CN103408570A - Naphthalimide derivant containing 1, 3-dithiol-2-yliden conjugation unit, preparation method and application - Google Patents
Naphthalimide derivant containing 1, 3-dithiol-2-yliden conjugation unit, preparation method and application Download PDFInfo
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- CN103408570A CN103408570A CN2013103229728A CN201310322972A CN103408570A CN 103408570 A CN103408570 A CN 103408570A CN 2013103229728 A CN2013103229728 A CN 2013103229728A CN 201310322972 A CN201310322972 A CN 201310322972A CN 103408570 A CN103408570 A CN 103408570A
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Abstract
The invention relates to a naphthalimide derivant containing 1, 3-dithiol-2-yliden conjugation units, a preparation method and application thereof. The chemical structure is shown in the specification, wherein when Pi-1 or Pi-2 is groups shown in the specification, R<1> or R<2> is a C1-30 alkyl (of which the formula is shown in the specification), and R<3> is H or alkyls of C1-4; when Pi-1 is equal to Pi-2 and further shown in the specification, the R<1> and the R<2> can not be alkyls at the same time; when the R<1> is equal to the R<2>, both the R<1> and the R<2> are alkyls. All variants of the derivant can be an n-type organic semi-conductor material when the derivant is used to prepare organic thin film transistor devices, and tests show that the electron mobility in the air can reach 0.2cm<2>V<-1>s<-1>.
Description
Technical field
The present invention relates to contain 1, the benzene-naphthalene diimide class organic semiconductor material of 3-bis-sulphur-2-ylide alkene conjugate unit, relate in particular to the benzene-naphthalene diimide derivative that contains 1,3-, bis-sulphur-2-ylide alkene conjugate unit, preparation method and as the application of n-type organic semiconductor material in organic film FET.
Background technology
OTFT (OTFT) is by electric field, to control the active part of solid-state organic semiconductor material conductive capability, is one of unit component the most basic in organic electronics.The OTFT device is comprised of electrode (source/drain/gate), insulation layer and organic semiconductor layer; The key parameter that characterizes the OTFT device performance comprises: (μ, unit are cm to carrier mobility
2V
-1s
-1), on-off ratio (I
On/ I
off) and threshold voltage (V
T, unit is V).OTFT has that preparation technology is simple, cost is low, quality is light, snappiness and the good advantages such as compatibility of plastic; it is at (the Forrest that has broad application prospects aspect the flexible electronic products such as smart card, electronic tag, Electronic Paper, Active Matrix LCD At, sensor, storer; S.R.Nature.2004; 428,911; Korzhov, M.et al.Physics Word.2008,29; Leenen, M.A.M.et al.Phys.Status Solidi A.2009,206,588; Special issue:Organic Electronics and Optoelectronics, Forrest, S.R.; Thompson, M.E.ed.Chem.Rev.2007,107,923; Gelinck, G.et al.Adv.Mater.2010,22,3778 etc.).The up-to-date prediction of Britain AIM, by 2029, the gross sales (GS) in flexible electronic product market, the whole world will reach 3,350 hundred million dollars, and wherein OTFT will be in very important effects of aspect performance such as the flexible display driver of tool growth potential, organic electronic label, organic sensors.
Organic semiconductor material is the key ingredient of OTFT, and the type by its transmission current carrier, be divided into p-type and n-type, and the former current carrier of transmission is mainly hole, and the latter is mainly electronics.Development for OTFT; p-type and n-type organic semiconductor material are of equal importance; by the two organic complementary circuit of jointly constructing (Organic complementary circuits) have that low in energy consumption, operating speed is fast, the advantage such as simplicity of design, noise tolerance limit are large; can be widely used in various organic Digital Logical Circuits; the basis (Crone that realizes the application of organic electronic functional device; B.et al.Nature2000,403,521.; Klauk, H.et al.Nature2007,445,745.).On the other hand; the development of OTFT; also require organic semiconductor material in suitable solvent, to have good solubleness; can be made into various active ink, utilize printed electronic (Printed electronics) technology, as: film, spray ink Printing, volume to volume printing etc. got rid of; big area, low cost, mass-producing prepare OTFT device and organic circuit (Arias; A.C.et al.Chem.Rev.2010,110,3).
Generally, the development of the p-type organic semiconductor material of solution processable is very fast, and the mobility of the OTFT device of some molecular material solution method film forming has met or exceeded the performance (0.1-1.0cm of amorphous silicon membrane device
2V
-1 s -1), wherein the OTFT device mobility of organic small molecule material is up to 1.0-31cm
2V
-1s
-1, the mobility of polymer materials reaches 0.6-10.5cm
2V
-1s
-1, and show good air stability (Minemawari, H.et al.Nature2011,475,364.; Li J.et al.Scientific Reports.2012, Doi:10.1038/srep00754).Yet; the development of n-type organic semiconductor material lags far behind p-type organic semiconductor material; the very shortage of n-type organic semiconductor material of high electron mobility, stable, solution processable; this has limited development (Anthony, J.E. based on the flexible electronic functional device of organic complementary circuit greatly; Et al.Adv.Mater.2010,22,3876).
Recently, the contriver has disclosed the benzene-naphthalene diimide class n-type organic semiconductor material (CN200910197611.9 that the thia ring of a series of solution processable condenses, CN201010207565.9 and CN201110225678.6), and prepared their OFET thin-film device by the method for solution processing, wherein 1, the benzene-naphthalene diimide compound that 3-bis-sulphur-2-ylide alkene condenses shows excellent device performance, and electronic mobility is many at 0.1cm
2V
-1s
-1Above, and device has good air stability and operational stability.Structure is various in order to seek, the regulatable novel thia benzene-naphthalene diimide compounds of energy level, what the contriver reported that other seven classes have no report contains 1, the benzene-naphthalene diimide class n-type organic semiconductor material of 3-bis-sulphur-2-ylide alkene conjugate unit: the I class is the 2-(1 that asymmetric N-replaces, 3-bis-sulphur-2-subunit) benzene-naphthalene diimide derivative that condenses of the third dicyan, wherein R
1For C
1～C
30Alkyl, R
2Benzyl for the 4-replacement; The II class is the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) third dicyan of asymmetric N-replacement condenses, wherein R
1For C
1～C
30Alkyl, R
2It is 2,2-phenylbenzene-ethyl; The III class is 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and Isosorbide-5-Nitrae-bis-sulphur-2, the asymmetric benzene-naphthalene diimide derivative condensed of 3-dicyano ethene; The IV class is 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2,3-dicyano thiophene; The V class is the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) Nitromethane 99Min. condenses; The VI class is the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) second cyanogen condenses; The VII class is 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2-(1,3-, bis-sulphur-2-subunit) second cyanogen, and will wherein be applied to the OTFT device.
Goal of the invention
The object of the present invention is to provide a class n-type organic semiconductor material, namely contain 1, the benzene-naphthalene diimide analog derivative of 3-bis-sulphur-2-ylide alkene conjugate unit: be the 2-(1 that asymmetric N-replaces as the I class, 3-bis-sulphur-2-subunit) benzene-naphthalene diimide derivative that condenses of the third dicyan, wherein R
1For C
1～C
30Alkyl, R
2Benzyl for the 4-replacement; The II class is the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) third dicyan of asymmetric N-replacement condenses, wherein R
1For C
1～C
30Alkyl, R
2It is 2,2-phenylbenzene-ethyl; The III class is 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and Isosorbide-5-Nitrae-bis-sulphur-2, the asymmetric benzene-naphthalene diimide derivative condensed of 3-dicyano ethene; The IV class is 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2,3-dicyano thiophene; The V class is the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) Nitromethane 99Min. condenses; The VI class is the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) second cyanogen condenses; The VII class is 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2-(1,3-, bis-sulphur-2-subunit) second cyanogen.
Another purpose of the present invention also is to provide the preparation method of the benzene-naphthalene diimide derivative that above-mentioned thia ring condenses.
Another object of the present invention is to provide the application of the benzene-naphthalene diimide derivative that above-mentioned thia ring condenses, construct the OTFT device as n-type organic semiconductor material.
Summary of the invention
The benzene-naphthalene diimide derivative that contains 1,3-, bis-sulphur-2-ylide alkene conjugate unit provided by the invention, its structure is shown below:
Wherein, π-1 or π-2=
Or
R
1Or R
2The alkyl of=C1～30 (alkyl of preferential C6～30, further recommend the alkyl of C8～24),
Or
R
3The alkyl of=H or C1～6; Wherein, as π-1=π-2=
The time, R
1And R
2Can not be alkyl simultaneously; Work as R
1=R
2The time, the two is alkyl.
Further example can be described as the following benzene-naphthalene diimide derivative that contains 1,3-, bis-sulphur-2-ylide alkene conjugate unit: the I class is the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) third dicyan of asymmetric N-replacement condenses, wherein R
1For C
1～C
30Alkyl, R
2Benzyl (R for the 4-replacement
3For C
1～C
4Alkyl, or H atom); The II class is the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) third dicyan of asymmetric N-replacement condenses, wherein R
1For C
1～C
30Alkyl, R
2It is 2,2-phenylbenzene-ethyl; The III class is 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and Isosorbide-5-Nitrae-bis-sulphur-2, the asymmetric benzene-naphthalene diimide derivative condensed of 3-dicyano ethene, wherein R
1=R
2, be C
1～C
30Alkyl; The IV class is 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2,3-dicyano thiophene, wherein R
1=R
2, be C1～C30 alkyl; The V class is the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) Nitromethane 99Min. condenses, wherein R
1=R
2, be C
1～C
30Alkyl; The VI class is the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) second cyanogen condenses, wherein R
1=R
2, be C
1～C
30Alkyl; The VII class is 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2-(1,3-, bis-sulphur-2-subunit) second cyanogen, wherein R
1=R
2, be C
1～C
30Alkyl.
The present invention prepares the method that the I～VII class contains the benzene-naphthalene diimide derivative of 1,3-, bis-sulphur-2-ylide alkene conjugate unit, the steps include:
(1) prepare the method for the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) the third dicyan that the asymmetric N-of I and II class replaces condenses, the steps include:
For naphthalenetetracarbacidic acidic dianhydride and 2,2-dicyano-ethene-1,1-bis-thiolate 1:2～6 in molar ratio reacted 0.5～12 hour under room temperature～80 ℃ in organic solvent by tetrabromo, then by two kinds of organic amine (R
1NH
2And benzylamine) or (R
1NH
2With 2,2-diphenyl-ethylamine) add in reaction solution, under ℃ condition of room temperature～80, reacted 1～12 hour; Described organic amine R
1NH
2, benzylamine (or 2,2-diphenyl-ethylamine) and tetrabromo be 1～3:1～3:1 for the mol ratio of naphthalenetetracarbacidic acidic dianhydride;
(2) prepare the method for the benzene-naphthalene diimide derivative of the asymmetric naphthalene core replacement of III and VII class, the steps include:
N-alkyl (R
1) replace 2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide and 2,2-dicyano ethene-1,1-bis-thiolate and 1,2-dicyano ethene-1,2-bis-thiolate or 2-cyano group ethene-1,1-bis-thiolate, reacted 0.5～3 hour under-10 ℃～50 ℃ in organic solvent with mol ratio 1:1～2:1～2;
(3) prepare the method for the benzene-naphthalene diimide derivative of the asymmetric naphthalene core replacement of IV class, the steps include:
By the hydrogen peroxide of III class benzene-naphthalene diimide derivative and 30% with mol ratio 1:50～80 in acetic acid or propionic acid, in 100～120 ℃ of lower heated and stirred 0.5～1.5 hour;
(4) prepare the method for the benzene-naphthalene diimide compound of the symmetrical naphthalene core replacement of V and VI class, the steps include:
N-alkyl (R
1) replace 2,3,6, the 7-tetrabromo is for benzene-naphthalene diimide and 2-nitroethylene-1,2-bis-thiolate or 2-cyano group ethene-1,2-bis-thiolate, reacted 0.5～3 hour with mol ratio 1:2～5 under room temperature～50 ℃ in organic solvent.
Described method, 2 in step (1), (2) wherein, 2-dicyano-ethene-1,2,3,6 in 1-bis-thiolate and step (1), 7-tetra-naphthalene bromide tetracid acid anhydrides are known compound, synthetic with reference to patent CN200910197611.9 method;
Described method, wherein the N-alkyl (R in step (2) and (4)
1) replace 2,3,6, the 7-tetrabromo is known compound for benzene-naphthalene diimide, synthetic with reference to patent CN200910197611.9 method;
Described method, 1 in step (2) wherein, 2-dicyano ethene-1,2-bis-thiolate are known compound, from TCI, buy or reference literature Inorg.Synth.1967,10,8. synthetic, 2-cyano group-ethene-1,1-bis-thiolate are known compound, reference literature Acta.Chem.Scand.1996,50,432 is synthetic;
Described method, the 2-nitro-ethene-1 in step (4) wherein, 1-bis-thiolate are known compound, reference literature Ber.Dtsch.Chem.Ges.1919,52,542 is synthetic;
Described method, wherein the organic solvent in step (1), (2), (4) is DMF, N,N-dimethylacetamide, tetrahydrofuran (THF) or dioxane;
Described method, reaction be in air or protection of inert gas under carry out, recommendation step (1), 2) and (4) in the reaction under protection of inert gas, carry out, described product is purified through silica gel column chromatography.
Described method, wherein the product of step (1) is the benzene-naphthalene diimide derivative (I class) that 2-(1,3-, bis-sulphur-2-subunit) the third dicyan that asymmetric N-replaces condenses, wherein R
1For C
1～C
30Alkyl, R
2Benzyl (R for the 4-replacement
3For C
1～C
4Alkyl, or H atom) and the benzene-naphthalene diimide derivative (II class) that condenses of 2-(1,3-, bis-sulphur-2-subunit) the third dicyan of replacing of asymmetric N-, wherein R
1For C
1～C
30Alkyl, R
2It is 2,2-phenylbenzene-ethyl.
Described method, wherein the product that obtains of step (2) is 2-(1,3-bis-sulphur-2-subunit) the third dicyan and 1,4-bis-sulphur-2, the asymmetric benzene-naphthalene diimide derivative condensed of 3-dicyano ethene (III class) and 2-(1,3-bis-sulphur-2-subunit) the asymmetric benzene-naphthalene diimide derivative condensed of the third dicyan and 2,3-dicyano thiophene (VII class), wherein R
1=R
2, be C1～C30 alkyl.
Described method, wherein the product that obtains of step (3) is 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2,3-dicyano thiophene (IV class), wherein R
1=R
2, be C1～C30 alkyl.
Described method, wherein the product that obtains of step (4) is 2-(1,3-bis-sulphur-2-subunit) benzene-naphthalene diimide derivative (VI class) that condenses of the benzene-naphthalene diimide derivative (V class) that condenses of Nitromethane 99Min. and 2-(1,3-, bis-sulphur-2-subunit) second cyanogen, wherein R
1=R
2, be C
1～C
30Alkyl.
Described method, the target compound that wherein step (1)-(4) obtain is purified through silica gel column chromatography, and eluent is methylene dichloride/sherwood oil or toluene/sherwood oil mixed solution.
Described method, step (1)-(4) gained new compound through mass spectrum (MS-TOF), nuclear magnetic resonance spectrum (
1H-NMR), one or more signs in ultimate analysis, structure is errorless.
The benzene-naphthalene diimide derivative that described method, the I of step (1)-(4) gained～VII class contain 1,3-, bis-sulphur-2-ylide alkene conjugate unit is applied in organic film FET as the semiconductor active layer.
As shown in above-mentioned chemical structural formula, the present invention has provided part instantiation compound 1～9 and the synthetic schemes thereof that the I～VII class contains the benzene-naphthalene diimide derivative of 1,3-, bis-sulphur-2-ylide alkene conjugate unit.An instantiation compound 1 of the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) the third dicyan that the asymmetric N-of I class replaces condenses, its substituent R
1For 2-octyl group-dodecyl, R
3For the tertiary butyl; An instantiation compound 2 of the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) the third dicyan that the asymmetric N-of II class replaces condenses, its substituent R
1For 2-octyl group-dodecyl; III class 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and Isosorbide-5-Nitrae-bis-sulphur-2, two instantiation compounds 3 of the asymmetric benzene-naphthalene diimide derivative condensed of 3-dicyano ethene and 4, wherein R
1=n-octyl (3), R
1=2-octyl group-dodecyl (4); Two instantiation compounds 5 of IV class 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2,3-dicyano thiophene and 6, wherein R
1=n-octyl (5), R
1=2-octyl group-dodecyl (6); Benzene-naphthalene diimide derivative instantiation compound 7, wherein a R that V class 2-(1,3-, bis-sulphur-2-subunit) Nitromethane 99Min. condenses
1=2-octyl group-dodecyl; Benzene-naphthalene diimide derivative instantiation compound 8, wherein a R that VI class 2-(1,3-, bis-sulphur-2-subunit) second cyanogen condenses
1=2-octyl group-dodecyl; VII class 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and the 2-asymmetric benzene-naphthalene diimide derivative condensed of (1,3-, bis-sulphur-2-subunit) second cyanogen instantiation compound 9, wherein a R
1=2-octyl group-dodecyl.
With ultra-violet absorption spectrum (UV), studied the photophysical property of compound 1～9; By cyclic voltammetry (CV), studied the electrochemical properties of compound 1～9; And by the method for solution processing, prepared compound 1,2,4 and the organic film FET device of 6-9.
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 obtained is high.
2. what prepared by the present invention contains 1, the benzene-naphthalene diimide derivative of 3-bis-sulphur-2-ylide alkene conjugate unit has different lumo energies :-4.1～-alkyl chain of 4.5eV, large pi-conjugated system and flexible dissolution, can be prepared with by the method low cost of solution processing organic electronic device (as OTFT etc.).
The accompanying drawing explanation
Fig. 1 is compound 1-3,5 and the ultra-violet absorption spectrum of 7-9 in methylene dichloride.
Fig. 2 is compound 1-3,5 and the cyclic voltammetry curve of 7-9 in methylene dichloride.
Fig. 3 is usingd the structural representation of compound 1 or 2 or 3 or 5 or 7 or 8 or 9 devices of the OTFT as organic layer.
Fig. 4 is the transition curve of the OTFT device of compound 1.
Fig. 5 is the transition curve of the OTFT device of compound 2.
Fig. 6 is the transition curve of the OTFT device of compound 3.
Fig. 7 is the transition curve of the OTFT device of compound 5.
Fig. 8 is the transition curve of the OTFT device of compound 7.
Fig. 9 is the transition curve of the OTFT device of compound 8.
Figure 10 is the transition curve of the OTFT device of compound 9.
Nomenclature
In Fig. 1 " Wavelength (nm) " be " absorbing wavelength (nanometer) ", " Absorbance (a.u.) " is " relatively absorption intensity ".
In Fig. 2, " Potential (V) " is " voltage (volt) ", and " Current (μ A) " is " electric current (microampere) ".
" V in Fig. 4-10
DS(V) " be " source-drain voltage (volt) ", " I
DS(μ A) " be " source-drain current (microampere) ", " V
GS(V) " be " grid voltage (volt) ".
Embodiment
Following embodiment will help further to understand the present invention, but can not limit content of the present invention.
(1) embodiment compound 1-9(I class: 1; II class: 2; III class: 3 and 9; IV class: 5 and 6; V class: 7; VI class: 8; VII class: preparation method 9)
Embodiment 1:N-(2-octyl group-dodecyl)-N '-(4-tertiary butyl benzyl)-[2,3-d:6,7-d ']-bis-[2-(1,3-bis-sulphur-2-subunit)-2-the third dicyan]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (1) synthetic.
Concrete synthesis step is:
Under nitrogen protection, by 2,3,6,7-tetrabromo naphthalenetetracarbacidic acidic dianhydride (TBNDA) (300mg, 0.51mmol) and 1,1-dicyano ethene-2,2-bis-sodium mercaptides (288mg, 1.54mmol) join in 50mL DMF, are heated to 50 ° of C.After stirring 1h, add 2-octyl group-lauryl amine (228mg, 0.77mmol) and 4-tert-butyl benzyl amine (125mg, 0.77mmol), under 50 ℃, continue reaction 5h.Be cooled to room temperature, by reaction solution impouring 100mL saturated ammonium chloride solution, filter, wash filter residue with water, vacuum-drying, the methylene dichloride/sherwood oil (2:1) of take is eluent, with silica gel column chromatography, thick product is carried out to separating-purifying, obtain the red-brown solid 50mg of compound 1, productive rate 10%.
Mass spectrum: [MS (TOF)] m/z:970.2 (M+1)
+; Proton nmr spectra:
1H-NMR (300MHz, CDCl
3) δ (ppm): 0.833 – 0.886 (m, 6H ， – CH
3), 1.228 – 1.269 (m, 32H ， – CH
2–), 1.580 (s, 9H ， – CH
3), 1.959 – 2.051 (m, 1H ， – CH –), 4.205 – 4.229 (d, 2H ， – CH
2–), 5.444 (s, 2H ， – CH
2–), 7.378 – 7.405 (d, 2H, Ph-H), 7.542-7.569 (d, 2H, Ph-H); Ultimate analysis calculated value (Anal.Calcd.For) C
53H
56N
6O
4S
4: C, 65.67; H, 5.82; N, 8.67; Measured value (Found): C, 65.54; H, 5.86; N, 8.45.
Embodiment 2:N-(2-octyl group-dodecyl)-N '-(2,2-phenylbenzene-ethyl)-[2,3-d:6,7-d ']-bis-[2-(1,3-bis-sulphur-2-subunit)-2-the third dicyan]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (2) synthetic.
Concrete synthesis step is:
With 2,2-diphenyl-ethylamine, replace tert-butyl benzyl amine, synthetic method, with step in embodiment 1, prepares red solid (2), productive rate 7%.
Mass spectrum: [MS (TOF)] m/z:1003.3 (M
+); Proton nmr spectra:
1H-NMR (300MHz, CDCl
3) δ (ppm): 0.839 – 0.891 (m, 6H ， – CH
3), 1.236 – 1.375 (m, 32H ， – CH
2–), 1.932-2.015 (b, 1H ， – CH-), 4.191 – 4.216 (d, 2H ， – CH
2–), 4.780 – 4.834 (t, 1H ， – CH –), 4.952-4.981 (d, 2H ， – CH
2–), 7.162 – 7.372 (m, 10H, Ph-H), 7.542-7.569 (d, 2H, Ph-H); Ultimate analysis calculated value (Anal.Calcd.For) C
56H
54N
6O
4S
4: C, 67.04; H, 5.42; N, 8.38; Measured value (Found): C, 67.32; H, 5.64; N, 8.51.
Embodiment 3:N, N '-bis-(2-octyl group-dodecyl)-[2,3-d]-[2-(1,3-, bis-sulphur-2-subunit)-2-the third dicyan]-[6,7-d '] [Isosorbide-5-Nitrae-bis-thiophene tetrahydrobenzene-2,3-dintrile]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (3) synthetic.
Concrete synthesis step is:
Under nitrogen protection; by N, N '-bis-(2-octyl group-dodecyl)-2,3; 6; 7-tetrabromo benzene-naphthalene diimide (TBNDI-C20) (500mg, 0.44mmol), 1,1-dicyano ethene-2; 2-bis-sodium mercaptides (122mg; 0.66mmol) and 1,2-dicyano ethene-1,2-bis-sodium mercaptides (150mg; 0.79mmol) join in 100mL THF; after-10 ℃ of lower stirring reaction 2.5h, be cooled to room temperature, by reaction solution impouring 200mL water; molten 4 * 100mL dichloromethane solution extraction; merge organic phase, after drying, desolventizing is revolved in decompression.Crude product is purified through silica gel column chromatography, and (leacheate is methylene dichloride/sherwood oil, V/V=1/1), obtains the red solid 182mg of compound 3, productive rate 38%.
Mass spectrum: MS (MALDI-TOF) m/z1140.1 (M+H)
+; Proton nmr spectra:
1H-NMR (300MHz, CDCl
3) δ (ppm): 0.869-0.898 (m, 6H ， – CH
3), 1.259 – 1.432 (m, 32H ， – CH
2–), 2.009 (br, 1H, CH), 4.194 – 4.213 (d, 2H, J=5.70Hz ， – CH
2– N); Carbon-13 nmr spectra:
13C-NMR (100MHz, CDCl
3): δ 14.104,22.652, and 22.665,26.183,29.269,29.327,29.510,29.562,29.623,29.998,31.458,31.862,31.901,36.519,46.305,111.360,111.565,117.566,121.554,122.659,125.838,140.302,145.331,161.583 (C=O), 182.125 (=CS
2); Ultimate analysis calculated value (Anal.Calcd) .For C
62H
82N
6O
4S
4: C, 67.48; H, 7.49; N, 7.62. measured value (Found): C, 67.60; H, 7.60; N, 7.51.
Embodiment 4:N, N '-bis-(n-octyl)-[2,3-d]-[2-(1,3-, bis-sulphur-2-subunit)-2-the third dicyan]-[6,7-d '] [Isosorbide-5-Nitrae-bis-thiophene tetrahydrobenzene-2,3-dintrile]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (4) synthetic.
Concrete synthesis step is:
Use N, N '-bis-(n-octyl)-2,3,6,7-tetrabromo benzene-naphthalene diimide (TBNDI-C8) replaces N, N '-bis-(2-octyl group-dodecyl)-2,3,6,7-tetrabromo benzene-naphthalene diimide (TBNDI-C20), synthetic method, with step in embodiment 3, prepares red-purple solid (4), productive rate 40%.
Mass spectrum: MS (MALDI-TOF) m/z766.94 (M+H)
+; Proton nmr spectra:
1H-NMR (300MHz, CDCl
3) δ (ppm): 0.87 – 0.89 (m, 3H ， – CH
3), 1.30 – 1.41 (m, 10H ， – CH
2–), 1.77 (m, 2H ， – CH
2–), 4.21 – 4.26 (m, 2H ， – CH
2– N); Ultimate analysis calculated value (Anal.Calcd): ForC
38H
34N
6O
4S
4: C, 59.51; H, 4.47; N, 10.96. measured value (Found): C, 59.42; H, 4.82; N, 10.89.
Embodiment 5:N, N '-bis-(2-octyl group-dodecyl)-[2,3-d]-[2-(1,3-, bis-sulphur-2-subunit)-2-the third dicyan]-[6,7-d '] [2,3-dicyano thiophene]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (5) synthetic.
Concrete synthesis step is:
In the 50mL there-necked flask, add 100mg (0.09mmol) N, N '-bis-(2-octyl group-dodecyl)-[2,3-d]-[2-(1,3-, bis-sulphur-2-subunit)-2-the third dicyan]-[6,7-d '] [1,4-bis-thiophene tetrahydrobenzene-2, the 3-dintrile]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (3) and 10mL propionic acid, heated and stirred be to dissolution of solid, to the H that adds 0.7mL30% in reaction solution
2O
2(6.8mmol), in 120 ℃ of lower heated and stirred reactions 40 minutes, reaction solution is down to room temperature, in impouring 50mL water, suction filtration, after the thick product drying of gained, through silica gel column chromatography, purifying, (leacheate is methylene dichloride/sherwood oil, V/V=1/1), obtain red solid (compound 5) 81mg, productive rate is 84%.
Mass spectrum: MS (MALDI-TOF) m/z1071.6 (M+H)
+, proton nmr spectra:
1H-NMR (300MHz, CDCl
3) δ (ppm): 0.846 – 0.883 (m, 6H ， – CH
3), 1.249 – 1.433 (m, 32H ， – CH
2–), 2.080 – 2.092 (br, 1H, CH), 4.292 – 4.331 (t, 2H ， – CH
2– N), carbon-13 nmr spectra:
13C-NMR (100MHz, CDCl
3): δ 14.095, 22.640, 22.660, 26.219, 26.320, 29.272, 29.319, 29.505, 29.557, 29.616, 29.990, 30.062, 31.477, 31.545, 31.851, 31.894, 36.544, 36.592, 46.295, 111.100, 111.320, 111.375, 111.480, 117.165, 117.186, 117.509, 118.221, 118.665, 120.942, 124.667, 125.336, 134.757, 134.778, 135.084, 142.705, 146.885, 147.911, 147.927, 161.003 (C=O), 162.133 (C=O), 162.167 (C=O), 162.269 (C=O), 181.788 (=CS
2), ultimate analysis calculated value (Anal.Calcd) .For C
62H
82N
6O
4S
3: C, 69.49, H, 7.71, N, 7.84. measured value (Found): C, 69.58, H, 7.73, N, 7.84.
Embodiment 6:N, N '-bis-(n-octyl)-[2,3-d]-[2-(1,3-, bis-sulphur-2-subunit)-2-the third dicyan]-[6,7-d '] [2,3-dicyano thiophene]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (6) synthetic.
Concrete synthesis step is:
Use N, N '-bis-(n-octyl)-[2,3-d]-[2-(1,3-bis-sulphur-2-subunit)-2-the third dicyan]-[6,7-d '] [Isosorbide-5-Nitrae-bis-thiophene tetrahydrobenzene-2, the 3-dintrile]-naphthalene-1,4,5,8-tetracarboxylic acid diimide (4) replaces N, N '-bis-(2-octyl group-dodecyl)-[2,3-d]-[2-(1,3-, bis-sulphur-2-subunit)-2-the third dicyan]-[6,7-d '] [1,4-bis-thiophene tetrahydrobenzene-2, the 3-dintrile]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (3), synthetic method, with step in embodiment 4, prepares red solid (6), productive rate 63%.
Mass spectrum: MS (MALDI-TOF) m/z734.96 (M+H)
+; Proton nmr spectra: H-NMR (300MHz, CDCl
3) δ (ppm): 0.85 – 0.87 (m, 6H ， – CH
3), 1.21 – 1.39 (m, 10H ， – CH
2–), 1.82 (br, 2H ， – CH
2–), 4.32 – 4.35 (m, 2H ， – CH
2– N); Carbon-13 nmr spectra:
13C-NMR (100MHz, CDCl
3): δ 0.03,0.99, and 14.07,22.59,26.99,27.02; 27.87,27.94,29.13,31.73,42.31,42.42; 72.44,76.68,77.00,77.32,111.13,111.28; 111.33,111.70,117.27,120.95,124.65; 125.34,134.89,134.95,142.61,146.86; 147.81,160.75,161.84,161.92,181.75; Ultimate analysis calculated value (Anal.Calcd) .For C
38H
34N
6O
4S
3: C, 62.10; H, 4.66; N, 11.44; Measured value (Found): C, 62.24; H, 4.81; N, 11.54.
Embodiment 7:N, N '-bis-(2-octyl group-dodecyl)-[2,3-d:6,7-d ']-bis-[2-(1,3-, bis-sulphur-2-subunit)-2-Nitromethane 99Min.]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (7) synthetic.
Concrete synthesis step is:
Under nitrogen protection; in the 100ml there-necked flask, add 500mg (0.44mmol) N; N '-bis-(2-octyl group-dodecyl)-2,3,6; the 7-tetrabromo is for benzene-naphthalene diimide; 280mg (1.31mmol) 2-nitroethylene-1,1-bis-mercaptan sodium salts, 100mL tetrahydrofuran (THF); room temperature reaction 1 hour, desolventizing was revolved in decompression.Crude product is purified through silica gel column chromatography, and (leacheate is toluene/sherwood oil, V/V=1/1), obtains blue solid (compound 7) 145mg, and productive rate is 30%.
Mass spectrum: MS (MALDI-TOF) m/z1094.1 (M+H)
+; Proton nmr spectra:
1H-NMR (300MHz, CDCl
3) δ (ppm): 0.859 (m, 6H ， – CH
3), 1.234 – 1.241 (m, 32H ， – CH
2–), 2.039 (br, 1H, CH), 4.222 – 4.241 (d, 2H ， – CH
2– N), 7.802 (s, 1H ,=CH – NO
2); Carbon-13 nmr spectra:
13C-NMR (100MHz, CDCl
3): δ 14.083,22.655, and 26.304,29.313,29.338,29.553; 29.631,29.664,30.050,31.480,31.870,31.899; 36.341,36.464,36.587,46.082,116.464; 116.728,117.469,117.713,124.777,124.876; 124.948,125.607,143.718,143.942,147.165; 147.422,161.641,161.694,162.007,162.339; Ultimate analysis calculated value (Anal.Calcd) .For C
58H
84N
4O
8S
4: C, 63.70; H, 7.74; N, 5.12; Measured value (Found): C, 63.92; H, 7.66; N, 4.91.
Embodiment 8:N, N '-bis-(2-octyl group-dodecyl)-[2,3-d:6,7-d ']-bis-[2-(1,3-, bis-sulphur-2-subunit)-2-second cyanogen]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (8) synthetic.
Concrete synthesis step is:
With 2-cyano group ethene-1,1-bis-mercaptan sodium salts replace 2-nitroethylene-1,1-bis-mercaptan sodium salts, and synthetic method, with step in embodiment 7, prepares bluish voilet solid (8), and productive rate is 87%.
Mass spectrum: MS (MALDI-TOF) m/z1053.9 (M+H)
+; Proton nmr spectra:
1H-NMR (300MHz, CDCl
3) δ (ppm): 0.871 (m, 6H ， – CH
3), 1.239 (m, 32H ， – CH
2–), 2.003 (br, 1H, CH), 4.170 – 4.190 (d, 2H ， – CH
2– N), 5.684 (s, 1H ,=CH – CN); Carbon-13 nmr spectra:
13C-NMR (100MHz, CDCl
3): δ 14.096,22.659, and 26.277,29.299,29.336,29.516; 29.569,29.626,30.004,31.465,31.865; 31.902,36.450,45.862,45.951,46.047; 84.956,115.517,115.686,115.779,115.862; 124.596,124.666,124.749,146.315,146.437; 146.585,146.682,161.927,162.064,164.425; Ultimate analysis calculated value (Anal.Calcd) .For C
60H
84N
4O
4S
4: C, 68.40; H, 8.04; N, 5.32; Measured value (Found): C, 68.48; H, 7.98; N, 5.22.
Embodiment 9:N, (2-octyl group-dodecyl)-[2,3-d]-[2-(1 for N '-bis-, 3-bis-sulphur-2-subunit)-2-the third dicyan]-[6,7-d '] [2-(1,3-, bis-sulphur-2-subunit)-2-second cyanogen]-naphthalene-1, synthesizing of 4,5,8-tetracarboxylic acid diimide (9).
Concrete synthesis step is:
Under nitrogen protection; by N, N '-bis-(2-octyl group-dodecyl)-2,3; 6; 7-tetrabromo benzene-naphthalene diimide (TBNDI-C20) (50mg, 0.044mmol), 2-cyano group ethene-1,1-bis-mercaptan sodium salt (11mg; 0.047mmol) and 1; 1-dicyano ethene-2,2-bis-sodium mercaptides (16mg, 0.086mmol) join in 10mL THF; after stirring reaction 1h under room temperature; continuation, at 50 ℃ of reaction 1h, is cooled to room temperature, by reaction solution impouring 20mL water; molten 4 * 15mL dichloromethane solution extraction; merge organic phase, after drying, desolventizing is revolved in decompression.Crude product is purified (leacheate is methylene dichloride/sherwood oil, V/V=1/2～2/3～2/1) through silica gel column chromatography, obtains the purple solid 16mg of compound 9, productive rate 34%.
Mass spectrum: MS (MALDI-TOF) m/z1078.6 (M+H)
+; Proton nmr spectra:
1H-NMR (300MHz, CDCl
3) δ (ppm): 0.845 – 0.869 (m, 6H ， – CH
3), 1.233 (m, 32H ， – CH
2–), 2.001 (br, 1H, CH), 4.193 – 4.223 (m, 2H ， – CH
2– N), 5.746 (s, 1H ,=CH – CN); Carbon-13 nmr spectra:
3C-NMR (100MHz, CDCl
3): δ 14.099,22.659, and 26.284,29.328,30.006,31.483; 31.676,31.867,31.897,36.514,46.187; 46.269,69.864,86.010,86.063,111.728; 115.299,115.811,115.875,117.594,117.704; 125.009,125.057,143.275,143.345,148.473; 148.790,161.910,162.040,164.076,182.535; Ultimate analysis calculated value (Anal.Calcd) .ForC
61H
83N
5O
4S
4: C, 67.93; H, 7.76; N, 6.49. measured value (Found): C, 67.96; H, 7.42; N, 6.45.
(2) the I-VII class contains ultra-violet absorption spectrum and the electrochemical properties of the benzene-naphthalene diimide derivative (instantiation compound 1-9) of 1,3-, bis-sulphur-2-ylide alkene conjugate unit
Ultra-violet absorption spectrum carries out on the U-3900 spectrograph, in the sample solution methylene dichloride, (volumetric molar concentration is 1 * 10-
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 working electrode, saturated calomel electrode (SCE) is as reference electrode, platinum filament is as to 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, and the saturated calomel of take is reference, 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 I class and II compounds and contriver's previous patent (CN200910197611.9, and CN201110225678.6) compound disclosed has identical conjugated backbone, it is N-substituting group difference, and the N-substituting group can be ignored spectrum and the Electrochemical Performances of compound parent nucleus, spectrum data just no longer is provided here, the maximum absorption band of the instantiation compound 1 of I class and II class benzene-naphthalene diimide derivative and 2 ultra-violet absorption spectrum, in the 575nm left and right, calculates optical band gap by formula (1) and is about 2.1eV.By the cyclic voltammetry curve of compound 1 and 2 and formula (2), can calculate its lumo energy is about-4.35eV.Naphthalenetetracarbacidic acidic diimide derivatives (the III class: 3 and 4 condensed because of similar thia ring; The IV class: 5 and 6) have similar ultra-violet absorption spectrum and electrochemical properties, the compound 3(R of take here is 2-octyl group-dodecyl), 5 (R is 2-octyl group-dodecyl) describe for example.Fig. 1 has provided respectively the ultra-violet absorption spectrum of instantiation compound 3,5 and 7-9, and its maximum absorption band lays respectively at as 558nm, 543nm, and 586nm, 603nm and 592nm left and right, the optical band gap that is calculated these compounds by formula (1) is 1.9-2.1eV.Fig. 2 has provided the cyclic voltammetry curve of compound 3,5 and 7-9, has all shown two reversible redox processeses, its half-wave potential E
1/2 Red1Be respectively-0.11,0.07 ,-0.17 ,-0.39 and-0.22eV, they are respectively-4.33 by the lumo energy that formula (2) calculates gained ,-4.51 ,-4.27 ,-4.05 and-4.22eV.
To sum up, from spectrum and the electrochemical research of instantiation compound 1-9, can find out: the I-VII class contains 1, the lumo energy of the benzene-naphthalene diimide derivative of 3-bis-sulphur-2-ylide alkene conjugate unit is in-4.0～-4.6eV between, the HOMO energy level >-6.0eV, optical band gap is 1.9-2.1eV, and they are typical n-type organic semiconductor material.
(3) compound 1-3,5 and 7-9 as the semiconductor active layer, prepare organic film FET
The invention provides the instantiation compound 1-3 that the I-VII class contains the benzene-naphthalene diimide derivative of 1,3-, bis-sulphur-2-ylide alkene conjugate unit, 5 and 7-9 as the application of semiconductor active layer in OTFT (OTFT) device.Fig. 3 has provided usings the structural representation of compound 1 or 2 or 3 or 5 or 7 or 8 or 9 devices of the OTFT as organic semiconductor layer.The preparation method of OTFT device is: the compound of 5-15mg 1 or 2 or 3 or 5 or 7 or 8 or 9 is dissolved in the 1mL chloroform, at the SiO of OTS modification
2In/Si substrate, (highly doped silicon substrate is as grid, and the thickness of thermooxidizing silicon dioxide insulating layer is 450nm, and electric capacity is 10nFcm
-2) get rid of the organic semiconductor thin film of the about 20-80nm thickness of last layer, on organic film, to utilize mask plate deposited gold or silver-colored 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 the Keithley4200 semi-conductor test instrument.Wherein, instantiation compound 1 and 2 OTFT device adopt silver-colored source-drain electrode, and its film adopts in air and anneals under 140 ° of C; Other compounds 3,5 and 7-9 adopt gold as source-drain electrode, adopt respectively under 80 and 120 ° of C and anneal.
Figure 4 and 5 have provided respectively the transition curve of the OTFT device of instantiation compound 1 and 2, and its electronic mobility can reach respectively 0.1 and 0.2cm
2V
-1s
-1, on-off ratio is 10
5-10
6, threshold voltage is 0-15V.Fig. 6-10 have provided respectively compound 3,5 and the transition curve of the OTFT device of 7-9, the electrical property characterization data of its OTFT device (>=10) is listed in table 1 (comprising mobility, on-off ratio and threshold voltage), and wherein the electronic mobility of the OTFT device of compound 5 can reach 0.11cm
2V
-1s
-1.
The invention is not restricted to 9 disclosed instantiation compounds, the benzene-naphthalene diimide derivative that contains 1,3-, bis-sulphur-2-ylide alkene conjugate unit is of a great variety, and protection scope of the present invention limits and is as the criterion with appended claims.
Table 1 is the electrical property characterization data of OTFT device (golden source-drain electrode) under unannealed and different annealing temperature based on compound 3,5 and 7-9, comprises the highest (on average) electronic mobility (μ
e, unit: cm
2/ Vs), on-off ratio (I
On/ I
off) and threshold voltage (V
T, unit: V).
Table 1
Claims (10)
1. contain the benzene-naphthalene diimide derivative of 1,3-, bis-sulphur-2-ylide alkene conjugate unit, have as shown in the formula structure:
Wherein, π-1 or π-2=
Or
R
1Or R
2The alkyl of=C1～30,
Or
R
3The alkyl of=H or C1～6; As π-1=π-2=
The time, R
1And R
2Can not be alkyl simultaneously; Work as R
1=R
2The time, the two is alkyl.
2. the benzene-naphthalene diimide derivative that contains 1,3-, bis-sulphur-2-ylide alkene conjugate unit as claimed in claim 1, its feature has following structural formula:
(1) I compounds is to contain the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) the third dicyan that the asymmetric N-of benzyl structure unit replaces condenses:
(2) II compounds is characterized in that containing the benzene-naphthalene diimide derivative that 2-(1,3-, bis-sulphur-2-subunit) the third dicyan that the asymmetric N-of 2,2-phenylbenzene-ethyl structure unit replaces condenses:
(3) III compounds, is characterized in that 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and Isosorbide-5-Nitrae-bis-sulphur-2,3-dicyano ethene
The asymmetric benzene-naphthalene diimide compound condensed:
(4) IV compounds is characterized in that the asymmetric benzene-naphthalene diimide compound condensed condensed of 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and 2,3-dicyano thiophene:
(5) V compounds is characterized in that the benzene-naphthalene diimide compound that 2-(1,3-, bis-sulphur-2-subunit) Nitromethane 99Min. condenses:
(6) VI compounds is characterized in that the benzene-naphthalene diimide compound that 2-(1,3-, bis-sulphur-2-subunit) second cyanogen condenses:
(7) VII compounds is characterized in that 2-(1,3-, bis-sulphur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide compound condensed condensed of 2-(1,3-, bis-sulphur-2-subunit) second cyanogen:
R in aforesaid structural formula
1, R
3Definition described with claim 1.
3. the benzene-naphthalene diimide derivative that contains 1,3-, bis-sulphur-2-ylide alkene conjugate unit as claimed in claim 2, is characterized in that described R
1And R
2For the alkyl of C6～30, R
3Alkyl for H or C1～6.
4. one kind prepares and as claimed in claim 2ly contains 1; the method of the benzene-naphthalene diimide derivative of 3-bis-sulphur-2-ylide alkene conjugate unit; it is characterized in that by following (1), (2), (2) and (3) or (4) step, in air or under protection of inert gas, react respectively and obtain:
(1) preparation method's of the benzene-naphthalene diimide derivative that condenses of 2-(1,3-, bis-sulphur-2-subunit) the third dicyan of replacing of the asymmetric N-of described I and II class step is:
In room temperature～80 ℃ and organic solvent, tetrabromo is for naphthalenetetracarbacidic acidic dianhydride and 2,2-dicyano-ethene-1, and 1-bis-thiolate are 1:2～6 reaction 0.5～12 hour in molar ratio, then with two kinds of organic amine R
1NH
2And benzylamine, or R
1NH
2With 2,2-diphenyl-ethylamine, reacted 1～12 hour under ℃ condition of room temperature～80; Described organic amine R
1NH
2, benzylamine or 2,2-diphenyl-ethylamine and tetrabromo be 1～3:1～3:1 for the mol ratio of naphthalenetetracarbacidic acidic dianhydride;
(2) preparation method's of the benzene-naphthalene diimide derivative of the asymmetric naphthalene core replacement of described III and VII class step is:
Under-10～50 ℃ of organic solvent neutralizations, N-alkyl (R
1) replace 2,3,6, the 7-tetrabromo is for naphthalenetetracarbacidic acidic diimide, 2,2-dicyano ethene-1,1-bis-thiolate, 1,2-dicyano ethene-1,2-bis-thiolate or 2-cyano group ethene-1,1-bis-thiolate are with mol ratio 1:1～2:1～2 reaction 0.5～3 hour;
(3) preparation method of the benzene-naphthalene diimide derivative of the asymmetric naphthalene core replacement of described IV class, the steps include:
In acetic acid or propionic acid and under 100～120 ℃, III class benzene-naphthalene diimide derivative reacts and mixes 0.5～1.5 hour with mol ratio 1:50～80 with 30% hydrogen peroxide;
(4) preparation method of the benzene-naphthalene diimide compound of the symmetrical naphthalene core replacement of described V and VI class, the steps include:
In organic solvent and under room temperature～50 ℃, N-alkyl (R1) replace 2,3,6, the 7-tetrabromo is for benzene-naphthalene diimide, 2-nitroethylene-1,2-bis-thiolate or 2-cyano group ethene-1,2-bis-thiolate are with mol ratio 1:2～5 reaction 0.5～3 hour;
Above-mentioned R
1And R
3Definition as claimed in claim 1.
5. in method as claimed in claim 4, it is characterized in that the organic solvent in step (1), (2), (4) is DMF, N,N-dimethylacetamide, tetrahydrofuran (THF) or dioxane
6. in method as claimed in claim 4, it is characterized in that the reaction of described step (1), (2) and (4) is carried out under protection of inert gas.
7. in method as claimed in claim 4, it is characterized in that described product purifies through silica gel column chromatography.
8. in method as claimed in claim 4, it is characterized in that described 2,2-dicyano-ethene-1,1-bis-thiolate, 1,2-dicyano ethene-1,2-bis-thiolate, 2-cyano group ethene-1,1-bis-thiolate, 2-nitroethylene-1,2-bis-thiolate or 2-cyano group ethene-1,2-bis-thiolate are their sodium salt, sylvite, lithium salts, calcium salt or barium salt.
9. one kind as claim 1, the 2 or 3 described purposes that contain the benzene-naphthalene diimide derivative of 1,3-, bis-sulphur-2-ylide alkene conjugate unit, it is characterized in that for the preparation of organic electronic devices.
One kind as claim 1, the 2 or 3 described benzene-naphthalene diimide derivatives of 1,3-, bis-sulphur-2-ylide alkene conjugate unit that contain as the application of semiconductor active layer in organic film FET.
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| US9997718B2 (en) | 2015-04-13 | 2018-06-12 | Samsung Electronics Co., Ltd. | Organic photoelectric device image sensor and electronic device |
| CN106058034A (en) * | 2016-07-12 | 2016-10-26 | 北京服装学院 | Preparation method of (1,3-dithio-2-carbonyl)-condensed naphthaldiimide/carbon nanotube composite thermoelectric material |
| CN109311909A (en) * | 2016-07-12 | 2019-02-05 | 国立研究开发法人理化学研究所 | Aromatic compound and application thereof |
| CN106058034B (en) * | 2016-07-12 | 2023-04-28 | 北京服装学院 | Preparation method of (1, 3-disulfide-2-carbonyl) fused naphthalimide/carbon nano tube composite thermoelectric material |
| CN109134514A (en) * | 2018-09-28 | 2019-01-04 | 郑州轻工业学院 | A kind of benzene-naphthalene diimide derivative and preparation method thereof, application |
| CN109776533B (en) * | 2019-02-12 | 2020-10-30 | 宁波卢米蓝新材料有限公司 | Naphthalene diimide derivative and preparation method and application thereof |
| CN109776533A (en) * | 2019-02-12 | 2019-05-21 | 宁波卢米蓝新材料有限公司 | A kind of benzene-naphthalene diimide derivative and its preparation method and application |
| CN110143970A (en) * | 2019-04-24 | 2019-08-20 | 郑州轻工业学院 | Sulfur-rich bigeminy benzene-naphthalene diimide derivative and preparation method thereof, application |
| CN112552304A (en) * | 2019-09-26 | 2021-03-26 | 广州华睿光电材料有限公司 | Aromatic ring pyrene quinone compound and application thereof |
| CN112552304B (en) * | 2019-09-26 | 2022-06-07 | 广州华睿光电材料有限公司 | Aromatic ring pyrene quinone compound and application thereof |
| 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 |
| CN110981890A (en) * | 2019-12-13 | 2020-04-10 | 中国科学院化学研究所 | Naphthalimide-dithiocyclopentanone azine compound, and preparation and application thereof |
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