JP2000086684A - New oligoferrocenylene derivative and production of thin film of electrochemically active cluster - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a new alkanethiol derivative of biffarrocene, capable of facilitating the control of a film thickness, excellent in reproducibility, and useful for production of electron device such as a single electron element at a low cost by a simple process. SOLUTION: This oligoferrocenylene derivative is a compound of formula I or II [(n) is 1-17], e.g. 8-biferrocenyloctanethiol-8-one. The compound of formula I or II is obtained, for example, by reacting a compound of formula III with an acid chloride of the formula Br(CH2)nCOCl in the presence of aluminum chloride to provide a compound of formula IV, refluxing the obtained compound of formula IV with thiourea of the formula CS(NH2)2 in ethanol, adding a diluted aqueous solution of NaOH to the refluxed mixture, and further refluxing the mixture with the added NaOH. A metal cluster having the surface chemically modified with the oligoferrocenylene is preferably prepared by reacting a metal cluster having a alkanethiol as a dispersion stabilizer with the alkanethiol derivative of the oligoferrocenylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the synthesis of a novel alkanethiol derivative of oligoferrosenylene, a method for electrochemically producing a nm-sized cluster thin film, and its application to a quantum effect device.

[0002]

2. Description of the Related Art Generally, beyond the size of atoms and molecules,
Particles with sizes up to several hundred nm are called mesoscopic sized particles. Among mesoscopic particles, particles having a small particle size are sometimes referred to as clusters, and large particles are sometimes referred to as ultrafine particles (Yoichi Kurokawa, Keiichiro Suzuki, coloring materials, 1995, 71 (5), 322-327).
There is no clear definition for its size. Therefore, in the present invention, “cluster” is defined as fine particles having a particle size on the order of nm (from about 1 nm to several hundred nm).

[0003] Methods for producing metal-containing mesoscopic particles (clusters and ultrafine particles) are roughly classified into physical methods and chemical methods. Physical methods include gas evaporation method,
Examples include a sputtering method, a metal vapor synthesis method, and a vacuum evaporation method on fluid oil. As a chemical method, a liquid phase method such as a colloid method in which a metal salt is reduced in the presence of a dispersion stabilizer, an alkoxide method using hydrolysis of a metal alkoxide, and a coprecipitation method in which a precipitant is added to a mixed solution of a metal salt. Gas phase methods such as thermal decomposition of organometallic compounds, reduction / oxidation / nitridation of metal chlorides, reduction in hydrogen, and solvent evaporation.

[0004] In mesoscopic particles such as metals, metal oxides, and semiconductors, characteristics different from ordinary particles having a particle size of the order of μm or more appear. It is said that this is due to an increase in specific surface area, an increase in the influence of surface energy, a quantum size effect, and the like.
The appearance of unique catalytic properties and the appearance of electronic properties, optical properties, magnetism, etc., which were not found in bulk, have been reported. In the case where a cluster of a metal or a semiconductor having such a unique property is to be made into a device, the thin-film forming technology naturally becomes very important. Several methods have been reported so far for producing cluster thin films.

[0005] JP-A-7-310107, MTReet
z et al., J. Am. Chem. Soc., 1994, 116, 7401-7402, MTRe
etz et al., Chem. Mater., 1995, 7, 227-228, MTReetze
t al., Angew.Chem.Int.Ed., 1995,34, No.20,2240-2241,
MTReetz et al., Science, 1995, 267, 367-369, MTRee
tz et al., J. Chem. Soc. Chem. Commun., 1997, 147-148, describe Pd, Pt, Rh, Ru, stabilized with tetraalkylammonium bromide using electrochemical methods.
A method of adjusting a metal cluster composed of one or two metals such as Mo, Ni, Co, Cu, Au, and Ag is disclosed. These metal clusters are soluble in an organic solvent, and a cluster thin film can be obtained by an appropriate coating method such as a spin coating method. In fact, the above-mentioned JP-A-7-3
No. 10107 discloses a method in which a cluster (colloid) is electrophoresed by applying a voltage of 30 V to a distance between electrodes of 6 mm using platinum as a cathode and graphite as an anode to form a cluster thin film on a graphite electrode. Is described.

M. Brust et al., J. Chem. Soc. Chem. Commu
n., 1994, 801-802, M. Brust et al., Adv. Mater., 1995, 7,
795-797, RWMurray et al., J. Am. Chem. Soc., 1995, 11
In 7,12537-12548, a method of synthesizing a gold cluster using alkanethiol as a stabilizer, a method of synthesizing a gold cluster using alkanedithiol as a cross-linking stabilizer, and forming a gold cluster thin film on a comb electrode by a casting method The law is described.

[0007] T. Vossmeyer et al, .Angew.Chem.Int.Ed.E
In ngl., 1997, 36, 1080-1082, a gold cluster stabilized with 12-aminododecane is laminated on a glass or silicon substrate according to the light pattern using a special reagent called nitroveratryloxycarbonylglycine. A method is described.

G. Schmid et al., Angew. Chem. Int. Ed. Eng.
l., 1995, 34, 1442-1443, G. Schmid et al., Adv. Mater., 19
98, 10, 515-526, G. Schmid et al., J. Chem. Soc. Chem. Com.
mun., 1995, 31-32, a method of preparing metal clusters such as Ni, Au, Pd, Pt, and Rh using stabilizing triphenylphosphine as well as one-dimensional, two-dimensional, A method for three-dimensionally arranging is described.

P. Mulvaney et al., J. Phys. Chem., 1993, 9
7,6334-6336 describes a method for depositing gold clusters stabilized by citrate ions on electrodes by electrophoresis. JHFendler et al., J. Phys. Chem.,
1995,99,13065-13069 use C
A method of laminating clusters of dS, PbS, and TiO _{2 on} a layer-by-layer basis is described. G. Decher et
al., Adv. Mater., 1997, 9, 61-65, reported that a gold cluster stabilized with citrate ions was layered on a polyethyleneimine substrate using polyallylamine hydrochloride and sodium polystyrene sulfonate. Is described. T. Kunitake et al.,
Chem. Lett., 1997, 125-126 describes the use of polydiallyldimethylammonium chloride as a polycation.
A method of laminating iO ₂ clusters layer by layer is described. R. Claus et al., J. Phys. Chem., 19
97, 101, 1385-1388 describe a method of laminating TiO ₂ clusters layer by layer using sodium polystyrene sulfonate.

X. Zhang et al., Adv. Mater., 1998, 10, 529-
No. 532 describes that a composite of a Cu ₂ S cluster / polystyrene sulfonic acid complex and polyvinyl pyridine can be obtained by laminating copper polystyrene sulfonate and polyvinyl pyridine in a layer-by-layer manner and then reacting with hydrogen sulfide. Have been. MJNatan et
al., Science, 1995, 267, 1629-1632 describes a method for obtaining an electrochemically active Au or Ag cluster thin film. That is, a conductive substrate (platinum) surface-treated with 3-mercaptopropyltrimethoxysilane in the case of gold and 3-aminopropyltrimethoxysilane in the case of silver is immersed in a cluster solution of Au or Ag. The thin film electrode composed of the cluster thin film / surface treatment agent layer / conductive substrate serves as an electrochemically active electrode, and the thin film electrode having only the surface treatment layer / conductive substrate without the cluster thin film does not serve as an electrode. It is described. JRHeath et al., Angew.Chem.Int.Ed.E
ngl., 1997, 36, 1078-1080, describes a method of arranging Ag clusters stabilized with dodecanethiol in a ring shape by utilizing its self-assembly function. CNR
Rao et al., J. Chem. Soc. Chem. Commun., 1997, 537-538 discloses a thin film of Au, Pt, and Ag clusters stabilized with alkanethiol obtained by drop-drying a toluene solution. Forming superstructures is described. T.Kunitake
et al., Adv. Mater., 1998, 10, 414-416, describe dense electrostatic adsorption of citrate-stabilized gold clusters on bilayer membranes.

As an application of the cluster thin film, the Coulomb Blokade Phenomena (Tunnel junction having a very small capacitance (C)) has an electrostatic energy (e ² / C) changes,
A phenomenon in which the tunnel effect is suppressed under the condition of k _B T≪e ² / C. Experimentally, in the measurement of current-voltage characteristics between electrodes, a step-like change based on the transfer of a single electron (Coulomb steer case) : Coulomb staircase) is observed; cf .; H. Gr
abert and MHDevorret `` Singlee Charge Tunneling, C
oulomb Blokade Phenomena in Nanostructures '' Plenu
m, NY, 1992., I. Giaever and HRZeller, Phys. Rev. Le
tt., 1968, 20, 1504., TAFulton and GJDolan, Phys.
Rev. Lett., 1981, 59, 109., M. Amman, SBField, and R.
C. Jaklevic, Phys. Rev. Bull. 1993, 48, 12104).

Japanese Patent No. 2,650,280 discloses that
An island-shaped thin film element (detection element) using a Pt-Pd cluster formed by a sputtering method is disclosed. Japanese Patent Application Laid-Open No. 9-69630 discloses that Au, Cd, Se, Ag, Cu, Pd,
A single electron tunnel device using a cluster such as Pt is disclosed. Japanese Patent Application Laid-Open No. 7-226522 discloses that silver clusters obtained by reducing silver nitrate or gold clusters obtained by reducing chloroauric acid with citric acid are arranged one by one using an atomic force microscope. There has been disclosed a method for producing a single electronic device by adsorbing a monomolecular layer or several molecular layers over the substrate, or arranging the substrate using self-organizing ability caused by wettability of a substrate.
Furthermore, Japanese Patent Application Laid-Open No. 9-275214 describes a micro charge control element in which gold clusters stabilized by alkanethiol are arranged between source and drain by Coulomb force.

Further, M. Amman et al., Phys. Rev. B, 1993, 4
8,12104-12109 reports the observation of the Coulomb blockade phenomenon of an island-shaped gold cluster formed by a vacuum evaporation method using a scanning tunneling microscope. M. Dorogi et al.,
Phys. Rev. B, 1995, 52, 9071-9077 and CPKubiak et a
l., Science, 1996, 272, 1323-1325, describe a self-assembled mono-assembly of p-xylene-α, α'-dithiol chemically adsorbed on a gold substrate using a gold cluster produced by a gas phase method as a molecular beam. It has been reported that a Coulomb blockade phenomenon was observed at room temperature using a scanning tunneling microscope by chemisorption on a molecular film. RPAndres et al., Scienc
e, 1996, 273, 1690-1693, describe that gold clusters cross-linked with dithiol or diisonitrile form a self-assembled monolayer, and that the current-voltage characteristics of this cross-linked self-assembled monolayer have a nonlinear response. It has been reported that MJNatan et al., J. Am. Chem. Soc., 1996, 118, 7640-
7641 includes metal (gold) / insulator thin film (composite of layered compound and polymer electrolyte) / nano cluster thin film (particle size 2.
MINIM (Metal-Insula) consisting of 5 nm citric acid-stabilized gold cluster) / insulator thin film (composite of layered compound and polymer electrolyte) / conductive layer (polypyrrole)
It has been reported that a tor-Nanocluster-Insulator-Metal) device was fabricated and the Coulomb blockade phenomenon was observed. Here, zirconium phosphate is used as the layered compound, polyacrylamine hydrochloride is used as the polymer electrolyte, the gold cluster thin film is prepared by an immersion method, and the polypyrrole film is a gas phase polymerization method using ferric chloride as a catalyst. It is made with.

As an application of the cluster thin film, an application to a field emission element (FED) can be considered. FE
Regarding D, Japanese Patent Publication No. 7-97473, M. Hartwe
ll et al., IEEE Trans.ED Conf., 1975, 519-521 and G.
Dittmer, Thin Solid Films, 1972, 9, 317-328.

Further, although not directly related to the cluster thin film, as for device fabrication technology,
Method for forming electrochemically active polymer thin films on electrodes with submicron order size and method for forming electrochemically active polymer thin films between electrodes with submicron to nm order spacing About MSWrighton et
al., J. Am. Chem. Soc., 1984, 106, 5375-5377, MSWrighto
n et al., J. Am. Chem. Soc., 1987, 109, 5226-5228, MSWr
ighton et al., Chem. Mater., 1993, 5, 914-916 and the like. Attempts to construct three-dimensional wiring using electropolymerization of conductive polymers with molecular devices and neurodevices in mind have been reported by MJSailor et al., Sc
ience, 1993,262,2014-2016, MJSailor et al., Adv.Ma
ter., 1994, 6,688-692, Yoshino et al., Synth. Met., 199
5,71,2223-2224. In addition, as for wiring by an electrochemical method, an example utilizing electrochemical crystal growth of an electrified transfer complex (MJSailor et al., Adv.
Mater., 1996, 8, 897-899) and one that enables three-dimensional wiring between metal particles using induced polarization without connection to external circuits (JCBradley et al., Nature, 1997, 389, 26
8,270).

The above-mentioned various methods for producing a cluster thin film are as follows.
In terms of applications, especially for electronic devices, it is hardly satisfactory. For example, in the case of a physical method (gas phase method) such as a sputtering method, the size of the apparatus increases,
It has disadvantages such as low productivity, difficulty in controlling the film thickness, and difficulty in obtaining a patterned thin film. Regarding chemical methods, for example, the spin coating method and the casting method are difficult to control the film thickness with excellent reproducibility, and when it is desired to selectively thin the film only on the electrode or between the electrodes, an extra thin film is etched or the like. Need a process to remove.

In addition, the electrophoresis method requires the use of an electrochemically stable solvent, cannot be applied to an uncharged cluster, and has a film thickness because the obtained thin film is not electrochemically active. Are difficult to control, the time required to form a thin film is long, and it is difficult to grow a thin film between electrodes.

Furthermore, the photochemical method using nitroveratryloxycarbonylglycine requires a uniform and high-precision exposure means, forms an amino group on the substrate surface using a suitable silane coupling agent or the like. Since the process of forming a photochemically active thin film by the reaction between the amino group of the lever and the carboxyl group of nitroveratryloxycarbonylglycine is employed, a cluster thin film cannot be formed directly on or between the electrodes. Further, it has disadvantages such as complicating the process.

[0019]

In view of the above, it is an object of the present invention to provide a low cost, simple process, and a film thickness suitable for manufacturing an electronic device such as a single electronic device. In addition to providing a cluster thin film preparation method that is easy to control, has excellent reproducibility, and can selectively form a thin film on or between electrodes, it also provides compounds necessary for the preparation method and methods for synthesizing the same. To provide.

[0020]

In order to solve the above problems, the present inventors have developed a novel method for electrochemically producing a cluster thin film of nm size. That is, by reacting a cluster stabilized by a dispersion stabilizer with an oligoferrosenylene derivative, a cluster whose surface is chemically modified with oligoferrosenylene is obtained, and this is electrochemically oxidized to form an electrode. While developing a method to fabricate a cluster thin film on or near the electrode,
We have found a new method for synthesizing the above-mentioned oligoferrosenylene derivatives. The biferrocene alkanethiol derivative (I) of the general formula (I) of the present invention is synthesized by the reaction represented by the reaction formula (1).

[0021]

Embedded image

The alkanethiol derivative of terferrocene of the general formula (II) is synthesized according to the reaction formula (2).

[0023]

Embedded image

[0024] In the above reaction formula (1) and (2), Bu ⁿ Li is n
-Butyl lithium (lithiation agent), TMEDA is N, N, N ', N'
- tetramethylethylenediamine (stabilizer lithium compounds), Bu ⁿ ₂ O represents each n- butyl ether (mainly solvent). As shown in the reaction formulas (1) and (2), oligoferrocene as a raw material of the novel oligoferrosenylene derivative in the present invention is synthesized from ferrocene and iodinated ferrocedenirinine. , EWNeuse, L. Bednarik, Macromolecules, 1979, 1
2,187, and Polymer Complex Study Group, Shinei Hagiwara, Akira Nakamura "Polymer Complex-Function and Application-Series 4
It is described in detail in "Organometallic Complex".

It is known that alkanethiol derivatives can stabilize not only Au but also at least Ag, Cu, Pt, Fe ₂ O _{3 and the} like. Therefore, at least Au, Ag, Cu, Pt, and Fe ₂ are used for clusters whose surfaces are chemically modified with oligoferrosenylene.
O ₃ can be produced.

As the dispersion stabilizer, in addition to the alkanethiol derivative, tetraalkylammonium bromide,
Tetraalkylphosphonium promide, 3- (dimethyldodecylammonio) propanesulfonate, carboxylic acid derivatives and the like are also effective. By these dispersion stabilizers, Au, Ag, Cu, Pt, Pb, Rh, Ru, M
o, Ni, Co, Hg, Fe ₂ O ₃ , Al ₂ O ₃ , Ag
Clusters such as ₂ O, In ₂ O ₃ , and SnO ₂ can be produced.

As the electrode material, any electrochemically stable conductor can be used. Depending on the purpose, the electrode may be a single conductor, or may be an electrode patterned on glass, plastic, a silicon substrate having an oxidized surface, or the like. As the solvent, any of those commonly used in electrochemistry can be used. For example, tetrahydrofuran, acetonitrile, dichloromethane, dimethoxyethane, propylene carbonate, water, chloroform and the like.

As the electrolyte, any of those commonly used in electrochemistry can be used. For example, examples of the supporting electrolyte cation include a tetraalkylammonium ion, an alkali metal ion, and a tetraalkylphosphonium ion. Examples of the anion include a halogen ion, a hexafluorophosphate ion, a carboxylate ion, and a tetrafluoroborate ion.

Next, the basic concept of the present invention will be described for a case where a gold cluster having a diameter of 4 nm using octanethiol as a dispersion stabilizer is modified with an alkanethiol derivative of biferrocenylene. As shown in the following reaction formula (3), the gold cluster stabilized by octanethiol can be obtained by the method described in M. Brust et al., J. Chem. Soc. Chem. Com.
mun., 1994, 801-802, RWMurray et al., J. Am. Chem. So
c., 1995, 117, 12537-12548, that is, a method of reducing gold ions in the presence of octanethiol. The diameter of the core part (fine gold particles) of the gold cluster is about 2 nm, and the thickness of the shell (octanethiol) is about 1 nm.

[0030]

Embedded image

In the above formula (3), “-Fc-Fc” represents a biferrocene skeleton, and N (C ₈ H ₁₇ ) ₄ Br represents an onium ion as a hydrophilic group and a long-chain alkyl as a hydrophobic group. As a surfactant having a group and forming a micelle, NaBH is used as a reducing agent, and C ₈ H ₁₇ SH is used as an addition reactant with gold particles reduced by NaBH. The gold cluster (1) thus obtained ((Au) m (C ₈ H
₁₇ S) n) is stable in both a powder state and a dispersed state. Disperse the obtained gold cluster powder in a suitable solvent,
Alkanethiol derivative of biferrosenylene represented by the general formula (I) (n = 7) (FcFcCO (CH ₂ ) ₇ SH)
By reacting with, a gold cluster (2) whose surface is chemically modified with oligoferrosenylene can be produced. Similarly, in the case of terferocenylene, a gold cluster (3) chemically modified with terferocenylene can be prepared as shown by the reaction formula (4).

[0032]

Embedded image

[0033]

Embedded image

This gold cluster (3) can be stably extracted similarly to the case of the gold cluster (2), and has a diameter of about 6 nm. From the NMR (nuclear magnetic resonance spectroscopy) spectrum, in this case, the ratio of the alkanethiol derivative of terferrosenylene to octanethiol is 1:15 to 15.
It turns out that it is 20. The gold cluster thus obtained, the surface of which has been chemically modified with oligoferrosenylene, is combined with a suitable electrolyte (in this case, 0.1 M Bu ₄ NC).
By dissolving it in 10 ₄ —CH ₂ Cl ₂ ) and causing an electrochemical reaction, a gold cluster thin film can be deposited on the electrode. According to this method, a cluster thin film can be easily formed on or near an electrode at low cost, with good controllability and reproducibility.

For example, this method is described in Japanese Patent No.
When applied to the island-shaped thin film element described in JP-A-650280 or the single-electron element described in JP-A-7-226522, first, the electrode between the electrodes on which the cluster thin film is to be formed is made electrochemically of the thin film. There is a method in which a cluster thin film is grown from one electrode to the other electrode by maintaining the potential at which growth can occur, and finally both electrodes are joined by the cluster thin film. Second, the aforementioned MSWrighton et
As described in al., J. Am. Chem. Soc., 1984, 106, 5375-5377, the two microelectrodes to be bonded are kept at the same potential, and the cluster thin film is electrically connected on and between the electrodes. There is a method of growing it chemically. In addition, the present invention is not limited to the case of using an orogoferosenylene derivative, and a cluster whose surface is chemically modified with an electrochemically active reactive group is synthesized from a cluster stabilized by a dispersion stabilizer, Obviously, the method can be extended to a more general method of forming a cluster thin film on an electrode by a chemical reaction.

[0036]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Example 1 (see Reaction Scheme 1) Synthesis of 8-biferrocenyloctanethiol-8-one (Compound I; n = 7) Under an Ar atmosphere, 325 mg of AlCl ₃ (2.43 mm)
ol) dissolved in 600 μl of dehydrated CH ₂ Cl ₂ , and 587 μl (2.43 mmol) of Br (CH ₂ ) ₇ COCl was added thereto.
l) It was added dropwise. This solution was slowly added dropwise to a solution of 900 mg (2.43 mmol) of biferrocene in CH ₂ Cl ₂ (30 ml) under a nitrogen atmosphere over 1 hour. After stirring at room temperature for 12 hours, the mixture was degassed and poured into ice-cooled distilled water. After transferring to a separatory funnel and washing well with water, a brown organic layer was taken out, dried over Na ₂ SO ₄ , and the solvent was distilled off. Br
Since a disubstituted substance is contained in addition to the monosubstituted (CH ₂ ) ₇ CO, fractionation is carried out using HPLC and FcFcCO (C
H ₂ ) ₇ Br was obtained. Yield 186.2 mg (0.324 m
mol). Yield 13.3%. FcFcC under nitrogen atmosphere
118.6 mg of O (CH ₂ ) ₇ Br (0.206 mmol)
l) Dissolve in 15 ml of ethanol and add 15.7 of thiourea
mg (0.206 mmol) was added and refluxed for 40 hours. Further, degassed 0.021 M NaOHaq was added to 20
Then, the mixture was refluxed for 8 hours. The product was separated by silica gel column chromatography using CHCl ₃ as a solvent, and the desired product FcFcCO (CH ₂ ) ₇
SH was collected. Yield 59.3 mg (0.112 mmol
l). Yield 54.5%. Elemental analysis: Calcd. C, 63.41%; H, 6.46%. Found C, 60.64%; H, 6.61%. ¹ HNMR (FIG. 1) Similarly, instead of Br (CH ₂ ) ₇ COCl, Br (C
By using H ₂ ) nCOCl, other alkanethiol derivatives of biferrocene can also be synthesized.

[0037] Example 2 8-ether ferrocenyl Octanethiol-8-one (Compound II; n = 7) Synthesis Ar atmosphere, the AlCl ₃ 1
200 μl of 11 mg (0.83 mmol) CH ₂ Cl ₂
In 200 μl of Br (CH ₂ ) ₇ COCl.
(0.83 mmol) was added dropwise. 13 of this solution
0 μl (0.27 mmol) of terferrocene 150 mg (0.27 mmol) of dehydrated CH ₂
The solution was slowly dropped into a Cl ₂ solution (13 ml) over 1 hour. After stirring at room temperature for 12 hours, the reaction solution was released to the atmosphere and poured into 50 ml of ice-cooled distilled water. The mixture was washed well with water using a separating funnel, and a brown organic layer was taken out. After drying over Na ₂ SO ₄
The solvent was distilled off. The residue was subjected to silica gel column chromatography using CHCl ₃ as a solvent, and the second band was collected. Further, this was converted to CHCl ₃ : hexane =
3: 2 solution TLC plate (silica gel, thickness 0.5
mm), the second band was collected. Orange powder [FcF
was obtained _{cFcCO (CH 2) 7 Br]} . yield 8.3
mg (4.1%). FcFcFcCO under nitrogen atmosphere
1.7 mg of thiourea was added to an ethanol solution (1.5 ml) of 16.4 mg (0.022 mmol) of (CH ₂ ) ₇ Br.
(0.022 mol) and refluxed for 24 hours. TL
C (silica gel) was used to confirm the disappearance of the raw materials, and degassed.
2.0 ml of 022M NaOHaq (0.044 mm
ol) and refluxed for 8 hours. After evaporating the solvent, CHCl
₃ extracted and separated by TLC plates with CHCl ₃ and solvent (silica gel, thickness 0.5 mm). 1st band red oil [FcFcFcCO (CH ₂ ) ₇ S
H] 10.1 mg (64.1%) yield. 2nd band red oil [(FcFcFcCO (CH ₂ ) ₇ )
₂ S] yield 5.5 mg (35.1%). ¹ HNMR (FIG. 2) Similarly, instead of Br (CH ₂ ) ₇ COCl, Br (C
By using H ₂ ) nCOCl, other alkanethiol derivatives of terferrocene can also be synthesized.

Example 3 FcFcFcCO (CH ₂ ) ₇ SH (Compound II (n = 7))
The gold disk electrode was immersed in an ethanol solution of the above to form a self-assembled film. From the immersion time dependence of the surface concentration, 1
The saturated adsorption amount is reached in 6 hours, and the surface concentration at that time is 2.
It was 3 × 10 ⁻¹⁰ molcm ⁻² . 0.1 of this electrode
In M Bu ₄ NClO ₄ cyclic voltammograms at in CH ₂ Cl ₂ (CV), but one-electron oxidation wave of reversible three stages appeared (Fig. 3), one-electron oxidation of 2 stages in 1N HClO ₄ aqueous solution Shows only a wave (FIG. 4: 0.1 Vs
^-1 ), suggesting that the aggregation state has a large effect on electron transfer. In place of the gold disk electrode of this embodiment, Ag or C
Even if an electrode u is used, an electrochemically active electrode can be produced in the same manner.

Example 4 The aforementioned RWMurray et al., J. Am. Chem. Soc., 1995, 117, 12
According to the method described in No. 537-12548, a gold cluster using octanethiol as a dispersion stabilizer (1) [(Au) m
(C ₈ H ₁₇ S) n] was synthesized. The diameter of the core of the gold cluster was about 2 nm, and the diameter of the entire cluster including the shell was about 4 nm.

Example 5 Biferrocene terminal-modified thiol ligand gold cluster (Gol
d cluster (2)) 0.203 g of (Au) m (C ₈ H ₁₇ S) n was added to a sample tube,
Further, 40.0 mg of FcFcCO (CH ₂ ) ₇ SH was added, dissolved in 1.0 ml of toluene, and stirred for 48 hours. This was poured into 300 ml of ethanol and left in a freezer (−17 ° C.) overnight. The colloid was filtered off with a membrane filter and washed well with ethanol. CH ₂ on filter paper
The target cluster (Au) m (C ₈ H ₁₇ S) n (FcFc) was dissolved in a Cl ₂ solution and the solvent was distilled off.
CO (CH ₂ ) ₇ SH) l was obtained. Yield 0.190 g (2.
71 × 10 ⁻³ mmol). 85.0% yield. Elemental analysis: Calculated C, 16.90%; H, 2.48%. Found C, 16.92%; H, 2.26%. (Octanethiol 75, Biferrocentiol 20 /
¹ HNMR (Fig. 5)

Example 6 Synthesis of terferrocene terminal-modified thiol ligand gold cluster In a 50 ml eggplant flask, 2 (Au) m (C ₈ H ₁₇ S) n were added.
8.1 mg (3.77 × 10 ⁻⁴ mmol) and Fc
6.3 mg of FcFcCO (CH ₂ ) ₇ SH (8.85 × 1
0 ^-4 mmol), and dissolved in 14 ml of toluene.
Stirred for 24 hours. This was poured into 100 ml of ethanol and left overnight in a freezer (−17 ° C.). The colloid was filtered off with a membrane filter and washed well with ethanol. The filter paper is dried and the desired cluster (A
_{u) m (C 8 H 17} S) n (FcFcFcCO (CH 2) 7 SH)
1 was obtained. If m = 309 and n = 95 (from literature)
From NMR, it was found that 1 = 5.6. Yield 2
6.3 mg (3.39 × 10 ⁻⁴ mmol). Yield 90.
0%.

Example 7 In Example 6, instead of the gold cluster using octanethiol as a dispersion stabilizer, the above-mentioned CNRRao et al.
Commun., 1997, 537-538 described in al., J. Chem. Soc. Chem. Commun., by reacting compound II (n = 11) with a silver cluster using dodecanethiol as a dispersion stabilizer. Similarly, silver clusters modified with terferrosenylene were obtained.

Example 8 4.5 μM of the gold cluster surface-modified with biphenylenenylene obtained in Example 5 was combined with 0.1 M Bu ₄ NCl
It was dissolved in CH ₂ Cl ₂ together with O ₄ , and the CV of this solution at a glassy carbon (GC) electrode was measured (FIG. 6).
The formal potential was about the same as the free biferrosenylene derivative. In the first sweep, a two-stage reversible wave appears due to the oxidation of biferrosenylene, but it was found that by repeating the sweep, gold clusters were deposited on the electrodes, and eventually a broad reversible wave with no structure was found. . Incidentally, in the case of a gold cluster surface-modified with a ferrocene monomer, no stacking of the gold cluster on the electrode was observed.

Example 9 4.5 μM of the terferrosenylene-modified gold cluster obtained in Example 6 was combined with 0.1 M Bu ₄ NCl
It was dissolved in CH ₂ Cl ₂ together with O ₄ , and the CV of this solution at a glassy carbon (GC) electrode was measured (FIG. 7).
The formal potential was almost the same as the free terferrosenylene derivative. In the first sweep, three-stage reversible waves appear due to the oxidation of terferrosenylene, but by repeating the sweep, gold clusters are deposited on the electrodes, and finally 2
It turned out to be a reversible wave of steps. A similar result is the IT
It was also obtained by CV measurement using an O electrode.

Example 10 A single electronic device as shown in FIG. 8 was manufactured. That is, an oxide film having a thickness of 10 nm is provided on a conductive silicon substrate, and gold electrodes (1) and (2) are provided on the oxide film. The distance between the electrodes was 100 nm. This electrode substrate was used in Example 9
The gold electrode (1) was immersed in the electrolytic solution of the gold cluster surface-modified with terferrosenylene used in (1), and the gold electrode (1) was set at 0.8 V
s. Ag / Ag ⁺ , the gold electrode (2) was set to 0 V vs. Ag / A
The electrode reaction is performed with g ⁺ . The gold cluster grows from the gold electrode (1) toward the gold electrode (2), and finally both electrodes are joined by the gold cluster. In this way, by using the method for electrochemically producing a gold cluster thin film according to the present invention, a single electronic device can be produced very easily.

Example 11 In Example 10, the distance between the electrodes was set to 50 nm, the gold electrode (1) and the gold electrode (2) were joined by external wiring, and the potential of the counter electrode (platinum electrode) was set to 0 V vs. 0 V. Ag / Ag ⁺ ,
The potential of the gold electrode (working electrode) is set to 0.8 V vs. Ag / Ag ⁺
Then, a gold cluster thin film is deposited. Electrode (1)
And the electrode (2) are sufficiently close to each other, and as a result, the gold cluster thin film is uniformly deposited on and between the gold electrodes, so that a single electronic device as shown in FIG. 9 can be manufactured. it can.

[0047]

As described above, the present invention provides a novel oligoferrocenylene alkanethiol derivative, its synthesis, and an electrochemically active electrode using the novel compound. Of metal clusters, synthesis of new metal clusters, electrochemically active metal cluster thin films using these new clusters, and methods for their preparation, and application of the manufactured metal cluster thin films to quantum effect devices It is to be.

[Brief description of the drawings]

[1] FcFcCO of the present invention (CH _{2) 7} SH of ¹ HNM
FIG. 3 is a diagram (Example 1) showing an R spectrum.

FIG. 2 shows ¹ H of FcFcFcCO (CH ₂ ) ₇ SH of the present invention.
FIG. 4 is a diagram showing an NMR spectrum (Example 2).

FIG. 3 shows a 0.1 M Bu ₄ NCl of a self-assembled film of FcFcFcCO (CH ₂ ) ₇ SH of the present invention on a gold disk electrode.
FIG. 10 is a diagram showing a cyclic voltammogram with an O ₄ CH ₂ Cl ₂ solution (Example 3).

FIG. 4 is a view showing a cyclic voltammogram of a self-assembled film of FcFcFcCO (CH ₂ ) ₇ SH of the present invention on a gold disk electrode in a 1N HClO ₄ aqueous solution (Example 3).

FIG. 5 is a diagram (Example 5) showing a ¹ H NMR spectrum (CH ₂ Cl ₂ solution) of the gold cluster (2) of the present invention.

FIG. 6 is a cyclic voltammogram (0.1 M Bu ₄ NCLO ₄ CH ₂ Cl ₂ ) of the gold cluster (2) of the present invention.
FIG. 15 is a diagram (Example 8) showing a glassy carbon disk electrode).

FIG. 7 is a cyclic voltammogram (0.1 M Bu ₄ NCLO ₄ CH ₂ Cl ₂ ) of the gold cluster (3) of the present invention.
FIG. 15 is a view showing a glassy carbon disk electrode) (Example 9).

FIG. 8 is a diagram showing a single electronic device manufactured on a conductive silicon substrate (Example 10).

FIG. 9 is a diagram showing a single electronic device manufactured on a conductive silicon substrate (Example 11).

[Explanation of symbols]

 Reference Signs List 1 gold electrode (1) 2 gold electrode (2) 3 gold cluster 4 silicon oxide film 5 conductive silicon substrate

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kenya Kubo 7-3-1 Hongo, Bunkyo-ku, Tokyo Department of Chemistry, Graduate School of Science, Tokyo University (72) Inventor Masato Kurihara 7, Hongo, Bunkyo-ku, Tokyo 3-1, Chome, Department of Chemistry, Graduate School of Science, University of Tokyo (72) Inventor Hiroshi Nishihara 7-3-1, Hongo, Bunkyo-ku, Tokyo F-term, Department of Chemistry, Graduate School of Science, Tokyo University (Reference) 4H050 AA01 AA03 AB78 AB80 AB91 WB11 WB22 WB23

Claims (10)

[Claims] 1. An alkanethiol derivative of biferrocene represented by the following general formula (I). Embedded image 2. An alkanethiol derivative of terferrocene represented by the following general formula (II). Embedded image 3. An electrochemically active metal electrode chemically modified with the alkanethiol derivative of oligoferrosenylene according to claim 1 or 2. 4. An electrochemically active gold electrode chemically modified with the alkanethiol derivative of oligoferrosenylene according to claim 1 or 2. 5. A metal cluster obtained by using alkanethiol as a dispersion stabilizer and an alkanethiol derivative of oligoferrosenylene according to claim 1 or 2, wherein the surface is chemically treated with oligoferrosenylene. Modified metal cluster. 6. A method comprising reacting a gold cluster containing alkanethiol as a dispersion stabilizer with an alkanethiol derivative of oligoferrosenylene according to claim 1 or 2, wherein the surface is chemically treated with oligoferrosenylene. Qualified gold cluster. 7. An electrolysis comprising a cluster obtained by reacting a cluster stabilized by a dispersion stabilizer with an oligoferrosenylene derivative according to claim 1 or 2, the surface of which is chemically modified with oligoferrosenylene. A method of forming a cluster thin film on an electrode substrate by electrochemically oxidizing a liquid. 8. The electrochemically active gold cluster thin film according to claim 6, comprising a gold cluster whose surface is chemically modified with oligoferrosenylene. 9. A method for producing an electrochemically active gold cluster thin film from an electrolytic solution comprising a gold cluster whose surface is chemically modified with oligoferrosenylene, according to claim 6. 10. A quantum effect device using a cluster thin film produced by the method according to claim 7. Description: