JP7133750B2 - Iodine-containing condensed ring compound and organic electronic material using iodine-containing condensed ring compound - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Law The 97th Chemical Society of Japan Annual Meeting (2017) (Announcement date: March 18, 2017)

Application of Article 30, Paragraph 2 of the Patent Law Proceedings of the 97th Annual Meeting of the Chemical Society of Japan (3C5-31) (Publication date: March 3, 2017)

TECHNICAL FIELD The present invention relates to novel iodine-containing condensed ring compounds for organic thin film transistors and organic electronic materials using the same.

Organic electronic materials with various electrical properties ranging from semiconductors to conductors are used in flexible displays, multifunctional switches, multifunctional sensors, organic solar cells, organic electrodes, and other thin and flexible electronic devices (all-organic materials) using organic compounds. It plays a central role in molecular electronics because it directly leads to the realization of electronics). In particular, research on thin film transistors using conductive materials and organic semiconductors has attracted a great deal of attention.

The original attraction of organic compounds is the fabrication of large-area devices by wet processes such as the inkjet method, and further development of materials exhibiting high solubility and high performance is desired. In order to achieve high performance, a high-order molecular arrangement is required in the crystalline thin film of the active layer. It's here. However, there is a trade-off relationship between the expansion of the π-electron system and the solubility, which is a major obstacle in wet processes.

Under such circumstances, in recent years, attention has been paid to the asymmetry of the molecular skeleton to obtain high solubility, and soluble organic semiconductor materials in which an alkyl group is introduced at one end of the molecule have been reported (Non-Patent Documents 1 to 4). However, it is difficult to control the orientation with alkyl groups, and there are still many unclear points about the interactions in molecular orientation, and they often do not provide clear superiority in semiconductor properties (Non-Patent Documents 5 and 6). Therefore, there is a demand for elucidation of a clear mechanism for achieving compatibility between molecular solubility and orientation, and a design concept for a new group of materials based on this mechanism.

Bao, C.; Yan, D.; Geng, Y.; Wang, F. Chem. Commun. 2012, 48 (29), 3557. Iino, H.; Kobori, T.; Hanna, J.-I. Jpn. J. Appl. Phys. 2012, 51 (11S), 11PD02. Iino, H.; Usui, T.; Hanna, J.-I. Nature Communications 2015, 6, 1. Ogawa, Y.; Yamamoto, K.; Miura, C.; Tamura, S.; Saito, M.; , 9 (11), 9902. Sawamoto, M.; Kang, M. J.; Miyazaki, E.; Sugino, H.; Osaka, I.; Takimiya, K. ACS Appl. Tang, M. L.; Reichardt, A. D.; Okamoto, T.; Miyaki, N.; Bao, Z. Adv. Pitayatanakul, O.; Iijima, K.; Ashizawa, M.; Kawamoto, T.; Matsumoto, H.;

The present invention has been made in view of the above circumstances, and its object is to provide an asymmetric extended π-conjugated condensed ring compound that exhibits high solubility and high performance as an organic electronic material used in organic thin-film transistors and the like. to do.

一般式（１）中、ｎは１～３の整数である。
本発明の含ヨウ素縮合環化合物は、下記一般式（２）で表されることを特徴とする。

一般式（２）中、ｎは１～３の整数であり、Ｙは一般式（ｓ１）～（ｓ７）に示される置換基である。

本発明の有機電子材料は、上記含ヨウ素縮合環化合物を用いたものであることを特徴とする。
上記含ヨウ素縮合環化合物は、分子同士が同方向に整然と配列したヘリンボーン（herringbone）構造を有するため、薄膜状態での高い分子配向性を実現し、高い半導体性能を有する。さらに、上記含ヨウ素縮合環化合物は、有機溶媒への高溶解性を維持しているため、有機薄膜トランジスタ等に用いる有機半導体材料として好適である。 The iodine-containing condensed ring compound of the present invention is characterized by being represented by the following general formula (1).

In general formula (1), n is an integer of 1-3.
The iodine-containing condensed ring compound of the present invention is characterized by being represented by the following general formula (2).

In general formula (2), n is an integer of 1 to 3, and Y is a substituent represented by general formulas (s1) to (s7).

The organic electronic material of the present invention is characterized by using the above iodine-containing condensed ring compound.
Since the iodine-containing condensed ring compound has a herringbone structure in which the molecules are arranged orderly in the same direction, it achieves high molecular orientation in a thin film state and has high semiconductor performance. Furthermore, since the iodine-containing condensed ring compound maintains high solubility in organic solvents, it is suitable as an organic semiconductor material for use in organic thin-film transistors and the like.

In the iodine-containing condensed ring compound of the present invention, the acene skeleton containing an iodine atom exhibits high solubility and high molecular orientation, so devices can be produced by a solution process.
Therefore, the iodine-containing condensed ring compound exhibits excellent performance as an organic conductive material or an organic semiconductor material for an organic thin film transistor.

FIG. 1 is a drawing showing a state of forming a film of an iodine-containing condensed ring compound by a drop casting method. FIG. 2 shows UV-vis absorption spectra (FIG. 2(a)) and cyclic voltammograms (FIG. 2(b)) of ATT and I-ATT in the form of chloroform solution and thin film, respectively. FIG. 3 is a diagram showing the result of X-ray structural analysis of single crystals of ATT and I-ATT that iodine atoms contribute to the improvement of molecular orientation in I-ATT as compared to ATT. FIG. 4 is a diagram showing the results of evaluating the FET characteristics of devices fabricated from I-ATT by the drop casting method. FIG. 4(a) represents transfer characteristics, and FIG. 4(b) represents output characteristics. FIG. 5 is a diagram showing the evaluation of the crystal structure of the thin film by AFM (atomic force microscope) and XRD (X-ray diffraction) obtained by forming a film of I-ATT by the drop casting method. The lower left panel shows the AFM height profile and the lower right panel shows the single crystal structure. FIG. 6(a) shows the Id-Vg characteristics of I-TNTT, and FIG. 6(b) shows the XRD measurement results. FIG. 7(a) represents the Id-Vg characteristics of I-TATT, and FIG. 7(b) represents the XRD measurement results.

また、上記含ヨウ素縮合環化合物は、下記一般式（２）で表される。

ただし、一般式（１）及び（２）中、ｎは１～３の整数であり、Ｙは下記一般式（ｓ１）～（ｓ７）に示される置換基である）。

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The iodine-containing condensed ring compound of the present invention is represented by the following general formula (1).

Further, the iodine-containing condensed ring compound is represented by the following general formula (2).

However, in general formulas (1) and (2), n is an integer of 1 to 3, and Y is a substituent represented by the following general formulas (s1) to (s7)).

さらに、高い溶解性及び高い分子配向性を有する観点で、Ｉ－ＡＴＴ、Ｉ－ＴＮＴＴが特に好ましい。 That is, the iodine-containing condensed ring compound has a condensed ring skeleton with 4 to 6 condensed rings. Among these, the following compounds are more preferable as the iodine-containing condensed ring compound.

Furthermore, I-ATT and I-TNTT are particularly preferred from the viewpoint of having high solubility and high molecular orientation.

The iodine-containing condensed ring compound can be synthesized, for example, by the method shown below. As an example, a method for synthesizing I-ATT is shown.

In an inert gas atmosphere, anthracenothieno[3,2-b]thiophene (ATT) is dissolved in a solvent such as THF, and n-butyllithium is added for lithiation, after which iodine is added and stirred. After quenching, concentration and purification yield a yellow solid of I-ATT in 77% yield.

ATT is capable of selective lithiation of the terminal thienothiophene site, and it is also possible to introduce a thiophene skeleton having an iodine atom using Stille coupling reaction after tination.
The iodine-containing condensed ring compound of the present invention is not limited to the method described above, and can be synthesized by various methods.

It has already been found that the acene skeleton constituting the iodine-containing condensed ring compound of the present invention has high solubility. For example, ATT exhibits a solubility of 1.9 g/L in hot chloroform, and the α-position (position adjacent to the sulfur atom) of the terminal thienothiophene moiety of ATT is substituted with a 2-octylthiophen-5-yl group. The compound presented exhibits a solubility of 3.8 g/L in hot chloroform (55° C.).
A molecule having an acene skeleton containing an iodine atom, such as the iodine-containing condensed ring compound of the present invention, exhibits high solubility in various solvents such as chloroform, toluene and tetrahydrofuran.

In addition, the iodine-containing condensed ring compound exhibits high molecular orientation. Iodine-unsubstituted ATT takes an alternate slip-stack type (Non-Patent Document 4), whereas iodine-containing ATT, that is, I-ATT, has a herringbone structure in which molecules are orderly arranged in the same direction. Form. As a result, I-ATT achieves high molecular orientation in a thin film state and exhibits excellent properties as an organic transistor material.

A symmetrical iodine-containing organic conductive material in which iodine atoms are introduced into the indigo skeleton has been reported (Non-Patent Document 7). , and because of its symmetrical structure, it has poor solubility and is limited to device fabrication by a vapor deposition process.

The iodine-containing condensed ring compound exhibits high solubility that enables solution processing, high molecular orientation in a thin film state, and transistor characteristics. For example, a top-contact field effect transistor (FET) using an I-ATT thin film formed by the drop casting method has a mobility (μ _FET ) of 0.9 cm ² /Vs and exhibits high p-type characteristics. Thin film X-ray diffraction (XRD) results show that I-ATT is edge-on oriented perpendicular to the substrate and forms a herringbone structure. Further, as a result of single-crystal X-ray structure analysis, it can be confirmed that there is a clear iodine-iodine interaction between the layers of I-ATT. A large transfer integral (12 to 64 meV on average) was obtained between I-ATT2 molecules, confirming interaction between iodine atoms. That is, as shown in FIG. 3, iodine-iodine interactions contribute to the highly ordered structure of I-ATT.

Here, the drop casting method is a representative wet process like the spin coating method. Since the film is formed over a long period of time by slowly evaporating the solvent, a film having excellent crystallinity can be formed as compared with the spin coating method. In the case of a top-contact FET, it is formed on the gate insulating film, and in the case of a bottom-contact FET, it is formed on the gate insulating film and the substrate on which the source electrode and the drain electrode are formed. FIG. 1 is a diagram showing how a film is formed by a drop casting method in such a device. The type and surface state of the insulating film material, the surface state of the substrate on which the organic semiconductor layer is formed, and the materials of the source electrode and the drain electrode may vary.
On the other hand, when ATT without iodine substitution is used, the FET device formed by the drop casting method does not exhibit transistor characteristics, and the molecular orientation in the thin film state is also low.

EXAMPLES The present invention will be more specifically described below based on examples, but the present invention is not limited to the following examples.

窒素雰囲気下、２００ｍＬ三口フラスコにＡＴＴ ４００ｍｇを入れ、ＴＨＦ １００ｍＬに溶解し、氷浴で０℃とした後、ｎ-ブチルリチウムを２ｍＬ加えて３０分間攪拌した。その後、ヨウ素を１．７４ｇ加え，室温で１２時間攪拌した。飽和亜硫酸ナトリウム水溶液１００ｍＬ加え、さらに３０分間攪拌した。ＴＨＦ層を分液し、ロータリーエバポレーターで濃縮し、析出した固体を吸引濾過によって得た。これをカラムクロマトグラフィー（充填剤；中性シリカゲル、溶離液：ジクロロメタン）を行い、黄色固体（Ｉ－ＡＴＴ）を４４０ｍｇ（収率７７％）得た。
得られたＩ－ＡＴＴの¹ＨＮＭＲ（日本電子（株）製（５００ＭＨｚ）ＪＮＭ－ＥＣＸ型）の結果を以下に示す。
¹ＨＮＭＲ（ＣＤＣｌ₃，５００ＭＨｚ）δ８．５９（ｓ，１Ｈ），８．４９（ｓ，１Ｈ），８．４５（ｓ，１Ｈ），８．４０（ｓ，１Ｈ），８．０３－８．０２（ｍ，２Ｈ），７．４７－７．４６（ｍ，３Ｈ）． [Example 1] Synthesis of I-ATT

Under a nitrogen atmosphere, 400 mg of ATT was placed in a 200 mL three-necked flask, dissolved in 100 mL of THF, cooled to 0° C. in an ice bath, 2 mL of n-butyllithium was added, and the mixture was stirred for 30 minutes. After that, 1.74 g of iodine was added and stirred at room temperature for 12 hours. 100 mL of a saturated sodium sulfite aqueous solution was added, and the mixture was further stirred for 30 minutes. The THF layer was separated, concentrated with a rotary evaporator, and the precipitated solid was obtained by suction filtration. This was subjected to column chromatography (filler: neutral silica gel, eluent: dichloromethane) to obtain 440 mg of yellow solid (I-ATT) (yield 77%).
The results of ¹ HNMR (JNM-ECX type (500 MHz) manufactured by JEOL Ltd.) of the obtained I-ATT are shown below.
¹ H NMR (CDCl ₃ , 500 MHz) δ 8.59 (s, 1H), 8.49 (s, 1H), 8.45 (s, 1H), 8.40 (s, 1H), 8.03-8. 02 (m, 2H), 7.47-7.46 (m, 3H).

[Example 2]
A 1.0×10 ⁻⁵ M solution of I-ATT obtained in Example 1 and iodine-unsubstituted ATT dissolved in chloroform, and a thin film cast from this solution were subjected to ultraviolet/visible (UV- vis) An absorption spectrum (UV-3150 manufactured by Shimadzu Corporation) was measured.
Further, to each of I-ATT and ATT, dichloromethane (6 mL), ferrocene (1.0 mg) and tetrabutylammonium tetrafluoroborate (170 mg) were added to prepare a 0.5 mM sample solution, and placed in a glove box. , under nitrogen, cyclic voltammetry (CV) (ALS 660B model electrochemical analyzer (BAS Co., Ltd.) was measured.
FIG. 2 shows the UV-vis absorption spectrum and CV measurement results.
From the absorption spectrum and oxidation potential, it is found that I-ATT forms an aggregate having stronger intermolecular interaction and is electrochemically more stable than ATT. Therefore, in I-ATT, the orientation and stability are clearly improved by the introduction of iodine atoms.

[Example 3]
Single crystal X-ray structure analysis (Saturn-724 manufactured by Rigaku Co., Ltd.) was performed for each of I-ATT and ATT.
As shown in FIG. 3, I-ATT exhibited intermolecular iodine-iodine interactions in single crystals. Since the iodine-unsubstituted ATT has an antiparallel orientation, the contribution of the iodine atoms to the orientation is clear.

[Example 4]
FET characteristics were evaluated for each of I-ATT and ATT.
I-ATT exhibited p-type semiconductor characteristics with a mobility of 0.9 cm ² /Vs when the device was fabricated by the drop casting method. I-ATT showed an ionization potential of -5.51 eV, and ATT showed an ionization potential of -5.30 eV, indicating an improvement in stability due to the introduction of iodine atoms. The results are shown in FIG.
On the other hand, ATT did not exhibit semiconductor characteristics in the solution method. Therefore, mono-iodination of asymmetric molecules has a clear advantage in device fabrication using the solution method.

[Example 5]
I-ATT and ATT were each formed by a drop casting method, and the crystal structure of the thin film was examined by AFM (Atomic Force Microscope) (Dimension Icon manufactured by Bruker) and XRD (X-ray diffraction) (SMART manufactured by Rigaku Co., Ltd.). Lab).
The results are shown in FIG.
I-ATT maintains the molecular orientation in the single crystal in the thin film structure. From this fact, the superiority in the production of crystalline thin films by the solution method of monoiodination is clear.
An enlarged view of ab in the AFM image is shown between the AFM image and the XRD chart. The distance ab is 300 nm, and the shading of the color in the enlarged view represents the unevenness.

窒素雰囲気下、２００ｍＬ三口フラスコにＮＴＴ ５００ｍｇを入れ、ＴＨＦ１３０ｍＬに溶解し、氷浴で０℃とした後、ｎ－ブチルリチウムを３．９ｍL加えて３０分撹拌した。その後、塩化トリメチルスズ１．２４ｇを加え、室温で１時間撹拌した。水５００ｍＬに加え室温で３０分間撹拌した。これを濾過により白色固体７６８ｍｇ（収率９１％）を得た。
得られたＳｎ－ＮＴＴの¹ＨＮＭＲ（日本電子（株）製（５００ＭＨｚ）ＪＮＭ－ＥＣＸ型）の結果を以下に示す。
¹ＨＮＭＲ（ＣＤＣｌ₃，５００ＭＨｚ）δ（ｐｐｍ）８．２９（ｓ，２Ｈ），７．９９－７．９７（ｍ，１Ｈ），７．９０－７．８８（ｍ，１Ｈ），７．４９－７．４７（ｍ，２Ｈ），７．５３（ｓ，１Ｈ），０．４６１（ｓ，９Ｈ），
ＨＲＭＳ（ＦＤ⁺）ｃａｌｃｄ ｆｏｒ Ｃ₁₇Ｈ₁₆Ｓ₂Ｓｎ（Ｍ⁺）ｍ／ｚ＝４０３．９７１５２、ｆｏｕｎｄ ４０３．９７０９８． [Example 6] Synthesis of I-TNTT (i) Synthesis of Sn-NTT

Under a nitrogen atmosphere, 500 mg of NTT was placed in a 200 mL three-necked flask, dissolved in 130 mL of THF, cooled to 0° C. in an ice bath, 3.9 mL of n-butyllithium was added, and the mixture was stirred for 30 minutes. After that, 1.24 g of trimethyltin chloride was added and stirred at room temperature for 1 hour. It was added to 500 mL of water and stirred at room temperature for 30 minutes. This was filtered to obtain 768 mg of white solid (yield 91%).
The results of ¹ HNMR (JNM-ECX type (500 MHz) manufactured by JEOL Ltd.) of the obtained Sn-NTT are shown below.
¹ H NMR (CDCl ₃ , 500 MHz) δ (ppm) 8.29 (s, 2H), 7.99-7.97 (m, 1H), 7.90-7.88 (m, 1H), 7.49 −7.47 (m, 2H), 7.53 (s, 1H), 0.461 (s, 9H),
HRMS (FD ⁺ )calcd for _C17H16S2Sn ^(M+ ₎ m/z = _403.97152 , found 403.97098.

窒素雰囲気下、３００ｍＬ三口フラスコにＳｎ－ＮＴＴ ６００ｍｇを入れ、トルエン２２０ｍＬに溶解させ、２－ブロモチオフェン６４７ｍｇ、テトラキス（トリフェニルホスフィン）パラジウム（０）１５３ｍｇを加え１３０℃で還流し、４時間撹拌した。その後、ロータリーエバポレーターで濃縮し、シリカゲルカラムクロマトグラフィー（ジクロロメタン）により黄色固体ＴＮＴＴ４０８ｍｇ（収率８５％）を得た。
得られたＴＮＴＴの^１ＨＮＭＲ（日本電子（株）製（５００ＭＨｚ）ＪＮＭ－ＥＣＸ型）の結果を以下に示す。
¹ＨＮＭＲ（ＣＤＣｌ₃，５００ＭＨｚ）δ（ｐｐｍ）８．２９（ｓ，１Ｈ），８．２４（ｓ，１Ｈ），７．９８－７．９６（ｍ，１Ｈ），７．８９－７．８８（ｍ，１Ｈ），７．４９－７．４７（ｍ，２Ｈ），７．４０（ｓ，１Ｈ），７．３０－７．２８（ｍ，２Ｈ），７．０８－７．０６（ｍ，１Ｈ），ＨＲＭＳ（ＦＤ⁺）ｃａｌｃｄ ｆｏｒ Ｃ₁₈Ｈ₁₀Ｓ₃（Ｍ⁺） ｍ／ｚ＝３２１．９９４４６，ｆｏｕｎｄ ３２１．９９３５６． (ii) Synthesis of TNTT

In a nitrogen atmosphere, 600 mg of Sn-NTT was placed in a 300 mL three-necked flask, dissolved in 220 mL of toluene, 647 mg of 2-bromothiophene, and 153 mg of tetrakis(triphenylphosphine)palladium (0) were added, refluxed at 130°C, and stirred for 4 hours. . Then, it was concentrated by a rotary evaporator and subjected to silica gel column chromatography (dichloromethane) to obtain 408 mg of yellow solid TNTT (yield 85%).
The results of ¹ HNMR (manufactured by JEOL Ltd. (500 MHz) JNM-ECX type) of the obtained TNTT are shown below.
¹ H NMR (CDCl ₃ , 500 MHz) δ (ppm) 8.29 (s, 1H), 8.24 (s, 1H), 7.98-7.96 (m, 1H), 7.89-7.88 (m, 1H), 7.49-7.47 (m, 2H), 7.40 (s, 1H), 7.30-7.28 (m, 2H), 7.08-7.06 (m , 1H), HRMS (FD ⁺ ) _calcd for _{C18H10S3 (} M ⁺ ) m/z = 321.99446, found 321.99356.

窒素雰囲気下において２００ｍＬ三口フラスコにＴＮＴＴ ２００ｍｇを入れ、ＴＨＦ５６ｍＬに溶解し、氷浴で０℃とした後ｎ－ブチルリチウムを１．１３ｍＬ加えて３０分撹拌した。その後、ヨウ素を４５８ｍｇ加え、室温で４時間撹拌した。５ｗｔ％亜硫酸ナトリウム１００ｍＬ加え、室温で３０分間撹拌した後、水５００ｍＬに入れ、１時間撹拌した。これを濾過により橙色固体を得た後、シリカゲルカラムクロマトグラフィー（ジクロロメタン）により褐色固体を４６．３ｍｇ（収率１１％）を得た。
得られたＩ－ＴＮＴＴの^１ＨＮＭＲ（日本電子（株）製（５００ＭＨｚ）ＪＮＭ－ＥＣＸ型）の結果を以下に示す。
¹ＨＮＭＲ（ＣＤＣｌ₃）δ（ｐｐｍ）８．３０（ｓ，１Ｈ），８．２５（ｓ，１Ｈ），７．９８－７．９６（ｍ，１Ｈ），７．９０－７．８８（ｍ，１Ｈ），７．５０－７．４８（ｍ，２Ｈ），７．３４（ｓ，１Ｈ），７．２２－７．２１（ｄ，Ｊ＝４．０Ｈｚ，２Ｈ），６．９７－６．９６（ｄ， Ｊ＝４．０Ｈｚ，１Ｈ），ＨＲＭＳ（ＦＤ⁺）ｃａｌｃｄ ｆｏｒ Ｃ₁₈Ｈ₉ＩＳ₃，（Ｍ⁺）ｍ／ｚ＝４４７．８９１１０，ｆｏｕｎｄ ４４７．８９１０７． (iii) Synthesis of I-TNTT

In a nitrogen atmosphere, 200 mg of TNTT was placed in a 200 mL three-necked flask, dissolved in 56 mL of THF, cooled to 0° C. in an ice bath, 1.13 mL of n-butyllithium was added, and the mixture was stirred for 30 minutes. After that, 458 mg of iodine was added, and the mixture was stirred at room temperature for 4 hours. After adding 100 mL of 5 wt % sodium sulfite and stirring at room temperature for 30 minutes, the mixture was poured into 500 mL of water and stirred for 1 hour. This was filtered to obtain an orange solid, and then subjected to silica gel column chromatography (dichloromethane) to obtain 46.3 mg (yield 11%) of a brown solid.
The results of ¹ HNMR (manufactured by JEOL Ltd. (500 MHz) JNM-ECX type) of the obtained I-TNTT are shown below.
¹ H NMR (CDCl ₃ ) δ (ppm) 8.30 (s, 1H), 8.25 (s, 1H), 7.98-7.96 (m, 1H), 7.90-7.88 (m , 1H), 7.50-7.48 (m, 2H), 7.34 (s, 1H), 7.22-7.21 (d, J = 4.0Hz, 2H), 6.97-6 .96 (d, J=4.0 Hz, ₁ H), HRMS (FD ⁺ )calcd for _{C18H9IS3 ,} (M ⁺ ) m/z=447.89110, found 447.89107.

窒素雰囲気下、３００ｍＬ三口フラスコにＳｎ－ＡＴＴ ４００ｍｇを入れ、トルエン１６０ｍＬに溶解させ、２－ブロモチオフェン４３０ｍｇ、テトラキス（トリフェニルホスフィン）パラジウム（０）１０２ｍｇを加え、１３０℃で還流し、４時間撹拌した。その後、０℃において１時間撹拌し、ろ過によって橙色固体ＴＡＴＴ２６２ｍｇ（収率７９％）を得た。
得られたＴＡＴＴの¹ＨＮＭＲ（日本電子（株）製（５００ＭＨｚ）ＪＮＭ－ＥＣＸ型）の結果を以下に示す。
¹ＨＮＭＲ（ＣＤＣｌ₃，５００ＭＨｚ）δ（ｐｐｍ）８．５７（ｓ，１Ｈ），８．４７（ｓ，１Ｈ），８．４４（Ｓ，１Ｈ），８．４０（ｓ，１Ｈ），８．０２－８．００（ｍ，２Ｈ），７．４５－７．４３（ｍ，２Ｈ），７．３８（ｓ，１Ｈ），７．３２－７．２９（ｍ，２Ｈ），７．０９－７．０７（ｍ，１Ｈ），ＨＲＭＳ（ＦＤ⁺）ｃａｌｃｄ ｆｏｒ Ｃ₂₂Ｈ₁₂Ｓ₃（Ｍ⁺）ｍ／ｚ＝３７２．０１０１１，ｆｏｕｎｄ ３７２．０１０２５． [Example 7] Synthesis of I-TATT (i) Synthesis of TATT

Put 400 mg of Sn-ATT in a 300 mL three-necked flask under a nitrogen atmosphere, dissolve in 160 mL of toluene, add 430 mg of 2-bromothiophene and 102 mg of tetrakis(triphenylphosphine)palladium(0), reflux at 130° C., and stir for 4 hours. did. After that, the mixture was stirred at 0° C. for 1 hour and filtered to obtain 262 mg of orange solid TATT (yield 79%).
The results of ¹ HNMR (JNM-ECX type (500 MHz) manufactured by JEOL Ltd.) of the obtained TATT are shown below.
¹ H NMR (CDCl ₃ , 500 MHz) δ (ppm) 8.57 (s, 1H), 8.47 (s, 1H), 8.44 (S, 1H), 8.40 (s, 1H), 8. 02-8.00 (m, 2H), 7.45-7.43 (m, 2H), 7.38 (s, 1H), 7.32-7.29 (m, 2H), 7.09- 7.07 (m, 1H), HRMS (FD ⁺ ) calcd for _{C22H12S3 (} M ⁺ ) m/z = _372.01011 , found 372.01025.

窒素雰囲気下において２００ｍＬ三口フラスコにＴＡＴＴ ２６０ｍｇを入れ、ＴＨＦ１００ｍＬに溶解し、氷浴で０℃とした後ｎ－ブチルリチウムを９７５μＬ加えて３０分撹拌した。その後、ヨウ素を８８０ｍｇ加え，室温で４時間撹拌した。飽和亜硫酸ナトリウム１３６ｍＬ加え室温で３０分間撹拌した後，水５００ｍＬに入れ、０℃で３０分間撹拌した。これを濾過により暗褐色固体を得た後、シリカゲルカラムクロマトグラフィー（ジクロロメタン）により褐色化合物（Ｉ－ＴＡＴＴ）を５７．１ｍｇ（１７％）得た。
得られたＩ－ＴＡＴＴの^１ＨＮＭＲ（日本電子（株）製（５００ＭＨｚ）ＪＮＭ－ＥＣＸ型）の結果を以下に示す。
¹ＨＮＭＲ（ＣＤＣｌ₃，５００ＭＨｚ）δ（ｐｐｍ）８．５８（ｓ，１Ｈ），８．４８（ｓ，１Ｈ），８．４４（ｓ，１Ｈ），８．４０（ｓ，１Ｈ），８．２０－８．００（ｍ，２Ｈ），７．４６－７．４５（ｍ，２Ｈ），７．３２（ｓ，１Ｈ），７．２３－７．２２（ｄ，Ｊ＝３．５Ｈｚ，２Ｈ），６．９９－６．９８（ｄ，Ｊ＝４．０Ｈｚ，１Ｈ），ＨＲＭＳ（ＦＤ⁺）ｃａｌｃｄ ｆｏｒ Ｃ₂₂Ｈ₁₁ＩＳ₃（Ｍ⁺）Ｍ／ｚ＝４９７．９０６７５，ｆｏｕｎｄ ４９７．９０６８５． (ii) Synthesis of I-TATT

In a nitrogen atmosphere, 260 mg of TATT was placed in a 200 mL three-necked flask, dissolved in 100 mL of THF, cooled to 0° C. in an ice bath, 975 μL of n-butyllithium was added, and the mixture was stirred for 30 minutes. After that, 880 mg of iodine was added, and the mixture was stirred at room temperature for 4 hours. After adding 136 mL of saturated sodium sulfite and stirring at room temperature for 30 minutes, the mixture was added to 500 mL of water and stirred at 0° C. for 30 minutes. After this was filtered to obtain a dark brown solid, 57.1 mg (17%) of a brown compound (I-TATT) was obtained by silica gel column chromatography (dichloromethane).
The results of ¹ H NMR (manufactured by JEOL Ltd. (500 MHz) JNM-ECX type) of the obtained I-TATT are shown below.
¹ H NMR (CDCl ₃ , 500 MHz) δ (ppm) 8.58 (s, 1H), 8.48 (s, 1H), 8.44 (s, 1H), 8.40 (s, 1H), 8. 20-8.00 (m, 2H), 7.46-7.45 (m, 2H), 7.32 (s, 1H), 7.23-7.22 (d, J=3.5Hz, 2H ), 6.99-6.98 (d, J = 4.0 Hz, 1 H), HRMS (FD ⁺ ) calcd for C ₂₂ H ₁₁ IS ₃ (M ⁺ ) M/z = 497.90675, found 497.90685 .

[Example 8]
Each of I-TNTT and I-TATT was formed into a film by a drop casting method, and the crystal structure of the thin film was evaluated by XRD (X-ray diffraction) (SMART-Lab manufactured by Rigaku Corporation). The results are shown in Figure 6b (I-TNTT) and Figure 7b (I-TATT).
The thin film structures of I-TNTT and I-TATT, like I-ATT in Example 1, had orientations favorable to charge transport. Furthermore, when the interplanar spacing was calculated from the lowest angle peak, a peak corresponding to two molecules in the long axis direction of the compound was obtained, indicating the repetition period of two molecules due to the iodine-iodine interaction.

[Example 9]
I-TNTT and I-TATT exhibited p-type semiconductor characteristics of 3.4×10 ^-5 and 0.056 cm ² /Vs, respectively, when devices were fabricated by the drop casting method. The results are shown in Figure 6a (I-TNTT) and Figure 7a (I-TATT).

窒素雰囲気下、２００ｍＬ三口フラスコにＮＴＴ ６６０ｍｇを入れ、ＴＨＦ １６０ｍＬに溶解し、氷浴で０℃とした後、ｎ－ブチルリチウムを１．７ｍＬ加えて３０分撹拌した。その後、ヨウ素３．２ｇを加え、室温で１時間撹拌した。水５００ｍＬに加え室温で３０分間撹拌した。これを濾過により白色固体を得た後、シリカゲルクロマトグラフィー（ジクロロメタン）により精製し、最後に再結晶（１，２－ジクロロエタン）によって白色固体２１３ｍｇ（収率：２３％）を得た。
得られたＩ－ＮＴＴの¹ＨＮＭＲ（日本電子（株）製（５００ＭＨｚ）ＪＥＯＬ－ＥＣＸ５００）の結果を以下に示す。
^１ＨＮＭＲ（ＣＤＣｌ₃，５００ＭＨｚ）δ（ｐｐｍ）８．２８（ｓ，１Ｈ），８．２２（ｓ，１Ｈ），７．９８－７．９６（ｍ，１Ｈ），７．８９－７．８７（ｍ，１Ｈ），７．５０－７．４８（ｍ，３Ｈ）． [Example 10]

Under a nitrogen atmosphere, 660 mg of NTT was placed in a 200 mL three-necked flask, dissolved in 160 mL of THF, cooled to 0° C. in an ice bath, 1.7 mL of n-butyllithium was added, and the mixture was stirred for 30 minutes. After that, 3.2 g of iodine was added and stirred at room temperature for 1 hour. It was added to 500 mL of water and stirred at room temperature for 30 minutes. A white solid was obtained by filtration, purified by silica gel chromatography (dichloromethane), and finally recrystallized (1,2-dichloroethane) to obtain 213 mg of a white solid (yield: 23%).
The results of ¹ HNMR (JEOL-ECX500 (500 MHz) manufactured by JEOL Ltd.) of the obtained I-NTT are shown below.
¹ H NMR (CDCl ₃ , 500 MHz) δ (ppm) 8.28 (s, 1H), 8.22 (s, 1H), 7.98-7.96 (m, 1H), 7.89-7.87 (m, 1H), 7.50-7.48 (m, 3H).

The iodine-containing condensed ring compound of the present invention is suitably used as an organic conductive material or an organic semiconductor material for organic thin film transistors.

Claims (3)

An iodine-containing condensed ring compound characterized by being represented by the following general formula (1);

(In general formula (1), n is an integer of 1 to 3). An iodine-containing condensed ring compound characterized by being represented by the following general formula (2);

(In general formula (2), n is an integer of 1 to 3, and Y is a substituent represented by general formulas (s1) to (s5) or (s7)).

An organic electronic material using the iodine-containing condensed ring compound according to claim 1 or 2.

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