JP6300311B2 - Novel organic charge transfer complex and method for producing the same - Google Patents
Novel organic charge transfer complex and method for producing the same Download PDFInfo
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- JP6300311B2 JP6300311B2 JP2014052727A JP2014052727A JP6300311B2 JP 6300311 B2 JP6300311 B2 JP 6300311B2 JP 2014052727 A JP2014052727 A JP 2014052727A JP 2014052727 A JP2014052727 A JP 2014052727A JP 6300311 B2 JP6300311 B2 JP 6300311B2
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- -1 indium tin oxide Chemical class 0.000 description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LLDJYFLUQDMPQI-UHFFFAOYSA-N 2-[4,5-bis(ethylsulfanyl)-1,3-dithiol-2-ylidene]-4,5-bis(ethylsulfanyl)-1,3-dithiole Chemical compound S1C(SCC)=C(SCC)SC1=C1SC(SCC)=C(SCC)S1 LLDJYFLUQDMPQI-UHFFFAOYSA-N 0.000 description 2
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- SGBKGXLBEGFMJB-UHFFFAOYSA-N 2-(5,6-dihydro-4h-cyclopenta[d][1,3]ditellurol-2-ylidene)-5,6-dihydro-4h-cyclopenta[d][1,3]ditellurole Chemical compound C1CCC([Te]2)=C1[Te]C2=C([Te]1)[Te]C2=C1CCC2 SGBKGXLBEGFMJB-UHFFFAOYSA-N 0.000 description 1
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- WOFKFNZIJZWWPZ-UHFFFAOYSA-N pyrene-1,3-diamine Chemical compound C1=C2C(N)=CC(N)=C(C=C3)C2=C2C3=CC=CC2=C1 WOFKFNZIJZWWPZ-UHFFFAOYSA-N 0.000 description 1
- BLYOXQBERINFDU-UHFFFAOYSA-N pyrene-1,8-diamine Chemical compound C1=C2C(N)=CC=C(C=C3)C2=C2C3=CC=C(N)C2=C1 BLYOXQBERINFDU-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/02—Five-membered rings
- C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/38—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms one oxygen atom in position 2 or 4, e.g. pyrones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D345/00—Heterocyclic compounds containing rings having selenium or tellurium atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
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Description
本発明は、新規有機電荷移動錯体及びその製造方法に関するものである。さらに詳しくは、従来、有効活用されてこなかった木質バイオマス由来の物質を電子受容性分子として活用することで、化石資源由来の導電性高分子材料と代替可能な新規の有機電荷移動錯体とその製造方法に関するものである。 The present invention relates to a novel organic charge transfer complex and a method for producing the same. More specifically, a novel organic charge transfer complex that can be substituted for a fossil resource-derived conductive polymer material by using a material derived from woody biomass that has not been effectively used as an electron-accepting molecule, and its production It is about the method.
樹木構成成分のリグニンは、地球上で最も多量に存在する芳香族系バイオマスであるが、一部が熱生産のための燃料や香料等として利用されるに留まっており、その大部分が廃棄されているのが現状である。このため、リグニンを付加価値の高い有機材料等に変換することで有用な用途を確立することができれば、循環型社会の形成に大きく貢献し得るものと期待される。 Tree component lignin is the most abundant aromatic biomass on earth, but some of it is used only as fuel and fragrance for heat production, and most of it is discarded. This is the current situation. For this reason, if a useful application can be established by converting lignin into an organic material with high added value, it is expected that it will greatly contribute to the formation of a recycling society.
近年、細菌を用いたリグニンの中間代謝物である次式で表わされる２−ピロン−４，６−ジカルボン酸（2-pyrone-4,6-dicarboxylic acid；ＰＤＣ）の生産技術が開発された（非特許文献１、２）。 In recent years, a technology for producing 2-pyrone-4,6-dicarboxylic acid (PDC) represented by the following formula, which is an intermediate metabolite of lignin using bacteria, has been developed ( Non-patent documents 1, 2).
ＰＤＣは、分極性の強い３つのカルボニル基、環内エーテル酸素を有し、擬芳香族二塩基酸の構造を有している。このことから、新しい物理化学的特性を備えた機能性有機材料への応用が期待されており、現在ＰＤＣの利用技術の研究開発が行われている。 PDC has three highly polarizable carbonyl groups, an intracyclic ether oxygen, and a pseudoaromatic dibasic acid structure. For this reason, application to functional organic materials with new physicochemical properties is expected, and research and development of PDC utilization technology is currently underway.
これまでにＰＤＣについては、Ｎａと錯体を形成すること（特許文献１）や、ＰＤＣを基本骨格としたポリアミド（特許文献２、３）、ポリウレタン（特許文献４）、ポリエステル（特許文献５）等の合成が報告されている。 So far, for PDC, complex formation with Na (Patent Document 1), polyamide with PDC as a basic skeleton (Patent Documents 2 and 3), polyurethane (Patent Document 4), polyester (Patent Document 5), etc. The synthesis of has been reported.
しかしながら、ＰＤＣの利用についての技術的進展はあまり進んでいない。 However, there has not been much technical progress on the use of PDC.
本発明は、以上のとおりの背景から、従来、有効活用されてこなかった木質バイオマス由来物質のＰＤＣを電子受容性分子として活用するとの観点から、化石資源由来の導電性高分子材料と代替可能な新規の有機電荷移動錯体とその製造方法を提供することを課題としている。 In view of the background as described above, the present invention can be replaced with a fossil resource-derived conductive polymer material from the viewpoint of utilizing a PDC of a woody biomass-derived material that has not been effectively used as an electron-accepting molecule. It is an object to provide a novel organic charge transfer complex and a method for producing the same.
本発明者らは、上記従来技術に鑑みて、木質バイオマス由来物質を電子受容性分子とした新しい有機電荷移動錯体素材とその製造方法を開発するために鋭意検討を進めた。その過程において、リグニンの中間代謝産物であるＰＤＣが、優れた電子受容性分子であるとともに優れた錯体形成能を有することを見出した。 In view of the above prior art, the present inventors have intensively studied to develop a new organic charge transfer complex material using a woody biomass-derived substance as an electron-accepting molecule and a method for producing the same. In the process, it was found that PDC, which is an intermediate metabolite of lignin, is an excellent electron accepting molecule and has an excellent complex forming ability.
本発明は、このような新しい知見に基づいて完成されたものである。 The present invention has been completed based on such new findings.
すなわち、本発明の有機電荷移動錯体は、電子受容性分子と電子供与性分子とからなる有機電荷移動錯体であって、電子受容性分子が、２−ピロン−４，６−ジカルボン酸（2-pyrone-4,6-dicarboxylic acid；ＰＤＣ）またはＰＤＣ誘導体であり、 電子供与性分子が、下記一般式（１）で表される化合物、 That is, the organic charge transfer complex of the present invention is an organic charge transfer complex composed of an electron accepting molecule and an electron donating molecule, and the electron accepting molecule is 2-pyrone-4,6-dicarboxylic acid (2- pyrone-4,6-dicarboxylic acid (PDC) or a PDC derivative, wherein the electron-donating molecule is represented by the following general formula (1):
（式中、Ａは、硫黄（Ｓ）又はセレン（Ｓｅ）、テルル（Ｔｅ）原子のうちのいずれかを示し、Ｂ、Ｃ、Ｄ、Ｅは、水素原子、炭化水素基、もしくはＢとＣ、ＤとＥは、炭素鎖が結合して環を形成していてもよく、この炭素鎖による環には、異種原子を介して結合しているものが含まれることを示す。）
または、下記一般式（２）で表されるアミノピレン、
(In the formula, A represents any of sulfur (S), selenium (Se), and tellurium (Te) atoms, and B, C, D, and E represent a hydrogen atom, a hydrocarbon group, or B and C. , D and E may indicate that the carbon chain may be bonded to form a ring, and that the ring formed by the carbon chain includes those bonded through different atoms.)
Or aminopyrene represented by the following general formula (2),
（アミノ基（ＮＲ１Ｒ２）nは、ピレン環の任意の位置に結合してよく、（ＮＲ１Ｒ２）nの式中、ｎは２〜４の整数を示し、Ｒ１およびＲ２ は、同一または別異の水素原子またはアルキル基もしくは相互に結合した炭素鎖を示す。）
または、下記一般式（３）で表される化合物、
(Amino group (NR 1 R 2 ) n may be bonded to any position of the pyrene ring, and in the formula of (NR 1 R 2 ) n , n represents an integer of 2 to 4, R 1 and R 2 Represents the same or different hydrogen atoms or alkyl groups or mutually bonded carbon chains.)
Or a compound represented by the following general formula (3),
（アミノ基（ＮＲ3Ｒ4）ｎおよび（ＮＲ5Ｒ6）ｍは、ベンゼン環の任意の位置に
結合してよく、（ＮＲ3Ｒ4）ｎおよび（ＮＲ5Ｒ6）ｍの式中、ｎ、ｍは１〜３の整数を示し、Ｒ3〜Ｒ10 は、同一または別異の水素原子またはアルキル基もしくは相互に結合した炭素鎖を示す。）であることを特徴としている。
(Amino group (NR 3 R 4 ) n and (NR 5 R 6 ) m may be bonded to any position of the benzene ring, and in the formula of (NR 3 R 4 ) n and (NR 5 R 6 ) m , N and m each represent an integer of 1 to 3 , and R 3 to R 10 represent the same or different hydrogen atoms, alkyl groups or mutually bonded carbon chains.
この有機電荷移動錯体は繊維状結晶であり、繊維の直径が１０ｎｍ〜５０μｍであることが好ましい。 The organic charge transfer complex is a fibrous crystal, and the fiber diameter is preferably 10 nm to 50 μm.
本発明の薄膜は、前記有機電荷移動錯体結晶を含むことを特徴としている。 The thin film of the present invention includes the organic charge transfer complex crystal.
本発明の電極は、前記有機電荷移動錯体結晶を含む薄膜を用いることを特徴としている。 The electrode of the present invention is characterized by using a thin film containing the organic charge transfer complex crystal.
本発明の拡散法による有機電荷移動錯体結晶の製造方法は、ＰＤＣまたはＰＤＣ誘導体を有機溶媒に溶解したＰＤＣ溶液と、電子供与性分子を有機溶媒に溶解した電子供与性分子溶液とを結晶成長容器中に滴下し、静置することを特徴としている。 The method for producing an organic charge transfer complex crystal by the diffusion method of the present invention comprises a crystal growth vessel comprising a PDC solution in which PDC or a PDC derivative is dissolved in an organic solvent, and an electron donating molecule solution in which an electron donating molecule is dissolved in an organic solvent. It is characterized by dripping inside and standing still.
本発明の液−液界面結晶析出法による有機電荷移動錯体結晶の製造方法は、ＰＤＣまたはＰＤＣ誘導体を有機溶媒に溶解したＰＤＣ溶液と、電子供与性分子を有機溶媒に溶解した電子供与性分子溶液とを混合し、貧溶媒の入った容器中に滴下し、静置することを特徴としている。 The method for producing an organic charge transfer complex crystal by the liquid-liquid interface crystal precipitation method of the present invention includes a PDC solution in which PDC or a PDC derivative is dissolved in an organic solvent, and an electron donating molecule solution in which an electron donating molecule is dissolved in an organic solvent. And is dropped into a container containing a poor solvent and allowed to stand.
本発明の再沈法による有機電荷移動錯体結晶の製造方法は、ＰＤＣまたはＰＤＣ誘導体を有機溶媒に溶解したＰＤＣ溶液と、電子供与性分子を有機溶媒に溶解した電子供与性分子溶液とを混合し、貧溶媒の入った容器中に注入することを特徴としている。 In the method for producing an organic charge transfer complex crystal by the reprecipitation method of the present invention, a PDC solution in which PDC or a PDC derivative is dissolved in an organic solvent and an electron donating molecule solution in which an electron donating molecule is dissolved in an organic solvent are mixed. Injecting into a container containing a poor solvent.
本発明の電解法による有機電荷移動錯体結晶の製造方法は、ＰＤＣまたはＰＤＣ誘導体を含む支持電解質と電子供与性分子とを有機溶媒に溶解して得られる溶液を電解セル中に添加し、電解することを特徴としている。 In the method for producing an organic charge transfer complex crystal according to the electrolysis method of the present invention, a solution obtained by dissolving a supporting electrolyte containing PDC or a PDC derivative and an electron donating molecule in an organic solvent is added to an electrolytic cell and electrolyzed. It is characterized by that.
この電解法による有機電荷移動錯体結晶の製造方法では、前記電解セルを窒素ガス雰囲気中で封止した後、電極に０．５〜１．０μＡの定電流を１〜６０日間流すことが好ましい。 In the method for producing an organic charge transfer complex crystal by this electrolysis method, it is preferable to flow a constant current of 0.5 to 1.0 μA to the electrode for 1 to 60 days after sealing the electrolytic cell in a nitrogen gas atmosphere.
この電解法による有機電荷移動錯体結晶の製造方法では、ＰＤＣまたはＰＤＣ誘導体を含む支持電解質と電子供与性分子とを有機溶媒に溶解して得られる溶液を電解セル中に添加し、前記電解セルを窒素ガス雰囲気中で封止した後、電極に１００〜２００μＡの定電流を２〜１０時間流すことが好ましい。 In this method for producing an organic charge transfer complex crystal by an electrolytic method, a solution obtained by dissolving a supporting electrolyte containing PDC or a PDC derivative and an electron donating molecule in an organic solvent is added to the electrolytic cell, After sealing in a nitrogen gas atmosphere, it is preferable to flow a constant current of 100 to 200 μA to the electrode for 2 to 10 hours.
前記のとおりの本発明によれば、従来、有効活用されてこなかった木質バイオマス由来物質のＰＤＣを電子受容性分子として活用することで、化石資源由来の導電性高分子材料と代替可能な新規の有機電荷移動錯体を製造することが可能となる。これにより、現在利活用が進んでいない再生可能資源であるリグニンに高い付加価値を与えることが可能となる。
本発明の有機電荷移動錯体は、電極材料、電磁遮蔽材料、帯電防止材料等の機能性材料として極めて有用である高分子半導体結晶を形成することが可能となる。
According to the present invention as described above, by utilizing the PDC of a woody biomass-derived material that has not been effectively used as an electron-accepting molecule, it is possible to replace the conductive polymer material derived from fossil resources. An organic charge transfer complex can be produced. This makes it possible to give high added value to lignin, which is a renewable resource that is not currently being used.
The organic charge transfer complex of the present invention can form polymer semiconductor crystals that are extremely useful as functional materials such as electrode materials, electromagnetic shielding materials, and antistatic materials.
この高分子半導体結晶は、極めて安定で、液相中で簡単に作成することが可能であり、この結晶をフィルム状にした際の光透過性も高いことから、フレキシブルな透明電極材料としての応用が期待できる。 This polymer semiconductor crystal is extremely stable and can be easily prepared in the liquid phase, and since it has a high light transmittance when formed into a film, it can be used as a flexible transparent electrode material. Can be expected.
また、この高分子半導体結晶は、透明性の導電フィルム材料として、フレキシブル透明電極等の各種用途に活用することが可能である。 Moreover, this polymer semiconductor crystal can be utilized for various uses, such as a flexible transparent electrode, as a transparent conductive film material.
さらに、本発明では、酸化インジウムスズ（ＩＴＯ）を電極として用いた電解法により、ＢＥＤＴ−ＴＴＦ−ＰＤＣ錯体薄膜をＩＴＯ基板上に直接成長させることが可能である。このため、無機系透明電極の特性改善、表面改質技術等への応用の可能性が考えられる。 Furthermore, in the present invention, a BEDT-TTF-PDC complex thin film can be directly grown on an ITO substrate by an electrolytic method using indium tin oxide (ITO) as an electrode. For this reason, the possibility of the application to the characteristic improvement of an inorganic type transparent electrode, surface modification technology, etc. is considered.
次に、本発明についてさらに詳しく説明する。 Next, the present invention will be described in more detail.
本発明の有機電荷移動錯体は、電子受容性分子と電子供与性分子とからなる。電子受容性分子は、２−ピロン−４，６−ジカルボン酸（2-pyrone-4,6-dicarboxylic acid；ＰＤＣ）またはＰＤＣ誘導体である。 The organic charge transfer complex of the present invention comprises an electron accepting molecule and an electron donating molecule. The electron accepting molecule is 2-pyrone-4,6-dicarboxylic acid (PDC) or a PDC derivative.
本発明の有機電荷移動錯体の第１実施形態では、電子供与性分子が、一般式（１）で表わされる化合物である。 In the first embodiment of the organic charge transfer complex of the present invention, the electron donating molecule is a compound represented by the general formula (1).
前記一般式（１）において、Ａは、硫黄（Ｓ）又はセレン（Ｓｅ）、テルル（Ｔｅ）原子を示し、Ｂ、Ｃ、Ｄ、Ｅは、水素原子、炭化水素基、もしくはＢとＣ、ＤとＥは、炭素鎖が結合して環を形成していてもよいことを示している。また、発明の作用効果を考慮して、ＢとＣ、ＤとＥにおける炭素鎖の環には、異種原子、例えば硫黄（Ｓ）、セレン（Ｓｅ）、テルル（Ｔｅ）、酸素（Ｏ）原子等を介して環を形成してもよいし、あるいは各種の官能基、例えば、水酸基、メトキシ基、その他アルコキシ基、アミノ基、メチルアミノ基、アルキルアミノ基、ジアルキルアミノ基、トリアルキルアミノ基、メチル基、その他アルキル基等を適宜に結合していてもよい。 In the general formula (1), A represents sulfur (S), selenium (Se), or tellurium (Te) atom, and B, C, D, and E represent a hydrogen atom, a hydrocarbon group, or B and C, D and E indicate that the carbon chain may be bonded to form a ring. In consideration of the effects of the invention, the ring of the carbon chain in B and C, D and E includes a hetero atom such as sulfur (S), selenium (Se), tellurium (Te), oxygen (O) atom. Or a variety of functional groups such as hydroxyl groups, methoxy groups, other alkoxy groups, amino groups, methylamino groups, alkylamino groups, dialkylamino groups, trialkylamino groups, A methyl group and other alkyl groups may be appropriately bonded.
前記一般式（１）で表わされる電子供与性分子は、例えば、以下のものが例示される。 Examples of the electron donating molecule represented by the general formula (1) include the following.
さらに、前記一般式（１）で表わされる電子供与性分子には、例えば、ＢＰＤＴ−ＴＴＦ、ＴＥＴ−ＴＴＦ、炭素鎖の環に酸素原子を含むＢＥＤＯ−ＴＴＦ、ＴＴＦ骨格の二重結合が還元されたＤＨＴＴＦやＭＤＨＴ、ＴＴＦ骨格の硫黄（Ｓ）原子をテルル（Ｔｅ）に置換したＨＭＴＴｅＦ、その他ＢＥＤＴ-ＴＳＦ（ＢＥＴＳ）などが含まれる。 Furthermore, in the electron donating molecule represented by the general formula (1), for example, BPDT-TTF, TET-TTF, BEDO-TTF containing an oxygen atom in a carbon chain ring, and a double bond of a TTF skeleton are reduced. DHTTF, MDHT, HMTTeF in which a sulfur (S) atom of the TTF skeleton is substituted with tellurium (Te), and other BEDT-TSF (BETS).
これら電子供与性分子については、公知の方法をはじめとして各種の方法による合成等により提供可能とされる。例えば、前記ＴＭＴＴＦの場合として例示すると次の反応式に従って合成される。 These electron donating molecules can be provided by synthesis by various methods including known methods. For example, in the case of TMTTF, it is synthesized according to the following reaction formula.
本発明の有機電荷移動錯体の第２実施形態では、電子供与性分子が、一般式（２）で表わされる化合物である。 In the second embodiment of the organic charge transfer complex of the present invention, the electron donating molecule is a compound represented by the general formula (2).
一般式（２）において、アミノ基（ＮＲ１Ｒ２）nは、ピレン環の任意の位置に結合してよく、（ＮＲ１Ｒ２）nの式中、ｎは２〜４の整数を示し、Ｒ１およびＲ２ は、同一または別異の水素原子またはアルキル基もしくは相互に結合した炭素鎖を示している。 In the general formula (2), the amino group (NR 1 R 2 ) n may be bonded to any position of the pyrene ring, and in the formula of (NR 1 R 2 ) n , n represents an integer of 2 to 4. , R 1 and R 2 represent the same or different hydrogen atoms or alkyl groups or mutually bonded carbon chains.
具体的には、一般式（２）表される化合物としては、例えば、１,３,６,８‐テトラアミノピレン（ＴＡＰ）、１,３−ジアミノピレン（１,３−ＤＡＰ）、１,６−ジアミノピレン（１,６−ＤＡＰ）、１,８−ジアミノピレン（１,８−ＤＡＰ）などを例示することができる。 Specifically, examples of the compound represented by the general formula (2) include 1,3,6,8-tetraaminopyrene (TAP), 1,3-diaminopyrene (1,3-DAP), 1, Examples include 6-diaminopyrene (1,6-DAP), 1,8-diaminopyrene (1,8-DAP), and the like.
この一般式（２）で表わされる電子供与性分子については、公知の合成法で合成されたものを利用することができる。 As the electron donating molecule represented by the general formula (2), those synthesized by a known synthesis method can be used.
本発明の有機電荷移動錯体の第３実施形態では、電子供与性分子が、一般式（３）で表わされる化合物である。 In the third embodiment of the organic charge transfer complex of the present invention, the electron donating molecule is a compound represented by the general formula (3).
一般式（３）において、アミノ基（ＮＲ3Ｒ4）ｎおよび（ＮＲ5Ｒ6）ｍは、ベンゼン環の任意の位置に結合してよく、（ＮＲ3Ｒ4）ｎおよび（ＮＲ5Ｒ6）ｍの式中、ｎ、ｍは１〜３の整数を示し、Ｒ3〜Ｒ10 は、同一または別異の水素原子またはアルキル基もしくは相互に結合した炭素鎖を示している。 In the general formula (3), the amino groups (NR 3 R 4 ) n and (NR 5 R 6 ) m may be bonded to any position of the benzene ring, and (NR 3 R 4 ) n and (NR 5 R 6 ) In the formula of m , n and m each represent an integer of 1 to 3 , and R 3 to R 10 represent the same or different hydrogen atoms or alkyl groups or mutually bonded carbon chains.
具体的には、一般式（２）表される化合物としては、例えば、３,３,’５,５’-テトラメチルベンジジン（３,３,’５,５’-ＴＭＢ）や３,３’-ジメチルベンジジン（３,３,’-ＤＭＢ）などを例示することができる。この一般式（３）で表わされる電子供与性分子についても、公知の合成法で合成されたものを利用することができる。 Specifically, examples of the compound represented by the general formula (2) include 3,3, '5,5'-tetramethylbenzidine (3,3,' 5,5'-TMB) and 3,3 '. -Dimethylbenzidine (3,3, '-DMB) and the like can be exemplified. As the electron donating molecule represented by the general formula (3), those synthesized by a known synthesis method can be used.
ＰＤＣまたはＰＤＣ誘導体を電子受容性分子とする本発明の有機電荷移動錯体では、電子供与性分子は、高電導性の観点から、TTF系の拡張共役型電子供与性分子であるＢＥＤＴ−ＴＴＦとの錯体が特に優れている。 In the organic charge transfer complex of the present invention using a PDC or PDC derivative as an electron-accepting molecule, the electron-donating molecule is bonded to BEDT-TTF, which is a TTF-based extended conjugated electron-donating molecule, from the viewpoint of high conductivity. The complex is particularly excellent.
本発明の有機電荷移動錯体は、リグニンより細菌を用いた中間代謝産物としてのＰＤＣまたはＰＤＣ誘導体と前記のような電子供与性分子との錯体形成によって製造される。 The organic charge transfer complex of the present invention is produced from lignin by complex formation between PDC or a PDC derivative as an intermediate metabolite using bacteria and the above electron donating molecule.
もちろんＰＤＣについては合成法によって得られたものであってもよい。また、ＰＤＣ誘導体は、公知の方法で合成されたものであってよく、ＰＤＣのカルボキシル基をモノエステル、ジエステル、モノアミド、ジアミド、モノニトリル、ジニトリル、モノアミン、ジアミン、モノケトン、ジケトン、モノ酸塩化物、ジ酸塩化物などの置換体が含まれる。 Of course, the PDC may be obtained by a synthesis method. The PDC derivative may be synthesized by a known method, and the carboxyl group of PDC is monoester, diester, monoamide, diamide, mononitrile, dinitrile, monoamine, diamine, monoketone, diketone, monoacid chloride. , Substitutions such as diacid chlorides are included.
錯体形成のための方法としては様々であってよいが、本発明においては、拡散法、液−液界面結晶析出法、電解法が好適なものとして提供される。 There are various methods for forming the complex, but in the present invention, a diffusion method, a liquid-liquid interface crystal deposition method, and an electrolysis method are preferably provided.
いずれの方法においても、ＰＤＣ（またはＰＤＣ誘導体）及び電子供与性分子を溶解する有機溶媒としては、例えば、アセトニトリル、アニソール等を例示することができる。 In any method, examples of the organic solvent that dissolves the PDC (or PDC derivative) and the electron donating molecule include acetonitrile and anisole.
ＰＤＣ（またはＰＤＣ誘導体）及び電子供与性分子の飽和溶液を用いて拡散法によって結晶形成を行う場合には、長さ０．２〜２ｍｍ、断面０．０４ｍｍ×０．０１ｍｍ〜０．００２５ｍｍ×０．００１ｍｍの黒色針状結晶や、直径数μｍの繊維状結晶を得ることができる。なお、ここで言う平均長さ及び平均直径は、得られた結晶の撮影画像をコンピュータに取り込み、画像解析ソフトウェアによって算出した値である。 When crystal formation is performed by a diffusion method using a saturated solution of PDC (or PDC derivative) and an electron donating molecule, the length is 0.2 to 2 mm, and the cross section is 0.04 mm × 0.01 mm to 0.0025 mm × 0. A black needle-like crystal having a diameter of 0.001 mm or a fibrous crystal having a diameter of several μm can be obtained. Note that the average length and average diameter referred to here are values obtained by taking a captured image of the obtained crystal into a computer and calculating by image analysis software.
電子供与性分子とＰＤＣ（またはＰＤＣ誘導体）のモル比を１：５０とし、アセトニトリルを有機溶媒として用いた場合、ＰＤＣ溶液の濃度を５０〜８３．３ｍｍｏｌ／Ｌ、電子供与性分子の溶液の濃度を１．５〜２．５ｍｍｏｌ／Ｌの範囲とすることによって、繊維状結晶のみの選択的成長及び結晶形態制御が可能となり、平均直径１０ｎｍ〜５０μｍ程度の範囲で繊維状結晶の直径制御が可能である。 When the molar ratio of the electron donating molecule to PDC (or PDC derivative) is 1:50 and acetonitrile is used as the organic solvent, the concentration of the PDC solution is 50 to 83.3 mmol / L, and the concentration of the electron donating molecule solution is By making the range of 1.5 to 2.5 mmol / L, it becomes possible to selectively grow and control the crystal morphology of only the fibrous crystal, and to control the diameter of the fibrous crystal in the range of an average diameter of about 10 nm to 50 μm. It is.
ＰＤＣ（またはＰＤＣ誘導体）と電子供与性分子からなる有機電荷移動錯体の結晶形成を行う際の容器としては、例えば、蓋付のサンプル管、Ｈ型結晶成長管等を例示することができる。 Examples of the container for crystal formation of an organic charge transfer complex composed of PDC (or a PDC derivative) and an electron donating molecule include a sample tube with a lid, an H-type crystal growth tube, and the like.
ＰＤＣ（またはＰＤＣ誘導体）と電子供与性分子からなる有機電荷移動錯体の結晶形成を、液−液界面結晶析出法で行う場合には、ＰＤＣ溶液と電子供与性分子の溶液との混合溶液を滴下する貧溶媒は、例えば、トルエン等が例示される。 When crystal formation of an organic charge transfer complex comprising PDC (or a PDC derivative) and an electron donating molecule is performed by a liquid-liquid interface crystal precipitation method, a mixed solution of a PDC solution and an electron donating molecule solution is dropped. An example of the poor solvent is toluene.
ＰＤＣ（またはＰＤＣ誘導体）及び電子供与性分子の飽和溶液を用いて液−液界面結晶析出法による結晶形成を行うと、平均直径２０〜４０ｎｍの繊維状結晶を得ることができる。 When crystal formation is performed by a liquid-liquid interface crystal precipitation method using a saturated solution of PDC (or PDC derivative) and an electron donating molecule, fibrous crystals having an average diameter of 20 to 40 nm can be obtained.
なお、ここで言う平均直径は、得られた結晶のＳＥＭ写真から画像解析ソフトウェアによって算出した値である。 The average diameter here is a value calculated by image analysis software from the SEM photograph of the obtained crystal.
このように、本発明の有機電荷移動錯体の製造方法によれば、結晶形成条件を最適化することにより直径２０ｎｍ〜８．５μｍ程度の高いアスペクト比を有する電気伝導性電荷移動錯体繊維状結晶を生成することができる。 Thus, according to the method for producing an organic charge transfer complex of the present invention, an electrically conductive charge transfer complex fibrous crystal having a high aspect ratio of about 20 nm to 8.5 μm in diameter can be obtained by optimizing crystal formation conditions. Can be generated.
ＰＤＣ（またはＰＤＣ誘導体）及び電子供与性分子を用いて電解法による結晶形成を行う場合、電子供与性分子の支持電解質として、ＰＤＣ塩を合成する。ＰＤＣ塩としては、例えば、モノプロトン化ＰＤＣ−テトラブチルアンモニア塩（Ｂｕ４Ｎ（ＰＤＣ））を例示することができる。 When crystal formation by an electrolytic method is performed using PDC (or a PDC derivative) and an electron donating molecule, a PDC salt is synthesized as a supporting electrolyte for the electron donating molecule. Examples of the PDC salt include monoprotonated PDC-tetrabutyl ammonia salt (Bu 4 N (PDC)).
これら支持電解質については、公知の方法をはじめとして各種の方法により提供可能とされる。例えば、前記Ｂｕ４Ｎ（ＰＤＣ）の場合として例示すると
電子供与性分子＋Ｂｕ４Ｎ（ＰＤＣ）→（電子供与性分子）ｘＰＤＣ
の電解反応を生じ、電解セルの陽極に有機電荷移動錯体の結晶が形成される。
These supporting electrolytes can be provided by various methods including known methods. For example, as an example of the case of Bu4N (PDC), electron donating molecule + Bu4N (PDC) → (electron donating molecule) x PDC
Thus, an organic charge transfer complex crystal is formed at the anode of the electrolytic cell.
また、ＰＤＣ塩と電子供与性分子とを溶解する有機溶媒としては、例えば、アセトニトリル、アニソール、ジメチルスルホキシド、ジクロロメタン、エタノール等を例示することができる。また、上記有機溶媒は１種又は２種以上の混合溶媒を用いてもよい。 Examples of the organic solvent that dissolves the PDC salt and the electron-donating molecule include acetonitrile, anisole, dimethyl sulfoxide, dichloromethane, ethanol, and the like. Moreover, the said organic solvent may use 1 type, or 2 or more types of mixed solvents.
上記の有機溶媒を用いて調製したＰＤＣ塩溶液の濃度は、ＣＨ２Ｃｌ２／ＣＨ３ＣＨ２ＯＨ（９７．５：２．５％Ｖ／Ｖ）の混合溶媒を用いた場合、ＢＥＤＴ−ＴＴＦ０．００３５ｍｍｏｌおよびＢｕ４Ｎ（ＰＤＣ）０．３５０ｍｍｏｌで良質の単結晶試料を得ることが出来る。 The concentration of the PDC salt solution prepared using the above organic solvent is BEDT-TTF0 when a mixed solvent of CH 2 Cl 2 / CH 3 CH 2 OH (97.5: 2.5% V / V) is used. A good quality single crystal sample can be obtained with .0035 mmol and Bu 4 N (PDC) 0.350 mmol.
電解法に用いる電極としては、例えば、陽極にアルミニウム、金、銀、ニッケル、パラジウム、白金等の金属、酸化インジウムスズ等の金属酸化物、ヨウ化銅等のハロゲン化金属、カーボンブラック、あるいは、ポリ（３−メチルチオフェン）、ポリピロール、ポリアニリン等の導電性高分子等を例示することができる。 As an electrode used in the electrolytic method, for example, the anode is a metal such as aluminum, gold, silver, nickel, palladium, platinum, a metal oxide such as indium tin oxide, a metal halide such as copper iodide, carbon black, or Examples thereof include conductive polymers such as poly (3-methylthiophene), polypyrrole, and polyaniline.
また、陽極の形成は通常、スパッタリング法、真空蒸着法などにより行われることが多い。また、銀等の金属微粒子、ヨウ化銅などの微粒子、カーボンブラック、導電性の金属酸化物微粒子、導電性高分子微粉末等の場合には、適当なバインダー樹脂溶液に分散し、基板上に塗布することにより陽極を形成することもできる。 Also, the anode is usually formed by sputtering, vacuum deposition, or the like. In addition, in the case of fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc., it is dispersed in a suitable binder resin solution, An anode can also be formed by coating.
基板は、電極の支持体となるものであり、石英やガラスの板、金属板や金属箔、プラスチックフィルムやソート等が用いられる。特に、ガラス板や、ポリエステル、ポリメタクリレート、ポリカーボネート、ポリスルホンなどの透明な合成樹脂の板が好ましい。
または、Ｐｔ等の棒状の電極を用いることもできる。
The substrate serves as a support for the electrode, and a quartz or glass plate, a metal plate or a metal foil, a plastic film, a sort, or the like is used. In particular, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable.
Alternatively, a rod-like electrode such as Pt can be used.
本発明では、０．１〜５．０μＡ、好ましくは０．５〜１．０μＡの範囲内の定電流を電解セルに流すことによって、電解法による結晶形成を行うことができる。 In the present invention, crystal formation by an electrolytic method can be performed by passing a constant current in the range of 0.1 to 5.0 μA, preferably 0.5 to 1.0 μA, through the electrolytic cell.
また、通電時間は数日から２ヵ月間程度である。 The energization time is about several days to two months.
ＰＤＣ塩及び電子供与性分子の溶液を用いて電解法による結晶形成を行うと、平均直径２０〜４０ｎｍの繊維状結晶を得ることができる。 When a crystal is formed by an electrolytic method using a solution of a PDC salt and an electron donating molecule, a fibrous crystal having an average diameter of 20 to 40 nm can be obtained.
なお、ここで言う平均直径は、得られた結晶のＳＥＭ写真から画像解析ソフトウェアによって算出した値である。 The average diameter here is a value calculated by image analysis software from the SEM photograph of the obtained crystal.
本発明の有機電荷移動錯体の結晶によれば、電極材料、電磁遮蔽材料、帯電防止材料等の機能性材料として極めて有用である高分子半導体結晶を形成することが可能となる。この高分子半導体結晶は、極めて安定で、液相中で簡単に作成することが可能であり、この結晶をフィルム状にした薄膜も光透過性も高いことから、フレキシブルな透明電極材料としての応用が期待できる。 According to the organic charge transfer complex crystal of the present invention, it is possible to form a polymer semiconductor crystal that is extremely useful as a functional material such as an electrode material, an electromagnetic shielding material, or an antistatic material. This polymer semiconductor crystal is extremely stable and can be easily prepared in the liquid phase. Since this film is a film-like thin film and has high optical transparency, it can be used as a flexible transparent electrode material. Can be expected.
また、この高分子半導体結晶は、透明性の導電フィルム材料として、フレキシブル透明電極等の各種用途に活用することが可能である。 Moreover, this polymer semiconductor crystal can be utilized for various uses, such as a flexible transparent electrode, as a transparent conductive film material.
さらに、本発明では、酸化インジウムスズ（ＩＴＯ）を電極として用いた電解法により、ＢＥＤＴ−ＴＴＦ−ＰＤＣ錯体薄膜をＩＴＯ基板上に直接成長させることが可能である。このため、無機系透明電極の特性改善、表面改質技術等への応用の可能性が考えられる。 Furthermore, in the present invention, a BEDT-TTF-PDC complex thin film can be directly grown on an ITO substrate by an electrolytic method using indium tin oxide (ITO) as an electrode. For this reason, the possibility of the application to the characteristic improvement of an inorganic type transparent electrode, surface modification technology, etc. is considered.
また、例えば、本発明の有機電荷移動錯体の結晶と、ポリ(3,4-エチレンジオキシチオフェン)-ポリ(スチレンスルホン酸)(ＰＥＤＯＴ−ＰＳＳ)などの帯電（静電気）防止材料と組み合わせて使用することができる。これにより、ＰＥＤＯＴ−ＰＳＳの導電性や溶解性などを改良することができ、タッチパネルや有機薄膜太陽電池用の透明電極材料などの性能をより高めることができる。 In addition, for example, the organic charge transfer complex crystal of the present invention is used in combination with an antistatic material such as poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS). can do. Thereby, the electroconductivity, solubility, etc. of PEDOT-PSS can be improved and performances, such as a transparent electrode material for touch panels and organic thin-film solar cells, can be improved more.
さらに、例えば、ゴムに本発明の有機電荷移動錯体の結晶を配合して、帯電防止材料を形成することもできる。 Furthermore, for example, the organic charge transfer complex crystal of the present invention can be blended with rubber to form an antistatic material.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.
＜実施例１＞ＰＤＣの電子受容性分子としての評価
植物由来のリグニンを組換え微生物発酵によって分解し、リグニンの中間代謝産物であるＰＤＣを得た。得られたＰＤＣを用いて、サイクリックボルタモグラフ測定を行った。
<Example 1> Evaluation of PDC as an electron-accepting molecule Plant-derived lignin was decomposed by recombinant microorganism fermentation to obtain PDC which is an intermediate metabolite of lignin. Cyclic voltammographic measurement was performed using the obtained PDC.
図１は、ＰＤＣのサイクリックボルタモグラムを、図２は、ＰＤＣのＨＯＭＯおよびＬＵＭＯのエネルギー準位図を示している。ＰＤＣが電子受容性分子であることが確認される。 FIG. 1 shows a cyclic voltammogram of PDC, and FIG. 2 shows an energy level diagram of HOMO and LUMO of PDC. It is confirmed that PDC is an electron accepting molecule.
＜実施例２＞拡散法によるＴＴＦ誘導体−ＰＤＣ繊維状結晶の作製
ＰＤＣ、ＴＴＦおよびＳＤＭ−ＴＴＦを、それぞれアセトニトリル（和光純薬工業、純度９９．５％ｖ/ｖ）に溶かし、飽和溶液（ＰＤＣ：０．０６９ｍｏｌ／Ｌ、ＴＴＦ：０．０１１ｍｏｌ／Ｌ、ＳＤＭ−ＴＴＦ：０．００８６ｍｏｌ／Ｌ）を調整した。次に、Ｈ型結晶成長管の片側からＰＤＣ／アセトニトリル飽和溶液を、もう一方の側からＴＴＦまたはＳＤＭ−ＴＴＦ／アセトニトリル飽和溶液を滴下し、Ｈ型結晶成長管内を窒素ガスで置換し、摺合平栓で封止した。その後、Ｈ型結晶成長管を室温、暗所で約１ヶ月間静置することにより結晶成長を行った。その結果、黒色針状結晶および繊維状結晶（直径数μｍ程度）が析出した。図３に拡散法によるＴＴＦ−ＰＤＣ結晶のＳＥＭ像を示した（撮影機種ＨＩＴＡＣＨＩ Ｓ−４５００、撮影条件加速電圧２０ｋＶ）。
<Example 2> Preparation of TTF derivative-PDC fibrous crystal by diffusion method PDC, TTF and SDM-TTF were dissolved in acetonitrile (Wako Pure Chemical Industries, Ltd., purity 99.5% v / v), respectively, and a saturated solution (PDC) : 0.069 mol / L, TTF: 0.011 mol / L, SDM-TTF: 0.0086 mol / L). Next, PDC / acetonitrile saturated solution is dropped from one side of the H-type crystal growth tube, and TTF or SDM-TTF / acetonitrile saturated solution is dropped from the other side, and the inside of the H-type crystal growth tube is replaced with nitrogen gas. Sealed with a stopper. Thereafter, crystal growth was performed by allowing the H-type crystal growth tube to stand at room temperature in a dark place for about one month. As a result, black needle crystals and fibrous crystals (diameter of about several μm) were precipitated. FIG. 3 shows an SEM image of the TTF-PDC crystal by the diffusion method (photographing model HITACHI S-4500, photographing condition acceleration voltage 20 kV).
＜実施例３＞溶液からの結晶析出法によるＴＴＦ誘導体−ＰＤＣ繊維状結晶の作製
ＰＤＣ／アセトニトリル溶液およびＴＴＦ、ＳＤＭ−ＴＴＦ、ＴＭＴＴＦ／アセトニトリル溶液の濃度調整により、繊維状結晶のみの選択的成長および結晶形態制御を行った。ＴＭＴＴＦ−ＰＤＣ結晶に関しては、液−液界面結晶析出法により、繊維状結晶の作成を行った。ＴＭＴＴＦ／アセトニトリル溶液およびＰＤＣ／アセトニトリル溶液の混合溶液を、混合してから約２４時間後に、貧溶媒であるトルエンの入った容器中に静かに滴下し、室温、暗所で数日間静置を行うことで、直径２０〜４０ｎｍ程度の繊維状ナノ結晶が析出した。図４に液−液界面結晶析出法の模式図とＴＭＴＴＦ−ＰＤＣ結晶のＳＥＭ像を示した。
Example 3 Preparation of TTF Derivative-PDC Fibrous Crystal by Crystal Precipitation Method from Solution By selectively adjusting the concentrations of PDC / acetonitrile solution and TTF, SDM-TTF, TMTTF / acetonitrile solution, Crystal form control was performed. Regarding the TMTTF-PDC crystal, a fibrous crystal was prepared by a liquid-liquid interface crystal precipitation method. About 24 hours after mixing, the mixed solution of TMTTF / acetonitrile solution and PDC / acetonitrile solution is gently dropped into a container containing toluene, which is a poor solvent, and allowed to stand at room temperature in the dark for several days. As a result, fibrous nanocrystals having a diameter of about 20 to 40 nm were precipitated. FIG. 4 shows a schematic diagram of the liquid-liquid interface crystal precipitation method and an SEM image of the TMTTF-PDC crystal.
＜実施例４＞電解法による電子供与性分子−ＰＤＣ電荷移動錯体結晶の作製
モノプロトン化ＰＤＣ−テトラブチルアンモニウム塩（Ｂｕ４Ｎ（ＰＤＣ））を合成し、電子供与性分子の電解酸化用支持電解質として使用することにより、電解法による電荷移動錯体（塩）の合成を行った。電子供与性分子ＴＴＦ、ＢＥＤＴ−ＴＴＦ、ＢＭＤＴ−ＴＴＦ、ＴＥＴ−ＴＴＦ、ＴＭＴＳＦを支持電解質であるＢｕ４Ｎ（ＰＤＣ）と有機溶媒に溶かし、電解セル中に入れ、セルを窒素ガス雰囲気中で封止した。図５に電解法の装置を示した。電極に０．５〜１．０μＡ程度の一定電流を数日から２か月間程度流すことにより、陽極の白金電極上に、上記ドナー−ＰＤＣ電荷移動錯体結晶が析出した。特に、ＢＥＤＴ−ＴＴＦ−ＰＤＣ錯体においては、ジクロロメタン／エタノール (９７．５：２．５％ｖ/ｖ)を溶媒として用いた時に、良質の結晶を得ることができた。１，２−ジアミノピレン（ＤＡＰ）−ＰＤＣ錯体については、アセトニトリルを溶媒として同様の電解法により、直径数１０ｎｍの繊維状結晶の高密度の束状の結晶を作製することができた。得られた高密度の束状の繊維状結晶のＳＥＭ像を図６に示した。
<Example 4> Preparation of electron donating molecule-PDC charge transfer complex crystal by electrolytic method Monoprotonated PDC-tetrabutylammonium salt (Bu4N (PDC)) was synthesized and used as a supporting electrolyte for electrooxidation of electron donating molecule. By using it, the charge transfer complex (salt) was synthesized by the electrolytic method. Electron donating molecules TTF, BEDT-TTF, BMDT-TTF, TET-TTF, and TMTSF were dissolved in supporting electrolyte Bu4N (PDC) and an organic solvent, placed in an electrolytic cell, and the cell was sealed in a nitrogen gas atmosphere. . FIG. 5 shows an electrolysis apparatus. The donor-PDC charge transfer complex crystal was deposited on the platinum electrode of the anode by applying a constant current of about 0.5 to 1.0 μA to the electrode for several days to 2 months. Particularly, in the BEDT-TTF-PDC complex, when dichloromethane / ethanol (97.5: 2.5% v / v) was used as a solvent, good quality crystals could be obtained. For the 1,2-diaminopyrene (DAP) -PDC complex, high-density bundle crystals of fibrous crystals having a diameter of several tens of nanometers could be produced by the same electrolytic method using acetonitrile as a solvent. The SEM image of the obtained high-density bundle-like fibrous crystal is shown in FIG.
＜実施例５＞電解法によるドナー−ＰＤＣ電荷移動錯体薄膜の作製
市販のＩＴＯ基板(Ｓｉｇｍａ−Ａｌｄｒｉｃｈ社製）に界面活性剤による超音波洗浄、超純水による超音波洗浄および流水洗浄後、窒素ブローで乾燥させ、最後に紫外線オゾン洗浄を行った後、例示化合物（５）を含有する有機電荷移動錯体結晶からなる薄膜を電解法により形成した。例示化合物（５）ＢＥＤＴ−ＴＴＦを支持電解質であるＢｕ４Ｎ（ＰＤＣ）とともにジクロロメタン／エタノール（９７．５：２．５％ｖ／ｖ）に溶かし、陽極にＩＴＯ基板をもちいた電解セル中に添加した。電解セルを窒素ガス雰囲気中で封止した後、電極に１００μＡ〜２００μＡ程度の一定電流を４時間程度流すことにより、ＩＴＯ基板表面上に板状およびリボン状のＢＥＤＴ−ＴＴＦ−ＰＤＣ薄膜が形成された。この時、得られた薄膜の厚さは、数ｎｍであった。薄膜形成の装置図（a）、及び得られた薄膜の光学顕微鏡像（b）、ＳＥＭ像（c）を図７に示す。図中のサンプルＡは、電極に１００μＡの一定電流を流した際に形成された薄膜を示す。また、サンプルＢは、電極に２００μＡの一定電流を流した際に形成された薄膜を示す。
＜実施例６＞
＜有機電荷移動錯体結晶の構造及び機能性評価＞
拡散法及び電解法により作製した単結晶試料について、Ｘ線回折法による結晶構造解析を行った（Ｒｉｇａｋｕ社製 ＲＡＸＩＳ−ＲＡＰＩＤおよび４１７６Ｆ０７ＣＣＤ−３）。
<Example 5> Preparation of donor-PDC charge transfer complex thin film by electrolytic method After commercially available ITO substrate (manufactured by Sigma-Aldrich), ultrasonic cleaning with surfactant, ultrasonic cleaning with ultrapure water and cleaning with running water, nitrogen After drying by blow and finally performing ultraviolet ozone cleaning, a thin film made of an organic charge transfer complex crystal containing the exemplified compound (5) was formed by an electrolytic method. Exemplified compound (5) BEDT-TTF was dissolved in dichloromethane / ethanol (97.5: 2.5% v / v) together with supporting electrolyte Bu4N (PDC), and added to an electrolytic cell using an ITO substrate as an anode. . After the electrolytic cell is sealed in a nitrogen gas atmosphere, a plate-like and ribbon-like BEDT-TTF-PDC thin film is formed on the surface of the ITO substrate by applying a constant current of about 100 μA to 200 μA to the electrode for about 4 hours. It was. At this time, the thickness of the obtained thin film was several nm. FIG. 7 shows an apparatus diagram (a) for forming a thin film, and an optical microscope image (b) and an SEM image (c) of the obtained thin film. Sample A in the figure shows a thin film formed when a constant current of 100 μA is passed through the electrode. Sample B shows a thin film formed when a constant current of 200 μA was passed through the electrode.
<Example 6>
<Structure and functionality evaluation of organic charge transfer complex crystals>
The single crystal sample produced by the diffusion method and the electrolytic method was subjected to crystal structure analysis by X-ray diffraction method (RAXIS-RAPID and 4176F07CCD-3 manufactured by Rigaku).
また、得られた有機電荷移動錯体の粉末試料について磁化率パラメータを算出した。結果を表１に示した。ここで、χ０は温度に依存しないパウリ磁化率の成分、Ｃはキュリー定数、θはワイス温度である。 Moreover, the magnetic susceptibility parameter was computed about the powder sample of the obtained organic charge transfer complex. The results are shown in Table 1. Here, χ 0 is a Pauli magnetic susceptibility component that does not depend on temperature, C is a Curie constant, and θ is a Weiss temperature.
その結果、χ０の値がＴＴＦ−ＰＤＣ、ＳＤＭ−ＴＴＦ−ＰＤＣ、ＴＭＴＴＦ−ＰＤＣの順に大きくなっており、ＴＴＦ誘導体の電気伝導率は上記の順に高いことが明らかになった。 As a result, the value of χ 0 was increased in the order of TTF-PDC, SDM-TTF-PDC, and TMTTF-PDC, and it was revealed that the electrical conductivity of the TTF derivative was higher in the above order.
また、ワイス温度θは負の値となっていることから、ＴＭＴＴＦ−ＰＤＣにおいては、低温で反強磁性的相互作用が存在していることが明らかになった。 Further, since the Weiss temperature θ is a negative value, it has been clarified that an antiferromagnetic interaction exists at a low temperature in the TMTTF-PDC.
その結果、拡散法及び電解法により作製したＴＴＦ−ＰＤＣ錯体結晶は、いずれも、ＰＤＣ分子間で形成される３次元的な水素結合ネットワークにより、高電導性が期待される分離積層型の安定した結晶構造を持ち、ＴＴＦおよびＰＤＣの１次元的カラム構造を有する。上記１次元的カラム構造を図８に示した。 As a result, the TTF-PDC complex crystals produced by the diffusion method and the electrolysis method are both stable and stable in a separated layer type in which high conductivity is expected due to the three-dimensional hydrogen bond network formed between PDC molecules. It has a crystal structure and a one-dimensional column structure of TTF and PDC. The one-dimensional column structure is shown in FIG.
さらに電解法により作製したＢＥＤＴ−ＴＴＦ−ＰＤＣ錯体結晶においても、結晶中でＢＥＤＴ−ＴＴＦ分子は水素結合ネットワークにより形成されたＰＤＣシートによって分離された１次元的な積層構造をとることを明らかにした。上記１次元的カラム構造を図９に示した。 Furthermore, in the BEDT-TTF-PDC complex crystal produced by the electrolytic method, it was clarified that BEDT-TTF molecules in the crystal have a one-dimensional laminated structure separated by a PDC sheet formed by a hydrogen bond network. . The one-dimensional column structure is shown in FIG.
＜実施例７＞ＰＤＣ誘導体の作製
ＰＤＣの４,６位の−ＣＯＯＨ基を、−ＣＯＯＣＨ３基、−ＣＯＯＣ２Ｈ５基に置換した２種の置換体を作製した。
Example 7 Production of PDC Derivatives Two types of substitution products were produced by substituting the —COOH group at the 4th and 6th positions of PDC with —COOCH 3 group and —COOC 2 H 5 group.
（１）ＣＯＯＣＨ３基置換体の合成
以下の材料を使用した。
(1) Synthesis of COOCH 3- group substitution product The following materials were used.
ＰＤＣ（23mg、0.13mmol）
ＤＭＴ−ＭＭ：4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium Chloride n-Hydrate（95mg 0.34mmol）
ＣＨ３ＯＨ（20mL）
Ｃ５Ｈ５Ｎ２（26mL）
具体的には、200 mL ナスフラスコにPDC を 23.3 mg (0.13 mmol) 入れ, メタノール20 mL を加えて溶解させた後, ピリジンを 26.3 mL (0.33 mmol) 加えた。10 min. 攪拌後, DMT-MM を94.5 mg (0.34 mmol) 加え, 室温で18 hrs 反応を行い、２-ピロンの４,６位ＣＯＯＣＨ３基置換体を得た。また、このＣＯＯＣＨ３基置換体については、１Ｈ-ＮＭＲでそのピークを確認した。
PDC (23 mg, 0.13 mmol)
DMT-MM: 4- (4,6-Dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium Chloride n-Hydrate (95mg 0.34mmol)
CH 3 OH (20 mL)
C 5 H 5 N 2 (26 mL)
Specifically, 23.3 mg (0.13 mmol) of PDC was placed in a 200 mL eggplant flask, 20 mL of methanol was added and dissolved, and then 26.3 mL (0.33 mmol) of pyridine was added. After stirring for 10 min., 94.5 mg (0.34 mmol) of DMT-MM was added and reacted at room temperature for 18 hrs to obtain a 4-pyrone 4,6-position COOCH 3- group substitution product. Moreover, about this COOCH 3 group substitution product, the peak was confirmed by 1H-NMR.
（２）ＣＯＯＣ２Ｈ５基置換体の合成
以下の材料を使用した。
(2) Synthesis of COOC 2 H 5 group substitution product The following materials were used.
ＰＤＣ（26mg、0.14mmol）
ＤＭＴ−ＭＭ（90mg 0.33mmol）
Ｃ２Ｈ５ＯＨ（20mL）
Ｃ５Ｈ５Ｎ２（26mL）
具体的には、200 mL ナスフラスコにPDC を 26.0 mg (0.14 mmol) 入れ, エタノール20 mL を加えて溶解させた後, ピリジンを 26.0 mL (0.32 mmol) 加えた。10 min. 攪拌後、DMT-MM を90.4 mg (0.33 mmol) 加え, 室温で 18 hrs 反応を行い、２-ピロンの４,６位ＣＯＯＣ２Ｈ５基置換体を得た。また、このＣＯＯＣ２Ｈ５基置換体については、１Ｈ-ＮＭＲでそのピークを確認した。
PDC (26 mg, 0.14 mmol)
DMT-MM (90mg 0.33mmol)
C 2 H 5 OH (20 mL)
C 5 H 5 N 2 (26 mL)
Specifically, 26.0 mg (0.14 mmol) of PDC was placed in a 200 mL eggplant flask, 20 mL of ethanol was added and dissolved, and then 26.0 mL (0.32 mmol) of pyridine was added. After stirring for 10 min, 90.4 mg (0.33 mmol) of DMT-MM was added and reacted at room temperature for 18 hrs to obtain a 4-pyrone 4,6-position COOC 2 H 5 group substitution product. As for the COOC 2 H 5 group substituents confirmed its peak in IH-NMR.
＜実施例８＞ＰＤＣ誘導体のエネルギー準位の計算
ＰＤＣと実施例７で合成した２種の置換体（ＣＯＯＣＨ３基置換体、ＣＯＯＣ２Ｈ５基置換体）およびＣＮ基置換体（ＰＤＣの４,６位の−ＣＯＯＨ基をＣＮ基に置換したもの）について、分子軌道法でエネルギー準位を計算した。計算には Gaussian 09W ver. 0.9 を使用した。モデル分子をGaussView ver. 5.0 で設計し、DFT計算を用いて構造最適化および振動数計算を行った。汎関数はB3LYP, 基底関数には 6-311G(d)を用いた。
<Example 8> Calculation of energy level of PDC derivative The PDC and the two types of substituents synthesized in Example 7 (COOCH 3 group substituents, COOC 2 H 5 group substituents) and CN group substituents (PDC 4) , 6-position -COOH group was replaced with CN group), the energy level was calculated by molecular orbital method. Gaussian 09W ver. 0.9 was used for the calculation. The model molecule was designed with GaussView ver. 5.0, and the structure optimization and frequency calculation were performed using DFT calculation. The functional was B3LYP and the basis function was 6-311G (d).
その結果、ＰＤＣの最低非占有分子軌道 ( LUMO ) のエネルギーは -3.26 eV, ＣＯＯＣＨ３基置換体の LUMO エネルギーは -3.04 eV, ＣＯＯＣ２Ｈ５基置換体の LUMO エネルギーは -2.98 eV, ＣＮ基置換体の LUMO エネルギーは -3.90 eVとなり、ＣＮ基置換体が最も電子親和力が大きくなり、高いアクセプター性を有していることが確認された。 As a result, the lowest unoccupied molecular orbital (LUMO) energy of the PDC is -3.26 eV, the LUMO energy of the COOCH 3 group substituent is -3.04 eV, and the LUMO energy of the COOC 2 H 5 group substituent is -2.98 eV, CN group The LUMO energy of the substitution product was -3.90 eV, and it was confirmed that the CN group substitution product had the highest electron affinity and high acceptor properties.
＜実施例９＞電子供与性分子としてのピレン誘導体
（１）ピレン誘導体
１,３-ＤＡＰ、１,６-ＤＡＰ、１,８-ＤＡＰは、市販のものを使用した（東京化成工業株式会社製）。また、以下の条件で、１,３,６,８−テトラアミノピレン（ＴＡＰ）を合成した。１,３,６,８−テトラアミノピレン（ＴＡＰ）は、１Ｈ-ＮＭＲでそのピークを確認した。
<Example 9> Pyrene derivatives as electron donating molecules (1) Pyrene derivatives 1,3-DAP, 1,6-DAP and 1,8-DAP were commercially available (manufactured by Tokyo Chemical Industry Co., Ltd.). ). Moreover, 1,3,6,8-tetraaminopyrene (TAP) was synthesized under the following conditions. The peak of 1,3,6,8-tetraaminopyrene (TAP) was confirmed by 1H-NMR.
（２）電子供与性
１,３-ＤＡＰ、１,６-ＤＡＰ、１,８-ＤＡＰおよびＴＡＰについて、酸化電位をサイクリックボルタンメトリー測定を行い、電子供与性の評価を行った。（ALS/「H」CH Instruments社製, Electrochemical Analyser Model600C、支持電解質としてテトラフルオロ硼酸テトラブシルアンモニウムを使用した。）その結果、1,3-DAPの第一酸化電位は0.3875 V(vs.Aｇ/AgCl）、1,6-DAPの第一酸化電位は0.3753 V(vs.Ag/AgCl), 1,8-DAPの第一酸化電位は0.3790V(vs.Ag/AgCl)であり、１,６-ＤＡＰが最も強い電子供与性を有していることが確認された。
(2) Electron donating properties The 1,3-DAP, 1,6-DAP, 1,8-DAP and TAP were subjected to cyclic voltammetry measurement of the oxidation potential, and the electron donating property was evaluated. (ALS / "H" manufactured by CH Instruments, Electrochemical Analyzer Model 600C, tetrabusylammonium tetrafluoroborate was used as the supporting electrolyte.) As a result, the primary oxidation potential of 1,3-DAP was 0.3875 V (vs. Ag / AgCl), 1,6-DAP has a first oxidation potential of 0.3753 V (vs. Ag / AgCl), 1,8-DAP has a first oxidation potential of 0.3790 V (vs. Ag / AgCl), It was confirmed that 6-DAP has the strongest electron donating property.
（３）ＳＥＭ観察
PDC とピレン誘導体との電荷移動錯体の合成は H 管を用いた拡散法により行った。溶媒としてCH3OC6H5 とCH3CNを9:1(重量比)で混合したものを用いた。具体的な合成条件を表２に示す。
(3) SEM observation
The charge transfer complex of PDC and pyrene derivative was synthesized by diffusion method using H tube. As a solvent, a mixture of CH 3 OC 6 H 5 and CH 3 CN at 9: 1 (weight ratio) was used. Specific synthesis conditions are shown in Table 2.
この１,３-ＤＡＰ‐ＰＤＣ、１,６-ＤＡＰ‐ＰＤＣ、１,８-ＤＡＰ‐ＰＤＣおよびＴＡＰ‐ＰＤＣについてＳＥＭで観察した結果を図１０に示す。TAP-PDC錯体および1,3-DAP-PDC錯体のSEM像には粒子状の錯体結晶が、1,6-DAP-PDC錯体のSEM像には繊維状の錯体結晶が確認された。 FIG. 10 shows the results of observation of the 1,3-DAP-PDC, 1,6-DAP-PDC, 1,8-DAP-PDC, and TAP-PDC by SEM. Particulate complex crystals were observed in the SEM images of the TAP-PDC complex and 1,3-DAP-PDC complex, and fibrous complex crystals were confirmed in the SEM image of the 1,6-DAP-PDC complex.
（４）磁化率（ＥＳＲ測定）
１,３-ＤＡＰ‐ＰＤＣ、１,６-ＤＡＰ‐ＰＤＣ、１,８-ＤＡＰ‐ＰＤＣおよびＴＡＰ‐ＰＤＣについて、ＥＳＲ（(Bruker社製 E-500) 9.4GHz帯(X-band)）を用いてスピン常磁性磁化率を検討した。
(4) Magnetic susceptibility (ESR measurement)
For 1,3-DAP-PDC, 1,6-DAP-PDC, 1,8-DAP-PDC and TAP-PDC, use ESR ((Bruker E-500) 9.4 GHz band (X-band)) The spin paramagnetic susceptibility was investigated.
結果を表３に示す。X0は、パウリ常磁性磁化率（emu/mol）、Ｃはキュリー定数（emu/mol・K）、θは、常磁性キュリー温度（K）を示している。 The results are shown in Table 3. X 0 is a Pauli paramagnetic susceptibility (emu / mol), C is a Curie constant (emu / mol · K), and θ is a paramagnetic Curie temperature (K).
表３に示したように、いずれの試料においてもX0の値は10-6 emu/molかそれ以下であった。 As shown in Table 3, the value of X 0 was 10 −6 emu / mol or less in any sample.
＜実施例１０＞電子供与性分子としてのベンジジン誘導体
（１）ベンジジン誘導体
３,３,’５,５’-テトラメチルベンジジン（ＴＭＢ）および３,３’-ジメチルベンジジン（ＤＭＢ）は、電解法で得たものを使用した。
<Example 10> Benzidine derivatives as electron donating molecules (1) Benzidine derivatives 3,3, '5,5'-tetramethylbenzidine (TMB) and 3,3'-dimethylbenzidine (DMB) What was obtained was used.
具体的には、ＴＭＢもしくはＤＭＢおよびＰＤＣのＴＢＡ塩(TBA(PDC))を表４に示す条件でAnisoleとCH3CN混合溶媒に溶かし、窒素雰囲気下で、白金電極を入れた状態で封管し、暗所にて1.0 μAの電流を３日間流すことにより錯体の作成を行った。 Specifically, TMB salt of TMB or DMB and PDC (TBA (PDC)) was dissolved in Anisole and CH 3 CN mixed solvent under the conditions shown in Table 4, and sealed with a platinum electrode in a nitrogen atmosphere. Then, a complex was prepared by passing a current of 1.0 μA for 3 days in the dark.
（２）電子供与性（ＣＶ測定）
ＴＭＢおよびＤＭＢについて、酸化電位をサイクリックボルタンメトリー測定を行い、電子供与性を検討した。（ALS/「H」CH Instruments社製, Electrochemical Analyser Model600C）、支持電解質としてテトラフルオロ硼酸テトラブシルアンモニウムを使用した。）
その結果、ＴＭＢの第一酸化電位は、0.547 V(vs.Ag/AgCl)であり、ＤＭＢの第一酸化電位は、0.604 V(vs.Ag/AgCl)であり、ＴＭＢの方が強い電子供与性を有していることが確認された。
(2) Electron donating property (CV measurement)
For TMB and DMB, the oxidation potential was measured by cyclic voltammetry, and the electron donating property was examined. (ALS / “H” manufactured by CH Instruments, Electrochemical Analyzer Model 600C), tetrabucil ammonium tetrafluoroborate was used as the supporting electrolyte. )
As a result, the first oxidation potential of TMB is 0.547 V (vs. Ag / AgCl), the first oxidation potential of DMB is 0.604 V (vs. Ag / AgCl), and TMB has a stronger electron donation. It was confirmed that it has sex.
（３）磁化率（ＥＳＲ測定）
電解法によって作成したＴＭＢ-ＰＤＣおよびＤＭＢ-ＰＤＣをＳＥＭ観察したところ、板状の結晶が確認された。
(3) Magnetic susceptibility (ESR measurement)
SEM observation of TMB-PDC and DMB-PDC prepared by the electrolytic method confirmed plate-like crystals.
このＴＭＢ-ＰＤＣおよびＤＭＢ-ＰＤＣについて、ＥＳＲ（(Bruker社製 E-500) 9.4GHz帯(X-band)）を用いてスピン常磁性磁化率を検討した。 About this TMB-PDC and DMB-PDC, spin paramagnetic susceptibility was examined using ESR ((Bruker E-500) 9.4 GHz band (X-band)).
結果を表５に示す。X0は、パウリ常磁性磁化率（emu/mol）、Ｃはキュリー定数（emu/mol・K）、θは、常磁性キュリー温度（K）を示している。 The results are shown in Table 5. X 0 is a Pauli paramagnetic susceptibility (emu / mol), C is a Curie constant (emu / mol · K), and θ is a paramagnetic Curie temperature (K).
表５に示したように、ＴＭＢ-ＰＤＣはＤＭＢ-ＰＤＣよりもパウリ常磁性磁化率が高く、いずれの試料においても10-6 emu/molのオーダーであることが確認された。 As shown in Table 5, it was confirmed that TMB-PDC has a higher Pauli paramagnetic susceptibility than DMB-PDC and is in the order of 10 −6 emu / mol in any sample.
（４）電解法と拡散法の比較
電解法で作製したＴＭＢと拡散法で作製したＴＭＢについて、ＰＤＣとの錯体を作成し、磁化率（ＥＳＲ測定）を比較した。
(4) Comparison of electrolysis method and diffusion method For TMB produced by the electrolysis method and TMB produced by the diffusion method, complexes with PDC were prepared and the magnetic susceptibility (ESR measurement) was compared.
拡散法においては、AnisoleとCH3CNの混合溶媒(体積比3:1)にＴＭＢおよびＰＤＣを溶かし、Ｈ管に窒素雰囲気下で封管後、暗所にて静置することにより錯体の作成を行った。電解法においては、ＴＭＢおよびＰＤＣのＴＢＡ塩(TBA(PDC))を表６に示す条件でAnisoleとCH3CN混合溶媒に溶かし、窒素雰囲気下で、白金電極を入れた状態で封管し、暗所にて1.0 μAの電流を３日間流すことにより錯体の作成を行った。 In the diffusion method, TMB and PDC are dissolved in a mixed solvent of Anisole and CH 3 CN (volume ratio 3: 1), sealed in an H tube under a nitrogen atmosphere, and then left in a dark place to form a complex. Went. In the electrolytic method, TBA salts of TMB and PDC (TBA (PDC)) were dissolved in a mixed solvent of Anisole and CH 3 CN under the conditions shown in Table 6, and sealed with a platinum electrode in a nitrogen atmosphere, The complex was prepared by passing a current of 1.0 μA for 3 days in the dark.
得られた錯体の磁化率の測定は上記（３）に準じて行った。 The measurement of the magnetic susceptibility of the obtained complex was performed according to the above (3).
結果を表７に示す。 The results are shown in Table 7.
表７に示したように、電解法ＴＭＢ-ＰＤＣは、拡散法ＴＭＢ-ＰＤＣよりもパウリ常磁性磁化率が高く、有機電荷移動錯体としての有用性により優れていることが確認された。 As shown in Table 7, it was confirmed that the electrolytic method TMB-PDC has a higher Pauli paramagnetic susceptibility than the diffusion method TMB-PDC, and is superior in usefulness as an organic charge transfer complex.
＜実施例１１＞電気抵抗の評価
実施例９と同様の方法によって作製した１,３-ＤＡＰ‐ＰＤＣ、１,６-ＤＡＰ‐ＰＤＣ、１,８-ＤＡＰ‐ＰＤＣと、実施例１０と同様の方法によって作製したＴＭＢ-ＰＤＣ、ＤＭＢ-ＰＤＣについて、めのう乳鉢による粉砕により粉末状にし、この粉末をプレス加工することによりペレット状に成形した。
<Example 11> Evaluation of electrical resistance 1,3-DAP-PDC, 1,6-DAP-PDC, 1,8-DAP-PDC produced by the same method as in Example 9 and the same as in Example 10 The TMB-PDC and DMB-PDC produced by the method were pulverized with an agate mortar and formed into a pellet by pressing.
この１,３-ＤＡＰ‐ＰＤＣ、１,６-ＤＡＰ‐ＰＤＣ、１,８-ＤＡＰ‐ＰＤＣ、ＴＭＢ-ＰＤＣおよびＤＭＢ-ＰＤＣのペレット状試料について、２端子法により電気抵抗率（室温）を測定した（使用機器：Keithley社製2001 MultimeterおよびAdvantest社製R8340A Ultra High resistance Meter）。 Measure the electrical resistivity (room temperature) of this 1,3-DAP-PDC, 1,6-DAP-PDC, 1,8-DAP-PDC, TMB-PDC and DMB-PDC pellets by the two-terminal method (Equipment used: Keithley 2001 Multimeter and Advantest R8340A Ultra High resistance Meter).
その結果、１,３-ＤＡＰ‐ＰＤＣは3.8×105Ωｍであり、１,６-ＤＡＰ‐ＰＤＣは1.9×103Ωｍであり、１,８-ＤＡＰ‐ＰＤＣは3.4×105Ωｍであり、ＴＭＢ-ＰＤＣは400Ωｍであり、ＤＭＢ-ＰＤＣは19.5Ωｍであった。 As a result, 1,3-DAP-PDC is 3.8 × 10 5 Ωm, 1,6-DAP-PDC is 1.9 × 10 3 Ωm, and 1,8-DAP-PDC is 3.4 × 10 5 Ωm. , TMB-PDC was 400 Ωm, and DMB-PDC was 19.5 Ωm.
以上の結果から、これらの錯体は電気伝導性を有することが確認された。 From the above results, it was confirmed that these complexes have electrical conductivity.
Claims (10)
電子受容性分子が、２−ピロン−４，６−ジカルボン酸（2-pyrone-4,6-dicarboxylic acid；ＰＤＣ）またはＰＤＣ誘導体であり、
ＰＤＣ誘導体は、ＰＤＣのカルボキシル基をモノエステル、ジエステル、モノアミド、ジアミド、モノニトリル、ジニトリル、モノアミン、ジアミン、モノケトン、ジケトン、モノ酸塩化物、ジ酸塩化物に置換した置換体のうちの１種または２種以上であり、
電子供与性分子が、下記一般式（１）で表される化合物、
または、下記一般式（２）で表されるアミノピレン、
または、下記一般式（３）で表される化合物、
であることを特徴とする有機電荷移動錯体。 An organic charge transfer complex comprising an electron accepting molecule and an electron donating molecule,
The electron accepting molecule is 2-pyrone-4,6-dicarboxylic acid (PDC) or a PDC derivative;
The PDC derivative is one of the substituents in which the carboxyl group of PDC is replaced with a monoester, diester, monoamide, diamide, mononitrile, dinitrile, monoamine, diamine, monoketone, diketone, monoacid chloride, or diacid chloride. Or two or more,
A compound represented by the following general formula (1):
Or aminopyrene represented by the following general formula (2),
Or a compound represented by the following general formula (3),
An organic charge transfer complex characterized in that
ＰＤＣ誘導体は、ＰＤＣのカルボキシル基をモノエステル、ジエステル、モノアミド、ジアミド、モノニトリル、ジニトリル、モノアミン、ジアミン、モノケトン、ジケトン、モノ酸塩化物、ジ酸塩化物に置換した置換体のうちの１種または２種以上であり、
電子供与性分子が、下記一般式（１）で表される化合物、
または、下記一般式（２）で表されるアミノピレン、
または、下記一般式（３）で表される化合物、
であることを特徴とする有機電荷移動錯体結晶の製造方法。 A PDC solution in which 2-pyrone-4,6-dicarboxylic acid (PDC) or a PDC derivative is dissolved in an organic solvent, and an electron donating property in which an electron-donating molecule is dissolved in the organic solvent was added dropwise a molecular solution in the crystal growth vessel, a manufacturing method of an organic charge transfer complex crystal by diffusion method you stand,
The PDC derivative is one of the substituents in which the carboxyl group of PDC is replaced with a monoester, diester, monoamide, diamide, mononitrile, dinitrile, monoamine, diamine, monoketone, diketone, monoacid chloride, or diacid chloride. Or two or more,
A compound represented by the following general formula (1):
Or aminopyrene represented by the following general formula (2),
Or a compound represented by the following general formula (3),
A method for producing an organic charge transfer complex crystal, characterized in that
ＰＤＣ誘導体は、ＰＤＣのカルボキシル基をモノエステル、ジエステル、モノアミド、ジアミド、モノニトリル、ジニトリル、モノアミン、ジアミン、モノケトン、ジケトン、モノ酸塩化物、ジ酸塩化物に置換した置換体のうちの１種または２種以上であり、
電子供与性分子が、下記一般式（１）で表される化合物、
または、下記一般式（２）で表されるアミノピレン、
または、下記一般式（３）で表される化合物、
であることを特徴とする有機電荷移動錯体結晶の製造方法。 A PDC solution in which 2-pyrone-4,6-dicarboxylic acid (PDC) or a PDC derivative is dissolved in an organic solvent, and an electron donating property in which an electron-donating molecule is dissolved in the organic solvent mixing a molecular solution was added dropwise into a vessel containing the poor solvent, the liquid you standing - a method for producing an organic charge transfer complex crystal by liquid interface crystal deposition method,
The PDC derivative is one of the substituents in which the carboxyl group of PDC is replaced with a monoester, diester, monoamide, diamide, mononitrile, dinitrile, monoamine, diamine, monoketone, diketone, monoacid chloride, or diacid chloride. Or two or more,
A compound represented by the following general formula (1):
Or aminopyrene represented by the following general formula (2),
Or a compound represented by the following general formula (3),
A method for producing an organic charge transfer complex crystal, characterized in that
ＰＤＣ誘導体は、ＰＤＣのカルボキシル基をモノエステル、ジエステル、モノアミド、ジアミド、モノニトリル、ジニトリル、モノアミン、ジアミン、モノケトン、ジケトン、モノ酸塩化物、ジ酸塩化物に置換した置換体のうちの１種または２種以上であり、
電子供与性分子が、下記一般式（１）で表される化合物、
または、下記一般式（２）で表されるアミノピレン、
または、下記一般式（３）で表される化合物、
であることを特徴とする有機電荷移動錯体結晶の製造方法。 A PDC solution in which 2-pyrone-4,6-dicarboxylic acid (PDC) or a PDC derivative is dissolved in an organic solvent, and an electron donating property in which an electron-donating molecule is dissolved in the organic solvent mixing a molecular solution, a manufacturing method of an organic charge transfer complex crystal by reprecipitation you injected into a vessel containing the poor solvent,
The PDC derivative is one of the substituents in which the carboxyl group of PDC is replaced with a monoester, diester, monoamide, diamide, mononitrile, dinitrile, monoamine, diamine, monoketone, diketone, monoacid chloride, or diacid chloride. Or two or more,
A compound represented by the following general formula (1):
Or aminopyrene represented by the following general formula (2),
Or a compound represented by the following general formula (3),
A method for producing an organic charge transfer complex crystal, characterized in that
ＰＤＣ誘導体は、ＰＤＣのカルボキシル基をモノエステル、ジエステル、モノアミド、ジアミド、モノニトリル、ジニトリル、モノアミン、ジアミン、モノケトン、ジケトン、モノ酸塩化物、ジ酸塩化物に置換した置換体のうちの１種または２種以上であり、
電子供与性分子が、下記一般式（１）で表される化合物、
または、下記一般式（２）で表されるアミノピレン、
または、下記一般式（３）で表される化合物、
であることを特徴とする有機電荷移動錯体結晶の製造方法。 A solution obtained by dissolving a supporting electrolyte containing 2-pyrone-4,6-dicarboxylic acid (PDC) or a PDC derivative and an electron-donating molecule in an organic solvent is an electrolytic cell. It was added to a manufacturing method of an organic charge transfer complex crystal according to that conductive solution to electrolysis,
The PDC derivative is one of the substituents in which the carboxyl group of PDC is replaced with a monoester, diester, monoamide, diamide, mononitrile, dinitrile, monoamine, diamine, monoketone, diketone, monoacid chloride, or diacid chloride. Or two or more,
A compound represented by the following general formula (1):
Or aminopyrene represented by the following general formula (2),
Or a compound represented by the following general formula (3),
A method for producing an organic charge transfer complex crystal, characterized in that
A solution obtained by dissolving a supporting electrolyte containing PDC or a PDC derivative and an electron-donating molecule in an organic solvent was added to the electrolytic cell, and the electrolytic cell was sealed in a nitrogen gas atmosphere, manufacturing method of organic charge-transfer complex crystal thin film according to claim 8, wherein flowing a constant current of 200 .mu.A 2 to 10 hours.
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