CN115028627B - Tetracyano-substituted acenaphthoquinone imide organic material and preparation method and application thereof - Google Patents

Tetracyano-substituted acenaphthoquinone imide organic material and preparation method and application thereof Download PDF

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CN115028627B
CN115028627B CN202210689420.XA CN202210689420A CN115028627B CN 115028627 B CN115028627 B CN 115028627B CN 202210689420 A CN202210689420 A CN 202210689420A CN 115028627 B CN115028627 B CN 115028627B
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acenaphthoquinone
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赵岩
陈华杰
杨鑫
吴锃
刘云圻
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Abstract

The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a tetracyano-substituted acenaphthoquinone imide organic material, and a preparation method and application thereof. The tetracyano-substituted bisacenaphthoquinone imide organic material is obtained by introducing cyano groups through Knoevenagel condensation reaction by utilizing active methylene of diketone carbon groups and acetonitrile groups of acenaphthoquinone imide, and is an organic micromolecular electron transport material; the electron affinity of the target molecule can be improved, and the energy level and spectral absorption of the material can be regulated and controlled; the pi-conjugated skeleton of the molecule is widened, four cyano groups are symmetrically introduced to strengthen the intermolecular acting force, and the planarity of the molecular skeleton is maintained to improve the intermolecular stacking mode. The organic micromolecular material has the advantages of strong absorption capacity, large framework conjugation, good solubility, excellent thermal stability, strong light absorption capacity and the like, and the preparation method is simple and efficient, good in repeatability and high in universality, can be used for preparing organic field effect transistors and the like, and has wide application prospects.

Description

Tetracyano-substituted acenaphthoquinone imide organic material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a tetracyano-substituted acenaphthoquinone imide organic small molecule electron transport material, a preparation method and application thereof.
Background
The acenaphthoquinone imide has a large pi conjugated framework, electron-deficient imide groups and a dicarbonyl structure, has a lower LUMO energy level, high electron affinity and adjustable absorption spectrum, and is therefore applied to the development of high-performance organic electronic transmission materials. Structurally, acenaphthoquinone imides are very similar to naphthalimides. Thus, acenaphthoquinone imide derivatives have the following advantages: 1) The imide group can effectively reduce the LUMO energy level of the material; 2) The solvent group (such as alkyl) is introduced into the imide group, so that the solubility of the target material can be effectively improved; 3) The highly reactive diketone carbonyl group imparts excellent structural modifiable properties to acenaphthoquinone imide. Based on acenaphthoquinone imide units, chemists develop a series of building units of electron-deficient organic/polymer electron-transporting materials, and successfully apply the building units to the fields of thin film transistors, solar cells and the like, and obtain ideal performances. Such as: ortiz et al obtained NIP-1T by a condensation reaction between acenaphthoquinone imide and 3, 4-diaminothiophene. The material exhibits strong electron deficient characteristics and has a LUMO value of-3.58 eV. Electron mobility of S13 annealed film OFETs device prepared by spin coating method was 2.87×10 -4 cm 2 v -1 s -1 (Chemistry-A European Journal,2013, 19:12458-12467). Furthermore, jenekhe's subject group developed an aza-fused ring containing acenaphthoquinone dicarboximide units, tetraazabenzobisfluoranthene dicarboximide (BFI). BFI shows excellent photophysical and electrochemical properties, its LUMO energy levels are-3.5 eV respectively, and based on BFI device 0.03cm is realized 2 V -1 s -1 High electron mobility (Angewandte Chemie International Edition,2013,125 (21): 5623-5627.). However, the electron transport process of the electron transport material is extremely easy to be deactivated by water/oxygen capture in the air, so that the electron transport material with high mobility and the field effect transistor device thereof which can stably run in the air are relatively few and significantly lag behind the organic hole transport material.The research shows that the LUMO energy level of the organic electron transport material is reduced to about-4.2 eV, so that the damage of water/oxygen in the air to the electron transport process can be slowed down, and stable electron transport can be realized. In order to reduce the LUMO energy level of the material, researchers usually introduce strong electricity-absorbing substituent groups such as halogen atoms or cyano groups to modify the material, but the method needs to use highly toxic compounds such as cuprous cyanide, operators must carefully operate in the experimental process, and the defects of low product yield, troublesome post-treatment, high cost and the like exist, so that the method is not suitable for large-scale industrial production. Therefore, the development of the high-performance air-stable organic electronic transmission material with simple and efficient preparation method, good repeatability and high universality has important significance.
Disclosure of Invention
The invention aims to provide a novel organic micromolecular electron transport material with strong electron affinity and stable air, and a preparation method and application thereof.
The invention provides an organic small molecule electron transport material, which is a tetracyano substituted acenaphthoquinone imide organic small molecule material, and has the structural formula:
Figure GDA0003782554580000021
wherein R may be C 6 -C 30 Branched alkyl groups.
The tetracyano-substituted acenaphthoquinone imide organic small molecular material and the conjugated material R is preferably C 8 -C 30 Branched alkyl groups, which may be specifically 2-ethylhexyl, 2-butylhexyl, 2-hexyloctyl, 4-hexyldecyl, 3-hexylundecyl, 2-octyldecyl, 2-octyldodecyl, 3-octyltridecyl, 2-decyldodecyl, 2-decyltetradecyl, 3-decylpentadecyl, 2-dodecylhexadecyl, 4-octyltetradecyl, 4-decylhexadecyl, 4-hexyldecyl, 4-octyldodecyl, 4-decyltetradecyl or 4-dodecylhexadecyl;
the tetracyano-substituted acenaphthoquinone imide organic small molecule material is preferably the following X1, X2 and X3, and the structural formulas are respectively as follows:
Figure GDA0003782554580000022
the invention also provides a preparation method of the tetracyano-substituted acenaphthoquinone imide small organic molecule, which comprises the following specific steps:
(1) Under the protection of nitrogen, carrying out amidation reaction on acenaphthene-5, 6-dicarboxylic anhydride and alkyl primary amine to obtain an intermediate a, wherein the structural formula of the intermediate a is as follows:
Figure GDA0003782554580000031
wherein R is C 6 -C 30 Branched alkyl;
(2) Under the protection of nitrogen, the intermediate a and chromium trioxide undergo oxidation reaction to obtain an intermediate b,
Figure GDA0003782554580000032
(3) Under the protection of nitrogen, the intermediate b and 1,2,4, 5-tetraethyl cyano benzene undergo Knoevenagel condensation reaction under the catalysis of alkali to obtain a target product:
Figure GDA0003782554580000033
further, the specific flow of the step (1) is as follows: mixing acenaphthene-5, 6-dicarboxylic anhydride, alkyl primary amine and a solvent under the protection of nitrogen, stirring and reacting for 10-20 hours at 70-150 ℃, extracting dichloromethane and saturated saline, separating an organic phase, drying anhydrous magnesium sulfate, filtering, removing the solvent in a rotating way, purifying a crude product by silica gel column chromatography to obtain an intermediate compound a, wherein the feeding mole ratio of the acenaphthene-5, 6-dicarboxylic anhydride to the alkyl primary amine is 1.0: (1.0 to 1.5);
further, the specific flow of the step (2) is as follows: mixing an intermediate a, chromium trioxide and a solvent under the protection of nitrogen, stirring and reacting for 10-15 hours at 50-80 ℃, extracting dichloromethane and saturated saline after the mixture solution is cooled to room temperature, separating an organic phase, drying anhydrous magnesium sulfate, filtering, removing the solvent by rotation, purifying a crude product by silica gel column chromatography to obtain an intermediate compound b, wherein the feeding mole ratio of the intermediate a to the chromium trioxide is 1.0: (2.0-3.0):
further, the specific flow of the step (3) is as follows: mixing an intermediate b, 1,2,4, 5-tetraethyl cyanobenzene, alkali and a solvent under the protection of nitrogen, stirring and reacting for 8-10 hours at 40-80 ℃, extracting dichloromethane and saturated saline after stopping the reaction, separating an organic phase, drying anhydrous magnesium sulfate, filtering, removing the solvent by rotation, purifying a crude product by silica gel column chromatography to obtain a target product, wherein the feeding mole ratio of the intermediate b, 1,2,4, 5-tetraethyl cyanobenzene to the alkali is 1.0: (0.4-0.6): (1.0-1.2).
In the invention, the alkali is at least one of sodium carbonate, potassium carbonate, trimethylamine, triethylamine, diethylenetriamine, sodium methoxide, sodium ethoxide, sodium tert-butoxide and pyridine.
In the invention, the solvent is at least one of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, acetic acid, acetic anhydride, chlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, trimethylbenzene, methanol, ethanol and tertiary butanol.
The invention also provides application of the tetracyano-substituted acenaphthoquinone imide small organic molecule electron transport material in preparation of organic field effect transistor devices.
The specific steps of the application are as follows:
(1) Dissolving a tetracyano substituted acenaphthoquinone imide small organic molecule electron transport material in chloroform solution, and then spin-coating the solution on the surface of a glass substrate which is used as a source electrode and a drain electrode and is used for evaporating gold to obtain a layer of organic semiconductor active layer film;
(2) Spin-coating a poly-Cytop perfluorinated resin solution on the surface of the semiconductor active layer in the step (1) to obtain a Cytop dielectric layer;
(3) And (3) evaporating a layer of aluminum on the CyTop dielectric layer in the step (2) to serve as a gate electrode, so as to obtain the organic field effect transistor device.
The invention also comprises an organic field effect transistor using the tetracyano-substituted acenaphthoquinone imide organic material as an electron transport material.
The tetracyano-substituted acenaphthoquinone imide organic small molecule electron transport material provided by the invention introduces cyano with strong electricity absorption, and researches the influence of a molecular structure on the photoelectric performance of the material. The design advantages are as follows:
(1) The cyano group is introduced by utilizing the active methylene of the diketone carbon group and the acetonitrile group of the acenaphthoquinone imide through a Knoevenagel condensation method, so that the electron affinity of a target molecule can be improved, and the energy level and spectral absorption of a regulating material can be improved;
(2) Widening the pi-conjugated skeleton of the molecule and symmetrically introducing four cyano groups, so that not only is the intermolecular acting force enhanced, but also the planarity of the molecular skeleton is maintained to improve the intermolecular stacking mode;
(3) The terminal alkyl substituted end group is changed, so that the processability of the material can be conveniently regulated and controlled.
Compared with the prior art, the invention has the advantages that:
(1) The synthetic technology route of the invention has the advantages of simplicity, high efficiency, easily available raw materials, low cost, strong universality and the like. The method is suitable for amplification synthesis and batch preparation, and can be popularized and developed to prepare the tetracyano substituted acenaphthoquinone imide organic conjugated material with strong absorption capacity, large skeleton conjugation, good solubility, excellent thermal stability and strong light absorption capacity;
(2) The target organic conjugated micromolecular material has cyano groups with strong electricity absorption and a large conjugated framework, so that the intermolecular assembly capacity is improved;
(3) Four cyano groups with strong electricity absorption are introduced, so that the photoelectric property of the material is successfully regulated and controlled;
(4) The invention provides an application of a tetracyano substituted acenaphthoquinone imide organic small molecule electron transport material, which is to use the organic small molecule electron transport material in an organic thin film field effect transistor device. Wherein the typical organic micromolecular electron transport materials X1, X2 and X3 respectively obtain the components of up to 0.26cm 2 V -1 s -1 、0.12cm 2 V -1 s -1 、0.19cm 2 V -1 s -1 The electron mobility of the organic micromolecular electron transport material fully shows the commercial application prospect of the organic micromolecular electron transport material in the fields of organic field effect transistors, organic photovoltaics, organic photodetectors, bioluminescence imaging and the like.
Drawings
FIG. 1 is an infrared spectrum of a tetracyano-substituted acenaphthoquinone imide small organic molecule electron transport material X1 of example 1.
FIG. 2 is an infrared spectrum of a tetracyano-substituted acenaphthoquinone imide small organic molecule electron transport material X2 of example 2.
FIG. 3 is an infrared spectrum of a tetracyano-substituted acenaphthoquinone imide small organic molecule electron transport material X3 of example 3.
FIG. 4 is a TGA curve of three tetracyano-substituted acenaphthoquinone imide organic small molecule electron transport materials X1, X2, and X3.
FIG. 5 is a DSC curve of the tetracyano-substituted acenaphthoquinone imide small organic molecule electron transport material X1 of example 1.
FIG. 6 is a DSC curve of the tetracyano-substituted acenaphthoquinone imide small organic molecule electron transport material X2 of example 2.
FIG. 7 is a DSC curve of the tetracyano-substituted acenaphthoquinone imide small organic molecule electron transport material X3 of example 3.
Fig. 8 is an ultraviolet-visible absorption spectrum of three tetracyano-substituted acenaphthoquinone imide organic small molecule electron transport materials X1, X2, and X3 in chloroform solution state.
FIG. 9 is a fluorescence spectrum of three tetracyano-substituted acenaphthoquinone imide organic small molecule electron transport materials X1, X2 and X3 in chloroform solution.
FIG. 10 is a cyclic voltammogram of three tetracyano-substituted acenaphthoquinone imide small organic molecule electron transport materials X1, X2, and X3 in chloroform solution.
Fig. 11 is a schematic diagram of a top gate structure organic field effect transistor device based on the tetracyano-substituted acenaphthoquinone imide organic small molecule electron transport material of the present invention.
Fig. 12 is an output curve and a transfer curve of a top gate structure organic field effect transistor device tested in a nitrogen atmosphere based on the tetracyano-substituted acenaphthoquinone imide organic small molecule electron transport material of the present invention.
Fig. 13 is an output curve and a transfer curve of a top gate structure organic field effect transistor device based on the tetracyano-substituted acenaphthoquinone imide organic small molecule electron transport material of the present invention tested in an air environment.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby. The examples described below are intended to facilitate an understanding of the invention and are not intended to be in any way limiting. The methods are conventional methods unless otherwise specified. The reaction materials can be purchased from published commercial sources unless otherwise specified.
Example 1:
a tetracyano substituted acenaphthoquinone imide organic small molecule electron transport material is marked as X1, and has the following structural formula:
Figure GDA0003782554580000061
the synthetic route of X1 is as follows:
Figure GDA0003782554580000062
the method comprises the following specific steps:
(1) Intermediate a1 synthesis: a mixed solution of acenaphthene-5, 6-dicarboxylic anhydride (1 g,4.46 mmol), 2-hexyl-decylamine (1.29 g,5.35 mmol) and 15mL of dry N, N-dimethylformamide was refluxed at 110℃for 12 hours under nitrogen protection. Then, the organic phase was collected by extraction with methylene chloride and then dried over anhydrous magnesium sulfate. After removal of the solvent under reduced pressure, the residue was further purified by column chromatography using petroleum ether: chloroform (2:1, v/v) to give 1.52g of colorless transparent mucus (yield=76%).
The structural characterization data are as follows: 1 H NMR(400MHz,CDCl3)δ(ppm)8.49(d,J＝7.6Hz,2H),7.55(d,J＝7.2Hz,2H),4.11(d,J＝7.2Hz,2H),3.56(s,4H),1.98(br,1H),1.39-1.20(m,24H),0.88-0.81(m,6H). 13 C NMR(100MHz,CDCl3)δ(ppm),164.79,153.67,137.78,132.77,126.43,120.91,119.23,44.40,36.69,31.93,31.90,31.81,31.75,31.71,30.09,29.80,29.61,29.34,26.61,26.58,22.70,14.16,14.14.HRMS:m/z[M]+calcd for(C 30 H 41 NO 2 ):457.39；found 457.74.
from the above, the structure of the compound was correct, and the compound was the intermediate a1 shown.
(2) Intermediate b1 synthesis: to a mixed solution of intermediate a1 (1.0 g,2.23 mmol) and 15mL of acetic anhydride under nitrogen protection was added chromium trioxide (0.67 g,6.70 mmol). The mixture was then stirred at 60℃for 12 hours. After cooling to room temperature, the organic phase was extracted with dichloromethane and then dried over anhydrous magnesium sulfate. After removal of the solvent, the crude product was further purified by column chromatography using petroleum ether: chloroform (2:1, v/v) as eluent to give 0.744g of a yellow solid (yield=70%).
The structural characterization data are as follows: 1 H NMR(400MHz,CDCl 3 )δ(ppm)8.81(d,J＝7.6Hz,2H),8.36(d,J＝7.2Hz,2H),4.17(d,J＝7.6Hz,2H),1.99(br,1H),1.42–1.22(m,24H),0.87–0.83(m,6H). 13 C NMR(100MHz,CDCl 3 )δ(ppm)186.29,162.92,143.83,132.19,131.99,126.74,126.26,122.97,45.12,36.66,31.89,31.84,31.66,31.63,30.02,29.71,29.57,29.30,26.44,26.41,22.67,22.65,14.14,14.11.HRMS:m/z[M]+calcd for(C 30 H 37 NO 4 ):485.71；found 485.35.
from the above, the structure of the compound was correct, and the compound was the intermediate b1 shown.
(3) Synthesis of target product X1: intermediate b1 (0.223 g,0.47 mmol), 1,2,4, 5-tetraethylcyanobenzene (0.05 g,0.21 mmol) and dried N, N-dimethylformamide (5 mL) were added to a 50mL round bottom flask under nitrogen, followed by stirring at room temperature, triethylamine (5 mL) was added dropwise to the mixture, followed by stirring at 80℃for 8 hours. The reaction solution was extracted with chloroform for 3 times, washed with water, and dried over anhydrous magnesium sulfate. The crude product was evaporated under reduced pressure. The resulting solid was purified by column chromatography (silica gel, petroleum ether/chloroform=1:4) to give 0.158g of the product as an orange solid (yield=68%).
The structural characterization data are as follows: 1 H NMR(400MHz,CDCl 3 )δ(ppm)9.22(s,2H),8.79(d,J＝7.6Hz,4H),8.66(d,J＝7.2Hz,4H),4.12(d,J＝7.2Hz,4H),1.97(br,2H),1.39–1.23(m,48H),0.87–0.84(m,12H). 13 C NMR(100MHz,CDCl 3 )δ(ppm)162.79,143.06,135.01,134.62,132.72,129.85,125.50,125.15,125.04,124.92,113.99,108.07,44.87,36.87,31.91,31.87,31.70,30.08,29.76,29.61,29.34,26.91,26.50,26.46,22.68,14.13.HRMS:m/z[M]+calcd for(C 74 H 76 N 6 O 4 ):1032.68；found:1033.51.
from the above, the structure of the compound was correct, which was the target product X1.
Example 2:
a tetracyano substituted acenaphthoquinone imide organic small molecule electron transport material is marked as X2, and has the following structural formula:
Figure GDA0003782554580000071
the synthetic route of X2 is as follows:
Figure GDA0003782554580000072
the method comprises the following specific steps:
(1) Intermediate a2 [1] Reference is made to synthesis.
(2) Intermediate b2 synthesis: to a mixed solution of intermediate a2 (1.0 g,1.99 mmol) and 15mL of acetic anhydride under nitrogen protection was added chromium trioxide (0.597 g,5.97 mmol); the mixture was then stirred at 60 ℃ for 12 hours; after cooling to room temperature, the organic phase is extracted with dichloromethane and then dried over magnesium sulfate; after removal of the solvent, the crude product was further purified by column chromatography using petroleum ether: chloroform (2:1, v/v) as eluent to give 0.824g of a yellow solid (yield=78%);
the structural characterization data are as follows: 1 H NMR(400MHz,CDCl 3 )δ(ppm)8.81(d,J＝7.2Hz,2H),8.36(d,J＝7.2Hz,2H),4.17(d,J＝7.2Hz,2H),1.32(br,1H),1.38–1.22(m,32H),0.86(q,J＝12.8,6.8Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ(ppm)186.26,162.91,143.82,132.17,131.99,126.75,126.26,122.94,45.14,36.65,31.92,31.88,31.66,30.02,29.63,29.61,29.56,29.34,29.29,26.44,22.69,22.66,14.12.HRMS:m/z[M]+calcd for(C 34 H 46 NO 4 ):541.41；found 541.82.
from the above, the structure of the compound was correct, and it was the intermediate b2 shown.
(3) Synthesis of target product X2: intermediate b2 (0.249 g,0.47 mmol), 1,2,4, 5-tetraethylcyanobenzene (0.05 g,0.21 mmol) and dried N, N-dimethylformamide (5 mL) were added to a 50mL round bottom flask under nitrogen protection, followed by stirring at room temperature, triethylamine (5 mL) was added dropwise to the mixture, followed by stirring at 80℃for 8 hours; extracting the reaction solution with chloroform for 3 times, washing with water, and drying with anhydrous magnesium sulfate; evaporating the crude product under reduced pressure; the resulting solid was purified by column chromatography (silica gel, petroleum ether/chloroform=1:4) to give 0.201g of an orange solid product (yield=78%);
the structural characterization data are as follows: 1 H NMR(400MHz,CDCl 3 )δ(ppm)9.10(s,2H),8.71(d,J＝7.2Hz,4H),8.60(d,J＝7.6Hz,4H),4.09(d,J＝7.2Hz,4H),1.95(br,2H),1.40–1.23(m,64H),0.88–0.84(m,12H). 13 C NMR(100MHz,CDCl 3 )δ(ppm)162.79,143.06,135.01,134.62,132.72,129.85,125.50,125.15,125.02,124.92,113.99,108.07,44.87,36.87,31.91,31.87,31.70,30.08,29.76,29.61,29.34,26.91,26.50,26.46,22.68,14.13.HRMS:m/z[M]+calcd for(C 78 H 92 N 6 O 4 ):1224.72；found1225.68.
from the above, the structure of the compound was correct, which was the target product X2.
Example 3:
a tetracyano substituted acenaphthoquinone imide organic small molecule electron transport material is marked as X3, and has the following structural formula:
Figure GDA0003782554580000081
the synthetic route of X3 is as follows:
Figure GDA0003782554580000091
the method comprises the following specific steps:
(1) Intermediate a3 [2] Reference is made to synthesis.
(2) Intermediate b3 [2] Reference is made to synthesis.
(3) Synthesis of target product X3: intermediate b3 (0.276 g,0.47 mmol), 1,2,4, 5-tetraethylcyanobenzene (0.05 g,0.21 mmol) and dried N, N-dimethylformamide (5 mL) were added to a 50mL round bottom flask under nitrogen protection, followed by stirring at room temperature, triethylamine (5 mL) solution was added dropwise to the mixture, followed by stirring at 80℃for 8 hours; extracting the reaction solution with chloroform for 3 times, washing with water, and drying with anhydrous magnesium sulfate; evaporating the crude product under reduced pressure; the resulting solid was purified by column chromatography (silica gel, petroleum ether/chloroform=1:4) to give 0.238g of an orange solid product (yield=85%);
the structural characterization data are as follows: 1 H NMR(400MHz,CDCl 3 )δ(ppm)9.10(s,2H),8.70(d,J＝7.6Hz,4H),8.60(d,J＝7.2Hz,4H),4.09(d,J＝7.2Hz,4H),1.95(br,2H),1.42–1.23(m,80H),0.88–0.84(m,12H). 13 C NMR(100MHz,CDCl 3 )δ(ppm)162.60,142.87,134.82,134.33,132.62,129.65,125.31,125.13,125.02,124.90,113.81,107.91,44.88,36.85,31.94,31.70,30.10,29.73,29.69,29.38,26.52,22.70,14.13.HRMS:m/z[M]+calcd for(C 78 H 92 N 6 O 4 ):1336.84；found 1337.89.
from the above, the structure of the compound was correct, which was the target product X3.
Test 1:
the infrared spectrum of the target products X1, X2, and X36 in examples 1 to 3 was measured:
FIGS. 1 to 3 show the IR spectra of the target products X1 to X3, respectively, with characteristic peaks of cyano groups appearing in the range of 2220 to 2230cm-1, respectively, of 2224cm -1 、2227cm -1 And 2225cm -1 。
Test 2:
measurement of the thermal stability of the target products X1, X2 and X36 in examples 1 to 3:
FIG. 4 shows TGA curves of target products X1-X3; FIGS. 5 to 7 show DSC curves of the target products X1 to X3. As can be seen from the graph, all the target products X1 to X3 show good thermal stability, td is more than 450 ℃, and the thermal stability of the molecules gradually weakens along with the extension of the alkyl chain.
Test 3:
measurement of absorption spectrum properties of the target products X1 to X3:
FIG. 8 is an ultraviolet-visible absorption spectrum of the target products X1 to X3 in chloroform solution; as can be seen from the figure, in chloroform solution (c=1×10 -5 M) the target products X1, X2 and X3 exhibit similar curves, the spectral absorption ranges from 350 to 520, and the molar extinction coefficient (. Epsilon.) at 400nm is approximately 1.35X 10 5 M -1 cm -1 。
Test 4:
the fluorescence emission spectrum of the target products X1 to X3 is measured:
FIG. 9 is a graph showing fluorescence emission spectra of the target products M1 to M3 in chloroform solution. As can be seen from the graph, the emission curves of X1, X2 and X3 are similar, and the maximum emission wavelength is 547nm.
Test 5:
electrochemical property measurement is carried out on target products X1 to X3:
FIG. 10 is a cyclic voltammogram of the target products X1, X2, and X3 in chloroform; the test conditions were: a three-electrode working system is adopted to measure oxidation-reduction potential, a glassy carbon electrode is selected as a working electrode, ag/AgCl is used as a reference electrode, a platinum wire electrode is used as a counter electrode, a chloroform solution of tetrabutylammonium hexafluorophosphate with the concentration of 0.1mol/L is used as a supporting electrolyte, ferrocene is used as an internal standard (0.38V vs. Ag/AgCl), and the scanning rate is 100mV/s. As can be seen from the figures of the drawing,initial reduction potentials of X1, X2 and X3 (E red ) Are all-0.09V, by the formula:
E LUMO ＝–(E red +4.42)eV
the LUMO level was found to be-4.33 eV.
Example 4:
preparation and performance test of a top gate structure organic field effect transistor device based on tetracyano substituted acenaphthoquinone imide organic small molecule electron transport material.
The preparation method of the top gate device comprises the following steps:
(1) The tetracyano-substituted acenaphthoquinone imide organic small molecule electron transport material is dissolved in a chloroform solvent with high purity (99.7%) to obtain a solution with the concentration of 5 mg/mL;
(2) Using glass as an organic field effect transistor device substrate, and evaporating gold with the thickness of 30nm on the glass substrate by using a metal mask with the channel length of 5-50 mu m as a source-drain electrode;
(3) Spin-coating a tetracyano-substituted acenaphthoquinone imide small organic molecule electron transport material on the substrate in the step (2) at a speed of 3000r/min, and obtaining a layer of organic semiconductor active layer film on the surface of the substrate;
(4) Spin-coating a CyTop solution on the surface of the organic semiconductor active layer film in the step (3) at a speed of 3000r/min to obtain a CyTop dielectric layer;
(5) And (3) evaporating 80nm aluminum on the poly CyTop dielectric layer in the step (4) to serve as a gate electrode.
Semiconductor electrical property measurements were performed on the top gate organic field effect transistor device prepared in example 4:
fig. 11 is a schematic structural diagram of a device, fig. 12 is an output curve and a transfer curve of the device in a nitrogen atmosphere, and fig. 13 is an output curve and a transfer curve of the device in an air atmosphere. As shown by test results, the organic field effect transistor with the top gate structure based on the tetracyano-substituted acenaphthoquinone imide organic small molecule electron transport material has higher electron mobility and good air stability, and the electron mobility of X1, X2 and X3 is respectively 0.26cm under the nitrogen environment 2 V -1 s -1 、0.12cm 2 V -1 s -1 、0.19cm 2 V -1 s -1 Under the air environment, the electron mobility of X1, X2 and X3 is 0.16cm respectively 2 V -1 s -1 、0.11cm 2 V -1 s -1 、0.14cm 2 V -1 s -1 The carrier mobility values are shown in table 1.
TABLE 1
X1 X2 X3
Mobility under Nitrogen atmosphere 0.26cm 2 V -1 s -1 0.12cm 2 V -1 s -1 0.19cm 2 V -1 s -1
Mobility in air environment 0.16cm 2 V -1 s -1 0.11cm 2 V -1 s -1 0.14cm 2 V -1 s -1
。
The above study results show that: the invention develops a tetracyano-substituted acenaphthoquinone imide organic micromolecule electron transport material X1-X3 through Knoevenagel condensation, which has high electron affinity, large coplanar skeleton and good solution processability, and the electron mobility reaches mu e ＝0.26cm 2 V -1 s -1 And stable OFET device performance is achieved in an air atmosphere. The material provided by the invention has the advantages of simple and efficient preparation method, easy raw material availability, strong popularization and the like. The four cyano-substituted acenaphthoquinone imide organic electronic transmission material with excellent comprehensive performance can be prepared by changing different solubilizing alkyl end groups, which has very important significance for researching the internal correlation between the molecular structure and the performance of an organic semiconductor and has guiding significance for developing high-performance organic semiconductor photoelectric functional materials in future.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Reference is made to:
[1]Ding L,Yang C,Su Z,Pei J.Synthesis,crystal structure,and application of an acenaphtho[1,2-k]fluordiimide derivative[J].Science China Chemistry,2015,58(2):364-369.
[2]Li H,Kim FS,Ren G,Hollenbeck EC,Subramaniyan S,Jenekhe SA.Tetraazabenzodifluoranthene diimides:building blocks for solution-processable n-type organic semiconductors[J].Angew Chem Int Ed Engl,2013,52(21):5513-5517。

Claims (10)

1. the tetracyano-substituted acenaphthoquinone imide organic material is a small molecule electron transport material, and is characterized by having the structural formula:
Figure FDA0003698957580000011
wherein R is selected from C 6 -C 30 Branched alkyl groups.
2. The tetracyano-substituted acenaphthoquinone imide organic material according to claim 1, wherein said R is 2-ethylhexyl, 2-butylhexyl, 2-hexyloctyl, 4-hexyldecyl, 3-hexylundecyl, 2-octyldecyl, 2-octyldodecyl, 3-octyltridecyl, 2-decyldodecyl, 2-decyltetradecyl, 3-decyltentadecyl, 2-dodecylhexadecyl, 4-octyltetradecyl, 4-decyltetradecyl, 4-hexyldecyl, 4-octyldodecyl, 4-decyltetradecyl or 4-dodecylhexadecyl.
3. The tetracyano-substituted acenaphthoquinone imide organic material according to claim 1 or 2, wherein the tetracyano-substituted acenaphthoquinone imide organic material is one of the following X1, X2, X3, and has a specific structural formula:
X1
Figure FDA0003698957580000012
X2
Figure FDA0003698957580000013
X3
Figure FDA0003698957580000014
4. a process for the preparation of tetracyano-substituted acenaphthoquinone imide organic material as claimed in any one of claims 1 to 3, characterized by the specific steps of:
(1) Under the protection of nitrogen, carrying out amidation reaction on acenaphthene-5, 6-dicarboxylic anhydride and alkyl primary amine to obtain an intermediate a, wherein the structural formula of the intermediate a is as follows:
Figure FDA0003698957580000021
wherein R is C 6 -C 30 Branched alkyl;
(2) Under the protection of nitrogen, the intermediate a and chromium trioxide undergo oxidation reaction to obtain an intermediate b, and the structural formula of the intermediate b is as follows:
Figure FDA0003698957580000022
(3) Under the protection of nitrogen, the intermediate b and 1,2,4, 5-tetraethyl cyano benzene undergo Knoevenagel condensation reaction under the catalysis of alkali to obtain a target product:
Figure FDA0003698957580000023
5. the method for preparing the tetracyano-substituted acenaphthoquinone imide organic material according to claim 4, wherein the method comprises the following steps:
the specific flow of the step (1) is as follows: mixing acenaphthene-5, 6-dicarboxylic anhydride, alkyl primary amine and a solvent under the protection of nitrogen, stirring and reacting for 10-20 hours at 70-150 ℃, extracting dichloromethane and saturated saline, separating an organic phase, drying anhydrous magnesium sulfate, filtering, removing the solvent in a rotating way, purifying a crude product by silica gel column chromatography to obtain an intermediate compound a, wherein the feeding mole ratio of the acenaphthene-5, 6-dicarboxylic anhydride to the alkyl primary amine is 1.0: (1.0 to 1.5);
the specific flow of the step (2) is as follows: mixing an intermediate a, chromium trioxide and a solvent under the protection of nitrogen, stirring and reacting for 10-15 hours at 50-80 ℃, extracting dichloromethane and saturated saline after the mixture solution is cooled to room temperature, separating an organic phase, drying anhydrous magnesium sulfate, filtering, removing the solvent by rotation, purifying a crude product by silica gel column chromatography to obtain an intermediate compound b, wherein the feeding mole ratio of the intermediate a to the chromium trioxide is 1.0: (2.0-3.0):
the specific flow of the step (3) is as follows: mixing an intermediate b, 1,2,4, 5-tetraethyl cyanobenzene, alkali and a solvent under the protection of nitrogen, stirring and reacting for 8-10 hours at 40-80 ℃, extracting dichloromethane and saturated saline after stopping the reaction, separating an organic phase, drying anhydrous magnesium sulfate, filtering, removing the solvent by rotation, purifying a crude product by silica gel column chromatography to obtain a target product, wherein the feeding mole ratio of the intermediate b, 1,2,4, 5-tetraethyl cyanobenzene to the alkali is 1.0: (0.4-0.6): (1.0-1.2).
6. The method for preparing the tetracyano-substituted acenaphthoquinone imide organic material according to claim 5, wherein the base is at least one of sodium carbonate, potassium carbonate, trimethylamine, triethylamine, diethylenetriamine, sodium methoxide, sodium ethoxide, sodium tert-butoxide and pyridine.
7. The method for preparing a tetracyano-substituted acenaphthoquinone imide organic material according to claim 5, wherein the solvent is at least one of N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, acetic acid, acetic anhydride, chlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, trimethylbenzene, methanol, ethanol, and t-butanol.
8. Use of a tetracyano-substituted acenaphthoquinone imide organic material according to any one of claims 1-5 for the preparation of an organic field effect transistor device.
9. The use according to claim 8, characterized by the specific steps of:
(1) Dissolving tetracyano substituted acenaphthoquinone imide organic material in chloroform solution, and spin-coating on the surface of a glass substrate which is used as a source electrode and a drain electrode and is used for evaporating gold to obtain a layer of organic semiconductor active layer film;
(2) Spin-coating a poly-Cytop perfluorinated resin solution on the surface of the semiconductor active layer in the step (1) to obtain a Cytop dielectric layer;
(3) And (3) evaporating a layer of aluminum on the CyTop dielectric layer in the step (2) to serve as a gate electrode, so as to obtain the organic field effect transistor device.
10. An organic field effect transistor using the tetracyano-substituted acenaphthoquinone imide organic material as claimed in any one of claims 1 to 5 as an electron transport material.
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KR20170057729A (en) * 2015-11-17 2017-05-25 주식회사 엘지화학 Nitrile based compound and organic light emitting device comprising the same

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KR20170057729A (en) * 2015-11-17 2017-05-25 주식회사 엘지화학 Nitrile based compound and organic light emitting device comprising the same

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