JPS63280086A - Dinuclear complex of salt thereof and langmuir-blodgett membrane - Google Patents

Abstract

NEW MATERIAL:A compound (salt) expressed by formula I (Mt is transition metal; R1 is alkylene; R2-R4 are alkyl). USE:Langmuir.Blodgett membrane for highly functional material such as energy converting material, electrochemical catalyst or oxygen carrying carrier. PREPARATION:For example, acetylene is reacted with the formula C12H25Br in the presence of n-butyllithium to afford the formula C12H25CidenticalCH, which is iodized to give the formula C12H25CidenticalCI, which is then reacted with propagyl alcohol and brominated and further reacted with malonic diester in the presence of NaH to provide a compound expressed by formula II (Et is ethyl), whose ester group is further subjected to reduction, azidation and the reduction to give a diamine compound expressed by formula III, which is reacted with a compound expressed by formula IV and the formula Cu(ClO4).6H2O to afford the aimed compound expressed by formula I. The compound expressed by formula I is mixed with heptadeca-2,4-diyn-1-ol and developed on distilled water to provide the Langmuir.Blodgett membrane.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to dinuclear complexes and Langmuir-Blodgett membranes containing the same.

Prior art and its problems Recently, the application of metal complexes as electronic devices has been actively researched, and their potential as molecular devices is also attracting attention.

However, during the redox reaction of general metal complexes,
It is necessary for electrons and counterions to move in and out from the outside, and this causes many problems. In particular, the slow rate of change in oxidation state is a problem.

However, among metal complexes, in the case of mixed valence complexes such as dinuclear complexes, electron transfer occurs between metal atoms, so
It is thought that the oxidation state can be changed at a high speed without involving the entry or exit of electrons or counterions from the outside.

By making these films thinner and realizing regular molecular orientation, it is expected that even more advanced functions will be developed.

Therefore, attempts are being made to form thin films.
Methods for producing such thin films include vacuum evaporation, suspension spraying, dispersion in polymers, and mechanical rubbing, but all of them have problems with uniformity of film thickness and reproducibility of the morphology of microcrystalline distribution. be.

Therefore, as a solution to these problems, the formation of reproducible and stable molecularly oriented films by the Langmuir-Blodgett (LB) method or the horizontal deposition method has recently attracted attention.

In the LB method, a substance with an appropriate balance of amphipathic properties (hydrophilicity and lipophilicity) is dissolved in a volatile solvent and dropped onto the water surface to form a monomolecular film, and a sufficient surface pressure is applied to the film. In this method, a monomolecular film is accumulated by moving the substrate up and down across the water surface while keeping it in a solid state.

In addition, the horizontal deposition method forms a monomolecular film on a substrate placed in a direction parallel to the water surface.

A film formed by the LB method or the horizontal deposition method is called a Langmuir-Blodgett (LB) film.

For these reasons, the formation of the LB film requires solubility in organic solvents. In addition, if a polymerized LB film is formed by polymerizing the LB film without changing the molecular orientation of the film-forming molecules through post-accumulation treatment, the mechanical strength and robustness of the film will improve, resulting in an excellent functional film. . Therefore, characteristics such as processability, mechanical strength, heat resistance, and corrosion resistance are also required in these respects.

Therefore, LB film formation is possible, and after forming LB film,
If mixed valence complexes that can be polymerized, especially photopolymerized, while maintaining the regular orientation of molecules can be realized, excellent functional films will be realized. - ■ Purpose of the invention The purpose of the present invention is to provide a material that is expected to be used as a highly functional material.
An object of the present invention is to provide a novel compound that is capable of forming a Langmuir-Blodgett film and that can be photopolymerized without changing the molecular orientation structure after film formation, and a Langmuir-Blodgett film that is formed thereby and has high durability. .

■Disclosure of invention Such objects are achieved by the invention described below.

That is, the first invention is a dinuclear complex or a salt thereof, characterized by being represented by the following formula (I).

(In the above formula (I), Mt represents a transition metal, R1 represents an alkylene group, and R2, R3, and R4 represent an alkyl group.) Furthermore, the second invention provides a dinuclear complex represented by the following formula (I). or a Langmuir salt thereof.
It is Blodgett's membrane.

Formula (I) (In the above formula (I), Mt represents a transition metal, R1 represents an alkylene group, and R2, R3, and R4 represent an alkyl group.) Furthermore, the third invention provides the following formula (I): This is a Langmuir-Blodgett film characterized by photopolymerizing a Langmuir-Blodgett film containing the shown dinuclear complex or its salt.

Formula (I) (In the above formula (I), Mt represents a transition metal, R1 represents an alkylene group, and R2, R3, and R4 represent an alkyl group.) ■ Specific structure of the invention The following is a specific structure of the present invention. will be explained in detail.

In the above formula (I) representing the dinuclear complex of the present invention, R1
represents an alkylene group.

As R1, an unsubstituted alkylene group is preferable, and a linear group having 1 to 8 carbon atoms, particularly 1 carbon number, is preferable.

Such alkylene groups include methylene, ethylene, propylene, butene, pentamethylene, hexamethylene, heptamethylene, octamethylene, etc. Among these, methylene is particularly preferred.

R2, R3 and R4 represent an alkyl group.

R2 is an unsubstituted alkyl group having 8 to 20 carbon atoms;
Particularly preferred are those having 12 to 20 carbon atoms, and straight chain ones are particularly preferred.

Such alkyl groups include n-octyl, n-decyl, n-dodecyl, n-butadecyl, n-hexadecyl, n-octadecyl, n-eicosyl, etc.
Among these, n-dodecyl, n-butadecyl, n-
-hexadecyl, n-octadecyl and n-eicosyl are preferred.

R3 and R4 are preferably unsubstituted alkyl groups, and are preferably linear and have 1 to 4 carbon atoms, particularly 1 carbon number.

Examples of such alkyl groups include methyl, ethyl, propyl, butyl, and among these, methyl is particularly preferred.

In addition, it is preferable that R3 and R4 are usually the same thing.

In the above formula (I), Mt represents a transition metal.

As the transition metal, Cu, Ni, Fe, Zn, Cr, etc. are used.

Note that the two Mts are usually the same, but may be different.

In addition to the compound represented by the above formula (I), the dinuclear complex of the present invention also includes a salt thereof represented by the following formula (II).

Formula (II) In the above formula (n), X is CIL-1Br''', ■-
These include halogens such as Q4-, acid anions such as BF4-1BPh4- (Ph=phenyl), and the like.

n is an integer appropriately selected from 0 to 4 depending on the valence of the dinuclear complex.

For example, when Mt is a combination of Cu2+ and Cu2÷, n=2. Further, in the case of a combination of Cu'ゝ and Cu2+, n==1.

Note that bound water may be bound to the salt represented by formula (II).

For example, when Mt is a combination of Cu2+ and Cu2+ and X is CIL, this salt body contains lH2O as bound water.

Such dinuclear complexes are described in reference (R, Longand
D., Hendrickson, J., Am., Chem.
Soc.

1983, 105. 1513. B. Tieke;
G.

Lieser, and G., Wegner, J., Pol.
ym, Sci,,Polym.

Chem, Ed, 1979. 17. 1631.
J.

Skarzewski and E., Daniluk;
Monatsch, Chem.

1983.114, 1077, etc.), for example, it may be synthesized according to the scheme shown below.

In the scheme below, Ts represents a tosyl group, M
s represents a mesyl group.

C00Et < tXn The dinuclear complex thus obtained has an IR spectrum,
It can be easily identified by electronic spectrum, I(-NMR, mass spectrum, elemental analysis, etc.).

Note that the IR spectrum is measured using KBrti: Criminal Law, and the electronic spectrum is measured in a solvent such as chloroform or benzene.

The IR spectrum includes 2930 cm-' and 2860 cm-'
'VC-H, 1635cm-'v. , 1560cm
' has νc, c.

The electronic spectrum shows 350~
370nra, and has an absorption maximum at 220-230nm.

The dinuclear complex of the present invention is not only expected to be used as a high-performance material such as an energy conversion material, an electrochemical catalyst, and an oxygen transport carrier, but also is useful in forming the Langmuir-Blodgett film described below. It can also be used as a material.

The dinuclear complex of the present invention also has sufficient solubility in organic solvents (chloroform, ethanol, etc.) required when forming a Langmuir-Blodgett film (can be dissolved at 10 -3 M or more).

It is also soluble in hot water.

A method for forming a Langmuir-Blodgett (LB) film using the complex or salt represented by the above formula (I) or (n) will be described.

A compound is dissolved in a developing solvent (for example, chloroform), and a monomolecular film is developed on the gas-liquid interface using distilled water as the aqueous phase. The temperature of the aqueous phase is set to about 3° C., and it is left to stand until a monomolecular film becomes uniform. The time is usually about 10 minutes. Then, it is compressed so that the surface pressure becomes, for example, 25 mN/m.

Thereafter, a cumulative film is produced by the following two methods.

(1) LB method A substrate (glass, quartz, alumina, silicon, etc.) is lowered at a speed of 20 mad/win, for example, and vertically immersed in an aqueous phase without compressing the interface so as to maintain a constant pressure.
It is then raised to transfer the monomolecular film onto the substrate. After transferring it onto the substrate, leave it until the attached water dries.
Repeat the same operation to obtain a cumulative film.

The accumulated film transferred onto the substrate in this way has a contact angle with the interface when the substrate is immersed (obtuse angle when descending, right angle when ascending), and the surface area decreases only during descending. This is considered to be a typical X-film morphology.

(2) Horizontal adhesion method A hydrophobic substrate (for example, glass, quartz, alumina, silicon, etc. that has been hydrophobically treated with dichlorodiphenylsilane) is supported horizontally, brought as close as possible to the water surface on which the film has been developed, and then gently The film is attached to the substrate by touching the monolayer surface. Next, a partition plate is placed on the water tank adjacent to the substrate, and after sweeping away the monomolecular film remaining around the substrate, the substrate is removed from the water surface, and the monomolecular film is lifted up as it is. transferred to the substrate surface.

Leave the substrate until it dries and repeat the same operation to produce a cumulative film.

In this method, since hydrophobic sites are always adsorbed, the structure of the resulting cumulative film is an ideal X film. In this case, the cumulative ratio is always 1, and since there is no flow of the film during accumulation, the agglomerated state of molecules in the monomolecular film can be directly transferred to the substrate surface. Furthermore, vertical immersion method (LB method)
In the case of the dinuclear complex of the present invention, it is preferable to use the horizontal deposition method because it can be applied to films in a relatively low pressure region where stacking is not possible.

As a result, a linear relationship is established between the number of accumulated layers and the absorbance, which suggests that a stable monomolecular film with reproducibility is transferred onto the substrate in each accumulation operation. .

Note that the LB film of the present invention is not limited to being formed only from the dinuclear complex or salt represented by the above formula (I) or (II), but also from the dinuclear complex or salt represented by the above formula (I) or (II). It may be formed from a body and a so-called matrix.

In this case, the molecular ratio of the complex or salt to the matrix is 1=2 to 1:15, particularly 1:5 to 1:10.
from the viewpoint of stability of the resulting LB film.

In addition, the matrix used is R2+C such as heptadeca-2,4-diyn-1-ol.
=C+2-RIOH (RI, R2 are as above)
, fatty acids, fatty acid esters, alkanes, etc. Among these, those having the same R2 as the complex or salt thereof to be used are preferred.

Such an LB film formed from the above-mentioned dinuclear complex or salt and a matrix can improve film stability, molecular orientation, etc. by appropriately selecting the combination of the dinuclear complex or salt and the matrix. As a result, the photopolymerizability can be improved, and the LB film has the same functionality as the LB film formed only from the above complex.

Such an LB film of the present invention is characterized in that the dinuclear complex of the present invention is LB
Because it is regularly oriented when forming a film, it exhibits optical anisotropy.

Specifically, the planar cyclic ligands are oriented substantially perpendicularly to the membrane surface, and the planar cyclic ligands of each molecule are regularly oriented substantially parallel to each other.

That the LB film of the present invention has such a structure can be estimated from measurement of the limit molecular occupied area, the anisotropy of νcN absorption in the polarized IR spectrum, and the like.

Furthermore, photopolymerization, which will be described later, makes it possible to firmly maintain such regular orientation.

Such regular orientation produces the properties described below and can be used for the following applications.

For example, if the complex is a mixed valence complex having Mt of Cu'' and Cu+, the valences of these metals average out to +1
．． It is known that an average valence state in which two metals exhibit a valence of 5 and a mixed valence state of +2 and +1 valences in which the valences are not averaged can be obtained reversibly by temperature changes. (R, long and D, Hendrickso
n J, Am, Chem.

Soc, 1983. 105. 1513).

In this case, in a solution state, the molecules are oriented in the same direction, so changes in the electronic microenvironment due to the localized and delocalized state of electrons exhibited by one molecule are canceled out.

However, if the molecules are regularly oriented in a certain direction, this property can be extracted as a function. An example of such a device is a nonlinear optical element.

Furthermore, this complex has diacetylene groups. Some polymers of diacetylene compounds contain 1 by doping.
Some have been reported to exhibit conductivity of 0-'S/cm (
Katsuyuki Naito, Masayoshi Okamoto Proceedings of the 35th Polymer Science Society p598
(1986)).

Therefore, when the oriented film of the complex of the present invention is polymerized as described below, the electrical conductivity in the direction parallel to the film surface of the film is reduced by the electric field, magnetic field or heat applied from the direction perpendicular to the film surface. It is thought that it can be changed by physical stimulation (for example, infrared laser), and is expected to be applied to so-called molecular devices such as switching devices, information conversion devices, memory devices, and molecular transistor devices.

Furthermore, the LB film of the present invention has a so-called electrochromism (EC) mechanism and can be used as a single-functional material.

However, since a film that is simply accumulated has insufficient fastness, it is preferable to carry out photopolymerization.

It is preferable to use ultraviolet light for photopolymerization, and a mercury lamp, a Xe lamp, or the like may be used as a light source.

Upon irradiation with ultraviolet rays, for example, the salt represented by the above formula (n) is photopolymerized as described below.

Such polymerization can be confirmed by electronic spectra, IR spectra, etc.

Moreover, even if such photopolymerization is performed, the regular molecular orientation of the LB film is maintained.

The LB film of the present invention becomes highly robust by performing such photopolymerization, and can be used as a highly durable functional material such as an electrochromic display device utilizing the above-mentioned EC function.

Further, the LB film of the present invention is expected to be used as various high-performance materials such as magnetic devices, oxygen carriers, electronic devices, modified electrodes, memory materials, and molecular devices.

■Specific effects of the invention The dinuclear complex of the invention is a novel compound and has an electrochromic function, so it can be used as a functional material for electrochromic display devices and the like. Further, it can be a highly functional material such as an energy conversion material, an electrochemical catalyst, an oxygen transport carrier, or a functional material that utilizes redox. These complexes are capable of forming Langmuir-Blodgett films.

In addition, the Langmuir-Blodgett film formed by these complexes can exhibit even more advanced functions and can be used in electrochromic display devices, memory devices, etc. that utilize EC functions.
It can be used as a highly functional material for magnetic devices, oxygen carriers, electronic devices, modified electrodes, optical memory materials, etc.

Furthermore, during the LB film removal process of the present invention, since the dinuclear complex of the present invention is regularly oriented, it has optical anisotropy and can be used as a nonlinear optical element, as well as a switch element, an information conversion element, etc. It has the potential of being used as a memory device, a molecular transistor device, etc.

Furthermore, the LB film of the present invention can be made into a highly durable and highly functional material because its robustness can be increased by photopolymerization, and the regular orientation of molecules is maintained during this process. .

■Specific embodiments of the invention Hereinafter, the present invention will be explained in detail by giving examples.

[Example 1] synthesis of.

ci-i=ci-x in the presence of n-BuLi
Reaction with S-Br yielded Cl2H25C=CH.
The yield was 82%.

Obtained (:+J2sC=CFI, (:2■6Mg
Reacted with I2 in the presence of Br to produce Cl2H2S (:!C
I got 1. The yield was 94%.

Obtain h Ta Cl2) + 25 = CHwo, CuCf1, c
2o, no.

and NH2OH-H(:u (7) in the presence of uc=
was reacted with -CH2-OH to form Cl2H2s-CG-C
=C-CH2oH was obtained.

The yield was 41%.

Obtain tL t= Cl2Hzs-CG-C= (knee C
React H20H with TsCIl to form Cl2H2s-C=
CC=C-CH2-0Ts was obtained. Yield is 60
%Met.

This is reacted with Li Br to +Jzs-C== (
Knee C! C-CH2Br was obtained. The yield was 89%.

In the presence of NaH(7), EtooCCH, (:0
0Et was obtained. The yield was 59%.

This is LiAj! Reduce with H4, I got it. The yield was 80%.

This is MsCJ! react with I got it. The yield was 62%.

This was azidized using NaN3 to obtain. The yield was 88%.

This is reduced with LiA1)14, I got it. The yield was 51%.

This was reacted with Cu(CIO4).6H20 to obtain the desired product. The yield was 45%.

The molecular weight of the salt of the dinuclear complex obtained in this way can be determined by irradiating a sample of this salt with glycerol and coating it on a metal surface with fast neutral atoms.
When the mass spectrum was measured using the ment) method, an ion beak was observed at a mass number (m/z, m: mass, 2: charge number) of 760, and this value was determined by the binding force of the salt molecules of the dinuclear complex. It was confirmed that the value was the molecular ion peak in which weak H2O and two CIL- ions were desorbed and two H were added.

In addition, when the IR spectrum was measured using the KBr tablet method, the results were 2930 cm-1 and 2860 cm-1.
νcH at 1635 cm-', νCmN at 1560
C-C (skeletal vibration of aromatic ring) was observed at cm-'.

Next, when an electronic spectrum was measured using chloroform as a solvent, an absorption of iLogε=2.25 was observed at 667 nm, and an absorption of 1 loge=4.15 was observed at 365 nm.

The salt form of the dinuclear complex obtained as described above was confirmed to be the one described above.

[Example 2] The salt form of the dinuclear complex obtained in Example 1 and heptadeca-2,4-diyn-j-oh 7L/ as a matrix
(C12H25-C=C-CIC-CH20H), a mixed LB film was produced.

The mixing ratio of the above salt body and matrix is salt body: matrix = 1:2.5 ((b) in Figure 1), 1:5 ((C
)) and 1:15 (same (d)), and a surface pressure-area (π-A) curve was prepared using a surface membrane pressure meter manufactured by Kyowa Interface Science ■.

Chloroform was used as the developing solvent, and the mixture was developed on pure water at 3°C. Further, the compression speed was set to 20 mml.

The results are shown in Figure 1.

As shown in FIG. 1, increasing the matrix mixing ratio did not change the ultimate molecular occupied area, but a decrease in the collapse pressure was observed.

[Example 3] A cumulative film was produced using the LB film obtained in Example 2 with a mixing ratio of salt body: matrix = 1:5.

A glass substrate that had been hydrophobically treated with diphenyldichlorosilane was supported horizontally, and the monomolecular film was transferred by gently touching the monomolecular film surface from one end. This operation was repeated to obtain an X-type cumulative film with a cumulative ratio of 0.8.

[Example 4] LB membrane obtained in Example 2 (salt body: matrix = 1 =
5. Photopolymerization was performed by irradiating ultraviolet rays at a surface pressure of 25 mN/m at the time of preparation. A 10 W mercury lamp was used as a light source, and irradiation was performed for 10 minutes.

When we measured the absorption spectrum of this film, we found that (
As shown in a), an absorption peak of 465 nm derived from the conjugated main chain appeared, confirming photopolymerization. In addition, in Figure 2 (
a) is the absorption spectrum of the sample not irradiated with ultraviolet rays.

Further, photopolymerization was also possible in the other LB films of Example 2 and the cumulative film obtained in Example 3.

[Example 5] According to each of the above examples, a cumulative film and a photopolymerized cumulative film were formed on a NESA substrate, and cyclic portammetry was performed using the NESA substrate as a counter electrode in a solution using tetraethylammonium chloride as an electrolyte. As a result, the negative side showed yellow and the positive side showed green, confirming that each had an electrochromic function.

Furthermore, when absorption was measured by exposing these to visible polarized light in directions parallel and perpendicular to the average orientation direction of the molecular plane, anisotropy was confirmed, and the LB film and cumulative film of the present invention It was confirmed that the film had a regular molecular orientation, which was maintained as it was even after photopolymerization, and a highly robust functional film was realized.

[Brief explanation of drawings]

FIG. 1 is a graph representing a surface pressure-area curve. FIG. 2 is a graph showing wavelength and absorbance.

Claims (3)

[Claims] (1) A dinuclear complex or a salt thereof, characterized by being represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the above formula (I), Mt represents a transition metal, R_1
represents an alkylene group, and R_2, R_3 and R_4 represent an alkyl group. } (2) A Langmuir-Blodgett membrane characterized by containing a dinuclear complex represented by the following formula (I) or a salt thereof. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the above formula (I), Mt represents a transition metal, and R_1
represents an alkylene group, and R_2, R_3 and R_4 represent an alkyl group. } (3) A Langmuir-Blodgett film, which is obtained by photopolymerizing a Langmuir-Blodgett film containing a dinuclear complex represented by the following formula (I) or a salt thereof. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ {In the above formula (I), Mt represents a transition metal, and R_1
represents an alkylene group, and R_2, R_3 and R_4 represent an alkyl group. }