 4 is. Y 1represents H (hydrogen atom), F (fluorine atom), Cl (chlorine atom), Br (bromine atom), I (iodine atom), or a substituted or unsubstituted aryl group having 6 to 22 ring carbon atoms; Y 1 If there are two Y 1 are the same or different from each other. Y 2 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), SO3 (S is sulfur atom, O is oxygen atom), SO2 (S is sulfur atom, O is oxygen atom), or PO3 (P is phosphorus atom, O is oxygen atom), and Y 2 If there are two Y 2 are the same or different from each other. R 1 ~R 4 are each independently H (hydrogen atom), a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 ring carbon atoms. R 1 If there are two R 1 are the same or different from each other. R 2 If there are two R 2 are the same or different from each other. R 3 If there are two R 3 are the same or different from each other. R 4 If there are two R 4 are the same or different from each other.]

[0015] [ka]

[0016] [In formula (1α), Q 1 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 1is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 1 are identical to each other. R 11 ~R 14 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. f is an integer of 1 to 3. If f is 2 or more, two or more R 13 are the same or different from each other, and two or more R 14 are the same or different from each other.]

[0017] [ka]

[0018] [In formula (1β), Q 2 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 2 is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 2 are identical to each other. R 21 ~R 24 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. g is an integer of 1 to 3. If g is 2 or more, two or more R 23 are the same or different from each other, and two or more R 24 are the same or different from each other.]

[0019] [ka]

[0020] [In formula (1γ), Q 3is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 3 is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 3 are identical to each other. R 31 ~R 34 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. h is an integer of 1 to 3. If h is 2 or more, two or more R 33 are the same or different from each other, and two or more R 34 are the same or different from each other.]

[0021] [ka]

[0022] [In formula (1δ), Q 4 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 4 is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 4 are identical to each other. R 41 ~R 44 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. i is an integer from 1 to 3. If i is 2 or more, two or more R 43 are the same or different from each other, and two or more R 44 are the same or different from each other.]

[0023] [ka]

[0024] [In formula (1ε), Q 5 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 5 is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 5 are identical to each other. R 51 ~R 54 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. j is an integer of 1 to 3. If j is 2 or more, two or more R 53 are the same or different from each other, and two or more R 54 are the same or different from each other.]

[0025] The compound according to this embodiment has excellent electrical conductivity. The reason why such an effect is obtained is not entirely clear, but is presumed to be as follows. First, considering the electronic state of the conductive oligomer disclosed in Patent Document 1, it is suggested that it is in a half-filled Mott insulator state, in which the Coulomb repulsion between electrons exceeds the band width. Therefore, in order to achieve even higher conductivity, it is thought that reducing the Coulomb repulsion by increasing the conjugation length associated with chain elongation would be effective. Figure 1 conceptually illustrates the inhibition of planarization and crystallization when oxygen or sulfur is bonded to the aromatic ring in a conventional conductive oligomer (for comparison). Oligomers composed of only identical units in which oxygen is bonded to an aromatic ring, as shown in Figures 1(a) and (b), exhibit increased oxidative instability and decreased solubility due to the increase in the highest occupied energy level caused by conjugation elongation, making their synthesis and isolation difficult. On the other hand, oligomers composed of only identical units in which sulfur is bonded to an aromatic ring, as shown in Figures 1(c) and (d), have improved oxidation stability and solubility due to their twisted structure. However, as the chain length increases, molecular planarization after dopant addition is hindered. This weakens the effect of reducing Coulomb repulsion after dopant addition (i.e., after oxidation), and also hinders crystallization. Furthermore, oligomers composed of only identical units tend to develop voids in the crystal as the chain length increases, making it difficult to form single crystals. As a result, there are limitations to improving conductivity.

[0026] In contrast, the compound according to the present embodiment is configured by linking specific multiple types of units, and therefore the inhibitory effect on the development of conductivity described above in the prior art is significantly reduced, and the activation energy E a This reduces the conductivity and provides excellent conductivity. The compound according to this embodiment allows for fine adjustment of the degree of planarization, solubility, and suppression of voids after oxidation. Specifically, by appropriately arranging blocks composed of units having solubility-enhancing groups, blocks in which the succession of units results in a twisted structure due to steric repulsion (such blocks can improve solubility and structural stability in the neutral state), and blocks that sterically fill voids (e.g., blocks composed of units sterically larger than other blocks, such as units with moderately bulky substituents or units with a large number of constituent atoms), it becomes possible to fill voids in the crystal while ensuring high solubility and stability against oxidation. This allows for sufficient reduction of Coulomb repulsion between electrons due to the increased conjugation length associated with chain elongation. It also allows for dimensionality to be achieved. Furthermore, effective intermolecular orbital interactions can be achieved. In this way, the activation energy E a can be further reduced, and better conductivity can be exhibited.

[0027] In one embodiment, the difference between the structure of unit α and the structure of unit β is Q 1 and Q 2 Difference between X and 1 and X 2 Difference between R 11 and R 21 Difference between R 12 and R 22 Difference between R 13 and R 23 Difference between R 14 and R 24 and one or more differences selected from the group consisting of differences in f and g. When f and g are different, f may be greater than g, or f <gであってもよい。

[0028] In one embodiment, the difference between the structure of unit β and the structure of unit γ is Q 2 and Q 3 Difference between X and 2 and X 3 Difference between R 21 and R 31 Difference between R 22 and R 32 Difference between R 23 and R 33 Difference between R24 and R 34 and one or more differences selected from the group consisting of differences in g and h. When g and h are different, g may be greater than h, or g <hであってもよい。

[0029] In one embodiment, the difference between the structure of unit γ and the structure of unit δ is Q 3 and Q 4 Difference between X and 3 and X 4 Difference between R 31 and R 41 Difference between R 32 and R 42 Difference between R 33 and R 43 Difference between R 34 and R 44 and one or more differences selected from the group consisting of differences in h and i. When h and i are different, h may be greater than i, or h <iであってもよい。

[0030] In one embodiment, the difference between the structure of unit δ and the structure of unit ε is Q 4 and Q 5 Difference between X and 4 and X 5 Difference between R 41 and R 51 Difference between R 42 and R 52 Difference between R 43 and R 53 Difference between R 44 and R 54 and one or more differences selected from the group consisting of differences between i and j. When i and j are different, i may be greater than j, or j <iであってもよい。

[0031] In one embodiment, Q 1 is S (sulfur atom), which further improves the conductivity.

[0032] In one embodiment, X 1 is S (sulfur atom) or O (oxygen atom), which further improves the conductivity.

[0033] In one embodiment, R 11 ~R 14 The number of carbon atoms in the alkyl group in each independently is 1 to 12, 1 to 11, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. In one embodiment, R 11 ~R 14 The number of carbon atoms in the alkyl groups in R is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. 11 ~R 14 The smaller the number of carbon atoms in the alkyl group in the formula (I), the more the electrical conductivity improves. In one embodiment, R 11 ~R 14 When the alkyl groups in R have 3 or more carbon atoms, they are each independently linear or branched. 11 ~R 14 The linear alkyl group in R further improves the conductivity of the compound. 11 ~R 14 The branched alkyl group in the formula (I) improves the solubility in various solvents.

[0034] In one embodiment, f is an integer of 1 to 3, an integer of 1 to 2, or 1. When f is 1 or 2, the conductivity is further improved.

[0035] In one embodiment, the unit α is represented by the following formula (2):

[0036] [ka]

[0037] [In formula (2), Q 6 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 6 is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 6 are identical to each other.]

[0038] In one embodiment, Q 6 is S (sulfur atom).

[0039] In one embodiment, X 6 is S (sulfur atom) or O (oxygen atom).

[0040] In one embodiment, the unit α is represented by the following formula (3):

[0041] [ka]

[0042] [In formula (3), Q 7 is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X 7 is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X 7 are identical to each other. R 73 and R 74 are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms.]

[0043] In one embodiment, Q 7 is S (sulfur atom).

[0044] In one embodiment, X 7 is S (sulfur atom) or O (oxygen atom).

[0045] In one embodiment, R 73 and R 74 are each independently an alkyl group having 1 to 12 carbon atoms.

[0046] In one embodiment, the unit α is represented by any one of the following formulas (U1) to (U3).

[0047] [ka]

[0048] In one embodiment, the number a of units α is an integer from 1 to 10, an integer from 1 to 9, an integer from 1 to 8, an integer from 1 to 7, an integer from 1 to 6, an integer from 1 to 5, an integer from 1 to 4, an integer from 1 to 3, an integer from 1 to 2, or 1. The number a of units α is preferably an integer from 1 to 6, and more preferably an integer from 1 to 4. This further improves the conductivity.

[0049] Q in units of β 2 , X 2 , R 21 ~R 24 , g and b, Q in units of α 1 , X 1 , R 11 ~R 14 The explanations given for , f and a are applicable. In one embodiment, the unit β is represented by any of the formulae (2), (3), and (U1) to (U3) shown for the unit α.

[0050] Q in units of γ 3 , X 3 , R 31 ~R 34 , h and c, Q in units of α 1 , X 1 , R 11 ~R 14 The explanations given for , f and a are applicable. In one embodiment, the unit γ is represented by any of the formulas (2), (3), and (U1) to (U3) shown for the unit α.

[0051] Q in units of δ 4 , X 4 , R 41 ~R 44 , i and d, Q in units α 1 , X 1 , R 11 ~R 14 The explanations given for , f and a are applicable. In one embodiment, the unit δ is represented by any of the formulas (2), (3), and (U1) to (U3) shown for the unit α.

[0052] Q in units of ε 5 , X 5 , R 51 ~R 54 , j and e, Q in units of α 1 , X 1 , R 11 ~R 14 The explanations given for , f and a are applicable. In one embodiment, the unit ε is represented by any of formulas (2), (3), and (U1) to (U3) shown for the unit α.

[0053] In one embodiment, the structures of two or more units selected from the group consisting of unit α, unit β, unit γ, unit δ, and unit ε are identical to each other.

[0054] In one embodiment, a and b are the same or different from each other, i.e., a=b, a>b, or a <bであってもよい。 In one embodiment, b and c are the same or different from each other, i.e., b=c, b>c, or b <cであってもよい。 In one embodiment, c and d are the same or different from each other, i.e., c=d, c>d, or c <dであってもよい。 In one embodiment, d and e are the same or different from each other, i.e., d=e, d>e, or d <eであってもよい。

[0055] In one embodiment, two or more selected from the group consisting of a, b, c, d, and e are the same value. Also, in one embodiment, two, three, four, or five selected from the group consisting of a, b, c, d, and e are the same value. In one embodiment, one or more selected from the group consisting of a, b, c, d, and e are integers of 1 to 6. In another embodiment, one, two, three, four, or five selected from the group consisting of a, b, c, d, and e are integers of 1 to 6. In one embodiment, one or more selected from the group consisting of a, b, c, d, and e are integers of 1 to 4. In another embodiment, one, two, three, four, or five selected from the group consisting of a, b, c, d, and e are integers of 1 to 4.

[0056] In one embodiment, one or more selected from the group consisting of f, g, h, i, and j are 1 or 2. Also, in one embodiment, one, two, three, four, or five selected from the group consisting of f, g, h, i, and j are 1 or 2. In one embodiment, one or more selected from the group consisting of f, g, h, i, and j is 1. Also, in one embodiment, one, two, three, four, or five selected from the group consisting of f, g, h, i, and j is 1.

[0057] In one embodiment, X 1 ~X 5 In one embodiment, one or more of the groups selected from the group consisting of X 1 ~X 5 are identical to each other. In one embodiment, X 1 ~X 5 In one embodiment, one or more selected from the group consisting of is S (sulfur atom) or O (oxygen atom). 1 ~X 5 one, two, three, four or five selected from the group consisting of are S (sulfur atom) or O (oxygen atom).

[0058] In one embodiment, Q 1 ~Q 5 In one embodiment, one or more of the groups selected from the group consisting of Q 1 ~Q5 are identical to each other. In one embodiment, Q 1 ~Q 5 In one embodiment, one or more selected from the group consisting of is S (sulfur atom). 1 ~Q 5 One, two, three, four or five selected from the group consisting of are S (sulfur atoms).

[0059] In one embodiment, one or more units selected from the group consisting of unit α, unit β, unit γ, unit δ, and unit ε are represented by formula (2). Also, in one embodiment, one, two, three, four, or five units selected from the group consisting of unit α, unit β, unit γ, unit δ, and unit ε are represented by formula (2). When two or more units selected from the group consisting of unit α, unit β, unit γ, unit δ, and unit ε are represented by formula (2), the structures of the two or more units are the same or different from each other. In one embodiment, one to four units selected from the group consisting of unit α, unit β, unit γ, unit δ, and unit ε are represented by formula (2), and among the unit α, unit β, unit γ, unit δ, and unit ε, any unit not represented by formula (2) is represented by formula (3).

[0060] In one embodiment, one or more units selected from the group consisting of unit α, unit β, unit γ, unit δ, and unit ε are represented by formula (3). Also, in one embodiment, one, two, three, four, or five units selected from the group consisting of unit α, unit β, unit γ, unit δ, and unit ε are represented by formula (3). When two or more units selected from the group consisting of unit α, unit β, unit γ, unit δ, and unit ε are represented by formula (3), the structures of the two or more units are the same or different from each other. In one embodiment, one to four units selected from the group consisting of unit α, unit β, unit γ, unit δ, and unit ε are represented by formula (3), and among the unit α, unit β, unit γ, unit δ, and unit ε, any unit not represented by formula (3) is represented by formula (2).

[0061] In the above description, the unit represented by formula (2) may be a unit represented by formula (U1) or formula (U2), and the unit represented by formula (3) may be a unit represented by formula (U3).

[0062] In one embodiment (hereinafter also referred to as the "three-block embodiment"), d = 0 and e = 0. In this case, the compound contains three blocks: a block composed of a number of α units, a block composed of b number of β units, and a block composed of c number of γ units. Such a compound is represented by the following formula (1-3): Z 1 -α a -β b -γ c -Z 2 (1-3) [In formula (1-3), unit α, unit β, unit γ, a, b, c, Z 1 and Z 2 is as defined in equation (1).

[0063] In one embodiment of the triblock embodiment, the structure of unit α and the structure of unit γ are identical to each other. In one embodiment of the three-block embodiment, a and c are the same as each other (a=c).

[0064] In one embodiment (hereinafter also referred to as the "four-block embodiment"), d is 1 or greater and e=0. In this case, the compound contains four blocks: a block composed of a units α, b units β, c units γ, and d units δ. Such a compound is represented by formula (1-4) below. Z 1 -α a -β b -γ c -δ d -Z 2 (1-4) [In formula (1-4), unit α, unit β, unit γ, unit δ, a, b, c, d, Z1 and Z 2 is as defined in formula (1), where d is 1 or greater.

[0065] In one embodiment of the four-block embodiment, the structure of unit α and the structure of unit γ are identical to each other. In one embodiment of the four-block embodiment, the structure of unit α and the structure of unit δ are identical to each other. In one embodiment of the four-block embodiment, a and c are the same as each other (a=c). In one embodiment of the four-block embodiment, a and d are the same as each other (a=d).

[0066] In one embodiment (hereinafter also referred to as the "five-block embodiment"), d is 1 or greater and e is 1 or greater. In this case, the compound contains five blocks: a block made up of a units α, a block made up of b units β, a block made up of c units γ, a block made up of d units δ, and a block made up of e units ε. Such a compound is represented by formula (1-5) below. Z 1 -α a -β b -γ c -δ d -ε e -Z 2 (1-5) [In formula (1-5), unit α, unit β, unit γ, unit δ, unit ε, a, b, c, d, e, Z 1 and Z 2 is as defined in formula (1), where d is 1 or more and e is 1 or more.

[0067] In one embodiment of the five-block embodiment, the structure of unit α and the structure of unit ε are identical to each other. In one embodiment of the five-block embodiment, the structure of unit β and the structure of unit δ are identical to each other. In one embodiment of the five-block embodiment, a and e are the same as each other (a=e). In one embodiment of the five-block embodiment, b and d are the same as each other (b=d).

[0068] In one embodiment, Y 1 The number of ring carbon atoms of the aryl group in Y is 6 to 22 or 6 to 14. 1 The smaller the number of ring carbon atoms of the aryl group in the formula (I), the more improved the solubility, electrical conductivity, and heat resistance. In particular, the aryl group is preferably a phenyl group. In one embodiment, Y 1 When the aryl group in the formula (I) is a substituted aryl group, specific examples of the substituent include a halogen group (halogen atom), SR 6 (S is sulfur atom), SeR 6 (Se is selenium atom), OR 6 (O is an oxygen atom), SO2R 6 (S is sulfur atom, O is oxygen atom), PO3R 6 (P is a phosphorus atom, and O is an oxygen atom), and an alkyl group having 1 to 12 carbon atoms. Specific examples of the halogen group include F (fluorine atom), Cl (chlorine atom), Br (bromine atom), and I (iodine atom). R 6 is H (hydrogen atom), an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 22 ring carbon atoms. In particular, the substituted aryl group is preferably an aryl group substituted with an alkyl group having 1 to 12 carbon atoms, and is preferably, for example, a p-toluyl group or an o-toluyl group. In one embodiment, R 1 ~R 4 The number of carbon atoms in the alkyl group in each independently is 1 to 12, 1 to 11, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. In one embodiment, R 1 ~R 4 The number of carbon atoms in the alkyl groups in the formula (I) is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. The smaller the number of carbon atoms in the alkyl group, the more improved the heat resistance. In particular, the number of carbon atoms in the alkyl group is preferably 1 to 6. In one embodiment, R 1 ~R 4When the alkyl groups in R have 3 or more carbon atoms, they are each independently linear or branched. 1 ~R 4 The linear alkyl group in R further improves the electrical conductivity. 1 ~R 4 The branched alkyl group in the formula (I) improves the solubility in various solvents. In one embodiment, R 1 ~R 4 When the alkyl group in the formula (I) is a substituted alkyl group, specific examples of the substituent include a halogen group (halogen atom), SR 5 (S is sulfur atom), SeR 5 (Se is selenium atom), OR 5 (O is an oxygen atom), SO2R 5 (S is sulfur atom, O is oxygen atom), PO3R 5 (P is a phosphorus atom, O is an oxygen atom), and an aryl group having 6 to 22 ring carbon atoms. Specific examples of the halogen group include F (fluorine atom), Cl (chlorine atom), Br (bromine atom), and I (iodine atom). R 5 is H (hydrogen atom), an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 22 ring carbon atoms.

[0069] In one embodiment, R 1 ~R 4 For the aryl group in Y 1 The explanation of the aryl group in the above is incorporated herein by reference.

[0070] In one embodiment, Z 1 and Z 2 are each independently, Y 2 R 1 and Y 2 is S (sulfur atom) or Se (selenium atom), and R 1 is an alkyl group having 1 to 12 carbon atoms. 1 and Z 2are each independently an alkylthio group having 1 to 12 carbon atoms or an alkylseleno group having 1 to 12 carbon atoms. Examples of alkylthio groups having 1 to 12 carbon atoms include a methylthio group. Examples of alkylseleno groups having 1 to 12 carbon atoms include a methylseleno group.

[0071] In one embodiment, Z 1 and Z 2 are identical to each other, which improves the thermal stability of the compound.

[0072] In one embodiment, the compound is represented by any one of the following formulas (E-4) to (E-16).

[0073] [ka] [ka] [ka] [ka]

[0074] [In formulas (E-4) to (E-16), Q 1 ~Q 5 , R 13 , R 14 , R 23 , R 24 , R 33 , R 34 , R 43 , R 44 , R 53 , R 54 , Z 1 and Z 2 is as defined in equation (1).

[0075] In one embodiment, in formulas (E-4) to (E-16), Q 1 ~Q 5 is S (sulfur atom). In one embodiment, in formulas (E-4) to (E-16), Q 1 ~Q 5 is S (sulfur atom), R 13 , R 14 , R 23 , R 24 , R 33 , R 34 , R 43 , R 44 , R 53 and R 54 are each independently an unsubstituted alkyl group having 1 to 12 carbon atoms, Z 1 and Z 2 are independently, SR 1 (S is a sulfur atom), R 1 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. In this embodiment, R 13 , R 14 , R 23 , R 24 , R 33 , R 34 , R 43 , R 44 , R 53 , R 54 and R 1 The number of carbon atoms in the alkyl groups in the formula (I) is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and when the number of carbon atoms is 3 or more, the alkyl group is linear or branched.

[0076] In one embodiment, in formulas (E-4) to (E-16), Q 1 ~Q 5 is Se (selenium atom). In one embodiment, in formulas (E-4) to (E-16), Q 1 ~Q 5 is Se (selenium atom), R 13 , R 14 , R 23 , R 24 , R 33 , R 34 , R 43 , R 44 , R 53and R 54 are each independently an unsubstituted alkyl group having 1 to 12 carbon atoms, Z 1 and Z 2 are independently, SR 1 (S is a sulfur atom), R 1 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. In this embodiment, R 13 , R 14 , R 23 , R 24 , R 33 , R 34 , R 43 , R 44 , R 53 , R 54 and R 1 The number of carbon atoms in the alkyl groups in the formula (I) is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and when the number of carbon atoms is 3 or more, the alkyl group is linear or branched.

[0077] In one embodiment, in formulas (E-4) to (E-16), Q 1 ~Q 5 is NH (N is a nitrogen atom, H is a hydrogen atom). In one embodiment, in formulas (E-4) to (E-16), Q 1 ~Q 5 is NH (N is a nitrogen atom, H is a hydrogen atom), R 13 , R 14 , R 23 , R 24 , R 33 , R 34 , R 43 , R 44 , R 53 and R 54 are each independently an unsubstituted alkyl group having 1 to 12 carbon atoms, Z 1 and Z 2 are independently, SR 1 (S is a sulfur atom), R 1 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. In this embodiment, R 13 , R 14 , R 23 , R 24 , R 33 , R 34 , R 43 , R 44 , R 53 , R 54 and R 1 The number of carbon atoms in the alkyl groups in the formula (I) is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and when the number of carbon atoms is 3 or more, the alkyl group is linear or branched.

[0078] In one embodiment, the compound is represented by any one of the following formulas (4) to (34). In another embodiment, the compound is represented by any one of formulas (4) to (8). The compounds represented by formulas (4) to (11), (17), (20), and (23) to (34) correspond to three-block embodiments. The compounds represented by formulas (12) to (14), (18), and (21) correspond to four-block embodiments. The compounds represented by formulas (15), (16), (19), and (22) correspond to five-block embodiments.

[0079] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0080] The compounds according to one aspect of the present invention are not limited to the compounds represented by formulas (4) to (34) (hereinafter also referred to as "specific compounds"), but may be any compounds represented by formula (1). It goes without saying that the structures of the compounds given as specific compounds can be partially modified within the scope of satisfying the conditions of formula (1). For example, a partial structure of each of the compounds given as specific compounds can be appropriately combined with a partial structure of a compound shown as an embodiment. For example, in each of the compounds given as specific compounds, two methylthio groups can be replaced by Z 1 and Z 2 Also preferred are compounds in which the two methyl groups in the unit represented by formula (U3) are replaced with other groups defined as R 73 and R 74 Furthermore, for example, in each of the compounds given as specific examples, compounds in which the number of each unit is changed within a range that satisfies the condition of formula (1) are also preferred specific examples.

[0081] In one embodiment, the compound according to this aspect (a collection of molecules represented by Formula (1)) has 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.7% by mass or more, 99.9% by mass or more, or substantially 100% by mass of the compound having the same molecular weight. The smaller the molecular weight distribution of the compound, the more preferable. The molecular weight distribution can be derived, for example, from each of the values ​​a, b, c, d, and e having a distribution. Furthermore, it is more preferable that the compound does not have a molecular weight distribution (each of the values ​​a, b, c, d, and e having no distribution). This allows the compound to preferably form an ordered arrangement and orientation, further improving the conductivity.

[0082] The compound according to this embodiment is produced, for example, by the method described in the Examples.

[0083] 2. Composition The composition according to one aspect of the present invention comprises a compound according to one aspect of the present invention and A dopant, Includes.

[0084] In the composition according to this embodiment, a dopant is added to the compound according to one embodiment of the present invention, and excellent electrical conductivity is exhibited.

[0085] In this specification, the term "dopant" refers to an additive substance that, when added to a compound according to one embodiment of the present invention, can provide excellent electrical conductivity as a composition. The dopant is not particularly limited, and any conventionally known dopant may be used. Examples of dopants include monovalent anion species of TCNQ or FxTCNQ (x is 2 or 4), halide ions such as chloride ion, bromide ion, and iodide ion; polyhalide ions such as triiodide ion; perchlorate ion; tetrafluoroborate ion; hexafluoroarsenate ion; sulfate ion; nitrate ion; thiocyanate ion; pentafluorosilicate ion; hexafluorosilicate ion; phosphate ions such as hexafluorophosphate ion, phosphate ion, phenylphosphate ion, and hexafluorophosphate ion; and trifluoroacetate ion. Preferred examples of such ions include alkylbenzenesulfonate ions such as tosylate ion, ethylbenzenesulfonate ion, and dodecylbenzenesulfonate ion; alkylsulfonate ions such as methylsulfonate ion, ethylsulfonate ion, and diisooctyl sulfosuccinate ion; gallium chloride ion; cobalt chloride ion; and polymer ions such as polyacrylic acid ion, polyvinylsulfonate ion, polystyrenesulfonate ion, and poly(2-acrylamido-2-methylpropanesulfonate) ion. These ions may be used alone or in combination of two or more.

[0086] More specific examples of the dopant include LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, LiCl, LiBr, LiB(C2H5)4, LiCH3SO3, LiC4F9SO3, Li(CF3SO2)2N, and Li[(CO2)2]2B. In one embodiment, the dopant is BF4 - , ClO4 - , PF6 - , HSO4 - , GaCl4 - , CoCl4 2- , SbF6 - , SCN - , Cl - , Br - , I - , Br3 - , I3 - , monovalent anion species of TCNQ, and F xThe anion is one or more species selected from the group consisting of monovalent anion species of TCNQ (x is 2 or 4). This further improves the conductivity. In this specification, "TCNQ" means tetracyanoquinodimethane. In one embodiment, the dopant is BF4 - , ClO4 - , PF6 - , HSO4 - , GaCl4 - , CoCl4 2- , SbF6 - , SCN - , Cl - , Br - , I - , Br3 - , I3 - , and TCNQ or F x The anion is one or more species selected from the group consisting of monovalent anion species of TCNQ (x is 2 or 4). This further improves the conductivity.

[0087] The percentage of the total number of moles of dopants (counter anions) relative to the total number of moles of units α, β, and γ constituting the compound according to one embodiment of the present invention (also referred to as the "doping ratio") is not particularly limited. In one embodiment, the doping rate is 6 to 120% or 10 to 100%, which further improves the conductivity.

[0088] In one embodiment, the composition includes other components in addition to the compound according to one aspect of the present invention and the dopant. The other components are not particularly limited, and one or more components can be appropriately selected depending on the purpose and application. The other components may also be the solvent used in preparing the composition. The solvent is not particularly limited, and examples thereof include acetone, acetonitrile, chloroform, methylene chloride, ethanol, methanol, chlorobenzene, o-dichlorobenzene, nitrobenzene, tetrachloroethane, tetrahydrofuran, and water.

[0089] In one embodiment, the composition comprises 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.7% by mass or more, 99.9% by mass or more, or substantially 100% by mass of the composition is the compound according to an aspect of the present invention and the dopant, or the compound according to an aspect of the present invention, the dopant, and the solvent. In the case of "substantially 100% by mass," unavoidable impurities may be contained.

[0090] In one embodiment, the composition comprises a single crystal structure comprised of a compound according to an aspect of the present invention and a dopant. In one embodiment, in the single crystal structure, the compounds according to one aspect of the present invention are π-stacked at equal intervals while tilting to each other.

[0091] In one embodiment, the composition has an electrical resistivity ρ of 10 5 Ωcm or less, 10 4 Ωcm or less, 4.4×10 3 Less than 4.3 x 10 Ωcm 3 Ωcm or less, 10 3 Ωcm or less, 10 2 Ωcm or less, 10Ωcm or less, 1Ωcm or less or 10 -1 The composition has an electrical resistivity ρ of 10 Ωcm or less at 25°C. -1 The lower limit is not particularly limited, and is, for example, 1.7 × 10 -6 Ωcm or more. The electrical resistivity ρ at 25° C. is a value measured by the method described in the Examples.

[0092] In one embodiment, the composition has an activation energy E a is 300 meV or less, 250 meV or less, 200 meV or less, 165 meV or less, or 150 meV or less. aHowever, it is preferable that the activation energy is 150 meV or less. There is no particular lower limit, and when the conductivity changes to metallic conductivity, the activation energy disappears and the electrical resistance increases with increasing temperature. Activation energy E at 0°C a is a value measured by the method described in the Examples.

[0093] The composition according to this embodiment is produced, for example, by the method described in the Examples. In one embodiment, the method for producing the composition includes a step of adding a dopant to a compound according to this aspect, and optionally includes other steps.

[0094] The use of the compound according to one embodiment of the present invention and the composition according to one embodiment of the present invention is not particularly limited. The compound according to an aspect of the present invention and the composition according to an aspect of the present invention have excellent electrical conductivity and are therefore extremely useful in various applications requiring high electrical conductivity, such as electrodes for capacitors, transparent electrodes, battery electrodes, and capacitor electrodes, and as a conductive additive for electrodes and the like.

[0095] 3.Conductive additives A conductive additive according to one aspect of the present invention includes the composition according to one aspect of the present invention. The conductive additive according to this embodiment has excellent conductivity. In one embodiment, a conductor having excellent conductivity can be formed by blending the conductive additive according to this aspect with other components for constituting a conductor. Here, the conductor is not particularly limited and may be, for example, an electrode.

[0096] 4. Electrode An electrode according to one aspect of the present invention is an electrode produced using either the composition according to one aspect of the present invention or the conductive additive according to one aspect of the present invention. The electrode according to this embodiment has excellent conductivity. In one embodiment, an electrode can be formed by coating a substrate with the composition according to one aspect of the present invention or the conductive additive according to one aspect of the present invention, and curing the coating as necessary. Here, the substrate itself may or may not be conductive. The use of the electrode according to this embodiment is not particularly limited. In one embodiment, the electrode is a capacitor electrode, a transparent electrode, a battery electrode, or a capacitor electrode.

[0097] 5.Laminate The laminate according to one aspect of the present invention comprises: A substrate; a layer including a composition according to one aspect of the present invention laminated on the substrate; Includes. In the laminate according to this embodiment, the layer containing the composition according to one embodiment of the present invention has excellent conductivity and functions well as a conductive layer. In one embodiment, a composition according to one aspect of the present invention can be coated on any substrate and cured as necessary to form a layer containing the composition according to one aspect of the present invention. Here, the substrate itself may or may not be electrically conductive. [Example]

[0098] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0099] The measurement methods carried out in the following examples are outlined below. Gel permeation chromatography (GPC) was performed using a preparative HPLC (LC-908, Japan Analytical Industry Co., Ltd.) equipped with a high-speed preparative GPC column (polystyrene column, 20 mmφ × (600 + 600) mm) (JAIGEL-1HR, -2HR, Japan Analytical Industry Co., Ltd.). proton( 1 H) and carbon ( 13 C) Nuclear magnetic resonance (NMR) spectra were measured using a JEOL JNM-AL300 ( 1 H:300MHz; 13 Measurements were performed using a 75 MHz (C: 75 MHz) spectrometer. Measurements were performed in CDCl1 H NMR spectrum and 13 C NMR spectra were corrected for solvent absorption. Mass spectrometry was measured using a JEOL JMS-AX500 (FD probe, positive mode) mass spectrometer. In the following examples, "room temperature" is 25°C.

[0100] 1. Synthesis of Compounds and Preparation of Compositions Example 1 Compound synthesis A compound (2MeS-4PS) represented by the following formula (4) was synthesized.

[0101] [ka]

[0102] The synthesis scheme is as follows:

[0103] [ka]

[0104] Details are as follows: Synthesis of ethylenedithiothiophene-type dimer (2Br-2S)

[0105] [ka]

[0106] Two 50 mL two-necked eggplant-shaped flasks (reaction vessels) were prepared. Each was fitted with a stirrer, stoppered with a septum, and the walls were heated with a heat gun for approximately 1 minute while reducing the pressure with a vacuum pump to remove moisture. The reaction vessels were then replaced with an argon atmosphere. This procedure was repeated three times. While flowing argon into one of the two-necked eggplant-shaped flasks, the septum was opened, and 300 mg of bis(3,4-ethylenedithiothiophene) (2H-2S) was added to the two-necked eggplant-shaped flask (reaction vessel). The flask was then stoppered with a septum. 30 mL of dichloromethane (Wako, super-dehydrated) was added to the reaction vessel via syringe and cooled to -40 °C while stirring with a magnetic stirrer. 309 mg of N-bromosuccinimide (Wako) was added to the other eggplant-shaped flask, and 7.5 mL of dichloromethane (Wako, super-dehydrated) was added via syringe. The flask was then cooled to 0 °C. Next, a dichloromethane suspension of N-bromosuccinimide (Wako) was added to the dichloromethane solution of 2H-2S using a cannula and stirred at -40 °C for 30 min. After that, saturated aqueous sodium bicarbonate (30 mL) was added to the reaction solution, and the mixture was washed three times with dichloromethane (30 mL). 0.2 M aqueous sodium thiosulfate (60 mL) was added to the washed organic layer and stirred for 30 min. The mixture was then extracted three times with dichloromethane (30 mL). Na2SO4 was added to the combined organic layer, and the mixture was stirred for approximately 30 min to remove water. The solids were removed, and the resulting solution was concentrated on a rotary evaporator to obtain 2Br-2S (483 mg crude product). 2Br-2S was used without further purification, with 400 mg of this mixture used in the subsequent synthesis of 2H-4PS.

[0107] Synthesis of propylenedioxythiophene-type monomer 2

[0108] [ka]

[0109] Two 50 mL two-necked eggplant-shaped flasks (reaction vessels) were prepared. Each was fitted with a stirrer, stoppered with a septum, and heated with a heat gun for approximately 1 minute while reducing the pressure with a vacuum pump to remove moisture. The reaction vessels were then purged with an argon atmosphere. This procedure was repeated three times. While flowing argon, the septum of one of the two-necked eggplant-shaped flasks was opened, and 342 mg of propylene-type monomer 1 was added. The flask was then stoppered with a septum. 6 mL of THF (Wako, ultra-dehydrated, stabilizer-containing) was added to the reaction vessel via syringe and cooled to -80 °C while stirring with a magnetic stirrer. 1.44 mL of n-BuLi (1.6 M in n-hexane) (Kanto Chemical Co., Inc.) was added dropwise over 5 minutes to the reaction solution via syringe. Stirring was continued at -80 °C for 3 hours, and 601 μL of tri(n-butyl)tin was added to the reaction vessel via syringe. After that, stirring was continued for 17 hours while warming to room temperature. The reaction solution was filtered through Celite and then washed with dichloromethane (Wako) (20 mL). The mixed solution was evaporated using a rotary evaporator to obtain propylenedioxythiophene type monomer 2 (crude product 1.00 g). This 2 was used directly in the subsequent reaction without further purification.

[0110] Synthesis of unsubstituted tetramer (2H-4PS)

[0111] [ka]

[0112] While flowing argon, the septum of the other two-necked eggplant flask was opened, and 400 mg of 2Br-2S (crude product), the entire amount of 2 (crude product) (1.00 g), and 91.7 mg of tetrakis(triphenylphosphine)palladium were added and sealed with a septum. 25 mL of toluene (Wako) was added and refluxed for 17 hours. After cooling to room temperature, the septum was opened and an additional 92.0 mg of tetrakis(triphenylphosphine)palladium was added while flowing argon. The flask was then sealed with a septum. After refluxing for 24 hours, the flask was cooled to room temperature and filtered through Celite to remove the black solid, yielding the crude product. The resulting crude product was purified using a preparative HPLC system equipped with a high-performance preparative GPC column, followed by reprecipitation using dichloromethane as a good solvent and hexane as a poor solvent, yielding 2H-4PS (223 mg) as a yellow powder. The overall yield of the two steps from 2H-2S was 44%. Physical properties: 1 H-NMR(CDCl3,300MHz)δ 1.05 (s, 12H) , 3.21 - 3.26 (m, 8H) ,3.76 (s, 4H) ,3.86(s,4H),6.56(s,2H); 13 C-NMR(CDCl3,75MHz)δ 21.7,28.2,28.8,39.1,80.1,80.4, 105.3, 115.1, 123.8, 124.6, 127.1, 128.6, 146.9, 150.0.

[0113] Synthesis of dimethylthiolated tetramer (2H-4PS)

[0114] [ka]

[0115] A 10 mL Schlenk flask (reaction vessel) was fitted with a stirrer, stoppered with a septum, and heated with a heat gun for approximately 1 minute while reducing the pressure with a vacuum pump to remove moisture. The atmosphere inside the reaction vessel was then replaced with argon. This procedure was repeated three times. While argon was flowing, the septum was opened, 142 mg of 2H-4PS was added, and the vessel was then stoppered with a septum. 3 mL of THF (Wako, ultra-dehydrated, stabilizer-containing) was added to the reaction vessel via syringe, and the mixture was cooled to -80 °C while stirring with a magnetic stirrer. 0.45 mL of n-BuLi (1.6 M in n-hexane) (Kanto Chemical Co., Inc.) was added dropwise over 1 minute to the reaction solution via syringe. Stirring was continued at -80 °C for 2 hours, and 0.18 mL of dimethyl disulfide (Wako) was added via syringe to the reaction vessel. The mixture was allowed to warm to room temperature and stirred for 17 hours. After removing the solvent using a vacuum pump, saturated aqueous sodium bicarbonate (6 mL) was added and the mixture was extracted three times with dichloromethane (20 mL). Na2SO4 was added to the combined organic layer and stirred for approximately 30 minutes to remove water. After filtering off the solids, the resulting solution was concentrated on a rotary evaporator to obtain the crude product. The resulting crude product was purified using a preparative HPLC system equipped with a high-speed preparative GPC column, and finally, 2MeS-4PS (the compound represented by formula (4)) was obtained from 2H-4PS as a yellow powder in a total yield of 58% over the two steps. Physical properties: 1 H-NMR(CDCl3,300MHz)δ 1.07 (s, 12H) , 2.43 (s, 6H) ,3.21 - 3.27 (m, 8H),3.88(s,4H),3.88(s,4H); 13 C-NMR(CDCl3,75MHz)δ 21.8,28.2,28.8,39.1, 80.1,80.4, 105.3, 115.1, 123.8, 124.6, 127.1, 128.6, 146.9, 150.0.

[0116] Preparation of Composition 1 (Electrolytic Oxidation Method) 1.0 mg of the compound represented by formula (4) was added to the oxidation side of an H-type electrolytic oxidation cell, and 18 mg of n-Bu4NPF6 (Sigma-Aldrich) was added to both sides as a dopant source. 18 mL of acetone (Wako, ultra-dehydrated) was slowly added along the wall. A current of 0.25 μA was applied to the platinum electrode in a thermostatic chamber at 50°C, and the mixture was left standing for 4 days. The precipitated, glossy, rod-shaped red crystals were then separated from the solution by filtration to obtain Composition 1. Single-crystal structure analysis revealed a doping rate of 50%.

[0117] Preparation of Composition 2 (Chemical Oxidation Method) A composition was prepared by the diffusion method. Specifically, 2.0 mg of the compound represented by formula (4) and 0.6 mg of FTCNQ (Tokyo Chemical Industry Co., Ltd.) as a dopant source were mixed in a 6 mL vial, and 6 mL of dichloromethane (Wako, special grade reagent) was added. After mixing, the mixture was allowed to stand for 3 days to concentrate and evaporate the solvent, yielding composition 2. Single crystal structure analysis revealed that the doping rate was 50%.

[0118] Example 2 Compound synthesis A compound (2MeS-3OP) represented by the following formula (5) was synthesized.

[0119] [ka]

[0120] The synthesis scheme is as follows:

[0121] [ka]

[0122] Details are as follows: A 6 mL screw-capped vial (reaction vessel) was charged with a stir bar, 99.0 mg of methylthiolated ethylenedioxythiophene-type monomer 3, 89.2 mg of dibrominated propylenedioxy-type monomer 8, 5.9 mg of palladium(II) acetate, and 336 mg of potassium carbonate, and then brought into a nitrogen-purged glove box. In the glove box, 13.1 mg of pivalic acid was added to the screw-capped vial (reaction vessel), followed by 5 mL of dimethylformamide (Wako, ultra-dehydrated) and the reaction vessel. The screw-cap lid was then closed. The reaction vessel was heated to 90 °C on a stage-type hot plate while stirring with a magnetic stirrer and continued stirring at that temperature for 40 h. The reaction solution was then cooled to room temperature, diluted with 50 mL of dichloromethane (Wako, special grade reagent), and the organic layer was washed once with 50 mL of water and once with saturated aqueous sodium thiosulfate. The organic layer was washed with NaSO and stirred for 10 minutes to remove water. The solid was filtered off and the resulting solution was concentrated on a rotary evaporator to obtain a crude product. The crude product was purified using a medium-pressure column chromatograph (Biotage®, Isorela One) with an automated purification system under the following conditions (50 g of Biotage® SNAP Ultra, eluent: n-hexane:CH2CH2 = 6:4 to 2:8). The crude product was then further purified using a preparative HPLC system equipped with a high-performance preparative GPC column to obtain 31 mg of a yellow powder of 2MeS-3OP (compound represented by formula (5)) in a 21% yield. Physical properties: 1 H-NMR (CDCl3, 300 MHz) δ 1.11 (s, 6H), 2.39 (s, 6H), 3.85 (s, 4H), 4.323 (brs, 8H); MS (FD) calcd for C 23 H 24 O6S5[M+·] 556.0, found 556.1.

[0123] Example 3 A compound (2MeS-3OS) represented by the following formula (6) was synthesized.

[0124] [ka]

[0125] The synthesis scheme is as follows:

[0126] [ka]

[0127] Details are as follows: Two 100 mL two-necked eggplant-shaped flasks (reaction vessels) were prepared. A stirrer bar was placed in each flask, and the septum was closed. The walls were heated with a heat gun for approximately 1 minute while the pressure was reduced with a vacuum pump to remove moisture. The atmosphere inside the reaction vessel was then replaced with an argon atmosphere. This procedure was repeated three times. While argon was flowing, the septum of the other two-necked eggplant-shaped flask was opened, and the entire amount of tri-n-butylstannylated ethylenedioxythiophene-type monomer 4 (crude product) synthesized from 306 mg of dibrominated ethylenedithiophene-type monomer 7 and methylthiolated ethylenedioxythiophene-type monomer 3 (630 mg, 3.35 mmol) and 109 mg of tetrakis(triphenylphosphine)palladium were added, and the flask was sealed with a septum. 20 mL of toluene (Wako) was added and refluxed for 17 hours. After cooling to room temperature, the septum was opened under argon flow, and an additional 109.0 mg of tetrakis(triphenylphosphine)palladium was added. The mixture was then sealed with a septum. After refluxing for 19 hours, the mixture was cooled to room temperature and the black solid was removed by filtration through Celite to obtain a crude product. The crude product was purified using a preparative HPLC equipped with a high-speed preparative GPC column, followed by reprecipitation using dichloromethane as a good solvent and hexane as a poor solvent. 255.3 mg (466.9 μmol) of 2MeS-3OS (compound represented by (6)) was obtained as a yellow powder in 51% yield. Physical properties: 1 H-NMR(CDCl3,300MHz) δ 2.42 (s, 6H), 3.26 (s, 4H), 4.33 (s, 8H).

[0128] Example 4 A compound (2MeS-4OS) represented by the following formula (7) was synthesized.

[0129] [ka]

[0130] The synthesis scheme is as follows:

[0131] [ka]

[0132] Details are as follows: Synthesis of tributylstannylated dioxythiophene-type monomer 4

[0133] [ka]

[0134] A 10 mL Schlenk flask (reaction vessel) was prepared, a stirrer bar was placed inside, and the flask was sealed with a septum. The flask walls were heated with a heat gun for approximately 1 minute while the pressure was reduced with a vacuum pump to remove moisture. The atmosphere inside the reaction vessel was then replaced with argon. This procedure was repeated three times. While argon was flowing, the septum of one two-necked eggplant-shaped flask was opened, and 82 mg of methylthioethylenedioxythiophene monomer 3 was added. The flask was then sealed with a septum. 1.2 mL of THF (Wako, ultra-dehydrated, stabilizer-containing) was added to the reaction vessel via syringe, and the mixture was cooled to -80 °C while stirring with a magnetic stirrer. 300 μL of n-BuLi (1.6 M in n-hexane) (Kanto Chemical Co., Inc.) was added dropwise over 5 minutes using a syringe. Stirring was continued at -80 °C for 1 hour, and 130 μL of tri(n-butyl)tin was added to the reaction vessel via syringe. The mixture was then stirred for 40 minutes while being heated to room temperature. The reaction solution was filtered through Celite and then washed with 10 mL of dichloromethane (Wako). The solvent was removed from the mixed solution using a rotary evaporator to obtain tributylstannylated dioxythiophene monomer 4. This monomer 4 was used directly in the subsequent reaction without further purification.

[0135] [ka]

[0136] A 50 mL two-necked eggplant-shaped flask (reaction vessel) was prepared, a stirrer bar was placed inside, the flask was plugged with a septum, and the flask wall was heated with a heat gun for approximately 1 minute while reducing the pressure with a vacuum pump to remove moisture. 4 (total crude product), 94 mg of 2Br-2S synthesized and isolated as in Example 1, and 21.6 mg of tetrakis(triphenylphosphine)palladium were added, and the flask was plugged with a septum. 5.5 mL of toluene (Wako) was added and refluxed for 52 hours. The crude product was then cooled to room temperature, and the black solid was removed by filtration through Celite to obtain the crude product. The crude product was purified using a preparative HPLC equipped with a high-speed preparative GPC column, followed by reprecipitation using dichloromethane as a good solvent and hexane as a poor solvent, yielding 62.8 mg (87.3 μmol) of 2MeS-4OS (compound represented by formula (7)) as a yellow powder in a 47% yield. Physical properties: 1 H-NMR(CDCl3,300MHz) δ 2.42 (s, 6H) , 3.22 - 3.29 (m, 8H) ,4.32 (s, 8H).

[0137] Example 5 Compound synthesis A compound (2MeS-6PS) represented by the following formula (8) was synthesized.

[0138] [ka]

[0139] The synthesis scheme is as follows:

[0140] [ka]

[0141] Details are as follows: Synthesis of tri-n-butylstannylated propylenedioxy monomer 6

[0142] [ka]

[0143] Two 10 mL Schlenk flasks (reaction vessels) were prepared. Each flask was fitted with a stirrer, stoppered with a septum, and heated with a heat gun for approximately 1 minute while reducing the pressure with a vacuum pump to remove moisture. The reaction vessels were then filled with argon. This procedure was repeated three times. While argon was flowing, the septum of one two-necked eggplant-shaped flask was opened, and 57 mg of methylthiolated propylenedioxy monomer 5 was added. The flask was then stoppered with a septum. 2 mL of THF (Wako, ultra-dehydrated, stabilizer-containing) was added to the reaction vessel via syringe, and the mixture was cooled to -80 °C while stirring with a magnetic stirrer. 0.24 mL of n-BuLi (1.6 M in n-hexane) (Kanto Chemical Co., Inc.) was added dropwise over 1 minute to the reaction solution via syringe. Stirring was continued at -80 °C for 2 hours, and 100 μL of tri(n-butyl)tin was added to the reaction vessel via syringe. The mixture was then stirred for 16 hours while being heated to room temperature. The reaction solution was filtered through Celite and then washed with 10 mL of dichloromethane (Wako). The solvent was removed from the mixed solution using a rotary evaporator to obtain tri-n-butylstannylated propylenedioxy monomer 6. This monomer 6 was used directly in the subsequent reaction without further purification.

[0144] Synthesis of dibrominated tetramer (2Br-4PS)

[0145] [ka]

[0146] Two 50 mL two-necked eggplant-shaped flasks (reaction vessels) were prepared. Each was fitted with a stirrer, stoppered with a septum, and the walls were heated with a heat gun for approximately 1 minute while the pressure was reduced with a vacuum pump to remove moisture. The reaction vessels were then replaced with an argon atmosphere. This procedure was repeated three times. While flowing argon into one of the two-necked eggplant-shaped flasks, the septum was opened, and 83 mg of 2H-4PS was added to the two-necked eggplant-shaped flask (reaction vessel). The flask was then stoppered with a septum. 8 mL of dichloromethane (Wako, super-dehydrated) was added to the reaction vessel via syringe and cooled to -40 °C while stirring with a magnetic stirrer. 41.7 mg of N-bromosuccinimide (Wako) suspended in 2 mL of dichloromethane (Wako, super-dehydrated) was added to the other eggplant-shaped flask and cooled to 0 °C. This suspension was added to a dichloromethane solution of 2H-4PS via cannula and stirred at -40 °C for 30 minutes. After that, saturated aqueous sodium bicarbonate (30 mL) was added to the reaction solution, and the mixture was washed three times with dichloromethane (30 mL). 0.2 M aqueous sodium thiosulfate (60 mL) was added to the washed organic layer (lower layer) and stirred for 30 minutes. The mixture was then extracted three times with dichloromethane (30 mL). Na2SO4 was added to the combined organic layer, and the mixture was stirred for approximately 30 minutes to remove water. The solid was then filtered off, and the resulting solution was concentrated on a rotary evaporator to yield 2Br-4PS (crude product, 97.3 mg). 2Br-4PS was used in the subsequent reaction without further purification.

[0147] Synthesis of dimethylthiolated hexamer (2MeS-6PS)

[0148] [ka]

[0149] Two 50 mL two-necked eggplant-shaped flasks (reaction vessels) were prepared. Each flask was fitted with a stirrer, stoppered with a septum, and the walls were heated with a heat gun for approximately 1 minute while the pressure was reduced with a vacuum pump to remove moisture. The atmosphere inside the reaction vessel was then replaced with argon. This procedure was repeated three times. While argon was flowing, the septum of the other two-necked eggplant-shaped flask was opened, and 97 mg of 2Br-4PS (crude product), the entire amount of 6 (crude product), and 13.2 mg of tetrakis(triphenylphosphine)palladium were added, and the flask was stoppered with a septum. 3.5 mL of toluene (Wako) was added and the mixture was refluxed for 17 hours. The mixture was then cooled to room temperature, and the black solid was removed by filtration through Celite to obtain the crude product. The obtained crude product was purified using a preparative HPLC equipped with a high-speed preparative GPC column, and then purified by reprecipitation using dichloromethane as a good solvent and hexane as a poor solvent, to obtain 74.4 mg (63.7 μmol) of 2MeS-6PS (the compound represented by formula (8)) as a yellow powder in a yield of 57%. Physical properties: 1 H-NMR(CDCl3,300MHz) δ 1.09 (s, 24H) , 2.41 (2, 6H) ,3.22 - 3.30 (m, 8H) ,3.83 - 3.88(m,16H); 13 C-NMR(CDCl3,75MHz) δ 21.4,21.7,21.8, 28.4,28.9,39.1,39.2, 80.2, 80.3, 80.3, 80.6, 113.2, 113.3, 115.4, 116.8, 123.9, 124.8, 127.3, 128.6, 145.0, 145.6, 146.6, 150.9.

[0150] (Comparative Example 1) Compound synthesis According to the method described in Example 1 of WO 2020 / 262443, a compound represented by the following formula (C1) was synthesized.

[0151] [ka]

[0152] Preparation of Composition 4 In the "Preparation of composition" of Example 1, 3.7 mg of the compound represented by formula (C1) was used instead of the compound represented by formula (4). In addition, as the dopant, n-Bu4NClO4 (manufactured by Tokyo Chemical Industry Co., Ltd.; counter anion is ClO4) was used instead of n-Bu4NPF6. - ) was used. Other than that, the same procedures as in "Preparation of composition" of Example 1 were carried out to obtain composition 4. As a result of single crystal structure analysis, the doping rate was found to be 50%.

[0153] (Comparative Example 2) Compound synthesis In the same manner as in Comparative Example 1, a compound represented by formula (C1) was synthesized. Preparation of Composition 5 In the "Preparation of composition" of Example 1, 3.7 mg of the compound represented by formula (C1) was used instead of the compound represented by formula (4). Otherwise, composition 5 was obtained in the same manner as in the "Preparation of composition" of Example 1. As a result of single crystal structure analysis, the doping rate was 50%.

[0154] 2. Measurement The compositions (single crystals) obtained in the examples and comparative examples were measured for the following items. (1) Electrical resistivity ρ A 15 μm diameter gold wire was bonded to the composition using conductive carbon paste (XC-12, manufactured by Fujikura Chemical Industries, Ltd.), and the electrical resistivity ρ at 25°C was measured using the four-terminal or two-terminal method. To alleviate distortion of the single crystal during bonding, the Au wire was crosslinked using Ag paste (DOTITE (D-500), manufactured by Fujikura Chemical Industries, Ltd.) and then connected to the substrate. The carbon paste and Ag paste were mixed with a small amount of butyl glycol acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) to achieve an appropriate viscosity. The results are shown in Table 1.

[0155] (2) Activation energy E a The electrical resistivity ρ of the composition was measured while changing the temperature in the range of 25°C to -263°C, and the results were plotted on a graph (x-axis: reciprocal of temperature [K] converted to Kelvin temperature, y-axis: natural logarithm of electrical resistivity ρ [Ωcm]). The slope at 0°C of the curve connecting the plots was determined as the activation energy E at 0°C. a The results are shown in Table 1.

[0156] [Table 1]

[0157] 3. Evaluation From Table 1, it was found that compositions 1 to 3 using the compound according to one embodiment of the present invention had a lower electrical resistivity ρ than compositions 4 and 5 using the comparative compound. a is significantly low, which is thought to contribute to the decrease in electrical resistivity ρ.

Claims

1. A compound represented by the following formula (1-3): Z 1 -α a -β b -γ c -Z 2 (1-3) [In formula (1-3), α is a unit represented by the following formula (1α), and a is 1 or 2. When a is 2 or more, two or more units α are the same as each other. β is a unit represented by the following formula (1β), and b is 1 or 2. When b is 2 or more, two or more units β are the same as each other. γ is a unit represented by the following formula (1γ), and c is 1 or 2. When c is 2 or more, two or more units γ are the same as each other. The structure of unit α is different from the structure of unit β. The structure of unit β is different from the structure of unit γ. Z １ and Z ２ are each independently Y 2 R 1 . Y ２ is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two Y ２ are the same or different from each other. R 1 is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Two R's １ are the same or different from each other. 【Chemistry 48】 [In formula (1α), Q １ is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X １ is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X １ are identical to each other. R １１ ~R １４ are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. f is an integer of 1 to 3. When f is 2 or more, two or more R １３ are the same or different from each other, and two or more R １４ are the same or different from each other. 【Chemistry 49】 [In formula (1β), Q ２ is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X ２ is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X ２ are identical to each other. R ２１ ~R ２４ are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. g is an integer of 1 to 3. When g is 2 or more, two or more R ２３ are the same or different from each other, and two or more R ２４ are the same or different from each other. [Transformation 50] [In formula (1γ), Q ３ is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X ３ is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X ３ are identical to each other. R ３１ ~R ３４ are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms. h is an integer of 1 to 3. When h is 2 or more, two or more R ３３ are the same or different from each other, and two or more R ３４ are the same or different from each other.

2. The compound according to claim 1 , wherein the structures of the unit α and the unit γ are identical to each other.

3. 3. The compound according to claim 1, wherein two or more selected from the group consisting of a, b, and c have the same value.

4. The compound according to any one of claims 1 to 3, wherein one or more selected from the group consisting of a, b, and c is 2.

5. The compound according to any one of claims 1 to 4, wherein one or more selected from the group consisting of a, b, and c is 1.

6. The compound according to any one of claims 1 to 5, wherein one or more selected from the group consisting of f, g and h is 1 or 2.

7. The compound according to any one of claims 1 to 6, wherein one or more selected from the group consisting of f, g and h is 1.

8. One or more units selected from the group consisting of the unit α, the unit β, and the unit γ are represented by the following formula (2): The compound according to any one of claims 1 to 7, wherein when two or more units selected from the group consisting of the unit α, the unit β, and the unit γ are represented by the following formula (2), the two or more units may include a combination of units having the same structure as each other, or may include a combination of units having different structures as each other: 【Chemistry 53】 [In formula (2), Q ６ is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X ６ is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X ６ are identical to each other.]

9. Q ６ The compound according to claim 8, wherein is S (sulfur atom).

10. X ６ The compound according to claim 8 or 9, wherein is S (sulfur atom) or O (oxygen atom).

11. One or more units selected from the group consisting of the unit α, the unit β, and the unit γ are represented by the following formula (3): The compound according to any one of claims 1 to 10, wherein when two or more units selected from the group consisting of the unit α, the unit β, and the unit γ are represented by the following formula (3), the two or more units may include a combination of units having the same structure as each other, or may include a combination of units having different structures from each other: 【Chemistry 54】 [In formula (3), Q ７ is S (sulfur atom), Se (selenium atom), O (oxygen atom), Te (tellurium atom), or NH. X ７ is S (sulfur atom), Se (selenium atom), O (oxygen atom) or Te (tellurium atom), and two X ７ are identical to each other. R ７３ and R ７４ are each independently H (hydrogen atom) or an unsubstituted alkyl group having 1 to 12 carbon atoms.

12. Q ７ The compound according to claim 11, wherein is S (sulfur atom).

13. X ７ The compound according to claim 11 or 12, wherein is S (sulfur atom) or O (oxygen atom).

14. R ７３ and R ７４ and each independently represent an alkyl group having 1 to 12 carbon atoms.

15. Z １ and Z ２ and each independently represent an alkylthio group having 1 to 12 carbon atoms or an alkylseleno group having 1 to 12 carbon atoms.

16. The compound according to any one of claims 1 to 15, wherein the structure of the unit α and the structure of the unit γ are identical to each other.

17. The compound according to any one of claims 1 to 16, which satisfies the relationship a = c.

18. A compound according to any one of claims 1 to 17; A dopant, A composition comprising:

19. The dopant is BF ４ － , ClO ４ － , P.F. ６ － , HSO ４ － , GaCl ４ － , CoCl ４ ２－ , SbF ６ － , SCN － , Cl － ,Br － , I － ,Br ３ － , I ３ － , and TCNQ or F ｘ 19. The composition according to claim 18, wherein the anion is one or more selected from the group consisting of monovalent anion species of TCNQ (x is 2 or 4).

20. Electrical resistivity ρ at 25°C is 10 ５ 20. The composition of claim 18 or 19, having a viscosity of Ωcm or less.

21. Activation energy E at 0°C ａ The composition according to any one of claims 18 to 20, wherein the energy of the electrons is 300 meV or less.

22. A conductive assistant comprising the composition according to any one of claims 18 to 21.

23. An electrode manufactured using the composition according to any one of claims 18 to 21 and the conductive assistant according to claim 22.

24. 24. The electrode according to claim 23, which is a capacitor electrode, a transparent electrode, a battery electrode or a capacitor electrode.

25. A substrate; a layer comprising the composition according to any one of claims 18 to 21 laminated on the substrate; A laminate comprising:

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