JP2010105945A - Tetrathiafulvalene derivative and nanofiber composed of the derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tetrathiafulvalene derivative that is a new compound having a chiral molecule and permitting control of self-organization, and to provide an electroconductive nanofiber excellent in stabilization and functionalization of an organized body by converting the derivative into a charge transfer complex. <P>SOLUTION: The D-isomer and/or the S-isomer of the tetrathiafulvalene derivatives are represented by chemical formula (I). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a tetrathiafulvalene derivative that is a novel compound and is self-assembled and formed by interaction with a chiral molecule, a charge-transfer complex in which an acceptor molecule is coordinated to the tetrathiafulvalene derivative, and a charge-transfer complex. It relates to an electrically conductive nanofiber.

  Disk-shaped molecules with developed π-conjugated systems are rich in electrons delocalized by the π-electron system, have excellent electrical and optical properties derived from the π-electrons, and π-π interaction Through self-organization into various organizations.

  This π-π interaction is a dispersion force that acts between aromatic rings, and affects the conformation and molecular structure formation of various molecules. For example, the double-helix higher-order structure of DNA constituting the living body Acts between nucleobases in the stabilization of Similarly, it has a helical structure wound in one direction on either side. In molecules such as nucleic acids and proteins, it is known that this molecular structure and the expression of unique and advanced functions of these substances are deeply related.

  Therefore, disc-like molecules that self-assemble through π-π interactions are formed by designing intermolecular interactions in the self-assembly process, and the structure and functionality of the molecules can be controlled. It is attracting attention as a highly functional material by self-organization control based on design.

  Patent Document 1 discloses a conductive peptide nanofiber obtained by adding a conductive substance to a peptide nanofiber formed from amino acids by utilizing molecular self-assembly. Biodegradability is possible by using amino acids that are biomolecules as materials, and it does not adversely affect the environment. However, it is necessary to add metal particles that become conductive substances when adding conductivity. Have.

JP 2006-117602 A

  The present invention has been made to solve the above-described problems, and is a novel compound that is capable of controlling self-organization by being chiralized by introducing an optically active hydrogen-bonded chain, that is, a chiral molecule, into tetrathiafulvalene. It is an object of the present invention to provide a tetrathiafulvalene derivative and an electrically conductive nanofiber excellent in stabilization and functionalization of a tissue body by using the derivative as a charge transfer complex.

The D-form and / or the S-form tetrathiafulvalene derivative according to claim 1, which has been made to achieve the above object,
The following chemical formula (I)

（式（Ｉ）中、ｎ＝１〜１９、＊はキラル中心）で表わされる。

(In formula (I), n = 1 to 19, * is a chiral center).

  The tetrathiafulvalene derivative according to claim 2 is the one according to claim 1, wherein at least one -NH- group in the molecule of the D-form tetrathiafulvalene derivative, and also the D-form tetrathiafulvalene. It is characterized in that a ═O group in another molecule of the derivative is self-assembled by hydrogen bonding.

  The tetrathiafulvalene derivative according to claim 3 is the one according to claim 1, and at least one —NH— group in the molecule of the S-form tetrathiafulvalene derivative, and also the S-form tetrathiafulvalene. It is characterized in that a ═O group in another molecule of the derivative is self-assembled by hydrogen bonding.

  The charge transfer complex described in claim 4 is characterized in that an acceptor molecule is coordinated to a tetrathiafulvalene derivative of D-form and / or S-form described in claim 1.

  The charge transfer complex described in claim 5 is the one described in claim 4, characterized in that the acceptor molecule is fluorinated tetracyanoquinodimethane.

  The electrically conductive nanofiber according to claim 6 is characterized in that the charge transfer complex in which an acceptor molecule is coordinated with the D-form tetrathiafulvalene derivative according to claim 4 is entangled with each other by right-handed twisting. And

  The electrically conductive nanofiber according to claim 7 is characterized in that the charge transfer complex in which an acceptor molecule is coordinated to the S-form tetrathiafulvalene derivative according to claim 4 is entangled with each other by left-handed twist. To do.

  Tetrathiafulvalene derivatives in the D (Dextro) form and / or the S (Sinistro) form can be obtained by introducing an optically active hydrogen-bonded chain, that is, a chiral molecule, into highly conductive tetrathiafulvalene. , A novel compound capable of controlling self-assembly.

  For this reason, a charge transfer body can be formed by complexing with the tetrathiafulvalene derivative and the acceptor molecule, and the three-dimensional structure of the D form or the S form is formed by the chiral molecule in the charge transfer body. A nanofiber which is a tissue body and has high electrical conductivity can be provided.

  The electrically conductive nanofibers can be used for antistatic, electrode films and the like.

Preferred form for carrying out the invention

  Hereinafter, although the preferable form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  The tetrathiafulvalene derivative (TTF derivative), which is a novel compound of the present invention, introduces an optically active hydrogen-bonded chain, ie, a chiral molecule, into tetrathiafulvalene, which has high conductivity, and chiralizes it to form D and S forms respectively. Forming a structure having

  A reaction scheme of the S-form tetrathiafulvalene derivative is shown below.

  As shown in the following reaction formula (a), a halogen-substituted fatty acid halide and a chiral molecule having an amino group are reacted to form an optically active hydrogen bond chain that is introduced into tetrathiafulvalene, that is, a chiral molecule. Compound 1-S can be synthesized when S (-)-phenylethylamine is used.

  The compound to be reacted with a chiral molecule having an amino group is preferably a halogen-substituted fatty acid halide, specifically, 6-bromohexanoic acid chloride, 12-bromolauric acid chloride, 4-bromopropanoic acid chloride, 1-bromo. Examples include acetic acid chloride.

  The size and molecular weight of the obtained S-form tetrathiafulvalene derivative differ depending on the difference in the fatty acid length of this compound. This fatty acid preferably has 6 carbon atoms, and if this carbon number is too large, the alkyl chain becomes long, and there are cases where it is not suitable for causing a reduction in synthesis efficiency, such as taking a long time for the synthesis reaction.

  The chiral molecule having an amino group is a chiral molecule having an S form, and specifically includes S (-)-phenylethylamine, S (-)-1- (p-tolyl) ethylamine, and the like.

  Synthesis is performed in the order of the following reaction formulas (b), (c), and (d) to obtain compound 3 to be reacted with compound 1-S obtained in the above reaction formula (a).

  By reacting in the order of the following reaction formulas (e), (f), and (g), an S-form tetrathiafulvalene derivative that is a compound 6-S in which a chiral molecule is introduced into tetrathiafulvalene can be synthesized.

  As shown in the reaction scheme, when S (-) phenylethylamine is used in the reaction (a), an S-form tetrathiafulvalene derivative can be obtained.

  For the S-form tetrathiafulvalene derivative, a D-form tetrathiafulvalene derivative is synthesized by using a chiral molecule having an amino group described in paragraph No. 0026 as a D-form substance based on the same reaction scheme. Here, D-form tetrathiafulvalene derivative is synthesized by using D (+) phenylethylamine.

As illustrated in the tetrathiafulvalene derivative 2 in FIG. 1, the structure is a disk-like molecule of 36Å × 27Å when n = 3 in —C _n H _2n — in the chemical formula (I).

  The S-form tetrathiafulvalene derivative is chiralized, and at least one group of —NH— group in the chiral molecule and a ═O group which is the same tetrathiafulvalene derivative and other molecule form a hydrogen bond. It forms and becomes an interactive substance self-organized by this hydrogen bond. By stabilizing the self-organizing force, it becomes an organization having reversible high order with respect to temperature change. Since the tissue body which is this interacting substance is self-organized by hydrogen bonds having a high dependence on temperature, the tissue body collapses due to heat, and the tissue body is reconstructed by cooling.

  A charge transfer complex can be formed by coordinating an acceptor molecule to an S-form tetrathiafulvalene derivative.

  Tetrathiafulvalene, an electron-donating molecule, is known to react with an electron acceptor molecule to form a charge transfer complex or a conductive mixed-valence complex. Similarly, a tetrathiafulvalene derivative is an electron-donating molecule. As a molecule, it reacts with an acceptor molecule, which is an electron acceptor, to enable formation of a charge transfer complex.

  The formed charge transfer complex is shown in FIG.

  As shown in FIG. 1, in the charge transfer complex, the chiral molecule existing in the S-form tetrathiafulvalene derivative remains as it is, and the charge-transfer complex is also chiralized in the same manner as the S-form tetrathiafulvalene derivative. Has been.

  The charge transfer complex has a chiral molecule, and can control self-organization and build an organization. The organization is strengthened and stabilized by charge transfer interaction.

Fluorinated tetracyanoquinodimethane (F ₄ TCQ), which is an acceptor molecule, is coordinated with one molecule of a tetrathiafulvalene derivative, and is bonded vertically and horizontally. The description of the overlapping portions is omitted.

  In addition, this tissue body has electrical conductivity due to charge transfer interaction.

  This acceptor molecule is preferably a conductive organic compound, specifically, fluorinated tetracyanoquinodimethane, 2,3-diiodo-5,6-dicyanobenzoquinone, tetranitrobiphenol, 2,4,7- And trinitrofluorenone.

  The acceptor molecule is preferably 1 mol compared to 1 mol of the S-form tetrathiafulvalene derivative.

  Furthermore, this constructed structure is given discipline by spatial interaction in the chiral molecule, becomes twisted by adding helicity by chiralization, and forms a bundle with each other. It is organized as electrically conductive nanofibers with a twist that depends on the.

  In the case of a charge transfer complex in which an acceptor molecule is coordinated to an S-type tetrathiafulvalene derivative, the electrically conductive nanofibers are twisted in a twisted manner.

  The electric conductive nanofibers preferably have a major axis of 80 nm and a minor axis of 20 nm, and the length is preferably 10 μm or more.

The tissue body, which is an electrically conductive nanofiber formed by controlling self-assembly, is a charge transfer complex of tetrathiafulvalene derivative with conductivity, and it exhibits a semiconductor-like behavior due to charge transfer interaction. Shows conductivity. The electrical conductivity is preferably 1 × 10 ⁻³ S / cm to 1 × 10 ⁻⁴ S / cm.

  For this reason, the strength and stability of the electrically conductive nanofibers with added functionality are versatile in various applications. For example, fiber support, antistatic, use of an electrode film, conductive wire and the like can be mentioned.

  The D-form tetrathiafulvalene derivative has similar properties, and the charge transfer complex / electrically conductive nanofiber obtained by coordinating the acceptor molecule to this has the same properties. However, since the structure differs depending on the chiral molecule, the twisted state of the electrically conductive nanofiber was entangled with the right-handed twist in the case of the charge transfer complex in which the acceptor molecule was coordinated with the D-form tetrathiafulvalene derivative. It becomes a form and changes depending on the chiral molecule.

(Example 1): Synthesis of S-form tetrathiafulvalene derivative 6.7 mmol of 6-bromohexanoic acid chloride was mixed with 4.47 mmol of S (-) phenylethylamine, 8 ml of tetrahydrofuran as a solvent, and 13.4 mmol of triethylamine as a base. To give compound 1-S. The yield of Compound 1-S was 0.95 g, and the yield was 97%. The analysis results of Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy ( ¹ H-NMR, ¹³ C-NMR) are shown below.

  In 200 ml of N, N-dimethylformamide, 1 mol of sodium is added to 3 mol of carbon disulfide, and a mixed solution of 4,5-bis (sodiothio) -1,3-dithiol-2-4one and disodium trithiocarbonate is added. Obtained. To this, 0.15 mol of zinc chloride was added and reacted in a methanol-water mixed solution, and further 0.25 mol of tetraethylammonium bromide was added and reacted to obtain Compound 2. The yield of Compound 2 was 77.0 g, and the yield was 86%.

  Further, 20.9 mmol of compound 2 and 100.8 mmol of 3-bromopropionitrile were added to acetonitrile to obtain compound 3. The yield of compound 3 was 9.78 g, and the yield was 77%.

Subsequently, compound 3 was mixed in dry acetonitrile-methanol mixed solution with 3.085 mmol of compound 1-S with respect to 0.385 mmol, and cesium hydroxide hydrate 0.85 mmol was added to obtain compound 4-S. . The yield of compound 4-S was 0.15 g, and the yield was 63%. The analysis results of FT-IR, ¹ H, ¹³ C-NMR, matrix-assisted laser desorption / ionization method—time of flight type—mass spectrometer (MALDI-TOF-Mass) are shown below.

  Further, compound 8-S 0.38 mmol and mercury acetate 1.95 mmol were reacted in an acetic acid-chloroform mixed solution to obtain compound 5-S. The yield of compound 5-S was 0.23 g, and the yield was 99%. The analysis results of MALDI-TOF-Mass are shown below.

Finally, 3 ml of triethyl phosphite was added to 0.376 mmol of compound 5-S, and the mixture was heated and stirred overnight at 120 ° C. to obtain compound 6-S. The yield of compound 6-S was 1128 mg, and the yield was 57%. This compound is an S-form tetrathiafulvalene derivative. The analysis results of FT-IR, ¹ H, ¹³ C-NMR, and MALDI-TOF-Mass are shown below.

  The observation result of the S-form tetrathiafulvalene derivative with a transmission electron microscope is shown in FIG.

(Each analysis result of the compound in Example 1)
Compound 1-S
^{FT-IR (ATR, cm -1} ):
ν = 3285 (—NH—), 2932 (—CH ₂ —), 1638 (—C═O)
¹ H-NMR (400.13 MHz Chloroform-D):
δ = 7.32 (m, 5H, Ar—H), 5.14 (q, J = 7, 20, 1H, ArC H (CH ₃ ) NH—), 3.39 (t, J = 6.6 Hz) _{, 2H, BrC H 2 CH 2} -), 2.18 (t, J = 8.0Hz, 2H, -CH 2 C H 2 CO -), 1.64 (m, 3H, -CHC H 3), 1.48 ( M , 6H, -C H _2- )

Compound 4-S
FT-IR (ATR, cm ⁻¹ ):
ν = 3304 (—NH—), 2972 (—CH ₂ —), 1643 (—C═O)
¹ H-NMR (400.13 MHz Chloroform-D):
δ = 7.29 (m, 10H, Ar-H), 5.11 (q, J = 7.2Hz, 2H, NH (CH 3) C H -Ar), 2.85 (t, J = 7. _{2Hz, 4H, -SC H 2 CH} 2 -), 2.16 (t, J = 7.6Hz, 4H, -CH 2 C H 2 CO -), 1.68 (m, 6H, -CHC H 3) _{, 1.47 (m, 12H, -CH} 2 -)
^{13 C-NMR (100.61MHz Chloroform-} D):
δ = 21.81, 25.11, 28.09, 29.42, 36.49, 36.66, 48.77, 126.23, 127.39, 128.71, 143.44, 171.59, 207.9
MALDI-TOF-Mass (Dithranol):
m / z = 634.20 [M + H] ⁺ , calc for C ₃₁ H ₄₀ N ₂ O ₂ S ₅ : 632.999

Compound 5-S
MALDI-TOF-Mass (Dithranol):
m / z = 617.5 [M + H] ⁺ , calc for C ₃₁ H ₄₀ N ₂ O ₃ S ₄ : 616.92

Compound 6-S
FT-IR (ATR, cm ⁻¹ ):
_{ν = 3305 (-NH -),} 2929 (-CH 2 -), 1643 (-C = O)
¹ H-NMR (400.13 MHz Chloroform-D):
δ = 7.25 (m, 20H, Ar-H), 5.09 (q, J = 7.20Hz, 4H, NH (CH 3) C H -Ar), 2.78 (t, J = 7. _{20Hz, 8H, -SC H 2 CH} 2 -), 2.14 (t, J = 7.20Hz, 8H, -CH 2 C H 2 CO -), 1.64 (m, 12H, -CHC H 3) _{, 1.44 (m, 24H, -CH} 2 -)
¹³ C-NMR (100.61 MHz Chloroform-D):
δ = 21.85, 25.22, 28.07, 29.19, 29.47, 36.51, 48.65, 126.20, 127.29, 127.75, 128.64, 143.44, 171.87
MALDI-TOF-Mass (Dithranol):
m / z = 1101.12 [M + H] ⁺ , calc for C ₅₂ H ₉₀ O ₄ : 1201.85

(Example 2): Synthesis of D-form tetrathiafulvalene derivative 6.7 mmol of 6-bromohexanoic acid chloride was mixed with 14.3 mmol of D (+) phenylethylamine, 8 ml of tetrahydrofuran as a solvent, and 13.4 mmol of triethylamine as a base. To give compound 1-D. The yield of compound 1-D was 0.5 g, and the yield was 7%. The analysis results of FT-IR are shown below.

  In the same manner as in Example 1, compounds 2 and 3 were synthesized, and in a dry acetonitrile-methanol mixed solution, compound 3 was mixed with 0.39 mmol, and 3.09 mmol of compound 1-D was mixed. 85 mmol was added to give compound 4-D. The yield of compound 4-D was 50 mg, and the yield was 36%. The analysis results of MALDI-TOF-Mass are shown below.

Further, 0.38 mmol of compound 4-D and 1.95 mmol of mercury acetate were reacted in an acetic acid-chloroform mixed solution to obtain compound 5-D. The yield of compound 5-D was 40 mg, and the yield was 82%.
Furthermore, 3 ml of triethyl phosphite was added to 0.376 mmol of compound 5-D, and the mixture was heated and stirred overnight at 120 ° C. to obtain compound 6-D. The yield of compound 6-D was 6 mg, and the yield was 15%. This compound is a D-form tetrathiafulvalene derivative. The analysis results of MALDI-TOF-Mass are shown below.

(Each analysis result of the compound in Example 2)
Compound 1-D
FT-IR (ATR, cm ⁻¹ ):
_{ν = 3285 (-NH -),} 2932 (-CH 2 -), 1639 (-C = O)

Compound 4-D
MALDI-TOF-Mass (Dithranol):
m / z = 632.6 [M + H] ⁺ , calc for C ₃₁ H ₄₀ N ₂ O ₂ S ₅ : 632.99

Compound 6-D
MALDI-TOF-Mass (Dithranol):
m / z = 1202.0 [M + H] ⁺ , calc for C ₆₂ H ₈₀ N ₄ O ₄ S ₈ : 1201.85

(Example 3): Formation of charge transfer complex 0.23 mM of S-form tetrathiafulvalene derivative was dissolved in 1 ml of toluene, and then 11.4 mM of fluorinated tetracyanoquinodimethane was added. As a result, a blackish green precipitate was obtained.

  The precipitate was subjected to ultraviolet-visible spectrophotometric (UV-Vis) spectrum measurement and FT-IR measurement. The UV-Vis spectrum is shown in FIG. Intramolecular transition of fluorinated tetracyanoquinodimethane was observed at 700 to 900 nm, and intramolecular transition of tetrathiafulvalene cation radical was observed at 396 nm. The FT-IR spectrum is shown in FIG. Here, broad absorption peculiar to the charge transfer body was observed in a high wavenumber region.

  The obtained charge transfer complex was observed with a transmission electron microscope and a scanning electron microscope. The observation result with a transmission electron microscope is shown in FIG. 5, and the observation result with an atomic force microscope is shown in FIG. Moreover, the observation result of a scanning electron microscope is shown in FIG.

  FIG. 5 shows that nanofibers are formed in comparison with the S-type tetrathiafulvalene derivative shown in FIG. 2 that is aggregated in a circular shape, and FIG. 6 is an enlarged view of FIG. It can be seen that the nanofiber is twisted counterclockwise.

  Furthermore, circular dichroism spectrum measurement of S-form tetrathiafulvalene derivative and D-form tetrathiafulvalene derivative was performed. As a result, positive and negative cotton effects were observed in the tetrathiafulvalene absorption region, confirming that the tissue was a helical tissue. This circular dichroism spectrum is shown in FIG.

  Conductivity measurement was performed on the structure of the charge transfer body. The result is shown in FIG. Furthermore, the electrical conductivity of one nanofiber was measured by a galvanostatic image atomic force microscope (PCI-AFM) measurement method. A graph of the measured values is shown in FIG. 10, and a photograph of the measurement location is shown in FIG.

  The tetrathiafulvalene derivative, which is a novel compound having a chiral molecule, forms a nanofiber with excellent electrical conductivity that enables self-organization control by complexing with an acceptor molecule.

  This electrically conductive nanofiber has a helical structure and can be used in various applications such as antistatic materials, electrodes, and conductive wires.

It is a schematic diagram of an electrophoretic transfer complex in which a fluorinated tetracyanoquinodimethane is coordinated to a tetrathiafulvalene derivative to which the present invention is applied. It is a photograph by the transmission electron microscope of the tetrathiafulvalene derivative which is S body to which this invention is applied. It is a figure which shows the ultraviolet visible spectrophotometric spectrum of the charge transfer complex to which this invention is applied. It is a figure which shows the Fourier-transform type | mold infrared spectroscopy spectrum of the charge transfer complex to which this invention is applied. It is a photograph by the transmission electron microscope of the charge transfer complex to which this invention is applied. It is a photograph by the atomic force microscope of the charge transfer complex to which this invention is applied. It is a photograph by the scanning electron microscope of the charge transfer complex to which this invention is applied. It is a figure which shows the circular dichroism spectrum of the charge transfer complex to which this invention is applied. It is a conductivity measurement result of the charge transfer complex to which the present invention is applied. It is a figure which shows the measured value of the contact current image atomic force microscope of the charge transfer complex to which this invention is applied. It is a photograph of the galvanostatic image atomic force microscope of the charge transfer complex to which the present invention is applied.

Explanation of symbols

  1 is a charge transfer complex, 2 is a tetrathiafulvalene derivative, and 3 is a fluorinated tetracyanoquinodimethane.

Claims (7)

The following chemical formula (I)

A tetrathiafulvalene derivative of D-form and / or S-form represented by (in formula (I), where n = 1 to 19, * is a chiral center).   At least one —NH— group in the molecule of the D-form tetrathiafulvalene derivative and ═O group in another molecule of the D-form tetrathiafulvalene derivative are hydrogen-bonded and self-assembled. The tetrathiafulvalene derivative according to claim 1.   At least one —NH— group in the molecule of the S-form tetrathiafulvalene derivative and a ═O group in another molecule of the S-form tetrathiafulvalene derivative are hydrogen-bonded and self-assembled. The tetrathiafulvalene derivative according to claim 1.   A charge transfer complex, wherein an acceptor molecule is coordinated to a tetrathiafulvalene derivative of D-form and / or S-form described in claim 1.   5. The charge transfer complex according to claim 4, wherein the acceptor molecule is fluorinated tetracyanoquinodimethane.   An electrically conductive nanofiber, wherein the charge transfer complex in which an acceptor molecule is coordinated to a D-form tetrathiafulvalene derivative according to claim 4 is entangled with each other by right-handed twisting.   An electrically conductive nanofiber, wherein the charge transfer complex in which an acceptor molecule is coordinated to an S-form tetrathiafulvalene derivative according to claim 4 is entangled with each other by left-handed twisting.

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