JP2011102355A - Inclusion complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inclusion complex composed of a cyclic compound having a triphenyl amine skeleton and an electron acceptor. <P>SOLUTION: The inclusion complex is constituted of an electron donor comprising a cyclic compound having a constitution unit represented by formula (1) and an electron acceptor. In the formula (1), R<SB>1</SB>, R<SB>2</SB>, R<SB>3</SB>, R<SB>4</SB>, R<SB>5</SB>, R<SB>6</SB>and R<SB>7</SB>each independently represents hydrogen or a substituent which may have a substituent, n represents an integer of 5-20, and a and b each independently represents an integer of 1-4. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an inclusion complex.

  It is known that compounds and polymers having triphenylamine as a skeleton exhibit hole transport properties. For example, Patent Document 1 describes an electrophotographic photoreceptor containing a cyclic compound of triphenylamine in a photosensitive layer. Patent Document 2 describes an organic electronic device including a polymer having triphenylamine in the main chain skeleton in a hole transport layer.

JP 05-323635 A JP 2008-098615 A

  An object of the present invention is to provide an inclusion complex of a cyclic compound having triphenylamine as a skeleton and an electron acceptor.

According to the present invention, an inclusion complex according to the following [1] to [8] is provided.
[1] An inclusion complex comprising an electron donor composed of a cyclic compound having a structural unit represented by the following formula (1) and an electron acceptor.

(In formula (1), each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ independently represents hydrogen or a substituent that may have a substituent, where n is And represents an integer of 5 to 20. a and b each independently represent an integer of 1 to 4.
[2] In the formula (1), R ₁ is an n-butyl group, and each of R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is hydrogen [1] ] The inclusion complex of description.
[3] The inclusion complex according to [1] or [2], wherein in the formula (1), n is 5 to 7.
[4] The inclusion complex according to any one of [1] to [3], wherein the cyclic compound is cyclic oligo (4-n-butyltriphenylamine).
[5] The inclusion complex according to any one of [1] to [4], wherein the electron acceptor is at least one selected from fullerenes.
[6] The fullerenes, inclusion complex according to [5], wherein the at least one selected from the fullerene C ₆₀ derivatives, fullerene C ₇₀ derivative.
[7] The inclusion complex according to any one of [1] to [4], wherein the electron acceptor is polyparaphenylene.
[8] The cyclic compound is obtained by carbon-nitrogen coupling polymerization of 4- (4′-bromophenyl) -4 ″ -butyldiphenylamine, which is a self-condensable monomer, in the presence of t-butoxypotassium with a palladium catalyst. The inclusion complex according to any one of [1] to [7], which is obtained by:

  According to the present invention, an inclusion complex of a cyclic compound having triphenylamine in the skeleton and an electron acceptor can be obtained.

^{1 is} a ¹ H-NMR measurement chart of 4- (4′-bromophenyl) -4 ″ -butyldiphenylamine. It is a ¹³ H-NMR measurement chart of 4- (4′-bromophenyl) -4 ″ -butyldiphenylamine. Is the ¹ H-NMR measurement chart of the cyclic oligosiloxane (4-triphenylamine). It is a ¹³ H-NMR measurement chart of cyclic oligo (4-butyltriphenylamine). Cyclic oligo (4-triphenylamine) and a fluorescence spectrum of a toluene solution of fullerene C _60. It is an infrared (IR) absorption spectrum of an inclusion complex. FIG. 5 is a graph showing the relationship between the concentration of electron acceptor and (I ₀ / I) as a result of PL measurement. It is an ultraviolet (UV) absorption spectrum of a polyrotaxane.

  Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.

  The inclusion complex to which the present embodiment is applied includes an electron donor composed of a cyclic compound having a structural unit represented by the following formula (1), and an electron acceptor.

Here, in formula (1), each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ independently represents hydrogen or a substituent that may have a substituent. n represents an integer of 5 to 20. a and b each independently represent an integer of 1 to 4;
Examples of the substituent include an alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms. Specifically, examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a pentyl group, and an octyl group. As a C1-C8 alkoxy group, a methoxy group, an ethoxy group, a propyloxy group, a hexyloxy group etc. are mentioned, for example.
In addition, each of the substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be bonded to each other to form a ring. In this case, the ring may be formed between substituents in the same triarylamine unit, or the substituents in different triarylamine units may form a ring. For example, R _{6 in} a triarylamine unit and R ₇ in another triarylamine unit adjacent thereto may form a ring.
As the structural unit represented by the formula (1), among the above, R ₁ is an n-butyl group, and each of R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is hydrogen. It is preferable. N is preferably 5, 6 or 7.

A method for synthesizing the cyclic compound having the structural unit represented by the formula (1) is not particularly limited. In the present embodiment, for example, a method of synthesizing a self-condensable monomer and further synthesizing a cyclic compound by carbon-nitrogen coupling polymerization of the self-condensable monomer can be mentioned.
Examples of the self-condensable monomer include, for example, 4,4′-dibromobiphenyl and 4-butylaniline in the presence of a palladium-based catalyst and a basic compound according to the following reaction scheme under predetermined reaction conditions. 4- (4′-bromophenyl) -4 ″ -butyldiphenylamine obtained from

The palladium catalyst used for the synthesis reaction of the self-condensable monomer is not particularly limited. For example, tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0), bis (tricyclohexyl) Palladium (0), dichlorobis (triphenylphosphine) palladium (II), dibromobis (triphenylphosphine) palladium (II), dichloro [1,4-bis (diphenylphosphino) butane] palladium (II), dichloro [1, 2-bis (diphenylphosphino) ethane] palladium (II), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (II), palladium (II) acetate and the like. Among these, dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) is preferable.
Although the usage-amount of a palladium catalyst is not specifically limited, For example, it is 0.005 equivalent-0.5 equivalent with respect to 1 mol of 4,4'- dibromobiphenyl, Preferably it is 0.01 equivalent-0.1 equivalent.

The basic compound is not particularly limited. For example, t-butoxy sodium, t-butoxy lithium, t-butoxy potassium, methoxy sodium, ethoxy sodium, potassium carbonate, sodium carbonate, cesium carbonate, t-butyl lithium, sec -Butyllithium, n-butyllithium, lithium diisopropylamide and the like.
The synthesis reaction is preferably performed in a solvent. The solvent used for the synthesis reaction is not particularly limited. For example, chlorinated hydrocarbons such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and trichlorobenzene; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and diethylbenzene; diethyl ether, tetrahydrofuran, dioxane and diglyme , Ketones such as anisole, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone and cyclopentane; esters such as methyl acetate, ethyl acetate, methyl lactate and ethyl lactate; heterocyclic compounds such as γ-butyrolactone and γ-butyrolactam Nitrogenation of N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylimidazolidinone, pyridine, nitrobenzene, etc. Compound: Sulfur-containing compounds such as carbon disulfide, nitromethane, dimethyl sulfoxide and the like can be mentioned.

  Further, the above-mentioned self-condensable monomer is subjected to carbon-nitrogen coupling polymerization in the presence of a palladium-based catalyst and a basic compound according to the reaction scheme shown below, for example, under predetermined reaction conditions, thereby forming a cyclic compound. Synthesize.

As the palladium-based catalyst, basic compound, and solvent used for the carbon-nitrogen coupling polymerization, those similar to the synthesis reaction of the self-condensable monomer can be used.
The polymerization temperature for carrying out the carbon-nitrogen coupling polymerization reaction is usually 0 ° C to 100 ° C, preferably 20 ° C to 80 ° C, more preferably 20 ° C to 50 ° C. The polymerization time is usually 1 hour to 48 hours, preferably 6 hours to 24 hours, more preferably 12 hours to 24 hours.

(Electron acceptor)
Examples of the electron acceptor used in the present embodiment include a spherical shell carbon molecule and a conductive polymer. As the spherical shell carbon molecule, fullerenes are preferable.
The fullerenes, carbon clusters having various three-dimensional structures, for _{example, C 60, C 70, C} 74, C 76, C 78, C 82, C 84, C 720, fullerene and fullerene derivatives such as _{C 860} etc. Can be mentioned. These fullerenes may be modified by introduction of a substituent or the like. The type of the substituent is not particularly limited, and examples thereof include C1-10 alkyl groups such as methyl group and t-butyl group; aryl groups such as phenyl group; aralkyl groups such as benzyl group; dioxolane unit, halogen or oxygen atom Is mentioned. Examples of the fullerenes encapsulating metal include fullerenes doped with metals such as Group 1A elements of the periodic table, Group 2A elements of the periodic table, lanthanoid group elements (La, etc.).
Examples of the conductive polymer include polyacetylene polymers; polyphenylene vinylene resins such as poly (p-phenylene) resins, poly (m-phenylene) resins, and poly (p-phenylene vinylenes); polyphenylene sulfide resins. Polyphenylene oxide resins, etc .; polythiophene resins such as polypyrrole and poly (3-alkylthiophene); polyfuran resins; polyselenophene resins; polytellurophene resins; polyaniline resins, poly (3-methyl-4- And pyrrole resins such as carboxypyrrole).

  In the present embodiment, since the structure of the cyclic compound having the structural unit represented by the formula (1) as the electron donor has a certain size of cavity, as shown below, electrons such as fullerenes The receptor is included as a guest molecule to form an inclusion complex. In the present embodiment, the number n of structural units represented by the formula (1) constituting the cyclic compound in the inclusion complex is preferably 5, 6 or 7.

  Further, a cyclic compound having a structural unit represented by the formula (1) as an electron donor is shown below in combination with an n-type polymer semiconductor such as poly (p-paraphenylene) (PPP). Such a polyrotaxane is formed.

  Hereinafter, the present embodiment will be described in more detail based on examples. The present embodiment is not limited to the following examples.

(1) High performance liquid chromatography (HPLC)
The product obtained by the synthesis reaction was measured by HPLC and subjected to composition analysis.
An ODS (PEGASIL ODS, ODS-2352), 4.6φ × 250 mm long column was used. UV-2075Plus manufactured by JASCO Corporation was used as a detector, PU-2080 manufactured by JASCO Corporation was used as a pump, and DG-2080-53 manufactured by JASCO Corporation was used as a degasser. As the mobile phase, a mixed solvent of chloroform: methanol = 1: 1 was used. A small amount of sample (less than 1 mg) was dissolved in 1 ml of chloroform: methanol = 1: 1 solvent, weighed with a 5 ml microsyringe, and introduced into the measurement system using a loop injector.

(2) Nuclear magnetic resonance spectrum (NMR)
In order to evaluate the structure of the product obtained by the synthesis reaction, ¹ H-NMR measurement and ¹³ C-NMR measurement were performed. ECX400 manufactured by JEOL Ltd. (measurement frequency 400 MHz, observation frequency ¹ H: 400 MHz, ¹³ C: 100 MHz) was used. For the measurement, a sample prepared by dissolving about 50 mg of sample in 1 ml of deuterated chloroform (ALDRICH, 99.8%, containing TMS 0.03%) and putting it in a 5 mm NMR tube so as to be about 4 cm from the bottom was used. In the case of monomer, the measurement temperature was room temperature and the number of integration was 32 times. In the case of the oligomer, the measurement was performed at a measurement temperature of 40 ° C. and a cumulative number of 128 or more.

(3) Visible / ultraviolet absorption spectrum measurement The maximum absorption wavelength was examined by UV-vis spectrum measurement. A JUSCO V-670 spectrometer manufactured by JASCO Corporation was used. The measurement was performed by adjusting the cyclic oligomer concentration to 1.43 × 10 ⁻⁷ M.

(Experiment 1)
<Synthesis of cyclic oligo (4-butyltriphenylamine)>
(1) First, 4- (4′-bromophenyl) -4 ″ -butyldiphenylamine, which is a self-condensable monomer, was synthesized according to the following procedure.
In a 100 ml two-necked eggplant flask equipped with a magnetic stirrer, an Allen condenser, and a three-way cock, 4.28 g (45.2 mmol) of 4,4′-dibromobiphenyl, 5.82 g (60.5 mmol) of t-butoxy sodium and [ 1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (Pd (dppf) Cl ₂ ) (0.351 g, 0.429 mmol) was added, and the mixture was deaerated and purged with nitrogen. Then, 6.75 ml (45.2 mmol) of 4-butylaniline and toluene (85 ml) were added and heated to reflux for 12 hours. Thereafter, the reaction solution was separated with toluene, 1N HCl and saturated brine, dried over anhydrous MgSO ₄ , and then toluene was distilled off with an evaporator. Subsequently, purification is performed by recrystallization with a column (developing solvent toluene: hexane = 1: 1), and the target 4- (4′-bromophenyl) -4 ″ -butyldiphenylamine (hereinafter simply referred to as “monomer”) (Yield 6.86 g, 42% yield).

FIG. 1 shows a ¹ H-NMR measurement chart of the synthesized 4- (4′-bromophenyl) -4 ″ -butyldiphenylamine. FIG. 1 (a) shows 0.8 to 7.8 ppm of ¹ H of the monomer. Fig. 1 (b) is a ¹ H-NMR measurement chart of the aliphatic part (0.8 to 2.8 ppm) of the monomer, and Fig. 1 (c) is an aromatic part of the monomer. ^{1 is} a ¹ H-NMR measurement chart of (7.0 to 7.6 ppm).

¹ H-NMR (CDCl ₃ ) δ: 7.49 (2H, d), 7.40 (4H, m), around 7.07 (6H, m), 5.66 (1H, s), 2.56 (2H, t), 1.58 (2H, dd), 1.37 (2H, m), 0.93 (3H, t)

Figure 2 is synthesized 4- (4'-bromophenyl) -4 '-. Shows the ¹³ H-NMR measurement chart of butyl diphenylamine FIG. 2 (a), a monomer aliphatic moiety of (0～150Ppm) ¹³ 2B is a ¹³ H-NMR measurement chart of the aromatic part (115 to 145 ppm) of the monomer.

(2) Next, using the self-condensable monomer 4- (4′-bromophenyl) -4 ″ -butyldiphenylamine synthesized by the above-described operation, a carbon-nitrogen (CN) cup is obtained according to the following procedure. Cyclic oligo (4-butyltriphenylamine) was synthesized by ring polymerization.
In a 100 ml two-necked eggplant flask equipped with a magnetic stirrer, an Allen cooler, and a three-way cock, 0.5 g (1.31 mmol) of the monomer synthesized by the above-described operation and 0.139 g of sodium t-butoxy as a basic compound ( 1.44 mmol) and 5.9 mg (2 mol%) of palladium (II) acetate were added, followed by deaeration and nitrogen substitution. Subsequently, toluene as a solvent and 25.4 μl (8 mol%) of tri-t-butylphosphine were added to prepare a reaction solution. The monomer concentration of the reaction solution is 0.0267 / M.
Next, the reaction solution was heated and refluxed for 24 hours. After the reaction, the mixture was separated with toluene, 1N HCl and saturated brine, dried over anhydrous MgSO ₄ , the solvent was distilled off with an evaporator, dissolved in chloroform, and purified by reprecipitation in methanol to obtain the product (yield) 0.286 g, yield 71.4%). Then, Soxhlet extraction (solvent acetone) was performed for about 15 hours. The residue (the product remaining on the Soxhlet filter paper) was subjected to GPC measurement. If the oligomer remained, it was purified again by reprecipitation, and the Soxhlet extraction operation was repeated. The obtained oligomer was analyzed by liquid chromatography (TLC), and a mixture of linear and cyclic oligomers was separated by column chromatography (developing solvent toluene: hexane = 2: 3).
The obtained product had a yield of 71.4%. Among them, the yield of cyclic oligo (4-butyltriphenylamine) was 4%, and the yield of linear oligo (4-butyltriphenylamine) was 2. 4%.

FIG. 3 shows a ¹ H-NMR measurement chart of cyclic oligo (4-butyltriphenylamine). FIG. 3A is a measurement chart in the range of 0.5 to 7.5 ppm. FIG.3 (b) is a measurement chart of an aromatic part (6.7-7.6 ppm).
FIG. 4 shows a ¹³ H-NMR measurement chart of cyclic oligo (4-butyltriphenylamine). FIG. 4A is a measurement chart in the range of 0 to 150 ppm. FIG.4 (b) is a measurement chart of an aromatic part (118-150 ppm).
From the results of FIG. 3 and FIG. 4, since the absorption spectrum due to hydrogen bonded to the terminal carbon and the absorption spectrum due to the terminal carbon observed in the case of the linear structure are not observed, the product has a cyclic structure. It was confirmed to have.
As a result of HPLC measurement, the obtained cyclic oligo (4-butyltriphenylamine) was a mixture of pentamer, hexamer and heptamer.

(Experiment 2 to Experiment 7)
The reaction solution was adjusted under the conditions described in Table 1 (monomer concentration / M, solvent, basic compound). Otherwise, cyclic oligo (4-butyltriphenylamine) was prepared in the same manner as in Experiment 1 described above. Synthesized. The results are shown in Table 1 together with the results of Experiment 1.

  The cyclic oligo (4-butyltriphenylamine) obtained in Experiment 6 was a mixture of pentamer: hexamer: 7mer = 65: 22: 13 (weight ratio) as a result of HPLC measurement.

Example 1
Toluene solution of fullerene C ₆₀ (fullerene concentration 3.33 × 10 ⁻ ) was added to the toluene solution (cyclic oligomer concentration 2.27 × 10 ⁻⁵ M) of cyclic oligo (4-butyltriphenylamine) obtained in Experiment 6 described above. ⁵ M) was added to prepare a mixed solution.
Next, the fluorescence spectrum of this mixed solution was measured with a spectroscope (JUSCO FP-6500 spectrometer manufactured by JASCO Corporation). Moreover, PL measurement was performed about the mixed solution using the light of excitation wavelength 340nm. As shown in Table 2, the PL measurement of the mixed solution was performed by gradually increasing the amount of fullerene C ₆₀ added to the toluene solution, measuring the fluorescence intensity I at each added amount, and the fluorescence when fullerene C ₆₀ was not added. The ratio (I ₀ / I) with the intensity I ₀ was determined. The results are shown in Table 2.
Figure 5 shows the fluorescence spectrum of the cyclic oligosiloxane (4-triphenylamine) and a toluene solution of fullerene C _60.
FIG. 6 shows an infrared (IR) absorption spectrum of the inclusion complex. 6 (a) is an infrared (IR) absorption spectrum wavenumber 400～4000Cm ^-1, 6 (b) is an enlarged view of the wave number 650~800cm ^-1. Note that the cyclic oligo (4-triphenylamine) and fullerene _{C 60,} respectively, were measured by the KBr method. The inclusion complex was measured after applying the toluene solution to the KBr plate and removing the toluene.

In the fluorescence spectrum shown in FIG. 5, quenching of the fluorescence spectrum is observed when a fullerene C ₆₀ solution having a concentration changed stepwise is added to a toluene solution of cyclic oligo (4-butyltriphenylamine) having a constant concentration. It was. Thus, it can be seen that the inclusion complex of cyclic oligo (4-triphenylamine) and fullerene C ₆₀ is formed.
Moreover, it can be seen from the results shown in Table 2 that (I ₀ / I) is increased by adding fullerene C ₆₀ solution by PL measurement.
From the infrared (IR) absorption spectrum shown in FIG. 6, the peak of the C—H out-of-plane bending vibration of the para disubstituted aromatic is shifted. This is because the fullerene C ₆₀ is inclusion in the cyclic oligomers, it is considered to have influence on the movement of the C-H, even in the solid state, the complex formation was suggested.

(Example 2)
In Example 1, the solvent of cyclic oligo (4-butyltriphenylamine) and the solvent of fullerene C ₆₀ were changed to a toluene / acetone (70:30) mixed solvent, and as shown in Table 3, fullerene C The addition amount of ₆₀ was increased stepwise, and the fluorescence intensity I at each addition amount was measured in the same manner as in Example 1 except that the ratio to the fluorescence intensity I ₀ when fullerene C ₆₀ was not added ( I ₀ / I) was determined. The results are shown in Table 3.

(Example 3)
In Example 1, the electron acceptor was changed to fullerene C ₇₀ , and as shown in Table 4, the addition amount of fullerene C ₇₀ was increased stepwise. The fluorescence intensity I in the amount was measured, and the ratio (I ₀ / I) to the fluorescence intensity I ₀ when no fullerene C ₇₀ was added was determined. The results are shown in Table 4.

(Comparative Example 1)
In Example 1, cyclic oligo (4-butyltriphenylamine) was converted to N, N′-diphenyl-N, N′-bis (4-mrylphenyl)-(1,1′-biphenyl) -4,4′-diamine. (TPD) Changed to ₀ , and as shown in Table 5, the amount of addition of fullerene C ₆₀ was increased stepwise, and the fluorescence intensity I at each addition amount was measured in the same manner as in Example 1 except that. The ratio (I ₀ / I) to the fluorescence intensity I ₀ when no fullerene C ₆₀ was added was determined. The results are shown in Table 5.

(Comparative Example 2)
In Comparative Example 1, the solvent was changed to a toluene / acetone (70:30) mixed solvent, and as shown in Table 6, the addition amount of fullerene C ₆₀ was increased stepwise. The fluorescence intensity I at each addition amount was measured by a simple operation, and the ratio (I ₀ / I) to the fluorescence intensity I ₀ when no fullerene C ₆₀ was added was determined. The results are shown in Table 6.

FIG. 7 is a graph showing the relationship between the electron acceptor concentration and (I ₀ / I) as a result of PL measurement based on the following equation.
I ₀ / I = 1 + K _q τ ₀ [electron acceptor]
I ₀ : Fluorescence intensity of cyclic oligomer / solvent only I: Fluorescence intensity K _q : Quenching constant τ ₀ : Fluorescence lifetime

FIG. 7A is a graph of PL measurement results of cyclic oligo (4-butyltriphenylamine) / fullerene C ₆₀ based on the results of Table 3 (indicated in the figure: cyclic oligomer), and based on the results of Table 6. TPD / PL measurement results of the graph of fullerene _{C 60} (display in Figure: TPD) shows a.
As shown in FIG. 7 (a), the gradient of the cyclic oligo (4-butyltriphenylamine) / fullerene C ₆₀ graph is larger than the gradient of the TPD / fullerene C ₆₀ graph. It can be seen that the inclusion complex composed of (triphenylamine) / fullerene C ₆₀ has a strong bond.

FIG. 7B shows a graph of PL measurement results of cyclic oligo (4-butyltriphenylamine) / fullerene C ₆₀ based on the results of Table 2 (indicated in the figure: C ₆₀ ), and the results of Table 4. cyclic based oligo (4-triphenylamine) / PL measurement results of the graph of fullerene _{C 70} (display in _{Figure: C 70)} shows a.
As shown in FIG. 7 (b), it is greater than the slope of the graph of the slope of the graph of cyclic oligo (4-triphenylamine) / fullerene _{C 70} is annular oligo (4-triphenylamine) / fullerene _{C 60} it from the binding of the fullerene C ₇₀ and the annular oligo (4-triphenylamine), it can be seen larger than the binding of the fullerene C ₆₀ and the annular oligo (4-triphenylamine).

Example 4
The mixed solution of cyclic oligo (4-butyltriphenylamine) and polyparaphenylene (PPP) used in Example 1 was subjected to ultrasonic treatment, and cyclic oligo (4-butyltriphenylamine) and polyparaphenylene (PPP) A polyrotaxane composed of was prepared.
1.0 × 10 ⁻⁵ mol / L cyclic oligomer in THF (0.5 mL) and 1.0 × 10 ⁻³ mol / L (monomer unit equivalent) poly (1,4-phenylene) (molecular weight 1,100) About 0), THF solution 0, 0.25, 0.5, 1.0, and 1.5 mL were mixed, respectively, and THF was added to adjust to 25 mL using a volumetric flask to prepare five types of mixed solutions. The concentration of the cyclic oligomer was fixed at 2.0 × 10 ⁻⁷ mol / L. The concentrations of poly (1,4-phenylene) (PPP) are 0, 1.0 × 10 ⁻⁵ , 2.0 × 10 ⁻⁵ , 4.0 × 10 ⁻⁵ , 6.0 × 10 ^{−5, respectively.} mol / L. Each solution was subjected to ultrasonic treatment for 30 minutes, and then a UV absorption spectrum was measured.

  FIG. 8 shows the ultraviolet (UV) absorption spectrum of polyrotaxane. In FIG. 8, the indication (oligomer) indicates cyclic oligo (4-butyltriphenylamine), the indication (PPP) indicates polyparaphenylene, and the indication (PPP + oligomer) indicates polyrotaxane. As shown in FIG. 8, in the mixed solution, it can be seen that the peak derived from PPP is shifted to the red light side. This is presumably because the formation of polyrotaxane resulted in the alignment of phenyl group surfaces and increased conjugation. Moreover, compared with the UV absorption spectrum of the PPP solution, the broad absorption band of 400 nm or more was decreased in the mixed solution, and it was confirmed that the aggregation of PPP was suppressed by forming a polyrotaxane.

In the inclusion complex obtained by the present invention, the hole transport site (cyclic triarylamine) and the electron transport site (fullerene) are nano-sized and phase-separated. It is an ideal structure. For this reason, improvement in photoelectric efficiency can be expected.
In addition, the inclusion complex of the present invention can be expected to construct a cylinder structure by overlapping cyclic complexes. If it becomes a cylinder structure, the transport path of a clear electric charge can be constructed | assembled and the application to the electronic device represented by the antistatic film and organic EL is possible.

Claims (8)

An electron donor comprising a cyclic compound having a structural unit represented by the following formula (1);
An inclusion complex comprising an electron acceptor.

(In formula (1), each of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ independently represents hydrogen or a substituent that may have a substituent, where n is And represents an integer of 5 to 20. a and b each independently represent an integer of 1 to 4. 2. The formula (1), wherein R ₁ is an n-butyl group, and each of R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is hydrogen. Inclusion complex.   The inclusion complex according to claim 1 or 2, wherein in the formula (1), n is 5 to 7.   The inclusion complex according to any one of claims 1 to 3, wherein the cyclic compound is cyclic oligo (4-n-butyltriphenylamine).   The inclusion complex according to any one of claims 1 to 4, wherein the electron acceptor is at least one selected from fullerenes. The inclusion complex of claim 5, wherein the fullerenes, characterized in that at least one selected from the fullerene C ₆₀ derivatives, fullerene C ₇₀ derivative.   The inclusion complex according to any one of claims 1 to 4, wherein the electron acceptor is polyparaphenylene.   The cyclic compound is obtained by subjecting 4- (4′-bromophenyl) -4 ″ -butyldiphenylamine, which is a self-condensable monomer, to carbon-nitrogen coupling polymerization with a palladium catalyst in the presence of potassium t-butoxy. The inclusion complex according to any one of claims 1 to 7, wherein:

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