JP5397802B2 - Porphycene and production method thereof, film, semiconductor material, fluorescent dye, and solar cell - Google Patents

Description

  The present invention relates to a porphycene having a bicyclo structure, a production method for obtaining a new conjugated extended porphycene from a porphycene having a bicyclo structure, a novel conjugated extended porphycene, a film containing the conjugated extended porphycene, a semiconductor, a fluorescent dye, It relates to solar cells.

  Porphycene is a structural isomer of porphyrin and has unique optical and electrochemical properties, so it is used for anti-counterfeiting using near-infrared light emission, fluorescent sensors such as photodynamic therapy and bioimaging, organic EL and organic semiconductors. As organic organic materials such as solar cells, application in a wide range of fields is expected.

  However, porphycene, like porphyrin, has a structure with very high planarity, poor solubility in a solvent, and it has been difficult to purify and purify. So far, many highly soluble porphycenes introduced with alkyl groups, phenyl groups, etc. have been reported, but if there are substituents with a high degree of freedom, they often involve a decrease in fluorescence intensity, a decrease in mobility, Application to fluorescent dyes and semiconductors has been difficult.

  Further, although the structure of the conjugated extended porphycene represented by the formula (1) is known, since it becomes a pigment insoluble in organic solvents, there is no example purified with high purity, and there are no reports on its derivatives. Absent.

J.L. Sessler et al. Chem. Soc. Rev., 2008, 37, 215.

  In view of the above-described conventional situation, an object of the present invention is to provide a porphycene having a novel bicyclo structure that can be used as, for example, a semiconductor material or a fluorescent dye while maintaining solubility. .

  As a result of intensive studies to solve the above problems, the present inventors have succeeded in producing a novel porphycene having a bicyclo structure and a conjugated extended porphycene having a precursor of the porphycene having the bicyclo structure, thereby achieving the present invention. It came to do.

  That is, the object of the present invention is achieved by porphycene represented by the following general formula.

Wherein R ′ and R ″ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group which may have a substituent, or a carboxyl group which may have a substituent. An alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent Represents an aromatic hydrocarbon group which may be substituted, or an aromatic heterocyclic group which may have a substituent, and adjacent R ′ and R ″ may form a ring with each other. M represents two hydrogen atoms. represents an atom or a metal atom, .Y have substituent or a ligand depending on the valence, or the both represent CH or a nitrogen atom.)

  The object of the present invention is also achieved by a porphycene represented by the following general formula.

Wherein R ′ and R ″ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group which may have a substituent, or a carboxyl group which may have a substituent. An alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent Represents an aromatic hydrocarbon group which may be substituted, or an aromatic heterocyclic group which may have a substituent, and adjacent R ′ and R ″ may form a ring with each other. M represents two hydrogen atoms. Represents an atom or a metal atom, and may have a substituent or a ligand, or both depending on the valence. Y represents a nitrogen atom when all of R ′ and R ″ are hydrogen atoms. When at least one of R ′ and R ″ is not a hydrogen atom, it represents CH or a nitrogen atom.)

  According to the present invention, for example, it is possible to provide a porphycene having a novel bicyclo structure that can be used as a semiconductor material or a fluorescent dye while maintaining solubility while suppressing the degree of freedom.

  Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and can be implemented in various forms.

  In the present embodiment, porphycene refers to a compound having the structure of formula (2) (porphycene skeleton).

[Porphycene having bicyclo structure]
The porphycene disclosed in the present embodiment further has a bicyclo structure.

  The bicyclo structure is not limited, but specifically, it preferably has a structure in which a 4π-electron-type cyclic compound and a 2π-electron-type compound are cyclized and added. A structure obtained by cyclization of a compound with a Diels-Alder reaction is more preferable.

  More specifically, the porphycene having a bicyclo structure according to this embodiment is preferably a porphycene having one or more structures represented by the following general formula (3).

In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group that may have a substituent, a carboxyl group that may have a substituent, or a substituent. An alkyl group that may have a group, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent It represents a good aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and R ¹ and R ² may form a ring with each other. X represents a divalent linking group. The ring represents a cyclic structure, and C ¹ and C ² represent carbon atoms of the porphycene skeleton. n represents an integer of 0 to 3.

  As an aromatic hydrocarbon group, a C6-C16 thing is preferable. These are not limited to monocyclic groups, and may be condensed polycyclic hydrocarbon groups. Specific examples include monocyclic groups such as phenyl groups, condensed polycyclic hydrocarbon groups such as biphenyl groups, phenanthryl groups, naphthyl groups, anthryl groups, and fluorenyl groups, and biphenyl groups and terphenyl groups. Preferable are a phenyl group and a naphthyl group which may have a substituent.

  As the aromatic heterocyclic group, those having 5 to 20 carbon atoms are preferable, and specific examples include pyridyl group, thienyl group, oxazole group, thiazole group, oxadiazole group, benzothienyl group, dibenzofuryl group, dibenzothienyl group. , Pyrazyl group, pyrimidyl group, pyrazoyl group, imidazolyl group, phenylcarbazoyl group and the like. A pyridyl group, a thienyl group, a benzothienyl group, a dibenzofuryl group, and a dibenzothienyl group are preferable.

  As an alkyl group, a C3-C20 thing is preferable and i-propyl group, t-butyl group, a cyclohexyl group etc. are mentioned as a specific example.

  The alkenyl group preferably has 2 to 20 carbon atoms, and specific examples include a styryl group and a diphenylvinyl group.

  As the alkynyl group, those having 2 to 20 carbon atoms are preferable, and specific examples include a methylethynyl group, a phenylethynyl group, a trimethylsilylethynyl group, and the like.

  These substituents may further have a substituent. Further, the substituents that may be included are aryl group, arylamino group, alkyl group, perfluoroalkyl group, halogen group, carboxyl group, cyano group, alkoxyl group, aryloxy group, carbonyl group, oxycarbonyl group, carboxyl group An acid group, a heterocyclic group, etc. are mentioned. Preferably, an aryl group having 6 to 16 carbon atoms, an arylamino group having 12 to 30 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a perfluoroalkyl group having 1 to 12 carbon atoms, a fluoro group, and 1 to 10 carbon atoms. An oxycarbonyl group, a cyano group, an alkoxyl group having 1 to 10 carbon atoms, an aryloxy group having 6 to 16 carbon atoms, a carbonyl group having 2 to 16 carbon atoms, and an aromatic heterocyclic group having 5 to 20 carbon atoms. Further, among the substituents that may be included, examples of the aryl group having 6 to 16 carbon atoms include a phenyl group, a naphthyl group, and a phenanthryl group. Examples of the arylamino group having 12 to 30 carbon atoms include a diphenylamino group, a carbazoyl group, and a phenylcarbazoyl group. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a butyl group, and a t-butyl group. A trifluoromethyl group etc. are mentioned as an example of a C1-C12 perfluoroalkyl group. Examples of the oxycarbonyl group having 1 to 10 carbon atoms include a methoxycarbonyl group and an ethoxycarbonyl group. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group and an ethoxy group. Examples of the aryloxy group having 6 to 16 carbon atoms include a phenyloxy group. Examples of the carbonyl group having 2 to 16 carbon atoms include an acetyl group and a phenylcarbonyl group. Examples of the aromatic heterocyclic group having 5 to 20 carbon atoms include pyridyl group, thienyl group, oxazole group, oxadiazole group, benzothienyl group, dibenzofuryl group, dibenzothienyl group, pyrazyl group, pyrimidyl group, pyrazoyl group And imidazolyl group.

  X represents a divalent linking group. Although it will not specifically limit if it is a bivalent coupling group, Specifically, the alkylene group which may have a C1-C3 substituent, an oxygen atom, -N = N- (diazo group),- COO——SONR—, —NR—, —CO—CO— and the like can be mentioned. An ethylene group which may have a substituent is preferable.

  The ring represents a cyclic structure. The cyclic structure is not particularly limited, and specifically, it may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. A benzene ring, a naphthalene ring, a thiophene ring, and a pyridine ring are preferable.

  n represents an integer of 0-3. Preferably, n is an integer of 0-2.

R ¹ and R ² may form a ring with each other. Specific examples include the structure represented by Formula (4), but are not limited thereto. These rings may have a substituent.

   The porphycene having a bicyclo structure according to this embodiment preferably contains 1 to 4 bicyclo structures. More preferably, it contains 2-4 bicyclo structures. However, the number of bicyclo structures contained is not limited to this.

  The position of the bicyclo structure in porphycene is not particularly limited, but preferably a bicyclo structure exists as shown by the following formula (5).

In formula (5), each R ′ is independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group which may have a substituent, a carboxyl group which may have a substituent, or a substituent. An alkyl group that may have a group, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent It represents a good aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and adjacent R ′ may form a ring with each other. M represents two hydrogen atoms or a metal atom, and may have a substituent, a ligand, or both depending on the valence. Of the four C ³ ═C ⁴ bonding moieties, at least one has a structure represented by the following formula (6), and the other C ³ ═C ⁴ bonding moieties may have a substituent —CH ₂ = CH ₂ - a group.

In formula (6), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group that may have a substituent, or a carboxyl that may have a substituent. Group, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent. An aromatic hydrocarbon group that may be substituted, or an aromatic heterocyclic group that may have a substituent, and R ¹ and R ² may form a ring with each other. X represents a divalent linking group. The ring represents a cyclic structure, and C ¹ and C ² represent carbon atoms of the porphycene skeleton. n represents an integer of 0 to 3.

  In Formula (5), M represents 2H or a metal atom, and may have a substituent, a ligand, or both depending on the valence. Examples of the metal atom include, but are not limited to, titanium, vanadium, iron, cobalt, nickel, copper, zinc, gallium, aluminum, silicon, iridium, platinum, silver, and lanthanum. Moreover, as a ligand, what is shown by Formula (7) is mentioned, However, It is not limited to these.

   More preferably, the porphycene having a bicyclo structure of the present invention is represented by the formula (8).

In formula (8), R ′ and R ″ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group which may have a substituent, or a substituent. A carboxyl group, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxyl group which may have a substituent, a substituent It represents an aromatic hydrocarbon group that may be present, or an aromatic heterocyclic group that may have a substituent, and adjacent R ′ and R ″ may form a ring with each other. M represents two hydrogen atoms or a metal atom, and may have a substituent, a ligand, or both depending on the valence. Y represents CH or a nitrogen atom.

  A specific example of the porphycene having a bicyclo structure of the present invention is shown in Formula (9).

  A general synthesis method for synthesizing a porphycene having a bicyclo structure according to the present invention will be described below with reference to reaction formula (I).

  In Reaction Formula (I), each R independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group that may have a substituent, a carboxyl group that may have a substituent, or a substituent. An alkyl group that may have a group, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent It represents a good aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and adjacent Rs may form a ring with each other.

  Step 1: First, a pyrrole derivative (10) having a bicyclo skeleton as a starting material is reacted with iodine or N-iodosuccinimide in an organic solvent such as chloroform to obtain an iodinated pyrrole derivative (11).

  Step 2: The pyrrole dimer (12) is obtained by dissolving the pyrrole derivative (11) in an organic solvent such as N, N-dimethylformamide and reacting in the presence of a catalyst such as copper or copper iodide.

  Process 3: A bisformyl body (13) is obtained by making a pyrrole dimer (12) react with phosphorus oxychloride in N, N-dimethylformamide.

  Step 4: The bisformyl body (13) is dissolved in an organic solvent such as tetrahydrofuran, and McMurry Coupling is performed using titanium tetrachloride and zinc in the presence of a base such as pyridine, whereby the bicyclo structure of the present embodiment is obtained. Porphycene (14) having is obtained.

  In addition, the porphycene which has a bicyclo structure shown by Formula (5) which has substituents other than a hydrogen atom in R 'can also be obtained by converting the aldehyde part of a bisformyl body (13) into a ketone. As an example, after an addition reaction is performed using a nucleophile including, but not limited to, a Grignard reagent to an aldehyde site of the bisformyl body (13), an oxidation reaction including but not limited to Jones oxidation is used. You can get a ketone.

  The α-position of pyrrole having a bicyclo skeleton is iodinated and dimerized by an Ullmann coupling reaction. Thereafter, the two α positions of the pyrrole dimer are formylated and condensed to porphycene by McMurry coupling. Porphycene can be converted to a zinc complex by treatment with zinc acetate.

[Conjugate extended porphycene]
The porphycene having a bicyclo structure of the present invention can be converted into a conjugated extended porphycene.

  Conversion methods such as heat conversion and light conversion can be used, and heat conversion is preferably used. The thermal conversion is preferably performed at 0 ° C to 400 ° C, more preferably 50 ° C to 300 ° C.

  The porphycene having a bicyclo structure of the present invention undergoes elimination reaction under reaction conditions such as thermal conversion, and the linking group X shown in Formula (3), which is a part of the bicyclo structure, is eliminated. The elimination reaction includes, but is not limited to, a retro-Diels-Alder reaction. Specifically, when porphycene having a bicyclo structure of formula (3) is used, porphycene having one or more structures represented by formula (15) is generated.

In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group that may have a substituent, a carboxyl group that may have a substituent, or a substituent. An alkyl group that may have a group, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent It represents a good aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and R ¹ and R ² may form a ring with each other. The ring represents a cyclic structure, and C ¹ and C ² represent carbon atoms of the porphycene skeleton. n represents an integer of 0 to 3.

  The elimination reaction is preferably performed using a porphycene having a bicyclo structure represented by the formula (5). In this case, a porphycene represented by the following formula (16) is generated.

In formula (16), each R ′ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group which may have a substituent, a carboxyl group which may have a substituent, or a substituent. An alkyl group that may have a group, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent It represents a good aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and adjacent R ′ may form a ring with each other. M represents two hydrogen atoms or a metal atom, and may have a substituent, a ligand, or both depending on the valence. Of the four C ³ ═C ⁴ bonding moieties, at least one has the structure shown in Formula (17), and the other C ³ ═C ⁴ bonding moiety may have a substituent —CH ₂ ═ is a group - CH _2.

In formula (17), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group that may have a substituent, or a carboxyl that may have a substituent. Group, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent. An aromatic hydrocarbon group that may be substituted, or an aromatic heterocyclic group that may have a substituent, and R ¹ and R ² may form a ring with each other. The ring represents a cyclic structure. n represents an integer of 0 to 3.

  It is more preferable to cause elimination reaction of porphycene having a bicyclo structure represented by the formula (8) to obtain a conjugated extended porphycene represented by the following formula (18).

In formula (18), R ′ and R ″ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group which may have a substituent, or a substituent. A carboxyl group, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxyl group which may have a substituent, a substituent It represents an aromatic hydrocarbon group that may be present, or an aromatic heterocyclic group that may have a substituent, and adjacent R ′ and R ″ may form a ring with each other. M represents two hydrogen atoms or a metal atom, and may have a substituent, a ligand, or both depending on the valence. Y represents CH or a nitrogen atom.

  Among the conjugated extended porphycenes represented by the formula (15), a conjugated extended porphycene having one or more of the structures represented by the following formula (19) is a novel compound. From the conjugated structure, unique optical characteristics and electrochemical characteristics are obtained. Have

In formula (19), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group that may have a substituent, or a carboxyl that may have a substituent. Group, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent. An aromatic hydrocarbon group that may be substituted, or an aromatic heterocyclic group that may have a substituent, and R ¹ and R ² may form a ring with each other. The ring represents a cyclic structure, and C ¹ and C ² represent carbon atoms of the porphycene skeleton. n is an integer of 1 to 3 in the case of both the hydrogen atom of ^{R 1} and ^{R 2,} if at least one of ^{R 1} and ^{R 2} is not hydrogen atom represents an integer of 0 to 3.

  Further, among the conjugated extended porphycenes represented by the formula (18), the conjugated extended porphycenes having the structure represented by the formula (20) is a novel compound, and has unique optical characteristics and electrochemical characteristics from the conjugated structure.

In formula (20), R ′ and R ″ each independently have a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group which may have a substituent, or a substituent. A carboxyl group, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxyl group which may have a substituent, a substituent It represents an aromatic hydrocarbon group that may be present, or an aromatic heterocyclic group that may have a substituent, and adjacent R ′ and R ″ may form a ring with each other. M represents two hydrogen atoms or a metal atom, and may have a substituent, a ligand, or both depending on the valence. Y represents a nitrogen atom when all of R ′ and R ″ are hydrogen atoms, and represents CH or a nitrogen atom when at least one of R ′ or R ″ is not a hydrogen atom.

[Usefulness of porphycene having bicyclo structure and conjugated extended porphycene]
The porphycene having a bicyclo structure and the conjugated extended porphycene of this embodiment can be applied to various uses. As an example, a method for processing into a film will be described.

  After the porphycene of this embodiment is uniformly dissolved in a solution in which a polymer such as polyethylene terephthalate (PET) or polymethyl methacrylate (PMMA) is dissolved in an organic solvent, it is molded into a shape suitable for the application, A film can be obtained by skipping.

  The film of this embodiment preferably contains 0.2 to 20% by weight, more preferably 0.2 to 10% by weight, of the porphycene of this embodiment. As the organic solvent, toluene, chloroform, or the like can be used as the organic solvent, but the organic solvent is not limited thereto.

  In addition, the porphycene of this embodiment can be used as a fluorescent dye (also referred to as a luminescent dye). When the porphycene of this embodiment is irradiated with light from a light source having an emission maximum in the wavelength range of 365 to 420 nm, the porphycene of this embodiment emits fluorescence. Using this property, for example, if the present compound is dissolved in an organic solvent and printed on a banknote or the like, it can be used as anti-counterfeiting. Further, the above-described film can be used for an optical display device such as illumination.

  The porphycene of the present invention usually has strong light absorption in the near ultraviolet to visible to near infrared region. By utilizing this, the porphycene of the present invention can also be used as an optical functional material. In this case, specific examples of the organic electronic device of the present invention include devices that function by causing charge separation by absorbed light. Examples of such an element include a solar cell that generates electromotive force by light, a photoelectric conversion element such as a photodiode that generates photocurrent, and a phototransistor. Here, the solar cell uses an internal electric field generated at a junction between a semiconductor and a metal or another semiconductor to cause charge separation by light and take it out to the outside. In addition, such an element can generate photo radicals by sensitizing a radical generator using an excited state generated by light absorption or generating radicals directly from the excited state. Can also be applied.

  The porphycene of this embodiment can also be used for electronic devices and the like. An example of the configuration of an electronic device is a device that has two or more electrodes and controls the current flowing between the electrodes and the voltage generated by electricity, light, magnetism, chemical substances, etc., or applied voltage And a device that generates light, an electric field, and a magnetic field by means of or current. In addition, for example, an element that controls current or voltage by application of voltage or current, an element that controls voltage or current by application of a magnetic field, an element that controls voltage or current by the action of a chemical substance, or the like can be given. Examples of this control include rectification, switching, amplification, and oscillation.

  Corresponding devices currently implemented with inorganic semiconductors such as silicon include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements, chemical sensors, etc., or these elements Combinations and integrated devices. In addition, a solar cell that generates an electromotive force by light, or an optical element such as a photodiode or a phototransistor that generates a photocurrent can be used. The porphycene of this embodiment can be used as an organic semiconductor in these electronic devices. Especially, it is preferable that the electronic device of this invention is a field effect transistor, a solar cell, or an electroluminescent element. In addition, when using the porphycene of this embodiment as an organic semiconductor, you may use organic semiconductors other than the porphycene of this embodiment together.

  You may use the porphycene of this embodiment for uses other than an organic semiconductor in an electronic device. For example, by using the porphycene of this embodiment, a film is formed at a desired position of the electronic device, and the conductivity of the film is controlled by the molecular structure or doping, so that this film can be used for wiring or in a capacitor or FET. It can also be used for other insulating layers.

  More specific examples of electronic devices are described in S.A. M.M. Examples include those described in Sze, Physics of Semiconductor Devices, 2nd Edition (Wiley Interscience 1981).

  A field effect transistor (FET) is mentioned as an example of an electronic device suitable for applying the porphycene of this embodiment. Hereinafter, this FET will be described in detail.

  FIG. 1 is a diagram schematically showing an example of the structure of an FET. In FIG. 1, 1 is a semiconductor layer, 2 is an insulator layer, 3 and 4 are source and drain electrodes, 5 is a gate electrode, and 6 is a substrate.

For example, platinum, gold, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, sodium, and other metals, as well as InO ₂ , SnO ₂ , ITO, are used for the source electrode, drain electrode, and gate electrode. Conductive oxides such as polyaniline, polypyrrole, polythiophene, polyacetylene, and acids such as hydrochloric acid, sulfuric acid, sulfonic acid, Lewis acids such as PF ₆ , AsF ₅ , FeCl ₃ , iodine, etc. Materials having conductivity such as those added with dopants such as metal atoms such as halogen atoms and sodium potassium, carbon black and conductive composite materials in which metal particles are dispersed are used.

  Examples of the material used for the insulator layer include polymers such as polymethyl methacrylate, polystyrene, polyvinyl phenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, epoxy resin, phenol resin, and the like. Copolymers, oxides such as silicon dioxide, aluminum oxide and titanium oxide, nitrides such as silicon nitride, ferroelectric oxides such as strontium titanate and barium titanate, or the above oxides and nitrides And a polymer in which particles of a ferroelectric oxide or the like are dispersed.

  In general, the larger the capacitance of the insulating film, the more advantageous is that the gate voltage can be driven at a lower voltage. This can correspond to using an insulating material having a large dielectric constant or reducing the thickness of the insulator layer. Insulator layers are tailored to the material properties such as coating (spin coating and blade coating), vapor deposition, sputtering, printing methods such as screen printing and inkjet, and a method of forming an oxide film on a metal like alumite on aluminum. Can be produced by a method.

  Moreover, FET is normally produced on a board | substrate. Any substrate can be used. For example, a polymer plate, film, glass, or a metal-coated insulating film formed by coating, a polymer-inorganic composite material, or the like can be used. Furthermore, the characteristics of the FET can be improved by subjecting the substrate to substrate processing. This is presumably due to the adjustment of the hydrophilicity / hydrophobicity of the substrate to improve the quality of the film obtained at the time of film formation, in particular, by improving the characteristics of the interface portion between the substrate and the semiconductor layer. Such substrate treatment includes hydrophobization treatment such as hexamethyldisilazane, cyclohexene, octadecyltrichlorosilane, etc., acid treatment such as hydrochloric acid, sulfuric acid, acetic acid, etc., and alkali treatment such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, etc. , Ozone treatment, fluorination treatment, plasma treatment with oxygen, argon, etc., Langmuir Blodget film formation treatment, and other insulator or semiconductor thin film formation treatment.

  Furthermore, in this FET, the semiconductor layer is formed of an organic semiconductor containing porphycene of this embodiment. The semiconductor layer is a film in which an organic semiconductor is formed on a substrate directly or via another layer. Here, in addition to the porphycene of the present embodiment, other compounds (such as other organic semiconductors) may be contained in the semiconductor layer. Further, the semiconductor layer may have a stacked structure in which a specific compound layer and other semiconductor layers are stacked.

  There is no limitation on the film thickness of the semiconductor layer. For example, in the case of a lateral field effect transistor, the element characteristics do not depend on the film thickness as long as the element characteristics exceed the required film thickness. However, since the leakage current often increases when the film thickness becomes too thick, the film thickness of the semiconductor layer is usually 1 nm or more, preferably 10 nm or more, and usually 10 μm or less, preferably 500 nm or less. In addition to the uniform film state formed on the substrate, the shape of the semiconductor layer may be, for example, when a coating liquid (a solution in which an organic semiconductor is dissolved in an appropriate solvent) is attached as droplets, The thickness of the deposit is preferably in the above range.

  The semiconductor layer is applied by, for example, dissolving the porphycene having a bicyclo structure according to the present embodiment in a solvent as necessary to form a solution (coating liquid), and applying the coating liquid to a coating target (substrate or the like). In addition, it can be formed by causing a deethylene derivative reaction (reverse Diels-Alder reaction) to proceed to a porphycene having a bicyclo structure in a porphycene layer having a bicyclo structure. In particular, a conjugated extended porphycene produced by the reverse Diels-Alder reaction, which is hardly soluble in the solvent of the coating solution, is useful for forming a film by a coating method. At this time, when the compound of the present invention is used as the bicyclo compound, the choice of the solvent can be expanded and a more suitable solvent can be used.

  Since the bicyclo structure is three-dimensionally bulky, the crystallinity is poor, the molecule having this structure has good solubility, and a low crystallinity or amorphous film is easily obtained when applied from a solution. Often has Furthermore, when a reverse Diels-Alder reaction is caused by heating to change to a benzene ring, a molecular structure with good planarity is obtained, so that it changes to a molecule with good crystallinity. Therefore, by utilizing a chemical change from porphycene having a bicyclo structure, an organic semiconductor layer having good crystallinity can be obtained by a simple method such as a coating method. Among porphycenes having a bicyclo structure, those converted into benzoporphyrin and its metal complex by heat treatment are particularly desirable because they have high properties as organic semiconductors.

  Examples of the solvent for the coating solution, that is, the solvent for dissolving porphycene having a bicyclo structure include organic solvents. Among these, any selected from the group consisting of ketone solvents, ester solvents, and halogen-free aromatic solvents is preferable. Specific examples of ketone solvents include methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonyl acetone, mesityl oxide, phorone, isophorone. , Cyclohexanone, cyclopentanone, methylcyclohexanone, acetophenone, camphor and the like. Of these, methyl ethyl ketone and cyclohexanone are more preferable.

  Specific examples of ester solvents include propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, sec-hexyl acetate, and 2-ethylbutyl acetate. , 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, butyric acid ester, isobutyric acid ester, isovaleric acid ester, stearic acid ester, benzoic acid ester, cinnamic acid Ethyl, abietic acid ester, bis (2-ethylhexyl) adipate, γ-butyrolactone, oxalic acid ester, malonic acid ester, maleic acid ester, dibutyl tartrate, tributyl citrate, sebacic acid ester, lid Ester, ethylene glycol monoacetate, ethylene diacetate, ethylene glycol esters, diethylene glycol acetate, monoacetin, diacetin, triacetin, monobutyrin, diethyl carbonate, propylene carbonate, boric acid esters and phosphoric acid esters. Among these, benzoic acid ester, ethylene glycol monoacetate, ethylene glycol ester, and diethylene glycol monoacetate are more preferable, benzoic acid ester is particularly preferable, and ethyl benzoate is most preferable.

  Furthermore, specific examples of the halogen-free aromatic solvent include benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene, dipentylbenzene, dodecylbenzene, tetralin, anisole, Examples include phenetole, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, methoxy toluene, aniline, veratrol, nitrobenzene and the like. Of these, toluene, xylene, tetralin, and anisole are more preferable. In addition, a solvent may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  In addition, coating methods such as casting with a solvent, spin coating, dipping, blade coating, wire bar coating, spray coating, ink jet printing, screen printing, offset printing, letterpress printing, etc. For example, a printing method such as a soft lithography method such as a microcontact printing method, or a combination of a plurality of these methods can be used. Furthermore, as a technique similar to coating, a Langmuir-Blodgett method in which a monomolecular film formed on a water surface is transferred to a substrate and laminated, a liquid crystal or a melt state is sandwiched between two substrates, or introduced between substrates by capillary action A method etc. are also mentioned.

Furthermore, a porphycene having a bicyclo structure can be formed on a substrate by a vacuum process to produce an FET. In this case, it is possible to use a vacuum vapor deposition method in which a bicyclo compound is placed in a crucible or a metal boat and heated in a vacuum to adhere to the substrate. At this time, the degree of vacuum is usually 1 × 10 ⁻³ Torr or less, preferably 1 × 10 ⁻⁵ Torr or less. Note that 1 Torr = 1.33322 × 10 ² Pa.

  Various methods can be employed by adjusting the conditions of the degree of vacuum and the heating temperature of the bicyclo compound which is the vapor deposition source. For example, the bicyclo compound can be deposited after first deethylene with a deposition source, or after being deposited at a temperature lower than the reaction temperature while the bicyclo compound is deposited, the film formed on the substrate is heated and removed. It can also be converted into an organic semiconductor layer by an ethylene reaction. By adopting such a method, a semiconductor layer containing conjugated extended porphycene with high purity can be obtained.

  In addition, since the device characteristics change depending on the substrate temperature, it is preferable to select an optimum substrate temperature. Specifically, the temperature during vapor deposition is preferably in the range of 0 ° C to 200 ° C. The deposition rate is usually 0.01 Å / second or more, preferably 0.1 Å / second or more, and usually 100 Å / second or less, preferably 10 Å / second or less. As a method for evaporating the material, a sputtering method in which ions such as accelerated argon collide can be used in addition to heating. Note that 1Å = 10 −10 m.

  Further, the deethylene reaction of the bicyclo compound is usually caused by heat treatment at 100 ° C. or higher, preferably 150 ° C. or higher. The upper limit is 400 ° C. or lower, preferably 300 ° C. or lower. The higher the temperature, the shorter the reaction time, and the lower the temperature, the longer the reaction time. Further, depending on the application of the FET, it is also possible to adjust the characteristics by partially converting the formed bicyclo compound film. In this case, for example, the processing is performed at a low temperature or in a short time. In addition to heating by heat transfer using a heater, a carbon dioxide laser, an infrared lamp, or light having a wavelength absorbed by the bicyclo compound can be used. At this time, it is possible to heat by providing a layer that absorbs light in the vicinity of the bicyclo compound and absorbing the light in this layer.

  Furthermore, the characteristics of the manufactured semiconductor layer can be improved by post-processing. For example, the heat treatment can relieve distortion in the film generated during film formation, and can improve and stabilize characteristics. Furthermore, a change in characteristics due to oxidation or reduction can be induced by exposure to an oxidizing or reducing gas or liquid such as oxygen or hydrogen. This can be used for the purpose of increasing or decreasing the carrier density in the film, for example.

In addition, by adding a small amount of atom, atomic group, molecule, or polymer called doping, the characteristics can be changed to be desirable. For example, doping with an acid such as oxygen, hydrogen, hydrochloric acid, sulfuric acid or sulfonic acid, a Lewis acid such as PF ₆ , AsF ₅ or FeCl ₃ , a halogen atom such as iodine, a metal atom such as sodium or potassium, etc. . This can be achieved by contact with these gases, immersion in a solution, or electrochemical doping treatment. These dopings can be added at the time of synthesizing the material, after the formation of the film, or can be added to the solution in the production process from the solution, or added at the stage of the precursor film. It is also possible to co-deposit materials to be added at the time of vapor deposition, to mix them in the atmosphere at the time of film formation, or to perform doping by accelerating ions in a vacuum and colliding with the film.

  These doping effects include a change in electrical conductivity due to an increase or decrease in carrier density, a change in carrier polarity (p-type, n-type), a change in Fermi level, etc., which are often used in semiconductor devices. It is what. The doping process can also be used in other electronic devices other than FETs.

  In addition, for electrodes and wiring for manufacturing electronic devices including FETs, metals such as gold, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, polyaniline, polypyrrole, polythiophene, polyacetylene, polydiacetylene, Conductive polymers such as, and doped materials thereof, semiconductors such as silicon, germanium, and gallium arsenide, and doped materials thereof, and carbon materials such as fullerene, carbon nanotube, and graphite can be used. As a method for forming them, a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method, or the like can be used. The patterning method is also a photolithography method combining photoresist patterning and etching with an etchant or reactive plasma, ink-jet printing, screen printing, offset printing, letterpress printing and other printing methods, micro-contact printing method, etc. The soft lithography technique and a combination of these techniques can be used. It is also possible to directly produce a pattern by irradiating an energy beam such as a laser or an electron beam to remove the material or change the conductivity of the material.

  Furthermore, the electronic device can be formed with a protective film in order to improve the semiconductor characteristics or minimize the influence of the outside air. This includes polymer films such as styrene resin, epoxy resin, acrylic resin, polyurethane resin, polyimide resin, polyvinyl alcohol, polyvinylidene chloride, polycarbonate resin, inorganic oxide films such as silicon oxide, silicon nitride, aluminum oxide, nitride films, etc. Is mentioned. Examples of the polymer film include a method of applying and drying a solution, and a method of polymerizing by applying or vapor-depositing a monomer. Further, a crosslinking treatment or a multilayer film can be formed. For the formation of the inorganic film, a formation method using a vacuum process such as a sputtering method or a vapor deposition method, or a formation method using a solution process typified by a sol-gel method can be used. The polymer film in contact with the semiconductor is preferably one containing an aromatic ring such as polystyrene, polyvinyl naphthalene, polybenzyl methacrylate, polyacenaphthylene, polycarbonate resin or the like for improving semiconductor characteristics, and a film having gas barrier properties thereon, for example, nitriding It is preferable to laminate an inorganic film such as silicon or silicon oxide, or a metal film such as aluminum or chromium. Moreover, according to a use etc., you may provide layers and members other than the above in an electronic device.

  EXAMPLES Hereinafter, although the Example of this invention is shown and this invention is demonstrated more concretely, this invention is not limited to a following example, unless it deviates from the summary.

  Example 1 Synthesis of a benzoporphycene precursor having a bicyclo structure

  In a reaction vessel, 1,1′-bis (4,7-ethano-3-ethoxycarbonyl-4,7-dihydroisoindole) (21) (2.16 g, 5.0 mmol), sodium hydroxide (1.8 g, 45 mmol), and substituted with argon. Ethylene glycol (50 ml) was added thereto and stirred at 170 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, water was added (50 ml), and the mixture was extracted with ethyl acetate (50 ml × 3). The obtained organic layer was washed with water (50 ml × 3) and saturated brine (50 ml × 1), dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel column chromatography (dichloromethane) and recrystallization (dichloroethane / hexane) gave 1,1′-bis (4,7-ethano-4,7-dihydroisoindole) (22) as colorless crystals ( 1.02 g, 3.5 mmol). The yield was 71%. Compound (21) was synthesized by the method described in N. Ono, K. Kuroki, E. Watanabe, N. Ochi, H. Uno, Heterocycles 2004, 62, 365-373.

  The reaction vessel was charged with compound (22) (1.01 g, 3.5 mmol) and purged with argon. Methylene chloride (30 ml) and N, N-dimethylformamide (10 ml) were added and dissolved therein. Then, phosphorus oxychloride (1.5 ml) was added over 5 minutes and refluxed for 1 hour. After cooling to room temperature, an aqueous sodium acetate solution (0.85 M, 30 ml) was added over 10 minutes and the mixture was further refluxed for 1 hour. After completion of the reaction, the organic layer and the aqueous layer were separated, and the aqueous layer was extracted with methylene chloride (10 ml × 3). The organic layer and the methylene chloride extract were combined, washed with a saturated aqueous sodium hydrogen carbonate solution (20 ml × 2), water (20 ml × 3) and saturated brine (20 ml), dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel column chromatography (dichloromethane: ethyl acetate = 4: 1), recrystallization (dichloromen / hexane), and 1,1′-bis (4,7-ethano-3-formyl-4,7-dihydroiso Indole) was obtained as yellow crystals (1.12 g, 3.3 mmol). The yield was 93%.

  Zinc (powder) (3.27 g) and copper (I) chloride (0.2 g, 2.0 mmol) were placed in a three-necked reaction vessel and purged with argon. Tetrahydrofuran (170 ml) was added thereto, and titanium tetrachloride (2.74 ml, 25 mmol) was added over 15 minutes in an ice bath, followed by refluxing for 2 hours. Then, a solution of compound (23) (0.34 g, 1.0 mmol) in tetrahydrofuran (170 ml) was added over 1 hour. The mixture was further refluxed for 1 hour and then cooled to 0 ° C. 6% aqueous ammonia (100 ml) was added thereto over 1 hour, and the mixture was further stirred for 30 minutes. The resulting solid was removed by filtration through celite, the organic layer and the aqueous layer were separated, and the organic layer was dried over anhydrous sodium sulfate and concentrated. Purification by silica gel column chromatography (dichloromethane) and recrystallization (dichloromethane / methanol) gave a benzoporphycene precursor (24) having a bicyclo structure as blue crystals (69 mg, 0.11 mmol). The yield was 22%.

  The purity and structure of the compound (24) were identified by NMR. Moreover, the mass of the obtained compound was measured by TOF-MS, and the product was identified. Compared to the calculated molecular weight 622 of compound (24), 623 and four peaks decreased by 28 from the value are observed, the target product is obtained, and four ethylene molecules are released under MS measurement conditions. I also confirmed that. Also, the number of leaving groups in the molecule is obtained by calculating the temperature at which the four ethylene molecules are desorbed during the inverse Diels-Alder reaction by heating and the rate of mass reduction by comparing them with the calculated values. And the purity (solvent content) was estimated. The calculated value of mass reduction due to the elimination of four molecules of ethylene was 18%, which almost coincided with the actually measured value of 19%.

  The 1H-NMR spectrum of the compound (24) was as follows. 1H NMR (CDCl3, 400 MHz) 9.79-9.76 (m, 4H, meso), 7.27-7.02 (m, 8H, -HC = CH-), 6.03 (m, 4H, bridge head), 5.29 (m, 4H, bridge head), 2.22-1.67 (m, 16H, bridge), 0.78 (m, 2H, -NH). A 1H-NMR spectrum (measuring instrument: JEOL AL-400, 400 MHz, deuterated chloroform solution) of the compound (24) is shown in FIG. In addition, thermal analysis data (measuring instrument: SII Exstar 600 TG / DTA 6200) of the compound (24) is shown in FIG. In addition, FIG. 4 shows the TOF-MS spectrum (measurement instrument: Applied Biosystems Voyager de Pro) of compound (24).

  [Example 2] Synthesis of zinc complex of benzoporphycene precursor

  To a solution of compound (24) (10 mg, 0.016 mmol) in chloroform (10 ml) was added zinc acetate saturated methanol solution (5 ml), and the mixture was refluxed for 24 hours. After completion of the reaction, the mixture was cooled to room temperature and concentrated. Purification by alumina column chromatography (chloroform) and recrystallization (chloroform / hexane) gave the benzoporphycene precursor zinc complex (25) as purple crystals (7.1 mg, 0.010 mmol). The yield was 66%.

  The purity and structure of the compound (25) were identified by NMR. In addition, with respect to the calculated molecular weight 684 of the compound (25), four peaks decreased by 684 and 28 each from the value are observed, and the target product is obtained. It was also confirmed that it was detached.

  The 1H-NMR spectrum of the compound (25) was as follows. 1H NMR (CDCl3, 400 MHz) 9.98-9.96 (m, 4H, meso), 7.26-7.14 (m, 8H, -HC = CH-), 6.10 (m, 4H, bridge head), 5.67 (m, 4H, bridge head), 2.25-1.91 (m, 16H, bridge). FIG. 5 shows the 1H-NMR spectrum of Compound (25) (measuring instrument: JEOL AL-400, 400 MHz, deuterated chloroform solution). In addition, FIG. 6 shows a TOF-MS spectrum (measuring instrument: Applied Biosystems Voyager de Pro) of compound (24). These data confirmed the structure of the compound (25).

  [Example 3] Conversion of benzoporphycene precursor to tetrabenzoporphycene

  The compound (24) was placed in a microtube and heated at 200 ° C. for 30 minutes under vacuum using a glass tube oven. Yield is quant. Met.

  The absorption spectra of the respective chloroform solutions of the compound (24) and the compound (26) are shown in FIG. In FIG. 7, the solid line represents the compound (24), and the dotted line represents the compound (26). According to the absorption spectrum, when the compound (24) is converted to the compound (26), the peaks of the Soret band and the Q band are shifted by a long wavelength, so that the reverse Diels-Alder reaction occurs and the π conjugation is expanded. Was suggested.

  [Example 4] Conversion of benzoporphycene precursor zinc complex to tetrabenzoporphycene zinc complex

  Compound (25) was placed in a microtube and heated at 200 ° C. for 30 minutes using a glass tube oven under vacuum. Yield is quant. Met.

  [Example 5] Synthesis of naphthoporphycene precursor

  In a reaction vessel, 4,9-ethano-1-ethoxycarbonyl-4,9-dihydrobenzo [f] isoindole (27) (1.1 g, 4.2 mmol), benzyltrimethylammonium dichloroiodate (BTMA · ICl2) (1.5 g, 4.3 mmol) and calcium carbonate (0.85 g, 8.5 mmol) were added, tetrahydrofuran (40 ml) and methanol (20 ml) were added and dissolved, and the mixture was refluxed for 4 hours. After completion of the reaction, water (100 ml) was added and the reaction solution was extracted with chloroform (50 ml × 3). The organic layer was washed with a saturated aqueous sodium hydrogen sulfite solution (50 ml), water (50 ml × 3) and saturated brine (50 ml), dried over anhydrous sodium sulfate, and concentrated. The resulting solid was washed with methanol (30 ml) to give 4,9-ethano-1-ethoxycarbonyl-4,9-dihydro-1-iodobenzo [f] isoindole (28) as a white solid (1.57 g 4.0 mmol). The yield was 94%. Compound (27) was synthesized by the method described in S. Uto, N. Ochi, H. Uno, T. Murashima, N. Ono Chem Commun. 2000, 893-894.

  In a three-necked reaction vessel, 4,9-ethano-1-ethoxycarbonyl-4,9-dihydro-1-iodobenzo [f] isoindole (28) (1.38 g, 3.5 mmol), 4-dimethylaminopyridine ( 24 mg, 0.2 mmol) was added and the atmosphere was replaced with argon. Tetrahydrofuran (15 ml), triethylamine (0.5 ml, 3.6 mmol) and di-tert-butyl dicarbonate (0.96 ml, 4.2 mmol) were added in this order, and the mixture was refluxed for 2 hours. After completion of the reaction, the solvent was removed, and the mixture was diluted with chloroform (30 ml). The diluted chloroform solution was washed with water (15 ml × 3) and saturated brine (15 ml), dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel column chromatography (chloroform) gave 4,9-ethano-1-ethoxycarbonyl-4,9-dihydro-1-iodo-2N-tert-butoxycarbonylbenzo [f] isoindole (29) ( 1.75 g, 3.5 mmol). Yield is quant. Met.

  In a reaction vessel, 4,9-ethano-1-ethoxycarbonyl-4,9-dihydro-1-iodobenzo-2N-tert-butoxycarbonylbenzo [f] isoindole (29) (1.68 g, 3.4 mmol), copper Powder (2.0 g) was added and replaced with argon. N, N-dimethylformamide (15 ml) was added thereto and stirred at 110 degrees for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, copper was filtered through celite, copper on the filter paper was washed with dichloromethane (50 ml), and dichloromethane and dimethylformamide were removed under reduced pressure. Purification by silica gel column chromatography (dichloromethane) gave 1,1′-bis (4,9-ethano-10-ethoxycarbonyl-4,9-dihydro-2N-tert-butoxycarbonylbenzo [f] isoindole) (30 ) Was obtained. Compound (30) was used in the next reaction without further purification.

  Next, 1,1′-bis (4,9-ethano-10-ethoxycarbonyl-4,9-dihydro-2N-tert-butoxycarbonylbenzo [f] isoindole) (30) was dissolved in ethyl acetate (30 ml). I let you. 12N hydrochloric acid (10 ml) was added thereto, and the mixture was stirred at room temperature for 17 hours. After completion of the reaction, water was added and extracted with ethyl acetate (20 ml × 3). The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution (20 ml × 2), water (20 ml × 3) and saturated brine (20 ml), dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel column chromatography (ethyl acetate: dichloromethane = 5: 95), 1,1′-bis (4,9-ethano-10-ethoxycarbonyl-4,9-dihydrobenzo [f] isoindole) (31) As a white solid (0.55 g, 1.0 mmol). The yield was 59% (2 steps).

  In a reaction vessel, 1,1′-bis (4,9-ethano-10-ethoxycarbonyl-4,9-dihydrobenzo [f] isoindole) (31) (0.52 g, 1.0 mmol), sodium hydroxide ( 1.0 g) and ethylene glycol (30 ml) were added, and the atmosphere was replaced with argon, followed by stirring at 170 degrees for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, water (30 ml) was added, and the mixture was extracted with ethyl acetate (20 ml × 3). The organic layer was washed with water (20 ml × 3) and saturated brine (20 ml) in this order, dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel column chromatography (dichloromethane) gave 1,1′-bis (4,9-ethano-4,9-dihydrobenzo [f] isoindole) (32) as a white solid (0.24 g, 0 .693 mmol). The yield was 63%.

  1,1'-bis (4,9-ethano-4,9-dihydrobenzo [f] isoindole) (32) (0.194 g, 0.5 mmol) was placed in the reaction vessel and purged with argon. Dichloromethane (10 ml) and N, N-dimethylformamide (5 ml) were added thereto. Then, phosphorus oxychloride (0.5 ml, 5.3 mmol) was slowly added over 5 minutes and refluxed for 1 hour. After cooling to room temperature, 30 ml of an aqueous sodium acetate solution (0.16M) was added and the mixture was further refluxed for 30 minutes. After completion of the reaction, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the aqueous layer was extracted with methylene chloride (10 ml × 3). The organic layer and the methylene chloride extraction layer were combined, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution (10 ml × 2), water (10 ml × 3), saturated brine (10 ml), dried over anhydrous sodium sulfate, and concentrated. . Purification by silica gel column chromatography (ethyl acetate: dichloromethane = 1: 4) and recrystallization (chloroform / hexane) gave 1,1′-bis (4,9-ethano-4,9-dihydro-10-formylbenzo [ f] Isoindole) (33) was obtained as yellow crystals (0.21 g, 0.46 mmol). The yield was 92%.

  Zinc (powder) (0.98 g) and copper (I) chloride (48 mg, 0.48 mmol) were placed in a three-necked reaction vessel and purged with argon. Tetrahydrofuran (50 ml) was added thereto, and then titanium tetrachloride (0.83 ml, 7.6 mmol) was slowly added over 5 minutes in an ice bath and then refluxed for 2 hours. Then, a solution of compound (33) (0.13 g, 0.3 mmol) in tetrahydrofuran (50 ml) was added over 1 hour. The mixture was further refluxed for 1 hour and then cooled to 0 ° C. To this, 6% aqueous ammonia (30 ml) was slowly added over 30 minutes, and the mixture was further stirred for 30 minutes. The resulting solid was removed with celite, and the organic layer was dried over anhydrous sodium sulfate and concentrated. Purification by silica gel column chromatography (dichloromethane) and recrystallization (chloroform / methanol) gave a naphthoporphycene precursor (34) as blue crystals (12 mg, 0.015 mmol). The yield was 10%. The purity and structure of the compound (34) were identified by NMR.

  The 1H-NMR spectrum of the compound (34) was as follows. 1H NMR (CDCl3, 400 MHz) 9.98-9.96 (m, 4H, meso), 7.26-7.14 (m, 8H, -HC = CH-), 6.10 (m, 4H, bridge head), 5.67 (m, 4H, bridge head), 2.25-1.91 (m, 16H, bridge). The 1H-NMR spectrum of compound (34) in deuterated chloroform is shown in FIG. Moreover, the absorption spectrum in chloroform of a compound (34) is shown in FIG.

  The absorption spectra and fluorescence spectra of the compounds (24), (25), (26), and (35) are shown in FIGS. When converted from compound (24) to (26) and from compound (25) to (35) according to the absorption spectrum, the reverse Diels-Alder reaction occurs because the peaks of the Soret band and Q band are shifted by a long wavelength. This suggests that π conjugation is extended.

  The absolute fluorescence quantum yields of the compounds (24), (25), (26), and (35) are as follows. BCODPc2H (compound (24)): 0.27%. BCODPcZn (compound (25)): 27.8%. BenzoPc2H (compound (26)): 26.5%. BenzoPcZn (compound (35)): 34.6%. The absolute fluorescence quantum yield was measured by Hamamatsu Photonics Ab PL PL Quantum Yield Measurement System C9920-02.

It is a figure which shows the structure of FET of this embodiment. 2 is a 1H-NMR spectrum of a compound represented by the formula (24) in Example 1. FIG. 2 is thermal analysis data of the compound represented by formula (24) in Example 1. FIG. 2 is a TOF-MS spectrum of a compound represented by the formula (24) in Example 1. 2 is a 1H-NMR spectrum of a compound represented by the formula (25) in Example 2. 4 is a TOF-MS spectrum of a compound represented by the formula (25) in Example 2. 2 is an absorption spectrum of a compound represented by formula (24) in Example 1 and a compound represented by formula (26) in Example 3. 4 is a 1H-NMR spectrum of a compound represented by the formula (34) in Example 5. 4 is an absorption spectrum of a compound represented by formula (34) in Example 5. 2 is an absorption spectrum and a fluorescence spectrum of a compound represented by the formula (24) in Example 1 and a compound represented by the formula (26) in Example 3. 2 is an absorption spectrum and a fluorescence spectrum of a compound represented by formula (25) in Example 2 and a compound represented by formula (35) in Example 4.

Claims (7)

Porphycene represented by the following general formula.
Wherein R ′ and R ″ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group which may have a substituent, or a carboxyl group which may have a substituent. An alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent Represents an aromatic hydrocarbon group which may be substituted, or an aromatic heterocyclic group which may have a substituent, and adjacent R ′ and R ″ may form a ring with each other. M represents two hydrogen atoms. Represents an atom or a metal atom, and may have a substituent or a ligand, or both depending on the valence. Y represents CH or a nitrogen atom.) A method for producing porphycene, comprising converting porphycene according to claim 1 to produce porphycene represented by the following general formula.
Wherein R ′ and R ″ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group which may have a substituent, or a carboxyl group which may have a substituent. An alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent Represents an aromatic hydrocarbon group which may be substituted, or an aromatic heterocyclic group which may have a substituent, and adjacent R ′ and R ″ may form a ring with each other. M represents two hydrogen atoms. Represents an atom or a metal atom, and may have a substituent or a ligand, or both depending on the valence. Y represents CH or a nitrogen atom.) Porphycene represented by the following general formula.
Wherein R ′ and R ″ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group which may have a substituent, or a carboxyl group which may have a substituent. An alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an alkoxyl group that may have a substituent, and a substituent Represents an aromatic hydrocarbon group which may be substituted, or an aromatic heterocyclic group which may have a substituent, and adjacent R ′ and R ″ may form a ring with each other. M represents two hydrogen atoms. Represents an atom or a metal atom, and may have a substituent or a ligand, or both depending on the valence. Y represents a nitrogen atom when all of R ′ and R ″ are hydrogen atoms. When at least one of R ′ and R ″ is not a hydrogen atom, it represents CH or a nitrogen atom.) Films containing Porufise down according to 請 Motomeko 3. Semiconductor material comprising Porufise down according to 請 Motomeko 3. Fluorescent dyes, including Porufise down according to 請 Motomeko 3. Solar cell including a Porufise down according to 請 Motomeko 3.