CN103408570B - Containing the benzene-naphthalene diimide derivative of 1,3-bis-sulfur-2-ylide alkene conjugate unit, preparation method and application - Google Patents
Containing the benzene-naphthalene diimide derivative of 1,3-bis-sulfur-2-ylide alkene conjugate unit, preparation method and application Download PDFInfo
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Abstract
The present invention relates to containing the benzene-naphthalene diimide derivative of 1,3-bis-sulfur-2-ylide alkene conjugate unit, preparation method and application, chemical constitution is as follows:Wherein, π-1 or π-2=WithR1Or R2The alkyl of=C1～30,OrR3The alkyl of=H or C1～4；As π-1=π-2=Time, R1And R2Can not be alkyl simultaneously；Work as R1=R2Time, both at alkyl.Be used for preparing organic thin film transistor device, be n-type organic semiconducting materials, in air test, electron mobility is up to 0.2cm2V-1s-1。
Description
Technical field
The present invention relates to containing 1, the benzene-naphthalene diimide class organic semiconducting materials of 3-bis-sulfur-2-ylide alkene conjugate unit, relate in particular to containing the benzene-naphthalene diimide derivative of 1,3-bis-sulfur-2-ylide alkene conjugate unit, preparation method and as the application in organic film FET of the n-type organic semiconducting materials.
Background technology
OTFT (OTFT) is the active device being controlled solid-state organic semiconducting materials conductive capability by electric field, is one of unit component most basic in organic electronics.OTFT device is made up of electrode (source/drain/gate), insulating barrier and organic semiconductor layer；The key parameter characterizing OTFT device performance includes: (μ, unit is cm to carrier mobility2V- 1s-1), on-off ratio (Ion/Ioff) and threshold voltage (VT, unit is V).The advantages such as OTFT has that preparation technology is simple, cost is low, light weight, pliability and the good compatibility of plastic, its (Forrest that has broad application prospects in the flexible electronic products such as smart card, electronic tag, Electronic Paper, Active Matrix LCD At, sensor, memorizer, S.R.Nature.2004,428,911;Korzhov, M.etal.PhysicsWord.2008,29;Leenen, M.A.M.etal.Phys.StatusSolidiA.2009,206,588;Specialissue:OrganicElectronicsandOptoelectronics, Forrest, S.R.;Thompson, M.E.ed.Chem.Rev.2007,107,923;Gelinck, G.etal.Adv.Mater.2010,22,3778 etc.).The up-to-date prediction of Britain AIM, by 2029, the gross sales amount in flexible electronic product market, the whole world is up to 335,000,000,000 dollars, and wherein the Flexible Displays in most growth potential is driven, plays the effect held the balance in organic electronic label, organic sensor etc. by OTFT.
Organic semiconducting materials is the key component of OTFT, by the type of its transmission carrier, is divided into p-type and n-type, and the former is mainly hole by the carrier of transmission, and the latter is mainly electronics.Development for OTFT, p-type and n-type organic semiconducting materials are of equal importance, the organic complementary circuit (Organiccomplementarycircuits) jointly constructed by the two has the advantages such as low in energy consumption, speed of operation fast, design simple, noise margin is big, can be widely applied to various organic Digital Logical Circuits, it is the basis (Crone realizing the application of organic electronic functional device, B.etal.Nature2000,403,521.;Klauk, H.etal.Nature2007,445,745.).On the other hand; the development of OTFT; also require that organic semiconducting materials has good dissolubility in suitable solvent; can be made into various active ink, utilize printed electronic (Printedelectronics) technology, as: rejection film, inkjet printing, volume to volume printing etc.; OTFT device and organic circuit (Arias are prepared in large area, low cost, scale; A.C.etal.Chem.Rev.2010,110,3).
Generally, the p-type organic semiconducting materials development of solution processable is very fast, and the mobility of the OTFT device of some molecular material solwution method film forming has met or exceeded the performance (0.1-1.0cm of amorphous silicon thin film device2V-1 s -1), wherein the OTFT device mobility of organic small molecule material is up to 1.0-31cm2V-1s-1, the mobility of polymeric material reaches 0.6-10.5cm2V-1s-1, and show good air stability (Minemawari, H.etal.Nature2011,475,364.;LiJ.etal.ScientificReports.2012, Doi:10.1038/srep00754).But, the development of n-type organic semiconducting materials lags far behind p-type organic semiconducting materials, high electron mobility, n-type organic semiconducting materials stable, solution processable are extremely short, which greatly limits development (Anthony, the J.E. of the flexible electronic functional device based on organic complementary circuit;Etal.Adv.Mater.2010,22,3876).
Recently, inventors have discovered that the benzene-naphthalene diimide class n-type organic semiconducting materials (CN200910197611.9 that the sulfur of a series of solution processable is heterocyclic fused, CN201010207565.9 and CN201110225678.6), and their OFET thin-film device it is prepared for by the method for solution processing, wherein 1, the benzene-naphthalene diimide compound that 3-bis-sulfur-2-ylide alkene condenses shows the device performance of excellence, and electron mobility is many at 0.1cm2V-1s-1Above, and device there is good air stability and operational stability.In order to seek various structures, the regulatable novel thia benzene-naphthalene diimide compounds of energy level, inventor report other seven classes have no report containing 1, the benzene-naphthalene diimide class n-type organic semiconducting materials of 3-bis-sulfur-2-ylide alkene conjugate unit: the Ith class is the asymmetric N-2-(1 replaced, 3-bis-sulfur-2-subunit) benzene-naphthalene diimide derivative that condenses of the third dicyan, wherein R1For C1～C30Alkyl, R2For the 4-benzyl replaced；IIth class is the benzene-naphthalene diimide derivative that asymmetric N-2-(1,3-bis-sulfur-2-subunit) the third dicyan replaced condenses, wherein R1For C1～C30Alkyl, R2For 2,2-diphenvl-ethvl；IIIth class is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 1,4-bis-sulfur-2,3-dicyanoethylene；IVth class is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2,3-dicyano thiophene；V class is the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) Nitrocarbol. condenses；Group VI is the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) second cyanogen condenses；VII class is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and 2-(1,3-bis-sulfur-2-subunit) the asymmetric benzene-naphthalene diimide derivative condensed of second cyanogen, and will wherein be applied to OTFT device.
Goal of the invention
It is an object of the invention to provide a class n-type organic semiconducting materials, namely 1 is contained, the benzene-naphthalene diimide analog derivative of 3-bis-sulfur-2-ylide alkene conjugate unit: if the Ith class is the asymmetric N-2-(1 replaced, 3-bis-sulfur-2-subunit) benzene-naphthalene diimide derivative that condenses of the third dicyan, wherein R1For C1～C30Alkyl, R2For the 4-benzyl replaced；IIth class is the benzene-naphthalene diimide derivative that asymmetric N-2-(1,3-bis-sulfur-2-subunit) the third dicyan replaced condenses, wherein R1For C1～C30Alkyl, R2For 2,2-diphenvl-ethvl；IIIth class is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 1,4-bis-sulfur-2,3-dicyanoethylene；IVth class is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2,3-dicyano thiophene；V class is the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) Nitrocarbol. condenses；Group VI is the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) second cyanogen condenses；VII class is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and 2-(1,3-bis-sulfur-2-subunit) the asymmetric benzene-naphthalene diimide derivative condensed of second cyanogen.
The preparation method that a further object of the present invention also resides in the benzene-naphthalene diimide derivative providing above-mentioned sulfur heterocyclic fused.
Another object of the present invention is to the application of the benzene-naphthalene diimide derivative providing above-mentioned sulfur heterocyclic fused, construct OTFT device as n-type organic semiconducting materials.
Summary of the invention
Benzene-naphthalene diimide derivative containing 1,3-bis-sulfur-2-ylide alkene conjugate unit provided by the invention, its structure is shown below:
Wherein, π-1 or π-2=Or
R1Or R2The alkyl of=C1～30 (alkyl of preferential C6～30, it is further recommended that the alkyl of C8～24),OrR3The alkyl of=H or C1～6；Wherein, as π-1=π-2=Time, R1And R2Can not be alkyl simultaneously；Work as R1=R2Time, both at alkyl.
Further example can be described as the following benzene-naphthalene diimide derivative containing 1,3-bis-sulfur-2-ylide alkene conjugate unit: the Ith class is the benzene-naphthalene diimide derivative that asymmetric N-2-(1,3-bis-sulfur-2-subunit) the third dicyan replaced condenses, wherein R1For C1～C30Alkyl, R2For the 4-benzyl (R replaced3For C1～C4Alkyl, or H atom)；IIth class is the benzene-naphthalene diimide derivative that asymmetric N-2-(1,3-bis-sulfur-2-subunit) the third dicyan replaced condenses, wherein R1For C1～C30Alkyl, R2For 2,2-diphenvl-ethvl；IIIth class is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and Isosorbide-5-Nitrae-two sulfur-2, the asymmetric benzene-naphthalene diimide derivative condensed of 3-dicyanoethylene, wherein R1=R2, for C1～C30Alkyl；IVth class is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2,3-dicyano thiophene, wherein R1=R2, for C1～C30 alkyl；V class is the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) Nitrocarbol. condenses, wherein R1=R2, for C1～C30Alkyl；Group VI is the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) second cyanogen condenses, wherein R1=R2, for C1～C30Alkyl；VII class is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and 2-(1,3-bis-sulfur-2-subunit) the asymmetric benzene-naphthalene diimide derivative condensed of second cyanogen, wherein R1=R2, for C1～C30Alkyl.
The present invention prepares the method that I～VII class contains the benzene-naphthalene diimide derivative of 1,3-bis-sulfur-2-ylide alkene conjugate unit, the steps include:
(1) method preparing the benzene-naphthalene diimide derivative that the Ith and the IIth asymmetric N-of class 2-(1,3-bis-sulfur-2-subunit) the third dicyan replaced condenses, the steps include:
By four bromo naphthalenetetracarbacidic acidic dianhydride and 2,2-dicyanos-ethylene-1,1-bis-mercaptides 1:2～6 in molar ratio are reacted 0.5～12 hour in organic solvent at room temperature～80 DEG C, then by two kinds of organic amine (R1NH2And benzylamine) or (R1NH2With 2,2-diphenyl-ethylamines) add in reactant liquor, react 1～12 hour under the condition of room temperature～80 DEG C；Described organic amine R1NH2, benzylamine (or 2,2-diphenyl-ethylamine) and four bromo naphthalenetetracarbacidic acidic dianhydrides mol ratio be 1～3:1～3:1；
(2) method preparing the benzene-naphthalene diimide derivative of ii I and the asymmetric naphthalene core replacement of VII class, the steps include:
N-alkyl (R1) replace 2,3,6,7-tetra-bromo naphthalenetetracarbacidic acidic diimide and 2,2-dicyanoethylene-1,1-bis-mercaptides and 1,2-dicyanoethylene-1,2-bis-mercaptides or 2-cyano vinyl-1,1-bis-mercaptides in organic solvent, is reacting 0.5～3 hour with mol ratio 1:1～2:1～2 at-10 DEG C～50 DEG C；
(3) method preparing the benzene-naphthalene diimide derivative that the asymmetric naphthalene core of iv class replaces, the steps include:
By group iii benzene-naphthalene diimide derivative and 30% hydrogen peroxide with mol ratio 1:50～80 in acetic acid or propanoic acid, heated and stirred 0.5～1.5 hour at 100～120 DEG C；
(4) method preparing the benzene-naphthalene diimide compound of V and the replacement of group VI symmetry naphthalene core, the steps include:
N-alkyl (R1) 2,3,6, the 7-tetra-bromo benzene-naphthalene diimides that replace and 2-nitroethylene-1,2-bis-mercaptides or 2-cyano vinyl-1,2-bis-mercaptides with mol ratio 1:2～5 in organic solvent, reacts 0.5～3 hour at room temperature～50 DEG C.
Described method, wherein step (1), 2,2-dicyanos-ethylene-1 in (2), 1-bis-mercaptides and 2,3,6,7-tetra-naphthalene bromide four anhydride in step (1) are known compound, with reference to the synthesis of patent CN200910197611.9 method；
Described method, wherein the N-alkyl (R in step (2) and (4)1) 2,3,6, the 7-tetra-bromo benzene-naphthalene diimides that replace are known compound, with reference to the synthesis of patent CN200910197611.9 method；
Described method, wherein 1,2-dicyanoethylene-1 in step (2), 2-bis-mercaptides is known compound, buy or reference literature Inorg.Synth.1967 from TCI, 10,8. synthesis, 2-cyano group-ethylene-1,1-bis-mercaptides is known compound, reference literature Acta.Chem.Scand.1996,50,432 synthesizes；
Described method, wherein 2-nitro-ethylene-1 in step (4), 1-bis-mercaptides is known compound, and reference literature Ber.Dtsch.Chem.Ges.1919,52,542 synthesizes；
Described method, wherein step (1), (2), organic solvent in (4) are DMF, N,N-dimethylacetamide, oxolane or dioxane；
Described method, reaction is in atmosphere or carries out under inert gas shielding, it is recommended that step (1), 2) and (4) in reaction carry out under inert gas shielding, described product through silica gel column chromatography purify.
Described method, wherein the product of step (1) is the benzene-naphthalene diimide derivative (the Ith class) that asymmetric N-2-(1,3-bis-sulfur-2-subunit) the third dicyan replaced condenses, wherein R1For C1～C30Alkyl, R2For the 4-benzyl (R replaced3For C1～C4Alkyl, or H atom) and the benzene-naphthalene diimide derivative (the IIth class) that condenses of 2-(1,3-bis-sulfur-2-subunit) the third dicyan that replaces of asymmetric N-, wherein R1For C1～C30Alkyl, R2For 2,2-diphenvl-ethvl.
Described method, the product that wherein step (2) obtains is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and 1,4-bis-sulfur-2, the asymmetric benzene-naphthalene diimide derivative (the IIIth class) condensed of 3-dicyanoethylene and 2-(1,3-bis-sulfur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative (the VIIth class) condensed of 2,3-dicyano thiophene, wherein R1=R2, for C1～C30 alkyl.
Described method, the product that wherein step (3) obtains is 2-(1,3-bis-sulfur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative (the IVth class) condensed of 2,3-dicyano thiophene, wherein R1=R2, for C1～C30 alkyl.
Described method, the product that wherein step (4) obtains is 2-(1,3-bis-sulfur-2-subunit) benzene-naphthalene diimide derivative (the VIth class) that condenses of the benzene-naphthalene diimide derivative (the Vth class) that condenses of Nitrocarbol. and 2-(1,3-bis-sulfur-2-subunit) second cyanogen, wherein R1=R2, for C1～C30Alkyl.
Described method, the target compound that wherein step (1)-(4) obtain purifies through silica gel column chromatography, and eluent is dichloromethane/petroleum ether or toluene/petroleum ether mixed liquor.
Described method, step (1)-(4) gained noval chemical compound through mass spectrum (MS-TOF), nuclear magnetic resoance spectrum (1H-NMR) one or more, in elementary analysis characterize, and structure is errorless.
Described method, the benzene-naphthalene diimide derivative that I～VII class of step (1)-(4) gained contains 1,3-bis-sulfur-2-ylide alkene conjugate unit is applied in organic film FET as semiconductor active layer.
As shown in above-mentioned chemical structural formula, The present invention gives the certain embodiments compound 1～9 of the benzene-naphthalene diimide derivative that the I～VII class contains 1,3-bis-sulfur-2-ylide alkene conjugate unit and synthetic schemes thereof.One Compound of Example 1 of the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) the third dicyan that the Ith asymmetric N-of class replaces condenses, its substituent R1For 2-octyl group-dodecyl, R3For the tert-butyl group；One Compound of Example 2 of the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) the third dicyan that the IIth asymmetric N-of class replaces condenses, its substituent R1For 2-octyl group-dodecyl；IIIth class 2-(1,3-bis-sulfur-2-subunit) the third dicyan and Isosorbide-5-Nitrae-two sulfur-2, two Compound of Example 3 and 4 of the asymmetric benzene-naphthalene diimide derivative condensed of 3-dicyanoethylene, wherein R1=n-octyl (3), R1=2-octyl group-dodecyl (4)；Two Compound of Example 5 and 6 of the IVth class 2-(1,3-bis-sulfur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide derivative condensed of 2,3-dicyano thiophene, wherein R1=n-octyl (5), R1=2-octyl group-dodecyl (6)；One Compound of Example 7 of benzene-naphthalene diimide derivative that V class 2-(1,3-bis-sulfur-2-subunit) Nitrocarbol. condenses, wherein R1=2-octyl group-dodecyl；Benzene-naphthalene diimide derivative one Compound of Example 8, wherein R that group VI 2-(1,3-bis-sulfur-2-subunit) second cyanogen condenses1=2-octyl group-dodecyl；VII class 2-(1,3-bis-sulfur-2-subunit) the third dicyan and asymmetric one Compound of Example 9 of the benzene-naphthalene diimide derivative condensed of 2-(1,3-bis-sulfur-2-subunit) second cyanogen, wherein R1=2-octyl group-dodecyl.
The photophysical property of compound 1～9 is have studied with ultra-violet absorption spectrum (UV)；The electrochemical properties of compound 1～9 is have studied by cyclic voltammetry (CV)；And the organic film FET device of compound 1,2,4 and 6-9 it is prepared for by the method for solution processing.
It is an advantage of the current invention that:
1. the synthetic method of present disclosure is simply effective；Raw material is readily synthesized preparation, and synthesis 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-sulfur-2-ylide alkene conjugate unit has different lumo energies: the alkyl chain of-4.1～-4.5eV, big pi-conjugated system and flexible dissolution, it is possible to prepare organic electronic device (such as OTFT etc.) by the method low cost of solution processing.
Accompanying drawing explanation
Fig. 1 is compound 1-3,5 and 7-9 ultra-violet absorption spectrum in dichloromethane.
Fig. 2 is compound 1-3,5 and 7-9 cyclic voltammetry curve in dichloromethane.
Fig. 3 is the structural representation using compound 1 or 2 or 3 or 5 or 7 or 8 or 9 as the OTFT device of organic layer.
Fig. 4 is the transfer curve of the OTFT device of compound 1.
Fig. 5 is the transfer curve of the OTFT device of compound 2.
Fig. 6 is the transfer curve of the OTFT device of compound 3.
Fig. 7 is the transfer curve of the OTFT device of compound 5.
Fig. 8 is the transfer curve of the OTFT device of compound 7.
Fig. 9 is the transfer curve of the OTFT device of compound 8.
Figure 10 is the transfer curve of the OTFT device of compound 9.
Symbol description
In Fig. 1 " Wavelength (nm) " be " absorbing wavelength (nanometer) ", " Absorbance (a.u.) " is " relative absorbance intensity ".
In Fig. 2, " Potential (V) " is " voltage (volt) ", and " Current (μ A) " is " electric current (microampere) ".
" V in Fig. 4-10DS(V) " it is " source-drain voltage (volt) ", " IDS(μ A) " it is " source-drain current (microampere) ", " VGS(V) " it is " grid voltage (volt) ".
Detailed description of the invention
Following embodiment will assist in and is further appreciated by the present invention, but can not limit present disclosure.
(1) embodiment compound 1-9(the Ith class: 1；IIth class: 2；IIIth class: 3 and 9；IVth class: 5 and 6；Vth class: 7；VIth class: 8；VIIth class: 9) preparation method
Embodiment 1:N-(2-octyl group-dodecyl) synthesis of-N '-(4-t-butylbenzyl)-[2,3-d:6,7-d ']-bis-[2-(1,3-bis-sulfur-2-subunit)-2-the third dicyan]-naphthalene-1,4,5,8-tetracarboxylic acid imidodicarbonic diamide (1).
Concrete synthesis step is:
Under nitrogen protection, by 2,3,6; 7-tetrabromo naphthalenetetracarbacidic acidic dianhydride (TBNDA) (300mg, 0.51mmol) and 1,1-dicyanoethylene-2; 2-bis-sodium mercaptides (288mg, 1.54mmol) joins in 50mLDMF, heats 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), at 50 DEG C, continue reaction 5h.It is cooled to room temperature, reactant liquor is poured in 100mL saturated ammonium chloride solution, filter, wash filtering residue with water, vacuum drying, with dichloromethane/petroleum ether (2:1) for eluent, is easily separated purification with silica gel column chromatography to thick product, obtain the brown-red solid 50mg of compound 1, productivity 10%.
Mass spectrum: [MS (TOF)] m/z:970.2 (M+1)+;Proton nmr spectra:1H-NMR(300MHz,CDCl3)δ(ppm):0.833–0.886(m,6H,–CH3),1.228–1.269(m,32H,–CH2–),1.580(s,9H,–CH3),1.959–2.051(m,1H,–CH–),4.205–4.229(d,2H,–CH2–),5.444(s,2H,–CH2), 7.378 7.405 (d, 2H, Ph-H), 7.542-7.569 (d, 2H, Ph-H);Elementary analysis value of calculation (Anal.Calcd.For) C53H56N6O4S4: 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) synthesis of-N '-(2,2-diphenvl-ethvl)-[2,3-d:6,7-d ']-bis-[2-(1,3-bis-sulfur-2-subunit)-2-the third dicyan]-naphthalene-1,4,5,8-tetracarboxylic acid imidodicarbonic diamide (2).
Concrete synthesis step is:
Replacing tert-butyl benzyl amine with 2,2-diphenyl-ethylamines, synthetic method, with step in embodiment 1, prepares red solid (2), productivity 7%.
Mass spectrum: [MS (TOF)] m/z:1003.3 (M+);Proton nmr spectra:1H-NMR(300MHz,CDCl3)δ(ppm):0.839–0.891(m,6H,–CH3),1.236–1.375(m,32H,–CH2–),1.932-2.015(b,1H,–CH-),4.191–4.216(d,2H,–CH2–),4.780–4.834(t,1H,–CH–),4.952-4.981(d,2H,–CH2), 7.162 7.372 (m, 10H, Ph-H), 7.542-7.569 (d, 2H, Ph-H);Elementary analysis value of calculation (Anal.Calcd.For) C56H54N6O4S4: 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 '-two (2-octyl group-dodecyl)-[2,3-d]-[2-(1,3-bis-sulfur-2-subunit)-2-the third dicyan]-[6,7-d '] [1,4-bis-thiophene cyclohexene-2,3-dintrile]-naphthalene-1, the synthesis of 4,5,8-tetracarboxylic acid diimide (3).
Concrete synthesis step is:
Under nitrogen protection; by N, N '-two (2-octyl group-dodecyls)-2,3; 6; 7-tetrabromo benzene-naphthalene diimide (TBNDI-C20) (500mg, 0.44mmol), 1,1-dicyanoethylene-2; 2-bis-sodium mercaptides (122mg; 0.66mmol) with 1,2-dicyanoethylene-1,2-bis-sodium mercaptides (150mg; 0.79mmol) join in 100mLTHF; at-10 DEG C after stirring reaction 2.5h, it is cooled to room temperature, reactant liquor is poured in 200mL water; molten 4 × 100mL dichloromethane solution extracts; merging organic facies, after drying, solvent is removed in decompression rotation.Crude on silica gel chromatographic column purifies (leacheate is dichloromethane/petroleum ether, V/V=1/1), obtains the red solid 182mg of compound 3, productivity 38%.
Mass spectrum: MS (MALDI-TOF) m/z1140.1 (M+H)+;Proton nmr spectra:1H-NMR(300MHz,CDCl3)δ(ppm):0.869-0.898(m,6H,–CH3),1.259–1.432(m,32H,–CH2–),2.009(br,1H,CH),4.194–4.213(d,2H,J=5.70Hz,–CH2N);Carbon-13 nmr spectra:13C-NMR(100MHz,CDCl3):δ14.104,22.652,22.665,26.183,29.269,29.327,29.510,29.562,29.623,29.998,31.458,31.862,31.901,36.519,46.305,111.360,111.565,117.566,121.554,122.659,125.838,140.302,145.331,161.583(C=O),182.125(=CS2);Elementary analysis value of calculation (Anal.Calcd) .ForC62H82N6O4S4: 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 '-two (n-octyl)-[2,3-d]-[2-(1,3-bis-sulfur-2-subunit)-2-the third dicyan]-[6,7-d '] [1,4-bis-thiophene cyclohexene-2,3-dintrile]-naphthalene-1, the synthesis of 4,5,8-tetracarboxylic acid diimide (4).
Concrete synthesis step is:
With N, N '-two (n-octyl)-2,3,6,7-tetrabromo benzene-naphthalene diimide (TBNDI-C8) replaces N, N '-two (2-octyl group-dodecyls)-2,3,6,7-tetrabromo benzene-naphthalene diimide (TBNDI-C20), synthetic method, with step in embodiment 3, prepares aubergine solid (4), productivity 40%.
Mass spectrum: MS (MALDI-TOF) m/z766.94 (M+H)+;Proton nmr spectra:1H-NMR(300MHz,CDCl3)δ(ppm):0.87–0.89(m,3H,–CH3),1.30–1.41(m,10H,–CH2–),1.77(m,2H,–CH2–),4.21–4.26(m,2H,–CH2N);Elementary analysis value of calculation (Anal.Calcd): ForC38H34N6O4S4: 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 '-two (2-octyl group-dodecyl)-[2,3-d]-[2-(1,3-bis-sulfur-2-subunit)-2-the third dicyan]-[6,7-d '] [2,3-dicyano thiophene]-naphthalene-1, the synthesis of 4,5,8-tetracarboxylic acid diimide (5).
Concrete synthesis step is:
50mL there-necked flask adds 100mg (0.09mmol) N, N '-two (2-octyl group-dodecyl)-[2,3-d]-[2-(1,3-bis-sulfur-2-subunit)-2-the third dicyan]-[6,7-d '] [1,4-bis-thiophene cyclohexene-2,3-dintrile]-naphthalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid diimide (3) and 10mL propanoic acid, heated and stirred is dissolved to solid, adds the H of 0.7mL30% in reactant liquor2O2(6.8mmol), at 120 DEG C, heated and stirred is reacted 40 minutes, reactant liquor is down to room temperature, being poured in 50mL water, sucking filtration, after the thick product drying of gained, through silica gel column chromatography purification, (leacheate is dichloromethane/petroleum ether, V/V=1/1), obtaining red solid (compound 5) 81mg, productivity is 84%.
Mass spectrum: MS (MALDI-TOF) m/z1071.6 (M+H)+;Proton nmr spectra:1H-NMR(300MHz,CDCl3)δ(ppm):0.846–0.883(m,6H,–CH3),1.249–1.433(m,32H,–CH2–),2.080–2.092(br,1H,CH),4.292–4.331(t,2H,–CH2N);Carbon-13 nmr spectra:13C-NMR(100MHz,CDCl3):δ14.095,22.640,22.660,26.219,26.320,29.272,29.319,29.505,29.557,29.616,29.990,30.062,31.477,31.545,31.851,31.894,36.544,36.592,46.295,111.100,111.320,111.375,111.480,117.165,117.186,117.509,118.221,118.665,120.942,124.667,125.336,134.757,134.778,135.084,142.705,146.885,147.911,147.927,161.003(C=O),162.133(C=O),162.167(C=O),162.269(C=O),181.788(=CS2);Elementary analysis value of calculation (Anal.Calcd) .ForC62H82N6O4S3: C, 69.49;H, 7.71;N, 7.84. measured value (Found): C, 69.58;H, 7.73;N, 7.84.
The synthesis of embodiment 6:N, N '-two (n-octyl)-[2,3-d]-[2-(1,3-bis-sulfur-2-subunit)-2-the third dicyan]-[6,7-d '] [2,3-dicyano thiophene]-naphthalene-1,4,5,8-tetracarboxylic acid imidodicarbonic diamide (6).
Concrete synthesis step is:
With N, N '-two (n-octyl)-[2, 3-d]-[2-(1, 3-bis-sulfur-2-subunit)-2-the third dicyan]-[6, 7-d '] [1, 4-bis-thiophene cyclohexene-2, 3-dintrile]-naphthalene-1, 4, 5, 8-tetracarboxylic acid diimide (4) replaces N, N '-two (2-octyl group-dodecyl)-[2, 3-d]-[2-(1, 3-bis-sulfur-2-subunit)-2-the third dicyan]-[6, 7-d '] [1, 4-bis-thiophene cyclohexene-2, 3-dintrile]-naphthalene-1, 4, 5, 8-tetracarboxylic acid diimide (3), synthetic method is with step in embodiment 4, prepare red solid (6), productivity 63%.
Mass spectrum: MS (MALDI-TOF) m/z734.96 (M+H)+;Proton nmr spectra: H-NMR (300MHz, CDCl3)δ(ppm):0.85–0.87(m,6H,–CH3),1.21–1.39(m,10H,–CH2–),1.82(br,2H,–CH2–),4.32–4.35(m,2H,–CH2N);Carbon-13 nmr spectra:13C-NMR(100MHz,CDCl3): δ 0.03,0.99,14.07,22.59,26.99,27.02,27.87,27.94,29.13,31.73,42.31,42.42,72.44,76.68,77.00,77.32,111.13,111.28,111.33,111.70,117.27,120.95,124.65,125.34,134.89,134.95,142.61,146.86,147.81,160.75,161.84,161.92,181.75;Elementary analysis value of calculation (Anal.Calcd) .ForC38H34N6O4S3: C, 62.10;H, 4.66;N, 11.44;Measured value (Found): C, 62.24;H, 4.81;N, 11.54.
The synthesis of embodiment 7:N, N '-two (2-octyl group-dodecyl)-[2,3-d:6,7-d ']-bis-[2-(1,3-bis-sulfur-2-subunit)-2-Nitrocarbol .]-naphthalene-1,4,5,8-tetracarboxylic acid imidodicarbonic diamide (7).
Concrete synthesis step is:
Under nitrogen protection; 100ml there-necked flask adds 500mg (0.44mmol) N; N '-two (2-octyl group-dodecyl)-2,3,6; 7-tetra-bromo benzene-naphthalene diimide; 280mg (1.31mmol) 2-nitroethylene-1,1-bis-mercaptan sodium salt, 100mL oxolane; room temperature reaction 1 hour, solvent was removed in decompression rotation.Crude on silica gel chromatographic column purifies (leacheate is toluene/petroleum ether, V/V=1/1), obtains blue solid (compound 7) 145mg, and productivity is 30%.
Mass spectrum: MS (MALDI-TOF) m/z1094.1 (M+H)+;Proton nmr spectra:1H-NMR(300MHz,CDCl3)δ(ppm):0.859(m,6H,–CH3),1.234–1.241(m,32H,–CH2–),2.039(br,1H,CH),4.222–4.241(d,2H,–CH2–N),7.802(s,1H,=CH–NO2);Carbon-13 nmr spectra:13C-NMR(100MHz,CDCl3): δ 14.083,22.655,26.304,29.313,29.338,29.553,29.631,29.664,30.050,31.480,31.870,31.899,36.341,36.464,36.587,46.082,116.464,116.728,117.469,117.713,124.777,124.876,124.948,125.607,143.718,143.942,147.165,147.422,161.641,161.694,162.007,162.339;Elementary analysis value of calculation (Anal.Calcd) .ForC58H84N4O8S4: C, 63.70;H, 7.74;N, 5.12;Measured value (Found): C, 63.92;H, 7.66;N, 4.91.
The synthesis of embodiment 8:N, N '-two (2-octyl group-dodecyl)-[2,3-d:6,7-d ']-bis-[2-(1,3-bis-sulfur-2-subunit)-2-second cyanogen]-naphthalene-1,4,5,8-tetracarboxylic acid imidodicarbonic diamide (8).
Concrete synthesis step is:
With 2-cyano vinyl-1,1-bis-mercaptan sodium salt replaces 2-nitroethylene-1, and 1-bis-mercaptan sodium salt, synthetic method, with step in embodiment 7, prepares bluish violet solid (8), and productivity is 87%.
Mass spectrum: MS (MALDI-TOF) m/z1053.9 (M+H)+;Proton nmr spectra:1H-NMR(300MHz,CDCl3)δ(ppm):0.871(m,6H,–CH3),1.239(m,32H,–CH2–),2.003(br,1H,CH),4.170–4.190(d,2H,–CH2N), 5.684 (s, 1H ,=CH CN);Carbon-13 nmr spectra:13C-NMR(100MHz,CDCl3): δ 14.096,22.659,26.277,29.299,29.336,29.516,29.569,29.626,30.004,31.465,31.865,31.902,36.450,45.862,45.951,46.047,84.956,115.517,115.686,115.779,115.862,124.596,124.666,124.749,146.315,146.437,146.585,146.682,161.927,162.064,164.425;Elementary analysis value of calculation (Anal.Calcd) .ForC60H84N4O4S4: C, 68.40;H, 8.04;N, 5.32;Measured value (Found): C, 68.48;H, 7.98;N, 5.22.
Embodiment 9:N, N '-two (2-octyl group-dodecyl)-[2,3-d]-[2-(1,3-bis-sulfur-2-subunit)-2-the third dicyan]-[6,7-d '] [2-(1,3-bis-sulfur-2-subunit)-2-second cyanogen]-naphthalene-1,4, the synthesis of 5,8-tetracarboxylic acid diimide (9).
Concrete synthesis step is:
Under nitrogen protection; by N, N '-two (2-octyl group-dodecyls)-2,3; 6; 7-tetrabromo benzene-naphthalene diimide (TBNDI-C20) (50mg, 0.044mmol), 2-cyano vinyl-1,1-bis-mercaptan sodium salt (11mg; 0.047mmol) He 1; 1-dicyanoethylene-2,2-bis-sodium mercaptides (16mg, 0.086mmol) joins in 10mLTHF; under room temperature after stirring reaction 1h; continue to react 1h at 50 DEG C, be cooled to room temperature, reactant liquor be poured in 20mL water; molten 4 × 15mL dichloromethane solution extracts; merging organic facies, after drying, solvent is removed in decompression rotation.Crude on silica gel chromatographic column purifies (leacheate is dichloromethane/petroleum ether, V/V=1/2～2/3～2/1), obtains the violet solid 16mg of compound 9, productivity 34%.
Mass spectrum: MS (MALDI-TOF) m/z1078.6 (M+H)+;Proton nmr spectra:1H-NMR(300MHz,CDCl3)δ(ppm):0.845–0.869(m,6H,–CH3),1.233(m,32H,–CH2–),2.001(br,1H,CH),4.193–4.223(m,2H,–CH2N), 5.746 (s, 1H ,=CH CN);Carbon-13 nmr spectra:3C-NMR(100MHz,CDCl3): δ 14.099,22.659,26.284,29.328,30.006,31.483,31.676,31.867,31.897,36.514,46.187,46.269,69.864,86.010,86.063,111.728,115.299,115.811,115.875,117.594,117.704,125.009,125.057,143.275,143.345,148.473,148.790,161.910,162.040,164.076,182.535;Elementary analysis value of calculation (Anal.Calcd) .ForC61H83N5O4S4: C, 67.93;H, 7.76;N, 6.49. measured value (Found): C, 67.96;H, 7.42;N, 6.45.
(2) the Ith-VII classes contain ultra-violet absorption spectrum and the electrochemical properties of the benzene-naphthalene diimide derivative (Compound of Example 1-9) of 1,3-bis-sulfur-2-ylide alkene conjugate unit
Ultra-violet absorption spectrum carries out on U-3900 spectrogrph, and in sample solution dichloromethane, (molar concentration is 1 × 10-6M), sweep limits is 800-200nm, and the optical band gap of compound is calculated by below equation and obtains:
Egap opt=1240nm/λonset(1)
Cyclic voltammetry test carries 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 new dichloromethane steamed, and (molar concentration is 1 × 10-3M), Bu4NPF6(0.1M) as supporting electrolyte, scanning speed is 50mV/s, and with saturated calomel for reference, saturated calomel energy level is-4.44eV relative to vacuum level, and the lumo energy of material can be calculated by the formula of following energy level and obtain:
ELUMO=-(E1/2 red1+4.44)eV(2)
Because of the Ith class and the IIth compounds and inventor's previous patent (CN200910197611.9, and CN201110225678.6) compound that discloses has identical conjugated backbone, simply N-substituent group is different, and spectrum and the Electrochemical Performances of compound parent nucleus can be ignored by N-substituent group, here spectrum data is not just reoffered, the maximum absorption band of the ultra-violet absorption spectrum of the Compound of Example 1 and 2 of the Ith class and the IIth class benzene-naphthalene diimide derivative, at about 575nm, is obtained optical band gap by formula (1) calculating and is about 2.1eV.Its lumo energy can be calculated by the cyclic voltammetry curve of compound 1 and 2 and formula (2) and be about-4.35eV.Because of naphthalenetetracarbacidic acidic diimide derivatives (the IIIth class: 3 and 4 that similar sulfur is heterocyclic fused；IVth class: 5 and 6) there is similar ultra-violet absorption spectrum and electrochemical properties, here with compound 3(R for 2-octyl group-dodecyl), 5 (R is 2-octyl group-dodecyl) illustrate for example.Fig. 1 sets forth the ultra-violet absorption spectrum of Compound of Example 3,5 and 7-9, and its maximum absorption band lays respectively at as about 558nm, 543nm, 586nm, 603nm and 592nm, formula (1) calculating the optical band gap obtaining these compounds is 1.9-2.1eV.Fig. 2 gives the cyclic voltammetry curve of compound 3,5 and 7-9, all shows two reversible oxidation-reduction processes, its half wave potential E1/2 red1Respectively-0.11,0.07 ,-0.17 ,-0.39 and-0.22eV, they are calculated lumo energy respectively-4.33 ,-4.51 ,-4.27 ,-4.05 and the-4.22eV of gained by formula (2).
To sum up, from the spectrum of Compound of Example 1-9 and electrochemical research it can be seen that the Ith-VII class contains 1, the lumo energy of the benzene-naphthalene diimide derivative of 3-bis-sulfur-2-ylide alkene conjugate unit is between-4.0～-4.6eV, HOMO energy level >-6.0eV, optical band gap is 1.9-2.1eV, and they are typical n-type organic semiconducting materials.
(3) compound 1-3,5 and 7-9 prepare organic film FET as semiconductor active layer
The invention provides the Compound of Example 1-3 that the Ith-VII class contains the benzene-naphthalene diimide derivative of 1,3-bis-sulfur-2-ylide alkene conjugate unit, 5 and 7-9 as semiconductor active layer application in OTFT (OTFT) device.Fig. 3 gives the structural representation using compound 1 or 2 or 3 or 5 or 7 or 8 or 9 as the OTFT device of organic semiconductor layer.The preparation method of OTFT device is: be dissolved in 1mL chloroform by the compound 1 or 2 or 3 or 5 or 7 or 8 or 9 of 5-15mg, at the OTS SiO modified2In/Si substrate, (as grid, the thickness of thermal oxide silicon dioxide insulating layer is 450nm to highly doped silicon substrate, and electric capacity is 10nFcm-2) get rid of last layer and be about the organic semiconductor thin-film of 20-80nm thickness, at the golden or silver-colored source-drain electrode above with mask plate deposition of organic film, thus preparing the OTFT device of upper electrode arrangement, the semiconductive channel length of device is 50 μm, and channel width is 3mm.Measure under the electrical property Keithley4200 semi-conductor test instrument room temperature in atmosphere of OTFT.Wherein, the OTFT device of Compound of Example 1 and 2 adopts silver source-drain electrode, and its thin film adopts annealing under 140 ° of C in air；Other compounds 3,5 and 7-9 adopt gold as source-drain electrode, are respectively adopted under 80 and 120 ° of C and anneal.
Figure 4 and 5 sets forth the transfer curve of the OTFT device of Compound of Example 1 and 2, and its electron mobility is respectively up to 0.1 with 0.2cm2V-1s-1, on-off ratio is 105-106, threshold voltage is 0-15V.Fig. 6-10 sets forth compound 3,5 and the transfer curve of OTFT device of 7-9, the electrical property of its OTFT device (>=10) characterizes data (including mobility, on-off ratio and threshold voltage) and is listed in table 1, and wherein the electron mobility of the OTFT device of compound 5 is up to 0.11cm2V-1s-1。
The invention is not restricted to disclosed 9 Compound of Example, the benzene-naphthalene diimide derivative containing 1,3-bis-sulfur-2-ylide alkene conjugate unit is of a great variety, and protection scope of the present invention limits with appended claims and is as the criterion.
The OTFT device (gold source-drain electrode) that table 1 is based on compound 3,5 and 7-9 characterizes data unannealed with the electrical property under different annealing temperature, including the highest (on average) electron mobility (μe, unit: cm2/ Vs), on-off ratio (Ion/Ioff) and threshold voltage (VT, unit: V).
Table 1
Claims (11)
1. a class contains the benzene-naphthalene diimide derivative of 1,3-bis-sulfur-2-ylide alkene conjugate unit, and its feature has following structure formula:
IIth compounds, is characterized in that the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) the third dicyan replaced of the asymmetric N-containing 2,2-diphenvl-ethvl construction units condenses:
IIIth compounds, is characterized in that 2-(1,3-bis-sulfur-2-subunit) the third dicyan and Isosorbide-5-Nitrae-two sulfur-2, the asymmetric benzene-naphthalene diimide compound condensed of 3-dicyanoethylene:
IVth compounds, is characterized in that 2-(1,3-bis-sulfur-2-subunit) the third dicyan and the asymmetric benzene-naphthalene diimide compound condensed condensed of 2,3-dicyano thiophene:
Vth compounds, is characterized in that the benzene-naphthalene diimide compound that 2-(1,3-bis-sulfur-2-subunit) Nitrocarbol. condenses:
VIth compounds, is characterized in that the benzene-naphthalene diimide compound that 2-(1,3-bis-sulfur-2-subunit) second cyanogen condenses:
VIIth compounds, is characterized in that 2-(1,3-bis-sulfur-2-subunit) the third dicyan and 2-(1,3-bis-sulfur-2-subunit) the asymmetric benzene-naphthalene diimide compound condensed of second cyanogen:
R in aforesaid structural formula1The alkyl of=C1～30,
R3The alkyl of=H or C1～6.
2. a class contains the benzene-naphthalene diimide derivative of 1,3-bis-sulfur-2-ylide alkene conjugate unit, and its feature has following structure formula:
Ith compounds, is the benzene-naphthalene diimide derivative that condenses of 2-(1,3-bis-sulfur-2-subunit) the third dicyan replaced of the asymmetric N-containing benzyl structure unit:
In aforesaid structural formulaR3The alkyl of=H or C1～6.
3. the benzene-naphthalene diimide derivative containing 1,3-bis-sulfur-2-ylide alkene conjugate unit as claimed in claim 1, is characterized in that described R1For the alkyl of C6～30, R3Alkyl for H or C1～6.
4. prepare as claimed in claim 1 containing 1 for one kind; the method of the benzene-naphthalene diimide derivative of 3-bis-sulfur-2-ylide alkene conjugate unit; it is characterized in that by following (1), (2), (2) and (3) or (4) step, in atmosphere or react under inert gas shielding respectively obtain:
(1) step of the preparation method of the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) the third dicyan that the IIth asymmetric N-of class described in replaces condenses is:
In room temperature～80 DEG C and organic solvent, four bromo naphthalenetetracarbacidic acidic dianhydride and 2,2-dicyanos-ethylene-1,1-bis-mercaptides 1:2～6 in molar ratio are reacted 0.5～12 hour, then with two kinds of organic amine R1NH2React 1～12 hour under the condition of room temperature～80 DEG C with 2,2-diphenyl-ethylamine；Described organic amine R1NH2, 2,2-diphenyl-ethylamine and four bromo naphthalenetetracarbacidic acidic dianhydrides mol ratio be 1～3:1～3:1；
(2) step of the preparation method of the benzene-naphthalene diimide derivative that ii I described in and the asymmetric naphthalene core of VII class replace is:
In organic solvent and-10～50 DEG C at, N-R1The 2,3,6,7-tetra-bromo naphthalenetetracarbacidic acidic diimide, 2,2-dicyanoethylene-1,1-two mercaptides, 1,2-dicyanoethylene-1,2-two mercaptides or 2-cyano vinyl-1,1-two mercaptides that replace react 0.5～3 hour with mol ratio 1:1～2:1～2；
(3) preparation method of the benzene-naphthalene diimide derivative that the asymmetric naphthalene core of iv class described in replaces, the steps include:
In acetic acid or propanoic acid and at 100～120 DEG C, group iii benzene-naphthalene diimide derivative with 30% hydrogen peroxide with mol ratio 1:50～80 reaction stirring 0.5～1.5 hour；
(4) preparation method of the benzene-naphthalene diimide compound that V described in and group VI symmetry naphthalene core replace, the steps include:
In organic solvent with at room temperature～50 DEG C, N-R1The 2,3,6,7-tetra-bromo benzene-naphthalene diimide, 2-nitroethylene-1,2-two mercaptides or 2-cyano vinyl-1,2-two mercaptides that replace react 0.5～3 hour with mol ratio 1:2～5；
Above-mentioned R1Definition as claimed in claim 1.
5. the method preparing the benzene-naphthalene diimide derivative containing 1,3-bis-sulfur-2-ylide alkene conjugate unit as claimed in claim 2, is characterized in that by following step, in atmosphere or react under inert gas shielding and obtain respectively:
The step of the preparation method of the benzene-naphthalene diimide derivative that 2-(1,3-bis-sulfur-2-subunit) the third dicyan that the Ith described asymmetric N-replaces condenses is:
In room temperature～80 DEG C and organic solvent, four bromo naphthalenetetracarbacidic acidic dianhydride and 2,2-dicyanos-ethylene-1,1-bis-mercaptides 1:2～6 in molar ratio are reacted 0.5～12 hour, then and R3The benzylamine and the 2,2-diphenyl-ethylamine that replace react 1～12 hour under the condition of room temperature～80 DEG C；Described organic amine R3The mol ratio of the benzylamine, 2,2-diphenyl-ethylamine and the four bromo naphthalenetetracarbacidic acidic dianhydrides that replace is 1～3:1～3:1；
Described organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, oxolane or dioxane；
Above-mentioned R3Definition as claimed in claim 2.
6., 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, oxolane or dioxane.
7., in method as claimed in claim 4, it is characterized in that the reaction of described step (1), (2) and (4) carries out under inert gas shielding.
8., in the method as described in claim 4 or 5, it is characterized in that described product purifies through silica gel column chromatography.
9. in method as claimed in claim 4, it is characterized in that described 2,2-dicyano-ethylene-1,1-bis-mercaptides, 1,2-dicyanoethylene-1,2-bis-mercaptides, 2-cyano vinyl-1,1-bis-mercaptides, 2-nitroethylene-1,2-bis-mercaptides or 2-cyano vinyl-1,2-bis-mercaptides is their sodium salt, potassium salt, lithium salts, calcium salt or barium salt.
10. the purposes of the benzene-naphthalene diimide derivative containing 1,3-bis-sulfur-2-ylide alkene conjugate unit as described in claim 1,2 or 3, is characterized in that for preparing organic electronic device.
11. the benzene-naphthalene diimide derivative containing 1,3-bis-sulfur-2-ylide alkene conjugate unit as described in claim 1,2 or 3 is as semiconductor active layer application in organic film FET.
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| KR100891130B1 (en) * | 2007-04-18 | 2009-04-06 | 이화여자대학교 산학협력단 | Napthalene diimide-Zn? complex having selectivity for pyrophosphate, preparation method thereof and detection method of pyrophosphate using the same |
| CN101885732B (en) * | 2010-06-23 | 2012-06-27 | 中国科学院上海有机化学研究所 | Heterocyclic-sulfur fused naphthalenetetracarboxylic acid diimide derivatives, preparation method and application thereof |
| CN101693719B (en) * | 2009-10-23 | 2012-07-04 | 中国科学院上海有机化学研究所 | Thia-conjugated compound taking naphthalene tetracarboxylic acid diimide as kernel as well as preparation method and application thereof |
| CN102351879B (en) * | 2011-08-08 | 2014-04-23 | 中国科学院上海有机化学研究所 | Heterocyclic-sulfur fused naphthalene diimide compounds, preparation method and application thereof |
| CN102344456B (en) * | 2011-08-08 | 2013-12-11 | 中国科学院上海有机化学研究所 | Method for preparing sulfur heterocyclic condensed naphthalimide derivants in one-pot method |
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