JP2019077673A - Dibenzopyrromethene boron chelate compound and use thereof - Google Patents

Abstract

To provide a dye having high light durability, workability which can be easily used for an organic electronics device or the like and an absorption band in the near infrared region.SOLUTION: There is provided a compound represented by the following formulas (1a) or (1b). (In the formulas (1a) and (1b), Rto Reach independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a hydroxy group, a mercapto group, a nitro group, a substituted amino group, an unsubstituted amino group, a cyano group, a sulfo group, an acyl group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group or an alkylcarbamoyl group; n and m each independently represent an integer of 1 to 4.)SELECTED DRAWING: Figure 1

Description

  The present invention relates to novel dibenzopyrromethene boron chelate compounds and applications of materials containing the same. The present invention relates particularly to novel dibenzopyrromethene boron chelate compounds having an absorption band in the near infrared light region, and applications to near infrared light absorbing materials, organic thin films and organic electronic devices comprising the compounds.

  Near infrared light absorbing materials having an absorption band in the wavelength range of 700 to 2500 nm are, for example, optical information recording media such as CD-R (Compact Disk-Recordable); thermal CTP (Computer To Plate), flash toner fixing, laser heat sensitive Printing applications such as recording; It is used in various applications such as heat blocking films, and is used for PDP (Plasma Display Panel) filters etc. by using the property of selectively absorbing light in a specific wavelength range It is also used in near-infrared light cut filters, films for regulating plant growth, and the like. Furthermore, a printed matter using a near-infrared light absorbing ink in which a near-infrared light absorbing dye is dissolved or dispersed in a solvent is difficult to visually recognize, and only with a near-infrared light detector or the like. Since it can be read, it is used, for example, for printed matter for the purpose of preventing forgery and the like.

  As such infrared light absorbing materials for forming an invisible image, inorganic infrared light absorbing materials and organic infrared light absorbing materials are known. Examples of inorganic infrared light absorbing materials include rare earth metals such as ytterbium, and glasses made of crystallized glass of copper phosphate. Inorganic infrared light absorbing materials generally have a light absorbing ability in the near infrared region. At low temperatures, a large amount of infrared light absorbing material is required per unit area when forming an invisible image. Therefore, when a visible image is further formed on an invisible image formed using an inorganic infrared light absorbing material, the unevenness of the surface of the invisible image affects the surface shape of the visible image. Met.

On the other hand, organic red light absorbing materials have high ability to absorb light in the near infrared region, and an infrared light absorbing material per unit area can form an invisible image with a small amount of inorganic red light. The disadvantages as in the case of using an external light absorbing material do not occur. Therefore, many organic near infrared light absorbing materials have been studied up to the present.
However, cyanine dyes, squalilium dyes, diimmonium dyes and the like exhibiting an absorption band in the near infrared region are all poor in fastness and their use is limited.

  Under these circumstances, in recent years, research on boron dipyrromethene dyes (hereinafter referred to as "BODIPY") showing absorption bands and fluorescence bands in the wavelength region of red light to near infrared light has been actively conducted. (See Non-Patent Document 1). BODIPY dyes with simple structures show strong absorption bands around 500 nm, but by extending the π-conjugated system or introducing aromatic groups with introduced electron-donating substituents, up to near-infrared light region It is possible to extend the absorption wavelength (Non-patent Document 2).

Non-patent documents 1 and 2 disclose that a dibenzopyrromethene boron chelate compound in which a pyrrole ring of a BODIPY skeleton is condensed has an absorption band shifted by a longer wavelength than a non-condensed BODIPY. Document 1 describes that the compound can be used as a near infrared light absorbing material in an optical recording medium.
Further, Non-Patent Documents 1 and 2 disclose that long wavelength shift can be achieved by forming a condensed ring structure by B-O chelation, and Patent Documents 2 to 4 disclose the said condensed ring structure. The organic thin film using the compound which it has is also reported.
Further, Patent Document 4 describes a B-O-chelated dipyrromethene boron chelate compound in which a heterocycle is linked to the 3,5 position of BODIPY, but examples of those compounds are not described.

JP, 1999-255774, A JP, 2012-199541, A JP, 2016-166284, A International Publication No. 2013/035303

Chem. Soc. Rev. , 2014, 43, 47778-4823. Chem. Rev. , 2007, 107, 4891-4932.

Presently mainstream near infrared light absorbing dyes have the problem of being inferior in heat resistance and light resistance, and development of materials having high industrial applicability and high light durability is desired. In particular, for materials used for various organic electronic device applications including organic photoelectric conversion elements, materials satisfying required properties such as electron transportability, hole transportability, heat resistance to process temperature, etc. are required.
BODIPY, which has relatively high heat resistance, is a promising material that may meet the above requirements, but only a few materials have an absorption band in the near-infrared light region, and an absorption band in the near-infrared light region. Most of the materials that have the main absorption wavelength in the visible light region are also difficult to synthesize. For example, although the application to the organic thin-film solar cell element is examined for the B—O chelate type dibenzopyrromethene boron chelate compound shown in Patent Document 2, the terminal of the photoelectric conversion wavelength reaches about 800 nm, It is not a near infrared light absorbing dye that has a near infrared light region as a main absorption band.

  An object of the present invention is a dye having high light durability, processability that can be easily used for organic electronic devices and the like, and a main absorption band in the near infrared light region (hereinafter referred to as “near infrared light absorbing dye Or “near infrared light absorbing material”.

  As a result of the investigations to solve the above problems, the present inventors have found that a novel dibenzopyrromethene boron chelate compound which forms a condensed ring structure by B-O chelation with a 5-membered ring substituted at the 3,5 position of BODIPY. It has been found that the above-mentioned problems are solved by using, and the present invention has been completed.

That is, the present invention is as follows.
[1] The following formula (1a) or (1b)

(R _{1 to} R _{4 in the} formulas (1a) and (1b) are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group Represents an unsubstituted amino group, cyano group, sulfo group, acyl group, sulfamoyl group, alkylsulfamoyl group, carbamoyl group, or alkylcarbamoyl group, and n and m each independently represent an integer of 1 to 4) A compound represented by
[2] the following formula (2)

(In the above formula (2), R _{1 to} R _{4 each} represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group, an unsubstituted amino group, A cyano group, a sulfo group, an acyl group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group or an alkylcarbamoyl group).
[3] The preceding clause [2] or [wherein R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group, an aromatic group or a halogen atom, and R ₃ and R ₄ are each independently a hydrogen atom or an aromatic group 2],
[4] A near infrared light absorbing material comprising the compound according to any one of the above [1] to [3],
[5] An organic thin film comprising the compound according to any one of the above [1] to [3],
[6] An organic electronic device comprising the compound according to any one of [1] to [3].
[7] A method for producing a compound represented by the formula (1a) or (1b) according to the preceding [1], which is a compound represented by the following formula (a) or (b)

(R _{1 to} R _{4 in the} formulas (a) and (b) are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group Represents an unsubstituted amino group, a cyano group, a sulfo group, an acyl group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group, or an alkylcarbamoyl group, R ₅ represents a hydrogen atom or an alkyl group, and n and m each represent A method of reacting a compound represented by 1.) independently with an integer of 1 to 4 with a boron trifluoride diethyl ether complex or a boron tribromide, and [8] the following formula (a) or (b)

(R _{1 to} R _{4 in the} formulas (a) and (b) are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group Represents an unsubstituted amino group, a cyano group, a sulfo group, an acyl group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group, or an alkylcarbamoyl group, R ₅ represents a hydrogen atom or an alkyl group, and n and m each represent A compound independently represented by 1 to 4).

  An organic compound which has a main absorption band in the near infrared light region and can be used for a near infrared photoelectric conversion device by using the dibenzopyrromethene boron chelate compound represented by the formula (1a) or (1b) of the present invention Since the thin film can be formed, the compound and / or the organic thin film can be used for various organic electronic devices.

FIG. 1 shows a cross-sectional view illustrating an embodiment of the photoelectric conversion element of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the layer configuration of the organic electroluminescent element. FIG. 3 shows measurement results of absorption spectra of chloroform solutions of the compounds obtained in Example 2 and Comparative Example 1. FIG. 4 shows the measurement results of absorption spectra of the organic thin films obtained in Example 3 and Comparative Example 2. FIG. 5 shows the results of measurement of absorption spectra of chloroform solutions of the compounds obtained in Example 1 and Comparative Example 1. FIG. 6 shows the measurement results of absorption spectra of the organic thin films obtained in Example 4 and Comparative Example 2.

  Hereinafter, the present invention will be described in detail. While the descriptions of the constituent elements described herein are based on representative embodiments and examples of the present invention, the present invention is not limited to such embodiments and examples. In addition, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. Further, in the present invention, the near infrared region refers to a wavelength region in the range of 700 nm to 2500 nm, and the near infrared light absorbing material (pigment) refers to a material having a main absorption wavelength in the near infrared light region. The near infrared light emitting material (pigment) means a material which emits light in the near infrared light region.

  The compound of the present invention is represented by the following formula (1a) or (1b).

R _{1 to} R _{4 in} formulas (1a) and (1b) each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group, It represents an unsubstituted amino group, a cyano group, a sulfo group, an acyl group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group or an alkylcarbamoyl group.
In addition, the compound represented by said Formula (1a) or (1b) is only what showed one of the resonant structures, and is not limited to the illustrated resonant structure.

As the alkyl group in the above formulas (1a) and (1b), methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group A linear or branched alkyl group having 1 to 12 carbon atoms such as a group; and a cyclic alkyl group having 3 to 6 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group.
Examples of the alkoxy group in the above formulas (1a) and (1b) include those in which an alkyl group is bonded to an oxygen atom, but the number, the position and the number of branches of the oxygen atom in the alkoxy group are not limited. As an alkyl group which an alkoxy group has, the same thing as the C1-C12 linear or branched alkyl group mentioned above and a C3-C6 cyclic alkyl group is mentioned.
Examples of the alkylthio group in the above formulas (1a) and (1b) include those in which an alkyl group is bonded to a sulfur atom, but the number, position and branch number of sulfur atoms in the alkylthio group are not limited. As an alkyl group which an alkylthio group has, the same thing as the above-mentioned C1-C12 linear or branched alkyl group and a C3-C6 cyclic alkyl group is mentioned.

The aromatic group in the above formulas (1a) and (1b) is an aromatic hydrocarbon group such as phenyl group, biphenyl group, indenyl group, naphthyl group, anthryl group, fluorenyl group and pyrenyl group; furanyl group, thienyl group Aromatic heterocyclic groups such as thienothienyl group, pyrrolyl group, imidazolyl group, N-methylimidazolyl group, thiazolyl group, oxazolyl group, pyridyl group, pyrazyl group and pyrimidyl group; quinolyl group, indolyl group, benzopyrazyl group, benzopyrimidyl group, Benzothienyl group, benzothiazolyl group, pyridino thiazolyl group, benzoimidazolyl group, pyridino imidazolyl group, N-methylbenzoimidazolyl group, pyridino-N-methylimidazolyl group, benzoxazolyl group, pyridino oxazolyl group, benzo Thiadiazolyl group, pyridinochi Condensed polycyclic aromatic compounds such as diazolyl group, benzooxadiazolyl group, pyridinooxadiazolyl group, carbazolyl group, phenoxazinyl group, phenothiazinyl group, N-methylphthalimide group and N-methyl-1,8-naphthalimide group A heterocyclic group etc. are mentioned, An aromatic hydrocarbon group is preferable and a phenyl group is more preferable. In addition, various substituents may be introduced into these aromatic groups, and as the substituent which may be introduced, hydrogen atoms other than hydrogen atoms represented by R _{1 to} R ₄ in formulas (1a) and (1b) may be introduced. And the same as the substituents of

As a halogen atom in said Formula (1a) and (1b), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
Examples of the substituted amino group in the above formulas (1a) and (1b) include those in which a substituent is introduced to the hydrogen atom of a non-substituted amino group (—NH ₂ group), and among these, substitution with the above aromatic group Are preferred.
The acyl group in the above formulas (1a) and (1b) is a carbonyl group to which an aromatic group or an alkyl group is bonded, and as the aromatic group in the acyl group and the alkyl group in the acyl group, The same groups as the alkyl group and acyl group represented by R _{1 to} R ₄ in the above-mentioned formulas (1a) and (1b) can be mentioned.

The alkylsulfamoyl group in the above formulas (1a) and (1b) is one in which the hydrogen atom of the sulfamoyl group is substituted with an alkyl group, and the alkyl group in the alkylsulfamoyl group is as described above The same as the alkyl group represented by R _{1 to} R _{4 in the} formulas (1a) and (1b) can be mentioned.
The alkylcarbamoyl group in the above formulas (1a) and (1b) is obtained by substituting the hydrogen atom of the carbamoyl group with an alkyl group, and as the alkyl group in the alkylcarbamoyl group, the above-mentioned formula (1a) And the same as the alkyl group represented by R _{1 to} R _{4 in} (1b).

R ₁ and R _{2 in the} above formulas (1a) and (1b) are preferably a hydrogen atom, an alkyl group, an aromatic group or a halogen atom, more preferably a hydrogen atom or a halogen atom, hydrogen More preferably, it is an atom.
As R ₃ and R _{4 in the} above formulas (1a) and (1b), an aromatic group or an aromatic group having a substituent is preferable, an aromatic hydrocarbon group is more preferable, and a phenyl group is still more preferable. By setting R ₃ and R ₄ in formulas (1a) and (1b) to be an aromatic group or an aromatic group having a substituent, the absorption wavelength of the compound represented by formula (1a) or (1b) can be extended It is possible to wavelengthize.
In addition, from the viewpoint of easy synthesis of the compound, it is preferable that the left and right substituents be identical and symmetrical. That is, it is preferable that R ₁ and R ₂ in the formulas (1a) and (1b) are the same, R ₃ and R ₄ are the same, and n and m described later are the same, for example, R ₁ = R ₃ = R ₂ = R ₄ may be adopted.

N and m in the formulas (1a) and (1b) each independently represent an integer of 1 to 4, preferably an integer of 1 to 2.
N and m in the formulas (1a) and (1b) are more preferably 1, and the compound represented by the formula (1a) is more preferable than the compound represented by the formula (1b). That is, the compound which is one of the preferable embodiment of this invention is represented by following formula (2).

R _{1 to} R ₄ in the above formula (2) are a hydrogen atom, alkyl group, alkoxy group, alkylthio group, aromatic group, halogen atom, hydroxyl group, mercapto group, nitro group, substituted amino group, unsubstituted amino group, cyano It represents a group, a sulfo group, an acyl group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group or an alkylcarbamoyl group.

Specific examples of the alkyl group, alkoxy group, alkylthio group, aromatic group, halogen atom, substituted amino group, acyl group, alkylsulfamoyl group and alkylcarbamoyl group represented by R _{1 to} R ₄ in the formula (2) are An alkyl group represented by R _{1 to} R _{4 in the} formulas (1a) and (1b), an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a substituted amino group, an acyl group, an alkylsulfamoyl group and an alkylcarbamoyl group The same applies to the groups, and preferred embodiments of these substituents and R _{1 to} R ₄ are also the same as the preferred embodiments of the formulas (1a) and (1b).

Next, methods for synthesizing the compounds of the present invention will be described.
Reaction step follows is represented by the general formula is one of the preferred embodiments of the present invention (1a), R ₁ and R ₂ are identical, one example of a synthesis method of the compound R ₃ and R ₄ are the same Is described.

Also, the reaction steps described below is represented by the general formula (1b) of the present invention, R ₁ and R ₂ are identical, are those described one example of a synthesis method of the compound R ₃ and R ₄ are the same .

In the above reaction step, Compound 1 can be obtained by reacting Diethyl bromomalonate with a compound having a Thioamide group in toluene in the same manner as a known method (J. Med. Chem., 2014, 57, 970-986) .
Compound 2 can be obtained by reacting potassium carbonate with iodomethane in N, N-dimethylformamide, referring to a known method (WO2007 / 089031 Al).
Compound 7 can be synthesized using Compound 2 as a starting material, with reference to a known method (Tetrahedron Letters, 2008, 49, 3716-3721). Specifically, first, Compound 2 or 12 is reacted with hydrazine monohydrate in alcohol to obtain Compound 3 or 13. Next, compound 3 or 13 is reacted with 2-Acetophenol or a derivative thereof in alcohol to obtain compound 4 or 14, and then the hydrazone in compound 4 or 14 is converted to a diketone with lead tetraacetate. 5 or 15 are obtained. Furthermore, compound 6 or 16 is obtained by adding an ammonium salt such as ammonium acetate to compound 5 or 15 in a solvent, and then obtained in the presence of a tertiary amine such as N, N-diisopropylethylamine. Compound 7 or 17 is obtained by reacting compound 6 or 16 with boron trifluoride (eg, boron trifluoride diethyl ether complex etc.). Finally, the compound 7 or 17 is treated with a demethylating agent such as boron tribromide in a solvent to give the compound of the present invention which is the object.
The purification method of these compounds obtained by the synthesis is not particularly limited. For example, known methods such as washing, recrystallization, column chromatography or vacuum sublimation may be adopted, and these methods may be combined as required. Can.

  The intermediate compounds 7 and 17 in the above reaction step have the same effects as the compounds represented by the above formulas (1a) or (1b), that is, they have a main absorption band in the near infrared region and are near Since an organic thin film that can be used for an infrared photoelectric conversion element can be formed, the compound can also be used for an infrared absorbing material, an organic thin film, and an organic electronic device. Therefore, a compound represented by the following formula (a) or (b) (compound 7 or 17 in the above reaction step) is also included in the category of the compound of the present invention.

Wherein (a) and (b), _{R 1} to _{R 4} have the same meanings as _{R 1} to _{R 4} in the formula (1a) and (1b), in preferred also formula (1a) and (1b) The same as R _{1 to} R ₄ .
In formulas (a) and (b), R ₅ represents a hydrogen atom or an alkyl group. Specific examples of the alkyl group represented by R _{5 in} formulas (a) and (b) include the same as the alkyl group in formulas (1a) and (1b) described above, and a linear alkyl group is preferable, A C1-C6 linear alkyl group is more preferable, a C1-C4 linear alkyl group is more preferable, a methyl group or an ethyl group is particularly preferable, and a methyl group is most preferable.
In formulas (a) and (b), m and n have the same meanings as m and n in formulas (1a) and (1b), and preferred ones also have m and n in formulas (1a) and (1b) It is the same.

Although the compound represented by Formula (1-1) thru | or (1-317) is shown below as a specific example of a compound represented by said Formula (1a) or (1b), this invention is not limited to this.
The structural formula shown as a specific example is merely one representing one of the resonant structures, and is not limited to the illustrated resonant structure.

As a specific example of a compound represented by said Formula (a) or (b), R < ₁ > -R < ₄ > in Formula (a) or (b), m, and n mentioned above Formula (1a) or (1b) The same compounds as R _{1 to} R ₄ , m and n in the specific example of the compound represented by the above, and a compound in which R ₅ is a hydrogen atom or an alkyl group can be mentioned.

  The molecular weight of the compound represented by the formula (1a) or (1b) is, for example, intended to form and use an organic layer containing the compound represented by the formula (1a) or (1b) by a vapor deposition method In some cases, it is preferably 1500 or less, more preferably 1200 or less, still more preferably 1000 or less, and particularly preferably 800 or less. The lower limit value of the molecular weight is the minimum value of the molecular weight which the compound represented by the formula (1a) or (1b) can take. The compound represented by the formula (1a) or (1b) may be formed into a film by a coating method regardless of the molecular weight. By using a coating method, even a compound having a relatively large molecular weight can be formed into a film. In addition, the molecular weight of the compound represented by Formula (a) or (b) is also the same.

The near infrared light absorbing material of the present invention contains the compound represented by the formula (a), (b), (1a) or (1b) of the present invention. Although the content of the compound represented by the formula (a), (b), (1a) or (1b) in the near infrared light absorbing material is not particularly limited, the content of the compound in the near infrared light absorbing material is usually 50 to 50 The near-infrared light absorbing material which is 100% by mass, preferably 70 to 100% by mass, more preferably 90 to 100% by mass, is represented by the formula (a), (b), (1a) or (1b) Any one or more compounds may be contained, and in the case of containing two or more compounds, the total content thereof may be in the above range.
A near infrared light absorbing material is a material that can be used in various fields and applications where the absorption characteristics of near infrared light are required. The form in which the near infrared light absorbing material is used may be selected according to the field or application.

An organic thin film can be produced using the compound of the present invention. Although the said organic thin film may be comprised only with the compound of this invention, you may contain the separately well-known near-infrared light absorption pigment | dye. The organic thin film preferably absorbs light of a wavelength of 750 nm or more, more preferably absorbs light of a wavelength of 800 nm or more, and more preferably light of a wavelength of 850 nm or more, for the purpose of absorbing near infrared light. It is further preferred to absorb. That is, the preferred absorption wavelength of the compound of the present invention is also the same as the preferred absorption wavelength of the organic thin film. Accordingly, in the absorption spectrum of the compound of the present invention, λmax (maximum absorption wavelength) on the long wavelength side of 500 nm or more is preferably 800 nm or more, and more preferably 850 nm or more.
The absorption spectrum in the present specification is a visible light spectrophotometer UV-1700 (Shimadzu Corporation), a chloroform solution of the compound of the present invention, or an organic thin film formed by depositing the compound of the present invention on a glass substrate. Means the result measured by

Examples of the method for forming an organic thin film of the present invention include a general dry film forming method and a wet film forming method. Specifically, vacuum processes such as resistance heating evaporation, electron beam evaporation, sputtering and molecular lamination, solution processes such as casting, spin coating, dip coating, blade coating, wire bar coating and spray coating, inkjet Examples of the method include printing methods such as printing, screen printing, offset printing and letterpress printing, and soft lithography methods such as microcontact printing.
Generally, it is desirable that near infrared light absorbing dyes can be used in a process (solution process) of applying a compound in a solution state from the viewpoint of ease of processing, but a plurality of organic thin films (organic layers) In the case of organic electronic device applications where a layer is used in layers, it is not necessary that the coating solution can be used in a solution process because the coating solution may attack the underlying organic thin film, but rather a dry deposition method such as resistance heating It is appropriate to use for deposition or the like. Therefore, a near infrared light absorbing dye having a main absorption wavelength in the near infrared region and which can be used in the dry film forming method is preferable as the near infrared photoelectric conversion material.

  You may employ | adopt the method which combined multiple said methods for film-forming of each layer. The thickness of each layer can not be limited because it depends on the resistance value / charge mobility of each material, but it is usually in the range of 0.5 to 5000 nm, preferably in the range of 1 to 1000 nm, more preferably 5 In the range of -500 nm.

[Organic electronics device]
An organic electronic device comprising the compound of the present invention or a near infrared light absorbing material or an organic thin film using them can be produced. As an organic electronic device, for example, a thin film transistor, an organic photoelectric conversion element, an organic solar cell element, an organic electroluminescent element (hereinafter referred to as "organic EL element" or "organic light emitting element"), an organic light emitting transistor element, an organic semiconductor A laser element etc. are mentioned. In the present invention, attention is particularly focused on organic photoelectric conversion elements and organic EL elements expected to be developed for near infrared applications. Here, a near infrared organic photoelectric conversion device used as a near infrared light absorbing material which is one of the embodiments of the present invention, an organic EL device using near infrared light emission characteristics, and an organic semiconductor laser device will be described. Although not described in detail here, near infrared light over 700 nm has high permeability to living tissue. Therefore, since it is possible to use for observation of in-vivo tissue, it can be applied in various modes according to the purpose in pathologic elucidation, diagnosis etc. of medical field such as near-infrared fluorescent probe etc. .

[Organic photoelectric conversion element]
The compound represented by the above formula (a), (b), (1a) or (1b) is a compound having near-infrared light absorption properties, and therefore, its use as a near-infrared organic photoelectric conversion device is expected Ru. In particular, it can use for the photoelectric converting layer in the organic photoelectric conversion element of this invention. In the element, it is preferable that the maximum absorption of the absorption band of the response wavelength light to light be 700 nm or more and 2500 nm or less. Here, as the near-infrared organic photoelectric conversion device, a near-infrared light sensor, an organic imaging device, a near-infrared light image sensor and the like can be mentioned.

  The organic photoelectric conversion element is an element in which a photoelectric conversion portion (film) is disposed between a pair of opposing electrode films, and light is incident on the photoelectric conversion portion from above the electrode film. The photoelectric conversion unit generates electrons and holes in response to the incident light, and a signal corresponding to the charge is read by the semiconductor, and an element showing an incident light amount in accordance with the absorption wavelength of the photoelectric conversion film unit. It is. There are also cases where a transistor for readout is connected to the electrode film on the side where light does not enter. When a large number of photoelectric conversion elements are arranged in the form of an array, in addition to the amount of incident light, they also indicate incident position information, and thus become an imaging element. When the photoelectric conversion element arranged closer to the light source does not block (transmit) the absorption wavelength of the photoelectric conversion element arranged behind it as viewed from the light source side, a plurality of photoelectric conversion elements are stacked. You may use.

The organic photoelectric conversion element of this invention can use the compound represented by said Formula (a), (b), (1a) or (1b) as a constituent material of the said photoelectric conversion part.
The photoelectric conversion portion is one or more selected from the group consisting of a photoelectric conversion layer, an electron transport layer, a hole transport layer, an electron block layer, a hole block layer, a crystallization prevention layer, an interlayer contact improvement layer, etc. It often comprises an organic thin film layer other than the photoelectric conversion layer. Although the compound of this invention can also be used besides a photoelectric converting layer, it is preferable to use as an organic thin film layer of a photoelectric converting layer. The photoelectric conversion layer may be composed of only the compound represented by the formula (a), (b), (1a) or (1b), but the formula (a), (b), (1a) or In addition to the compounds represented by (1b), known near infrared light absorbing materials and others may be contained.

  In the electrode film used in the organic photoelectric conversion element of the present invention, when the photoelectric conversion layer contained in the photoelectric conversion portion described later has hole transportability or the organic thin film layer other than the photoelectric conversion layer has hole transportability When it is a hole transport layer, it plays a role of taking out holes from the photoelectric conversion layer and other organic thin film layers and collecting the holes, and the photoelectric conversion layer included in the photoelectric conversion portion has electron transportability In the case where the organic thin film layer is an electron transporting layer having an electron transporting property, it plays a role of taking out electrons from the photoelectric conversion layer and other organic thin film layers and discharging the electrons. Therefore, the material that can be used as the electrode film is not particularly limited as long as it has a certain degree of conductivity, but adhesion to adjacent photoelectric conversion layers and other organic thin film layers, electron affinity, ionization potential, stability, etc. It is preferable to select in consideration of As a material which can be used as an electrode film, for example, conductive metal oxides such as tin oxide (NESA), indium oxide, indium tin oxide (ITO) and zinc indium oxide (IZO); gold, silver, platinum, chromium, aluminum Metals such as iron, cobalt, nickel and tungsten: Inorganic conductive substances such as copper iodide and copper sulfide: Conductive polymers such as polythiophene, polypyrrole and polyaniline: Carbon and the like. A plurality of these materials may be mixed and used as needed, and a plurality of these materials may be stacked and used in two or more layers. The conductivity of the material used for the electrode film is not particularly limited as long as the light reception of the photoelectric conversion element is not disturbed more than necessary, but it is preferable that it is as high as possible from the viewpoint of signal strength of the photoelectric conversion element and power consumption. For example, an ITO film having a sheet resistance value of 300 ohms / square or less functions sufficiently as an electrode film, but a commercially available substrate having an ITO film having a conductivity of several ohms / square or so is also available. Therefore, it is desirable to use a substrate having such high conductivity. The thickness of the ITO film (electrode film) can be arbitrarily selected in consideration of the conductivity, but it is usually 5 to 500 nm, preferably about 10 to 300 nm. Examples of the method for forming a film such as ITO include a conventionally known vapor deposition method, an electron beam method, a sputtering method, a chemical reaction method, a coating method and the like. The ITO film provided on the substrate may be subjected to UV-ozone treatment, plasma treatment or the like as required.

The material of the transparent electrode film used for at least one of the electrode films on the light incident side includes ITO, IZO, SnO ₂ , ATO (antimony-doped tin oxide), ZnO, AZO (Al-doped zinc oxide) GZO (gallium-doped zinc oxide), TiO ₂ , FTO (fluorine-doped tin oxide), and the like. The transmittance of light incident through the transparent electrode film at the absorption peak wavelength of the photoelectric conversion layer is preferably 60% or more, more preferably 80% or more, and particularly preferably 95% or more .

  In addition, in the case where a plurality of photoelectric conversion layers having different wavelengths to be detected are stacked, an electrode film (which is an electrode film other than the pair of electrode films described above) used between each photoelectric conversion layer It is necessary to transmit light of a wavelength other than that detected by the conversion layer, and it is preferable to use a material that transmits 90% or more of incident light for the electrode film, and uses a material that transmits 95% or more of light Is more preferred.

  The electrode film is preferably made plasma free. By forming these electrode films without using plasma, the influence of plasma on the substrate on which the electrode film is provided can be reduced, and the photoelectric conversion characteristics of the photoelectric conversion element can be improved. Here, plasma-free means that no plasma is generated during deposition of the electrode film, or the distance from the plasma source to the substrate is 2 cm or more, preferably 10 cm or more, more preferably 20 cm or more, and reaches the substrate It means that the plasma can be reduced.

  As an apparatus which plasma does not generate | occur | produce at the time of film-forming of an electrode film, an electron beam vapor deposition apparatus (EB vapor deposition apparatus), a pulse laser vapor deposition apparatus, etc. are mentioned, for example. A method of forming a transparent electrode film using an EB vapor deposition apparatus is referred to as EB vapor deposition, and a method of forming a transparent electrode film using a pulsed laser vapor deposition apparatus is referred to as pulsed laser vapor deposition.

  As an apparatus capable of realizing a state capable of reducing plasma during film formation (hereinafter, referred to as a film forming apparatus which is free from plasma), for example, a facing target sputtering apparatus, an arc plasma deposition apparatus, etc. can be considered.

  When the transparent conductive film is an electrode film (for example, the first conductive film), DC shorting or an increase in leak current may occur. One of the causes is that fine cracks generated in the photoelectric conversion layer are covered with a dense film such as TCO (Transparent Conductive Oxide) and the conduction between the transparent conductive film and the electrode film on the opposite side is increased. it is conceivable that. Therefore, when a material such as Al, which is inferior in film quality, is used for the electrode, the increase of the leak current hardly occurs. By controlling the film thickness of the electrode film in accordance with the film thickness (depth of the crack) of the photoelectric conversion layer, it is possible to suppress an increase in leak current.

  Usually, when the conductive film is thinner than a predetermined value, a sharp increase in resistance occurs. The sheet resistance of the conductive film in the photoelectric conversion element for an optical sensor of the present embodiment is usually 100 to 10000 Ω / □, and the degree of freedom of the film thickness is large. In addition, the thinner the transparent conductive film, the smaller the amount of light absorbed, and generally the higher the light transmittance. When the light transmittance is high, the light absorbed by the photoelectric conversion layer is increased to improve the photoelectric conversion ability, which is very preferable.

  The photoelectric conversion part which the organic photoelectric conversion element of the present invention has may include an organic thin film layer other than the photoelectric conversion layer and the photoelectric conversion layer. Although an organic semiconductor film is generally used for the photoelectric conversion layer constituting the photoelectric conversion portion, the organic semiconductor film may be a single layer or a plurality of layers, and in the case of a single layer, a p-type organic semiconductor film, n Type organic semiconductor film, or a mixed film thereof (bulk heterostructure) is used. On the other hand, when it is a plurality of layers, it is about 2 to 10 layers, and is a structure in which any of a p-type organic semiconductor film, an n-type organic semiconductor film, or a mixed film thereof (bulk heterostructure) is stacked. A buffer layer may be inserted in In addition, when forming a photoelectric converting layer by said mixed film, the compound represented by Formula (a), (b), (1a) or (1b) of this invention is used as a p-type-semiconductor material, and an n-type semiconductor As a material, it is preferable to use a general fullerene or a derivative thereof.

  In the organic photoelectric conversion device of the present invention, the organic thin film layer other than the photoelectric conversion layer constituting the photoelectric conversion part is a layer other than the photoelectric conversion layer, for example, an electron transport layer, a hole transport layer, an electron block layer, a hole block It is also used as a layer, an anti-crystallization layer or an interlayer contact improvement layer. In particular, by using as a thin film layer of one or more selected from the group consisting of an electron transport layer, a hole transport layer, an electron block layer and a hole block layer (hereinafter also referred to as "carrier block layer") It is preferable because an element capable of efficiently converting an electric signal is obtained.

  In addition, for example, organic imaging devices are generally considered to aim to improve performance by reducing dark current for the purpose of achieving high contrast and power saving, so a method of inserting a carrier block layer in the layer structure is preferable. These carrier block layers are generally used in the field of organic electronic devices, and often have a function of controlling the reverse movement of holes or electrons in the component film of the device.

  The electron transport layer plays a role of transporting electrons generated in the photoelectric conversion layer to the electrode film and a role of blocking movement of holes from the electrode film of the electron transport destination to the photoelectric conversion layer. The hole transport layer plays a role of transporting generated holes from the photoelectric conversion layer to the electrode film and a role of blocking transfer of electrons from the electrode film of the hole transport destination to the photoelectric conversion layer. The electron blocking layer prevents the movement of electrons from the electrode film to the photoelectric conversion layer, prevents recombination in the photoelectric conversion layer, and plays a role in reducing dark current. The hole blocking layer has a function of blocking movement of holes from the electrode film to the photoelectric conversion layer, preventing recombination in the photoelectric conversion layer, and reducing dark current.

  Although the typical element structure of the organic photoelectric conversion element of this invention is shown in FIG. 1, this invention is not limited to this structure. In the embodiment of FIG. 1, 1 is an insulating portion, 2 is one electrode film, 3 is an electron blocking layer, 4 is a photoelectric conversion layer, 5 is a hole blocking layer, 6 is the other electrode film, 7 is an insulating group Material or other organic photoelectric conversion element respectively. Although a transistor for reading is not shown in the drawing, it may be connected to the electrode film of 2 or 6, and further, if the photoelectric conversion layer 4 is transparent, the side opposite to the light incident side The film may be formed on the outside of the electrode film. The incidence of light on the organic photoelectric conversion element is not limited from the upper or lower part unless the components excluding the photoelectric conversion layer 4 extremely inhibit the incidence of light of the main absorption wavelength of the photoelectric conversion layer. It may be from.

[Organic EL element]
Next, the organic EL element will be described.
Since the compound represented by Formula (a), (b), (1a) or (1b) of this invention is a compound which has a near-infrared luminescent property, utilization as an organic EL element is anticipated.

  Organic EL elements are attracting attention because they can be used for applications such as solid-state, self-luminous large-area color display and illumination, and many developments have been made. The constitution is that of a structure having two layers of a light emitting layer and a charge transporting layer between counter electrodes consisting of a cathode and an anode; an electron transporting layer, a light emitting layer and a hole transporting layer laminated between the counter electrodes Those having a structure having three layers; and those having three or more layers are known, and those having a single light emitting layer are known.

  Here, the hole transport layer has a function of injecting holes from the anode, transporting the holes to the light emitting layer, and facilitating the injection of holes to the light emitting layer and a function of blocking electrons. In addition, the electron transport layer has a function of injecting electrons from the cathode, transporting the electrons to the light emitting layer, and facilitating the injection of the electrons into the light emitting layer and a function of blocking holes. Furthermore, in the light emitting layer, excitons are generated by recombination of the injected electrons and holes, and energy emitted in the process of radiation deactivation of the excitons is detected as light emission. The preferable aspect of an organic EL element is described below.

  An organic EL element is an element in which an organic thin film of one or more layers is formed between electrodes of an anode and a cathode, and is an element which emits light by electric energy.

  The anode that can be used in the organic EL device is an electrode having a function of injecting holes into the hole injecting layer, the hole transporting layer, and the light emitting layer. In general, metal oxides, metals, alloys, conductive materials and the like having a work function of 4.5 eV or more are suitable. Specifically, although not particularly limited, conductive metal oxides such as tin oxide (NESA), indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), gold, silver, platinum, chromium And metals such as aluminum, iron, cobalt, nickel and tungsten, inorganic conductive substances such as copper iodide and copper sulfide, conductive polymers such as polythiophene, polypyrrole and polyaniline, and carbon. Among them, it is preferable to use ITO or NESA.

  The anode may be formed of two or more layers, if necessary, using a plurality of materials. The resistance of the anode is not limited as long as a current sufficient for light emission of the device can be supplied, but in view of the power consumption of the device, a low resistance is preferable. For example, an ITO substrate having a sheet resistance value of 300 Ω / sq or less functions as an element electrode, but since it is possible to supply a substrate of several Ω / sq, it is desirable to use a low resistance product. The thickness of ITO can be optionally selected in accordance with the resistance value, but it is usually used in the range of 5 to 500 nm, preferably 10 to 300 nm. Examples of the film formation method such as ITO include a vapor deposition method, an electron beam method, a sputtering method, a chemical reaction method, and a coating method.

  A cathode that can be used in the organic EL element is an electrode having a function of injecting electrons into the electron injecting layer, the electron transporting layer, and the light emitting layer. In general, metals and alloys having a small work function (approximately 4 eV or less) are suitable. Specifically, platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, calcium, magnesium can be mentioned, but the electron injection efficiency is improved to improve the device characteristics. Lithium, sodium, potassium, calcium and magnesium are preferred for this purpose. As the alloy, an alloy with a metal such as aluminum or silver containing such a low work function metal, or an electrode having a structure in which these are stacked can be used. It is also possible to use an inorganic salt such as lithium fluoride for the electrode of the laminated structure. In the case of taking out light emission not to the anode side but to the cathode side, it may be a transparent electrode which can be formed into a film at low temperature. The film forming method may, for example, be a vapor deposition method, an electron beam method, a sputtering method, a chemical reaction method or a coating method, but it is not particularly limited. The resistance of the cathode is not limited as long as a current sufficient for light emission of the element can be supplied, but from the viewpoint of the power consumption of the element, the resistance is preferably low, and several hundreds to several ohms / square or so is preferable. The film thickness is usually 5 to 500 nm, preferably 10 to 300 nm.

  Furthermore, for sealing and protection, oxides such as titanium oxide, silicon nitride, silicon oxide, silicon nitride oxide, germanium oxide, nitrides, or mixtures thereof, polyvinyl alcohol, vinyl chloride, hydrocarbon polymers, fluorine The cathode can be protected with a system polymer or the like and sealed together with a dehydrating agent such as barium oxide, phosphorus pentoxide or calcium oxide.

In order to extract light, it is generally preferable to fabricate an electrode on a substrate having sufficient transparency in the light emission wavelength region of the device. Examples of transparent substrates include glass substrates and polymer substrates. Soda lime glass, non-alkali glass, quartz or the like is used as the glass substrate, and the thickness is sufficient if it has a thickness sufficient to maintain mechanical and thermal strength, and a thickness of 0.5 mm or more is preferable. As for the material of the glass, it is preferable that the amount of ions eluted from the glass be small, and alkali-free glass is preferable. As such, soda lime glass having a barrier coating such as SiO ₂ is commercially available and can also be used. In addition, as substrates made of polymers other than glass, polycarbonate, polypropylene, polyether sulfone, polyethylene terephthalate, acrylic substrates and the like can be mentioned.

  The organic thin film of the organic EL element is formed of one or more layers between the anode and the cathode. By containing the compound represented by the said Formula (a), (b), (1a) or (1b) in the organic thin film, the element light-emitted by an electrical energy is obtained.

  The “layer” of one or more layers forming the organic thin film means a hole transporting layer, an electron transporting layer, a hole transporting light emitting layer, an electron transporting light emitting layer, a hole blocking layer, an electron blocking layer, a positive electrode As shown in the hole injection layer, the electron injection layer, the light emitting layer, or the following structural example 9), it means a single layer having the functions of these layers. As a structure of the layer which forms the organic thin film in this invention, the following structural examples 1) to 9) are mentioned, and any structure may be sufficient.

Structural example 1) Hole transport layer / electron transportable light emitting layer.
2) Hole transport layer / luminescent layer / electron transport layer.
3) Hole transportable light emitting layer / electron transport layer.
4) Hole transport layer / light emitting layer / hole blocking layer.
5) Hole transport layer / light emitting layer / hole blocking layer / electron transport layer.
6) Hole transportable light emitting layer / hole blocking layer / electron transport layer.
7) In each of the combinations 1) to 6), a hole injection layer is additionally provided in front of the hole transport layer or the hole transportable light emitting layer.
8) In each of the combinations 1) to 7), an electron injection layer is further provided in front of the electron transport layer or the electron transport light emitting layer.
9) Composition which mixes only the material used in the combination of said 1) to 8), and has only one layer containing this mixed material.
In the above 9), only a single layer formed of a material generally referred to as a bipolar light emitting material; or a layer containing a light emitting material and a hole transporting material or an electron transporting material may be provided. In general, a multilayer structure can efficiently transport charges, that is, holes and / or electrons, and recombine these charges. In addition, quenching of charge and the like can be suppressed, whereby the stability of the element can be prevented from being lowered and the efficiency of light emission can be improved.

  The hole injection layer and the hole transport layer are formed by laminating a hole transport material alone or a mixture of two or more of the materials. As the hole transport material, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diphenyl-1,1'-diamine, N, N'-dinaphthyl-N , N'-diphenyl-4,4'-diphenyl-1,1'-diamine and the like, triphenylamines such as bis (N-allylcarbazole) or bis (N-alkylcarbazoles), pyrazoline derivatives, stilbene compounds, Hydrazone compounds, triazole derivatives, heterocyclic compounds represented by oxadiazole derivatives and porphyrin derivatives, and in polymer systems, polycarbonates or styrene derivatives having the above-mentioned monomer in the side chain, polyvinylcarbazole, polysilane, etc. can be preferably used. It is not particularly limited as long as it is a substance capable of forming a thin film necessary for device fabrication, injecting holes from the electrode, and transporting holes. As a hole injection layer provided between the hole transport layer and the anode for improving the hole injection property, a phthalocyanine derivative, m-MTDATA (4,4 ′, 4 ′ ′-tris [phenyl (m-tolyl And the like. Starburst amines such as (amino) triphenylamine), polythiophenes such as PEDOT (poly (3,4-ethylenedioxythiophene)) in the polymer system, polyvinyl carbazole derivatives and the like.

  The electron transport layer is formed by laminating an electron transport material alone or a mixture of two or more of the materials. As an electron transport material, it is necessary to efficiently transport electrons from the negative electrode between electrodes to which an electric field is applied. The electron transporting material preferably has a high electron injection efficiency and efficiently transports the injected electrons. For this purpose, it is required that the substance has a large electron affinity, a large electron mobility, and is excellent in stability, and is a substance which hardly generates an impurity serving as a trap during production and use. As a substance satisfying such conditions, quinolinol derivative metal complex represented by tris (8-quinolinolato) aluminum complex, tropolone metal complex, perylene derivative, perinone derivative, naphthalimide derivative, naphthalic acid derivative, oxazole derivative, oxadiazole The derivative, thiazole derivative, thiadiazole derivative, triazole derivative, bisstyryl derivative, pyrazine derivative, phenanthroline derivative, benzoxazole derivative, quinoxaline derivative and the like can be mentioned, but it is not particularly limited. Although these electron transport materials may be used alone, they may be used as laminated or mixed with different electron transport materials. Examples of the electron injection layer provided between the electron transport layer and the cathode for improving the electron injection property include metals such as cesium, lithium and strontium, and lithium fluoride.

  The hole blocking layer is formed by laminating and mixing a hole blocking substance alone or two or more kinds of substances. As the hole blocking substance, phenanthroline derivatives such as bathophenanthroline and vasocuproin, silole derivatives, quinolinol derivative metal complexes, oxadiazole derivatives, oxazole derivatives and the like are preferable. The hole blocking substance is not particularly limited as long as it is a compound that can block the decrease in luminous efficiency due to the flow of holes from the cathode side to the outside of the device.

  The light emitting layer means an organic thin film that emits light, and can be said to be, for example, a hole transporting layer having strong luminescence, an electron transporting layer, or a bipolar transporting layer. The light emitting layer may be formed of a light emitting material (host material, dopant material, etc.), and may be a mixture of the host material and the dopant material, or may be the host material alone. The host material and the dopant material may each be of one type or a combination of a plurality of materials.

  The dopant material may be contained in the entire host material, partially contained or may be contained. The dopant material may be either stacked or dispersed. As a light emitting layer, the above-mentioned hole transport layer and electron transport layer are mentioned, for example. Materials used for the light emitting layer include carbazole derivative, anthracene derivative, naphthalene derivative, phenanthrene derivative, phenyl butadiene derivative, styryl derivative, pyrene derivative, perylene derivative, quinoline derivative, tetracene derivative, perylene derivative, quinacridone derivative, coumarin derivative, Examples thereof include porphyrin derivatives and phosphorescent metal complexes (such as Ir complex, Pt complex, and Eu complex).

  Generally, the method of forming the organic thin film of the organic EL element is vacuum process resistance heating evaporation, electron beam evaporation, sputtering, molecular layering method, solution process casting, spin coating, dip coating, blade coating, wire bar Coating methods such as coating, spray coating etc., printing methods such as inkjet printing, screen printing, offset printing, letterpress printing, soft lithography methods such as micro contact printing method, etc. Furthermore, a method combining a plurality of these methods is adopted It can. The thickness of each layer depends on the resistance value / charge mobility of each material and can not be limited, but is selected from 0.5 to 5000 nm. Preferably, it is 1 to 1000 nm, more preferably 5 to 500 nm.

  Among the organic thin films constituting the organic EL element, one or more layers of thin films such as a light emitting layer, a hole transporting layer, and an electron transporting layer, which are present between the anode and the cathode, are the above formulas (a) and (b) A device that emits light efficiently even with low electrical energy can be obtained by containing the compound represented by (1a) or (1b).

  The compound represented by the said Formula (a), (b), (1a) or (1b) can be used suitably as a positive hole transport layer, a light emitting layer, and an electron transport layer. For example, they can be used in combination with or mixed with the above-mentioned electron transport material, hole transport material, light emitting material and the like.

As a specific example of a dopant material when using as a host material which combined the compound represented by said formula (a), (b), (1a) or (1b) with the dopant material, bis (diisopropylphenyl) perylene tetracarbonide Perylene derivatives such as acid imides, perinone derivatives, 4- (dicyanomethylene) -2methyl-6- (p-dimethylaminostyryl) -4H pyran (DCM) and analogues thereof, metal phthalocyanines such as magnesium phthalocyanine and aluminum chlorophthalocyanine Derivatives, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, oxazine compounds, squarylium compounds, biolanthrone compounds, pyromethene derivatives such as nile red, 5-cyanopyromethene-BF ₄ complex, and acetylacetone as a phosphorescent material And Eu complexes having ligands such as benzoylacetone and phenanthroline, porphyrins such as Ir complexes, Ru complexes, Pt complexes, Os complexes etc., ortho metal complexes, etc. can be used, but it is not particularly limited thereto. Absent. In addition, when two types of dopant materials are mixed, it is also possible to efficiently transfer energy from the host dye by using an assist dopant such as rubrene to obtain light emission with improved color purity. In any case, in order to obtain high luminance characteristics, it is preferable to dope one having a high fluorescence quantum yield.

  The amount of the dopant material to be used is usually 30% by mass or less with respect to the host material because concentration quenching phenomenon occurs if the amount is too large. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. As a method of doping the host material with the dopant material in the light emitting layer, it can be formed by co-evaporation with the host material, but it may be simultaneously deposited after being mixed with the host material in advance. Moreover, it is also possible to sandwich and use it in host material. In this case, one or two or more dopant layers may be stacked with the host material.

  These dopant layers may be used alone to form each layer, or may be used as a mixture. In addition, as a dopant material, polyvinyl chloride, polycarbonate, polystyrene, polystyrene, polystyrene sulfonic acid, poly (N-vinylcarbazole), poly (methyl) (meth) acrylate, polybutyl methacrylate, polyester, polysulfone, as a polymer binder Solvent-soluble resins such as polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polysulfone, polyamide, ethylcellulose, vinyl acetate, ABS resin (acrylonitrile-butadiene-styrene resin), polyurethane resin, phenol resin, xylene resin, It is also possible to use it by dissolving or dispersing it in a curable resin such as petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin and silicone resin. .

  The organic EL element can be suitably used as a flat panel display. Moreover, it can be used also as a flat back light, and in this case, either what emits colored light or what emits white light can be used. Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit light themselves, and are used for liquid crystal display devices, clocks, audio equipment, automobile panels, display boards, signs, and the like. In particular, conventional backlights for personal computer applications, in which reduction in thickness has become an issue, have been difficult to reduce in thickness because they are composed of fluorescent lamps and light guide plates, but the light emission of the present invention The above problems are eliminated because the backlight using the element is characterized by thinness and lightness. It can be usefully used for lighting as well.

  By using the compound represented by the above formula (a), (b), (1a) or (1b) of the present invention, it is possible to obtain an organic EL display device having a high luminous efficiency and a long life. Furthermore, by combining the thin film transistor elements, it is possible to supply at low cost an organic EL display device in which the on / off phenomenon of the applied voltage is electrically controlled with high accuracy.

[About organic semiconductor laser device]
Since the compound represented by the said Formula (a), (b), (1a) or (1b) is a compound which has a near-infrared luminescent property, utilization as an organic-semiconductor laser element is anticipated. That is, the resonator structure is incorporated into the organic semiconductor laser device containing the compound represented by the above formula (a), (b), (1a) or (1b), carriers are efficiently injected, and the density of the excited state is It is expected that the light will be amplified and lead to laser oscillation if it can be raised sufficiently. Conventionally, it is very difficult to inject a high density of carriers into an organic semiconductor device and generate a high density excited state, which is required only for laser oscillation by light excitation, and which is required for laser oscillation by electrical excitation. Although it has been proposed, highly efficient light emission (electroluminescence) can occur by using an organic semiconductor device containing the compound represented by the above formula (a), (b), (1a) or (1b) Sex is expected.

  EXAMPLES The present invention will be described in more detail by way of the following examples, but the present invention is not limited to these examples. The compounds described in the synthesis examples were structurally determined by mass spectrometry spectrum and nuclear magnetic resonance spectrum (NMR) as needed.

Example 1 Synthesis of Compound A6 of the Present Invention

  Compound A1 was synthesized with reference to the method described in WO2007 / 089031 Al. Compound A5 was synthesized by the same method as in Tetrahedron Letters, 2008, 49, 3716-3721, using Compound A1 as a raw material.

Compound A5 (1.7 mmol), dichloromethane (40 mL) and diisopropylamine (2 mL) were added to a flask and stirred, and then boron trifluoride diethyl etherate (2 mL) was slowly added, followed by heating and stirring at 40 ° C. for 1 hour . Saturated aqueous sodium bicarbonate solution is added to the obtained reaction solution, and after stirring for a while, dichloromethane is added for liquid separation, and the obtained crude product is purified by silica gel column chromatography (developing solvent: dichloromethane) to obtain a green powder compound I got A6. (1.0 mmol, yield: 58%).
The measurement results of the nuclear magnetic resonance spectrum (NMR) of compound A6 were as follows.
¹ H NMR (400 MHz, CD ₂ Cl ₂ ) δ (ppm) = 8.02 to 7.99 (m, 4 H), 7.89 (d, 2 H), 7.75 (d, 2 H), 7.73 (S, 1 H), 7.47 (t, 2 H), 7.44-7.41 (m, 6 H), 7. 30 (t, 2 H), 4. 15 (s, 6 H)
The measurement results of mass spectrometry of compound A6 were as follows.
EI-MS (m / z): 670 [M] ^<+> .

Example 2 Synthesis of the Compound Represented by Formula (1-6) of the Above Specific Example Compound A6 (1.5 mmol) and dichloroethane (120 mL) were added to a flask and stirred, and then boron tribromide (18 mL) Was added dropwise, and the mixture was heated and stirred at 80 ° C. for 6 hours. The reaction solution obtained is cooled to room temperature, then the reaction solution is poured into a saturated aqueous sodium bicarbonate solution, the precipitate is filtered, and the filter cake is washed successively with water, methanol and chloroform to obtain a dark green formula (1-6). The compound represented was obtained. (1.4 mmol, yield: 92%).
The measurement result of the mass spectrometry spectrum of the compound represented by Formula (1-6) was as follows.
EI-MS (m / z): 602 [M] ^<+> .

Comparative Example 1 Synthesis of Comparative Compound Represented by the Following Formula (2-1) B-O-Chelated with a Benzene Ring Substituted at the 3,5 Position of BODIPY Represented by the Following Formula (2-1) The comparative compound was synthesized in the same manner as in Example 1.
The measurement results of the nuclear magnetic resonance spectrum (NMR) of the obtained compound represented by the formula (2-1) are as follows.
¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm) = 8.25 (d, 4 H), 7.99 (d, 2 H), 7.76 (s, 1 H), 7.53 (t, 2 H), 7.43-7.36 (m, 4H), 7.17 (t, 2H), 6.98 (d, 2H)
The measurement result of the mass spectrometry spectrum of the compound represented by Formula (2-1) was as follows.
EI-MS (m / z): 436 [M] ^<+> .

[Absorption Spectrum Measurement of Compound Solution Represented by Formula (1-6)]
The compound of the present invention represented by the formula (1-6) is subjected to sublimation purification, and then a solution dissolved in chloroform is prepared and the absorption spectrum is measured. As a result, λmax of the absorption spectrum of the compound solution of the present invention is It was 831 nm. The results are shown in FIG.

[Absorption Spectrum Measurement of Compound Solution Represented by Formula (2-1)]
[Measurement of absorption spectrum of compound solution represented by formula (1-6)] except that the compound represented by formula (2-1) is used instead of the compound represented by formula (1-6) As a result of measuring the absorption spectrum of the compound represented by Formula (2-1) according to the method, (lambda) max of the absorption spectrum was 721 nm. The results are shown in FIGS.

[Example 3] Preparation of an organic thin film containing the compound of the present invention represented by the formula (1-6) and measurement of absorption spectrum After subjecting the compound of the present invention represented by the formula (1-6) to sublimation Then, it was dissolved in chloroform to prepare a 1 mg / mL chloroform solution. The chloroform solution obtained above is coated on a glass substrate by spin coating (1000 rpm, 30 seconds), and the substrate is dried by heating at 120 ° C. for 30 minutes to form the organic thin film of the present invention formed on the glass substrate. I got As a result of measuring the absorption spectrum of the obtained organic thin film on the glass substrate, λmax of the absorption spectrum was 922 nm. Further, the absorbance at λmax was 0.022. The results are shown in FIG.

Comparative Example 2 Preparation of Organic Thin Film Containing Comparative Compound Represented by Formula (2-1) and Absorption Spectrum Measurement Instead of the compound of the present invention represented by Formula (1-6), Formula (2-) Comparative organic thin film formed on a glass substrate according to Example 2 except that the comparative compound represented by 1) was used, and the absorption spectrum was measured. Of λ was 670 nm. Further, the absorbance at λmax was 0.009. The results are shown in FIGS. 4 and 6. The compound represented by the formula (2-1) has a low absorbance value, and the chart on the same scale as the example compound (the compound represented by the formula (2-1) and the compound A6) discriminates the peak position. Since it was difficult, the chart which described the light absorbency of the peak part of the compound represented by Formula (2-1) tripled, and was described is shown in FIG. 4 and 6 with the dotted line.

[Absorption Spectrum Measurement of Compound A6 Solution]
According to the method of [Measurement of absorption spectrum of compound solution represented by Formula (1-6)] except that Compound A6 of the present invention is used instead of the compound of the present invention represented by Formula (1-6) As a result of measuring the absorption spectrum of the compound A6, λmax of the absorption spectrum was 719 nm. The results are shown in FIG.

Example 4 Preparation of Organic Thin Film Containing Compound A6 and Measurement of Absorption Spectrum According to Example 3 except that the compound A6 of the present invention was used instead of the compound of the present invention represented by Formula (1-6) As a result of preparing an organic thin film formed on a glass substrate and measuring its absorption spectrum, λmax of the absorption spectrum was 766 nm. Further, the absorbance at λmax was 0.04. The results are shown in FIG.

  While λmax of the absorption spectrum of the organic thin film containing the compound for comparison represented by the formula (2-1) was 800 nm or less, B—O was substituted with a thiazole ring substituted at the 3,5 position of the BODIPY skeleton. The compound of the present invention which has been chelated achieves a long wavelength shift of the absorption wavelength, the λmax of the absorption spectrum of the chloroform solution is 800 nm or more, and the λmax of the absorption spectrum of the organic thin film containing the compound of the present invention is 900 nm or more Met. That is, in the existing compounds, the ability to absorb near infrared light in the long wavelength region is insufficient, but the compound of the present invention is excellent in the ability to absorb near infrared light in the long wavelength region. In addition, λmax of the absorption spectrum of the organic thin film containing the compound A6 of the present invention is 766 nm, and the wavelength is about 100 nm longer than the organic thin film using the comparative compound represented by the formula (2-1) Has been achieved.

  The compound of the present invention has all of synthetic simplicity, absorption characteristics in the near infrared region and vapor-depositable characteristics, and is very useful as an organic electronic device material operating in the near infrared region.

(Figure 1)
Reference Signs List 1 insulating part 2 upper electrode 3 electron block layer 4 photoelectric conversion layer 5 hole block layer 6 lower electrode 7 insulating substrate or other photoelectric conversion element

(Figure 2)
1 substrate 2 anode 3 hole injection layer 4 hole transport layer 5 light emitting layer 6 electron transport layer 7 cathode

Claims (8)

The following formula (1a) or (1b)

(R _{1 to} R _{4 in the} formulas (1a) and (1b) are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group Represents an unsubstituted amino group, cyano group, sulfo group, acyl group, sulfamoyl group, alkylsulfamoyl group, carbamoyl group, or alkylcarbamoyl group, and n and m each independently represent an integer of 1 to 4) A compound represented by Following formula (2)

(In the above formula (2), R _{1 to} R _{4 each} represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group, an unsubstituted amino group, A cyano group, a sulfo group, an acyl group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group or an alkylcarbamoyl group. The compound according to claim 1 or 2, wherein R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aromatic group or a halogen atom, and R ₃ and R ₄ each independently represent a hydrogen atom or an aromatic group. .   A near infrared light absorbing material comprising the compound according to any one of claims 1 to 3.   An organic thin film comprising the compound according to any one of claims 1 to 3.   An organic electronic device comprising the compound according to any one of claims 1 to 3. A method for producing a compound represented by the formula (1a) or (1b) according to claim 1,
The following formula (a) or (b)

(R _{1 to} R _{4 in the} formulas (a) and (b) are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group Represents an unsubstituted amino group, a cyano group, a sulfo group, an acyl group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group, or an alkylcarbamoyl group, R ₅ represents a hydrogen atom or an alkyl group, and n and m each represent Independently represent an integer of 1 to 4)
The manufacturing method which makes a boron trifluoride diethyl ether complex or a boron tribromide react with the compound represented by these. The following formula (a) or (b)

(R _{1 to} R _{4 in the} formulas (a) and (b) are each independently a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aromatic group, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a substituted amino group Represents an unsubstituted amino group, a cyano group, a sulfo group, an acyl group, a sulfamoyl group, an alkylsulfamoyl group, a carbamoyl group, or an alkylcarbamoyl group, R ₅ represents a hydrogen atom or an alkyl group, and n and m each represent A compound independently represented by 1 to 4).

Images