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CN101885732A - Thioheterocyclic fused naphthalene tetracarboxylic acid diimide derivative, its preparation method and application - Google Patents

Thioheterocyclic fused naphthalene tetracarboxylic acid diimide derivative, its preparation method and application Download PDF

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CN101885732A
CN101885732A CN 201010207565 CN201010207565A CN101885732A CN 101885732 A CN101885732 A CN 101885732A CN 201010207565 CN201010207565 CN 201010207565 CN 201010207565 A CN201010207565 A CN 201010207565A CN 101885732 A CN101885732 A CN 101885732A
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tetracarboxylic acid
fused
naphthalene tetracarboxylic
diimide derivatives
derivatives
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CN101885732B (en
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高希珂
狄重安
胡云宾
朱道本
刘云圻
李洪祥
姜标
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Shanghai Institute of Organic Chemistry of CAS
Institute of Chemistry CAS
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Shanghai Institute of Organic Chemistry of CAS
Institute of Chemistry CAS
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Priority to JP2012534531A priority patent/JP5416282B2/en
Priority to KR20127013047A priority patent/KR101496931B1/en
Priority to PCT/CN2010/077932 priority patent/WO2011047624A1/en
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Abstract

The invention heterocyclic-sulfur fused naphthalenetetracarboxylic acid diimide derivatives, a preparation method and application thereof. In the preparation method, 2,3,6,7-tetrabromo-naphthalene diimide reacts with 2-alkyl cyanoacetate-ethylene-1,1-dithiol sodium salt, 2-mandelonitrile-ethylene-1,1-dithiol sodium salt or 2-(4-phenylacetonitrile bromide)-ethylene-1,1-dithiol sodium salt to prepare 1,3-heterocyclic-disulfide fused naphthalenetetracarboxylic acid diimide derivatives; and the 2,3,6,7-tetrabromo-naphthalene diimide reacts with 1,2-dicyanoethylene-1,2-dithiol sodium salt to prepare 1,4-dithiin cyclohexadiene-2,3-dinitrile fused naphthalenetetracarboxylic acid diimide derivatives, which further reacts to prepare alpha,beta-dicyanothiophene fused naphthalenetetracarboxylic acid diimide derivatives. The compounds are n-type organic semiconductor materials, and have wide application prospect in the field of organic electronics (organic field effect transistors, organic solar cells and the like).

Description

Thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives, and method for making and application
Technical field
The present invention relates to thia ring condensed naphthalenetetracarbacidic acidic diimide class organic semiconductor material, relate in particular to four class thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives, and preparation method and as the application of n-type organic semiconductor material in organic film FET etc.
Background technology
With respect to inorganic semiconductor material (silicon, oxide compound etc.), advantages such as organic semiconductor material has that preparation technology is simple, cost is low, light weight, snappiness and plastic favorable compatibility, it has wide application prospect (Forrest at aspects such as flexibility demonstration, organic radio frequency electric trade mark (ORFID), organic sensor, organic solar batteries, S.R.Nature.2004,428,911-918; Korzhov, M.et al.Physics Word.2008,29-33; Leenen, M.A.M.et al.Phys.Status Solidi A.2009,2006,588-597; Special issue:Organic Electronics and Optoelectronics, Forrest, S.R.; Thompson, M.E.ed.Chem.Rev.2007,107,923-1386 etc.).Development along with organic semiconductor material and device related-art technology, frivolous, portable, flexible, can next to the shinly dress, the organic electronic product of individual character fashion will progressively come into people's life, and will bring revolutionary variation to electronic industry and human life.
Organic semiconductor material is the key component of organic electronic devices, and the type by its transmission current carrier is divided into p-type organic semiconductor material/organic donor material (hole transport) and n-type organic semiconductor material/organic receptor material (electric transmission).Generally, the development of p-type organic semiconductor material/organic donor material is very fast, the organic film FET of the molecular material of some solution processable (OTFT) performance can compare favourably with unformed silicon (McCulloch, I.et al.Nat.Mater.2006,5,328-333.; Ebata, H.; Et al.J.Am.Chem.Soc.2007,129,15732-15733.; Osaka, I.Et al.J.Am.Chem.Soc.2010,132,5000-5001.), the photoelectric transformation efficiency of the organic heterojunction solar cell that the polymer donor material of some D-A structures and organic receptor material (PCBM, a kind of fullerene derivate) are constructed is up to 7.4% (Liang, Y.et al.Adv.Mater.2010,22, DOI:10.1002/adma.200903528.).In organic film FET (OTFT) field, n-type organic semiconductor material has very important effect (Newman for the complementary circuit of constructing organic p-n junction diode, bipolar transistor and reduce power consumption, strong noise tolerance limit, C.R.et al Chem.Mater.2004,16,4436-4451; Klauk, H.et al.Nature.2007,445,745-748; Yan, H.et al.Nature.2009,457,679-686).In organic solar batteries (OPV) field, the n-type organic semiconductor material (organic receptor material) that the body heterojunction organic solar batteries extensively adopts is limited to fullerene derivate (as PCBM etc.) more; In organic sensitization solar battery, the organic semiconductor sensitizing agent of employing mostly be p-type organic semiconductor material (Odobel, F.et al.Acc.Chem.Res.2010,43, DOI:10.1021/ar900275.).Therefore, n-type organic semiconductor material/organic receptor material development lags behind, and has become the technical bottleneck that organic electronic is learned development.
Naphthalenetetracarbacidic acidic diimide (NDI) is the n-type organic semiconductor material of a quasi-representative, is widely used in preparation n-type OTFT device.Yet the conjugation aromatic ring that it is less is difficult to form effective pi-pi accumulation in solid structure, and the electronic mobility of its OTFT device is lower.Recently, the contriver has disclosed the 2-(1 of a class formation novelty, solution processable, 3-two thiophenes cyclopentenes-2-subunit) the third dicyan condensed naphthalenetetracarbacidic acidic diimide class n-type organic semiconductor material (CN200910197611.9, J.Am.Chem.Soc.2010,132,3697-3699.), and having prepared their OFET thin-film device with the solution method for processing, electronic mobility is up to 0.51cm 2V -1s -1, and device has good air stability and operational stability, is the n-type organic small molecule material of the solution processable that electronic mobility is the highest so far, stability is best.In order to seek to have concurrently high electron mobility, ambient stable, the n-type organic semiconductor material of workability energy and the organic solar batteries acceptor material of excellent property, the contriver reports the thiation condensed naphthalenetetracarbacidic acidic diimide class n-type organic semiconductor material that other four classes are not appeared in the newspapers: 2-cyano group-2-(1,3-two thiophenes cyclopentenes-2-subunit) alkyl acetate condensed naphthalenetetracarbacidic acidic diimide derivatives, 2-(1,3-two thiophenes cyclopentenes-2-subunit)-2-phenethyl cyanogen condensed naphthalenetetracarbacidic acidic diimide derivatives, 1,4-two thiophene cyclohexadiene-2,3-dintrile condensed naphthalenetetracarbacidic acidic diimide derivatives and α, β-dicyano thiophene condensed naphthalenetetracarbacidic acidic diimide derivatives, and wherein part of compounds is applied to the OTFT device.
Goal of the invention
The object of the present invention is to provide four class thiation condensed naphthalenetetracarbacidic acidic diimide derivatives: 2-cyano group-2-(1,3-two thiophenes cyclopentenes-2-subunit) alkyl acetate condensed naphthalenetetracarbacidic acidic diimide derivatives, 2-(1,3-two thiophenes cyclopentenes-2-subunit)-2-phenethyl cyanogen condensed naphthalenetetracarbacidic acidic diimide derivatives, 1,4-two thiophene cyclohexadiene-2,3-dintrile condensed naphthalenetetracarbacidic acidic diimide derivatives and α, β-dicyano thiophene condensed naphthalenetetracarbacidic acidic diimide derivatives.
Another purpose of the present invention also is to provide the preparation method of above-mentioned four class thiation condensed naphthalenetetracarbacidic acidic diimide derivatives.
Another object of the present invention is to provide the application of above-mentioned four class thiation condensed naphthalenetetracarbacidic acidic diimide derivatives, construct the OTFT device as n-type organic semiconductor material.
Summary of the invention
Four class thiation condensed naphthalenetetracarbacidic acidic diimide derivatives provided by the invention, its structure is shown below:
Figure BSA00000167806000031
R in the formula on the thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives 1Be C 1～C 30Positive alkyl or branch's alkyl: the I class is 2-cyano group-2-(1,3-two thiophenes cyclopentenes-2-subunit) alkyl acetate condensed naphthalenetetracarbacidic acidic diimide derivatives, wherein R 2Be C 1～C 12Positive alkyl or branch's alkyl; The II class is 2-(1,3-two thiophenes cyclopentenes-2-subunit)-2-phenethyl cyanogen condensed naphthalenetetracarbacidic acidic diimide derivatives, wherein R 3Be H or Br; The III class is 1,4-two thiophene tetrahydrobenzene-2,3-dintrile condensed naphthalenetetracarbacidic acidic diimide derivatives; The IV class is α, β-dicyano thiophene condensed naphthalenetetracarbacidic acidic diimide derivatives.
Above-mentioned thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives specifically describes as follows:
Figure BSA00000167806000032
R in the formula 1, R 2, R 3As previously mentioned.
The present invention prepares the method for four class thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives, and its recommendation step is as follows:
A) alkyl cyanoacetates (CNCH 2COOR 2) or phenethyl cyanogen or 4-bromine phenethyl cyanogen, sodium hydride (NaH) and dithiocarbonic anhydride (CS 2) with mol ratio 1: 2～3: 1～1.5 (further recommending mol ratio to be followed successively by 1: 2～2.1: 1～1.1) at organic solvent such as tetrahydrofuran (THF), dioxane or N, in the dinethylformamide, successively under 0～5 ℃ and room temperature, reacted respectively 0.5～1 hour and 2～4 hours, obtain 2-alkyl cyanoacetates-ethene-1,1-two mercaptan sodium salts or 2-phenethyl cyanogen-ethene-1,1-two mercaptan sodium salts or 2-(4-bromine phenethyl cyanogen)-ethene-1,1-two mercaptan sodium salts;
B) to steps A) in the reaction solution of preparation (containing 2-alkyl cyanoacetates-ethene-1,1-two mercaptan sodium salts or 2-phenethyl cyanogen-ethene-1,1-two mercaptan sodium salts or 2-(4-bromine phenethyl cyanogen)-ethene-1,1-two mercaptan sodium salts) add N-alkyl (R 1) replace 2,3,6, the 7-tetrabromo for naphthalenetetracarbacidic acidic diimide (with CS in the steps A 2Mol ratio be 1: 5～10), under room temperature, reacted 0.5～2 hour;
C) N-alkyl (R 1) replace 2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide and 1,2-dicyano ethene-1,2-two mercaptan sodium salts (are recommended to buy or reference literature Inorg.Synth.1967 from TCI, 10,8. synthetic) with mol ratio 1: 2～3.5 at organic solvent such as tetrahydrofuran (THF), dioxane or N, in the dinethylformamide, under room temperature, reacted 0.5～1 hour;
D) compound that step C is made and hydrogen peroxide (recommend 30% hydrogen peroxide) with mol ratio 1: 50～80 acid as acetate or propionic acid in, in 100～120 ℃ of following heated and stirred 0.5～1.5 hour;
Recommend:
Described method, steps A～C reacts under rare gas element (high pure nitrogen or argon gas) protection.
Described method, the alkyl cyanoacetates (CNCH in the steps A 2COOR 2) reference literature Adv.Synth.Catal.2005,347,33-38. is synthetic.
Described method, used reactant among step B and the C wherein, N-alkyl (R 1) replace 2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, and is synthetic with reference to patent CN200910197611.9.
Described method, wherein the product of step B is 2-cyano group-2-(1,3-two thiophenes cyclopentenes-2-subunit) alkyl acetate condensed naphthalenetetracarbacidic acidic diimide (I class, R 1And R 2Be respectively C 1～C 30And C 1～C 12Positive alkyl or branch's alkyl) or 2-(1,3-two thiophenes cyclopentenes-2-subunit)-2-phenethyl cyanogen condensed naphthalenetetracarbacidic acidic diimide derivatives (II class, R 1Be C 1～C 30Positive alkyl or branch's alkyl, R 2Be H or Br).
Described method, wherein the product that obtains of step C is 1,4-two thiophene cyclohexadiene-2,3-dintrile condensed naphthalenetetracarbacidic acidic diimide derivatives (III class, R 1Be C 1～C 30Positive alkyl or branch's alkyl).
Described method, wherein the product that obtains of step D is α, β-dicyano thiophene condensed naphthalenetetracarbacidic acidic diimide derivatives (IV class, R 1Be C 1～C 30Positive alkyl or branch's alkyl).
Described method, wherein the target compound that obtains of step B～D is purified through silica gel column chromatography, and eluent is methylene dichloride/sherwood oil or toluene/sherwood oil mixed solution, and productive rate is 30～86%.
Described method, among step B～D the gained new compound through mass spectrum (MS-TOF), nuclear magnetic resonance spectrum ( 1H-NMR), one or more signs in the ultimate analysis, structure is errorless.
Shown in reaction formula among the embodiment, the present invention has provided the I～IV class thia ring and has condensed the part instantiation compound 1～13 and the synthetic schemes thereof of naphthalenetetracarbacidic acidic diimide derivatives.Three instantiation compounds 1～3 of 2-cyano group-2-(1,3-two thiophenes cyclopentenes-2-subunit) alkyl acetate condensed naphthalenetetracarbacidic acidic diimide derivatives (I class), its substituent R 1And R 2Be respectively 2-octyl group-dodecyl, ethyl (1); 2-octyl group-dodecyl, n-hexyl (2); N-octyl, 2-ethyl-hexyl (3).Two instantiation compound 5 (R of 2-(1,3-two thiophenes cyclopentenes-2-subunit)-2-phenethyl cyanogen condensed naphthalenetetracarbacidic acidic diimide derivatives (II class) 1And R 2Be respectively 2-octyl group-dodecyl and H) and 6 (R 1And R 2Be respectively 2-decyl-tetradecyl and Br).1,4-two thiophene cyclohexadiene-2, four instantiation compounds 6～9 of 3-dintrile condensed naphthalenetetracarbacidic acidic diimide derivatives (III class), its substituent R 1Be respectively 2-decyl-tetradecyl (6), 2-octyl group-dodecyl (7), 2-butyl-hexyl (8) and n-octyl (9).α, four instantiation compounds 10～13 of β-dicyano thiophene condensed naphthalenetetracarbacidic acidic diimide derivatives (IV class), its substituent R 1Be respectively 2-decyl-tetradecyl (10), 2-octyl group-dodecyl (11), 2-butyl-hexyl (12) and n-octyl (13).
Thiation condensed naphthalenetetracarbacidic acidic diimide derivatives of the present invention can be used as the semiconductor active layer and is used in the organic film FET.
Studied the photophysical property of compound 1～13 with ultra-violet absorption spectrum (UV); Studied the electrochemical properties of compound 1～13 with cyclic voltammetry (CV); And prepared the organic film FET device of compound 1,7 and 10 with the solution method for processing.
The invention has the advantages that:
1. the synthetic method of the present invention's disclosure is simply effective; Raw material is easy to synthetic preparation, and synthetic cost is low; The target compound purity height that obtains.
2. the thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives of the present invention's preparation has big pi-conjugated system and flexible short molten alkyl chain, can use the low-cost preparation of solution method for processing organic electronic devices (as OTFT and OPV etc.); Except the application on n-raceway groove OTFT device, the I compounds is expected to as n-type organic semiconductor material sensitizing agent play a role in dye sensitization solar battery (after the hydrolysis and coordination such as nickel oxide compound); Two bromo derivatives in the II compounds are expected to construct the D-A conjugated polymers semiconductor material that the arrowband gap length absorbs for the body polymerized unit as polymerization single polymerization monomer and other, are expected to can arrive application in organic solar batteries; The IV compounds has lower lumo energy and (4.6eV), is expected to be applied in organic electronic is learned as p-doping reagent.
Description of drawings
Fig. 1 is the ultra-violet absorption spectrum of compound 1 in methylene dichloride.
Fig. 2 is the cyclic voltammetry curve of compound 1 in methylene dichloride.
Fig. 3 is the ultra-violet absorption spectrum of compound 4 in methylene dichloride.
Fig. 4 is the cyclic voltammetry curve of compound 4 in methylene dichloride.
Fig. 5 is the ultra-violet absorption spectrum of compound 7 in methylene dichloride.
Fig. 6 is the cyclic voltammetry curve of compound 7 in methylene dichloride.
Fig. 7 is the ultra-violet absorption spectrum of compound 10 in methylene dichloride.
Fig. 8 is the cyclic voltammetry curve of compound 10 in methylene dichloride.
Fig. 9 is for being the structural representation of the OTFT device of organic layer with compound 1 or 7 or 10.
Figure 10 is the curve of output of the OTFT device of compound 1.
(electronic mobility is Figure 11: 0.016cm for the transition curve of the OTFT device of compound 1 2/ Vs, on-off ratio are 10 6, threshold voltage is 10 volts).
Figure 12 is the curve of output of the OTFT device of compound 7.
(electronic mobility is Figure 13: 10 for the transition curve of the OTFT device of compound 7 -3Cm 2/ Vs, on-off ratio are 10 4, threshold voltage is 8 volts).
Figure 14 is the curve of output of the OTFT device of compound 10.
(electronic mobility is Figure 15: 10 for the transition curve of the OTFT device of compound 10 -3Cm 2/ Vs, on-off ratio are 10 5, threshold voltage is 10 volts).
Embodiment
Following embodiment will help further to understand the present invention, but can not limit content of the present invention.
(1) embodiment compound 1-13 (I class: 1-3; II class: 4 and 5; III class: 6-9; IV class: preparation method 10-13)
The synthetic route of embodiment 1-3 is shown below:
Figure BSA00000167806000071
1:R 1=2-octyldodecyl (2-octyl group dodecyl), R 2=ethyl (ethyl)
2:R 1=2-octyldodecyl (2-octyl group dodecyl), R 2=n-hexyl (n-hexyl)
3:R 1=n-octyl (n-octyl), R 2=2-ethylhexyl (2-ethylhexyl)
THF is a tetrahydrofuran (THF), and rt represents room temperature.
Reaction formula: the synthetic route of 2-cyano group-2-(1,3-two thiophenes cyclopentenes-2-subunit) alkyl acetate condensed naphthalenetetracarbacidic acidic diimide derivatives
Embodiment 1:N, N '-two (2-octyl group-dodecyl)-[2,3-d:6,7-d ']-two [2-cyano group-2-(1,3-two thiophenes cyclopentenes-2-subunit) ethyl acetate]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (1) synthetic.
Concrete synthesis step is:
With ethyl cyanacetate (CNCH 3COOEt, 297mg, 2.63mmol) and dithiocarbonic anhydride (CS 20.16mL; 2.63mmol) be dissolved among the 25mL THF; under 0～5 ℃, under nitrogen protection, slowly drip above-mentioned solution to 132mg (5.3mmol) sodium hydride (NaH is housed; 96%) and in the there-necked flask of 5mL THF; last 0.5 hour, reaction solution is risen to room temperature, continued stirring reaction 4 hours; the N that in reaction solution, adds 300mg (0.26mmol); N '-two (2-octyl group-dodecyl)-2,3,6; the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide; at room temperature, continue reaction 0.5 hour, decompression is revolved and is desolvated.Crude product is purified through silica gel column chromatography, and (leacheate is methylene dichloride/sherwood oil, V/V=3/2), obtains garnet solid (compound 1) 270mg, productive rate 86%.
Mass spectrum: [MS (TOF)] m/z:1196.6 (M +).
Ultimate analysis: molecular formula: C 66H 92N 4O 8S 4Theoretical value: C, 66.18; H, 7.74; N, 4.68; Measured value: C, 66.24; H, 7.79; N, 4.45.
Nucleus magnetic hydrogen spectrum: 1H-NMR (300MHz, CDCl 3) δ (ppm): 0.847-0.857 (m, 6H, CH 3), 1.224 (b, 32H, CH 2), 1.415-1.464 (t, J=7.35Hz, 3H, (OCH 2) CH 3), 2.041 (b, 1H, CH), 4.228-4.252 (d, J=7.2Hz, 2H ,-CH 2-N), 4.398-4.467 (q, J=6.9Hz, 2H ,-CH 2-O).
Embodiment 2:N, N '-two (2-octyl group-dodecyl)-[2,3-d:6,7-d ']-two [2-cyano group-2-(1,3-two thiophenes cyclopentenes-2-subunit) n-hexyl acetate]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (2) synthetic.
Concrete synthesis step is:
Replace ethyl cyanacetate with the just own ester of cyanoacetic acid, synthetic method prepares dark brown solid (2), productive rate 59% with step among the embodiment 1.
Mass spectrum: [MS (TOF)] m/z:1308.7 (M +).
Ultimate analysis: molecular formula: C 74H 108N 4O 8S 4Theoretical value: C, 67.85; H, 8.31; N, 4.28; Measured value: C, 67.87; H, 8.57; N, 3.85.
Nucleus magnetic hydrogen spectrum: 1H-NMR (300MHz, CDCl 3) δ (ppm): 0.854-0.942 (m, 9H, CH 3), 1.223-1.368 (m, 38H, CH 2), 1.741-1.832 (m, 2H, CH 2), 2.043 (b, 1H, CH), 4.227-4.251 (d, J=7.2Hz, 2H ,-CH 2-N), 4.335-4.378 (t, J=6.5Hz, 2H ,-CH 2-O).
Embodiment 3:N, N '-two (n-octyl)-[2,3-d:6,7-d ']-two [2-cyano group-2-(1,3-two thiophenes cyclopentenes-2-subunit) acetate 2-ethylhexyl]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (3) synthetic.
Concrete synthesis step is:
Use cyanoacetic acid 2-ethylhexyl and N respectively, N '-two (n-octyl)-2,3,6, the 7-tetrabromo replaces ethyl cyanacetate and N for naphthalenetetracarbacidic acidic diimide, N '-two (2-octyl group-dodecyl)-2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, synthetic method prepares dark brown solid (3), productive rate 40.8% with step among the embodiment 1.
Mass spectrum: [MS (TOF)] m/z:1051.1 (M ++ Na), 1074.1 (M ++ 2Na).
Ultimate analysis: molecular formula: C 54H 68N 4O 8S 4Theoretical value: C, 63.01; H, 6.66; N, 5.44; Measured value: C, 63.03; H, 6.61; N, 5.34.
Nucleus magnetic hydrogen spectrum: 1H-NMR (300MHz, CDCl 3) δ (ppm): 0.926-0.932 (m, 9H, CH 3), 1.302 (b, 18H, CH 2), 1.784-1.1.814 (m, 3H, overlapped, (CH 3) CH 2(CH) and CH), 4.282-4.295 (m, 4H, overlapped ,-CH 2-N and-CH 2-O).
Embodiment 4 and 5 synthetic route are shown below:
Figure BSA00000167806000091
4:R 1=2-decyltetradecyl (2-decyl tetradecyl), R 2=H (hydrogen)
5:R 1=2-octyldodecyl (2-octyl group dodecyl), R 2=Br (bromine)
The synthetic route of reaction formula: 2-(1,3-two thiophenes cyclopentenes-2-subunit)-2-phenethyl cyanogen condensed naphthalenetetracarbacidic acidic diimide derivatives
Embodiment 4:N, N '-two (2-decyl-tetradecyl)-[2,3-d:6,7-d ']-two [2-(1,3-two thiophenes cyclopentenes-2-subunit)-2-phenethyl cyanogen]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (4) synthetic.
Concrete synthesis step is:
Under nitrogen protection; with 40.9mg (1.7mmol) sodium hydride (NaH, 96%), 92 μ L phenethyl cyanogens (0.8mmol) and 5mL DMF add in the there-necked flask of 50mL; under 0～5 ℃; react adding 53 μ L (0.88mmol) dithiocarbonic anhydride after 0.5 hour, reaction solution rises to room temperature, continues reaction 2 hours; in reaction solution, add 103mg (0.08mmol) N; N '-two (2-decyl-tetradecyl)-2,3,6; the 7-tetrabromo is for the naphthalenetetracarbacidic acidic diimide ethyl cyanacetate; under the room temperature, continue reaction 0.5 hour, in reaction solution impouring 100mL water; molten 4 * 50mL dichloromethane solution extraction; merge organic phase, after the drying, decompression is revolved and is desolvated.Crude product is purified through silica gel column chromatography, and (leacheate is methylene dichloride/sherwood oil, V/V=4/5), obtains bluish voilet solid (compound 4) 52mg, productive rate 48%.
Mass spectrum: [MS (TOF)] m/z:1317.7 (M +).
Nucleus magnetic hydrogen spectrum: 1H-NMR (300MHz, CDCl 3) δ (ppm): 0.837-0.878 (m, 6H, CH 3), 1.217 (b, 40H, CH 2), 2.014 (m, 1H, CH), 4.158-4.185 (m, 2H ,-CH 2-N), 7.419-7.471 (m, 1H, Ar-H), 7.518-7.568, (m, 2H, Ar-H), 7.677-7.704, (d, J=8.1Hz, 2H, Ar-H).
Embodiment 5:N, N '-two (2-octyl group-dodecyl)-[2,3-d:6,7-d ']-two [2-(1,3-two thiophenes cyclopentenes-2-subunit)-2-(4-bromine phenethyl cyanogen)]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (5) synthetic.
Concrete synthesis step is:
Use 4-bromo phenethyl cyanogen and N respectively, N '-two (2-octyl group-dodecyl)-2,3,6, the 7-tetrabromo replaces phenethyl cyanogen and N for naphthalenetetracarbacidic acidic diimide, N '-two (2-decyl-tetradecyl)-2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, synthetic method prepares bluish voilet solid (5), productive rate 60% with step among the embodiment 4.
Mass spectrum: [MS (TOF)] m/z:1364.7 (M+H) +.
Nucleus magnetic hydrogen spectrum: 1H-NMR (300MHz, CDCl 3) δ (ppm): 0.855 (b, 6H), 1.221 (b, 32H), 1.993 (b, 1H, CH), 4.165 (b, 2H ,-CH 2-N), 7.580 (m, 2H, Ar-H), 7.664, (m, 2H, Ar-H).
The synthetic route of embodiment 6～9 is shown below:
Figure BSA00000167806000101
6:R 1=2-decyltetradecyl (2-decyl-tetradecyl)
7:R 1=2-octyldodecyl (2-octyl group dodecyl)
8:R 1=2-butylhexyl (2-butyl hexyl)
9:R 1=n-octyl (n-octyl)
Reaction formula: 1,4-two thiophene cyclohexadiene-2, the synthetic route of 3-dintrile condensed naphthalenetetracarbacidic acidic diimide derivatives
Embodiment 6:N, N '-two (2-decyl-tetradecyl)-[2,3-d:6,7-d ']-two [1,4-two thiophene tetrahydrobenzene-2,3-dintrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (6) synthetic.
Under the nitrogen protection; in the 100ml there-necked flask, add 700mg (0.56mmol) N, N '-two (2-decyl-tetradecyl)-2,3; 6; the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, 313mg (1.68mmol) 1,2-dicyano ethene-1; 2-two mercaptan sodium salts; the 70mL tetrahydrofuran (THF), room temperature reaction 1 hour, decompression was revolved and is desolvated.Crude product is purified through silica gel column chromatography, and (leacheate is toluene/sherwood oil, V/V=2/1), obtains red solid (compound 6) 270mg, and productive rate is 39.6%.
Mass spectrum: [MS (TOF)] m/z:1217.3 (M+2H) 2+.
Ultimate analysis: molecular formula: C 70H 98N 6O 4S 4Theoretical value: C, 69.15; H, 8.12; N, 6.91; Measured value: C, 69.45; H, 7.96; N, 6.86.
Nucleus magnetic hydrogen spectrum: 1H-NMR (300MHz, CDCl 3) δ (ppm): 0.852-0.895 (m, 6H, CH 3), 1.246 (b, 40H, CH 2), 1.929-1.970 (m, 1H, CH), 4.113-4.138 (d, J=7.5Hz, 2H ,-CH 2-N).
Embodiment 7:N, N '-two (2-octyl group-dodecyl)-[2,3-d:6,7-d ']-two [1,4-two thiophene tetrahydrobenzene-2,3-dintrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (7) synthetic.
Concrete synthesis step is:
Use N, N '-two (2-octyl group-dodecyl)-2,3,6, the 7-tetrabromo replaces N for naphthalenetetracarbacidic acidic diimide, N '-two (2-decyl-tetradecyl)-2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, synthetic method prepares red solid (7) with step among the embodiment 6, and productive rate is 34.5%.
Mass spectrum: [MS (TOF)] m/z:1105.7 (M+2H) 2+.
Ultimate analysis: molecular formula: C 62H 82N 6O 4S 4Theoretical value: C, 67.48; H, 7.49; N, 7.62; Measured value: C, 67.66; H, 7.35; N, 7.61.
Nucleus magnetic hydrogen spectrum: 1H-NMR (300MHz, CDCl 3) δ (ppm): 0.871 (m, 6H, CH 3), 1.251 (b, 32H, CH 2), 1.951 (b, 1H, CH), 4.116-4.138 (d, J=6.6Hz, 2H ,-CH 2-N).
Embodiment 8:N, N '-two (2-butyl-hexyl)-[2,3-d:6,7-d ']-two [1,4-two thiophene tetrahydrobenzene-2,3-dintrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (8) synthetic.
Concrete synthesis step is:
Use N, N '-two (2-butyl-hexyl)-2,3,6, the 7-tetrabromo replaces N for naphthalenetetracarbacidic acidic diimide, N '-two (2-decyl-tetradecyl)-2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, and synthetic method prepares red solid (8), productive rate 72.5% with step among the embodiment 6.
Mass spectrum: [MS (TOF)] m/z:882.0 (M+3H) 3+., 902.0 (M+Na) +.
Nucleus magnetic hydrogen spectrum: 1H-NMR (500MHz, CDCl 3) δ (ppm): 0.854-0.928 (m, 6H, CH 3), 1.281 (b, 16H, CH 2), 1.958 (b, 1H, CH), 4.121-4.145 (d, J=7.2Hz, 2H ,-CH 2-N).
Embodiment 9:N, N '-two (n-octyl)-[2,3-d:6,7-d ']-two [1,4-two thiophene tetrahydrobenzene-2,3-dintrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (9) synthetic.
Concrete synthesis step is:
Use N, N '-two (n-octyl)-2,3,6, the 7-tetrabromo replaces N for naphthalenetetracarbacidic acidic diimide, N '-two (2-decyl-tetradecyl)-2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, and synthetic method prepares red solid (9), productive rate 66% with step among the embodiment 6.
Mass spectrum: [MS (TOF)] m/z:769.9, (M+3H) 3+
Nucleus magnetic hydrogen spectrum: 1H-NMR (500MHz, CDCl 3) δ (ppm): 0.868-0.913 (t, J=6.75Hz, 3H, CH 3), 1.253-1.400 (m, 10H, CH 2), 1.721-1.749 (m, 2H, CH 2), 4.149-4.199 (t, J=7.5Hz, 2H ,-CH 2-N).
The synthetic route of embodiment 10～13 is shown below:
Figure BSA00000167806000121
10:R 1=2-decyltetradecyl (2-decyl-tetradecyl)
11:R 1=2-octyldodecyl (2-octyl group dodecyl)
12:R 1=2-butylhexyl (2-butyl hexyl)
13:R 1=n-octyl (n-octyl)
Reaction formula α, the synthetic route of β-dicyano thiophene condensed naphthalenetetracarbacidic acidic diimide derivatives (comprising two kinds of cis-trans isomerism compounds)
Embodiment 10:N, N '-two (2-decyl-tetradecyl)-[2,3-d:6,7-d ']-two [α, β-dicyano thiophene]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (10) synthetic.
Concrete synthesis step is:
In the 100ml there-necked flask, add 118mg (0.1mmol) N, N '-two (2-decyl-tetradecyl)-[2,3-d:6,7-d ']-two [1,4-two thiophene tetrahydrobenzene-2, the 3-dintrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (6) and 50mL propionic acid, heated and stirred to solid dissolves, and adds the H of 1.74mL 30% in reaction solution 2O 2(17mmol), in 120 ℃ of following heated and stirred reactions 1 hour, reaction solution is reduced to room temperature, in the impouring 200mL water, suction filtration is behind the thick product drying of gained, (leacheate is methylene dichloride/sherwood oil through the silica gel column chromatography purification, V/V=2/1), obtain shiny red solid (compound 10) 34mg, productive rate is 30.4%.
Mass spectrum: [MS (TOF)] m/z:1174.6 (M+Na) +, 1196.7 (M+2Na) 2+, 1212.6 (M+Na+K) 2+. ultimate analysis: molecular formula: C 70H 98N 6O 4S 2Theoretical value: C, 73.00; H, 8.58; N, 7.30; Measured value: C, 73.16; H, 8.55; N, 6.90.
Nucleus magnetic hydrogen spectrum: 1H-NMR (300MHz, CDCl 3) δ (ppm): 0.848-0.890 (m, 6H, CH 3), 1.230-1.410 (m, br, 40H, CH 2), 2.055-2.134 (m, 1H, CH), 4.299-4.375 (m, 2H, CH 2-N).
Embodiment 11:N, N '-two (2-octyl group-dodecyl)-[2,3-d:6,7-d ']-two [α, β-dicyano thiophene]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (11) synthetic.
Use N, N '-two (2-octyl group-dodecyl)-2,3,6, the 7-tetrabromo replaces N for naphthalenetetracarbacidic acidic diimide, N '-two (2-decyl-tetradecyl)-2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, synthetic method prepares red solid (11) with step among the embodiment 10, and productive rate is 52%.
Mass spectrum: [MS (TOF)] m/z:1142.0 (M+3H) 3+, 1064.0 (M+2H+Na) 3+,
1085.0(M+2Na) 2+，1101.0(M+Na+K) 2+.
Nucleus magnetic hydrogen spectrum: 1H-NMR (300MHz, CDCl 3) δ (ppm): 0.837-0.867 (m, 6H, CH 3), 1.230-1.411 (m, 32H, CH 2), 2.053-2.127 (m, 1H, CH), 4.297-4.375 (m, 2H, CH 2-N).
Embodiment 12:N, N '-two (2-butyl-hexyl)-[2,3-d:6,7-d ']-two [α, β-dicyano thiophene]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (12) synthetic.
Concrete synthesis step is:
Use N, N '-two (2-butyl-hexyl)-2,3,6, the 7-tetrabromo replaces N for naphthalenetetracarbacidic acidic diimide, N '-two (2-decyl-tetradecyl)-2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, and synthetic method prepares shiny red solid (12), productive rate 37.4% with step among the embodiment 10.
Mass spectrum: [MS (TOF)] m/z:838.6 (M+Na) +, 860.7 (M+2Na) 2+, 876.6 (M+Na+K) 2+.
Nucleus magnetic hydrogen spectrum: 1H-NMR (500MHz, CDCl 3) δ (ppm): 0.831-0.900 (m, 6H, CH 3), 1.253-1.417 (m, 16H, CH 2), 2.066-2.147 (m, 1H, CH), 4.300-4.377 (m, 2H, CH 2-N).
Embodiment 13:N, N '-two (n-octyl)-[2,3-d:6,7-d ']-two [α, β-dicyano thiophene]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (13) synthetic.
Concrete synthesis step is:
Use N, N '-two (n-octyl)-2,3,6, the 7-tetrabromo replaces N for naphthalenetetracarbacidic acidic diimide, N '-two (2-decyl-tetradecyl)-2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, and synthetic method prepares shiny red solid (13), productive rate 46.5% with step among the embodiment 10.
Mass spectrum: [MS (TOF)] m/z:705.5 (M+3H) 3+, 727.5 (M+2H+Na) 3+, 748.5 (M+2Na) 2+, 764.5 (M+Na+K) 2+, 780.5 (M+2K) 2+.
Nucleus magnetic hydrogen spectrum: 1H-NMR (500MHz, CDCl 3) δ (ppm): 0.864-0.896 (t, 3H, CH 3), 1.254-1.512 (m, 10H, CH 2), 1.799-1.903 (m, 2H, CH 2), 4.366-4.445 (m, 2H, CH 2-N).
More than four class thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives (1～13), dissolve in common organic solvent, as chloroform, tetrahydrofuran (THF), chlorobenzene etc.
The ultra-violet absorption spectrum and the electrochemical properties of (2) the I-IV class thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives (compound 1-13)
Ultra-violet absorption spectrum carries out on the U-3900 spectrograph, and (volumetric molar concentration is 1 * 10 in the sample solution methylene dichloride -6M), sweep limit is 800-200nm, and the optical band gap of compound is calculated by following formula:
E gap opt＝1240nm/λ onset (1)
The cyclic voltammetry test is carried out on computer-controlled CHI610D electrochemical analyser, adopt three traditional electrode test systems, platinum electrode is a working electrode, saturated calomel electrode (SCE) is as reference electrode, platinum filament is as counter electrode, and sample is dissolved in the methylene dichloride of new steaming, and (volumetric molar concentration is 1 * 10 -3M), Bu 4NPF 6(0.1M) as supporting electrolyte, sweep velocity is 50mV/s, is reference with saturated calomel, and saturated calomel energy level is-4.44eV that the lumo energy of material can be calculated by the formula of following energy level with respect to vacuum level:
E LUMO＝-(E 1/2 red1+4.44)eV (2)
Because of similar thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives (I class: 1-3; II class: 4 and 5; III class: 6-9; IV class: 10-13) have similar ultra-violet absorption spectrum and electrochemical properties, here with compound 1 (R 1Be 2-octyl group-dodecyl, R 2Be ethyl), 4 (R 1Be 2-decyl-tetradecyl, R 2Be H), 7 (R 1Be 2-octyl group-dodecyl) and 10 (R 1Be 2-decyl-tetradecyl) describe for example.
Fig. 1 has provided the ultra-violet absorption spectrum of compound 1, and its maximum absorption peak position is about 581nm, and calculating optical band gap by formula (1) is 2.1eV.Fig. 2 has provided the cyclic voltammetry curve of compound 1, has shown two reversible redox processeses, and its half-wave potential is respectively E 1/2 Red1=-0.21eV and E 1/2 Red2=-0.66eV, the lumo energy that is calculated gained by formula (2) is-4.2eV.As shown in Figure 3, the maximum absorption peak position of the absorption spectrum of compound 4 is about 655nm, and calculating optical band gap by formula (1) is 1.8eV.The cyclic voltammetry curve of compound 4 (Fig. 4) has shown an irreversible redox processes (acromion having occurred) and a reversible redox processes (E 1/2 Red2=-0.81eV), its initial reduction potential E Red Onset=-0.23eV, the lumo energy that is calculated gained by following formula (3) is-4.2eV.
E LUMO＝-(E red onset+4.4)eV (3)
Fig. 5 has provided the ultra-violet absorption spectrum of compound 7, and its maximum absorption peak position is about 551nm, and calculating optical band gap by formula (1) is 2.0eV.Fig. 6 has provided the cyclic voltammetry curve of compound 7, has shown two reversible redox processeses, and its half-wave potential is respectively E 1/2 Red1=-0.17eV and E 1/2 Red2=-0.64eV, the lumo energy that is calculated gained by formula (2) is-4.3eV.
Fig. 7 has provided the ultra-violet absorption spectrum of compound 10, and its maximum absorption peak position is at 250～318nm, and the end absorption peak value is 568nm, but a little less than absorbing, demonstrates more weak intramolecular charge and shift, and calculating optical band gap by formula (1) is 2.2eV.Fig. 8 has provided the cyclic voltammetry curve of compound 10, has shown two reversible redox processeses, and its half-wave potential is respectively E 1/2 Red1=0.19eV and E 1/2 Red2=-0.40eV, the lumo energy that is calculated gained by formula (2) is-4.63eV.The IV compounds has lower lumo energy, is a class good electron acceptor material.
(3) compound 1,7 and 10 prepares organic film FET as the semiconductor active layer
It is the structural representation of the organic film FET (OTFT) of semiconductor layer that Fig. 9 has provided with compound 1 or 7 or 10.As shown in Figure 9, OTFT preparation of devices method is among the present invention: the compound 1 or 7 or 10 of 5-20mg is dissolved in the 1ml chloroform, at the SiO of OTS modification 2(highly doped silicon substrate is as grid, and the thickness of thermooxidizing silicon dioxide insulating layer is 450nm, and electric capacity is 10nFcm in the/Si substrate -2) get rid of the organic semiconductor thin film of the about 10-80nm thickness of last layer, on organic film, to utilize mask plate deposited gold source-drain electrode, thereby make the OTFT device of upper electrode arrangement, the semiconductor channel length of device is 50 μ m, channel width is 3mm.The electrical property of OTFT measures under air at room temperature with Keithley 4200 semi-conductor test instruments.
Figure 10 and Figure 11 have provided the curve of output and the transition curve figure of an OTFT device of compound 1 respectively, Figure 12 and Figure 13 have provided the curve of output and the transition curve of an OTFT device of compound 7 respectively, and Figure 14 and Figure 15 have provided the curve of output and the transition curve of an OTFT device of compound 10 respectively.The present invention has prepared a plurality of OTFT devices based on novel thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives with the solution method for processing, and the electronic mobility of device can reach 0.02cm 2/ Vs, on-off ratio is greater than 10 5
The invention is not restricted to 13 disclosed instantiation compounds, thia ring condensed naphthalenetetracarbacidic acidic diimide derivatives is of a great variety, and protection scope of the present invention limits with appended claims and is as the criterion.

Claims (9)

1.一类硫杂环稠合的萘四羧酸二酰亚胺衍生物，具有如下结构式：1. A class of sulfur heterocyclic fused naphthalene tetracarboxylic acid diimide derivatives, having the following structural formula:
Figure FSA00000167805900011
Figure FSA00000167805900011
 式中R1为C1～C30正烷基或分支烷基，R2为C1～C12正烷基或分支烷基，R3为H或Br。In the formula, R 1 is a C 1 -C 30 normal or branched alkyl group, R 2 is a C 1 -C 12 normal or branched alkyl group, and R 3 is H or Br. 2.根据权利要求1所述的一类硫杂环稠合的萘四羧酸二酰亚胺衍生物，其特征是具有结构式如下式所示的1，3-二硫杂环稠合的萘四羧酸二酰亚胺衍生物：2. the naphthalene tetracarboxylic acid diimide derivatives of a class of sulfur heterocycle fused according to claim 1, characterized in that there is a 1,3-dithio heterocycle fused naphthalene shown in the following formula Tetracarboxylic diimide derivatives:
Figure FSA00000167805900012
Figure FSA00000167805900012
 式中R1、R2、R3如权利要求1所述。In the formula, R 1 , R 2 , and R 3 are as described in claim 1. 3.根据权利要求1所述的一类硫杂环稠合的萘四羧酸二酰亚胺衍生物，其特征是具有结构式如下式所示的1，4-二硫杂环稠合的萘四羧酸二酰亚胺衍生物和α，β-二氰基噻吩稠合的萘四羧酸二酰亚胺衍生物：3. the naphthalene tetracarboxylic acid diimide derivatives of a class of sulfur heterocycle fused according to claim 1, characterized in that there is a 1,4-dithio heterocycle fused naphthalene shown in the following formula Tetracarboxylic diimide derivatives and α, β-dicyanothiophene fused naphthalene tetracarboxylic diimide derivatives:
Figure FSA00000167805900013
Figure FSA00000167805900013
 式中R1如权利要求1所述。In the formula, R 1 is as described in claim 1. 4.一种制备如权利要求1和2所述的一类硫杂环稠合的萘四羧酸二酰亚胺衍生物，其特征是通过步骤A)和B)获得1，3-二硫杂环稠合的萘四羧酸二酰亚胺衍生物Ⅰ和Ⅱ，通过步骤C)获得1，3-二硫杂环稠合的萘四羧酸二酰亚胺衍生物Ⅲ，通过步骤D)获得1，3-二硫杂环稠合的萘四羧酸二酰亚胺衍生物Ⅳ：4. A kind of naphthalene tetracarboxylic acid diimide derivative that prepares a class of sulfur heterocyclic fused as claimed in claim 1 and 2, it is characterized in that by step A) and B) obtain 1,3-disulfide Heterocyclic fused naphthalene tetracarboxylic diimide derivatives I and II by step C) to obtain 1,3-dithioheterocyclic fused naphthalene tetracarboxylic diimide derivative III by step D ) to obtain 1,3-dithioheterocyclic fused naphthalene tetracarboxylic acid diimide derivative IV: A)氰基乙酸烷基酯CNCH2COOR2或苯乙氰或4-溴苯乙氰、氢化钠NaH和二硫化碳CS2以摩尔比1∶2～3∶1～1.5在有机溶剂中，先后于0～5℃和室温下分别反应0.5～1小时和2～4小时；A) Alkyl cyanoacetate CNCH 2 COOR 2 or phenethyl cyanide or 4-bromo phenacetin cyanide, sodium hydride NaH and carbon disulfide CS 2 in an organic solvent with a molar ratio of 1:2～3:1～1.5, followed by React at 0-5°C and room temperature for 0.5-1 hour and 2-4 hours, respectively; B)向步骤A)制备的反应液中(含2-氰基乙酸烷基酯-乙烯-1，1-二硫醇钠盐或2-苯乙氰-乙烯-1，1-二硫醇钠盐或2-(4-溴苯乙氰)-乙烯-1，1-二硫醇钠盐)加入N-烷基R1取代的2，3，6，7-四溴代萘四羧酸二酰亚胺，所述的N-烷基R1取代的2，3，6，7-四溴代萘四羧酸二酰亚胺与步骤A中CS2的摩尔比为1∶5～10，于室温下反应0.5～2小时；B) In the reaction solution prepared in step A) (containing 2-alkyl cyanoacetate-ethylene-1,1-dithiol sodium salt or 2-phenylacetonitrile-ethylene-1,1-dithiol sodium salt or 2-(4-bromophenethylcyanide)-ethylene-1,1-dithiol sodium salt) by adding N-alkyl R 1 substituted 2,3,6,7-tetrabromonaphthalene tetracarboxylic acid di imide, the 2,3,6,7- tetrabromonaphthalene tetracarboxylic acid diimide substituted by the N-alkyl R and the molar ratio of CS in step A are 1: 5～10, React at room temperature for 0.5 to 2 hours; C)N-烷基R1取代的2，3，6，7-四溴代萘四羧酸二酰亚胺与1，2-二氰基乙烯-1，2-二硫醇钠盐以摩尔比1∶2～3.5在有机溶剂中，于室温下反应0.5～1小时；C) N-alkyl R substituted 2,3,6,7-tetrabromonaphthalene tetracarboxylic acid diimide and 1,2-dicyanoethylene-1,2-dithiol sodium salt in moles Ratio 1:2~3.5 in an organic solvent, react at room temperature for 0.5~1 hour; D)将1，4-二噻环己二烯-2，3-二腈稠合的萘四羧酸二酰亚胺衍生物与双氧水以摩尔比1∶50～80在酸中，于100～120℃下反应0.5～1.5小时；D) 1,4-dithiacyclohexadiene-2,3-dinitrile condensed naphthalene tetracarboxylic diimide derivatives and hydrogen peroxide in the acid at a molar ratio of 1:50 to 80, at 100 to React at 120°C for 0.5 to 1.5 hours; 其中，R1、R2、R3如权利要求1所述；硫杂环稠合的萘四羧酸二酰亚胺衍生物Ⅰ、Ⅱ、Ⅲ和Ⅳ如权利要求1至3所述。Wherein, R 1 , R 2 , R 3 are as described in claim 1; sulfur heterocyclic fused naphthalene tetracarboxylic diimide derivatives I, II, III and IV are as described in claims 1-3. 5.如权利要求4所述的方法中，其特征是所述的有机溶剂为四氢呋喃、二氧六环或N，N-二甲基甲酰胺。5. In the method as claimed in claim 4, it is characterized in that described organic solvent is THF, dioxane or N, N-dimethylformamide. 6.如权利要求4所述的方法，其特征是所述的反应步骤A-C是在惰性气体保护下进行，所述的产物经硅胶柱提纯。6. The method according to claim 4, characterized in that said reaction steps A-C are carried out under the protection of an inert gas, and said product is purified through a silica gel column. 7.如权利要求4所述的方法，其特征是步骤D)中所述的酸为乙酸或丙酸。7. The method according to claim 4, characterized in that the acid described in step D) is acetic acid or propionic acid. 8.一种如权利要求1至3任一项所述的硫杂环稠合的萘四羧酸二酰亚胺衍生物的用途，其特征是用于制备有机电子器件。8. The use of the sulfur heterocyclic fused naphthalene tetracarboxylic acid diimide derivative according to any one of claims 1 to 3, characterized in that it is used for the preparation of organic electronic devices. 9.如权利要求8所述的硫杂化稠合的萘四羧酸二酰亚胺衍生物的用途，其特征是用于作为半导体活性层制备有机薄膜场效应晶体管或者用于制备有机太阳能电池。9. the purposes of the naphthalene tetracarboxylic acid diimide derivatives of thia hybridization as claimed in claim 8 is characterized in that being used for preparing organic thin film field-effect transistor as semiconductor active layer or being used for preparing organic solar cell .
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US9997718B2 (en) 2015-04-13 2018-06-12 Samsung Electronics Co., Ltd. Organic photoelectric device image sensor and electronic device
WO2018012508A1 (en) 2016-07-12 2018-01-18 国立研究開発法人理化学研究所 Aromatic compound and use thereof
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CN110981890A (en) * 2019-12-13 2020-04-10 中国科学院化学研究所 Naphthalenetetracarboximide dithiocyclopentanone azine compound and its preparation and application
CN110981890B (en) * 2019-12-13 2020-11-17 中国科学院化学研究所 Naphthalimide-dithiocyclopentanone azine compound, and preparation and application thereof

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