JP3511092B2 - Luminescent materials and new fullerene derivatives - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to fullerene derivatives
The luminescent material consisting of

[0002]

2. Description of the Related Art Fullerenes have a large pi-electron conjugated system, and their utilization as a light emitting material is being investigated. However, in general, fullerene C
_{60 and the} like have a problem that light emission is weak because of good symmetry.

In order to solve the problem that the light emission is weak, attempts have been made to improve the light emission by breaking the symmetry by introducing a functional group into a fullerene having good symmetry, but there are many functional groups. Had to be introduced, and their introduction was not easy.

On the other hand, as the fullerene derivative having an aziridine group, a 4-acyl-2,3,5,6-tetrafluoro group is bonded to the nitrogen atom of an aridiridine group.
(M. Yan, SX Cai, and JFW Keana, J. Org. Ch
em., 1994, 59, 5951-5954), in which a phenyl group and a 4-cyanophenyl group are bonded (J. Averdung and J. Mat.
tay, Tetrahedron, 1996, 52, 5407-5420) or a bisazidofullerene derivative synthesized from 1,4-bis (2-azidophenyl) -1,3-butadiene derivative and C _60.
(G. Schick, T. Jarrosson, and Y. Rubin, Angew. Ch
Em. Int. Ed. Engl., 1999, 38, 2360-2363), but their properties as light emitting materials have not been reported.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides fullerene
Aiming to provide a novel light emitting material composed of a derivative
To do.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned objects, the present inventors have introduced one or more aziridine functional groups into fullerenes, and use them as aromatic substituents on the nitrogen atom of aziridine functional groups. The present inventors have found that a fullerene derivative having a group group is effective as a light emitting material, and completed the present invention.

That is, according to the present invention, firstly, a light emitting material comprising a fullerene derivative represented by the following general formula (1) is provided.

[Chemical 2] (Ar represents an aromatic group, and n represents a natural number.) Secondly, the fullerene derivative is represented by the general formula (1) in which Ar is
Is an aromatic monocyclic hydrocarbon group which may have a substituent, a condensed polycyclic aromatic hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent and which has aromaticity. A luminescent material of the first invention is provided, which is at least one selected from the group consisting of a monocyclic group and a fused heterocyclic group which may have a substituent and which has aromaticity. Thirdly, there is provided a luminescent material of the second invention, wherein Ar is a condensed polycyclic aromatic hydrocarbon group which may have a substituent.

The luminescent material of the present invention comprises the fullerene derivative represented by the general formula (1). This fullerene derivative has a structure in which the nitrogen atom of the aziridine functional group introduced into fullerene is substituted with an aromatic group. Conventionally, attempts have been made to increase the emission intensity by breaking the symmetry by introducing a functional group into a fullerene having good symmetry, but in this case, the introduction of one functional group seems to increase the emission intensity as much as possible. Although it is necessary to select a functional group, a conventionally known functional group does not significantly improve the emission intensity of fullerene. In the present invention, as the light emitting material, the one in which the aromatic group is substituted on the nitrogen atom of the aziridine functional group introduced into the fullerene is selected and used, so that the emission intensity of the fullerene can be significantly increased.

In the above general formula (1), which is the object of the present invention, as the fullerene forming the fullerene (skeleton), in addition to the fullerene consisting of only carbon, some of the carbons of these fullerenes are atoms other than carbon. , Fullerenes in which at least one atom is attached or bound to the inside or outside of these fullerenes, at least inside or outside the heterofullerene in which a part of carbon of the fullerene is changed to an atom other than carbon Heterofullerenes in which one atom is attached or bonded are included.

The number (n) of aziridine functional groups introduced is not particularly limited, but in the case of fullerene C ₆₀ , it is preferably 1-30, particularly preferably 1-6. It is preferable to introduce the aziridine functional group into other fullerenes at the same ratio.

As the group (Ar) substituted on the nitrogen atom of the aziridine functional group, an aromatic group having steric or electronic interaction with the fullerene body is used. This aromatic group has easily moving electrons such as pi-electrons, and the steric or electronic interaction between the aromatic group and the fullerene body is adjusted by selecting the substitution position of the aromatic moiety. can do.

Examples of the aromatic group include an aromatic monocyclic hydrocarbon group which may have a substituent, a condensed polycyclic aromatic hydrocarbon group which may have a substituent and a substituent. Examples thereof include a heteromonocyclic group exhibiting aromaticity and a fused heterocyclic group exhibiting aromaticity, which may have a substituent.

A phenyl group is used as the aromatic monocyclic hydrocarbon group, and a naphthyl group is used as the condensed polycyclic aromatic hydrocarbon group.
Anthryl group, phenanthryl group, etc., as a heteromonocyclic group exhibiting aromaticity, a 5-membered ring containing one hetero atom such as a furanyl group, a thiophenyl group, a pyrrolyl group, a hetero atom such as a pyridinyl group. 6-membered ring, oxazolyl group,
Five-membered ring containing two heteroatoms such as thiazolyl group, pyridazinyl group, six-membered ring containing two heteroatoms such as pyrimidinyl group, and others, five containing at least one heteroatom,
The condensed heterocyclic group in which the 6- or 7-membered ring exhibits aromaticity includes
Bicyclic fused hetero group containing one heteroatom such as indolyl group, quinolinyl group, bicyclic fused hetero group containing two hetero atoms such as quinoxalinyl group, tricyclic containing one hetero atom such as acridinyl group Examples thereof include a fused hetero group, a bicyclic fused hetero group containing two hetero atoms such as an indazolyl group, and a polycyclic fused hetero group containing at least one hetero atom. Further, the substituent is not particularly limited,
Alkyl group, aryl group, carboxy group, sulfonyl group, alkoxycarbonyl group, carbamoyl group, imide group, amidino group, cyano group, isocyano group, formyl group, carbonyl group, thiocarbonyl group, hydroxy group,
Examples thereof include mercapto group, amino group, imino group, alkoxy group, alkylthio group, halogen group and nitro group.
Also, the number thereof is not limited, and the aromatic group may have one or more substituents, and the aromatic group may not have a substituent.

All of the fullerene derivatives represented by the above general formula (1) can be used in the light emitting material of the present invention, but preferably, aromatic monocyclic hydrocarbon group in which Ar may have a substituent, a substituent A condensed polycyclic aromatic hydrocarbon group which may have
A heteromonocyclic group which may have a substituent and which has aromaticity, and a condensed heterocyclic group which has a substituent and which has aromaticity, more preferably Ar has a substituent. May condensation
Of a polycyclic aromatic hydrocarbon group, that is, the following general formula (2)
The fullerene derivative represented by is used.

[Chemical 3] (Ar is a condensed polycyclic aromatic hydrocarbon which may have a substituent.
Represents a base. )

The light emitting material of the present invention can be used as a light emitting body such as an organic light emitting diode by forming a thin film mixed with a polymer electrolyte or the like between two thin film electrodes and the like. It can also be used as a photoluminescent material by forming a thin film of the light emitting material of the present invention on a substrate.

The fullerene derivatives represented by the above general formulas (1) and (2) of the present invention synthesize N-arylazafulleroids by thermal reaction of fullerene and aromatic azide, and photochemically rearrange this compound. It can be synthesized by reacting. Specifically, in the general formula (2), a compound in which fullerene is C ₆₀ and Ar is a phenyl group is prepared by adding a phenyl azide 1,2-dichlorobenzene to a C ₆₀ 1,2-dichlorobenzene solution at _{60 to} 100 ° C. The solution may be added dropwise to synthesize N-phenylaza- [60] fulleroid, and this toluene solution may be irradiated with ultraviolet rays to synthesize it.

[0017]

The present invention will be described in more detail based on the following examples.

Example 1 N-phenylaza- [60] fulleroid was synthesized from fullerene C ₆₀ and phenyl azide as raw materials, and this toluene solution was irradiated with ultraviolet rays to introduce a phenylaziridinyl group to obtain 1,2- (N-phenylaziridino)
-[60] Fullerene was synthesized. In order to investigate the characteristics as a photoluminescence light emitting material, a 10 ⁻⁴ M toluene solution of this compound was prepared and excited with 500 nm light, and the emission intensity at 690 nm was 123 counts.

Example 2 N-1-naphthylaza- [60] fulleroid was synthesized from fullerene C ₆₀ and 1-azidonaphthalene as raw materials, and this toluene solution was irradiated with ultraviolet rays to give 1
-Naphthylaziridinyl group is introduced, and 1,2- (N-1
-Naphthylaziridino)-[60] fullerene was synthesized. When the characteristics of this material as a photoluminescent light emitting material were examined in the same manner as in Example 1, the emission intensity was 500.
It was a count.

Example 3 Fullerene C ₆₀ and 2-azidonaphthalene were used as raw materials to synthesize N-2-naphthylaza- [60] fulleroid, and this toluene solution was irradiated with ultraviolet rays to give
Introducing a 2-naphthylaziridinyl group to give 1,2- (N-
2-Naphthylaziridino)-[60] fullerene was synthesized. When the characteristics of this material as a photoluminescent light emitting material were examined in the same manner as in Example 1, the emission intensity was 62.
It was a count.

Comparative Example 1 When fullerene C ₆₀ was measured in the same manner as in Example 1, the emission intensity was 48 counts.

[0022]

In the present invention, as the light emitting material, the one in which the aromatic group is substituted on the nitrogen atom of the aziridine functional group introduced into the fullerene is selected and used, and therefore the emission intensity of the fullerene is remarkably increased. You can

Claims (3)

(57) [Claims] 1. A light emitting material comprising a fullerene derivative represented by the following general formula (1). [Chemical 1] (Ar represents an aromatic group and n represents a natural number.) 2. The fullerene derivative according to general formula (1), wherein Ar is an aromatic monocyclic hydrocarbon group which may have a substituent or a condensed polycyclic aromatic carbon which may have a substituent. At least one selected from a hydrogen group, a heteromonocyclic group which may have a substituent and which has aromaticity, and a condensed heterocyclic group which may have a substituent and which has aromaticity. The light-emitting material according to claim 1, which is characterized. 3. The light emitting material according to claim 2, wherein Ar is a condensed polycyclic aromatic hydrocarbon group which may have a substituent.