JPH0232087A - Charge transfer complex of metallocene derivative and langmuir-blodgett's membrane - Google Patents

Abstract

NEW MATERIAL:An charge transfer complex of a metallocene derivative formed from a metallocene derivative having a group of the formula (R1 is alkylene; R2 is alkyl) on at least one cyclohexane ring thereof and an electron acceptor compound. USE:An electric field effect type transistor, display element or photoelectric transfer element. PREPARATION:An alcohol is reacted with metallocene monocarboxylic acid chloride and the reaction product is filtered and recrystallized in petroleum ether, etc., to provide the metallocene derivative. The obtained derivative is reacted with an electron acceptable compound (e.g., iodine or tetracyanoethylene) in an organic solvent such as benzene at 30-70 days, followed by distilling away the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel charge transfer complex of a metallocene derivative and a Langmuir-Prodgett film containing the same.

<Prior art> Metal complexes have attracted attention as high-performance materials such as energy conversion materials and electrochemical catalysts, and have been actively researched [N,
Oyama, S., Yamaguehi.

M., Kaneko, A., Yamada, J.
Eleetroanal, Chew, 139°215 (1982), Itaya, N., 5hoji
, 1. Uchida.

J, A+y+, Chem, Soc, , 106
．． 3423 (19g4) etc.].

By making these into thin films and forming regular molecular aggregates, it is expected that even more sophisticated functions will be developed. Therefore, attempts are being made to form thin films.

There are various methods for manufacturing such thin films, such as vacuum deposition, suspension spraying, dispersion in polymers, and mechanical rubbing, but all of them have problems with the uniformity of the thick film and the reproducibility of the morphology of the microcrystalline distribution. be.

Therefore, as a way to solve these problems, reproduction using the Langmuir-Prodgett (LB) method has been used in fields such as field effect transistors, display elements, photoelectric conversion elements, nonlinear optical elements, two-dimensional magnetic materials, and biophysics. In recent years, the formation of stable and molecularly oriented films has attracted attention [G., Roberts, 5 sensors and
Actuators.

4131 (1983); Contemp, Phy.
s;, 25.109 (1984); G, G.

Roberts, et al., 1. E.E.Proe
,,128. I, 197 (1981): H, Kuhn
, et al., J.Chem., Phys.
61.5009 (1974); 1bid, 68
．． 3918 (1978); F, Kajzar,
et al., Opt.

Commun, , 45.133 (1983);
J, phys. , 44. C-3, 709 (1983)
:M, Pomerantz, 5olid 5tate
Commun, 39, 707 (1981); 5urf
, Sei, , 142, 556 (1984) Ko.

A characteristic feature of this flexible LB membrane is that it can be expected to actively express functions through the systematic aggregation of molecules.

It is conceivable to apply metallocene complexes such as ferrocene, which are known as functional complexes, to such LB films, and their actual application has also been reported [Th1n 5oli
d Films, 133. (1985)].

In general, metallocene complexes such as ferrocene can be used as electrode materials, conductive materials, sensors, physiologically active catalysts, etc. due to their ability to have mixed valences, conductivity, and scales that exhibit magnetism. This is because functionality is expected.

For this reason, the present inventors previously determined that "=C-0-R1-C
Cocoon C-C diC-R2 (However, Ro is an alkylene group,
R2 represents an alkyl group. ) and an LB film containing the metallocene complex (Japanese Patent Application No. 115595/1982).

<Problem to be solved by the invention> However, with the above complex, it is possible to form an LB film, and furthermore, after forming the LB film, polymerization, especially photopolymerization, is possible while maintaining the molecular orientation. However, it has not been possible to realize an electrochemical mixed valence state. The reason for this is that since the LB film contains alkyl chains, which are important for forming LB films, a layer backed by alkyl chains is formed, which acts as an insulating layer against electrolytes and ions. It is an electrochemically inert film that acts as a shield.

Therefore, if a mixed valence state can be realized electrochemically using a polymer LB film formed by photopolymerization or the like, it is expected that an excellent functional film can be obtained.

The present invention provides a novel metallocene derivative charge transfer complex that is expected to be used as a highly functional material, is capable of forming a Langmuir-Prodgett film, and is photopolymerizable, and a Langmuir-Prodgett film using the same. It is intended to.

<Means for Solving the Problems> In order to achieve the above object, in the charge transfer complex of the metallocene derivative of the present invention, at least one cyclopentadienyl ring has the following structure: =CO-R+ C=CC=CR2 (however, R3 represents an alkylene group, R2 represents an alkyl group, and is formed from a metallocene derivative having a group represented by the formula (2) and an electron-accepting compound.

In the above, the electron-accepting compound is preferably iodine, tetracyanoethylene, or substituted or unsubstituted tetracyanoquinodimethane.

Further, the Langmuir-Prodgett film of the present invention is made of the above metallocene derivative! It contains a cargo transfer complex.

The configuration of the present invention will be explained below.

The charge transfer complex of the metallocene derivative of the present invention is schematically represented by the following formula (I).

Formula (I) F C-+EA In the above formula (I), Fc represents a metallocene derivative, and EA represents an electron-accepting compound.

The metallocene derivative (Fc) has a group represented by -C-0-R, -c*c-cmiC-R, on at least the - side of the cyclopentadienyl ring.

Here, R represents a substituted or unsubstituted alkylene group, and an unsubstituted one is preferred.

R3 preferably has 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms, and may be linear or branched.

Specific examples include methylene, ethylone, propylone, butylene, pentamethylene, heptamethylene, heptamethylene, octamethylene, etc. Among these, methylene 1/one is particularly preferred.

Further, R2 represents a substituted or unsubstituted alkyl group, and an unsubstituted one is preferable.

R2 preferably has 9 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and may be linear or branched, but is preferably linear.

Specific examples include n-dodecyl, n-tridecyl, n-butadecyl, n-pentadecyl, n-hexadecyl, and the like.

Such a group represented by the above formula is directly bonded to the cyclopentagenyl ring constituting the metallocene complex.

In the metallocene complex of the present invention, either one of the pair of cyclopentadienyl rings facing in parallel with the central metal atom in between has only to have at least one group represented by the above formula.

Therefore, although various numbers and positions of substitution are possible for the group represented by the above formula, one cyclopentagenyl group is preferably monosubstituted, and 1- or 1-,
The 1'-substitution position is preferred.

The one substituted at the 1-position is represented by the following formula (n).

Formula (n) In the above formula (II), Mt is a transition metal, for example, C0
1 represents Ni, Cu, Fe, Zn, Cr, Ru, O8.

Note that, as described above, a group represented by the above formula may be bonded to the cyclopentadienyl ring located lower in the above formula (II).

Moreover, in the above, the cyclopentadienyl ring may be a conjugate.

Examples of the substituent include halogens such as Cβ, alkoxy groups such as OCH, and nido and tetra groups.

In addition, as an electron-accepting compound (EA), iodine (I
2) Examples include tetracyanoethylene (TCNE) and substituted or unsubstituted tetracyanoquinodimethane (TCNQ).

Specific examples of substituted TCNQ include those in which the quinone skeleton of rCNQ is substituted with a long-chain alkyl group having 12 to 20 carbon atoms (eg, octadecyl, dodecyl, hexadecyl, etc.).

Among the electron-accepting compounds, 1. , itadecyl TC
Substitutions such as NQ and TCNQ are preferred.

Preferred specific examples of the charge transfer complex of the ferrocene derivative of the present invention are shown below, but the present invention is not limited thereto.

Next, a method for synthesizing a charge transfer complex of a ferrocene derivative according to the present invention will be explained.

First, a ferrocene derivative is synthesized. In this case, for example, the compound represented by formula (TI) is as follows.

First, the starting material, alcohol, follows the scheme below.

NHa OH, HCρ R2-Cmi C-Cmi CR, -OH More specifically, the literature [W, Beekmann et al.

5ynthesis 1975, 423. T, H, Va
ughm, J. Am, Chem.

Soc, 55.3456 (1935) etc.] 1-alkyl-2-iodoacetylene R2-C=
CI (for example, 1-dodecyl-2-iodoacetylene, etc.) is mixed with an acetylene derivative CHyoC-R, -OH (for example, propargyl alcohol, 3-butyn-1-ol, etc.), copper chloride and Add to the mixed solution of ethylamine and stir. After making the solution acidic and extracting with ether, impurities are removed by filtration and evaporation is carried out using the solvent to obtain the desired alcohol.

This alcohol is then reacted with metallocene monocarboxylic acid chloride.

More specifically, the above alcohol and metallocene monocarboxylic acid chloride (e.g., ferrocene monocarboxylic acid chloride) are dissolved in an organic solvent (e.g., 1,2-dichloroethane, ethyl acetate, etc.), and the mixture is dissolved in a non-oxidizing atmosphere (e.g., At room temperature for about 2 hours in a N2 stream, etc.), then
Stir at about 55°C for about 16 hours.

The reaction product thus obtained is filtered and recrystallized from petroleum ether, n-hexane, etc. to obtain the desired metallocene derivative.

In the above, the carboxylic acid chloride substituted at the 1-position of the metallocene is used, but if one substituted at the 1.1-position etc. is used, a corresponding metallocene derivative can be obtained in the same manner.

The metallocene derivative thus obtained can be easily identified by IR spectrum, electronic spectrum, H-NMR, mass spectrum, elemental analysis, etc.

A charge transfer complex is obtained from the metallocene derivative thus synthesized.

In this case, the metallocene derivative and the electron-accepting compound are reacted in an organic solvent such as benzene or acetone for about 30 to 70 days, and then the solvent is distilled off.

Reaction conditions such as reaction temperature vary depending on the electron-accepting compound, and in the case of Step 2, it is necessary to carry out the reaction in a dark place.

The obtained charge transfer complex can be identified by IR spectrum, electronic spectrum, elemental analysis, etc.

The IR spectrum is according to the KBrBr method (, v c,, N2570-2380 am-'νc
,, cH2235-2240 cm-'V C81:
A characteristic absorption between 0 1720 and 1725 cm-' is observed.

A CT band is observed in the electronic spectrum.

The charge transfer complex of the present invention is not only expected to be used as a high-performance material such as an energy conversion material and an electrochemical catalyst (but also as a material for forming the Langmuir-Prodgett film described below). You can also.

The charge transfer complex of the present invention also has sufficient solubility in organic solvents (chloroform, benzene, etc.) required when forming a Langmuir-Blodgett film (10-"M
can be dissolved).

To prepare the LB film of the charge transfer complex of the present invention, usually,
Horizontal attachment method can be applied.

This horizontal adhesion method may be performed by following a conventional method.

At this time, benzene, chloroform, etc. may be used as the developing solvent.

Incidentally, the LB peritoneum may contain stearate or the like as a matrix substance.

The charge transfer complex of the present invention is photopolymerizable.

Therefore, after polymerizing a monomolecular film, a LB film may be formed using a horizontal deposition method or a vertical dipping method.

Alternatively, the LB film may be photopolymerized.

Specifically, a normal method may be followed.

The LB film thus obtained can realize an electrochemical mixed valence state, and can be used as various high-performance films such as electronic devices, switching elements, and information conversion elements.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1゜ was added to the mixed solution and stirred.

Next, add hydrochloric acid (20 mρ) to this solution to make it acidic.
After extraction with ether, impurities were removed by filtration, and solvent evaporation was performed to obtain the desired heptadeca-2,4-diyn-1-ol (8.99 g, 3X
10-2moρ) was obtained. The yield was 31%.

(1-1-1) Synthesis literature of hebutadec-2,4-diyn-1-ol [W, Beckmann et al, 5ynt
hesis 1975゜423, T, H, Vaugh
m, J, Am, Chem, Soe, 55.3
1-dodecyl-2-iodoacetylene (IXIO-'moβ, 5.6
1 g) was dissolved in equimolar amounts of propargyl alcohol previously dissolved in methanol (50 mI2.) and hydroxyamine hydrochloride (6,55X10-''m0f2.0.
46g) Copper chloride (2,27X10-2m oβ, 2
．． 25g) and ethylamine (2,82X10 mo
β, 12.72 g) ferrocene monocarboxylic acid chloride 4.79 g (2xlO-2moff) and the diacetylene derivative (heptadeca-2,4
-diyn-1-ol) 4.97g (2X10""rn
oβ) in 1,2-dichloroethane (20 mI2) and heated at room temperature in a nitrogen stream for 2 hours, then at 55°C.
The mixture was stirred for 16 hours.

The obtained crude product was purified by column chromatography using a mixed solvent of benzene:acetone = 3:1 as a developing solvent, and recrystallized from n-hexane to obtain 2,4-hebutadecadinylfuerocenecarboxylate. (4,59g,
The yield was 96%.

This substance was identified by elemental analysis, IR spectrum, electronic spectrum, etc.

1-1-3 A 2.4-hebutadecadinyl fluorocene
1.0.12g (2,6xlO-'moff) and 0.3g of iodine (2,6xlO-'moff) were mixed in a benzene solution, left in a dark place at room temperature for 30 days, and then the solvent was distilled off. A colored complex was obtained.

In the above, iodine is a commercially available product (Wako Tsumugi Kogyo Co., Ltd.
Co., Ltd.) was used as it was, and benzene was purified from a commercially available special grade product.

This charge transfer complex has an IR spectrum, an electronic spectrum,
and identified by elemental analysis.

These results are shown below.

IR spectrum (KBr tablet method)
0 1718°m- Electron vector (in chloroform solution) λmmx
440 nm max 580 nm Elemental analysis (ferrocene derivative: ■221:3) Calculated value C27, 50%, H2, 94% Actual value C27
, 24%, H3, 25% and the above charge transfer complex is soluble in benzene at a concentration of 3X10
-'M) was uniformly dropped onto distilled water to develop a monomolecular film. The temperature of the aqueous phase was 10°C. This was left for 10 minutes until the monomolecular film became uniform.

The surface pressure-area (1r, -A) curve of this monomolecular film was measured using a surface membrane pressure meter manufactured by Kyowa Interface Science Co., Ltd. In this case, the water surface residence time is 10-20 minutes, and the compression speed is 10 mm/m.
The temperature of the aqueous phase was set at 15°C. The results are shown in FIG. Compared to ferrocene derivatives,
It was found that there was almost no change in the ultimate area or the shape of the curve.

Next, a surface membrane pressure gauge HB M − was attached to the above monomolecular membrane on the water surface.
Using an AP type device (manufactured by Kyowa Interface Science Co., Ltd.),
It was irradiated with light for 0.3 hours at 20°C or 20°C.

The relationship between the light irradiation time and the surface area is shown in FIG. 2, and the π-A curve of the monomolecular film after light irradiation is shown in FIG. 3 in comparison with ferrocene derivatives.

It was confirmed that the behavior of increase/decrease in surface area of the monolayer upon light irradiation is clearly different from that of ferrocene derivatives.

In other words, compared to the case of ferrocene derivatives, in the case of charge transfer complexes, the degree of volume expansion and contraction is thicker. It is thought that as the diacetylene groups link together through polymerization, the movement of the entire molecule increases, which causes twisting and bending from the planar structure, increasing the degree of volumetric expansion and contraction.

Furthermore, when the surface pressure was returned to 0 and measurements were taken again, there was no significant difference in the ultimate area in charge transfer complexes with iodine, but the collapse pressure was low.

Next, a cumulative film was prepared using the photopolymerized charge transfer complex. The cumulative film could be produced by either the vertical dipping method or the horizontal deposition method.

In this case, a surface membrane pressure gauge HBM-AP type device (manufactured by Kyowa Interface Science Co., Ltd.) was used at a temperature of 5°C and a surface pressure of 15 mN/
m or 25 m N/m set to cumulative speed 10
A polymer film was accumulated on the ITO substrate at a rate of 30 mm/min (vertical dipping method applied). Good accumulation was obtained up to about 30M.

The LB film accumulated as a 40-layer Y film on a photopolymerized and grafted calcium fluoride board was measured for thickness. This result is shown in FIG. 4 together with the ferrocene derivative and the 2 charge transfer complex in chloroform solution.

As a result, the π-
When focusing on the peak attributed to the π* transition, it was observed that the wavelength was shifted to shorter wavelengths compared to the solution state11.

This shows that the cyclopentadienyl ring is oriented perpendicularly to the film surface based on Kasha's theory.
From the spectrum of the solution, a peak of 12 charge transfer complex formation was observed around 680 nm.

Further, in the LB film, broad absorption was observed around 330 nm.

Furthermore, when comparing the spectra of a cumulative film of a ferrocene derivative doped with iodine, it showed almost the same absorption peak as that of ferrocene fertilizer, which also supports the formation of a complex with iodine. Furthermore, a broad absorption band with a G-shape characteristic of a charge transfer complex was also observed in the near-infrared region of 900 to 1400 nm.

Next, a 6ON sample was prepared on an ITO substrate using the LB method, and the contact angle was measured using a contact angle meter DT type (manufactured by Kyowa Interface Science Co., Ltd.).

The contact angle shows a value of about 82°, which decreases in the case of the ferrocene long chain derivative (1]0°), indicating that the hydrophobicity of the membrane surface is weakened. This indicates that the film has changed from a neutral state to an ionic state (oxidized state).

Forty layers were accumulated on an ITO substrate, and the thick film was measured using a DVA-36L automatic ellipsometer (manufactured by Shojo Kogaku Co., Ltd.).

The thick film had 19 molecules per layer, which was higher than that of the ferrocene derivative. This is because the iodine-doped cumulative film shows the same value of 15 as the film with ferrocene derivative alone, indicating that the orientation in the film is maintained as it is, whereas the iodine charge transfer complex has a surface pressure of - Based on the area curve and the results of thick film measurements, it is expected that the orientation changes due to the influence of iodine.

In addition, scanning electron microscope (SEM) photographs and fluorescence microscope photographs were taken (Figures 5a to 5d) to observe the surface state of the LB film of the charge transfer complex with iodine. A SEM photograph is shown in Figure 5b and fluorescence micrographs are shown in Figures 58.5c and 5d.

These photos show that the polymer film is quite dense and tightly packed.

In addition, in ferrocene derivatives, B1+Ye excitation and Green
Even with excitation, the flea photoreceptor could not be confirmed, but in the case of the iodine complex, it could be seen as a white part in the photograph.

This seems to be due to the difference between the ferrocene derivative alone and the iodine complex due to the higher order structure of the polymer.

Note that scanning electron micrographs were taken and observed for samples in which 40 to 60 layers were accumulated on an ITO substrate by the LB method.

In addition, fluorescence micrographs were similarly observed for 40 layers accumulated on a quartz plate.

LB method (vertical immersion method: set pressure 15 mN) onto ITO substrate
X-ray photoelectron spectroscopy (ESCA) was measured using a sample in which 60 layers were accumulated at /m).

The results are shown in FIG.

Two broad peaks were observed near 713 eV and 711 eV. The force of 7L3eV is ferridinium ion (III), and the force of 711eV is ferrocene (I).
I), but judging from the spectral intensity and other factors, it is thought that the iron atoms are in a fairly close to equivalent state.

Next, cyclic portammetry was measured.

As a working electrode, a substrate with 17 layers accumulated on an ITO electrode by Method B is used, and the electrolyte contains O and I as supporting electrolytes.
Measurement was performed using an ace1-nitrile solution containing MTBAP. At the same time, acetonitrile solutions of charge transfer complexes and acetonitrile solutions of ferrocene derivatives were also measured.

The results are shown in FIG.

In Figure 7, the solid line is L of the charge transfer complex with iodine.
In film B, the dotted line is an acetonitrile solution thereof, and the - dotted chain point is an example of an acetonitrile solution of the ferrocene derivative alone for comparison.

It can be seen that when a charge transfer complex is formed with iodine, ferrocene becomes a ferridinium cation by the iodine anion, as expected, and becomes easier to be electrochemically oxidized.

The oxidation peak potential (Eap) was 0.89■, the reduction peak potential (Ecp) was 0.69V vs. SCE.

Furthermore, FIG. 8 shows changes in absorption spectra due to electrochemical redox reactions.

Similar to the ferrocene derivative, a peak attributed to excitation of the ferricium ion from the ligand orbit to the ion orbit was observed at 625 nm. This indicates that the electrochemical oxidation state was achieved by forming a charge transfer complex.

Example 2, 2,4-hebutadecadinyl fluorocene rupoxylate O0Ig (2,2X], 0-'moρ) of Example 1
and octadecyl TCNQO, 05g (1,1xlO-
'moβ) was mixed in an acetone solution, heated for 70 days (55-60°C), and the solvent was distilled off to obtain a dark orange complex.

In the above, octadecyl TCNQ was manufactured by Nippon Kanko Shiki Co., Ltd., and acetone was purified from a commercially available special grade product.

This charge transfer complex was identified by IR spectra, electronic spectra, and elemental analysis.

These results are shown below.

IR spectrum (KBr tablet method) νc YO N 2380cm'''l/c,,c,2240cm-']
c = 0 1 720cm-
'Electronic spectrum (in chloroform solution) wax
350 nm λ□x 450 nm Elemental analysis (ferrocene derivative: TCNQ derivative = 1:
1.2) Calculated value C68,98% H7,71% N5.34%
Actual value C68,52% H7,92% N 5.50
% or more 11Ω±1 A monomolecular film was developed in the same manner as in Example 1, and the π-8 line was measured in the same manner (FIG. 9).

It was confirmed that the ultimate area was slightly larger than that of the ferrocene derivative, probably due to the influence of the octadecyl TCNQ molecule.

Next, as in the case of iodine complexes, we investigated the relationship between light irradiation time and surface area (Figure 10), and found that it was larger than that for ferrocene derivatives, but smaller than that for iodine complexes. It was.

Comparing octadecyl TCNQ and iodine, it is thought that octadecyl TCNQ is more difficult to move than the iodine molecule due to its molecular size, and the space is also smaller.

As a result, compared to iodine complexes, the degree of volumetric expansion and contraction is thought to be smaller because twisting and bending are less likely to occur.

The results of the surface pressure-area curve after irradiation are shown in Figure 11.
The ultimate area became larger as in the case of the monomer, and the collapse pressure also became higher.

Next, in the same manner as in Example 1, a cumulative film was produced using the photopolymerized charge transfer complex. The cumulative film could be produced by either the vertical dipping method or the horizontal deposition method.

In the accumulation by the vertical immersion method, the accumulation ratio was about 0.98 for both rising and falling, indicating a good cumulative value.

It was possible to accumulate uniformly up to about the 50th layer.

As in Example 1, the electron svector of the LB film was measured. This is shown in FIG.

As a result, the peak assigned to the π-π* transition along the plane of the cyclopentadienyl ring in the LB film has shifted to shorter wavelengths than in the case of the solution, so as with the iodine complex,
It was found that the cyclopentadienyl ring was oriented close to perpendicular to the film surface. Also, when comparing the cases of the ferrocene derivative alone and the octadecyl TCNQ complex, the spectrum of octadecyl TCNQ appears from around 500 nm to 27 nm.
A broad but fairly large absorption was observed around 0 nm, and it was confirmed from the spectrum of octadecyl TCNQ alone that this was due to the influence of TCNQ.

Furthermore, when the contact angle was measured, it was found that the value was about 87°, which was more hydrophilic than that of the ferrocene derivative.

Furthermore, when a thick film was measured in the same manner as in Example 1, 21
The value of people was obtained. Such a large value is due to the long alkyl chain of octadecyl TCNQ.

It can be said that the film in which the charge transfer complex is formed using octadecyl TCNQ has undergone a change in orientation, similar to the iodine complex.

Furthermore, the SEM photograph (Fig. 13b) showed the uniformity of the surface. Fluorescence micrographs (Figures 13a and 13c)
Figure 13d) showed the difference in the higher-order structure of the polymer from the ferrocene derivative and the iodine complex.

As a result of measuring ESCA on a sample of 60 layers accumulated on an ITO substrate using the LB method at 15 mN/m, a peak was observed around 713 eV (Figure 14).
.

It is thought that one equivalent peak was given because the ferridinium cation and the TCNQ anion were close to 1:1 (forming a charge transfer complex).

Next, cyclic portammetry was measured in the same manner as in Example 1.

Figure 15 shows the results for the solution of the octadecyl TCNQ complex and the ferrocene derivative, and also shows the results for the solution of the octadecyl TCNQ complex and a sample in which 17 layers of polymerized monomolecular film were accumulated on an ITO substrate by the LB method in the same manner as in Example 1. 16
As shown in the figure.

From the results shown in Figures 2 and 3, the octadecyl TCNQ charge transfer complex in solution is less susceptible to oxidation than the ferrocene derivative, but in the polymerized monolayer it is much more electrically active than in solution. It can be seen that it is easily oxidized. This is considered to be due to the arrangement effect.

In this case, the oxidation peak potential (Eap) is 0.76V.
, the reduction peak potential (Ecp) was 0.6 V, and it can be said that it is more active than the polymerized monomolecular film of the iodine complex of Example 1.

<Effects of the Invention> According to the present invention, a novel charge transfer complex of a metallocene derivative formed with an electron-accepting compound such as iodine and octadecyl TCNQ can be obtained.

Therefore, the charge transfer complex of the present invention can be used as a highly functional material such as an electromagnetic field sensitive element.

In addition, it is possible to form a Langmuir-Prodgett (L B ) film, and forming an LB film makes it easier to electrochemically oxidize, so it can be used as a high-performance film for electronic devices, switching elements, information conversion elements, etc. will be obtained.

[Brief explanation of the drawing]

The figure shows the π-8 line of the monomolecular film, Figure 2 shows the light irradiation time and surface area, Figure 3 shows the π-A @ line after photopolymerization, Figure 4 shows the measurement results of the electronic spectrum, and Figures 5a to 5a. Figure 5d is an SEM photo and fluorescence micrograph showing the particle structure, which is a substitute for a drawing, Figure 6 is the ESCA measurement results, Figure 7 is a cyclic portamogram, and Figure 8 is an electrochemical redox reaction. The graphs show the changes in absorption spectra due to the change in absorption spectra. Figures 9 to 16 show φ→→ characteristics of the zone T CN Q complex in the present invention, Figure 9 is the π-A curve of the monolayer, and Figure 10 is the irradiation time and Surface area, Figure 11 is the π-A curve after photopolymerization, Figure 12
The figure shows the measurement results of electronic spectra, 13th s, ~ 13d
The figures are SEM photographs and fluorescence micrographs, which are used as drawings to show the particle structure. Figure 14 is the ESCA measurement results.
5 and 16 show cyclic portamograms, respectively.

Claims (3)

[Claims] (1) At least one of the cyclopentadienyl rings has a metallocene derivative having a group represented by ▲a mathematical formula, a chemical formula, a table, etc.▼ (where R_1 represents an alkylene group and R_2 represents an alkyl group) and an electron A charge transfer complex of a metallocene derivative, characterized in that it is formed from an accepting compound. (2) The charge transfer complex of a metallocene derivative according to claim 1, wherein the electron-accepting compound is iodine, tetracyanoethylene, or substituted or unsubstituted tetracyanoquinodimethane. (3) A Langmuir-Blodgett film comprising a charge transfer complex of the metallocene derivative according to claim 1 or 2.