CN109912630B - Selenophen derivative, preparation method thereof and application of selenophen derivative as organic semiconductor material - Google Patents
Selenophen derivative, preparation method thereof and application of selenophen derivative as organic semiconductor material Download PDFInfo
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Abstract
The invention relates to a selenophene derivative, which has the following structural formula:
. The selenophene derivative is prepared through selenophene [3,2-b]Aldehyde group of selenophene and subsequent Wittig reaction. The invention is found by experiments that: the selenophene derivative is a novel organic semiconductor material, and has better hole mobility when used as an organic semiconductor material.
Description
Technical Field
The invention belongs to the technical field of preparation of heterocyclic compounds, and particularly relates to a selenophene derivative, a preparation method thereof and application thereof as an organic semiconductor material.
Background
Thiophene derivatives, as a new class of organic semiconductor materials, have attracted extensive attention in the field of organic semiconductor materials due to their excellent photoelectric properties, and research on the internal relationship and rules between their structures and properties has also made significant progress. However, since thiophene derivatives are limited in their own structure such as small radius of S atom, low degree of polarization, etc., further improvement of their performance is under serious examination. Selenium and sulfur are oxygen group elements, and selenophene and thiophene have many similar physical and chemical properties, but the selenophene derivative has the following superior performance compared with the thiophene derivative:
1) the strong interaction of Se can enhance the charge transfer between molecules and is beneficial to the transmission of current carriers;
2) selenophene has lower oxidation-reduction potential than thiophene, and can enhance the stability of the material to oxygen;
3) the selenium atom is larger than the sulfur atom, so that selenophene can accommodate more charge injection than thiophene;
4) selenophene has a narrower band gap than thiophene, and both the absorption of light and its own color are different from thiophene (see literature: a) j.w. Shi, y.b. Li, m. Jia, l.xu, h. Wang.J. Mater. Chem., 2011, 21, 17612-17614. b) J. Shi, L. Xu, Y. Li, M. Jia, Y. Kan, H. Wang, Organic Electronics, 2013, 14, 934-941.
K. Takimiya, Y. Kunugi, Y. Konda, N. Niihara, T. Otsubo. J. Am. Chem. Soc., 2004, 126, 5084-5085.
A. Patra, M. Bendikov. J. Mater. Chem., 2010, 20, 422-433.
Z. Chen, H. Lemke, S. Albert-Seifried, et al.Adv. Mater., 2010, 22, 2371-2375.）
The characteristics of selenophene make selenophene and derivatives thereof attract more and more attention in the fields of organic synthesis, organic photoelectric devices and the like, but the preparation and performance research of selenophene derivatives is far behind the research of thiophene derivatives by people. The lag in research on the preparation of selenophene derivatives is mainly due to the weak overlap of orbitals when the bonding atoms contain selenium atoms and the high reactivity of carbon-selenium bonds, making the preparation of selenophene derivatives challenging (j. Wei, d. Meng, l. Zhang, z. Wang,Chem. Asian J. 2017, 12, 1879-1882.）。
at present, the fused selenophene derivatives reported in the literature are mainly three of (a) H. Kong, Y.K. Jung, N.S. Cho,et al.Chem. Mater., 2009, 21, 2650-2660. b) K. S. Choi, K. Sawada, J. Nakayama, et al.Heterocycles, 1994, 38, 143-149.）：β-dimethylated selenopheno [3,2-b]Selenophene (1),
Tetramethylated selenopheno [3,2-b]Selenophene (2) and 2-selenopheno [3,4-b]The synthetic route of selenophenecarboxylic acid methyl ester (3) is shown below. Compound 1 was prepared by reacting 2, 5-dimethyl-hex-3-yne-2, 5-diol or 2, 5-dimethyl-hex-1, 5-dien-3-yne with selenium in benzene solution at 220 ℃ for eight hours, with the yields: 16% and 22%. The compound 2 is prepared by reacting 3, 6-dimethyl-4-octyne-3, 6-diol with selenium in a benzene solution at 220 ℃ for eight hours, and the yield is as follows: 15 percent. The compound 3 is prepared by providing a selenium source through sodium selenide: sodium selenide aqueous solution is dropped into the ethanol solution of methyl 2, 3-dichloromethyl-5-selenophenecarboxylate for reaction for 30 minutes to form a selenium-connected dimer (73 percent), and the dimer is heated to 600 ℃ under vacuum to generate methoxycarbonyl dihydroselenophen [3,4-b]Selenophen (56%) was oxidized with hydrogen peroxide to give compound 3 with a yield of 62% (h.a. Saadeh, l.lu, l.yu,et al.ACS Macro Lett., 2012, 1, 361-365.）。
in conclusion, although the preparation of the fused selenophene derivative is reported, the preparation process has the problems of harsh reaction conditions, more steps, less method, complex raw materials, low yield and the like. Therefore, research and development of novel selenophen derivatives and efficient preparation methods thereof are key scientific problems which are first solved by the rapid development of selenophen chemistry at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel selenophene derivative, a preparation method thereof and application thereof as an organic semiconductor material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a selenophene derivative has a structural formula as follows:
the invention provides a preparation method of the selenophene derivative, which comprises the following steps:
1) 2, 5-bis (trimethylsilyl) selenopheno [3,2-b]Selenophen (compound 4) reacts with NBS in solvent to prepare compound 2, 5-dibromo-selenopheno [3,2-b]Selenophene (compound 5);
2) compound 2, 5-dibromo-selenopheno [3,2-b]Adding an inert organic solvent into selenophene, then adding a metal alkyl compound at-70 ℃ to-80 ℃, reacting for 2-3 hours at-70 ℃ to-80 ℃, adding DMF, raising the temperature to room temperature, stirring and reacting for 6-8 hours, and quenching with methanol to obtain selenopheno [3,2-b]Selenophene-2, 5-dicarbaldehyde (compound 6);
3) selenopheno [3,2-b]Selenophene-2, 5-dicarbaldehyde is dissolved in methanol under inert environment in potassium tert-butoxide (B), (C)tReacting with (4-octylbenzyl) -triphenylphosphine bromide under the action of-BuOK at 100-120 ℃ through Wittig reaction to obtain (a compound 7, (b) and (c)E) -2, 5-bis (4-octylstyryl) -selenopheno [3,2-b]Selenophene).
Specifically, in the step 1), 2, 5-bis (trimethylsilyl) selenopheno [3,2-b]Selenophene and NBS (N-bromosuccinimide) are stirred and react for 2-4 hours at room temperature in a mixed solvent of chloroform and acetic acid.
Specifically, in the step 2), the inert organic solvent is tetrahydrofuran, and the metal alkyl compound is n-butyllithium (n-butyllithium:)n-BuLi) or tert-butyllithium (t-BuLi）。
The invention also provides application of the selenophen derivative in the aspect of being used as an organic semiconductor material.
Compared with the prior art, the invention has the beneficial effects that:
the selenophene derivative has strong Se-Se interaction, so that the molecular arrangement is more compact and ordered in the solid state, the charge transfer among molecules is enhanced, and the selenophene derivative is favorable for the transmission of current carriers. As early as in the year 2003,the tetraselenophene has been used as a semiconductor layer to be applied to the research of organic field effect transistors, and the mobility of the tetraselenophene is 0.8-3.6 multiplied by 10-3 cm2 V-1s-1. The selenophene ring and the ring are fused together, so that not only can the conjugated structure deterioration caused by the deflection of the ring in the film forming process be avoided, but also the pi electron cloud interaction among molecules is facilitated, and the strong pi-pi and Se-Se interaction is shown, thereby effectively promoting the improvement of the carrier mobility. However, the application of the condensed selenophene derivative in the field of organic semiconductor materials is limited due to the difficulty in synthesizing the condensed selenophene derivative. The invention uses selenophene [3,2-b]The hydroformylation of selenophene and the subsequent Wittig reaction synthesize a novel organic semiconductor material 7 based on condensed selenophene, which has better hole mobility when used as an organic semiconductor material.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of compound 5 prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of Compound 5 prepared in example 1 of the present invention;
FIG. 3 is high resolution mass spectrometry data of Compound 5 prepared in example 1 of the present invention;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of Compound 6 prepared in example 2 of the present invention;
FIG. 5 is a nuclear magnetic resonance carbon spectrum of Compound 6 prepared in example 2 of the present invention;
FIG. 6 is high resolution mass spectrometry data of Compound 6 prepared in example 2 of the present invention;
FIG. 7 is high resolution mass spectrometry data of Compound 7 prepared in example 3 of the present invention;
FIG. 8 is a device structure with bottom gate top contact, where A modifies the insulating layer with OTS, and B does not modify the insulating layer;
FIG. 9 is a transfer characteristic curve and a basic parameter characterization of a thin film transistor;
FIG. 10 is a transfer curve (left) and an output curve (right) for Compound 7 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
The raw material 2, 5-di (trimethylsilyl) selenophene [3,2-b]The synthetic route for Selenophene (Compound 4) is shown below, and the specific synthetic procedures can be found in the literature Wan Xu, Mengjie Wang, Zhouying Ma, Zhen Shan, Chunli Li, and Huang Wang, Selenophene-Based heterocycles: Synthesis, Structure, and physiochemical Behaviors, J. org. chem. 2018, 83, 12154 and 12163.
Example 12, 5-dibromo-selenopheno [3,2-b]Preparation of selenophene (Compound 5)
Adding 2, 5-di (trimethylsilyl) selenopheno [3,2-b]Selenophene (compound 4, 0.248 g, 0.66 mmol) was added to 50 mL (v/v = 3/2) of a mixed solvent of chloroform and acetic acid, and stirred to completely dissolve compound 4. NBS (0.256 g, 1.44 mmol, 2.2 eq) was added at room temperature and the reaction stirred for 3 hours. The reaction was quenched with saturated sodium bicarbonate solution, extracted with dichloromethane (3X 50 mL), the organic phases combined and washed with saturated sodium bicarbonate solution (50 mL), water (2X 50 mL), then anhydrous MgSO4Drying, filtering, removing solvent to obtain crude product, and purifying by column chromatography (eluent: petroleum ether) to obtain yellow solid (0.244 g, 95%), to obtain compound 5. The nmr hydrogen, nmr carbon and high resolution mass spectra data for compound 5 are shown in figures 1, 2 and 3, respectively, and the specific data are listed below:
M.P.：145-146℃。1H NMR (400 MHz, CDCl3) δ (ppm): 7.40 (s, 2 H). 13C NMR (100 MHz, CDCl3) δ(ppm): 139.6, 127.5, 115.3. HRMS (DART-FTICR) m/z: [M]+calcd for C6H2Br2Se2, 391.6843; found, 391.6833。
example 2 selenopheno [3,2-b]Preparation of selenophene-2, 5-dicarboxaldehyde (Compound 6)
Compound 5 (0.115 g, 0.029 mmol) was added to a 100 mL Schlenk flask and dried under vacuum for 0.5 h; then adding 30 mL of inert organic solvent anhydrous tetrahydrofuran under the protection of Ar gas, and stirring to ensure thatCompound 5 was completely dissolved. Then cooling to-78 ℃, and dropwise addingnBuLi (0.26 mL, 2.42M in n-hexane, 0.064 mmol, 2.2 equiv), and stirred at-78 deg.C for 2h, added with anhydrous DMF (0.09 mL, 0.117 mmol, 4.0 equiv), allowed to warm to room temperature naturally, and stirred overnight (12 h). The reaction was quenched with methanol at-78 deg.C, extracted with dichloromethane (3X 50 mL), the organic phases combined and washed with water (3X 50 mL), anhydrous MgSO4Drying, filtering, removing solvent to obtain crude product, and washing with chloroform (3 × 15 mL) to obtain light yellow solid (0.064, 76%), which is compound 6. The nmr hydrogen, nmr carbon and high resolution mass spectra data for compound 6 are shown in figures 4, 5 and 6, respectively, and the specific data are listed below:
M.P.：234-235 oC。1H NMR (400 MHz, CDCl3) δ (ppm): 8.26 (s, 2 H), 9.94 (s, 2 H); 13C NMR (100 MHz, DMSO-d 6 ) δ (ppm): 187.2, 153.4, 145.7, 137.5. HRMS (DART-FTICR) m/z: [M+H]+ calcd for C8H5O2Se2, 292.8614; found, 292.8612. IR (KBr): 3070, 1766, 1650, 1477, 843 cm-1。
example 3 (E) -2, 5-bis (4-octylstyryl) -selenopheno [3,2-b]Preparation of selenophene (Compound 7)
Compound 6 (0.041g, 0.140 mmol) and (4-octylbenzyl) -triphenylphosphine bromide (0.306 g, 0.562 mmol, 4.0eq) were added to a 100 mL Schlenk flask and dried under vacuum for 0.5 h. 20 m L absolute methanol was added and stirred to make the reaction well miscible. Dropwise addition at 0 DEG Ct-BuOK in methanol (0.047 g (0.42 mmol, 3.0 eq) of potassium tert-butoxide in 10 mL of anhydrous methanol) was heated to 100 ℃ and reacted at 110 ℃ for 12 hours. After the reaction is finished, the temperature is naturally reduced to room temperature, the mixture is kept stand for layering, and the solid is washed by diethyl ether (3X 20 mL) to obtain a bright yellow solid (0.053 g, 57 percent), namely the compound 7. The high resolution mass spectral data for compound 7 is shown in fig. 7, and the specific data is listed below:
M.P. ＞ 300℃。HRMS (DART-FTICR) m/z: [M+H]+ calcd for C38H49Se2, 665.2159; found, 665.2161. IR (KBr): 3059, 2958, 2919, 2851, 1618, 944, 827 cm-1。
example 4
Fig. 8 shows a device structure of a bottom gate top contact, where a is to modify an insulating layer with OTS, and B is to not modify the insulating layer. And the bottom grid top contact is that Si at the bottom of the insulating layer is used as a grid electrode, an organic material is grown on the insulating layer in a vacuum deposition mode, and then high-purity gold is deposited on the top of the organic layer by adopting a mask plate to be used as a source drain electrode. In the process of constructing the device, the compound 7 of the present invention is deposited as an organic material on the surface of the insulating layer or on the surface of the insulating layer modified by OTS.
The mobility is usually calculated by using the formula I-V of the saturation region (μ)：
I SDIs a source-drain current; w、L is the width and length of the conductive channel respectively;μis the carrier mobility;V Tis the threshold voltage;V Gis the gate voltage;C irefers to the capacitance per unit area of the insulating layer. To be provided with
Is the vertical axis, inV GAs the horizontal axis, from the slope of the tangentμThe tangent line corresponding to the intersection of the transverse axisV GI.e. the threshold voltageV T. The transfer characteristic and the basic parameter characterization of the thin film transistor are detailed in fig. 9.
In the test process, the transfer curve is a curve that the source-drain current changes along with the change of the grid voltage under different source-drain voltages (-20V, -40V, -60V, -80V, -100V); the output curve is a curve of source-drain current varying with source-drain voltage under different gate voltages, as detailed in fig. 10.
And (3) test results: device mode: bottom gate top contact; semiconductor film processing mode: vacuum deposition; unmodified at room temperatureThe highest mobility of 0.38 cm is obtained for the silicon dioxide substrate2 V-1 s-1On-off ratio of 106The threshold voltage is-45 +/-2V.
In summary, it can be seen that: the performance characterization result of the field effect transistor with the compound 7 as the active layer shows that the compound can be a p-type organic semiconductor material, and the maximum mobility is 0.38 cm2 V-1 s-1。
The examples of the present invention are only for illustrating and not limiting the technical scheme of the present invention, and the organic solvent for washing and extracting the organic phase in the technical scheme of the present invention can be adjusted, which is obvious to those skilled in the art and should fall into the protection scope of the present invention.
Claims (5)
1. A selenophene derivative has a structural formula as follows:
the selenophene derivative has better hole mobility when being used as an organic semiconductor material, and the maximum mobility is 0.38 cm2 V-1 s-1。
2. A process for the preparation of a selenophene derivative as claimed in claim 1, which comprises the steps of:
1) 2, 5-bis (trimethylsilyl) selenopheno [3,2-b]Selenophene reacts with NBS in solvent to prepare the compound 2, 5-dibromo-selenopheno [3,2-b]Selenophene;
2) compound 2, 5-dibromo-selenopheno [3,2-b]Adding an inert organic solvent into selenophene, then adding a metal alkyl compound at-70 ℃ to-80 ℃, reacting for 2-3 hours at-70 ℃ to-80 ℃, adding DMF, raising the temperature to room temperature, stirring and reacting for 6-8 hours, and quenching with methanol to obtain selenopheno [3,2-b]Selenophene-2, 5-dicarbaldehyde;
3) selenopheno [3,2-b]Selenophene-2, 5-dicarbaldehyde is dissolved in methanol under inert environment intReaction with (4-octyl) bromide under the action of-BuOKThe benzyl) -triphenylphosphine is obtained by a Wittig reaction at the temperature of 100-120 ℃.
3. The method for preparing a selenophene derivative as claimed in claim 2, wherein the 2, 5-bis (trimethylsilyl) selenopheno [3,2-b]Selenophen and NBS are stirred to react for 2-4 hours in a mixed solvent of chloroform and acetic acid at room temperature.
4. A process for the preparation of a selenophene derivative according to claim 2, wherein the inert organic solvent in the step 2) is tetrahydrofuran, and the metal alkyl compound is n-butyllithium or t-butyllithium.
5. Use of a selenophene derivative according to claim 1 as an organic semiconductor material.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006089413A (en) * | 2004-09-24 | 2006-04-06 | Japan Science & Technology Agency | New organic semiconductor compound, method for producing the same and organic semiconductor device using the same |
| JP2009302328A (en) * | 2008-06-13 | 2009-12-24 | Nippon Kayaku Co Ltd | Organic transistor and organic semiconductor element using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006089413A (en) * | 2004-09-24 | 2006-04-06 | Japan Science & Technology Agency | New organic semiconductor compound, method for producing the same and organic semiconductor device using the same |
| JP2009302328A (en) * | 2008-06-13 | 2009-12-24 | Nippon Kayaku Co Ltd | Organic transistor and organic semiconductor element using the same |
Non-Patent Citations (3)
| Title |
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| Selenophene-Based Heteroacenes: Synthesis, Structures, and Physicochemical Behaviors;Wan Xu et al.;《J. Org. Chem.》;20180902;第83卷;第12154页摘要部分，第12158页左栏最后一段以及右栏第一段,第12155页Scheme 2，第12159页右栏实验部分 * |
| Synthesis and Properties of Thieno[3,2-b]thiophene Derivatives for Application of OFET Active Layer;Hiroki Ito et al.;《Heteroatom Chemistry》;20131231;第24卷(第1期);第25页摘要部分，第26页SCHEME 1,右栏化合物合成部分 * |
| 硒吩衍生物的制备与应用研究进展;李春丽等;《河南大学学报（自然科学版）》;20130531;第43卷(第3期);第258-264页 * |
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