JP2006143680A - New compound, method for producing the same, and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound increased in carrier transport capacity and/or improved in optical absorptivity and having a phthalocyanine skeleton and an oligothiophene skeleton, to provide a method for producing the same, and to provide a use of the same. <P>SOLUTION: This compound has at least the phthalocyanine skeleton and the oligothiophene skeleton, wherein the phthalocyanine skeleton and the oligothiophene skeleton are conjugated. The compound comprises the new compound which is greatly increased in the carrier transport capacity and/or improved in the optical absorptivity, when compared with conventional compounds having the phthalocyanine skeleton and the oligothiophene skeleton. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a novel compound used for an organic semiconductor electronic material that can be used for optoelectric, optoelectronic, electrical, and electronic devices / parts, a manufacturing method thereof, and use thereof, and more particularly, a dye-sensitized solar cell material. The present invention relates to a novel compound used for an organic organic semiconductor electronic material that can be used for a thin film photoelectric conversion element, a liquid crystal, an organic thin film transistor, a light emitting device having an organic carrier transport layer, and the like, and a method for producing the same.

  In recent years, thin film devices using organic semiconductor electronic materials such as organic EL devices, organic FET devices, and organic thin film photoelectric conversion devices have attracted attention, and some of them have been put into practical use. In addition, dye-sensitized solar cells in which titanium oxide and an organic dye are combined have been actively researched, and organic materials having characteristics suitable for these device applications have been energetically searched.

  In general, an organic electronic material that can be used in electrical and electronic devices such as an organic thin film transistor is required to have a carrier transport capability. On the other hand, photoelectric properties such as light absorption and emission are required in addition to carrier transport capability for photoelectric and photoelectric devices such as thin film photoelectric conversion elements, dye-sensitized solar cells, and organic EL devices. It is said. Furthermore, from the viewpoint of application to practical devices, the stability of organic materials is one of the important performances.

  In consideration of the above points, the use of a compound having a phthalocyanine skeleton that has been conventionally used as a stable organic pigment or a functional dye has been studied. However, when phthalocyanine is used as an electronic material as it is, sufficient electron carrier transport performance cannot be obtained. Further, when phthalocyanine is used as an optical material, there is a disadvantage that the absorption wavelength is biased and a wide absorption spectrum cannot be obtained.

For this reason, an attempt has been made to create a new novel functional material by combining the phthalocyanine skeleton with the same π-electron thiophene skeleton. For example, Non-Patent Documents 1 to 4 disclose a plurality of compounds having a phthalocyanine skeleton and a thiophene skeleton.
Michael J. Cook and Ali Jafari-Fini, J. Mater. Chem., 1997, 7 (1), p5-7 Douglas M. Knawby and Timothy M. Swager, Chem. Mater. 1997, 9, p535-538 Michael J. Cook and Ali Jafari-Fini, Tetrahedron 56 (2000) p4085-4094 M. Victoria Martinez-Diaz, et al., Tetrahedron Letters 44 (2003) p8475-8478

  Since the compounds disclosed in Non-Patent Documents 1 to 4 each have a phthalocyanine skeleton and a thiophene skeleton, a slight improvement in performance is recognized in terms of carrier transport ability and light absorption ability. However, its performance is still not perfect.

  For this reason, there has been a strong demand for the creation of a novel compound that can further improve the carrier transport ability or the light absorption ability.

  The present invention has been made in view of the above problems, and its object is to provide a novel compound having a phthalocyanine skeleton and a thiophene skeleton, which has improved carrier transport ability and / or improved light absorption ability, and its It is to provide a manufacturing method and use thereof.

  As a result of intensive studies to solve the above problems, the present inventors have created a novel compound in which a π electron system in a phthalocyanine skeleton and a π electron system in a thiophene skeleton are conjugated, and a light absorption spectrum of the compound is obtained. As a result of the evaluation, strong absorption was observed over the entire visible region, and therefore, it was found that it was useful as an optoelectronic device material such as at least a thin film photoelectric conversion element and a dye-sensitized solar cell, and the present invention was completed. It was. The present invention has been completed based on such novel findings, and includes the following inventions.

  (1) A compound having at least a phthalocyanine skeleton and an oligothiophene skeleton, wherein the phthalocyanine skeleton and the oligothiophene skeleton are conjugated.

  (2) A compound represented by the following general formula (I),

  In the general formula (I), Ar is represented by the following general formula (II),

  In the general formulas (I) and (II), R1 to R12, R, and R ′ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, An alkyl group in which one or more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkyloxy group having 1 to 18 carbon atoms, and one in the alkyloxy group Or an alkyloxy group in which more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, and one or more of the alkylthio groups A compound in which the carbon atom is an alkylthio group which may be substituted with an oxygen atom, a nitrogen atom and / or a sulfur atom, or an aromatic group.

  (3) A compound represented by the following general formula (III),

  In the general formula (III), Ar is represented by the following general formula (II),

  In the general formulas (II) and (III), R1 to R8, R, and R ′ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, An alkyl group in which one or more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkyloxy group having 1 to 18 carbon atoms, and one in the alkyloxy group Or an alkyloxy group in which more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, and one or more of the alkylthio groups A compound in which the carbon atom is an alkylthio group which may be substituted with an oxygen atom, a nitrogen atom and / or a sulfur atom, or an aromatic group.

  (4) A compound represented by the following general formula (IV),

  In the general formula (IV), Ar is represented by the following general formula (II),

  In the general formulas (II) and (IV), R1 to R4, R, and R ′ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, An alkyl group in which one or more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkyloxy group having 1 to 18 carbon atoms, and one in the alkyloxy group Or an alkyloxy group in which more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, and one or more of the alkylthio groups A compound in which the carbon atom is an alkylthio group which may be substituted with an oxygen atom, a nitrogen atom and / or a sulfur atom, or an aromatic group.

  (5) A compound represented by the following general formula (V),

  In the general formula (V), Ar is represented by the following general formula (II),

  In the general formula (II), R and R ′ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, and one or more carbon atoms in the alkyl group are An alkyl group optionally substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, or an alkyloxy group having 1 to 18 carbon atoms, wherein one or more carbon atoms in the alkyloxy group are oxygen atoms , A nitrogen atom, and / or an alkyloxy group optionally substituted with a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, wherein one or more carbon atoms in the alkylthio group are an oxygen atom and a nitrogen atom And / or a compound which is an alkylthio group optionally substituted with a sulfur atom or an aromatic group.

  (6) A compound represented by the following chemical formula (VI).

  (7) A compound represented by the following chemical formula (VII).

  (8) The compound according to any one of (1) to (7) above, wherein the phthalocyanine skeleton forms a complex with a metal ion.

  (9) A compound represented by the following general formula (VIII),

  In the general formula (VIII), Ar is represented by the following general formula (II),

  In the general formula (II), R and R ′ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, and one or more carbon atoms in the alkyl group are An alkyl group optionally substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, or an alkyloxy group having 1 to 18 carbon atoms, wherein one or more carbon atoms in the alkyloxy group are oxygen atoms , A nitrogen atom, and / or an alkyloxy group optionally substituted with a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, wherein one or more carbon atoms in the alkylthio group are an oxygen atom and a nitrogen atom And / or a compound which is an alkylthio group optionally substituted with a sulfur atom or an aromatic group.

  (10) A compound represented by the following general formula (IX),

  In the general formula (IX), compounds wherein B is a halogen atom.

  (11) The compound according to (10), wherein B is an iodine atom in the general formula (IX).

  (12) In the method for producing the compound according to (10) above, a first step of reacting a compound represented by the following general formula (X) with an organometallic reagent, and after the first step, And a second step of reacting with a halogenating reagent.

  (13) The production method according to (12), wherein the halogenating reagent is an iodination reagent.

  (14) A process for producing the compound according to any one of (1) to (8) above, wherein the compound represented by the following general formula (X) is reacted with an organometallic reagent And a second step of reacting with a halogenating reagent after the first step.

  (15) A device comprising the compound according to any one of (1) to (8) above.

  (16) The device according to (15), wherein the device is a light-emitting element having a photoelectric conversion element, a dye-sensitized solar cell element, an organic EL element, a liquid crystal display element, an organic thin film transistor element, or an organic carrier transport layer.

  The compound according to the present invention is a phthalocyanine-oligothiophene multicomponent in which an oligothiophene skeleton that has been attracting attention as a photoelectron and electronic functional organic material is incorporated into a phthalocyanine skeleton that has been used as a stable organic pigment or functional dye. It is a novel compound having a system configuration. In this novel compound, the π electron systems in the phthalocyanine skeleton and the thiophene skeleton are conjugated with each other. Therefore, the carrier transport ability and the light absorption ability are remarkably improved as compared with the conventional compound having a phthalocyanine skeleton and a thiophene skeleton.

  Therefore, the compound according to the present invention is very useful as an optoelectronic device material such as a thin film photoelectric conversion element and a dye-sensitized solar cell.

  In addition to the manufacturing method of the said compound, the intermediate compound at the time of manufacturing the said compound is also contained in this invention. In particular, the intermediate compound according to the present invention is not only used for producing the above compound, but is also very useful as an intermediate of a semiconductor material having a thiophene skeleton, for example.

  The present invention relates to a novel compound that can be used as an optoelectronic device material, an intermediate thereof, a production method thereof, and use thereof. Therefore, in the following, first, the novel compound will be described, then its intermediate and production method, and finally its usage will be described.

<1. Compound according to the present invention>
The compound according to the present invention may be a compound having at least a phthalocyanine skeleton and an oligothiophene skeleton, and may be any compound in which the phthalocyanine skeleton and the oligothiophene skeleton are conjugated.

  In this specification, the term “oligothiophene skeleton” refers to a structure in which a plurality of (preferably 2 to 21) thiophene skeletons are bonded in a state in which the π-electron system is conjugated. Specific examples include those represented by the above general formula (II), but are not limited to this structure.

  Moreover, the phrase “the phthalocyanine skeleton and the thiophene skeleton are conjugated” means that the π electron system of the phthalocyanine skeleton and the π electron system of the oligothiophene skeleton interact (for example, through a single bond). It means that it is delocalized.

  As said compound, the compound which concerns on this invention can mention the compound represented by the said general formula (I), (III), (IV), and (V), for example. In the general formulas (I), (III), (IV), and (V), Ar represents the oligothiophene represented by the general formula (II), and in the general formula (II), n is 1 to 1 It is an integer of 20. Moreover, in said general formula (I)-(V), R1-R12, R, and R 'are respectively independently a hydrogen atom, a halogen atom, and a C1-C18 alkyl group, Comprising: The said alkyl group An alkyl group in which one or more carbon atoms therein may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, or an alkyloxy group having 1 to 18 carbon atoms, in the alkyloxy group One or more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, It may be an alkylthio group or an aromatic group in which further carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom.

  More specifically, for example, the above chemical formula (VI) and chemical formula (VII) can be mentioned.

  Since the above compound has a chemical structure in which the phthalocyanine skeleton and the oligothiophene skeleton are conjugated, the compound having only the phthalocyanine skeleton, the compound having only the oligothiophene skeleton, and the phthalocyanine skeleton and the oligothiophene skeleton are not conjugated. Compared with the compound bonded with, its properties are remarkably different.

  Specifically, for example, a compound having only a phthalocyanine skeleton is known to have a strong absorption band in the vicinity of 300 nm to 400 nm and in the vicinity of 650 nm to 700 nm when the absorption spectrum is measured. Cannot be absorbed (see, for example, FIG. 2A in the examples described later). For this reason, since the light of a wide wavelength cannot be utilized, the compound which has only a phthalocyanine frame | skeleton is inadequate as a solar cell material or a photoelectric conversion element material as it is. A compound having only an oligothiophene skeleton has an absorption spectrum peak in the vicinity of 400 nm to 600 nm so as to supplement the absorption band of the phthalocyanine compound, but cannot absorb light in other regions.

  Further, the absorption spectrum of a compound in which the phthalocyanine skeleton and the oligothiophene skeleton are bonded in a non-conjugated state is, for example, as shown in “Figure 1” of Non-Patent Document 4 above, compared with a compound having only a phthalocyanine skeleton. In the position from 400 nm to 500 nm, a slight improvement in the absorption spectrum is observed, but the absorption spectrum from 500 nm to 700 nm hardly changes, indicating that light in this region cannot be absorbed.

  On the other hand, the compound according to the present invention has an even absorption spectrum in a wide visible region of 300 nm to 800 nm. For example, as shown in the Examples described later, the absorption spectrum of 400 nm to 600 nm in a compound having one oligothiophene skeleton conjugated with a phthalocyanine skeleton is greatly increased as compared with that of a compound having a phthalocyanine skeleton.

  Furthermore, the above properties of the compound according to the present invention become more prominent as the number of oligothiophene skeletons conjugated to the phthalocyanine skeleton increases. That is, when the number of oligothiophene skeletons conjugated with the phthalocyanine skeleton increases from one to four, the absorption spectrum is larger than expected and changes significantly.

  Specifically, for example, as shown in the examples described later, an oligothiophene skeleton conjugated with a phthalocyanine skeleton is an oligoconjugated with a phthalocyanine skeleton compared to one compound (for example, a compound represented by the above chemical formula (VI)). A compound having four thiophene skeletons (for example, a compound represented by the above chemical formula (VII)) has its absorption spectrum peak shifted to the longer wavelength side (350 nm peak is 420 nm), and the absorption spectrum is broadly observed from 500 nm to 800 nm. Be able to.

  The above properties are recognized because the phthalocyanine skeleton and the oligothiophene skeleton are conjugated, and the same applies to the above general formulas (I), (III), (IV), and (V). It will be clear to those skilled in the art that this can be said.

  Further, although the phthalocyanine skeleton has a property of forming a stable complex with a metal ion, it goes without saying that a compound in which the phthalocyanine skeleton of the compound according to the present invention forms a complex with a metal ion is also included in the present invention. Absent. Although data are not shown, it has been confirmed that a copper complex is formed. As such metal ions, for example, metal ions used in conventionally known phthalocyanine complexes such as iron, copper, nickel and cobalt can be suitably used. By forming a complex with such a metal ion, for example, it has properties of electrical conductivity, magnetism, and semiconductor characteristics.

  As described above, the compound according to the present invention has a broad absorption spectrum that is wide in the entire visible region. That is, conventionally known compounds can only absorb and use light in a specific wavelength region, but the compounds according to the present invention can absorb and use light in the entire visible region evenly. Therefore, the compound according to the present invention is very useful as an optoelectronic device material such as a thin film photoelectric conversion element and a dye-sensitized solar cell that can widely use light in the entire visible region.

  Moreover, since the compound according to the present invention has a phthalocyanine skeleton and an oligothiophene skeleton, it is chemically stable and is an excellent organic material.

  Furthermore, since it is suggested that the compound according to the present invention is in an associated state in nuclear magnetic resonance spectrum measurement in a solution, there is a high possibility of having a liquid crystal phase even in an aggregated state. Therefore, it can be used for various optoelectronic devices using liquid crystals, such as display elements, and organic semiconductor layers composed of highly oriented molecular thin films using the self-association property of the liquid crystal phase.

<2. Intermediate according to the present invention and production method according to the present invention>
The compound described in the above section <1> is a completely new compound that has not been reported for synthesis. Since the compound represented by the general formula (VIII) could not be obtained, the compound could not be synthesized so far. Further, the compound represented by the general formula (VIII) could not be synthesized because the compound represented by the general formula (IX) could not be obtained.

  That is, it can be said that the present invention was completed because the compound represented by the general formula (IX) was obtained.

  Therefore, both of the compound represented by the general formula (VIII) and the compound represented by the general formula (IX) are useful intermediates for obtaining the compound according to the present invention described in the section <1>. It can be said to be a body. For this reason, the intermediate compound is also included in the present invention. Such an intermediate is also very useful for producing a semiconductor material having an oligothiophene skeleton.

  In addition, as a method for obtaining the compound according to the present invention described in the section <1>, there is a method via a compound represented by the above general formula (VIII) and a compound represented by the above general formula (IX). . Therefore, the method for producing the compound represented by the above general formula (VIII) and the compound represented by the above general formula (IX) is a method for producing the compound according to the present invention explained in the above section <1>. This process is very useful. Therefore, the present invention also includes a method for producing the above-described intermediate and a method for producing the compound in the above-described <1> column including the method for producing the intermediate.

  The manufacturing method includes at least a first step of reacting the compound represented by the general formula (X) with an organometallic reagent, and a second step of reacting with a halogenating reagent after the first step. As for other processes, reaction conditions, materials, catalysts, manufacturing equipment / manufacturing equipment, etc., conventionally known ones can be suitably used and are not particularly limited. That is, it can be said that the manufacturing method according to the present invention may include any other process as long as it includes the first process and the second process, and is not particularly limited.

  The compound represented by the general formula (X) is a conventionally known compound. For example, a person skilled in the art can refer to a document (DWH MacDowell and F. l. Ballas, J. Org. Chem., Vol. .42 No. 23, p3717-3721 1977) can be easily obtained.

  The “organometallic reagent” is not particularly limited as long as it is a reagent capable of extracting a hydrogen atom from the compound represented by the above general formula (X). It is preferable that the substance is When the organometallic reagent has high nucleophilicity, it reacts with the nitrile group of the thiophene skeleton represented by the above general formula (X), which is not preferable because the yield of the desired product is lowered. Similarly, when the steric hindrance of the organometallic reagent is small, it similarly reacts with the nitrile group of the thiophene skeleton, which is not preferable.

  As such an organometallic reagent, for example, LDA (lithium diisopropylamide), LiTMP (lithium tetramethyltetramethylpiperidine), LiHMDS (lithium hexamethyldisilazane), etc., which are also used in the examples described later, are preferably used. However, it is not limited to these reagents.

As the “halogenation reagent”, a conventionally known halogenation reagent can be used, and its specific configuration and the like are not particularly limited. For example, when iodine is used as the halogen, I ₂ can be used in addition to C ₂ H ₄ I ₂ described later.

  That is, in the production method, the first step is a step of extracting a hydrogen atom from the compound represented by the general formula (X) to form an anion, and the second step is a step in which the hydrogen atom of the anion is It can be said that this is a step of introducing a halogen atom into the extracted position.

  Through the first step and the second step, the compound represented by the general formula (IX) can be obtained efficiently.

  As described above, it has not been possible to obtain the compound represented by the general formula (IX) from the compound represented by the general formula (X) until now. A compound represented by the general formula (IX) could be obtained. The following reasons can be considered as a reason why the above-mentioned compound was successfully obtained.

  Usually, when a halogen atom is introduced into a compound having a thiophene skeleton, an electrophilic halogenating reagent is generally added because thiophene is electron-rich. However, in this case, since the nitrile group (CN) of the thiophene skeleton attracts electrons, the halogenating reagent and the hydrogen atom of the thiophene skeleton do not react, and the nitrile group and the halogenating reagent preferentially react. I was sorry.

  Therefore, the present inventors have developed a method for obtaining a desired compound by once extracting hydrogen of a thiophene skeleton with a hydrogen abstraction reagent (organometallic reagent) to form an anion and then reacting the anion with a halogenating reagent. did. However, even in this case, since the nitrile group reacts with the hydrogen abstraction reagent (organometallic reagent), it is preferable to control the conditions such as the reaction temperature.

  For example, in the present invention, under the reaction conditions that suppress the reaction between the nitrile group of the thiophene skeleton and the hydrogen abstraction reagent (organometallic reagent) as much as possible, for example, in a low temperature environment, It is preferable to perform the process of 2. For example, as shown in the Example mentioned later, the method of reacting at -106 degrees C or less can be mentioned. In the examples described later, in order to perform the reaction in a low temperature environment, liquid nitrogen and ethanol are mixed to form a sherbet, and “−106 ° C. or lower” means that this liquid nitrogen and This is the temperature when mixing with ethanol to form a sherbet.

  In addition, at the reaction temperature of -70 degreeC or more, the compound represented by the said general formula (IX) was not able to fully be obtained. This is presumably because when the reaction temperature is high, the nitrile group and the organometallic reagent react with each other, so that the yield is remarkably deteriorated.

  In addition, as described above, if the compound represented by the above general formula (IX) is obtained, the above-described compound in the <1> column can be produced by a conventionally known organic chemical synthesis method. Specifically, for example, as shown in Examples described later, known literature (DW MacDowell et al., J. Org. Chem. 1977, 42, 3717, MJ Cook et al., J. Mater. Chem. 1997, 7, 5 , MJ Cook et al., Tetrahedoron. 2000, 56, 4085. DM Knawby et al., Chem. Mater. 1997, 9, 535. M. Victoria Martinez-Diaz et al., Tetrahedron Lett. 2003, 44, 8475. An oligothiophene compound can be obtained by performing a cross-coupling reaction under a transition metal catalyst. Furthermore, by using a plurality of oligothiophene compounds thus obtained and ring-closing in the presence of Li (lithium), a compound having a desired structure in which the oligothiophene skeleton and the phthalocyanine skeleton are conjugated is obtained. be able to.

  Furthermore, by appropriately setting the type of oligothiophene compound to be used and the reaction conditions, a compound having any one of oligothiophene skeletons 1 to 4 can be appropriately produced for one phthalocyanine skeleton. Specifically, for example, a dicyano compound having an oligothiophene skeleton represented by the above general formula (VIII) and a phthalonitrile derivative are mixed at an arbitrary ratio, and ring-closing is performed as described above, whereby 1 to 4 A phthalocyanine derivative having an oligothiophene skeleton can be produced. Moreover, according to the mixing ratio, the number of oligothiophene skeletons of the phthalocyanine derivative obtained preferentially among a plurality of products can be adjusted. As described above, since the properties of the phthalocyanine skeleton may change depending on the shape and quantity of the oligothiophene skeleton, a compound having a wide variety of phthalocyanine skeletons and oligothiophene skeletons can be easily and efficiently produced. The production method according to the present invention which can be used is very useful.

<3. Use according to the present invention>
As described above, the compound according to the present invention has a unique property that a strong light absorption spectrum is observed in the entire visible region. Therefore, the compound according to the present invention is a photoelectric conversion element, a dye-sensitized solar cell element, an organic EL element, a liquid crystal display element, an organic thin film transistor element, a light emitting element having an organic carrier transport layer, or an organic semiconductor electronic material. Can be suitably used. The device according to the present invention only needs to use the above compound, and other specific configurations, materials, sizes, shapes, uses, and the like are not particularly limited.

  When the compound according to the present invention is used for, for example, a photoelectric conversion element or a solar cell, a photoelectric conversion element or solar cell excellent in photoelectric conversion ability that absorbs light in a wide range of wavelengths can be produced efficiently. Electric energy can be obtained. In particular, in the case of solar energy, since the energy in the visible region of about 400 nm to 1300 nm is large, development of a photoelectric conversion element and a solar cell that can be used has been strongly desired. Therefore, it can be said that the device according to the present invention capable of efficiently converting such light energy into electric energy is very useful.

  In particular, a compound having a plurality of oligothiophene skeletons exhibits a wide light absorption spectrum with respect to the phthalocyanine skeleton. For this reason, the element which has the very outstanding photoelectric conversion ability which can utilize the light of the wavelength of a wide area | region can be obtained. Further, as described above, the compound according to the present invention has properties as a liquid crystal. Therefore, it can be used for various optoelectronic devices using liquid crystals, such as display elements, and organic semiconductor layers composed of highly oriented molecular thin films using the self-association property of the liquid crystal phase.

  Furthermore, it goes without saying that both the oligothiophene skeleton and the phthalocyanine skeleton are excellent in electron carrier transport ability and can be used as useful electronic materials.

  The subject of the device according to the present invention resides in providing a novel device with improved carrier transport capability and / or improved light absorption capability, and the individual devices specifically described in the present specification. It does not exist in the specific example. Therefore, it should be noted that devices / parts other than the specific devices belong to the scope of the present invention.

  Hereinafter, examples will be shown, and the embodiment of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Furthermore, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the embodiments obtained by appropriately combining the respective technical means disclosed are also included in the present invention. It is included in the technical scope of the invention.

  FIG. 1 shows a production scheme for producing an example of the compound according to the present invention. Details of each reaction are as follows.

[1] 2,3-Dicyanothiophene (compound indicated by “1” in FIG. 1)
According to the literature (DW MacDowell et al., J. Org. Chem. 1977, 42, 3717), it was synthesized as follows. Under a nitrogen atmosphere, 2,3-Dibromothiophene (2.8 ml, 24.8 mmol) and cuprous cyanide (7.2 g, 80.4 mmol) were added to DMF (150 ml) and refluxed for 7 hours. After cooling, this was added to a mixed solution of FeCl ₃ (28.6 g) and 2N hydrochloric acid (150 ml), kept at 60 to 70 ° C., and stirred for 1 hour while blowing nitrogen gas. The mixed solution was extracted with methylene chloride (180 ml × 4), and washed successively with 2N hydrochloric acid (200 ml × 3), water (600 ml), saturated aqueous sodium hydrogencarbonate (200 ml × 2), and water (600 ml). The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. After fractionation by column chromatography (silica gel, methylene chloride: hexane = 3: 1, Rf = 0.4), recrystallization was performed with a mixed solvent of chloroform: hexane, and the compound “1” was obtained as colorless needle crystals. Obtained. (2.26 g, 68%); mp 116-122 ° C (literature value 115-122 ° C). ¹ H NMR (400 MHz, CDCl ₃ , TMS) δ 7.83 (d, 1H, J = 5.2 Hz), 7.44 (d, 1H, J = 5.2 Hz)
[2] 2,3-Dicyano-5-iodothiophene (compound indicated by “2” in FIG. 1)
Under a nitrogen atmosphere, THF (30 ml) was added to a 0.33 M LDA-THF solution (9.6 ml, 3.1 mmol) while cooling the reaction vessel, and 2,3-dicyanothiophene ( 0.4 g, 3 mmol) / THF solution (8 ml) was added dropwise. After further stirring for 40 minutes, 1,2-diiodoethane (1.1 g, 4 mmol) was added, and the temperature was slowly returned to room temperature. Water (100 ml) was added and extracted with methylene chloride (80 ml × 3). The extract was washed successively with water (150 ml), saturated brine (150 ml) and water (150 ml), and then dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, purification by column chromatography (silica gel, methylene chloride: hexane = 3: 1, Rf = 0.4), recrystallization (chloroform-hexane) mixed solvent, pale yellow needle-like crystals As a result, a compound of “2” was obtained. (0.52 g, 67%); mp 115-117 ° C
¹ H NMR (60 MHz, CDCl ₃ , TMS); δ 7.47 (s, 1H)
¹³ C NMR (100 MHz, CDCl ₃ , TMS); δ 138.09, 123.00, 120.24, 109.99, 109.46, 82.77
Elemental analysis: calculated C ₆ HIN ₂ S: C, 27.71; H, 0.39; N, 10.77. Found: C, 27.70; H, 0.39; N, 10.69.
[3] 2,3-Dicyano-3 ', 3''''-dihexyl-5,5'2', 5 '';'2'',5'''; 2 ''',5''''-quinquethiophene (compound indicated by “3” in FIG. 1)
Under a nitrogen atmosphere, 2,3-Dicyano-5-iodothiophene (the compound indicated by “2” in FIG. 1, 206 mg, 0.79 mmol) and 2-tributylstanyl-4,3 ′ ″-dihexyl-5,2 ′; 5′2 ″; 5 ″, 2 ′ ″-quaterthiophene (660 mg, 0.84 mmol, synthesized according to T. Yamashiro et al., Chem. Lett., 1999, 443.) was dissolved in anhydrous toluene (40 ml) After degassing by blowing argon gas for 30 minutes, Pd (PPh ₃ ) ₄ (70 mg, 60 mmol) was added and refluxed for 18 hours. Then, celite filtration was performed and the solvent was distilled off under reduced pressure. Purification by column chromatography (silica gel, methylene chloride: hexane = 5: 3, Rf = 0.4) gave a compound represented by a red solid “3”. (270 mg, 54%); mp 88-93 ° C
MS (MALDI-TOF) m / z 630.52 (calculated value 630.98)
¹ H NMR (400 MHz, CDCl ₃ , TMS) δ 7.27 (s, 1 H), 7.20 (d, 1 H, J = 5.1 Hz), 7.15 (d, 1 H, J = 3.9 Hz), 7.13 (d, 1H, J = 3.9 Hz), 7.15 (s, 1H), 7.09 (d, 1H, J = 3.8 Hz), 7.03 (d, 1H, J = 3.8 Hz), 6.95 (d, 1H, J = 5.1 Hz), 2.78 (t, 2H, J = 6.7 Hz), 2.79 (t, 2H, J = 6.7 Hz) , 1.87 (m, 12H), 1.39 (m, 8H), 1.26 (m, 8H), 0.92 (t, 3H, J = 7.2 Hz), 0.89 (t, 3H) , J = 7.2 Hz).
¹³ C NMR (100 MHz, CDCl ₃ , TMS) δ 145.20, 140.76, 139.79, 138.08, 135.97, 135.74, 134.16, 133.04, 130.12, 130.10 , 129.96, 129.67, 127.23, 126.16, 124.14, 123.89, 123.70, 123.64, 119.85, 113.85, 111.73, 110.87, 31 .54, 31.48, 30.43, 30.15, 29.37, 29.26, 29.13, 29.09, 22.52, 22.50, 14.01 (× 2).
Calcd _{C 34 H 34 N 22 S 5} : C, 64.72; H, 5.43; N, 4.44. Found: C, 64.99; H, 5.42; N, 4.63.
[4] Tetrakis (3 ', 3''''-dihexyl-5,5'; 2 ', 5'';' 2 '', 5 ''';2''', 5 ''''-quinquethiopheno ) [2,3] porphyrazine (compound indicated by “4” in FIG. 1)
Under a nitrogen atmosphere, the compound represented by “3” (250 mg, 0.4 mmol) was dissolved in 1-pentanol (3 ml) at 80 ° C., metallic lithium (120 mg) was added little by little, and the mixture was stirred at 110 ° C. for 19 hours. After completion of the reaction, acetone (50 ml) was added and stirred for 30 minutes, insoluble matter was filtered and washed with acetone. The filtrate was concentrated to 20 ml, acetic acid (100 ml) was added and stirred overnight, and then the crude “4” compound was collected by filtration as a precipitate. Further, the filtrate was concentrated, diluted with water (50 ml), and extracted with methylene chloride (50 ml × 3). The extract is washed with water, dried over sodium sulfate, concentrated under reduced pressure, combined with the previous product, the green component is separated by column chromatography (alumina chloroform), and gel permeation liquid chromatography (column : JAIGEL-3H, 4H, V _R = 250 ml) to obtain a green solid (40 mg, 16%). mp> 300 ° C
MS (MALDI-TOF) m / z 2528.83 (calcd. 2525.92). Elemental analysis: calculated value C ₁₃₆ H ₁₃₈ N ₈ S ₂₀ : C, 64.67, H, 5.51, N, 4.44. Actual value: C, 64.64, H, 5.49, N, 4.50.
[5] Hexakis (butoxymethyl) tribenzo [d, i, n] -5- (3,3 ''-dihexyl-2,2 ';5', 2 ''; 5 '', 2 '''-quarterthiophene- 5-yl) thiopheno [2,3-s] porphyrazine (compound indicated by “5” in FIG. 1)
In a nitrogen atmosphere, the compound represented by “3” (130 mg, 0.2 mmol) and 4,5-bis (n-butoxymethyl) phthalonitrule (371 mg, 1.24 mmol) are dissolved in 1-pentanol at 80 ° C. to obtain metallic lithium. (0.3 g) was added little by little, and the mixture was stirred at 110 ° C. for 16 hours. After completion of the reaction, acetone (30 ml) was added and stirred for 30 minutes, the precipitate was filtered off and washed with acetone. The filtrate was concentrated, acetic acid (20 ml) was added, and the mixture was stirred for 1 hour, and the target product was collected as a precipitate by filtration. The filtrate was concentrated under reduced pressure, water (100 ml) was added, and the mixture was extracted with methylene chloride (80 ml × 3). The extract was washed with water (200 ml), dried over sodium sulfate, concentrated under reduced pressure, and combined with the previous crude product by column chromatography (methylene chloride: THF = 100: 1, Rf = 0.3). , To give the compound represented by “5” as a green solid (99 mg, 18%). mp 133-141 ° C
¹ H NMR (400 MHz, CDCl ₃ , TMS); δ 8.92 (s, 1H), 8.85 (s, 1H), 8.59 (s, 1H), 8.49 (s, 1H), 8. 48 (s, 1H), 8.37 (s, 1H), 7.79 (s, 1H), 7.20 (d, 1H, J = 5.4 Hz), 7.15 (s, 1H), 7 .03 (d, 1H, J = 3.7 Hz), 7.01 (d, 1H, J = 3.7 Hz), 6.98 (d, 1H, J = 3.7 Hz), 6.97 (s, 1H), 6.97 (d, 1H, J = 5.4 Hz), 6.94 (d, 1H, J = 3.7 Hz), 4.99 (s, 2H), 4.98 (s, 2H) ), 4.92 (s, 2H), 4.88 (s, 2H), 4.88 (s, 2H), 4.81 (s, 2H), 3.80 (m, 12H), 2.80 (T, 2H, J = 6.7H z), 2.65 (t, 2H, J = 6.7 Hz), 1.87 (d, 12H, J = 3.7 Hz), 1.63 (m, 24H), 1.43 (m, 8H) 1.36 (m, 8H), 1.11 (m, 18H), 1.01 (t, 3H, J = 7.2 Hz), 0.95 (t, 3H, J = 7.2 Hz)
MS (MALDI-TOF) m / z 1531.97 (calcd. 1534.18).
Calcd _{C 88 H 108 N 8 O 6} S 5: C, 68.89; H, 7.10; N, 7.30 Found: C, 69.74, H, 7.23 , N, 7.26.
In addition, in the above description, unless otherwise mentioned, related documents (DW MacDowell et al., J. Org. Chem. 1977, 42, 3717, MJ Cook et al., J. Mater. Chem. 1997, 7, 5. MJ Cook et al. Tetrahedoron. 2000, 56, 4085. DM Knawby et al. Chem. Mater. 1997, 9, 535. M. Victoria Martinez-Diaz et al. Tetrahedron Lett. 2003, 44, 8475.) went.

  Next, the absorption spectrum of each of the compound having a phthalocyanine skeleton, the compound represented by “4”, and the compound represented by “5” was examined. The result is shown in FIG.

  As shown in FIG. 2A, the compounds having only the phthalocyanine skeleton were observed to have strong peaks in the vicinity of 300 nm to 400 nm and 650 nm to 700 nm, as is conventionally known.

  In addition, as shown in FIG. 2B, the compound “4” in which the phthalocyanine skeleton and the four oligothiophene skeletons are conjugated has a strong peak in the vicinity of 400 nm and a wide absorption from 300 to 800 nm. Was recognized.

  In addition, as shown in FIG. 2C, the compound “5” in which the phthalocyanine skeleton and one oligothiophene skeleton are conjugated has substantially the same position of the strongest absorption peak as the compound having only the phthalocyanine skeleton. However, it was further found that the absorption at 400 nm to 600 nm was stronger than that of the compound having only the phthalocyanine skeleton.

  As described above, the compound in which the phthalocyanine skeleton and the oligothiophene skeleton are conjugated exhibits an unprecedented absorption spectrum, and the nature of the compound increases as the number of oligothiophene skeletons conjugated with the phthalocyanine skeleton increases. It turned out to be remarkable. Therefore, this compound is a compound having completely new properties, and is considered to be very useful as an organic semiconductor electronic material that can be used for, for example, a photoelectric, photoelectronic, electrical, and electronic component.

  The compound according to the present invention includes, for example, a photoelectric-sensitized solar cell material, a thin-film photoelectric conversion element, a liquid crystal, an organic thin-film transistor, a light-emitting device having an organic carrier transport layer, and the like. Therefore, there is a very promising industrial applicability.

It is a figure which shows an example of the manufacturing scheme of the compound shown in the Example which concerns on this invention. (A)-(c) is a figure which shows the result of having investigated the absorption spectrum of the compound shown in the Example based on this invention.

Claims (16)

A compound having at least a phthalocyanine skeleton and an oligothiophene skeleton,
A compound in which the phthalocyanine skeleton and the oligothiophene skeleton are conjugated. A compound represented by the following general formula (I),

In the general formula (I), Ar is represented by the following general formula (II),

In the general formulas (I) and (II), R1 to R12, R, and R ′ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, An alkyl group in which one or more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkyloxy group having 1 to 18 carbon atoms, and one in the alkyloxy group Or an alkyloxy group in which more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, and one or more of the alkylthio groups A carbon atom is an alkylthio group which may be substituted with an oxygen atom, a nitrogen atom and / or a sulfur atom, or an aromatic group. A compound represented by the following general formula (III),

In the general formula (III), Ar is represented by the following general formula (II),

In the general formulas (II) and (III), R1 to R8, R, and R ′ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, An alkyl group in which one or more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkyloxy group having 1 to 18 carbon atoms, and one in the alkyloxy group Or an alkyloxy group in which more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, and one or more of the alkylthio groups A carbon atom is an alkylthio group which may be substituted with an oxygen atom, a nitrogen atom and / or a sulfur atom, or an aromatic group. A compound represented by the following general formula (IV),

In the general formula (IV), Ar is represented by the following general formula (II),

In the general formulas (II) and (IV), R1 to R4, R, and R ′ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, An alkyl group in which one or more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkyloxy group having 1 to 18 carbon atoms, and one in the alkyloxy group Or an alkyloxy group in which more carbon atoms may be substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, and one or more of the alkylthio groups A carbon atom is an alkylthio group which may be substituted with an oxygen atom, a nitrogen atom and / or a sulfur atom, or an aromatic group. A compound represented by the following general formula (V),

In the general formula (V), Ar is represented by the following general formula (II),

In the general formula (II), R and R ′ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, and one or more carbon atoms in the alkyl group are An alkyl group optionally substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, or an alkyloxy group having 1 to 18 carbon atoms, wherein one or more carbon atoms in the alkyloxy group are oxygen atoms , A nitrogen atom, and / or an alkyloxy group optionally substituted with a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, wherein one or more carbon atoms in the alkylthio group are an oxygen atom and a nitrogen atom And / or an alkylthio group which may be substituted with a sulfur atom, or an aromatic group. A compound represented by the following chemical formula (VI).

A compound represented by the following chemical formula (VII).

  The compound according to any one of claims 1 to 7, wherein the phthalocyanine skeleton forms a complex with a metal ion. A compound represented by the following general formula (VIII),

In the general formula (VIII), Ar is represented by the following general formula (II),

In the general formula (II), R and R ′ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 18 carbon atoms, and one or more carbon atoms in the alkyl group are An alkyl group optionally substituted with an oxygen atom, a nitrogen atom, and / or a sulfur atom, or an alkyloxy group having 1 to 18 carbon atoms, wherein one or more carbon atoms in the alkyloxy group are oxygen atoms , A nitrogen atom, and / or an alkyloxy group optionally substituted with a sulfur atom, an alkylthio group having 1 to 18 carbon atoms, wherein one or more carbon atoms in the alkylthio group are an oxygen atom and a nitrogen atom And / or an alkylthio group which may be substituted with a sulfur atom, or an aromatic group. A compound represented by the following general formula (IX),

In the above general formula (IX), B is a halogen atom.   In the said general formula (IX), B is an iodine atom, The compound of Claim 10 characterized by the above-mentioned. A method for producing the compound of claim 10,
A first step of reacting a compound represented by the following general formula (X) with an organometallic reagent;
And a second step of reacting with a halogenating reagent after the first step.

  The production method according to claim 12, wherein the halogenating reagent is an iodination reagent. It is a manufacturing method of the compound of any one of Claims 1-8,
A first step of reacting a compound represented by the following general formula (X) with an organometallic reagent;
And a second step of reacting with a halogenating reagent after the first step.

  A device comprising the compound according to claim 1. The device according to claim 15, wherein the device is a photoelectric conversion element, a dye-sensitized solar cell element, an organic EL element, a liquid crystal display element, an organic thin film transistor element, or a light emitting element having an organic carrier transport layer. .

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