JP5004656B2 - Single molecule transistors and fullerene derivatives used in single molecule transistors - Google Patents

Description

  The present invention relates to a single molecule transistor and a fullerene derivative used for the transistor. Specifically, the present invention relates to a fullerene derivative for a transistor having functions of a source, a drain, and a gate, and a transistor using the fullerene derivative.

Conventionally, as a device used for information processing, a transistor using a silicon semiconductor has been mainly used, and improvement in performance has been achieved by reducing a processing dimension of a gate or the like (Y. Wada , et. al., J. Appl. Phys., 74 (12), 7321 (1993). (Non-Patent Document 1)).
On the other hand, single-molecule transistors using one molecule have been studied in order to increase the functionality of the transistors. Specifically, single molecule transistor using fullerene C ₆₀ (Park, H .; Park, J .; Lim, AKL; Anderson, EH; Alivisatos, AP; McEuen, PL Nature 2000, 407, 57. (non-patent Reference 2)) has been reported.
However, when fullerene C ₆₀ is used in a single molecule transistor, the function as a transistor can be exhibited only when predetermined atoms constituting fullerene C ₆₀ are fixed to a source electrode, a drain electrode, a gate electrode, and the like. Thus, in the monomolecular transistor using fullerene C _60, so functions as only the transistor when the fullerene C ₆₀ is fixed in position in the electrode by chance, its production is difficult, is also unstable.
A single molecule transistor using a fullerene derivative in which an additional group is added to fullerene has also been reported (Japanese Patent Laid-Open No. 11-266007 (Patent Document 1)). However, the fullerene derivative used in the transistor disclosed in this document has a low function as a transistor, and further, it is difficult to synthesize a fullerene derivative, which increases the synthesis cost.
JP-A-11-266007 Y. Wada, et.al., J. Appl. Phys., 74 (12), 7321 (1993). Park, H .; Park, J .; Lim, AKL; Anderson, EH; Alivisatos, AP; McEuen, PL Nature 2000, 407, 57.

Under the above situation, for example, there is a demand for a monomolecular transistor that can exhibit a stable function or has a high function. For example, a single molecule transistor using a fullerene derivative that can be synthesized at low cost is desired.
Furthermore, for example, fullerene derivatives used in these single-molecule transistors are demanded.

The present inventors have found a fullerene C ₇₀ derivative bound with metal in place of the fullerene C _70, and completed the present invention based on this finding. The present invention provides the following fullerene C ₇₀ derivatives for unimolecular transistor like and monomolecular transistor or the like.

[1] The following formula (1), (21), (22), (31) or (32)
[In the above formula, each R ³ is independently an organic group;
R ⁴ is an organic group;
Each R ⁵ is independently an organic group;
Mtl is each independently a metal atom;
L are each independently a single bond, an alkylene good C ₁ -C ₁₀ which may have a substituent, it may have a alkenylene or substituent of C ₂ -C ₁₀ which may have a substituent Good C _{2 to} C ₁₀ alkynylene, in which any —CH ₂ — in the alkylene, alkenylene or alkynylene may be replaced by —O—, —S—, —COO—, —CO— or —OCO—. Well, in these alkylene, alkenylene or alkynylene, any hydrogen may be replaced with fluorine or chlorine;
m is each independently an integer of 0 to 5;
q is each independently an integer of 0 to 4;
n is an integer from 0 to 4;
Ar independently represents the following formula (A)
(In formula (A), each R ¹ is independently a C ₁ -C ₅ alkyl group,
Each R ² is independently a C ₁ -C ₅ alkyl group;
p is an integer of 0-4. )
It is group represented by these. ]
Having a partial structure represented in, fullerene C ₇₀ derivatives for monomolecular transistor.
[2] In the above formulas (1), (21), (22), (31) and (32),
Each R ³ is independently a C ₁ -C ₅ alkyl group;
R ⁴ is a C ₁ -C ₅ alkyl group;
Each R ⁵ is independently a C ₁ -C ₅ alkyl group;
Each of Mtl is independently Fe or Ru;
L are each independently a single bond, an alkylene good C ₁ -C ₅ may have a substituent, an alkenylene good C ₂ -C ₅ may have a substituent, which may have a substituent Good C ₂ -C ₅ alkynylene or optionally substituted C ₆ -C ₃₀ phenylene, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —S -, -COO-, -CO- or -OCO- may be replaced, and in these alkylene, alkenylene, alkynylene or phenylene, any hydrogen may be replaced by fluorine or chlorine;
m is each independently an integer of 0 to 5;
q is each independently an integer of 0 to 4;
n is an integer from 0 to 2;
In formula (A),
Each R ¹ is independently a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer from 0 to 2,
Fullerene C ₇₀ derivatives for monomolecular transistor according to [1].

[3] The following formula (1)
[In the above formula,
Each R ³ is independently a C ₁ -C ₂ alkyl group;
R ⁴ is a C ₁ -C ₃ alkyl group;
Each R ⁵ is independently a C ₁ -C ₅ alkyl group;
Each of Mtl is independently Fe or Ru;
L is a single bond, C ₁ -C ₅ alkylene which may have a substituent, C ₂ -C ₅ alkenylene which may have a substituent, or C ₂ -C which may have a substituent. ₅ alkenylene or C ₆ -C ₃₀ phenylene which may have a substituent, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each m is independently 0 or 5;
n is an integer from 0 to 2;
In formula (A),
Each R ¹ is independently a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer from 0 to 2,
Ar independently represents the following formula (A)
(In formula (A), R ¹ is a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer of 0-2. )
It is group represented by these. ]
A fullerene C ₇₀ derivative for a single molecule transistor having a partial structure represented by:
Two groups having Mtl, appended to the fullerene C ₇₀ is the source terminal and the drain terminal, respectively, a group having a ferrocene are added to the fullerene C ₇₀ is a gate terminal, fullerene C ₇₀ for monomolecular transistor Derivative.
The fullerene C ₇₀ derivatives, for example, is preferably used in the monomolecular transistor having electrochemical gate terminal.
[4] according to [3], a monomolecular transistor including a fullerene C ₇₀ derivatives for monomolecular transistor,
In the above formula (1),
Each R ³ is independently methyl or ethyl;
R ⁴ is methyl or ethyl;
Each R ⁵ is independently methyl or ethyl;
Each of Mtl is independently Fe or Ru;
L is a single bond, C ₁ -C ₅ alkylene which may have a substituent, C ₂ -C ₅ alkenylene which may have a substituent, or C ₂ -C which may have a substituent. ₅ alkenylene or C ₆ -C ₃₀ phenylene which may have a substituent, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each m is independently 0 or 5;
n is an integer from 0 to 2;
In formula (A),
Each R ¹ is independently methyl or ethyl;
Each R ² is independently methyl or ethyl;
p is an integer from 0 to 2,
A single molecule transistor in which a source terminal and a drain terminal added to fullerene C ₇₀ are joined to a conductive electrode, and a gate terminal is operated electrochemically.

[5] A fullerene C ₇₀ derivative represented by the following formula (21) or (22)
[In the above formula,
Each R ³ is independently a C ₁ -C ₂ alkyl group;
R ⁴ is a C ₁ -C ₃ alkyl group;
Each R ⁵ is independently a C ₁ -C ₅ alkyl group;
Each of Mtl is independently Fe or Ru;
L is a single bond, C ₁ -C ₅ alkylene which may have a substituent, C ₂ -C ₅ alkenylene which may have a substituent, or C ₂ -C which may have a substituent. ₅ alkenylene or C ₆ -C ₃₀ phenylene which may have a substituent, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each m is independently 0 or 5;
n is an integer from 0 to 2;
In formula (A),
Each R ¹ is independently a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer from 0 to 2,
Ar independently represents the following formula (A)
(In formula (A), R ¹ is a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer of 0-2. )
It is group represented by these. ]
A fullerene C ₇₀ derivative for a single molecule transistor having a partial structure represented by:
Each two groups having Mtl, appended to the fullerene C ₇₀ is the source terminal and the drain terminal, a group having a carboxyl group or a thiol group are added to the fullerene C ₇₀ is a gate terminal, a monomolecular transistor Fullerene C ₇₀ derivative.
The fullerene C ₇₀ derivative is preferably used in the monomolecular transistor having, for example, the electrode gate terminal.
[6] according to [5], a monomolecular transistor including a fullerene C ₇₀ derivatives for monomolecular transistor,
In the above formula (21) or (22),
Each R ³ is independently methyl or ethyl;
R ⁴ is methyl or ethyl;
Each R ⁵ is independently methyl or ethyl;
Each of Mtl is independently Fe or Ru;
L is a single bond, C ₁ -C ₅ alkylene which may have a substituent, C ₂ -C ₅ alkenylene which may have a substituent, or C ₂ -C which may have a substituent. ₅ alkenylene or C ₆ -C ₃₀ phenylene which may have a substituent, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each m is independently 0 or 5;
n is an integer from 0 to 2;
In formula (A),
Each R ¹ is independently methyl or ethyl;
Each R ² is independently methyl or ethyl;
p is an integer from 0 to 2,
The source and drain terminals, appended to the fullerene C ₇₀ is a conductive electrode, a gate terminal is bonded to the ITO electrode, the monomolecular transistor.

[7] A fullerene C ₇₀ derivative represented by the following formula (31) or (32)
[In the above formula,
Each R ³ is independently a C ₁ -C ₂ alkyl group;
Each of Mtl is independently Fe or Ru;
L is a single bond, C ₁ -C ₅ alkylene which may have a substituent, C ₂ -C ₅ alkenylene which may have a substituent, or C ₂ -C which may have a substituent. ₅ alkenylene or C ₆ -C ₃₀ phenylene which may have a substituent, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each q is independently 0 or 4;
In formula (A),
Each R ¹ is independently a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer from 0 to 2,
Ar independently represents the following formula (A)
(In formula (A), R ¹ is a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer of 0-2. )
It is group represented by these. ]
A fullerene C ₇₀ derivative for a single molecule transistor having a partial structure represented by:
Are two groups the source and drain terminals respectively having a metal atom Mtl, appended to the fullerene C _70, fullerene C ₇₀ skeleton and gate terminal, fullerene C ₇₀ derivatives for monomolecular transistor.
The fullerene C ₇₀ derivatives, for example, is preferably used in the monomolecular transistor having electron injection gate terminal and the hole injection gate terminal.
[8] according to [7], a monomolecular transistor including a fullerene C ₇₀ derivatives for monomolecular transistor,
In the above formula (31) or (32),
Each R ³ is independently methyl or ethyl;
Each of Mtl is independently Fe or Ru;
L is a single bond, C ₁ -C ₅ alkylene which may have a substituent, C ₂ -C ₅ alkenylene which may have a substituent, or C ₂ -C which may have a substituent. ₅ alkenylene or C ₆ -C ₃₀ phenylene which may have a substituent, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each q is independently 0 or 4;
In formula (A),
Each R ¹ is independently methyl or ethyl;
Each R ² is independently methyl or ethyl;
p is an integer from 0 to 2,
A single molecule transistor in which a source terminal and a drain terminal attached to a fullerene C ₇₀ are joined to a conductive electrode, and electrons are injected into a fullerene C ₇₀ skeleton to operate a gate terminal.

In this specification, the fullerene C ₇₀ derivative having a specific partial structure includes a fullerene derivative appended groups are added to the carbon atoms constituting the fullerene C ₇₀ other than the identified partial structures.

The monomolecular transistor according to a preferred embodiment of the present invention can exhibit a stable function, for example. The monomolecular transistor according to a preferred embodiment of the present invention can exhibit a high function, for example. The monomolecular transistor according to a preferred embodiment of the present invention can be manufactured at a low cost, for example.
The fullerene derivative used for the monomolecular transistor according to a preferred embodiment of the present invention can exhibit, for example, a stable function or can be used for a highly functional monomolecular transistor. Moreover, the fullerene derivative used for the monomolecular transistor according to a preferred embodiment of the present invention can be synthesized at a low cost.

  Although the aspect of the transistor in which the fullerene derivative of the present invention is used is not particularly limited, (1) a monomolecular transistor having an electrochemical gate terminal, (2) a monomolecular transistor having an electrode gate terminal, and (3) electron injection It is preferably used for a monomolecular transistor having a type gate terminal, and (4) a monomolecular transistor having a hole injection type gate terminal.

1. Fullerene Derivative Used for Monomolecular Transistor Having Electrochemical Gate Terminal Fullerene derivative used for a single molecular transistor having an electrochemical gate terminal of the present invention is, for example, fullerene C ₇₀ having a partial structure represented by the above formula (1). A derivative (hereinafter referred to as “derivative 1”).
Here, in the derivative 1, as fullerene C ₇₀ skeleton quantum dots, respectively as two additional groups bonded via a metal atom (Mtl) to the fullerene skeleton source terminal and the drain terminal, and bonded to the fullerene skeleton The additional group having ferrocene functions as a gate electron.

In the unimolecular transistor using the derivative 1, the metal atom (Mtl), R ³ and m constituting the two additional groups having the metal atom (Mtl) are as described above, but Mtl is preferably Fe or Ru. The group bonded to the tip of Mtl is as shown in the above formula (1), but preferably m is 0 or 5. When m is 1 or more, R ³ is preferably methyl. The group bonded to the tip of the metal atom (Mtl) is particularly preferably a cyclopentadienyl group (Cp) or a pentamethylcyclopentadienyl group (Cp ^* ).

In the single-molecule transistor using the derivative 1, the two additional groups functioning as the source terminal and the drain terminal in the derivative 1 can be bonded to the conductive electrode, respectively, but are preferably bonded to the gold electrode. Also, the additional group that functions as a gate terminal can be operated electrochemically. Specifically, for example, when the oxidized ferrocenyl group is removed, the electron density on the fullerene C ₇₀ skeleton increases, and the electronic mutual relationship between the source terminal and the drain terminal (for example, between metal atoms (Mtl)). The action increases. In this way, the derivative 1 can be used as a fullerene derivative having an electrochemical gate terminal.

The derivative 1 can be synthesized, for example, by the following method. (1) by reacting the fullerene C ₇₀ and the copper reagent and pyridine, 6 aryl group to synthesize sextuple adduct obtained by adding regioselective simultaneously fullerene C _70. (2) A hexaaddition type binuclear metal complex is synthesized by performing a reaction in which a metal atom having an organic group is added to the hexaadduct. (3) An organocopper reagent having a ferrocenyl group is reacted with the hexaaddition type binuclear metal complex thus synthesized.

2. Fullerene derivative used for single molecule transistor having electrode gate terminal The fullerene derivative used for the single molecule transistor having the electrode gate terminal of the present invention is, for example, fullerene C ₇₀ having a partial structure represented by the above formula (21) or (22). Derivatives (hereinafter, the two types of derivatives are collectively referred to as “derivative 2”).
Here, in the derivative 2, as a fullerene C ₇₀ skeleton quantum dots, respectively as two additional groups bonded via a metal atom (Mtl) to the fullerene skeleton source terminal and the drain terminal, and bonded to the fullerene skeleton The added group having a carboxyl group or thiol group functions as a gate electron.

In the monomolecular transistor using the derivative 2, the metal atom (Mtl), R ³ and m constituting the two additional groups having the metal atom (Mtl) are as described above, but Mtl is preferably Fe or Ru. The group bonded to the tip of Mtl is as shown in the above formula (21) or (22), but preferably m is 0 or 5. When m is 1 or more, R ³ is preferably methyl. The group bonded to the tip of the metal atom (Mtl) is particularly preferably a cyclopentadienyl group (Cp) or a pentamethylcyclopentadienyl group (Cp ^* ).

  In the unimolecular transistor using the derivative 2, the two additional groups functioning as the source terminal and the drain terminal in the derivative 2 can be bonded to the conductive electrode, respectively, but are preferably bonded to the gold electrode. In addition, the additional group that functions as a gate terminal is preferably bonded to the ITO electrode.

The derivative 2 can be synthesized, for example, by the following method. (1) by reacting the fullerene C ₇₀ and the copper reagent and pyridine, 6 aryl group to synthesize sextuple adduct obtained by adding regioselective simultaneously fullerene C _70. (2) A hexaaddition type binuclear metal complex is synthesized by performing a reaction in which a metal atom having an organic group is added to the hexaadduct. (3) By reacting the synthesized hexaaddition type dinuclear metal complex with an organic copper reagent having a carboxylic acid ester group or a thioester group, the octaaddition type fullerene binuclear metal complex having a carboxylic acid ester group or a thioester group Is synthesized. (4) by deprotection treatment of the carboxylic acid ester group of the thus synthesized metal complex to synthesize a fullerene C ₇₀ derivative having a partial structure represented by the formula (21). Similarly, by performing the deprotection treatment of the carboxylic acid thiol group of the metal complex, to synthesize a fullerene C ₇₀ derivative having a partial structure represented by the formula (22).

3. Fullerene Derivative Used for Monomolecular Transistor Having Electron Injection Gate Terminal The fullerene derivative used for a monomolecular transistor having an electron injection gate terminal of the present invention has, for example, a partial structure represented by the above formula (31) or (32). It is a fullerene C ₇₀ derivative (hereinafter referred to as “derivative 3”).
Here, in the derivative 3, as the fullerene C ₇₀ skeleton quantum dots, as two additional groups source and drain terminals respectively bonded via a metal atom (Mtl) to the fullerene skeleton, fullerene C ₇₀ skeleton gate Functions as a terminal.

In the single molecule transistor using the derivative 3, the metal atom (Mtl), R ³ , q and L constituting the two additional groups having the metal atom (Mtl) are as described above, but Mtl is preferably Fe or Ru. . The group bonded to the tip of Mtl is as shown in the above formula (31) or (32), but preferably q is 0 or 4. When q is 1 or more, R ³ is preferably methyl.

  In the unimolecular transistor using the derivative 3, the two additional groups functioning as the source terminal and the drain terminal in the derivative 3 can be bonded to the conductive electrode, respectively, but are preferably bonded to the gold electrode.

In the single molecule transistor using the derivative 3, the _C70 skeleton can be operated as a gate terminal by directly injecting electrons into the _C70 skeleton using an electron gun or the like. The dithiol and the dicarboxylic acid constituting the derivative 3 are placed on a nanogap electrode such as gold, and a gate voltage is applied on the pi-conjugated system of the fullerene C70 skeleton, so that it is between the source terminal and the drain terminal (between two metals). In addition, transistor characteristics can be obtained.

The derivative 3 can be synthesized, for example, by the following method. (1) by reacting the fullerene C ₇₀ and the copper reagent and pyridine, 6 aryl group to synthesize sextuple adduct obtained by adding regioselective simultaneously fullerene C _70. (2) A hexaaddition type binuclear metal complex is synthesized by performing a reaction in which a metal atom having an organic group is added to the hexaadduct. (3) The synthesized hexaaddition type binuclear metal complex is subjected to Friedel-Crafts reaction using an acid chloride having an alkyl group having a functional group at the terminal, and two such as cyclopentadienyl group A functional group is introduced into an organic group. (4) Then, (3) converting the introduced terminal functional groups, the fullerene C ₇₀ derivative having a partial structure represented by the formula (31) is a dicarboxylic acid of 6 polyaddition type binuclear metal complex Is synthesized. Similarly, to synthesize a fullerene C ₇₀ derivative having a partial structure represented by the formula (32) is a dithiol in sextuple-added dinuclear metal complexes.

In the present specification, the “organic group” is not particularly limited. For example, the C _{1 to} C ₂₀ hydrocarbon group which may have a substituent, or C which may have a substituent. _{1 to} C ₂₀ alkoxy group, C _{6 to} C ₂₀ aryloxy group which may have a substituent, amino group which may have a substituent, silyl group which may have a substituent, substituted alkylthio group which may have a group (-SY ^1, in the formula, Y ¹ is a good C ₁ -C ₂₀ alkyl group which may have a substituent.), which may have a substituent A good arylthio group (—SY ² , wherein Y ² represents an optionally substituted C ₆ -C ₁₈ aryl group), and an optionally substituted alkylsulfonyl group (—SO 2; ₂ Y ^3, in the formula, Y ³ represents a good C ₁ -C ₂₀ alkyl group which may have a substituent.) may have a substituent Reel sulfonyl group (-SO ₂ Y ^4,: in the formula, Y ⁴ is. Showing a good C ₆ -C ₁₈ aryl group which may have a substituent group),.

In the present specification, the hydrocarbon group of the “C ₁ -C ₂₀ hydrocarbon group” may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. When the C ₁ -C ₂₀ hydrocarbon group is acyclic, it may be linear or branched. The “C ₁ -C ₂₀ hydrocarbon group” includes a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group, a C ₄ -C ₂₀ alkyl dienyl group, a C _6- C ₁₈ aryl group, C ₇ -C ₂₀ alkylaryl group, C ₇ -C ₂₀ arylalkyl group, C ₄ -C ₂₀ cycloalkyl group, C ₄ -C ₂₀ cycloalkenyl group, (C ₃ ~C ₁₀ cycloalkyl) C ₁ -C ₁₀ alkyl groups and the like are included.

In the present specification, "C ₁ -C ₂₀ alkyl group" is preferably C ₁ -C ₁₀ alkyl group, more preferably a C ₁ -C ₆ alkyl group. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, "C ₂ -C ₂₀ alkenyl group" is preferably C ₂ -C ₁₀ alkenyl group, more preferably a C ₂ -C ₆ alkenyl group. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, 2-butenyl and the like.

In the present specification, "C ₂ -C ₂₀ alkynyl group" is preferably C ₂ -C ₁₀ alkynyl group, more preferably a C ₂ -C ₆ alkynyl group. Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, butynyl, and the like.

In the present specification, "C ₄ -C ₂₀ alkyldienyl group" is preferably C ₄ -C ₁₀ alkadienyl group, more preferably a C ₄ -C ₆ alkadienyl group. Examples of alkyldienyl groups include, but are not limited to, 1,3-butadienyl and the like.

In the present specification, the “C ₆ -C ₁₈ aryl group” is preferably a C ₆ -C ₁₀ aryl group. Examples of the aryl group include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

In the present specification, the “C ₇ -C ₂₀ alkylaryl group” is preferably a C ₇ -C ₁₂ alkylaryl group. Examples of alkylaryl groups include, but are not limited to, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, o-cumenyl, m -Cumenyl, p-cumenyl, mesityl and the like can be mentioned.

In the present specification, the “C ₇ -C ₂₀ arylalkyl group” is preferably a C ₇ -C ₁₂ arylalkyl group. Examples of arylalkyl groups include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenyl Examples include phenylbutyl and 5-phenylpentyl.

In the present specification, the “C ₄ -C ₂₀ cycloalkyl group” is preferably a C ₄ -C ₁₀ cycloalkyl group. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

In the present specification, the “C ₄ -C ₂₀ cycloalkenyl group” is preferably a C ₄ -C ₁₀ cycloalkenyl group. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and the like.

In the present specification, the “C ₁ -C ₂₀ alkoxy group” is preferably a C ₁ -C ₁₀ alkoxy group, and more preferably a C ₁ -C ₆ alkoxy group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy and the like.

In the present specification, the “C ₆ -C ₂₀ aryloxy group” is preferably a C ₆ -C ₁₀ aryloxy group. Examples of aryloxy groups include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy, and the like.

In the present specification, “alkylthio group (—SY ¹ , wherein Y ¹ represents an optionally substituted C ₁ -C ₂₀ alkyl group)” and “alkylsulfonyl group (—SO ₂ Y ³ In the formula, Y ³ represents an optionally substituted C ₁ -C ₂₀ alkyl group.) ”, Y ¹ and Y ³ are preferably C ₁ -C ₁₀ alkyl groups, it is more preferably ₁ -C ₆ alkyl group. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, “arylthio group (—SY ² , wherein Y ² represents an optionally substituted C ₆ -C ₁₈ aryl group)” and “arylsulfonyl group (—SO ₂ Y ⁴ In the formula, Y ⁴ represents an optionally substituted C ₆ -C ₁₈ aryl group.) ”, It is preferable that Y ² and Y ⁴ are C ₆ -C ₁₀ aryl groups. Examples of the aryl group include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

“C ₁ -C ₂₀ hydrocarbon group”, “C ₁ -C ₂₀ alkoxy group”, “C ₆ -C ₂₀ aryloxy group”, “amino group”, “silyl group”, “alkylthio group”, “arylthio group” ”,“ Alkylsulfonyl group ”, and“ arylsulfonyl group ”may have a substituent introduced therein. Examples of the substituent include an ester group, a carboxyl group, an amide group, an alkyne group, a trimethylsilyl group, an amino group, a phosphonyl group, a thio group, a carbonyl group, a nitro group, a sulfo group, an imino group, a halogeno group, and an alkoxy group. Can be mentioned. In this case, one or more substituents may be introduced at the substitutable position up to the maximum number that can be substituted, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

  In the present specification, examples of the “amino group which may have a substituent” include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

  In this specification, examples of “optionally substituted silyl group” include, but are not limited to, dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenyl Examples include methylsilyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, and methylmethoxyphenyl.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to an Example.
In this specification, “Ph” represents a phenyl group, “Me” represents a methyl group, “Et” represents an ethyl group, “Bu” represents a butyl group, and “tBu” represents tertiary butyl. “IPr” represents a secondary propyl group, “Ac” represents an acetyl group, “Cp” represents a cyclopentadienyl group, and “Cp ^* ” represents a pentamethylcyclopentadienyl group. , “Fc” represents a ferrocenyl group.

[Synthesis Example 1] Synthesis of Fe ₂ C ₇₀ [4-tBuC ₆ H ₄ ] 6Cp ^* ₂
As shown in Scheme 1, a solution of ^t BuOK in THF (80 μL, 1.0 M, 80 μmol) against a THF solution (1.0 mL) of C ₇₀ [4-tBuC ₆ H ₄ ] ₆ H ₂ (120 mg, 73 μmol) Was added. After 10 minutes, [FeCp ^* (CH ₃ CN) ₃ ] PF ₆ acetonitrile solution (0.10 M, 0.85 mL, 85 μmol) was added. After stirring for 5 minutes, THF solution (80 μL, 1.0 M, 80 μmol) of ^t BuOK and [FeCp ^* (CH ₃ CN) ₃ ] PF ₆ acetonitrile solution (0.10 M, 0.85 mL, 85 μmol) were added again. . Toluene (10 mL) was added to the reaction mixture, filtered directly through a SiO ₂ pad and concentrated. The resulting crude product was purified by HPLC separation (Buckyprep, 250 mm, toluene: hexane = 3: 7) and Fe ₂ C ₇₀ [4-tBuC ₆ H ₄ ] 6Cp ^* ₂ (57.8 mg, Yield 39%). A single crystal for X-ray crystal structure analysis was obtained from a toluene / ethanol solution.

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR and MS analysis. The results were as follows.

¹ H NMR (500 MHz, CDCl ₃ ) δ1.07 (br, 30H, Cp *), 1.34 (s, 18H, CH ₃ ), 1.39 (s, 18H, CH ₃ ), 1.62 (s, 18H, CH ₃ ), 7.36 (d, J _HH = 8.6 Hz, 4H, C ₆ H ₅ ), 7.49 (d, J _HH = 8.0 Hz, 4H, C ₆ H ₅ ), 7.67 (d, J _HH = 8.0 Hz, 4H, C ₆ H ₅ ), 7.79 (d, J _HH = 8.0 Hz, 4H, C ₆ H ₅ ), 7.98 (d, J _HH = 8.0 Hz, 4H, C ₆ H ₅ ), 8.80 (d, J _HH = 8.0 Hz, 4H, C ₆ H ₅ ); ¹³ C NMR (125 MHz, CDCl ₃ ) δ 9.71 (10C, Cp *), 31.40 (6C, C (CH ₃ ) ₃ ), 31.44 (6C, C (CH ₃ ) ₃ ), 31.64 (6C, C (CH ₃ ) ₃ ), 34.47 (2C, C (CH ₃ ) ₃ ), 34.56 (6C, C (CH ₃ ) ₃ ), 34.82 (6C, C (CH ₃ ) ₃ ) , 55.55 (2C, C ₇₀ ), 57.03 (2C, C ₇₀ ), 58.73 (2C, C ₇₀ ), 80.44 (2C, Cp *), 88.78 (2C, C ₇₀ ), 89.27 (2C, C ₇₀ ), 90.02 (2C, C ₇₀ ), 91.42 (2C + 2C, C ₇₀ ), 125.00 (4C, C ₆ H ₄ ), 125.23 (4C, C ₆ H ₄ ), 125.31 (4C, C ₆ H ₄ ), 127.81 (2C ), 129.09 (4C, C ₆ H ₄ ), 129.34 (4C, C ₆ H ₄ ), 129.79 (4C, C ₆ H ₄ ), 132.41 (2C), 133.21 (2C), 133.73 (2C), 137.35 (2C ), 137.66 (2C), 137.85 (2C), 139.58 (2C), 140.18 (2C), 140.48 (2C), 142.76 (2C), 142.87 (2C), 143.6 1 (2C), 144.80 (2C), 145.00 (2C), 145.98 (2C), 146.23 (2C), 146.60 (2C), 146.95 (2C), 147.09 (2C), 147.77 (2C), 148.38 (2C), 148.50 (2C + 2C), 149.69 (2C), 150.03 (2C), 150.08 (2C), 150.24 (2C), 150.49 (2C), 150.65 (2C), 152.02 (2C), 159.65 (2C), 163.07 (2C) ); APCI-TOF MS calcd for C ₁₅₀ H ₁₀₈ Fe ₂ (M + H) ⁺ ; 2022.7267, found m / z = 2022.7203.

Moreover, the single crystal obtained from the toluene / ethanol solution was analyzed by X-ray crystal diffraction. The results were as follows ((a) is an ORTEP diagram, (b) is a CPK model viewed from one side, and (c) is a CPK model viewed from the other side).

[Synthesis Example 2]: Synthesis of Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ Cp ₂
As shown in Scheme 2, THF solution (60 mL) of C ₇₀ [4-tBuC ₆ H ₄ ] ₆ H ₂ (300 mg, 0.183 mmol) was added to THF solution (0.20 mL, 0.20 mmol) of ^t BuOK. ) Was added. After 10 minutes, an acetonitrile solution of [RuCp (CH ₃ CN) ₃ ] PF ₆ (96 mg, 0.22 mmol) was added. After stirring for 5 minutes, it was added in the same manner again ^t BuOK in THF (0.20 mL, 0.20 mmol) and _{[RuCp (CH 3 CN) 3} ] PF 6 (96mg, 0.22mmol) in acetonitrile. THF was distilled off and the mixture was concentrated. Toluene (10 mL) was added to the reaction mixture, and the mixture was filtered directly through a SiO ₂ pad and concentrated. The resulting crude product was purified by HPLC separation (Buckyprep, 250 mm, toluene: hexane = 3: 7), and Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ Cp ₂ (249 mg, yield). 69%).

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR and MS analysis. The results were as follows.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δ1.36 (s, 18H, t-Bu), 1.38 (s, 18H, t-Bu), 1.42 (s, 18H, t-Bu), 3.82 (s , 10H, Cp), 7.40 (d, J = 8.6 Hz, 4H, C ₆ H ₄ ), 7.43 (d, J = 8.6 Hz, 4H, C ₆ H ₄ ), 7.49 (d, J = 8.3 Hz, 4H , C ₆ H ₄ ), 7.77 (d, J = 8.3 Hz, 4H, C ₆ H ₄ ), 7.99 (d, J = 8.3 Hz, 4H, C ₆ H ₄ ), 8.07 (d, J = 8.3 Hz, 4H, C ₆ H ₄ ); ¹³ C NMR (CD ₂ Cl ₂ , 125 MHz) δ31.47 (6C + 6C, t-Bu (Me)), 31.49 (6C, t-Bu (Me)), 34.83 ( 2C, t-Bu (C)), 34.85 (2C, t-Bu (C)), 34.88 (2C, t-Bu (C)), 55.13 (2C, C ₇₀ (sp ³ )), 56.88 (2C, C ₇₀ (sp ³ )), 59.18 (2C, C ₇₀ (sp ³ )), 74.43 (10C, Cp), 93.44 (2C, FCp), 94.00 (2C, FCp), 96.72 (2C, FCp), 97.28 ( 2C, FCp), 105.73 (2C, FCp), 124.86 (4C), 124.95 (4C), 125.24 (4C), 127.20 (2C), 128.25 (4C), 128.29 (4C), 128.96 (4C), 132.21 (2C) ), 133.91 (2C), 134.56 (2C), 136.99 (2C), 138.37 (2C), 141.77 (2C), 142.77 (2C), 143.01 (2C), 143.24 (2C), 143.33 (2C), 144.19 (2C) ), 145.36 (2C), 145.72 (2C), 146.32 (2C), 146.56 (2C), 147.11 (2C), 147.58 (2C), 147.65 (2C), 148.04 (2C), 149 .07 (2C), 149.26 (2C), 149.39 (2C), 150.06 (2C), 150.34 (2C), 150.74 (2C), 150.80 (2C), 150.86 (2C), 151.24 (2C), 151.68 (2C) , 151.75 (2C), 159.78 (2C), 163.41 (2C); HRMS (APCI-TOF, positive) m / z calcd for C ₁₄₀ H ₈₉ Ru ₂ ⁺ [M + H] ⁺ 1973.5046, found 1973.5038.

Synthesis Example 3 Synthesis of Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ Cp ^* ₂
As shown in Scheme 3, a THF solution (40 mL) of C ₇₀ [4-tBuC ₆ H ₄ ] ₆ H ₂ (200 mg, 0.122 mmol) was added to a THF solution (0.15 mL, 0.15 mmol) of ^t BuOK. Was added. After 10 minutes, [RuCp ^* (CH ₃ CN) ₃ ] PF ₆ (80 mg, 0.158 mmol) in acetonitrile was added. After stirring for 5 minutes, it was again added in the same manner THF solution (0.15 mL, 0.15 mmol) of ^t BuOK and _{^{[RuCp * (CH 3 CN)}} 3] PF 6 (80mg, 0.158mmol) in acetonitrile . THF was distilled off and the mixture was concentrated. Toluene (10 mL) was added to the reaction mixture, and the mixture was filtered directly through a SiO ₂ pad and concentrated. The resulting crude product was purified by HPLC separation (Buckyprep, 250 mm, toluene: hexane = 3: 7), and Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ Cp ^* ₂ (190 mg, yield). 74%).

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR and MS analysis. The results were as follows.

¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ1.17 (s, 30H, C ₅ Me ₅ ), 1.29 (s, 18H, t-Bu), 1.40 (s, 18H, t-Bu), 1.58 ( s, 18H, t-Bu), 7.23 (d, J = 8.5 Hz, 4H, C ₆ H ₄ ), 7.35 (d, J = 8.5 Hz, 4H, C ₆ H ₄ ), 7.50 (d, J = 8.3 Hz, 4H, C ₆ H ₄ ), 7.73 (d, J = 8.5 Hz, 4H, C ₆ H ₄ ), 7.90 (d, J = 8.2 Hz, 4H, C ₆ H ₄ ), 8.59 (d, J = 8.2 Hz, 4H, C ₆ H ₄ ); ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz) δ 10.43 (10C, Cp * (Me)), 31.42 (6C, t-Bu (Me)), 31.53 ( 6C, t-Bu (Me)), 31.67 (6C, t-Bu (Me)), 34.62 (2C, t-Bu (C)), 34.83 (2C, t-Bu (C)), 35.04 (2C, t-Bu (C)), 55.93 (2C, C ₇₀ (sp ³ )), 57.63 (2C, C ₇₀ (sp ³ )), 59.24 (2C, C ₇₀ (sp ³ )), 86.85 (10C, Cp * (C (sp ² ))), 92.48 (2C, FCp), 94.26 (2C, FCp), 94.92 (2C, FCp), 95.28 (2C, FCp), 107.16 (2C, FCp), 125.34 (4C), 125.55 (4C), 125.66 (4C), 126.69 (2C), 128.80 (4C), 129.14 (4C), 129.44 (4C), 132.51 (2C), 133.63 (2C), 134.24 (2C), 135.49 (2C), 138.31 (2C), 140.38 (2C), 140.83 (2C), 140.90 (2C), 141.21 (2C), 143.27 (2C), 143.45 (2C), 144.12 (2C), 145.32 (2C), 145.60 (2C), 146.38 (2C), 146.91 (2C), 147.29 (2C), 147.44 (2C), 147.61 (2C), 148.53 (2C), 148.60 (2C), 148.75 (2C), 149.02 (2C), 150.01 (2C), 150.07 (2C), 150.53 (2C), 150.87 (2C), 151.56 (2C), 152.04 (2C), 153.56 (2C), 159.24 (2C), 164.33 (2C); HRMS (APCI-TOF, positive) m / z calcd for C ₁₅₀ H ₁₀₉ Ru ₂ ⁺ [M + H] ⁺ 2113.6611, found 2113.6596.

[Example _{1] Fe 2 {C 70 [} 4-tBuC 6 H 4] 6 [FcC 6 H 4] Me} Cp * 2 Synthesis
As shown in Scheme 4, the copper reagent CuBr · SMe ₂ (90.6 mg, 0.440 mmol) and the Fe ₂ C ₇₀ [4-tBuC ₆ H ₄ ] 6Cp ^* ₂ (89.0 mg) obtained in Synthesis Example 1 were used. , 44.0 mmol) in a mixed solution of pyridine (9.0 mL) and orthodichlorobenzene (9.0 mL), Grignard reagent XMgBr (wherein X = FcC ₆ H ₄ , 0.45 M, 0.98 mL,. 44 mmol) in THF was added at room temperature, followed by stirring at 40 ° C. for 13 hours, and 2.0 mL of methyl iodide was added to stop the reaction. The product solution was concentrated and purified by silica gel column chromatography (eluent: hexane / carbon disulfide = 10/0 to 0/10). A strong red fraction was collected and the solvent was removed in vacuo. The obtained crude product was purified by HPLC separation (RPFullerene, 250 mm, toluene / acetonitrile = 5/5), and Fe ₂ {C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [FcC ₆ H ₄ ]. Me} Cp ^* ₂ (59.2 mg, 25.7 mmol, 59% yield) was obtained.

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR and MS analysis. The results were as follows.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δ 1.04 (s, 15H, C ₅ Me ₅ ), 1.11 (s, 15H, C ₅ Me ₅ ), 1.34 (s, 9H, t-Bu), 1.37 ( s, 9H, t-Bu), 1.39 (s, 9H, t-Bu), 1.41 (s, 9H, t-Bu), 1.61 (s, 9H, t-Bu), 1.65 (s, 9H, t- Bu), 2.16 (s, 3H, C (sp ³ ) -Me), 4.03 (s, 5H, Cp), 4.32 (t, J = 1.7 Hz, 2H, C ₅ H ₄ ), 4.68 (d, J = 1.8 Hz, 2H, C ₅ H ₄ ), 7.35-7.90 (m, 23H, C ₆ H ₄ ), 8.04 (dd, J = 2.3, 8.0 Hz, 1H, C ₆ H ₄ ), 8.63 (d, J = 8.0 Hz, 2H, C ₆ H ₄ ), 8.93 (d, J = 8.1 Hz, 2H, C ₆ H ₄ ); ¹³ C NMR (CD ₂ Cl ₂ , 125 MHz) δ 9.99 (5C, Cp * (Me) ), 10.01 (5C, Cp * (Me)), 31.48 (3C, t-Bu (Me)), 31.51 (3C, t-Bu (Me)), 31.52 (3C, t-Bu (Me)), 31.55 (3C, t-Bu (Me)), 31.72 (3C, t-Bu (Me)), 31.76 (3C, t-Bu (Me)), 32.73 (1C, Me-C ₇₀ (sp ³ )), 34.70 (1C, t-Bu (C)), 34.78 (1C + 1C + 1C, t-Bu (C)), 35.04 (1C, t-Bu (C)), 35.12 (1C, t-Bu (C)) , 55.61 (1C, C ₇₀ (sp ³ )), 56.13 (1C, C ₇₀ (sp ³ )), 56.24 (1C, C ₇₀ (sp ³ )), 57.23 (1C, C ₇₀ (sp ³ )), 57.94 (1C, C ₇₀ (sp ³ )), 58.60 (1C, C ₇₀ (sp ³ )), 59.54 (1C, C ₇₀ (sp ³ )), 63.10 (1C, C _{7 0} (sp ³ )), 66.85 (1C, C ₅ H ₄ ), 67.00 (1C, C ₅ H ₄ ), 69.40 (1C, C ₅ H ₄ ), 69.42 (1C, C ₅ H ₄ ), 70.01 (5C , Cp), 80.87 (5C, Cp * (C (sp ² ))), 80.92 (5C, Cp * (C (sp ² ))), 85.12 (1C, C ₅ H ₄ ), 88.24 (1C, FCp) , 88.85 (1C, FCp), 89.23 (1C, FCp), 90.06 (1C, FCp), 90.31 (1C, FCp), 91.32 (1C, FCp), 91.94 (1C, FCp), 92.95 (1C, FCp), 102.60 (1C, FCp), 104.25 (1C, FCp), 125.31 (2C), 125.55 (2C), 125.57 (2C + 2C), 125.59 (2C), 125.73 (2C), 125.87 (1C), 125.95 (1C) , 127.96 (1C), 128.24 (1C), 128.49 (1C), 128.97 (2C), 129.51 (2C), 129.68 (2C), 129.75 (1C), 129.82 (2C), 129.86 (2C), 129.95 (2C) , 130.56, 131.21, 131.79, 133.16, 133.32, 135.24, 136.85, 136.97, 138.26, 138.58, 138.69, 138.72, 139.64 (1C + 1C), 140.15, 140.29, 140.42, 140.58, 140.66, 140.72, 140.89, 140.92, 141.05 141.29, 142.34, 142.81, 143.94 (1C + 1C), 143.98, 144.21, 144.30, 144.33, 145.57, 145.83, 146.24, 146.27, 147.27, 147.52, 147.66, 147.85, 147.88, 148.02, 148.64, 148.80, 149.60, 150.55 (1C + 1C), 150.58, 150.61, 150.86, 15 1.01, 151.41, 152.71, 154.44, 154.55, 155.04, 156.51, 157.62, 158.96, 159.93, 160.88, 161.02, 161.63; HRMS (APCI-TOF, positive) m / z calcd for C ₁₆₇ H ₁₂₄ Fe ₃ ⁺ [M] ⁺ 2296.7751, found 2296.7733.

Example 2 Synthesis of Ru ₂ {C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [FcC ₆ H ₄ ] Me} Cp ₂
As shown in Scheme 5, copper reagent CuBr · SMe ₂ (104 mg, 0.505 mmol) and Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ Cp ₂ (100 mg, 50.7 mmol) synthesized in Synthesis Example 2 To a mixed solution of pyridine (10.0 mL) and orthodichlorobenzene (10.0 mL), a THF solution of Grignard reagent XMgBr (X = FcC ₆ H ₄ , 0.45M, 1.12 mL, 0.50 mmol) was added at room temperature. Then, the mixture was stirred at 40 ° C. for 18 hours, and 1.0 mL of methyl iodide was added to stop the reaction. The product solution was concentrated and purified by silica gel column chromatography (eluent: hexane / carbon disulfide = 10/0 to 0/10). A strong red fraction was collected and the solvent was removed in vacuo. The obtained crude product was purified by HPLC separation (RPFullerene, 250 mm, toluene / acetonitrile = 5/5), and Ru ₂ {C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [FcC ₆ H ₄ ]. Me} Cp ₂ (43.4 mg, 19.3 mmol, 38% yield) was obtained.

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR and MS analysis. The results were as follows.

¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ1.33 (s, 9H, t-Bu), 1.34 (s, 9H, t-Bu), 1.36 (s, 9H, t-Bu), 1.40 (s , 9H, t-Bu), 1.41 (s, 9H, t-Bu), 1.45 (s, 9H, t-Bu), 2.23 (s, 3H, Me), 3.82 (s, 5H, Cp), 3.84 ( s, 5H, Cp), 4.02 (s, 5H, Cp), 4.33 (m, 2H, C ₅ H ₄ ), 4.67 (m, 2H, C ₅ H ₄ ), 7.34-7.50 (m, 15H, C ₆ H ₄ ), 7.71 (d, J = 8.2 Hz, 2H, C ₆ H ₄ ), 7.80 (d, J = 8.5 Hz, 2H, C ₆ H ₄ ), 7.91 (d, J = 8.5 Hz, 2H, C ₆ H ₄ ), 7.97-8.00 (m, 5H, C ₆ H ₄ ), 8.13 (d, J = 8.5 Hz, 2H, C ₆ H ₄ ); ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz) δ31. 45 (3C, t-Bu (Me)), 31.47 (3C + 3C + 3C, t-Bu (Me)), 31.53 (3C + 3C, t-Bu (Me)), 32.73 (1C, Me-C ₇₀ (sp ³ )), 34.77 (1C, t-Bu (C)), 34.78 (1C, t-Bu (C)), 34.79 (1C, t-Bu (C)), 34.82 (1C, t-Bu ( C)), 34.86 (1C, t-Bu (C)), 34.87 (1C, t-Bu (C)), 55.28 (1C, C ₇₀ (sp ³ )), 55.38 (1C, C ₇₀ (sp ³ ) ), 55.74 (1C, C ₇₀ (sp ³ )), 56.54 (1C, C ₇₀ (sp ³ )), 57.36 (1C, C ₇₀ (sp ³ )), 58.73 (1C, C ₇₀ (sp ³ )), 59.52 (1C, C ₇₀ (sp ³ )), 63.19 (1C, C ₇₀ (sp ³ )), 66.83 (1C, C ₅ H ₄ ), 67.01 (1C, C ₅ H ₄ ), 69.45 (1C, C ₅ H ₄ ), 69.47 (1C, C ₅ H ₄ ), 70.03 (5C, Cp), 74.29 (5C, Cp), 74.35 (5C, Cp), 85.01 (1C, C ₅ H ₄ ), 93.44 (1C, FCp), 94.10 (1C, FCp), 94.46 (1C, FCp), 95.22 (1C, FCp), 95.77 (1C, FCp), 96.62 (1C, FCp), 96.84 (1C, FCp), 98.03 (1C, FCp), 104.96 (1C, FCp), 106.34 (1C, FCp), 124.75 (2C), 124.77 (2C), 124.90 (2C), 124.95 (2C), 125.05 (2C), 125.14 (2C), 125.93 (1C), 125.94 (1C), 125.95 (1C), 125.96 (1C), 128.00 (2C), 128.17 (2C), 128.19 (2C), 128.39 (1C), 128.42 (2C), 128.63 (2C), 129.03 (1C), 129.04 (2C), 130.61, 130.94, 131.21, 133.56, 133.68, 134.55, 136.11, 137.54, 137.65, 138.49, 138.68, 138.75, 139.21, 140.43, 141.23, 141.42, 141.88, 142.59, 142.50, 142.59 142.98, 143.14, 143.54, 143.73, 143.75, 143.77, 144.27, 145.06, 145.13, 145.77, 146.60, 146.64, 146.86, 147.07, 147.19, 147.43, 147.86 (1C + 1C), 148.15, 149.90, 149.15 , 150.48, 150.54 (1C + 1C), 150.58 (1C + 1C), 150.67 (1C + 1C + 1C), 151.53, 153.41, 153.43, 153.76, 155.64, 156.42, 158.11, 158.95, 159.86, 160 .95, 161.16, 161.65; HRMS (APCI-TOF, positive) m / z calcd for C ₁₅₇ H ₁₀₅ FeRu ₂ ⁺ [M + H] ⁺ 2249.5647, found 2249.5662.

[Example 3] Synthesis of Ru ₂ {C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [FcC ₆ H ₄ ] Me} Cp ^* ₂
As shown in Scheme 6, copper reagent CuBr · SMe ₂ (58.5 mg, 0.284 mmol) and Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ Cp ^* ₂ (60.0 mg) synthesized in Synthesis Example 3 , 28.4 mmol) in a mixed solution of pyridine (6.0 mL) and orthodichlorobenzene (6.0 mL), Grignard reagent XMgBr (X = FcC ₆ H ₄ , 0.45 M, 0.631 mL, 0.28 mmol). Of THF was added at room temperature, followed by stirring at 40 ° C. for 22 hours, and 2.0 mL of methyl iodide was added to stop the reaction. The product solution was concentrated and purified by silica gel column chromatography (eluent: hexane / carbon disulfide = 10/0 to 0/10). A strong red fraction was collected and the solvent was removed in vacuo. The obtained crude product was purified by HPLC separation (RPFullerene, 250 mm, toluene / acetonitrile = 5/5), and Ru ₂ {C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [FcC ₆ H ₄ ]. Me} Cp ^* ₂ (39.6 mg, 16.6 mmol, 58% yield) was obtained.

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR and MS analysis. The results were as follows.

¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δ1.17 (s, 15H, C ₅ Me ₅ ), 1.22 (s, 15H, C ₅ Me ₅ ), 1.26 ・ (s, 9H, t-Bu), 1.33 (s, 9H, t-Bu), 1.36 (s, 9H, t-Bu), 1.38 (s, 9H, t-Bu), 1.56 (s, 9H, t-Bu), 1.61 (s, 9H, t-Bu), 2.20 (s, 3H, Me), 4.02 (s, 5H, Cp), 4.33 (m, 2H, C ₅ H ₄ ), 4.68 (m, 2H, C ₅ H ₄ ), 7.17-7.83 (m, 23H, C ₆ H ₄ ), 8.08 (m, 1H, C ₆ H ₄ ), 8.44 (d, J = 8.6 Hz, 2H, C ₆ H ₄ ), 8.72 (d, J = 8.6 Hz, 2H , C ₆ H ₄ ); ¹³ C NMR (CD ₂ Cl ₂ , 125 MHz) δ 10.45 (5C, Cp * (Me)), 10.50 (5C, Cp * (Me)), 31.43 (3C, t-Bu (Me)), 31.50 (3C, t-Bu (Me)), 31.53 (3C, t-Bu (Me)), 31.55 (3C, t-Bu (Me)), 31.68 (3C, t-Bu (Me )), 31.72 (3C, t-Bu (Me)), 32.78 (1C, Me-C ₇₀ (sp ³ )), 34.59 (1C, t-Bu (C)), 34.68 (1C, t-Bu (C )), 34.78 (1C, t-Bu (C)), 34.79 (1C, t-Bu (C)), 35.00 (1C, t-Bu (C)), 35.08 (1C, t-Bu (C)) , 55.68 (1C, C ₇₀ (sp ³ )), 56.05 (1C, C ₇₀ (sp ³ )), 56.13 (1C, C ₇₀ (sp ³ )), 57.35 (1C, C ₇₀ (sp ³ )), 58.13 (1C, C ₇₀ (sp ³ )), 58.63 (1C, C ₇₀ (sp ³ )), 59.61 (1C, C ₇₀ (sp ³ )), 63.20 (1C, C ₇₀ (sp ³ )), 66 .85 (1C, C ₅ H ₄ ), 67.02 (1C, C ₅ H ₄ ), 69.41 (1C, C ₅ H ₄ ), 69.98 (1C, C ₅ H ₄ ), 70.02 (5C, Cp), 85.15 ( 1C, C ₅ H ₄ ), 86.66 (5C, Cp * (C (sp ² ))), 86.70 (5C, Cp * (C (sp ² ))), 92.55 (1C, FCp), 93.31 (1C, FCp ), 94.16 (1C, FCp), 94.35 (1C, FCp), 94.81 (1C, FCp), 95.10 (1C, FCp), 95.41 (1C, FCp), 96.03 (1C, FCp), 106.28 (1C, FCp) , 107.83 (1C, FCp), 125.20 (2C), 125.40 (2C), 125.42 (2C), 125.49 (2C), 125.55 (2C), 125.57 (2C), 125.89 (1C), 125.96 (1C), 126.59 ( 1C), 127.99 (1C), 128.02 (1C), 128.73 (1C + 2C), 128.77 (2C), 128.98 (2C), 129.18 (2C), 129.27 (2C), 129.37 (2C), 130.63, 131.26, 131.37 , 133.28, 133.45, 134.57, 134.97, 136.22, 136.75, 138.50, 138.61, 138.71, 139.70, 140.42, 140.43, 141.00, 141.10, 141.19, 141.20, 141.24, 141.32, 141.41 (1C + 1C), 141.62, 142.43, 143.00, 143.19, 144.27, 144.28, 144.63, 144.78, 144.89, 145.94, 146.38, 146.69, 147.35, 147.56, 147.61, 147.78, 147.98, 148.12, 148.32, 148.46, 148.56, 149.92, 149.93, 150.00, 150.29, 150.33, 150, 150.78, 152.10, 154.08, 155.33, 155.58, 155.65, 157.09, 157.72, 158.13, 160.47, 160.51, 160.98, 161.50; HRMS (APCI-TOF, positive) m / z calcd for C ₁₆₇ H ₁₂₅ FeRu ₂ ⁺ [M + H] ⁺ 2389.7212, found 2389.7252.

[Comparative Example _{1] Ru 2 {C 70 [} 4-tBuC 6 H 4] 6 [FcC 6 H 4] Me} Cp * 2 Synthesis
As shown in Scheme 7, the copper reagent CuBr · SMe ₂ (58.5 mg, 0.284 mmol) and Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ Cp ^* ₂ (60.0 mg, 28.4 mmol) To a mixed solution of pyridine (6.0 mL) and orthodichlorobenzene (6.0 mL), a THF solution of Grignard reagent PhMgBr (0.967M, 0.294 mL, 0.284 mmol) was added at room temperature, and then at 40 ° C. The mixture was stirred for a period of time, and 2.0 mL of methyl iodide was added to stop the reaction. The product solution was concentrated and purified by silica gel column chromatography (eluent: hexane / carbon disulfide = 10/0 to 0/10). A strong red fraction was collected and the solvent was removed in vacuo. The obtained crude product was purified by HPLC separation (RPFullerene, 250 mm, toluene / acetonitrile = 5/5), and Ru ₂ {C ₇₀ [4-tBuC ₆ H ₄ ] ₆ PhMe} Cp ^* ₂ ( 30.8 mg, 14.0 mmol, 49% yield).

[Comparative Test] Comparison between the compound synthesized in Example 3 and the compound synthesized in Comparative Example 1 Ru ₂ {C ₇₀ [4-tBuC6H4] ₆ (C ₆ H ₄ Fc) Me} Cp ^* synthesized in Example 3 ₂ and Ru ₂ {C ₇₀ [4-tBuC ₆ H ₄ ] ₆ PhMe} Cp ^* ₂ synthesized in Comparative Example 1 were subjected to cyclic voltammetry in dichloromethane in ⁿ Bu ₄ NB (3,5- The measurement was performed in the presence of (CF ₃ ) ₂ C ₆ H ₃ ) ₄ .
FIG. 1 is a cyclic voltammogram of these compounds.
The value of the difference δE between the oxidation potential of the two compounds and the oxidation potential between the two ruthenium atoms was also measured. The results are shown in Table 1.

As shown in FIG. 1, the compound of Example 3 reversibly oxidized three electrons, while the compound of Comparative Example 1 reversibly oxidized two electrons. Further, as shown in Table 1, when δE (0.31 V, 0.29 V) of the compound of Example 3 and the compound of Comparative Example 1 were compared, it was 0.02 V different. The fact that the compound of Example 3 has a smaller δE value than the compound of Comparative Example 1 is that the electron density on the fullerene C ₇₀ skeleton is reduced as a result of introducing a ferrocenyl group that undergoes oxidation, and the compound directly binds to fullerene 2 This means that the electronic interaction between two ruthenium atoms has decreased. Thus, by applying a positive voltage to the ferrocene site functioning as the gate terminal, electron transfer between two ruthenium atoms on the fullerene could be suppressed.

Example 4 Synthesis of Ru ₂ {C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C ₆ H ₄ COOEt] Me} Cp ₂
To a mixed solution of ethyl 4-iodobenzoate (0.051 mL, 0.30 mmol) and THF, THF solution (0.86M, 0.32 mL, 0.28 mmol) of iPrMgBr as a Grignard reagent was −25 ° C. And stirring was carried out for 2 hours. As shown in Scheme 8, this mixed solution was mixed with a copper reagent CuBr · SMe ₂ (62.7 mg, 0.304 mmol) and Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ Cp ₂ (50.0 mg, 25 To a mixed solution of .3 mmol of pyridine (5.0 mL) and orthodichlorobenzene (5.0 mL) at −25 ° C., then stirred at 40 ° C. for 18 hours, and added with 2.0 mL of methyl iodide to react. The product solution was concentrated and purified by silica gel column chromatography (eluent: hexane / toluene = 10/0 to 0/10) A strong red fraction was collected and the solvent was distilled off under reduced pressure. the crude product was purified by HPLC separation (RPFullerene, 250mm, toluene / acetonitrile = 5/5) to perform, Ru ₂ {C ₇₀ [4 _{tBuC 6 H 4] 6 [C} 6 H 4 COOEt] Me} Cp 2 was obtained (5.9mg, 2.8mmol, 11% yield).

¹ H-NMR was performed on the synthesized compound. The results were as follows.

¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ1.34 (s, 9H + 9H, t-Bu), 1.36 (s, 9H, t-Bu), 1.38 (t, J = 7.0 Hz, 3H, CH ₃ CH ₂ ) 1.39 (s, 9H, t-Bu), 1.41 (s, 9H, t-Bu), 1.45 (s, 9H, t-Bu), 2.18 (s, 3H, Me), 3.82 (s, 5H, Cp), 3.84 (s, 5H, Cp), 4.36 (q, J = 7.0 Hz, 2H, CH ₃ CH ₂ ), 7.33-8.22 (m, 28H, C ₆ H ₄ ).

The resulting Ru ₂ {C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C ₆ H ₄ COOEt] Me} Cp ₂ is subjected to deprotection treatment to form a carboxyl group, whereby Ru ₂ {C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C ₆ H ₄ COOH] Me} can be synthesized.

Synthesis Example 4 Synthesis of Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C ₅ H ₄ COCH ₂ CH ₂ CH ₂ Br] ₂
As shown in Scheme 9, Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ Cp ₂ (139 mg, 70.5 mmol) synthesized in Synthesis Example 2 and CS ₂ (5.0 mL) mixed with dark red To the solution, a mixed solution of AlCl ₃ (46.9 mg, 0.352 mmol), ClCOCH ₂ CH ₂ CH ₂ Br (0.041 mL, 0.35 mmol) and CS ₂ (5.0 mL) was added at room temperature. Then, the mixture was stirred for 15 minutes, and about 10 mL of water was added to stop the reaction. The reaction mixture was extracted with chloroform, the extract was dried over anhydrous MgSO ₄ , purified by silica gel column chromatography (eluent: toluene), and Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C _{5 H 4 COCH 2 CH 2 CH 2} Br] 2 (87.6mg, 38.6mmol, 55%) was obtained.

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR and MS analysis. The results were as follows.

¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ1.27 (m, 4H, CH ₂ CH ₂ CH ₂ ), 1.38 (s, 18H, t-Bu), 1.40 (s, 18H, t-Bu), 1.42 (s, 18H, t-Bu), 2.07 (m, 4H, CH ₂ CO), 2.75 (m, 4H, CH ₂ Br), 3.52 (s, 2H + 2H, C ₅ H ₄ ), 4.49 (s , 2H, C ₅ H ₄ ), 4.55 (s, 2H, C ₅ H ₄ ), 7.42 (d, J = 8.2 Hz, 4H, C ₆ H ₄ ), 7.49 (d, J = 8.2 Hz, 4H, C ₆ H ₄ ), 7.56 (d, J = 8.3 Hz, 4H, C ₆ H ₄ ), 7.68 (d, J = 8.3 Hz, 4H, C ₆ H ₄ ), 7.94 (d, J = 8.0 Hz, 4H, C ₆ H ₄ ), 8.07 (d, J = 8.3 Hz, 4H, C ₆ H ₄ ); ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz) δ27.04 (2C, CCCBr), 31.47 (6C, t- Bu (Me)), 31.48 (6C + 6C, t-Bu (Me)), 34.02 (2C, CBr), 34.86 (2C, t-Bu (C)), 34.92 (2C, t-Bu (C)) , 34.94 (2C, t-Bu (C)), 37.22 (2C, CCO), 55.33 (2C, C ₇₀ (sp ³ )), 56.84 (2C, C ₇₀ (sp ³ )), 59.13 (2C, C ₇₀ (sp ³ )), 74.11 (2C, C ₅ H ₄ ), 74.80 (2C, C ₅ H ₄ ), 78.01 (2C, C ₅ H ₄ ), 78.33 (2C, C ₅ H ₄ ), 84.66 (2C, C ₅ H ₄ ), 93.71 (2C, FCp), 94.28 (2C, FCp), 98.86 (2C, FCp), 99.64 (2C, FCp), 106.80 (2C, FCp), 125.11 (4C), 125.29 (4C) , 125.53 (4C), 125.71 (2C), 128.14 (4C ), 128.21 (4C), 128.78 (4C), 132.25 (2C), 133.98 (2C), 134.58 (2C), 135.77 (2C), 138.38 (2C), 142.20 (2C), 142.33 (2C), 142.51 (2C) ), 142.59 (2C), 143.34 (2C), 144.37 (2C), 145.35 (2C), 146.03 (2C), 146.65 (2C), 147.08 (2C), 147.63 (2C), 147.65 (2C + 2C), 148.05 (2C), 149.05 (2C), 149.08 (2C), 149.17 (2C), 149.91 (2C), 150.02 (2C), 151.07 (2C), 151.09 (2C), 151.23 (2C), 151.26 (2C), 151.34 (2C), 151.87 (2C), 159.07 (2C), 163.35 (2C), 199.47 (2C, CO); HRMS (APCI-TOF, positive) m / z calcd for C ₁₄₈ H ₉₉ Br ₂ O ₂ Ru ₂ ⁺ [M + H] ⁺ 2269.4093, found 2269.4049.

Synthesis Example 5 Synthesis of Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C ₅ H ₄ COCH ₂ CH ₂ CH ₂ SAc] ₂
As shown in Scheme 10, Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C ₅ H ₄ COCH ₂ CH ₂ CH ₂ Br] ₂ synthesized in Synthesis Example 4 (80.0 mg, 35.2 mmol) Potassium thioacetate (40.3 mg, 0.353 mmol) was added at room temperature to a dark red solution obtained by mixing water, tetrahydrofuran (8.0 mL) and N, N-dimethylformamide (8.0 mL), and the mixture was stirred for 10 minutes. About 20 mL was added to stop the reaction. The reaction mixture was extracted with chloroform, the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (eluent: toluene), and Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C ₅ H ₄ COCH ₂ CH ₂ CH ₂ SAc] ₂ (72.7 mg, 32.2 mmol, 91%) was obtained.

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR and MS analysis. The results were as follows.

¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ1.20-1.32 (m, 4H, CH ₂ CH ₂ CH ₂ ), 1.36 (s, 18H, t-Bu), 1.41 (s, 18H, t-Bu ), 1.43 (s, 18H, t-Bu), 1.94 (t, J = 7.4 Hz, 4H, CH ₂ CO), 2.18 (s, 6H, CH ₃ CO), 2.21-2.31 (m, 4H, CH ₂ S), 3.53 (s, 2H, C ₅ H ₄ ), 3.58 (s, 2H, C ₅ H ₄ ), 4.44 (s, 2H, C ₅ H ₄ ), 4.55 (s, 2H, C ₅ H ₄ ) , 7.44 (d, J = 8.2 Hz, 4H, C ₆ H ₄ ), 7.45 (d, J = 8.2 Hz, 4H, C ₆ H ₄ ), 7.57 (d, J = 8.5 Hz, 4H, C ₆ H ₄ ), 7.62 (d, J = 8.2 Hz, 4H, C ₆ H ₄ ), 7.96 (d, J = 8.2 Hz, 4H, C ₆ H ₄ ), 8.08 (d, J = 8.4 Hz, 4H, C ₆ H ₄ ); ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz) δ24.12 (2C, CCCS), 28.51 (2C, CH ₂ S), 30.72 (2C, CH ₃ CO), 31.45 (6C, t-Bu ( Me)), 31.48 (6C, t-Bu (Me)), 31.49 (6C, t-Bu (Me)), 34.87 (2C + 2C, t-Bu (C)), 34.95 (2C, t-Bu ( C)), 37.54 (2C, CH ₂ CO), 55.35 (2C, C ₇₀ (sp ³ )), 56.85 (2C, C ₇₀ (sp ³ )), 59.13 (2C, C ₇₀ (sp ³ )), 74.17 (2C, C ₅ H ₄ ), 74.59 (2C, C ₅ H ₄ ), 78.07 (2C, C ₅ H ₄ ), 78.20 (2C, C ₅ H ₄ ), 84.84 (2C, C ₅ H ₄ ), 93.43 (2C, FCp), 94.33 (2C, FCp), 98.80 (2C, FCp), 99.75 (2C, FCp), 106.66 (2C, FCp), 125.10 (4C), 125.24 (4C), 125.52 (4C), 125.92 (2C), 128.05 (4C), 128.23 (4C), 128.82 (4C), 132.23 ( 2C), 133.98 (2C), 134.57 (2C), 135.55 (2C), 138.38 (2C), 142.31 (2C), 142.38 (2C), 142.45 (2C), 142.54 (2C), 143.32 (2C), 144.36 ( 2C), 145.35 (2C), 146.04 (2C), 146.64 (2C), 147.08 (2C), 147.44 (2C), 147.59 (2C), 147.64 (2C), 148.09 (2C), 148.99 (2C), 149.06 ( 2C), 149.18 (2C), 149.89 (2C), 149.92 (2C), 150.93 (2C), 151.11 (2C), 151.26 (2C), 151.43 (2C), 151.51 (2C), 152.03 (2C), 158.93 ( 2C), 163.48 (2C), 195.45 (2C, CH ₃ CO), 199.69 (2C, CH ₂ CO); HRMS (APCI-TOF, positive) m / z calcd for C ₁₅₂ H ₁₀₅ O ₄ Ru ₂ S ₂ ⁺ [M + H] ⁺ 2261.5536, found 2261.5569.

Example 5 Synthesis of Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C ₅ H ₄ COCH ₂ CH ₂ CH ₂ SH] ₂
As shown in Scheme 11, Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C ₅ H ₄ COCH ₂ CH ₂ CH ₂ SAc] ₂ (6.3 mg, 2.8 mmol) synthesized in Synthesis Example 5 was used. ) And tetrahydrofuran (1.0 mL) mixed with a solution of potassium hydroxide in methanol (0.60 M, 0.092 mL, 55.2 mmol) at room temperature and stirred for 10 minutes, saturated aqueous ammonium chloride solution The reaction was stopped by adding 0.02 mL. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 10/0 to 9/1), and Ru ₂ C ₇₀ [4-tBuC ₆ H ₄ ] ₆ [C ₅ H ₄ COCH ₂ CH ₂ CH ₂ SH] ₂ (3.8 mg, 1.7 mmol, 63%) was obtained.

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR and MS analysis. The results were as follows.

¹ H NMR (CD ₂ Cl ₂ , 400 MHz) δ1.33 (s, 18H, t-Bu), 1.44 (s, 18H, t-Bu), 1.46 (s, 18H, t-Bu), 1.64-1.67 (m, 4H, CH ₂ CH ₂ CH ₂ ), 2.06-2.24 (m, 4H, CH ₂ CO), 2.39-2.55 (m, 4H, CH ₂ S), 3.62 (s, 2H, C ₅ H ₄ ) , 3.71 (s, 2H, C ₅ H ₄ ), 4.14 (s, 2H, C ₅ H ₄ ), 4.92 (s, 2H, C ₅ H ₄ ), 7.37 (d, J = 8.5 Hz, 4H, C ₆ H ₄ ), 7.49 (d, J = 8.5 Hz, 4H, C ₆ H ₄ ), 7.54 (d, J = 8.5 Hz, 4H, C ₆ H ₄ ), 7.61 (d, J = 8.5 Hz, 4H, C ₆ H ₄ ), 8.01 (d, J = 8.2 Hz, 4H, C ₆ H ₄ ), 8.19 (d, J = 8.5 Hz, 4H, C ₆ H ₄ ); ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz ) δ24.23 (2C, CCCS), 31.45 (6C, t-Bu (Me)), 31.52 (6C + 6C, t-Bu (Me)), 34.84 (2C, t-Bu (C)), 34.94 ( 2C, t-Bu (C)), 35.01 (2C, t-Bu (C)), 37.66 (2C, CCO), 39.50 (2C, CH ₂ S), 55.32 (2C, C ₇₀ (sp ³ )), 56.79 (2C, C ₇₀ (sp ³ )), 59.09 (2C, C ₇₀ (sp ³ )), 73.02 (2C, C ₅ H ₄ ), 76.01 (2C, C ₅ H ₄ ), 77.77 (2C, C ₅ H ₄ ), 78.31 (2C, C ₅ H ₄ ), 85.98 (2C, C ₅ H ₄ ), 94.10 (2C, FCp), 94.59 (2C, FCp), 98.37 (2C, FCp), 98.78 (2C, FCp ), 106.84 (2C, FCp), 125.11 (4C), 125.35 (4C), 125.46 (4C), 126.21 (2C), 127.83 (4C), 128.41 (4C), 129.01 (4C), 131.94 (2C), 133.93 (2C), 134.54 (2C), 136.43 (2C), 138.40 (2C), 141.69 (2C), 142.30 (2C), 142.41 (2C), 142.55 (2C), 143.28 (2C), 144.34 (2C), 145.32 (2C), 146.16 (2C), 146.51 (2C), 146.94 (2C), 147.07 (2C), 147.56 (2C), 147.70 (2C), 148.22 (2C), 148.29 (2C), 148.47 (2C), 148.69 (2C), 149.28 (2C), 149.82 (2C), 150.94 (2C), 151.32 (2C), 151.47 (2C), 151.78 (2C), 152.67 (2C), 152.84 (2C), 158.23 (2C), 163.73 (2C), 200.60 (2C, CO); HRMS (APCI-TOF, positive) m / z calcd for C ₁₄₈ H ₁₀₀ O ₂ Ru ₂ S ₂ ⁺ [M] ⁺ 2176.5252, found 2176.5195.

  Examples of the utilization method of the present invention include electronic devices such as transistors.

The cyclic voltammograms of the compound of Example 3 and the compound of Comparative Example 1 are shown.

Claims (7)

The following formula (1), (21), (22), (31) or (32)

[In the above formula, each R ³ is independently a C ₁ -C ₅ alkyl group;
R ⁴ is a C ₁ -C ₅ alkyl group;
Each R ⁵ is independently a C ₁ -C ₅ alkyl group;
Each of Mtl is independently Fe or Ru;
L are each independently a single bond, an alkylene good C ₁ -C ₅ may have a substituent, an alkenylene good C ₂ -C ₅ may have a substituent, which may have a substituent C ₂ -C ₅ alkynylene or C ₆ -C ₃₀ phenylene which may have a substituent , and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —S -, -COO-, -CO- or -OCO- may be replaced, and in these alkylene, alkenylene, alkynylene or phenylene, any hydrogen may be replaced by fluorine or chlorine;
m is each independently an integer of 0 to 5;
q is each independently an integer of 0 to 4;
n is an integer from 0 to 2;
Ar independently represents the following formula (A)


(In formula (A) , each R ¹ is independently a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer of 0-2 . )
It is group represented by these. ]
Having a partial structure represented in, fullerene C ₇₀ derivatives for monomolecular transistor. Following formula (1)


[In the above formula,
Each R ³ is independently a C ₁ -C ₂ alkyl group;
R ⁴ is a C ₁ -C ₃ alkyl group;
Each R ⁵ is independently a C ₁ -C ₅ alkyl group;
Each of Mtl is independently Fe or Ru;
L is a single bond, C _{1 to} C ₅ alkylene which may have a substituent, C _{2 to} C ₅ alkenylene which may have a substituent, or C _{2 to} C which may have a substituent. ₅ alkenylene or optionally substituted C ₆ -C ₃₀ phenylene, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each m is independently 0 or 5;
n is an integer from 0 to 2;
In formula (A),
Each R ¹ is independently a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer from 0 to 2,
Ar independently represents the following formula (A)

(In formula (A), R ¹ is a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer of 0-2. )
It is group represented by these. ]
A fullerene C ₇₀ derivative for a single molecule transistor having a partial structure represented by:
Two groups having Mtl, appended to the fullerene C ₇₀ is the source terminal and the drain terminal, respectively, a group having a ferrocene are added to the fullerene C ₇₀ is a gate terminal, fullerene C ₇₀ for monomolecular transistor Derivative. According to claim 2, a single-molecule transistor including a fullerene C ₇₀ derivatives for monomolecular transistor,
In the above formula (1),
Each R ³ is independently methyl or ethyl;
R ⁴ is methyl or ethyl;
Each R ⁵ is independently methyl or ethyl;
Each of Mtl is independently Fe or Ru;
L is a single bond, C _{1 to} C ₅ alkylene which may have a substituent, C _{2 to} C ₅ alkenylene which may have a substituent, or C _{2 to} C which may have a substituent. ₅ alkenylene or optionally substituted C ₆ -C ₃₀ phenylene, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each m is independently 0 or 5;
n is an integer from 0 to 2;
In formula (A),
Each R ¹ is independently methyl or ethyl;
Each R ² is independently methyl or ethyl;
p is an integer from 0 to 2,
A monomolecular transistor in which a source terminal and a drain terminal attached to fullerene C ₇₀ are joined to a conductive electrode, and a gate terminal is operated electrochemically. A fullerene _{C 70} derivative represented by the following formula (21) or (22)

[In the above formula,
Each R ³ is independently a C ₁ -C ₂ alkyl group;
R ⁴ is a C ₁ -C ₃ alkyl group;
Each R ⁵ is independently a C ₁ -C ₅ alkyl group;
Each of Mtl is independently Fe or Ru;
L is a single bond, C _{1 to} C ₅ alkylene which may have a substituent, C _{2 to} C ₅ alkenylene which may have a substituent, or C _{2 to} C which may have a substituent. ₅ alkenylene or optionally substituted C ₆ -C ₃₀ phenylene, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each m is independently 0 or 5;
n is an integer from 0 to 2;
In formula (A),
Each R ¹ is independently a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer from 0 to 2,
Ar independently represents the following formula (A)

(In formula (A), R ¹ is a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer of 0-2. )
It is group represented by these. ]
A fullerene C ₇₀ derivative for a single molecule transistor having a partial structure represented by:
Two groups having Mtl added to fullerene C ₇₀ are a source terminal and a drain terminal, respectively, and a group having a carboxyl group or a thiol group added to fullerene C ₇₀ is a gate terminal. fullerene _{C 70} derivatives. According to claim 4, a monomolecular transistor including a fullerene C ₇₀ derivatives for monomolecular transistor,
In the above formula (21) or (22),
Each R ³ is independently methyl or ethyl;
R ⁴ is methyl or ethyl;
Each R ⁵ is independently methyl or ethyl;
Each of Mtl is independently Fe or Ru;
L is a single bond, C _{1 to} C ₅ alkylene which may have a substituent, C _{2 to} C ₅ alkenylene which may have a substituent, or C _{2 to} C which may have a substituent. ₅ alkenylene or optionally substituted C ₆ -C ₃₀ phenylene, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each m is independently 0 or 5;
n is an integer from 0 to 2;
In formula (A),
Each R ¹ is independently methyl or ethyl;
Each R ² is independently methyl or ethyl;
p is an integer from 0 to 2,
The source and drain terminals, appended to the fullerene C ₇₀ is a conductive electrode, a gate terminal is bonded to the ITO electrode, the monomolecular transistor. A fullerene _{C 70} derivative represented by the following formula (31) or (32)

[In the above formula,
Each R ³ is independently a C ₁ -C ₂ alkyl group;
Each of Mtl is independently Fe or Ru;
L is a single bond, C _{1 to} C ₅ alkylene which may have a substituent, C _{2 to} C ₅ alkenylene which may have a substituent, or C _{2 to} C which may have a substituent. ₅ alkenylene or optionally substituted C ₆ -C ₃₀ phenylene, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each q is independently 0 or 4;
In formula (A),
Each R ¹ is independently a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer from 0 to 2,
Ar independently represents the following formula (A)

(In formula (A), R ¹ is a C ₁ -C ₃ alkyl group;
Each R ² is independently a C ₁ -C ₃ alkyl group;
p is an integer of 0-2. )
It is group represented by these. ]
A fullerene C ₇₀ derivative for a single molecule transistor having a partial structure represented by:
Are two groups the source and drain terminals respectively having a metal atom Mtl, appended to the fullerene C _70, fullerene C ₇₀ skeleton and gate terminal, fullerene C ₇₀ derivatives for monomolecular transistor. According to claim 6, a monomolecular transistor including a fullerene C ₇₀ derivatives for monomolecular transistor,
In the above formula (31) or (32),
Each R ³ is independently methyl or ethyl;
Each of Mtl is independently Fe or Ru;
L is a single bond, C _{1 to} C ₅ alkylene which may have a substituent, C _{2 to} C ₅ alkenylene which may have a substituent, or C _{2 to} C which may have a substituent. ₅ alkenylene or optionally substituted C ₆ -C ₃₀ phenylene, and in these alkylene, alkenylene, alkynylene or phenylene, any —CH ₂ — is —O—, —COO—, —CO—. Or may be replaced by -OCO-;
each q is independently 0 or 4;
In formula (A),
Each R ¹ is independently methyl or ethyl;
Each R ² is independently methyl or ethyl;
p is an integer from 0 to 2,
Joining the source and drain terminals, appended to the fullerene C ₇₀ is a conductive electrode, the monomolecular transistor to operate the gate terminal by electrons to fullerene C ₇₀ skeleton is injected.