JP2000344764A - C60 fullerene molecular derivative and synthesis of c60 fullerene molecular derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject novel C60 fullerene compound that solves the defects of a linear type C60 fullerene compounds, and is a novel opposition type donor-acceptor compound and is useful as an element for electronic devices, optical devices and as an conductive element. SOLUTION: This compound is represented by formula I [n is 0-5; X and Y are each a (1-5C alkyl-substituted) methylene or the like; Z is a carbonyl oxygen or the like; R1 and R3 are each H, OH, a 1-5C alkoxy, a (substituted) alkoxy or the like; R5 is a 1-5C alkoxy, a (substituted) aryl or the like],typically a compound of formula II. The compound of formula I is prepared by reaction of a bis-malonic ester derivative of formula III with the C60 fluorine molecule in the presence of iodine (I2) and 1,8-diazabicyclo[5.4.0]-undecene-7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a C ₆₀ fullerene molecule as an electron acceptor, and a molecule in which various electron donating groups are introduced into a benzene ring of a bismalonate ester as an electron donor.
The present invention relates to a novel functional organic compound comprising a face-to-face donor / acceptor compound.

[0002]

Since having BACKGROUND ART C ₆₀ fullerene molecule highly electrophilic, donor-acceptor compound that the C ₆₀ fullerene molecule and an electron receptor, electronic devices, optical devices, conductive elements such as functional organic molecules ,Attention has been paid. Donor with C ₆₀ fullerene molecule as electron acceptor
The acceptor compound, heretofore has been linear compound connected is known a C ₆₀ fullerene molecule and an electron donor at a point, their electronic or optical properties and function are known. However, when using them as a material stack between molecules for specific shapes of C ₆₀ fullerene molecule is insufficient, sufficient properties as an aggregate, function did not express.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention solves the shortcomings of the linear C ₆₀ fullerene compounds, provides a novel donor-acceptor compounds, thus electronic devices, optical devices, material such as a conductive element It is an object of the present invention to provide a novel compound suitable for use as a compound, that is, a face-to-face donor / acceptor compound.

[0004]

Means for Solving the Problems Conventionally connected at one point
Straight type C₆₀To solve the problem of fullerene molecule,
C that is an electron acceptor (acceptor)₆₀Fullerene molecule
And an aromatic compound that is an electron donor (donor) at two points
The inventors noted the linked diadduct. Face to face
By fixing, the above-mentioned disadvantages are overcome and the electronic
It is expected that the efficiency of transfer will be improved. Donor Access
The charge transfer interaction between the putters is the face-to-face configuration of fullerenes.
Often observed in the position. Face-to-face donor access
Putter C ₆₀In compounds, the donor and acceptor are
Since it is fixed at two points, C₆₀Of fullerene molecular sites
Suppression of motion and strong intermolecular stacks
It becomes a crystal. Face-to-face donor-acceptor system C₆₀Frare
Since the compound is a bifunctional compound,
Synthetic material, C₆₀Including fullerene molecules in the polymer backbone
Constructed Donor / Acceptor Polymers Combining Main and Side Chains
it can. These organic materials are new electronic materials, optical materials
It can be expected to be used as a material (Figure 1).

Meanwhile, the C ₆₀ fullerene molecule, and a Bisumaron ester as Teta (I tie), I ₂
And 1,8-diazabicyclo [5.4.0] undec-7
- by reacting in the presence of ene (DBU), C ₆₀
A method of synthesizing a diadduct in which a fullerene molecule and an aromatic compound are linked at two points has been reported (Nierengart).
en. et al. Angew. Chem. Int. E
d. Engel. , 1996, 35, 2101: F. D
idederich et al. Helvetica
Chemica Acta. , 1997, 80, 223
8). The inventors paid their attention to this technique and tried to obtain better donor-acceptor interaction by introducing various electron donating groups into the benzene ring of the bismalonate ester as a tether.

[0006]

DETAILED DESCRIPTION OF THE INVENTION face-to-face donor-acceptor C ₆₀ fullerene compounds of the present invention, by introducing a variety of electron-donating groups on the benzene ring of Bisumaron ester,
And an electron donor is Teta in the rich electrons and a C ₆₀ fullerene molecule is an electron acceptor is bound in two places

Embedded image It is a compound shown by these.

It is necessary that at least two places on the benzene ring of the bismalonate ester as an electron donor are substituted with various electron donating groups. That is, at least two of R ¹ , R ² , R ³ and R ⁴ shown in Chemical Formula 12 are a hydroxyl group, a linear or branched alkoxy group having 1 to 5 carbon atoms, an unsubstituted or substituted aryloxy group. A straight-chain or branched alkylthio group having 1 to 5 carbon atoms, an unsubstituted or substituted arylthio group, an amino group, a straight-chain or branched alkyl group having 1 to 5 carbon atoms, a monosubstituted amino group, Need to be substituted with a linear or branched alkyl group disubstituted amino group, an unsubstituted or substituted aryl group monosubstituted amino group, or an unsubstituted or substituted aryl group disubstituted amino group. Substitution of the benzene ring with these molecules enriches the electrons of the electron donor and improves the efficiency of electron transfer.

Furthermore, C ₆₀ fullerene molecule and Teta molecules may need to be bound in two places. Formula 1 above
2, X and Y are X and Y are methylene, carbon number 1
To 5 linear or branched alkyl group monosubstituted methylene, 1 to 5 carbon atom linear or branched alkyl group disubstituted methylene, unsubstituted or substituted aryl group monosubstituted methylene, unsubstituted or substituted aryl group Examples include substituted methylene, ether oxygen, thioether sulfur, amino nitrogen, C1-C5 linear or branched alkyl-substituted amino nitrogen, or unsubstituted or substituted aryl-substituted amino group.

Also, between X and Y in the above chemical formula (12)
It is possible that n contains an alkylene chain of 0 to 5
You. Z is carbonyl oxygen or thiocarbonyl sulfur, etc.
R ^Five Is a linear or molecular alkyl having 1 to 5 carbon atoms
Group, unsubstituted or substituted aryl group or silyl group, etc.
is there. Also, C₆₀Two substitution methods attached to the fullerene molecule
The position of the tano group is cis-3, cis-2, cis-1,
Trial, Trans-4, Trans-3, Trans
2, Trans-1. The positions of the substituents are shown in FIG.
You.

A method for synthesizing the above compound is also within the scope of the present invention. Bismalonic acid ester derivatives and C ₆₀
The compound of the present invention can be synthesized by reacting a fullerene molecule with I ₂ at room temperature in the presence of DBU in an organic solvent such as toluene.

[0011]

EXAMPLES a derivative and C ₆₀ fullerene molecules Bisumaron ester, it is reacted in the presence of I ₂ and DBU in toluene (F.Diederich et a
l. Helvetica Chemica Act
a. , 1997, 80, 2238) to give a trans-4 adduct. The reaction was carried out at room temperature overnight. This reaction is shown in FIG. (1) Unsubstituted parent compound (2) Disubstituted methoxy group (R ¹ is methoxy group, R ² is hydrogen) (3) Tetrasubstituted methoxy group (R ¹ is methoxy group, R ² Is a methoxy group.) (4) Disubstituted bismethylenedioxy group, (R ¹
—R ² is cross-linked by a bismethylenedioxy group)

In this reaction, despite the fact that the yield of the unsubstituted parent compound of (1) is 33%, (2)
The yield of the disubstituted methoxy group of (3) was 71%, the yield of the tetrasubstituted methoxy group of (3) was 43%, and the yield of the disubstituted bismethylenedioxy group of (4) was 35%. . These results show that the yield and selectivity of the product are improved with respect to the parent compound of (1), especially in the case of the disubstituted methoxy group of (2).

The physical properties of the product were measured by a UV / Vis spectrum and examined. As a result, 470 nm
The absorption in the vicinity shifted to a shorter wavelength side by 1 nm for the disubstituted methoxy group of (2) and 7 nm for the tetrasubstituted methoxy group of (3) as the polarity of the solvent increased (FIG. 4). When the fluorescence spectrum was measured (excitation wavelength: 415 nm),
In (2), (3) and (4), the fluorescence around 720 nm decreased (FIG. 5). When the CV spectrum of the product was measured, the first reduction oxidation potential was higher than that of (1).
In (2), it decreased by 0.08 V, and in (3), it decreased by 0.16 V. From these results, it is found that the electron-rich aromatic ring as the electron donor and C as the acceptor having electrophilic properties
_It was shown that there is an effective charge transfer interaction with ₆₀ fullerene molecules.

[0014]

Effect of the Invention] According to the present invention, an electron acceptor to C ₆₀ fullerene molecule, an electron donor molecules introduced various electron donating groups on the benzene ring of Bisumaron acid ester, a new face-to-face donor-acceptor compound sponsored. The compound, due to its charge transfer interaction, electronic devices,
It can be used for optical devices, conductive elements, and the like.

[Brief description of the drawings]

FIG. 1 is a diagram showing the electronic interaction with the C ₆₀ fullerene molecule and the donor molecules.

Figure 2 shows the C ₆₀ fullerene molecule is a diagram showing the position of the substituent.

FIG. 3 is a diagram showing the generation of a face-to-face donor / acceptor compound by the reaction of a bismalonate derivative with a fullerene molecule and the yield of the product.

FIG. 4 shows the result of measuring the UV / Vis spectrum of the product.

FIG. 5 shows the fluorescence spectrum of the product at 415n.
It is a result measured at an excitation wavelength of m.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Jung Kenyu 1-43-1 Irumacho, Chofu-shi, Tokyo Shimizuso 205 (72) Inventor Shuichi Noguchi 10-14 Kita-Kapira-cho, Adachi-ku, Tokyo Subway Kita Ayase B107 (72 ) Inventor Takenori Miyauchi 2-4-4 Heiwadai, Nagareyama-shi, Chiba F-term (reference) 4C022 MA01

Claims (8)

[Claims] [Claim 1](N is 0 to 5, X and Y are methylene, carbon number
1 to 5 linear or branched alkyl group monosubstituted methylates
Linear or branched alkyl group having 1 to 5 carbon atoms
Substituted methylene, unsubstituted or substituted aryl group monosubstituted methylene
Unsubstituted or substituted aryl group disubstituted methylene, ether
No oxygen, thioether sulfur, amino nitrogen, 1 carbon
5 straight-chain or branched-chain alkyl-substituted amino nitrogens,
Or an unsubstituted or substituted aryl group-substituted amino group,
Z is carbonyl oxygen or thiocarbonyl sulfur;
¹ , R^Three Is hydrogen, a hydroxyl group, a straight chain having 1 to 5 carbon atoms or
Branched-chain alkoxy group, unsubstituted or substituted aryloxy
A linear or branched alkylthio group having 1 to 5 carbon atoms
Group, unsubstituted or substituted arylthio group, amino group, carbon number
1 to 5 linear or branched alkyl group monosubstituted amino
A linear or branched alkyl group having 1 to 5 carbon atoms
Substituted amino group, unsubstituted or substituted aryl group monosubstituted amino
Group or unsubstituted or substituted aryl group disubstituted amino group
And R^Two , R^Four Is a hydroxyl group, a straight-chain having 1 to 5 carbon atoms.
Chain or branched alkoxy, unsubstituted or substituted aryl
An oxy group, a linear or branched alkyl having 1 to 5 carbon atoms
Ruthio group, unsubstituted or substituted arylthio group, amino group,
Mono-substituted linear or branched alkyl group having 1 to 5 carbon atoms
Amino group, linear or branched alkyl having 1 to 5 carbon atoms
Disubstituted amino group, unsubstituted or substituted aryl group monosubstituted
Amino group or unsubstituted or substituted aryl group
A amino group;^Five Is linear or branched having 1 to 5 carbon atoms
Chain alkyl group, unsubstituted or substituted aryl group or
C which is a aryl group) ₆₀Fullerene molecular derivatives. ## STR2 ## (R ^1, of R ^2, at least one is an electron-donating group) C ₆₀ fullerene molecule derivative. (3) C ₆₀ fullerene molecule derivative of. (4) C ₆₀ fullerene molecule derivative of. (5) C ₆₀ fullerene molecule derivative of. (6) (R ¹ is hydrogen, a hydroxyl group, a linear or branched C1-C5 alkoxy group, an unsubstituted or substituted aryloxy group, a linear or branched C1-C5 alkylthio group, unsubstituted or substituted Arylthio group, amino group, C1-C5 linear or branched alkyl group monosubstituted amino group, C1-C5 linear or branched alkyl group disubstituted amino group, unsubstituted or substituted aryl group A monosubstituted amino group or an unsubstituted or substituted aryl group; a disubstituted amino group; R ² is a hydroxyl group, a linear or branched alkoxy group having 1 to 5 carbon atoms, an unsubstituted or substituted aryloxy group, A straight-chain or branched alkylthio group having 1 to 5 carbon atoms, an unsubstituted or substituted arylthio group, an amino group, a mono-substituted straight-chain or branched alkyl group having 1 to 5 carbon atoms, an amino group having 1 to 5 carbon atoms, Straight or branched chain alkyl group disubstituted amino group of the unsubstituted or substituted aryl group monosubstituted amino group, or an Bisumaron acid ester derivative represented by unsubstituted or substituted aryl group disubstituted amino group), and C ₆₀ fullerene molecules a, I ₂ and 1,8-diazabicyclo [5.
4.0] by reacting in the presence of undec-7-ene. (R ¹ is hydrogen, a hydroxyl group, a linear or branched C1-C5 alkoxy group, an unsubstituted or substituted aryloxy group, a linear or branched C1-C5 alkylthio group, unsubstituted or substituted Arylthio group, amino group, linear or branched alkyl group having 1 to 5 carbon atoms, monosubstituted amino group, linear or branched alkyl group having 1 to 5 carbon atoms, disubstituted amino group, unsubstituted or substituted aryl group A monosubstituted amino group or an unsubstituted or substituted aryl group; a disubstituted amino group; R ² is a hydroxyl group, a linear or branched alkoxy group having 1 to 5 carbon atoms, an unsubstituted or substituted aryloxy group, A straight-chain or branched alkylthio group having 1 to 5 carbon atoms, an unsubstituted or substituted arylthio group, an amino group, a mono-substituted straight-chain or branched alkyl group having 1 to 5 carbon atoms, an amino group having 1 to 5 carbon atoms, Made of straight-chain or branched-chain alkyl group disubstituted amino group, an unsubstituted or substituted aryl group monosubstituted amino group, or unsubstituted or shown in the substituted aryl group disubstituted amino group) process for obtaining the C ₆₀ fullerene molecule derivative, synthesis of C ₆₀ fullerene molecule derivative. (7) (R ^1, of R ^2, at least one is an electron-donating group) and Bisumaron ester derivative represented, and C ₆₀ fullerene molecules, I ₂ and 1,8-diazabicyclo [5.
4.0] by reacting in the presence of undec-7-ene. (R ^1, of R ^2, at least one a is an electron-donating group) consisting of a process of obtaining the C ₆₀ fullerene molecule derivative shown in the synthesis method of C ₆₀ fullerene molecule derivative. (8)(R¹ Is a methoxy group and R^Two Is hydrogen, or R¹ Is met
A xy group and R^Two Is a methoxy group, or R¹ -R^Two Is a screw
Bismalo cross-linked with a methylenedioxy group)
Acid ester derivative and C₆₀A fullerene molecule is represented by I_Two 
And 1,8-diazabicyclo [5.4.0] undec-7
-By reacting in the presence of ene(R¹ Is a methoxy group and R^Two Is hydrogen, or R¹ Is met
A xy group and R^Two Is a methoxy group, or R¹ -R^Two Is a screw
Cross-linked by a methylenedioxy group) ₆₀Hula
Comprising a process of obtaining a molecular derivative of₆₀Fullerene
A method for synthesizing a molecular derivative.