JP5437566B2 - Bicyclotetraazaporphyrin compound, method for producing tetraazaporphyrin compound using the same, organic electronic device and method for producing the same - Google Patents

Description

  The present invention relates to a novel bicyclotetraazaporphyrin compound, a method for producing a tetraazaporphyrin compound using the same, an organic electronic device using the same as an organic semiconductor, and a method for producing the same.

  Tetraazaporphyrin compounds typified by phthalocyanine are used in solar cells, photocatalysts, organic EL hole injection layers, organic transistors, electrophotographic photoreceptors, etc. due to their semiconductor properties derived from large cyclic π-conjugated electrons. .

  In general, a molecule having high planarity has good π conjugation and a large interaction between molecules. Therefore, when used as a semiconductor material, the molecule often exhibits high semiconductor characteristics. However, when the molecule is a phthalocyanine compound, it becomes a so-called pigment and the solubility is often lowered. Phthalocyanine-based compounds have low solubility, making it difficult to perform general-purpose purification such as chromatography and recrystallization, which may make it difficult to obtain high-purity materials, and it may be difficult to test purity. Also, when forming a film, it is difficult to form a film from a solution, and only a limited film such as a fine particle dispersion film or a vapor deposition film may be obtained. For this reason, a phthalocyanine compound having low solubility may be an obstacle to obtaining high characteristics, and may require a lot of time to form a film and may be expensive (Patent Document 1).

  On the other hand, induction from a precursor has been proposed as a method for improving the handling of hardly soluble materials. This is a conversion from a highly soluble precursor to a sparingly soluble pigment.

  A highly soluble precursor can be formed into a film by applying it as a solution, or can be dissolved in a matrix of another material such as a polymer. Using this, the precursor is formed into a film, and then converted into a target hardly soluble material by heating or the like. If this conversion proceeds quantitatively, a highly pure hardly soluble material can be obtained, and film formation by a coating process of the hardly soluble material becomes possible (Patent Document 2).

JP-A-11-251601 JP 2005-93990 A

  Tetraazaporphyrin compounds having high semiconductor characteristics are highly expected as raw materials for organic semiconductors. However, due to the poor solubility of the tetraazaporphyrin compound, it is difficult to apply it to the semiconductor field, and a product having satisfactory performance has not yet been obtained.

  The present invention was devised in view of the above problems, and can be used as a precursor of a novel tetraazaporphyrin compound having a good solvent solubility, and a novel tetraazaporphyrin bicyclo compound and tetra It aims at providing the manufacturing method of an azaporphyrin compound, an organic electronic device, and its manufacturing method.

  As a result of various investigations, the inventors of the present invention can improve the solubility of a tetraazaporphyrin compound having a bicyclo structure at a predetermined site and can be used as a precursor of the tetraazaporphyrin compound. It has been found that there is an advantage, and the present invention has been reached.

｛構造式（Ｉ）及び構造式（II）において、Ｒ¹〜Ｒ⁸はそれぞれ独立に一価の原子又は原子団を表わす。ただし、（Ｒ¹、Ｒ²）、（Ｒ³、Ｒ⁴）、（Ｒ⁵、Ｒ⁶）及び（Ｒ⁷、Ｒ⁸）は、それぞれ独立に下記式（VI）で表わされる基である。また、構造式（II）において、Ｍは金属原子を表わす。｝

｛式（VI）において、Ｒ ⁹ 〜Ｒ ¹⁶ は炭素数６以下のアルキル基、水酸基、ハロゲン原子又はアルコキシ基であり、Ｒ ^x 及びＲ ^y は、直接結合又はＲ ^x 及びＲ ^y が一体となって芳香環を形成する構造を表わす。｝ That is, the gist of the present invention resides in a bicyclotetraazaporphyrin compound represented by the following structural formula (I) or structural formula (II) (claim 1).

{In Structural Formula (I) and Structural Formula (II), R ^{1 to} R ⁸ each independently represents a monovalent atom or atomic group. However, (R ¹ , R ² ), (R ³ , R ⁴ ), (R ⁵ , R ⁶ ) and (R ⁷ , R ⁸ ) are each independently a group represented by the following formula (VI) . In Structural Formula (II), M represents a metal atom. }

{In the formula (VI), R ^{9 to} R ¹⁶ are an alkyl group, a hydroxyl group, a halogen atom or an alkoxy group having 6 or less carbon atoms, and R ^x and R ^y are a direct bond or R ^x and R ^y are integrated. Represents a structure forming an aromatic ring. }

｛構造式（IV）及び構造式（Ｖ）において、Ｑ¹〜Ｑ⁸はそれぞれ独立に一価の原子又は原子団を表わす。また、（Ｑ¹、Ｑ²）、（Ｑ³、Ｑ⁴）、（Ｑ⁵、Ｑ⁶）及び（Ｑ⁷、Ｑ⁸）は、それぞれ独立に各組内で結合して芳香族炭化水素又は複素環を形成する構造である。また、構造式（Ｖ）において、Ｍは金属原子を表わす。｝ Another gist of the present invention is to obtain a tetraazaporphyrin compound having a tetraazaporphyrin skeleton represented by the following structural formula (IV) or structural formula (V) from the bicyclotetraazaporphyrin compound by reverse Diels-Alder reaction. It exists in the manufacturing method of the tetraaza porphyrin compound characterized by the above-mentioned (Claim 2 ).

{In Structural Formula (IV) and Structural Formula (V), Q ^{1 to} Q ⁸ each independently represent a monovalent atom or atomic group. Further, (Q ¹ , Q ² ), (Q ³ , Q ⁴ ), (Q ⁵ , Q ⁶ ) and (Q ⁷ , Q ⁸ ) are each independently bonded within each group to form an aromatic hydrocarbon or a structure that to form a heterocyclic ring. In Structural Formula (V), M represents a metal atom. }

Still another subject matter of the present invention lies in an organic electronic device comprising a tetraazaporphyrin compound having a tetraazaporphyrin skeleton represented by the structural formula (IV) or the structural formula (V) as a semiconductor. (Claim 3 ).
At this time, organic electronic device is preferably a field effect transistor (claim 4).

Still another subject matter of the present invention is a method for producing the above organic electronic device, comprising the step of obtaining the tetraazaporphyrin compound from the bicyclotetraazaporphyrin compound by a reverse Diels-Alder reaction. to resides in a method of manufacturing an organic electronic device (claim 5).

  According to the present invention, a novel bicyclotetraazaporphyrin compound having high solvent solubility, a method for producing a tetraazaporphyrin compound using the same, an organic electronic device using the same as an organic semiconductor, and a method for producing the same are provided. Is possible.

  Hereinafter, the present invention will be described with reference to embodiments. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the scope of the present invention.

｛構造式（Ｉ）及び構造式（II）において、Ｒ¹〜Ｒ⁸はそれぞれ独立に一価の原子又は原子団を表わす。ただし、（Ｒ¹，Ｒ²）、（Ｒ³，Ｒ⁴）、（Ｒ⁵，Ｒ⁶）及び（Ｒ⁷，Ｒ⁸）の少なくとも一組は、下記構造式（III）で表わされる置換されていてもよいビシクロ構造を有する基を表す。また、構造式（II）において、Ｍは金属原子を表わす。｝

[1. Bicyclotetraazaporphyrin compound]
(Structure of bicyclotetraazaporphyrin compound)
The bicyclotetraazaporphyrin compound of the present invention is a compound having a structure represented by the following structural formula (I) or (II).

{In Structural Formula (I) and Structural Formula (II), R ^{1 to} R ⁸ each independently represents a monovalent atom or atomic group. However, at least one set of (R ¹ , R ² ), (R ³ , R ⁴ ), (R ⁵ , R ⁶ ) and (R ⁷ , R ⁸ ) is substituted by the following structural formula (III) Represents a group having a bicyclo structure which may be present. In Structural Formula (II), M represents a metal atom. }

Details will be described below.
In the structural formulas (I) and (II), R ^{1 to} R ⁸ each independently represents a monovalent atom or atomic group. The monovalent atom or atomic group to be R ^{1 to} R ⁸ is arbitrary as long as the effects of the present invention are not significantly impaired. However, at least one set of (R ¹ , R ² ), (R ³ , R ⁴ ), (R ⁵ , R ⁶ ) and (R ⁷ , R ⁸ ) has a bicyclo structure represented by the structural formula (III). Group (hereinafter referred to as “bicyclo-containing group” as appropriate). M represents a metal atom.

  Introducing a bicyclo-containing group into the tetraazaporphyrin compound is to introduce a substituent having a large steric hindrance, thereby increasing the solubility of the bicyclotetraazaporphyrin compound. By increasing the solubility, the bicycloazaporphyrin compound can be easily purified and can be easily obtained in high purity. In addition, it is possible to test purity using various techniques such as absorption spectrum and NMR. Furthermore, the film can be formed by applying a solution, or can be dissolved in a matrix of another material such as a polymer.

However, the introduction of a substituent having a large steric hindrance can increase the solubility, but has the effect of weakening the intermolecular interaction, so that the semiconductor properties may be deteriorated and the durability of the material may be deteriorated. .
However, the compound containing a bicyclo-containing group of the present invention (hereinafter referred to as a bicyclo compound as appropriate) becomes a monocyclic structure by the reverse Diels-Alder reaction. Here, the reverse Diels-Alder reaction is a reaction (deethylation) in which ethylene (or a derivative thereof) is eliminated.
That is, the bicyclotetraazaporphyrin compound of the present invention has a high solubility due to a three-dimensionally bulky structure, and by deethylenating, the bulky structure can be eliminated and a high planar structure can be obtained.
Therefore, the bicyclotetraazaporphyrin compound can be used as a precursor of a tetraazaporphyrin compound, which is a so-called pigment, and is preferable as a material for an organic semiconductor.

ここで、ビシクロ構造のＲ⁹〜Ｒ¹⁶は、一価の原子又は原子団を表し、具体的にはビシクロ含有基以外のＲ¹〜Ｒ⁸（後述する）と同様のものが挙げられる。また、Ｒ⁹〜Ｒ¹⁶は、任意の組み合わせで結合して環を形成していても良い。ただし、本発明のビシクロテトラアザポルフィリン化合物から製造されるテトラアザポルフィリン化合物を有機半導体として機能させる観点から、Ｒ¹³〜Ｒ¹⁶は、エチレン誘導体の脱離後に形成されるπ電子共役分子が機能を発揮する有機基を用いることが好ましい。 The bicyclo-containing group is not limited as long as it has a bicyclo structure represented by the structural formula (III). When such a suitable bicyclo-containing group is generalized and expressed, it is represented by the following structural formula (VI).

Here, R ^{9 to} R ¹⁶ of the bicyclo structure represent a monovalent atom or atomic group, and specific examples thereof include those similar to R ^{1 to} R ⁸ (described later) other than the bicyclo-containing group. R ^{9 to} R ¹⁶ may combine with any combination to form a ring. However, from the viewpoint of allowing the tetraazaporphyrin compound produced from the bicyclotetraazaporphyrin compound of the present invention to function as an organic semiconductor, R ^{13 to} R ¹⁶ are functions of a π-electron conjugated molecule formed after elimination of the ethylene derivative. It is preferable to use an organic group that exhibits.

R ^x and R ^y each independently represents a direct bond or a divalent or higher valent group bonded to a tetraazaporphyrin skeleton. Here, the tetraazaporphyrin skeleton means a part other than R ^{1 to} R ⁸ in the structural formula (I) and the structural formula (II), or Q ^{1 to} Q ^{8 in the} structural formula (III) and the structural formula (IV). The part other than is shown. R ^x and R ^y may be bonded to each other.

Among such R ^{9 to} R ¹⁶ , preferred examples include an alkyl group having 6 or less carbon atoms, a hydroxyl group, a halogen atom, and an alkoxy group.
Further, among R ^x and R ^y , preferred examples include a structure that extends a direct bond or a conjugated system of a tetraazaporphyrin compound. Specifically, those in which R ^x and R ^y are combined to form an aromatic ring are preferable. Among these, direct bonding is particularly preferable.
However, R ^{13 to} R ¹⁶ , R ^x , and R ^y are substituents that may remain in the organic semiconductor after the reverse Diels-Alder reaction. What it has is not preferable. This is because when an organic semiconductor is produced from the tetraazaporphyrin compound of the present invention, the orientation and crystallinity of the organic semiconductor are likely to be lowered. Further, R ^{9 to} R ¹² serve as leaving groups during the reverse Diels-Alder reaction, and therefore, a substituent that easily volatilizes is preferable in order to prevent remaining in the organic semiconductor film.

｛ここでＲ^a、Ｒ^bはＲ¹〜Ｒ⁸と同様の置換基を表す。｝ Examples of such bicyclo-containing groups include the following.

{Wherein R ^a and R ^b represent the same substituents as R ^{1 to} R ⁸ . }

  The bicyclo-containing group can have any number of bicyclo structures at any site. However, the bicyclo structure is preferably located closer to the tetraazaporphyrin skeleton, and more preferably directly bonded. This is because the effect of improving the solubility is great.

  The number of bicyclo-containing groups that the bicyclotetraazaporphyrin compound of the present invention has is arbitrary and may be any one of 1-4. However, the bicyclotetraazaporphyrin compound of the present invention preferably has 2 or more, more preferably 3 or more bicyclo-containing groups. This is because the more bicyclo-containing groups, the higher the solubility.

  In addition, when the bicycloazaporphyrin compound of the present invention has a plurality of bicyclo-containing groups, all the bicyclo-containing groups may have the same structure, or may have bicyclo-containing groups having different structures in any combination. . However, it is preferable that all the bicyclo-containing groups have the same structure. This is because synthesis is easy.

  The molecular weight of the bicyclo structure portion of the bicyclo-containing group is arbitrary. On the other hand, the molecular weight of the leaving group moiety is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 28 or more, usually 200 or less, preferably 150 or less, more preferably 100 or less. This is because the smaller the molecular weight of the leaving group, the easier it is to volatilize and it is difficult to remain as a residue.

The bicyclotetraazaporphyrin compound of the present invention has at least one selected from (R ¹ , R ² ), (R ³ , R ⁴ ), (R ⁵ , R ⁶ ) and (R ⁷ , R ⁸ ). The pair may be a bicyclo-containing group.
As for R ^{1 to} R ⁸ that are not bicyclo-containing groups, R ^{1 to} R ⁸ can use any monovalent atom or atomic group as long as the effects of the present invention are not significantly impaired. For example, a monovalent organic group can be mentioned.

  Examples of such a group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-heptyl group, which may be substituted. -18 linear or branched alkyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group and the like, optionally substituted cyclic alkyl group having 3 to 18 carbon atoms; vinyl group, propenyl group, hexenyl group, etc. An optionally substituted linear or branched alkenyl group having 2 to 18 carbon atoms; an optionally substituted cyclic alkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; a propynyl group and a hexynyl group An optionally substituted linear or branched alkynyl group having 2 to 18 carbon atoms; 2-thienyl group, 2-pyridyl group, 4-piperidyl An optionally substituted heterocyclic group such as morpholino group; an optionally substituted aryl group having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group; benzyl group, phenethyl group, etc. Aralkyl group having 7 to 20 carbon atoms which may be substituted; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, etc. A linear or branched alkoxy group having 1 to 18 carbon atoms; a linear or branched alkenyloxy group having 3 to 18 carbon atoms which may be substituted, such as a propenyloxy group, a butenyloxy group, or a pentenyloxy group; Group, ethylthio group, n-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, etc. And the like may linear or branched alkylthio group having 1 to 18 carbon atoms.

Other specific examples include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a nitro group; a nitroso group; a cyano group; an isocyanato group; an isocyanato group; an isocyanato group; an isothiocyanato group; an isothiocyanato group; Hydroxy group; hydroxyamino group; formyl group; sulfonic acid group; carboxyl group; acyl group represented by —COR ¹⁷ ; amino group represented by —NR ¹⁸ R ¹⁹ ; acylamino group represented by —NHCOR ²⁰ ; Carbamate group represented by NHCOOR ²¹ , Carboxylic ester group represented by -COOR ²² , Acyloxy group represented by -OCOR ²³ , Carbamoyl group represented by -CONR ²⁴ R ²⁵ , -SO ₂ R ²⁶ is the sulfonyl group, sulfamoyl group represented by -SO ₂ NR ²⁷ R ^28, sulfonic acid ester represented by -SO ₃ R ²⁹ Group, a sulfonamide group represented by -NHSO ₂ R ^30, such as a sulfinyl group represented by -SOR ^31. Here, R ¹⁷ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁶ , R ²⁹ , R ³⁰ , R ³¹ are a hydrocarbon group that may be substituted or a heterocyclic group that may be substituted. R ¹⁸ , R ¹⁹ , R ²⁴ , R ²⁵ , R ²⁷ , and R ^{28 each} represent a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group.

The hydrocarbon group represented by R ^{17 to} R ³¹ is arbitrary as long as the effects of the present invention are not significantly impaired. For example, a linear or branched alkyl group, a cyclic alkyl group, a linear or branched alkenyl group , Cyclic alkenyl group, aralkyl group, aryl group and the like. Among them, a linear or branched alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-heptyl group is preferable. A cyclic alkyl group having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and an adamantyl group; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group; C3-C18 cyclic alkenyl group such as pentenyl group and cyclohexenyl group; C7-C20 aralkyl group such as benzyl group and phenethyl group; C6 such as phenyl group, tolyl group, xylyl group and mesityl group -18 aryl groups. The aryl group portion of these groups may be further substituted with the same substituent as R ^{1 to} R ⁸ described above.

Any heterocyclic group represented by R ^{17 to} R ³¹ can be used as long as the effects of the present invention are not significantly impaired. Examples of such heterocycles include 2-furyl group, 2-pyridyl group, 2-thiazolyl group, 2-piperidyl group, morpholino group, 2-morpholinyl group, piperazyl group and the like. An aromatic heterocyclic ring such as a quinolyl group may be used. These may contain a plurality of heteroatoms, may further have a substituent, and may have any bonding position. Preferred structures for the heterocyclic ring are a 5- or 6-membered saturated heterocyclic ring, a 5- or 6-membered monocyclic ring and an aromatic heterocyclic ring thereof.

Furthermore, R ^{1 to} R ⁸ may each independently be substituted with a substituent. Therefore, for example, the linear or branched alkyl group, the cyclic alkyl group, the linear or branched alkenyl group, the cyclic alkenyl group, the linear or branched alkynyl group, the linear or branched, which the R ^{1 to} R ⁸ may have. And the alkyl chain part of the alkyl group represented by R ^{17 to} R ³¹ may further have a substituent. Examples of the substituent include the following.

That is, examples of the substituent for R ^{1 to} R ⁸ include carbon such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, and tert-butoxy group. Alkoxy group having 1 to 10 carbon atoms; alkoxy alkoxy group having 2 to 12 carbon atoms such as methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group, methoxybutoxy group; methoxymethoxymethoxy group, methoxymethoxy Alkoxyalkoxyalkoxy groups having 3 to 15 carbon atoms such as ethoxy group, methoxyethoxymethoxy group, ethoxymethoxymethoxy group, and ethoxyethoxymethoxy group; aryl groups having 6 to 12 carbon atoms such as phenyl group, tolyl group, and xylyl group (these Is further substituted with any substituent C6-12 aryloxy groups such as phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group; alkenyloxy groups having 2-12 carbon atoms such as allyloxy group, vinyloxy group, etc. .

Furthermore, as other substituents substituted on R ^{1 to} R ⁸ , for example, heterocyclic groups such as 2-thienyl group, 2-pyridyl group, 4-piperidyl group, morpholino group; cyano group; nitro group; hydroxyl group; Amino group; C1-C10 alkylamino group such as N, N-dimethylamino group, N, N-diethylamino group; C1 such as methylsulfonylamino group, ethylsulfonylamino group, n-propylsulfonylamino group To 6 alkylsulfonylamino groups; halogen atoms such as fluorine atom, chlorine atom and bromine atom; carbon such as carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group and n-butoxycarbonyl An alkoxycarbonyl group of 2 to 7; methylcarbonyloxy group, ethylcarbonyloxy An alkylcarbonyloxy group having 2 to 7 carbon atoms such as a group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, Examples thereof include an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as an isopropoxycarbonyloxy group and an n-butoxycarbonyloxy group. In addition, the substituent substituted by R < ¹ > -R < ⁸ > may be used individually by 1 type, and may use 2 or more together by arbitrary combinations and ratios.

R ^{1 to} R ⁸ may be bonded to each other to form a ring, and may be bonded to the tetraazaporphyrin skeleton as an atomic group (group) of a ring structure. However, when the number of bicyclo-containing groups introduced into the bicyclotetraazaporphyrin compound of the present invention is small, R ^{1 to} R ⁸ are introduced groups that improve the solubility of alkyl groups and the like separately from the bicyclo-containing groups. Things are desirable. Examples of such groups include groups having a ring structure that does not have a bicyclo structure, such as the following. In addition, the group which has a ring structure which does not have a bicyclo structure may be used individually by 1 type, and may use 2 or more by arbitrary combinations and a ratio.

The metal atom which is M in the structural formula (II) is arbitrary as long as the effects of the present invention are not significantly impaired. For example, a single metal atom such as Cu, Zn, Mg, Co, Fe, etc .; AlCl, TiO, FeCl And an atomic group in which a trivalent or higher metal such as SiCl ₂ and another element are combined to form a divalent atom.

Hereinafter, examples of the bicyclotetraazaporphyrin compound of the present invention will be given. However, the bicyclotetraazaporphyrin compound of the present invention is not limited to the following examples.

(Synthesis of bicyclotetraazaporphyrin compound)
Although there is no restriction | limiting in particular in the manufacturing method of the bicyclotetraazaporphyrin compound of this invention, For example, it can manufacture by reaction through Diels-Alder reaction in the following ways. In addition, the substituent shown by R < ⁹ > -R < ¹² > can be combined with the part regarding a bicyclo structure in the arbitrary steps of reaction.

(Solubility of bicyclotetraazaporphyrin compound)
The bicyclotetraazaporphyrin compound of the present invention is excellent in solubility in a solvent. Specific solubility is arbitrary, but at normal temperature and normal pressure (25 ° C., 1.013 × 10 ³ hPa), the bicyclotetraazaporphyrin compound of the present invention is usually 0.1 g or more per 1 kg of chloroform, preferably Dissolves 1 g or more, more preferably 5 g or more. There is no limit on the upper limit.

[2. Synthesis of tetraazaporphyrin compounds]
(Deethylenation)
Hereinafter, deethylation will be described with reference to an example.
By removing ethylene or a derivative thereof represented by the following structural formula (VIII) from the bicyclo-containing group represented by the structural formula (VI), a substituent represented by the following structural formula (VII) (hereinafter referred to as “ Specific substituents ”).

（構造式（VI）、構造式（VII）、及び構造式（VIII）中、Ｒ⁹〜Ｒ¹⁶は任意の１価の原子又は１価の原子団を表わす。また、Ｒ^x及びＲ^yは、それぞれ独立に直接結合、又はテトラアザポルフィリン骨格に結合する２価以上の基を表す。）

(In Structural Formula (VI), Structural Formula (VII), and Structural Formula (VIII), R ^{9 to} R ¹⁶ represent any monovalent atom or monovalent atomic group. Also, R ^x and R ^y represent And each independently represents a direct bond or a divalent or higher valent group bonded to a tetraazaporphyrin skeleton.)

Details will be described below.
In Structural Formula (VI), Structural Formula (VII), and Structural Formula (VIII), R ^{9 to} R ¹⁶ , R ^x, and R ^y are as described above.
As shown in the above reaction formula, the bicyclo-containing group represented by the structural formula (VI) is a substituent having high planarity by eliminating ethylene or a derivative thereof represented by the structural formula (VIII) by reverse Diels-Alder reaction. (A specific substituent represented by the structural formula (VII)). This series of reverse Diels-Alder reactions is called deethylenation.
By utilizing deethylenization, it becomes possible to synthesize a tetraazaporphyrin compound from the bicyclotetraazaporphyrin compound of the present invention, improve the coating property of the coating liquid during the production of the organic semiconductor, and simplify the production of the organic semiconductor Is possible.

The deethylation reaction conditions are arbitrary as long as the reverse Diels-Alder reaction proceeds, but are usually as follows.
That is, the temperature condition is usually 100 ° C. or higher, preferably 130 ° C. or higher, and usually 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 is often required.
Furthermore, the reaction atmosphere is preferably performed in a vacuum or in an inert gas atmosphere such as nitrogen or a rare gas.

Moreover, the conversion rate by deethylenation is 100% normally. The conversion rate can be measured, for example, by examining a reaction progress phenomenon by measuring a change in weight due to heating (TG method).
For the reverse Diels-Alder reaction, see, for example, Japanese Patent Application Laid-Open No. 2003-304014, Chem. Commun. 1998, P1661-P1662 HETEROCYCLES, vol. 1,2000, P399-P411 and the like can be referred to.

｛構造式（IV）及び構造式（Ｖ）において、Ｑ¹〜Ｑ⁸はそれぞれ独立に一価の原子又は原子団を表わす。また、（Ｑ¹，Ｑ²）、（Ｑ³，Ｑ⁴）、（Ｑ⁵，Ｑ⁶）及び（Ｑ⁷，Ｑ⁸）は、それぞれ互いに結合して環を形成しても良い。また、構造式（Ｖ）において、Ｍは金属原子を表わす。｝ (Tetraazaporphyrin compound)
By performing the deethylenation on the bicyclotetraazaporphyrin compound of the present invention, a tetraazaporphyrin compound represented by the following structural formula (IV) or (V) (hereinafter referred to as the tetraazaporphyrin compound of the present invention as appropriate) is obtained. Can be obtained.

{In Structural Formula (IV) and Structural Formula (V), Q ^{1 to} Q ⁸ each independently represent a monovalent atom or atomic group. (Q ¹ , Q ² ), (Q ³ , Q ⁴ ), (Q ⁵ , Q ⁶ ) and (Q ⁷ , Q ⁸ ) may be bonded to each other to form a ring. In Structural Formula (V), M represents a metal atom. }

Q ^{1 to} Q ⁸ include the same atoms and atomic groups as R ^{1 to} R ⁸ , but preferably do not include a bicyclo-containing group.
Furthermore, in order for the tetraazaporphyrin compound to exhibit semiconductor characteristics, it is desirable that Q ^{1 to} Q ⁸ have high planarity. Among the specific examples of R ^{1 to} R ⁸ , for example, a hydrogen atom; a halogen atom such as a fluorine atom and a chlorine atom; an unbranched alkyl group having 10 or less carbon atoms, an alkene group, and an alkenyl group are preferable.
Furthermore, (Q ¹ , Q ² ), (Q ³ , Q ⁴ ), (Q ⁵ , Q ⁶ ), and (Q ⁷ , Q ⁸ ) are combined in each group, and a conjugated system of π electrons is formed as a whole. An expanding structure is preferable, for example, a structure having a ring structure is preferable. Specific examples of suitable ones include those that form aromatic hydrocarbons such as benzene, naphthalene, and anthracene rings; furan, thiophene, pyrrole, benzothiophene, indole, isoindole, indolizine, carbazole, pyridine, Examples include quinoline, isoquinoline, oxazole, isoxazole, thiazole, isothiazole, furazane, imidazole, quinoxaline and the like that form a heterocyclic ring. These rings may be further substituted with a monovalent organic group such as an alkyl group; and a substituent such as a halogen atom.
The metal atom which is M in the structural formula (V) is the same as M in the structural formula (II).
The compounds of structural formulas (IV) and (V) are preferably derived from compounds of structural formulas (I) and (II) as precursors.

Examples of the tetraazaporphyrin compound of the present invention include compounds having the following structures, but are not limited thereto.

[3. Organic electronic device]
(Electronic device)
The tetraazaporphyrin compound of the present invention can be used for organic electronic devices and the like.
Here, as an example of the configuration of an electronic device, 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, or the like, or Examples thereof include a device that generates light, an electric field, and a magnetic field according to an applied voltage 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.
Examples of devices include resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements, chemical sensors, etc., or combinations or integrated devices of these elements. It is done. 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 tetraazaporphyrin compound of the present invention can be used as an organic semiconductor in these electronic devices. In addition, when using a specific compound as an organic semiconductor, you may use organic semiconductors other than a specific compound together.

  Furthermore, the tetraazaporphyrin compound of the present invention may be used in applications other than organic compounds in electronic devices. For example, a film is formed at a desired position of an electronic device using the tetraazaporphyrin compound of the invention, and the electrical conductivity of the film of the specific compound is controlled by a molecular structure or doping. It can also be used for an insulating layer in a capacitor or a field effect transistor (FET).

  A more specific example of the electronic device is S.I. M.M. Examples include those described in Sze, Physics of Semiconductor Devices, 2nd Edition (Wiley-Interscience 1981).

(Uses of tetraazaporphyrin compounds)
Although the use of the tetraazaporphyrin compound of the present invention is not particularly limited, it can be suitably used as a semiconductor material for organic electronic devices and the like because it effectively exhibits optical or electrical functions. Specific examples thereof include the following three.

  Since the tetraazaporphyrin compound of the present invention is a π-conjugated molecule with high planarity, it can be used as an organic semiconductor. Here, a semiconductor is a material that can transport charges, and exhibits various functions by controlling the carrier density in the semiconductor by doping impurities or applying an electric field. Examples of such applications include rectifying elements and transistors. Among these semiconductors, a semiconductor made of an organic substance is called an organic semiconductor, and the tetraazaporphyrin compound of the invention can be a material for an organic semiconductor.

  Semiconductors include a p-type that transports holes and an n-type that transports electrons. The majority of organic semiconductors are p-type semiconductors, whereas the tetraazaporphyrin compound of the present invention operates as an n-type. There are many things. However, it is possible to operate as a p-type by devising an electrode material so that holes can be injected or by bonding an electron donating substituent to an atom involved in the π-conjugated system.

を用いた場合、Ｒ^a及びＲ^bとして極性の異なる基を用いることが好適である。このようにπ共役分子で形成されたベシクルやナノチューブは、良好な電気物性あるいは光・物性を有する半導体として期待される。 In addition, a special molecular assembly can be synthesized using the tetraazaporphyrin compound of the present invention. For example, if amphiphilicity is imparted to the tetraazaporphyrin compound of the present invention by introducing groups having different polarities as the groups R ¹⁴ and R ¹⁵ in the above formula (VI), And the possibility of producing nanotubes. For example, as a bicyclo-containing group

When is used, it is preferable to use groups having different polarities as R ^a and R ^b . Thus, vesicles and nanotubes formed of π-conjugated molecules are expected as semiconductors having good electrical properties or optical / physical properties.

  The tetraazaporphyrin compound of the present invention has a strong light absorption band. By utilizing this, it can be used as an optical functional material. One example is a device that functions by causing charge separation by absorbed light. Specific examples thereof include a solar cell and a photoelectric conversion element (photodiode). A solar cell uses an internal electric field generated at a junction with a metal or other semiconductor to cause charge separation by light and take it out to the outside. In addition, it can be applied to photo radical generation by sensitizing a radical generator using an excited state generated by light absorption or generating a radical directly from the excited state.

  Since the tetraazaporphyrin compound of the present invention has an absorption band in the wavelength region of visible to near-ultraviolet light, it can be used as a dye. By utilizing this characteristic as a dye, it can be applied to dyes for dyeing, recording such as ink jet and thermal transfer, storage of optical disks, optical filters such as displays, and the like.

(Field effect transistor)
A field effect transistor (FET) is mentioned as another example of another suitable electronic device using the tetraazaporphyrin compound of this invention. Hereinafter, an embodiment of the FET will be described in detail.
1A to 1D are diagrams schematically showing examples of the structure of an FET. 1A to 1D, 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.

The source electrode, the drain electrode, and the gate electrode are not limited. For example, in addition to metals such as platinum, gold, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, and sodium, InO ₂ and SnO ₂ , conductive oxides such as ITO, conductive polymers such as polyaniline, polypyrrole, polythiophene and polyacetylene, and acids such as hydrochloric acid, sulfuric acid and sulfonic acid, Lewis acids such as PF ₆ , AsF ₅ and FeCl ₃ In addition, a material having conductivity such as a material added with a dopant such as a halogen atom such as iodine, a metal atom such as sodium potassium, or a conductive composite material in which carbon black or metal particles are dispersed is used. In addition, only 1 type may be used for the material of an electrode, and 2 or more types may be used together by arbitrary combinations and a ratio.

  Moreover, as a material used for the insulator layer, any insulator can be used. For example, polymethyl methacrylate, polystyrene, polyvinyl phenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, Polymers such as epoxy resins and phenol resins and copolymers thereof, oxides such as silicon dioxide, aluminum oxide and titanium oxide, nitrides such as silicon nitride, and ferroelectric oxides such as strontium titanate and barium titanate Or a polymer in which particles of the above oxide, nitride, ferroelectric oxide or the like are dispersed. In addition, only 1 type may be used for the material of an insulator layer, and 2 or more types may be used together by arbitrary combinations and a ratio.

  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 layer, for example, coating (spin coating or blade coating), vapor deposition, sputtering, printing method such as screen printing or ink jet, and a method of forming an oxide film on metal like alumite on aluminum, etc. It can be manufactured by the 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 presumed to be caused by adjusting the hydrophilicity / hydrophobicity of the substrate to improve the film quality obtained at the time of film formation, particularly by improving the properties of the interface portion between the substrate and the semiconductor layer. Examples of such substrate treatment include hydrophobization treatment such as hexamethyldisilazane, cyclohexene, and octadecyltrichlorosilane, acids such as hydrochloric acid, sulfuric acid, and acetic acid, and alkalis such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia. Treatment, ozone treatment, fluorination treatment, plasma treatment of oxygen or argon, Langmuir Blodgett film formation process, other insulator or semiconductor thin film formation process.

  Furthermore, in this FET, the semiconductor layer is formed of an organic semiconductor containing the tetraazaporphyrin compound of the present invention. 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 tetraazaporphyrin compound of the present invention, the semiconductor layer may contain other compounds (such as other organic semiconductors). 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.

[4. Manufacture of organic electronic devices]
(Manufacture of field effect transistors)
When a specific substituent is introduced into a highly planar molecule, it has high properties as a semiconductor. By utilizing this, it is possible to produce an organic semiconductor.
For example, a coating solution in which the bicyclotetraazaporphyrin compound of the present invention is dissolved in an appropriate solvent is prepared, and this coating solution is applied to a substrate or the like to prepare a coating film, and the bicyclotetraazaporphyrin in the coating film is heated or the like. If the above-described deethylenation (that is, reverse Diels-Alder reaction) proceeds to a compound, an organic semiconductor layer of the specific compound containing the specific substituent can be easily produced. Thus, an organic semiconductor can be produced by a production method having a step of removing ethylene or a derivative thereof from a bicyclo-containing group by the above deethylation.

(Method for producing a field effect transistor using a bicyclotetraazaporphyrin compound)
Specifically, an example of a method for producing the semiconductor layer of the above-described field effect transistor using the bicyclotetraazaporphyrin compound of the present invention is shown.
First, the coating method will be described. In the coating method, the bicyclotetraazaporphyrin compound of the present invention is dissolved in a necessary solvent to form a solution (coating solution), the coating solution is applied to a coating target (substrate, etc.), and the bicyclo content in the coated layer is contained. It is formed by proceeding deethylenation to the group. At this time, the bicyclotetraazaporphyrin compound of the present invention can expand the range of choice of solvent and use a more suitable solvent.

  Since the bicyclo structure is sterically 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 deethylenation 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 the chemical change of the bicyclo structure, an organic semiconductor layer having good crystallinity can be obtained by a simple method called a coating method.

  Therefore, according to this production method, the tetraazaporphyrin compound synthesized by deethylation (or elimination of the corresponding derivative) is a coating method although it is hardly soluble in the solvent of the coating solution. Thus, film formation is possible.

Examples of the solvent for the coating solution 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 the ketone solvent 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, spin coating, dipping, blade coating, wire bar coating, spray coating, etc., 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 tetraazaporphyrin compound can be formed on a substrate by a vacuum process to produce an FET. In this case, a vacuum vapor deposition method can be used in which a bicyclotetraazaporphyrin compound is placed in a crucible or a metal boat and heated in 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 adopted by adjusting the conditions of the degree of vacuum and the heating temperature of the bicyclotetraazaporphyrin compound of the present invention which is a vapor deposition source. For example, a bicyclotetraazaporphyrin compound can be vapor-deposited after first being deethyleneated with a vapor deposition source, or after being vapor-deposited with a bicyclo-containing group at a temperature lower than this reaction temperature, heating of the film formed on the substrate It can also be processed and converted to an organic semiconductor layer by deethylenation. By adopting such a method, a semiconductor layer containing a tetraazaporphyrin compound 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 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. It should be noted that 1 = 10 ⁻¹⁰ m.

Furthermore, deethylation of the bicyclotetraazaporphyrin 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 possible to adjust the characteristics by partially converting the film of the formed bicyclotetraazaporphyrin compound. 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, irradiation with light having a wavelength absorbed by a carbon dioxide laser, an infrared lamp, or this bicyclotetraazaporphyrin compound can be used. At this time, it is also possible to heat by providing a layer that absorbs light in the vicinity of the bicyclotetraazaporphyrin 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 such as FETs, for example, metals such as gold, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, polyaniline, polypyrrole, polythiophene, polyacetylene, polydiethylene, etc. A conductive polymer such as acetylene and a doped material thereof, a semiconductor such as silicon, germanium, and gallium arsenide, and a doped material thereof, and a carbon material such as fullerene, carbon nanotube, and graphite can be used. In addition, these may use only 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
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. For example, polymer films such as styrene resin, epoxy resin, acrylic resin, polyurethane resin, polyimide resin, polyvinyl alcohol, polyvinylidene chloride, and polycarbonate resin, inorganic oxide films and nitride films such as silicon oxide, silicon nitride, and aluminum oxide Etc. Although there is no restriction | limiting in the formation method of a polymer film, For example, the method of apply | coating and drying a solution, the method of apply | coating or vapor-depositing a monomer, and polymerizing are mentioned, Furthermore, a crosslinking process and a multilayer film can also be formed. For the formation of the inorganic film, for example, a formation method in a vacuum process such as a sputtering method or a vapor deposition method, or a formation method in 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.

  In addition, when using the tetraazaporphyrin compound of this invention as an organic semiconductor, you may use together another organic semiconductor. That is, the organic semiconductor containing the tetraazaporphyrin compound of the present invention falls within the scope of the present invention. There is no restriction | limiting in the organic semiconductor which can be used together, It is possible to use arbitrary things. Moreover, the organic semiconductor used together may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof. In the following description, DMSO means dimethyl sulfoxide, TFAA means trifluoroacetic anhydride, Et means an ethyl group, Pr means a propyl group, and TFA means trifluoroacetic acid.

Example 1 Synthesis of Bicyclotetraazaporphyrin Compound <Synthesis of Bicyclo [2.2.2] octa-5-ene-2,3-carbonate (hereinafter Compound 1)>

  1,3-cyclohexadiene (20 mmol, 1.89 ml) and vinylene carbonate (20 mmol, 1.27 ml) were dissolved in 30 ml of toluene, and the mixture was heated and stirred at 140 ° C. for 120 hours in an autoclave. The reaction solution was cooled to room temperature, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using chloroform as a solvent to obtain 2.26 g (yield 68%) of Compound 1.

<Synthesis of Bicyclo [2.2.2] octa-5-ene-2,3-diol (hereinafter referred to as Compound 2)>

  1.66 g of Compound 1 was added to a mixed solvent of 10 ml of 4N NaOH and 50 ml of 1,4-dioxane under nitrogen. The mixture was refluxed for 2 hours. After cooling to room temperature, the reaction solution was neutralized with 2N hydrochloric acid. Water was added and extracted with chloroform, and the organic phase was washed with water and dried over anhydrous sodium sulfate. Thereafter, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using chloroform as a solvent to obtain 0.98 g (yield 90%) of Compound 2.

<Synthesis of Bicyclo [2.2.2] octa-5-ene-2,3-dione (hereinafter, compound 3)>

  A solution obtained by adding 3 ml of dimethyl sulfoxide to 22.5 ml of dichloromethane was cooled to −78 ° C. in argon, and 5.5 ml of trifluoroacetic anhydride was added dropwise over 10 minutes. A solution prepared by dissolving 0.702 g of Compound 2 in 10 ml of dichloromethane was added dropwise thereto. Thereafter, the temperature was raised to room temperature and neutralized with 2N hydrochloric acid. The reaction solution was washed with water and saturated brine. Thereafter, the organic phase was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using chloroform as a solvent to obtain 0.60 g (yield 89%) of Compound 3.

<Synthesis of 5,8-Dihydro-5,8-ethanoquinoxaline-2,3-dicarbonitile (hereinafter, Compound 4)>

  0.68 g of diketone compound 3 and 0.65 g of diaminomaleonitrile were added to 200 ml of chloroform and stirred at room temperature for 3 hours. After completion of the reaction, the reaction solution was washed with water and saturated brine. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography on silica gel using a 1: 1 mixed solvent of hexane-ethyl acetate to obtain 0.74 g (yield 71%) of Compound 4.

マグネシウム５３．６ｍｇと触媒量（５〜１０ｍｇ程度）のヨウ素をプロパノール７８ｍｌ中で加熱還流した。マグネシウムが溶解した後、室温に冷却し、化合物４を０．６２ｇ添加し、２４時間還流した。反応溶液を室温に冷却し、減圧で溶媒を留去した。残渣をクロロホルム／トリフルオロ酢酸（５／１）の混合溶媒１００ｍｌに溶解し、３時間撹拌した。この反応溶液を飽和炭酸水素ナトリウム水溶液、水、飽和食塩水で洗浄した。有機相を無水硫酸ナトリウムで乾燥し、溶媒を減圧で留去した。残渣をクロロホルム／メタノールから再結晶し、ビシクロテトラアザポルフィリン化合物である、化合物６が得られた。 <Synthesis of Tetra bicycle [2.2.2] octadiene-fused tetrapyrazinoporphyrazine (hereinafter, compound 6)>

Magnesium (53.6 mg) and a catalytic amount (about 5 to 10 mg) of iodine were heated to reflux in 78 ml of propanol. After magnesium was dissolved, the mixture was cooled to room temperature, 0.62 g of compound 4 was added, and the mixture was refluxed for 24 hours. The reaction solution was cooled to room temperature, and the solvent was distilled off under reduced pressure. The residue was dissolved in 100 ml of a mixed solvent of chloroform / trifluoroacetic acid (5/1) and stirred for 3 hours. The reaction solution was washed with a saturated aqueous sodium hydrogen carbonate solution, water, and saturated brine. The organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was recrystallized from chloroform / methanol to obtain Compound 6, which is a bicyclotetraazaporphyrin compound.

[Example 2] Synthesis of tetraazaporphyrin compound from bicyclotetraazaporphyrin compound The bicyclotetraazaporphyrin compound obtained in Example 1 was subjected to calorimetric analysis. Since the weight corresponding to the following change was observed by heating, the formation of the tetraazaporphyrin compound was confirmed. A thermogravimetric analysis chart is shown in FIG.
The vertical axis at the left end of FIG. 2 indicates the TG scale, the vertical axis at the right end indicates the Temp scale, and the horizontal axis indicates the Time scale. Here, TG is the percentage change in weight with respect to the weight of the bicyclotetraazaporphyrin compound at the start of heating, expressed in percentage. In FIG. 2, it is indicated by a broken line. Temp indicates the temperature of the sample, and the unit is ° C. In FIG. 2, it is shown by a solid line. Furthermore, Time is the heating time, and the unit is minutes (indicated as min in FIG. 2).

Example 3 Organic Transistor A field effect transistor was prepared and evaluated using the tetraazaporphyrin synthesized in Example 1.

<Fabrication of field effect transistor>
On an N-type silicon (Si) substrate (Sb-doped, resistivity 0.02 Ωcm or less, manufactured by Sumitomo Metal Industries, Ltd.) on which an oxide film having a thickness of 300 nm is formed, the length (L) 10 μm and width (W ) Gold electrodes (source and drain electrodes) having a gap of 500 μm were formed. Further, chromium was vapor-deposited on the exposed Si portion by scraping off the oxide film at a position different from that of the electrode, and a voltage was applied to the silicon substrate as the gate electrode using this portion.

  7 mg of tetraazaporphyrin obtained in Example 1 was dissolved in 1 mL of chloroform. Thereafter, the operation was performed in a glove box under a nitrogen atmosphere. A good film was obtained by spin-coating the solution on the substrate on which the electrode was formed. Thereafter, heat treatment was performed at 210 ° C. for 60 minutes to form a semiconductor film on the substrate over which the electrodes were formed.

<Evaluation of field effect transistor>
As a result of evaluating the electric characteristics of the FET (field effect transistor) element thus obtained by using a semiconductor parameter analyzer 4155C manufactured by Agilent, it showed n-type FET characteristics and had a saturation mobility of 1.1 × 10 ⁻⁵ cm ^2. / Vs was obtained.

[Example 4] Improvement of transistor characteristics 5 mg of a bicycloazaporphyrin compound synthesized in the same manner as in Example 1 and further purified by column chromatography and preparative liquid chromatograph of alumina was dissolved in 1 mL of chloroform. As in Example 3, a good film was obtained by spin coating on a substrate on which an electrode was formed. Thereafter, a heat treatment was carried out at 230 ° C. for 10 minutes to produce a tetrabenzoazaporphyrin film on the substrate on which the electrodes were formed.

As a result of evaluating the electrical characteristics of the obtained FET (field effect transistor) element, it showed good n-type FET characteristics, saturated electron mobility of 1.2 × 10 ⁻³ cm ² / Vs, and threshold voltage of 25.7 V. The on / off ratio 520 was shown.

[Example 5] Copper complex Compound 6 (102.1 mg) synthesized in the same manner as in Example 1 was dissolved in chloroform (20.0 mL), and a methanol saturated solution of copper acetate (20.0 mL) was added thereto. The mixture was refluxed for 4 days until the raw material disappeared as determined by mass spectrometry.
Thereafter, the mixture was extracted with chloroform, washed with water and saturated brine, and concentrated under reduced pressure.
After purifying the obtained composition with an alumina column using chloroform, the target copper complex was purified by preparative chromatography using chloroform again (manufactured by Japan Analytical Industrial Co., Ltd., column: JAIGEL-1H + JAIGEL-2H). Only the peaks were separated.

[Example 6] Electrical characteristics of copper complex A field effect transistor was prepared from the copper complex obtained in Example 5 in the same manner as in Example 4, and the electrical characteristics were evaluated. As a result, good n-type FET characteristics were exhibited, a saturation electron mobility of 1.3 × 10 ⁻⁴ cm ² / Vs, a threshold voltage of 21.5 V, and an on / off ratio of 48 were exhibited.

  The present invention can be used in any industrial field, and in particular, resistors, rectifiers (diodes), switching elements (transistors, thyristors), amplifier elements (transistors), memory elements, chemical sensors, solar cells, It is suitable for an element to which an organic semiconductor can be applied, such as a photodiode or a phototransistor that generates a photocurrent.

It is a figure which shows the example of the structure of FET typically. It is a chart of the thermogravimetric analysis of Example 2 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor layer 2 Insulator layer 3 Source electrode 4 Drain electrode 5 Gate electrode 6 Substrate

Claims (5)

A bicyclotetraazaporphyrin compound represented by the following structural formula (I) or structural formula (II):

{In Structural Formula (I) and Structural Formula (II), (R ¹ , R ² ), (R ³ , R ⁴ ), (R ⁵ , R ⁶ ) and (R ⁷ , R ⁸ ) are each independently It is a group represented by the following formula (VI) . In Structural Formula (II), M represents a metal atom. }

{In the formula (VI), R ^{9 to} R ¹⁶ are an alkyl group, a hydroxyl group, a halogen atom or an alkoxy group having 6 or less carbon atoms, and R ^x and R ^y are a direct bond or R ^x and R ^y are integrated. Represents a structure forming an aromatic ring. } A tetraazaporphyrin compound having a tetraazaporphyrin skeleton represented by the following structural formula (IV) or structural formula (V) is obtained from the bicyclotetraazaporphyrin compound according to claim 1 by reverse Diels-Alder reaction. And a method for producing a tetraazaporphyrin compound.

{In Structural Formula (IV) and Structural Formula (V), (Q ¹ , Q ² ), (Q ³ , Q ⁴ ), (Q ⁵ , Q ⁶ ) and (Q ⁷ , Q ⁸ ) are each independently bound in each set is the structure that to form an aromatic hydrocarbon or heterocyclic ring. In Structural Formula (V), M represents a metal atom. } An organic electronic device comprising a tetraazaporphyrin compound having a tetraazaporphyrin skeleton represented by the following structural formula (IV) or structural formula (V) as a semiconductor.

{In Structural Formula (IV) and Structural Formula (V), (Q ¹ , Q ² ), (Q ³ , Q ⁴ ), (Q ⁵ , Q ⁶ ) and (Q ⁷ , Q ⁸ ) are each independently bound in each set is the structure that to form an aromatic hydrocarbon or heterocyclic ring. In Structural Formula (V), M represents a metal atom. } The organic electronic device according to claim 3 , wherein the organic electronic device is a field effect transistor. A method for producing an organic electronic device according to claim 3 or 4 ,
A method for producing an organic electronic device, comprising the step of obtaining the tetraazaporphyrin compound from the bicyclotetraazaporphyrin compound according to claim 1 by a reverse Diels-Alder reaction.

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