JP5837390B2 - Conductive coating conjugated polymer and method for producing the same - Google Patents

Description

  The present invention relates to a conductive coated conjugated polymer having a π-conjugated structure coated with a plurality of organic cyclic compounds. Further, the present invention relates to a method for producing a conductive coated conjugated polymer having a π-conjugated structure coated with a plurality of organic cyclic compounds.

As one of the conductive coated conjugated polymers having a π-conjugated structure coated with a plurality of organic cyclic compounds, the organic polymer shown in Patent Document 1 is known, but Patent Document 1 includes data indicating conductivity. Is not shown at all.
The data showing the conductivity of the representative conductive coated conjugated polymer of Patent Document 1 has been published as a non-patent document 1 by the authors including the inventor of Patent Document 1, and the data on conductivity The data shown show that the charge mobility is 0.5 cm ² / Vs, but this polymer is used as an organic semiconductor that constitutes a molecular device because the chain structure has a linear structure. However, sufficient conductivity is not obtained.
Non-Patent Document 2 shows that the charge mobility is 0.9 cm ² / Vs as data indicating the conductivity of a polymer in which polypyrrole has a chain structure.
However, the conductivity shown in these prior arts is insufficient for use as an organic semiconductor constituting a molecular device.

WO2008 / 069274

Terao, J. et al. J. Am. Chem. Soc. 2009, 131, 18046 Sugiyasu, K. et al. J. Am. Chem. Soc. 2010, 132, 14754

  An object of this invention is to provide the electroconductive coating conjugated polymer with a larger charge mobility in view of such a situation. That is, an object of the present invention is to provide a conductive coated conjugated polymer having a charge mobility one order higher than that of a conventional conductive polymer.

  As a result of investigations to solve the above problems, it has been conventionally considered that a phenylene ethynylene unit having no ionic functional group is linear and has a π-conjugated structure to increase charge mobility. On the other hand, by introducing a meta bond to the chain structure, a conductive coated conjugated polymer having a charge mobility that has not been obtained has been found, and the following invention has been completed.

〔２〕導電性被覆共役ポリマーが下記構造式（３）又は構造式（４）で示されることを特徴とする前記〔１〕に記載の導電性被覆共役ポリマー。

上記式中、ｎは２から２０の整数であり、より好ましくは３から１２の整数である。

上記式中、ｎは２から２０の整数であり、より好ましくは３から１２の整数である。
〔３〕前記有機環状化合物が、シクロデキストリン誘導体であり、前記シクロデキストリン誘導体の１つの−ＣＨ２ＯＨが−ＣＨ２Ｏ−の形で鎖状構造中のフェニレン基と結合していることを特徴とする前記〔１〕又は〔２〕に記載の導電性被覆共役ポリマー。
〔４〕前記シクロデキストリン誘導体が、下記化学式（５）で表されるα−シクロデキストリン誘導体（Ｒは、Ｈ又はアルキル基）であることを特徴とする前記〔３〕に記載の導電性被覆共役ポリマー。

〔５〕前記構造式（１）と前記構造式（２）を有するモノマーを共重合すること、又は、前記構造式（１）若しくは前記構造式（２）を有するモノマーとｍ−ジハライドベンゼン若しくはｍ−ジエチニルベンゼンを共重合すること、を特徴とする前記〔１〕に記載の導電性被覆共役ポリマーの製造方法。 [1] A conductive coated conjugated polymer having a π-conjugated structure coated with a plurality of organic cyclic compounds, wherein the π-conjugated structure is a phenylene ethynylene unit, and the following structural formulas (1) and (2) As a structural unit, or the following structural formula (1) and / or structural formula (2) and a metadiethynylene phenylene chain as a structural unit.

[2] The conductive coated conjugated polymer according to [1], wherein the conductive coated conjugated polymer is represented by the following structural formula (3) or structural formula (4).

In said formula, n is an integer of 2-20, More preferably, it is an integer of 3-12.

In said formula, n is an integer of 2-20, More preferably, it is an integer of 3-12.
[3] The organic cyclic compound is a cyclodextrin derivative, and one —CH 2 OH of the cyclodextrin derivative is bonded to a phenylene group in a chain structure in the form of —CH 2 O—. The conductive coating conjugated polymer according to [1] or [2].
[4] The conductive coating conjugate according to [3], wherein the cyclodextrin derivative is an α-cyclodextrin derivative (R is H or an alkyl group) represented by the following chemical formula (5): polymer.

[5] copolymerizing the monomer having the structural formula (1) and the structural formula (2), or the monomer having the structural formula (1) or the structural formula (2) and m-dihalide benzene, m-diethynylbenzene is copolymerized, The manufacturing method of the conductive coating conjugated polymer as described in said [1] characterized by the above-mentioned.

The conductive coated conjugated polymer of the present invention introduces a cross-linked structure in which a part of the phenylene chain is meta-positioned, thereby reducing the energy level deviation of the phenylene ethylene unit between the meta-cross-linked parts. Energy loss due to inter-popping is reduced, and high charge mobility can be secured. As a result, high conductivity can be secured.
As a result, the conductive coated conjugated polymer of the present invention has excellent conductivity due to a large charge mobility compared to the conventionally known conductive polyrotaxane, and is applied to an organic semiconductor constituting a molecular device. Is possible.

  In addition, the method for producing a conductive coated conjugated polymer of the present invention allows the polymerization reaction to proceed without returning to the non-inclusion state even if an organic solvent is used for the polymerization reaction, and facilitates the progress of the polymerization reaction. There is an effect that was not in an aqueous solution, such as easy control of the degree of polymerization.

FIG. 1 is a diagram showing a method for synthesizing a monomer precursor having structural formulas (1) and (2).

FIG. 2 is a diagram showing a method for synthesizing the structural formula (1 ′).

FIG. 3 is a diagram illustrating a synthesis method of the structural formula (2 ′).

FIG. 4 shows a method for synthesizing the polymer represented by the structural formula (3 ″).

FIG. 5 is a view showing a method for synthesizing the polymer of the structural formula (4 ′).

FIG. 6 is a diagram showing a method for synthesizing the polymer of the structural formula (8).

  The conductive coated conjugated polymer of the present invention is a conductive coated conjugated polymer having a π-conjugated structure coated with a plurality of organic cyclic compounds, wherein the π-conjugated structure is a phenylene ethynylene unit and has a pseudo-rotaxane structure. The structural formula (1) and the structural formula (2) in which two molecules of a self-inclusion complex are bonded via a benzene ring, or the structural formula (1) and / or the structural formula (2) and metadietinylene. It has a phenylene chain as a structural unit.

  The organic cyclic compound represented by the structural formulas (1) to (4) is soluble in an organic solvent and self-inclusion within a molecule by hydrophilic-hydrophobic interaction in a π-conjugated molecule and an aqueous solvent solution (for example, aqueous methanol solution). Although not particularly limited, it is usually selected from cyclodextrin derivatives, cyclic polyether derivatives, cyclic polysiloxane derivatives and the like, and is bonded to the phenylene group in the chain structure by an ether bond.

  Among the above organic cyclic compounds, the α cyclodextrin derivative does not have a π-electron conjugated structure and is preferable as the organic cyclic compound, and more preferably a completely methylated α cyclodextrin (PM α-CD).

  When the cyclodextrin derivative is an organic cyclic compound, one —CH 2 OH of the cyclodextrin is bonded to the phenylene group in the chain structure in the form of —CH 2 O—.

  In the conductive coated conjugated polymer of the present invention having the structural formula (1) and the structural formula (2) as structural units, the structural units of the structural formulas (1) and (2) are bonded with one or more ethynylene chains. Obtained as a conductive coated conjugated polymer. Conductivity of the present invention having various structural formulas (1) and (2) as structural units by controlling the ratio of structural units of structural formula (1) and structural formula (2) and the number of ethynylene chains. It is possible to produce a conductive coating conjugated polymer.

Examples of the conductive coating conjugated polymer obtained by polymerizing the monomer having the structural formula (1) and the monomer having the structural formula (2) at 1: 1 include those represented by the following structural formula (6).

  The conductive coating conjugated polymer of the present invention having the structural formula (1) and / or the structural formula (2) and a metadiethynylene phenylene chain as a structural unit has the structure of the structural formula (1) and / or the structural formula (2). It can be obtained as a conductive coated conjugated polymer comprising a metadiethynylene phenylene chain in which the units are linked with a metadiethylene phenylene chain.

  The conductive coating conjugated polymer containing a metadiethylene alkylene chain is obtained by polymerizing a monomer having the structural formula (1) with a metadiethylene polyethylene chain, and (b) a monomer having the structural formula (2). And (c) a monomer having the structural formula (1) and a monomer having the structural formula (2) which are polymerized with the metadiethynylene phenylene chain. Can do.

  The conductive coated conjugated polymers (a) to (c) can be used for various conductive materials by controlling the ratio of the structural units of the structural formula (1) and / or the structural formula (2) and the number of metadiethylene phenylene chains. It is possible to produce a conductive coating conjugated polymer.

構造式（１）を有するモノマーのモル比がメタジエチニレンフェニレン鎖に対してｍ（ｍは２以上の整数）になるように重合させた導電性被覆共役ポリマーとしては、下記構造式（３’）に示すものがあげられる。

Examples of the conductive coating conjugated polymer polymerized so that the monomer having the structural formula (1) and the metadiethylene phenylene chain are 1: 1 include those represented by the following structural formula (3).

As the conductive coated conjugated polymer polymerized so that the molar ratio of the monomer having the structural formula (1) is m (m is an integer of 2 or more) with respect to the metadiethylene phenylene chain, the following structural formula (3 ′ ).

Examples of the conductive coating conjugated polymer polymerized so that the monomer having the structural formula (2) and the metadiethylene phenylene chain are 1: 1 include those represented by the following structural formula (4).

  Next, the manufacturing method of the electroconductive coating conjugated polymer of this invention is demonstrated.

  The conductive coating conjugated polymer of the present invention is obtained by copolymerizing a monomer having the structural formula (1) and the structural formula (2), or a monomer having the structural formula (1) or the structural formula (2). And m-dihalidebenzene or m-diethynylbenzene can be copolymerized.

  The method for producing a conductive coated conjugated polymer of the present invention is characterized in that a polymerization reaction is carried out using a monomer having the structural formula (1) and the structural formula (2). The monomer having the structural formula (1) and the structural formula (2) can maintain the inclusion structure because two molecules of the self-inclusion complex having a pseudorotaxane structure are bonded via a benzene ring. Is a coated π-conjugated monomer having

Therefore, even if an organic solvent is used for the polymerization reaction, the effect that the polymerization reaction can be performed without returning to the non-inclusion body state can be exhibited.
In addition, by reacting in an organic solvent, there is an effect that was not in an aqueous solution, for example, the polymerization reaction can easily proceed and the degree of polymerization can be easily controlled. (Add any other benefits.)

  First, the conductive coating conjugated polymer of the present invention having the structural formula (1) and the structural formula (2) as structural units has both ends of a monomer having the structural formula (1) or the structural formula (2) having both ends of an ethynyl group. Is copolymerized with a monomer having the structural formula (1) or structural formula (2), or the structural formula (1) and structural formula (2) having one end having an ethynyl group and the other end having a halogen group. ).

  In the above case, various conductive coated conjugated polymers with varying linearity of the chain portion are produced by controlling the molar ratio of the monomer having the structural formula (1) and the monomer having the structural formula (2). Is possible.

  Next, the conductive coating conjugated polymer of the present invention having the structural formula (1) and / or the structural formula (2) and the metadiethynylene phenylene chain as a structural unit includes the structural formulas (1) and / or Alternatively, a monomer having the structural formula (2) and m-dihalide benzene are copolymerized, or a monomer having the structural formula (1) and / or the structural formula (2) having both ends being halogen groups and m-di. Ethynylbenzene can be produced by copolymerizing a monomer having the structural formula (1) or the structural formula (2) in which both ends are halogen groups.

A monomer having the structural formula (1) or the structural formula (2) is obtained by reacting a known pseudorotaxane precursor (the following compound (7)) with 1,4-diiodobenzene or 1,3-diiodobenzene. Can be manufactured.

  Specifically, the pseudorotaxane precursor (the compound (7)) is self-inclusion intramolecularly in a methanol-water mixed solvent, and two molecules of the self-inclusion complex and 1,4-diiodobenzene or 1,3-di- It can be produced by a cross-coupling reaction with iodobenzene.

  The produced monomer having the structural formula (1) or the structural formula (2) remains as an acetamide group at both ends, but by substituting the acetamide group with a halogen group (preferably an iodo group) or an ethynyl group, It can be set as the monomer which has Structural formula (1) or Structural formula (2) used as the raw material of this invention.

Hereinafter, embodiments of the present invention will be specifically described by way of examples.

[Synthesis of Precursor Material for Monomer Having Structural Formula (1) or Structural Formula (2)]
FIG. 1 shows a method for synthesizing the monomer precursor used in the examples.
5-Acetoamide-2-iodophenol (1.67 mmol), PM α-CD (1.52 mmol), K ₂ CO ₃ (15.2 mmol) are added to a 50 ml two-necked eggplant flask purged with argon, and dissolved in 10 ml of dehydrated DMF. And stirred at 100 ° C. for 16 hours. Thereafter, an aqueous sodium hydrogen carbonate solution was added, the mixture was extracted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated. Purification was performed by silica gel column chromatography to obtain iodinated PM α-CD derivative with a yield of 98%.

Subsequently, the iodinated PM α-CD derivative (0.67 mmol) was added to a 50 ml two-necked eggplant flask substituted with argon and dissolved in 5 ml of diisopropylamine. Diethynylbenzene derivative (0.74 mmol), Pd (PPh ₃ ) ₄ (0.00268 mmol), CuI (0.0134 mmol) were added, and the mixture was stirred at 45 ° C. for 16 hours. After the solvent was distilled off, extraction was performed with ethyl acetate, washed with saturated brine and dried over sodium sulfate, and then the solvent was distilled off. Purification by silica gel column chromatography gave [(4-ethynylphenyl) ethynyl] trimethylsilylated PM α-CD derivative in 94% yield.

Subsequently, (4-ethynylphenyl) ethynyl] trimethylsilylated PM α-CD derivative (0.448 mmol) was added to a 50 ml eggplant flask and dissolved in 20 ml of methanol. 2.5 ml (2.24 mmol) of 1M-K ₂ CO ₃ was added and stirred at room temperature for 2 hours. After the solvent was distilled off, extraction was performed with ethyl acetate, washed with saturated brine and dried over sodium sulfate, and then the solvent was distilled off. Purification was performed by silica gel column chromatography to obtain ethynyltolane-linked PM α-CD derivative (7 ′) as a monomer precursor in a yield of 95%. ((7 ′) is a substance in which the organic cyclic compound of the structural formula (7) is PM α-CD.)

[Synthesis of Monomer Having Structural Formula (1)]

FIG. 2 shows a method for synthesizing a monomer having the structural formula (1) used in the examples.
In a 100 ml eggplant flask, ethynyltolane-bound PM α-CD derivative (7 ′) (0.85 mmol) as a monomer precursor and methanol / water = 30 ml: 30 ml were mixed. After reacting at 60 ° C. for 1 hour, it was cooled to room temperature. The system was purged with argon, and 1,4-iodobenzene (0.425 mmol), Pd (OAc) ₂ (0.18 mmol), TXPTS (0.085 mmol), CuI (0.0043 mmol), sodium carbonate (6.8 mmol) ), 3 ml of triethylamine was added. Stir at room temperature for 48 hours. The mixture was diluted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated. The product was purified by silica gel column chromatography to obtain a coating monomer (1 ′) having an acetamide group at the terminal in a yield of 82%. ((1 ′) is a substance in which the organic cyclic compound of the structural formula (1) is PM α-CD, and acetamido groups are substituted on both ends.)

MALDI-TOF MS (CHCA): m / z 3033 ([M + Na] ⁺ ,
C ₁₄₈ H ₂₁₂ N ₂ O ₆₂ Na, cald 3034); ¹ H
NMR (400 MHz, CDCl ₃ ): δ _H = 8.25 (d, J = 8.2 Hz, 4H, ArH), 7.61 (d, J = 8.2 Hz,
4H, ArH), 7.45-7.36 (m, 6H, ArH), 7.21 (s, 2H, NH), 5.10-4.96 (m, 12H, CD-H ₁ ),
4.87-2.83 (m, 174H, CD-H, OCH ₃ ), 2.22 (s, 6H, CH ₃ CO); ¹³ C
NMR (400MHz, CDCl ₃ , rt): δ _c = 168.585, 162.453, 140.744, 139.643, 133.511-131.183 (several peaks
overlapped), 123.212, 122.848, 113.891, 112.540, 111.563,
100.651-99.913 (several peaks overlapped), 98.323, 93.418, 90.591,
83.607-80.781 (several peaks overlapped), 83.783-81.167 (several peaks
overlapped), 71.709-70.233 (several peaks overlapped), 62.148,
59.321-57.606 (several peaks overlapped); Anal.Calcd for C ₁₄₈ H ₂₁₂ N ₂ O ₆₂・ 2H ₂ O: C, 58.33; H, 7.14; N, 0.92; O, 33.60%; Found: C,
57.01; H, 7.18; N, 0.87; O, 33.80%.

[Synthesis of Monomer Having Structural Formula (2)]
FIG. 3 shows a method for synthesizing the monomer having the structural formula (2) used in the examples.
In a 50 ml eggplant flask, the monomer precursor ethynyltolane-bound PM α-CD derivative (7 ′) (0.48 mmol) and methanol / water = 15 ml: 15 ml were mixed. After reacting at 65 ° C. for 1 hour, it was cooled to room temperature. The system was purged with argon, and 1,3-iodobenzene (0.24 mmol), Pd (OAc) ₂ (0.24 mmol), TXPTS (0.096 mmol), CuI (0.0024 mmol), sodium carbonate (3.84 mmol) ), 3 ml of triethylamine was added. Stir at room temperature for 24 hours. The mixture was diluted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated. The product was purified by silica gel column chromatography to obtain a coating monomer (2 ′) having an acetamide group at the terminal in a yield of 82%. ((2 ′) is a substance in which the organic cyclic compound of the structural formula (2) is PM α-CD, and acetamido groups are substituted on both ends.)

MALDI-TOF MS (CHCA): m / z 3033 ([M + Na] ⁺ ,
C ₁₄₈ H ₂₁₂ N ₂ O ₆₂ Na, cald 3034); ¹ H
NMR (400 MHz, CDCl ₃ ): δ _H = 8.05 (d, J = 8.2 Hz, 4H, ArH), 7.62-7.61 (m, 5H, ArH),
7.45-7.35 (m, 9H, ArH), 5.01-4.96 (m, 12H, CD-H ₁ ), 4.87-2.83 (m, 174H,
CD-H, OCH ₃ ), 2.22 (s, 6H, CH ₃ CO); ¹³ C NMR
(400MHz, CDCl ₃ , rt): δ _c = 162.58, 139.77, 133.76-131.31 (several peaks overlapped), 123.46,
122.85, 113.90, 112.54, 111.56, 101.88-98.22 (several peaks overlapped),
93.418, 90.23, 83.97-80.91 (several peaks overlapped), 72.57-69.87 (several
peaks overlapped), 62.02, 59.45-57.48 (several peaks overlapped); Anal. Calcd
for C ₁₄₈ H ₂₁₂ N ₂ O ₆₂・ 2H ₂ O: C, 58.33; H, 7.14; N, 0.92; O, 33.60%; Found: C,
58.05; H, 7.02; N, 0.98; O, 33.21%.

Example 1
FIG. 4 shows a method for synthesizing the meta-crosslinking coating polymer having the structural formula (3) used in Example 1.
To a 1 L eggplant flask, 100 ml of tetrahydrofuran and 500 ml of 1M HCl aqueous solution were added, and the coating monomer (1 ′) (0.332 mmol) was added. The system was purged with nitrogen and stirred at 40 ° C. for 24 hours. The mixture was diluted with ethyl acetate, washed with saturated sodium hydrogen carbonate and saturated brine, dried over sodium sulfate, and the solvent was evaporated. Purification by silica gel column chromatography gave an amine derivative in which the terminal acetamide group was hydrolyzed in a yield of 70%.

MALDI-TOF MS: (m / z) 2949 ([M + Na] ⁺ ,
C ₁₄₄ H ₂₀₈ N ₂ O ₆₀ Na, calcd. 2950); ¹ H
NMR (400MHz, CDCl ₃ , rt): δ _H = 8.01 (d, J
= 8.2 Hz, 4H, ArH), 7.60 (d, J = 8.2 Hz, 4H, ArH), 7.44 (s, 4H,
ArH), 7.22 (d, J = 8.2 Hz, 2H, ArH), 6.44 (m, 4H, ArH), 5.10-4.96 (m,
12H, CD-H ₁ ), 4.87-2.85 (d, 178H, NH, CD-H, OCH ₃ ); ¹³ C
NMR (400MHz, CDCl ₃ , rt): δ _c = 163.367,
160.560, 148.795, 148.393, 134.194, 132.077-131.158 (several peaks overlapped),
124.384, 123.206, 122.976, 122.775, 109.870, 107.983, 107.523, 105.367,
102.618, 100.721-98.000 (several peaks overlapped),
83.783-81.167 (several peaks overlapped), 72.095-70.083 (several peaks
overlapped), 61.767, 59.018-57.351 (several peaks overlapped); Anal.Calcd for C ₁₄₄ H ₂₀₈ N ₂ O ₆₀・ 2H ₂ O:
C, 58.37; H, 7.21; N, 0.95; O, 33.48%; Found: C, 58.01; H, 7.18; N, 0.87; O,
33.82%.

A 50 ml eggplant-shaped flask was charged with the above-described both-terminal amine derivative (0.102 mmol) and 20 ml of 20% sulfuric acid and cooled to 0 to 5 ° C. This solution was added dropwise to NaNO ₂ (0.306 mmol) dissolved in 0.5 ml of water and cooled to 0-5 ° C. The reaction solution was stirred at 0 to 5 ° C. for 1 hour, then added to a KI (1.00 mmol) solution, and stirred at room temperature for 1 hour. The mixture was diluted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated. Purification by silica gel column chromatography gave iodinated derivatives at both ends in a yield of 60%.

MALDI-TOF MS: (m / z) 3172 ([M + Na] ⁺ ,
C ₁₄₄ H ₂₀₄ I ₂ O ₆₀ Na, calcd. 3172); ¹ H
NMR (400MHz, CDCl ₃ , rt): δ _H = 8.07 (d, J
= 8.3 Hz, 4H, ArH), 7.62 (d, J = 8.3 Hz, 4H, ArH), 7.54 (s, 2H, ArH),
7.50 (d, J = 8.6 Hz, 2H, ArH), 7.44 (s, 2H, ArH), 7.24 (d, J =
8.3 Hz, 2H, ArH), 5.09-4.96 (m, 12H, CD-H ₁ ), 4.82-2.90 (m, 174H,
CD-H, OCH ₃ ); ¹³ C NMR (400 MHz, CDCl ₃ , rt): δ _c = 163.367,
132.077-131.158 (several peaks overlapped), 124.384, 123.206, 122.976,
100.721-98.000 (several peaks overlapped), 83.783-81.167 (several peaks
overlapped), 72.095-70.083 (several peaks overlapped), 61.767,
59.018-57.351 (several peaks overlapped); Anal.Calcd for C ₁₄₄ H ₂₀₄ I ₂ O ₆₀・ H ₂ O:
C, 54.61; H, 6.56; I, 8.01; O, 30.82%; Found: C, 53.98; H, 7.02; O, 31.94%.

Then, in a recovery flask of 30 ml, both ends iodide derivative (9.53μmol) and 1,3-diethylbenzene (9.53μmol), placed _{Pd (PPh 3) 4 (1.91μmol} ), was dissolved in piperidine. After stirring at room temperature for 24 hours, the mixture was diluted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated. Purification by preparative thin phase chromatography gave a meta-crosslinked coating polymer (3 ″). ((3 ″) is a polymer in which the organic cyclic compound of the structural formula (3) is PM α-CD.)

¹ H NMR (400MHz, CDCl ₃ ,
rt): δ _H = 8.18-8.02 (br, ArH), 7.74-7.58
(br, ArH), 7.57-7.38 (br, ArH), 5.18-4.93 (m, CD-H ₁ ), 4.90-2.80 (m,
CD-H, OCH ₃ ).

(Example 2)
FIG. 5 shows a method for synthesizing a meta-meta crosslinked coating polymer having the structural formula (4) used in Example 2.
To a 500 ml eggplant flask, 40 ml of tetrahydrofuran and 200 ml of 1M HCl aqueous solution were added, and the coating monomer (2 ′) (0.10 mmol) was added. The system was purged with nitrogen and stirred at 40 ° C. for 24 hours. The mixture was diluted with ethyl acetate, washed with saturated sodium hydrogen carbonate and saturated brine, dried over sodium sulfate, and the solvent was evaporated. Purification by silica gel column chromatography gave an amine derivative in which the terminal acetamide group was hydrolyzed in a yield of 68%.

MALDI-TOF MS: (m / z) 2949 ([M + Na] ⁺ ,
C ₁₄₄ H ₂₀₈ N ₂ O ₆₀ Na, calcd. 2950); ¹ H
NMR (400MHz, CDCl ₃ , rt): δ _H = 7.95 (d, J = 8.2 Hz, 4H, ArH), 7.53-7.51 (m, 5H,
ArH), 7.38-7.14 (m, 9H, ArH), 6.37 (m, 4H, ArH), 5.04-4.90 (m, 12H, CD-H ₁ ),
4.86-2.78 (d, 178H, NH, CD-H, OCH ₃ ); ¹³ C NMR (400 MHz,
CDCl ₃ , rt): δ _c = 1638.92, 154.33, 139.74, 139.37, 137.78, 136.80, 134.10,
128.95-128.34 (several peaks overlapped), 115.47, 113.63, 111.05, 106.63-105.41
(several peaks overlapped), 103.69, 97.19, 95.35-93.73 (several peaks
overlapped), 89.71-86.40 (several peaks overlapped), 78.06-75.49 (several peaks
overlapped), 67.88-66.90 (several peaks overlapped), 64.69-62.61 (several peaks
Analped Calcd for C ₁₄₄ H ₂₀₈ N ₂ O ₆₀・ 3H ₂ O: C, 58.01; H, 7.24; N, 0.94; O, 33.81%; Found: C,
58.11; H, 7.02; N, 0.94; O, 33.88%.

A 20 ml eggplant-shaped flask was charged with the above-mentioned amine derivative at both ends (0.0684 mmol) and 10 ml of 20% sulfuric acid, and cooled to 0-5 ° C. This solution was added dropwise to NaNO ₂ (0.202 mmol) dissolved in 0.5 ml of water and cooled to 0-5 ° C. The reaction solution was stirred at 0 to 5 ° C. for 1 hour, then added to a KI (0.682 mmol) solution, and stirred at room temperature for 1 hour. The mixture was diluted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated. Purification by silica gel column chromatography gave a iodinated derivative at both ends in a yield of 71%.

MALDI-TOF MS: (m / z) 3172 ([M + Na] ⁺ ,
C ₁₄₄ H ₂₀₄ I ₂ O ₆₀ Na, calcd. 3172); ¹ H
NMR (400MHz, CDCl ₃ , rt): δ _H = 8.06 (d, J = 8.3 Hz, 4H, ArH), 7.62-7.61 (m, 5H, ArH),
7.54-7.35 (m, 9H, ArH), 5.09-4.95 (m, 12H, CD-H ₁ ), 4.81-2.89 (m,
174H, CD-H, OCH ₃ ); ¹³ C NMR (400 MHz, CDCl ₃ ,
rt): δ _c = 159.51,
132.07-131.15 (several peaks overlapped), 124.38, 123.20, 122.97, 100.53-99.3
(several peaks overlapped), 82.01-81.03 (several peaks overlapped), 72.1-71.5
(several peaks overlapped), 62.06, 60.55, 59.08-57.86 (several peaks
Analped Calcd for C ₁₄₄ H ₂₀₈ I ₂ O ₆₀・ 3H ₂ O: C, 54.00; H, 6.61; I, 7.92; O, 31.47%; Found: C,
53.59; H, 7.45; O, 30.99%.

Next, an iodine substituted derivative (0.048 mmol) was added to a 20 ml eggplant flask purged with argon, and 1 ml of diisopropylamine and 5 ml of tetrahydrofuran were added. Trimethylsilylacetylene (0.144 mmol), Pd (PPh ₃ ) ₂ Cl (0.0051 mmol), and CuI (0.0010 mmol) were added and stirred at room temperature for 5 hours. The reaction solution was filtered through celite and concentrated. Purification was performed by silica gel column chromatography to obtain a TMS derivative at both ends in a yield of 66%.

MALDI-TOF MS: (m / z) 3111 ([M + Na] +,
C154H222O60Si2Na, calcd. 3111).

  Next, a TMS derivative (0.032 mmol) at both ends was placed in a 20 ml eggplant flask, and 5 ml of tetrahydrofuran was added. TBAF tetrahydrofuran solution was added and stirred at room temperature for 30 minutes. 5 ml of methanol was added to the reaction solution, and the solvent was distilled off. Purification by preparative thin-layer chromatography yielded a biterminal ethynyl derivative (meta-crosslinking coated π-conjugated monomer) in which the trimethylsilyl group was deprotected in a yield of 62%.

MALDI-TOF MS: (m / z) 2967 ([M + Na] ⁺ ,
C ₁₄₈ H ₂₀₆ O ₆₀ Na, calcd. 2968); ¹ H NMR
(400MHz, CDCl ₃ , rt): δ _H = 8.05 (d, J = 8.3 Hz, 4H, ArH), 7.63-7.61 (m, 5H,
ArH), 7.48-7.35 (m, 9H, ArH), 5.01-4.96 (m, 12H, CD-H ₁ ),
4.80-2.87 (m, 174H, CD-H, OCH ₃ ); ¹³ C NMR (400 MHz, CDCl ₃ ,
rt): δ _c = 167.03,
139.42, 138.69-134.08 (several peaks overlapped), 132.40, 130.98, 129.45,
128.71, 127.67, 122.94, 106.19, 106.19-103.53 (several peaks overlapped),
100.70, 95.75, 94.80, 93.72, 89.31-85.22 (several peaks overlapped),
77.80-75.73 (several peaks overlapped), 67.35, 63.00-562.01 (several peaks
Analped Calcd for C ₁₄₈ H ₂₀₆ O ₆₀・ H ₂ O: C, 59.99; H, 7.08; O, 32.94%; Found: C, 60.17; H,
7.30; O, 33.32%

Next, both ends of the ethynyl derivative (0.012 mmol), 1,3-diiodobenzene (0.012 mmol), Pd ₂ (dba) ₃ (0.0024 mmol), PPh ₃ (0.0048 mmol) were placed in a 20 ml eggplant flask. ), CuI (0.6 μmol) was added and dissolved in 2.5 ml of tetrahydrofuran. After adding 0.5 ml of triethylamine and stirring at room temperature for 24 hours under an argon atmosphere, the mixture was diluted with ethyl acetate, washed with saturated brine and dried over sodium sulfate, and then the solvent was distilled off. Purification by preparative thin layer chromatography gave a meta-meta cross-linked coating polymer (4 ′). ((4 ′) is a polymer in which the organic cyclic compound of the structural formula (4) is PM α-CD.)

1H NMR (400MHz, CDCl3, rt): δ _H δ _H = 8.05 (br, ArH),
7.63-7.61 (br, ArH), 7.55-7.44 (br, ArH), 7.30 (br, ArH), 5.01-4.96 (m, CD-H1),
4.80-2.87 (m, CD-H, OCH ₃ ).

(Comparative Example 1)

FIG. 6 shows a method for synthesizing the coating polymer (8) used in Comparative Example 1.
The process up to the synthesis of the iodinated derivatives at both ends is the same as in Example 1.
Subsequently, both ends of the iodinated derivative (6.67 μmol), 1,4-diethynylbenzene (6.67 μmol), and Pd (PPh ₃ ) ₄ (1.33 μmol) were placed in a 20 ml eggplant flask and dissolved in 2 ml of piperidine. did. After stirring at room temperature for 24 hours, the mixture was diluted with ethyl acetate, washed with saturated brine, dried over sodium sulfate, and the solvent was evaporated. Purification by preparative thin phase chromatography gave the coated polymer (8).

1H NMR (400MHz, CDCl3, rt): δ _H = 8.13-7.88 (br, ArH), 7.68-7.23
(br, ArH), 5.16-4.83 (m, CD-H1), 4.70-2.81 (m, CD-H, OCH3).

[Intramolecular charge mobility measurement by TRMC-TAS method]
Intramolecular charge mobility in the solid state was measured by the TRMC-TAS method for the meta-crosslinked coating polymer. (The TRMC-TAS method is a method published in the literature: Proceedings of the 1st Annual Meeting of Participant Accelerator Meeting in Japan (August 4-6, 2004, Funabashi Japan), without producing a bulk material in the body. Can be measured.)
The value of intramolecular charge mobility was determined using the conductivity determined from TRMC-TAS measurement and the value of charge separation efficiency φ.

As a result, remarkably improved than the value 0.7 cm ² / Vs mobility para crosslinked coating polymer (8) by meta-crosslinked, meta crosslinked coating polymer (3 '') is 3.0 cm ² / Vs, Meta-meta cross-linking coating polymer (4 ′) was 2.1 cm ² / Vs.
This is the highest value of intramolecular charge mobility of conjugated polymers currently reported.

TMRC measurement: Time-resolved dielectric absorption measurement (Time-Resolved Microwave Conductivity). Conductivity can be measured in bulk solids and liquids without electrode preparation.
TAS: Transient Absorption Spectroscopy. A method for examining the electronic level of active species.

The conductive coated conjugated polymer of the present invention has excellent conductivity due to a large charge mobility compared to conventionally known conductive polyrotaxanes, and can be applied to organic semiconductors constituting molecular devices. .

Claims (5)

A conductive coated conjugated polymer having a π-conjugated structure coated with a plurality of organic cyclic compounds, wherein the π-conjugated structure is a phenylene ethynylene unit, and the following structural formulas (1) and (2) are structural units: Or a conductive coated conjugated polymer comprising the following structural formula (1) and / or structural formula (2) and a metadiethynylene phenylene chain as structural units.

The conductive coated conjugated polymer according to claim 1, wherein the conductive coated conjugated polymer is represented by the following structural formula (3) or structural formula (4).

In said formula, n is an integer of 2-20, More preferably, it is an integer of 3-12.

In said formula, n is an integer of 2-20, More preferably, it is an integer of 3-12.   The organic cyclic compound is a cyclodextrin derivative, and one -CH2OH of the cyclodextrin derivative is bonded to a phenylene group in a chain structure in the form of -CH2O-. Item 3. The conductive coated conjugated polymer according to Item 2. The conductive coated conjugated polymer according to claim 3, wherein the cyclodextrin derivative is an α-cyclodextrin derivative (R is H or an alkyl group) represented by the following chemical formula (5).

Copolymerizing a monomer having the structural formula (1) and the structural formula (2), or a monomer having the structural formula (1) or the structural formula (2) and m-dihalidebenzene or m-di The method for producing a conductive coated conjugated polymer according to claim 1, wherein ethynylbenzene is copolymerized.

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