CN102977084A - Thiophene pyrroloquinone type structure n-type semiconductor material synthesis and semiconductor device containing thiophene pyrroloquinone type structure n-type semiconductor material - Google Patents
Thiophene pyrroloquinone type structure n-type semiconductor material synthesis and semiconductor device containing thiophene pyrroloquinone type structure n-type semiconductor material Download PDFInfo
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Abstract
The present invention relates to a compound having the following general formula and an organic semiconductor device adopting the compound, particularly to an organic field effect transistor (OFET) containing the compound represented by a formula I.
Description
Technical field
The present invention relates to thiophene pyrrole quinonoid structure n-N-type semiconductorN material and use its organic semiconductor equipment, especially, comprise the organic field effect tube (OFET) of above-mentioned materials.
Background technology
Nearly decades, along with the design of novel organic semi-conductor material synthetic with the continuing to optimize of device technology of preparing, organic field effect tube (OFETs) has been obtained the development of advancing by leaps and bounds aspect device performance.P-N-type semiconductorN not only field-effect mobility has reached the degree that compares favourably with the inorganic silicon-based material of tradition, and has obtained good air stability.Yet the common field-effect mobility of n-N-type semiconductorN is lower, and air stability is poor, so its development lags behind the p-N-type semiconductorN always.Until in recent years, in view of the n-N-type semiconductorN plays an important role in constructing bipolar transistor and logical complement circuit, the high-performance n-N-type semiconductorN material of air-stable has more and more caused investigator's interest.
Existing this area still has demand to obtain novel n-N-type semiconductorN material, preferably possess excellent over-all properties, as, high-performance, air-stable, and even some solution processable, at organic semiconductor equipment, especially show superperformance among the organic field effect tube OFETs.
Summary of the invention
The purpose of this invention is to provide thiophene pyrrole quinonoid structure n-N-type semiconductorN material and use its organic semiconductor equipment, especially, comprise the organic field effect tube (OFET) of above-mentioned materials.
The inventor has found that purpose of the present invention can realize by having by the ad hoc structure thiophene pyrrole quinonoid compound of following general formula (I) expression and its derivative.
That is, the invention provides the compound that is represented by following general formula (I):
Formula I
Wherein,
W, identical or different, represent independently electron-withdrawing group, prerequisite is that at least one W represents cyano group;
A, identical or different, be independently selected from hydrogen and monovalence electron-withdrawing group;
X, identical or different, be independently selected from hydrogen and monovalence electron-withdrawing group;
D, identical or different, represent the heteroatoms of VIA family element;
G represents the heteroatoms of VA family element, or represents G '-Y ', and wherein G ' represents the heteroatoms of IVA family element;
Y and Y ', identical or different, be independently selected from hydrogen and monovalence solubility group;
Z, identical or different, be independently selected from hydrogen, monovalence electron-withdrawing group and monovalence solubility group;
M, identical or different, represent independently 0 to 8 integer;
N, identical or different, represent independently 1 to 4 integer.
In an embodiment of the compounds of this invention, the monovalence electron-withdrawing group is independently selected from cyano group, halogen, C
2-C
60Carboxylicesters, it is chosen wantonly and is substituted, C
2-C
60Acyl group, it is chosen wantonly and is substituted, C
1-C
60Perhalogenation alkyl, C
1-C
60Perhalogenation mix alkyl, C
1-C
60Partially halogenated alkyl and C
1-C
60Partially halogenated assorted alkyl.
In another embodiment of the compounds of this invention, monovalence solubility group is independently selected from C
1-C
60Alkyl and assorted alkyl, its optional being substituted is preferably selected from: alkyl, assorted alkyl, acyl group, assorted acyl group, alkyl acyl, assorted alkyl acyl and the assorted acyl group of alkyl.
In another embodiment of the compounds of this invention, each W represents cyano group.
In another embodiment of the compounds of this invention, each A and each X represent hydrogen atom.
In another embodiment of the compounds of this invention, each A represents electron-withdrawing group and each X represents hydrogen atom.
In another embodiment of the compounds of this invention, Y and Y ' represent the solubility group, preferably, and the optional C that replaces
1-C
60Alkyl, more preferably C
2-C
30Alkyl.
In another embodiment of the compounds of this invention, each D represention oxygen atom.
In another embodiment of the compounds of this invention, G represents the heteroatoms of VA family element.
In another embodiment of the compounds of this invention, G represents nitrogen-atoms.
In another embodiment of the compounds of this invention, G represents Si-Y '.
In another embodiment of the compounds of this invention, each m is greater than 0, and each Z represents hydrogen atom.
In another embodiment of the compounds of this invention, each m equals 0.
In another embodiment of the compounds of this invention, the compounds of this invention has following logical
Formula (II):
Formula (II)
In another embodiment of the compounds of this invention, the compounds of this invention is:
Another object of the present invention relates to the isomer of the invention described above compound.Be reluctant to be subjected to the restriction of any theory, have cis-trans isomerism owing to connect two two keys of thiophene, pyrroles at least, so can there be configurational isomer more than three kinds or three kinds in the compounds of this invention, for example:
Cis-cis, cis-trans and trans-trans:
The cis-cis configurational isomer:
Formula I;
The cis-trans configurational isomer:
Formula (III);
Or
The trans-trans configurational isomer:
Formula (IV)
In another embodiment of the compounds of this invention, above-mentioned isomer has following general formula (III):
Formula (III)
In another embodiment of the compounds of this invention, above-mentioned isomer has following general formula (IV):
Formula (IV)
Another object of the present invention relates to the mixture of the invention described above compound and at least a above-mentioned its isomer.
In another embodiment of the compounds of this invention, said mixture comprises (i) the invention described above general formula (I) compound, and (ii) or the isomer of general formula (III) isomer of the invention described above general formula (I) compound and/or general formula (IV).
Another object of the present invention relates to above-claimed cpd and/or its isomer at organic semiconductor device, particularly the purposes in the organic field effect tube (OFETs).Described compound and/or its isomer content as described above.
Another object of the present invention relates to organic semiconductor device, organic field effect tube (OFETs) particularly, it contains compound, isomer or the mixture for preparing such as the isomer of the described compound of above-mentioned content or the compounds of this invention or the invention described above mixture or following public the inventive method.
Described organic semiconductor device can be organic semiconductor device traditional in any this area equally, and it contains such as the described compound of above-mentioned content.
Another object of the present invention also relate to the isomer of preparation the invention described above compound or the invention described above compound or the invention described above compound and or the method for the mixture of its isomer, it comprises the steps A:
With at least a Compound C 1 with following formula
With at least a Compound C 2 reactions with following formula
Wherein, T represents halogen atom, preferred Br,
Wherein, A, X, D, G, Y, Z, W and m state as defined above.
Another embodiment according to the present invention further comprised step B before steps A, carry out following reaction:
Wherein, T represents halogen atom, preferred Br,
X ' represents (valence number of G)-1, for example, and 1,2,3 or 4,
Wherein, A, X, D, G, Y, Z and W state as defined above.
Another embodiment according to the present invention further comprised step C before step B, carry out following reaction:
Wherein, T represents halogen atom, preferred Br,
Wherein, A, X, D, G, Y, Z and W state as defined above.
Another embodiment according to the present invention, the product of steps A are mixtures as the aforementioned, and described method and then steps A further comprises step I, with aforesaid compound of the present invention isomer separation at least a with it.
Another object of the present invention also relates to the intermediate product in preparation above-claimed cpd process of the present invention.In preparation method's steps A, can produce target compound of Formula I and/or intermediate product compound 4:
The method of producing compound of the present invention and/or its isomer is described below, summing-up ground, the synthetic route of the compounds of this invention and its isomer is shown in the following reaction scheme 1.
Wherein, x ' represents (valence number of G)-1, for example, and 1,2,3 or 4,
Wherein, n, m, A, X, D, G, Y, Z and W state as defined above.
Another embodiment according to the present invention in preparation method's steps A, might obtain the dihalo derivative (compound 4a-c) of following the compounds of this invention:
Be reluctant to be bound by any theory restrictions and to fetter, can be based on thiophene oligomer parent nucleus, quinoid structure compound with the dicyano methylene end-blocking, generally all be that employing α-bromine substituted thiophene oligomer is precursor, under catalyzer (such as zeroth order palladium (Pd (PPh3) 4)) katalysis, for example with nitrile salt (such as the propane dinitrile sodium salt) (being generated by sodium hydride and the third two eyeball original positions) nucleophilic substitution reaction occuring generates two negative ion intermediates, at last under oxidizing condition, for example oxidation or be exposed to direct oxidation in the air under the saturated bromine water condition can obtain the target compound of final quinoid structure.
According to an embodiment of the inventive method, can also be in the inventive method scope the conditioned reaction condition, oxidizing condition for example, as use saturated bromine water or air (to contain O
2) direct oxidation (that is, for example directly is exposed in the air oxidation or advertises O to system by the reaction system that directly will contain two negative ion intermediates after acidification
2Bubble) condition.
In another embodiment according to the inventive method, the initial reaction product is the mixture of aforesaid the compounds of this invention isomer at least a with it, described method further comprises separating step, with above-claimed cpd of the present invention isomer separation at least a with it.
All products have preferably solvability, can be dissolved in (such as methylene dichloride, trichloromethane, acetonitrile, acetone etc.) in the common solvent.In addition, can also the column chromatography and recrystallization come separating-purifying, prepare highly purified product.
More specifically, be that example specifically describes synthetic route with following target compound (being labeled as 3a-c, i.e. 3a, 3b, 3c), such as reaction scheme 2:
Target compound 3a-c
Wherein, in preparation method's steps A, might obtain the dihalo derivative (compound 4a-c) of the compounds of this invention:
Particularly, corresponding to the compound 4a-c of target compound 3a-c, compound 4a-c is two halogenide of the target compound 3a-c of correspondence.For example, the compound 4 of target compound 3a has following formula:
Description of drawings
Fig. 1 shows below compound 3b low temperature 213K's
1The HNMR spectrogram (is wherein marked the ownership of the main hydrogen atom of A system, 600MHz).
Compound 3b
There is in some cases isomery in order further to inquire into the compound possibility, it has been carried out the sign of solution state two dimension NOESY spectrum.The below will be take the following isomer of 3b as example,
Discuss for its existence form when the solution state.Solution (CD
2Cl
2) during attitude,
1HNMR spectrogram (Fig. 1) shows that there are two individual system (referred to as A and B system) in 3b: the A system is to exist with the cis-cis configurational isomer during low temperature.For the B system, low thermogram shows, has at least two keys of a trans-(transconfiguration) in the B system, that is to say that this system may be cis-trans or trans-trans configurational isomer.Show that by atlas analysis the B system more generally exists with the cis-trans configurational isomer during low temperature.
NOESY spectrogram (the CD of Fig. 2 compound 3b low temperature 213K
2Cl
2).
Fig. 3 compound 3a-c and 4 DSC curve adopt the thermostability of thermogravimetric analysis (TGA) and differential thermal analysis (DSC) characterizing compounds 3a-c and 4.
Fig. 4 compound 3a-c and 4 TGA curve adopt the thermostability of thermogravimetric analysis (TGA) and differential thermal analysis (DSC) characterizing compounds 3a-c and 4.
By the passable heat decomposition temperature that obtains them of TGA curve, be respectively 298 ℃ (3a), 256 ℃ (3b), 344 ℃ (3c) and 263 ℃ (4).Can be seen that by DSC 3a-c has obvious fusing point, be respectively 197 ℃, 219 ℃, 163 ℃; Do not observe fusing point before 4 decomposition temperatures.As seen, compound 3a-c and 4 has preferably thermostability.
The ultraviolet-visible absorption spectroscopy of Fig. 5 compound 3a-c and 4 in dichloromethane solution.Ultraviolet-visible absorption spectroscopy in the solution (Fig. 5) shows that compound 3a-c has essentially identical two absorption bands, and their maximum absorption wavelength is respectively 739,738 and 738nm.By comparison, contain br-derivatives 4 and also have similar absorption band, but its maximum absorption band red shift 33-34nm (772nm), show that the existence of bromine atoms has further increased effective conjugated degree of whole molecule.
The cyclic voltammetry curve of Fig. 6 compound 3a-c and 4 in dichloromethane solution.
AFM (the 5 μ ms * 5 μ ms) figure of Fig. 7 compound 3a-c film when different annealing temperature: (a), (b) with (c) be spun on SiO for 3a
2/ Si substrate; (d), (e) and the SiO that (f) is spun on the OTS modification for 3b
2/ Si substrate; (g), (h) and the SiO that (i) is spun on the OTS modification for 3c
2/ Si substrate.
The XRD figure of Fig. 8 compound 3a-c film when different annealing temperature: (a) be spun on SiO for 3a
2/ Si substrate; (b) be spun on the SiO that OTS modifies for 3b
2/ Si substrate; (c) be spun on the SiO that OTS modifies for 3c
2/ Si substrate.
Fig. 9 compound 3a-c is in the ultraviolet-visible absorption spectroscopy in solution and film (normalization method).
The ultraviolet-visible absorption spectroscopy of Figure 10 compound 3a-c film when different annealing temperature: (a) 3a, (b) 3b, (c) 3c are spun on quartz plate.
Figure 11 compound 3a is spun on the SiO of unmodified at solution
2The characteristic curve of typical n-type organic field effect tube device in the/Si substrate: (a) 120 ℃, (c) 150 ℃, (e) 180 ℃ of curves of output; (b) 120 ℃, (d) 150 ℃, (f) 180 ℃ of transition curves (VD=100V).
Figure 12 compound 3a is spun on the SiO of unmodified at solution
2Typical bipolar organic effect in the/Si substrate.
Embodiment
One, synthetic
Particularly, specifically describe synthetic route take following target compound as example, such as reaction scheme 2:
Be reluctant to be bound by any theory restrictions and to fetter, can be based on thiophene oligomer parent nucleus, quinoid structure compound with the dicyano methylene end-blocking, generally all be that employing α-bromine substituted thiophene oligomer is precursor, under catalyzer (such as zeroth order palladium (Pd (PPh3) 4)) katalysis, for example with nitrile salt (such as the propane dinitrile sodium salt) (being generated by sodium hydride and the third two eyeball original positions) nucleophilic substitution reaction occuring generates two negative ion intermediates, at last under oxidizing condition, for example oxidation or be exposed to direct oxidation in the air under the saturated bromine water condition can obtain the target compound of final quinoid structure.
According to an embodiment of the inventive method, can also be in the inventive method scope the conditioned reaction condition, oxidizing condition for example, as use saturated bromine water or air (to contain O
2) direct oxidation (that is, for example directly is exposed in the air oxidation or advertises O to system by the reaction system that directly will contain two negative ion intermediates after acidification
2Bubble) condition.
In another embodiment according to the inventive method, the initial reaction product is the mixture of aforesaid the compounds of this invention isomer at least a with it, described method further comprises separating step, with above-claimed cpd of the present invention isomer separation at least a with it.
All products have preferably solvability, can be dissolved in (such as methylene dichloride, trichloromethane, acetonitrile, acetone etc.) in the common solvent.In addition, can also the column chromatography and recrystallization come separating-purifying, prepare highly purified product.
Of the present invention compound of Formula I of the below take R as 2-n-octyl dodecyl specifies synthetic method as example, and wherein compound is as follows:
(1) reagent, instrument and method
Other common solvent and reagent are all bought from the Beijing Chemical Plant.Before use, glycol dimethyl ether needs heavily steaming, and specific practice is: add sodium and reflux, until indicator benzophenone color becomes blue rear distillation.
2 instruments and method
1H-NMR and
13C NMR Bruck DMX-400 nmr determination.Mass spectrometric measurement carries out at UK CT-Mieromass or SHIMADZU GCMS-QP2010 spectrograph.
High resolution mass spectrum carries out at Bruker APEX II FT-ICRMS spectrograph.Ultimate analysis is tested with Carlo Erba 1106 type elemental analysers.
UV, visible light (UV-vis) spectrum: JASCO V-570 type ultraviolet-visual spectrometer thermogravimetric analysis (TGA) is to be measured by TA Instruments SDT2960 type thermogravimetric analyzer, and under nitrogen atmosphere, heat-up rate is 10 ℃ of per minutes.
Electro-chemical test: cyclic voltammetry (CV) test is carried out at the CHI660C electrochemical workstation.Adopt traditional three-electrode system, platinum electrode is working electrode, and Ag/AgCl is as reference electrode, and the platinum filament conduct is to electrode; Sample is dissolved in the methylene dichloride of new steaming, and Bu4NPF6 (0.1Mm) is as supporting electrolyte, with ferrocene (ferrocene) as reference.Before the test, with high pure nitrogen bubbling 3 minutes with the oxygen in the desolventizing.
X-ray diffraction (XRD): Rigaku D/max-2500X x ray diffractometer x, (Cu K α radiation, λ=1.54
), room temperature, 2kW adopts reflective-mode to characterize the degree of order of film.
Atomic force microscope (AFM): Digital Instruments Nanoscope III atomic force microscope (AFM) adopts the pattern that raps the modeling film.
FET device preparation method: adopt bottom gate top electrode device architecture.The surface with the highly doped silicon (Si++) of 500nm silicon-dioxide (SiO2) insulation layer as gate electrode (electric capacity 7.5nF cm-2).By steam accumulation method, (Octadecane base trichlorosilane octadecyltrichlorosilane) is modified with OTS in the Si/SiO2 substrate.The organic semiconductor active coating adopts the method preparation of solution spin coating: the solution (concentration is 10mg/mL) that compound 3a-c is dissolved in trichloromethane drips and casts from the Si/SiO2 substrate that unmodified or OTS modify, on sol evenning machine, rotated for 30 seconds with 2000 rev/mins speed, seasoning in the air.Before the gold evaporation electrode, film was annealed 20-30 minute respectively at 80,100,120,150 or 180 ℃ under vacuum condition.At last, the thick golden source-drain electrode of 20nm adopts the spun gold of 25 micron diameters as the method evaporation of mask.Channel length (L) and width (W) are respectively 0.11mm and 5.30mm.
FET device electrical performance testing: adopt 6150 type probe stations at room temperature to test in the air, test macro is Keithley 4200 SCS instruments.
The X-ray crystallography data are collected with Bruker Smart CCD diffractometer, with Mo K α radioactive rays (λ=0.71073 of graphite monochromator monochromatization
).Collect data at 173K.Use the direct method analytic structure, use the method for least squares refine.Calculate with the SHELXL-97 program.
(2), synthetic and sign
(1) the synthetic logical method (take 2-n-octyl lauryl amine as example) of branched-chain alkyl primary amine
2-n-octyl lauryl bromide
Under the protective condition of nitrogen, triphenyl phosphorus (15g, 57mmol) is dissolved in the methylene dichloride (90mL), temperature is down to 0 ℃, continues to stir 15 minutes.In system, drip bromine (2.93mL, 57mmol), drip and finish rear the stirring a moment, remove ice bath.After system temperature is upgraded to room temperature, in system, slowly drip 2-n-octyl dodecyl alcohol (20.41mL, 57mmol).Drip and finish stirred overnight at room temperature.Solvent is spin-dried for, and residue washes with Skellysolve A, suction filtration, and filtrate is concentrated, and (sherwood oil: methylene dichloride=5: 1), obtain faint yellow oily thing 16.1g, productive rate is 78% to the thick product column chromatography of gained yellow oily.1H?NMR(400MHz，CDCl3，ppm)δ3.45(d，2H，J＝4.7Hz)，1.55(m，1H)，1.39-1.27(m，32H)，0.88(t，6H，J＝6.7Hz)；MS(EI，m/z)：361[M+]。
N-(2-n-octyl dodecyl) phthalic imidine
Under the protective condition of nitrogen; with potassium phthalimide (8.26g; 44.5mmol) the disposable 2-n-octyl lauryl bromide (15g that joins; 41.5mmol) DMF (N; the N-N,N-DIMETHYLACETAMIDE; 50mL) in the solution, system temperature rises to 90 ℃, continues to stir 16 hours.Be down to room temperature, system is injected 150mL water, with dichloromethane extraction (100mL * 3 time), merge organic phase, use successively potassium hydroxide solution (200mL), water, the saturated aqueous ammonium chloride of 0.2N to wash anhydrous magnesium sulfate drying, be spin-dried for solvent, (sherwood oil: methylene dichloride=1: 1), obtain nearly colorless oil 12.1g, productive rate is 68% to the thick product column chromatography of gained yellow oily.1H?NMR(400MHz，CDCl3，ppm)δ7.84(m，2H)，7.70(m，2H)，3.56(d，2H，J＝7.2Hz)，1.75(m，1H)，1.36-1.23(m，32H)，0.87(m，6H)；MS(EI，m/z)：428[M+]。
2-n-octyl lauryl amine
With N-(2-n-octyl dodecyl) phthalic imidine (4.52g, 10.6mmol), 85% hydrazine hydrate (1.52mL, 24.4mmol) add successively in the methyl alcohol (100mL), system temperature rises to 95 ℃, continue to stir, with TLC monitoring reaction process, after TLC shows that raw material disappears substantially, stopped reaction, revolve desolventizing, residue is with methylene dichloride (50mL) dilution, and 10% potassium hydroxide aqueous solution (25mL * 2 time) is washed separatory, use again the dichloromethane extraction water, merge organic phase, saturated sodium-chloride is washed, anhydrous magnesium sulfate drying.Be spin-dried for solvent and obtain faint yellow oily thing 2.5g, productive rate 79%.Directly drop into the next step, be not further purified.1H?NMR(400MHz，CDCl3，ppm)δ2.67(d，2H，J＝5.8Hz)，1.45(m，1H)，1.29-1.25(m，32H)，0.87(t，6H，J＝6.7Hz)；MS(EI，m/z)：297[M+]。
(2) compound 1
With aluminum chloride (16g, 0.12mol) in the disposable adding methylene dichloride (25mL), stirring at room for a moment, slowly splash into 2-bromothiophene (11.6mL to system, 0.12mol) and oxalyl chloride (6.51mL, 0.05mol) be dissolved in the solution of methylene dichloride (25mL), to drip and finish, stirring is spent the night.Be warming up to backflow, continue 1 hour, be cooled to room temperature, it is injected 0 ℃ dilute hydrochloric acid solution (the 5mL concentrated hydrochloric acid is dissolved in 100mL) lentamente, and ceaselessly stir.Dichloromethane extraction is washed anhydrous magnesium sulfate drying with dilute hydrochloric acid, water, the saturated aqueous ammonium chloride of 2N successively.Suction filtration revolves desolventizing, and (sherwood oil: methylene dichloride=2: 1), use at last ethyl alcohol recrystallization, obtain orange solids powder 6.9g, productive rate is 34% to the brown thick product column chromatography of gained.1H?NMR(400MHz，CDCl3，ppm)δ7.54(d，J＝4.0Hz，2H)，7.12(d，J＝4.0Hz，2H)，3.29(s，4H)；MS(EI，m/z)：408[M+]。
(3) the synthetic logical method of compound 2a-c
Under the protective condition of nitrogen, compound 1 (2.04g, 5mmol) is dissolved in the toluene (25mL); in system, inject corresponding primary amine (7.25mmol), propionic acid (0.5mL successively; 6.5mmol), system is heated to backflow, continues to stir 24 hours.Be down to room temperature, revolve desolventizing, residue sherwood oil column chromatography obtains the dibromo thiophene pyrroles precursor 2a-c that various alkyl chains replace.
Compound 2a
Obtain faint yellow oily thing 1.8g, productive rate is 72%.1H?NMR(400MHz，CDCl3)δ7.03(s，2H)，6.80(s，2H)，6.28(s，2H)，4.05(t，J＝7.7Hz，2H)，1.53(m，2H)，1.26(m，2H)，1.17-1.14(m，8H)，0.87(t，J＝6.9Hz，3H)；13CNMR(400MHz，CDCl3)δ136.6，130.3，127.9，126.6，111.8，111.5，45.4，31.9，31.3，29.1，29.0，26.5，22.8，14.2；EI-MS：m/z＝501[M+]；HREIMS：Calc.500.9618，Found?500.9624[M+]。
Compound 2b
Obtain faint yellow oily thing 1.8g, productive rate is 72%.1H?NMR(400MHz，CDCl3)δ7.02(d，J＝3.7Hz，2H)，6.79(d，J＝3.7Hz，2H)，6.28(s，2H)，4.04(d，J＝7.5Hz，2H)，1.45(m，1H)，1.11-0.90(m，8H)，0.79(t，J＝7.2Hz，3H)，0.60(t，J＝7.4Hz，3H)；13C?NMR(400MHz，CDCl3)δ136.9，130.3，128.7，126.6，111.7，111.6，49.5，39.8，30.5，28.4，23.9，22.9，14.1，10.7；EI-MS：m/z＝501[M+]；HREIMS：Calc.500.9618，Found500.9626?[M+]。
Compound 2c
Obtain faint yellow oily thing 2.5g, productive rate is 75%.1H?NMR(400MHz，CDCl3)δ7.02(d，J＝3.8Hz，2H)，6.78(d，J＝3.8Hz，2H)，6.26(s，2H)，4.02(d，J＝7.5Hz，2H)，1.48(m，1H)，1.26-1.13(m，32H)，0.95-0.87(m，6H)；13CNMR(400MHz，CDCl3)δ137.0，130.3，130.3，128.7，126.5，111.7，49.8，38.2，32.1，32.1，31.3，29.9，29.8，29.8，29.7，29.7，29.5，29.4，26.2，22.9，22.8，14.3；EI-MS：m/z＝669[M+]；HREIMS：Calc.669.1496，Found?669.1488[M+]。
(4) the synthetic logical method of compound 3a-c
Under the protective condition of nitrogen; with sodium hydride (0.111g; 4.63mmol) be suspended in the glycol dimethyl ether (10mL); temperature is down to 0 ℃, lentamente with in the third two eyeball (0.092g, 1.39mmol) the adding systems; finish in this temperature and stirred 10 minutes; remove ice bath, be warming up to room temperature, stirred 30 minutes.In system, add compound 2 (0.58mmol) and tetrakis triphenylphosphine palladium (0) (0.067g, 0.058mmol) successively, be heated to backflow.Along with the increase of return time, system gradually becomes orange by yellow, shows the generation of two negative ion intermediates.After 4-6 hour, be down to room temperature, add ice bath to 0 ℃, in system, inject dilute hydrochloric acid (2M, 60mL), rise to room temperature, continue the drum oxygen bubbles, stirred 2 days.Add methylene dichloride (50mL * 3 time), extraction merges organic phase, and saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.Suction filtration is spin-dried for, residue column chromatography (sherwood oil: methylene dichloride=1: 4), use acetone and acetonitrile mixed solvent recrystallization again, obtain target compound 3.
Compound D TPQ-C8-TCN (3a)
Recrystallization obtains olive-green tabular crystal 0.080g, and productive rate is 30%.M.p.197℃；1H?NMR(400MHz，CD2Cl2)δ7.66(d，J＝5.4Hz，2H)，7.23(s，2H)，7.20(d，J＝5.4Hz，2H)，4.31(t，J＝8.3Hz，2H)，1.91-1.87(m，2H)，1.50(m，2H)，1.43-1.41(m，2H)，1.30(m，6H)，0.88(t，3H)；13C?NMR(400MHz，CD2Cl2)δ170.5，145.0，141.7，127.5，126.2，125.4，114.6，113.9，65.9，47.2，31.8，30.6，29.2，26.4，22.7，14.2；EI-MS：m/z＝471[M+]；MALDI-TOF：470.2[M+]；Anal.Calc.For?C26H23N5S2：C，66.50；H，4.94；N，14.91；Found：C，66.47；H，4.98；N，14.82。
Compound D TPQ-C2C6-TCN (3b)
Recrystallization obtains olive-green needle-like crystal 0.080g, and productive rate is 30%.M.p.219℃；?1H?NMR(400MHz，CD2Cl2)δ7.69(d，J＝5.5Hz，2H)，7.25(s，2H)，7.14(d，J＝5.4Hz，2H)，4.26(d，J＝8.1Hz，2H)，1.96-1.94(m，1H)，1.39-1.19(m，8H)，0.88(t，J＝7.4Hz，3H)，0.82(t，J＝6.7Hz，3H)；13CNMR(400MHz，CD2Cl2)δ171.1，146.6，142.9，127.6，127.0，126.4，115.2，114.3，65.5，51.8，40.4，30.4，29.0，24.0，23.5，14.2，11.1；MALDI-TOF：469.1[M+]；Anal.Calc.For?C26H23N5S2：C，66.50；H，4.94；N，14.91；Found：C，66.51；H，4.96；N，14.85。
Compound D TPQ-C8C12-TCN (3c)
Recrystallization obtains olive-green pressed powder 0.078g, and productive rate is 20%.M.p.163℃；1H?NMR(400MHz，CD2Cl2)δ7.68(d，J＝5.5Hz，2H)，7.24(s，2H)，7.14(d，J＝5.4Hz，2H)，4.25(d，J＝8.1Hz，2H)，2.00-1.99(m，1H)，1.33-1.19(m，32H)，0.86-0.83(m，6H)；13C?NMR(400MHz，CD2Cl2)δ171.1，146.6，142.8，127.6，127.0，126.5，115.2，114.4，65.6，52.1，39.2，32.5，32.4，31.3，30.4，30.2，30.0，29.9，29.9，29.8，26.9，23.3，23.2，14.5；MALDI-TOF：637.3[M+]；Anal.Calc.For?C38H47N5S2：C，71.54；H，7.43；N，10.98；Found：C，71.56；H，7.44；N，11.06。
(5) compound 2Br-DTPQ-C8-TCN (4)
Under the protective condition of nitrogen; with sodium hydride (0.111g; 4.63mmol) be suspended in the glycol dimethyl ether (10mL); temperature is down to 0 ℃, lentamente with in the third two eyeball (0.092g, 1.39mmol) the adding systems; finish in this temperature and stirred 10 minutes; remove ice bath, be warming up to room temperature, stirred 30 minutes.In system, add compound 2a (0.289g, 0.58mmol) and tetrakis triphenylphosphine palladium (0) (0.067g, 0.058mmol) successively, be heated to backflow.Along with the increase of return time, system gradually becomes orange by yellow, shows the generation of two negative ion intermediates.After 4 hours, be down to room temperature, add ice bath to 0 ℃, splash into saturated bromine water (25mL) in system, solution turned blue has the sap green Precipitation gradually.System keeps low temperature to stir 1 hour.Direct suction filtration, washing (10mL * 3 time), (sherwood oil: methylene dichloride=1: 4), use acetone and methylene dichloride mixed solvent recrystallization again, obtain bright green needle-like crystal 0.14g, productive rate is 39% to thick product column chromatography.
1H?NMR(400MHz，CDCl3)δ7.67(s，2H)，7.20(s，2H)，4.24(t，J＝8.4Hz，2H)，1.88(m，2H)，1.50(m，2H)，1.42(m，2H)，1.30(m，6H)，0.88(t，3H)；EI-MS：m/z＝628[M+]；MALDI-TOF：628.2[M+]；Anal.Calc.For?C26H21Br2N5S2：C，49.77；H，3.37；N，11.16；Found：C，49.76；H，3.46；N，10.94。
And then, by further conditioned reaction condition, in oxidising process, use air (O
2) condition of direct oxidation, after acidification, directly be exposed to oxidation in the air by the reaction system that directly will contain two negative ion intermediates, or advertise O to system
2Bubble obtains the 3a product, and the separating-purifying ratio is easier to reaction yield better (30-40%).
All products all have preferably solvability, can be dissolved in (such as methylene dichloride, trichloromethane, acetonitrile, acetone etc.) in the common solvent.
Two, spectrum and electrochemical properties
The ultraviolet-visible absorption spectroscopy of Fig. 5 compound 3a-c and 4 in dichloromethane solution.
The cyclic voltammetry curve of Fig. 6 compound 3a-c and 4 in dichloromethane solution.
As show optical physics and the electrochemical properties that 4-2 has shown compound 3a-c and 4.
Show optical physics and the electrochemical properties of 4-2 compound 3a-c and 4.
A V vs Ag/AgCl, all electromotive forces use the Fc/Fc+ (E that measures under similarity condition
1/2The calibration of=+ 0.43V)
B is equation E=-(4.40+E rule of thumb
Onset) the eV estimation
C is by λ
OnsetCalculate
Three, film morphology
The pattern of film and crystallinity affect the organic effect performance of devices to a great extent, adopt atomic force microscope (AFM) and X-ray diffraction (XRD) to characterize respectively pattern and the crystallinity of compound 3a-c film.All be method preparation by solution spin coating (spin-coating) based on the film of 3a-c.
Compound 3a is at SiO
2Form film in the/Si substrate, and the SiO that modifies at OTS
2Fail in/Si the substrate to obtain to cover substrate, continuous thin film; Compound 3b and 3c can be at SiO
2The SiO that modifies in/Si the substrate and at OTS
2Obtain preferably film in the/Si substrate.
Four, the electric property of thin film transistor
Device is the bottom gate upper electrode arrangement, at SiO
2The SiO that/Si substrate or OTS modify
2With the method fabricate devices of getting rid of film (spin-coating), in air, test in/Si the substrate.All devices have all shown typical N-shaped field-effect characteristic, and namely the main current carrier of transmission is electronics; Part of devices has demonstrated the bipolarity characteristic, simultaneously transmission electronic and hole.Take compound 3a as example, Figure 11 has provided the characteristic curve of its typical N-shaped device under the different annealing temperature condition; The characteristic curve of typical bipolar device when Figure 12 is room temperature.
Figure 11 compound 3a is spun on the SiO of unmodified at solution
2The characteristic curve of typical n-type organic field effect tube device in the/Si substrate: (a) 120 ℃, (c) 150 ℃, (e) 180 ℃ of curves of output; (b) 120 ℃, (d) 150 ℃, (f) 180 ℃ of transition curves (VD=100V).
Figure 12 compound 3a is spun on the SiO of unmodified at solution
2The characteristic curve of typical bipolar organic field effect tube device in the/Si substrate: (a) with (b) room temperature curve of output; (c) with (d) room temperature transition curve (VD=100V or-100V).
Table 4-3 compound 3a-c solution is spun on the SiO of unmodified or OTS modification
2The device performance of the suprabasil organic field effect tube of/Si.
Table 4-3 has provided the performance perameter based on compound 3a-c organic field effect tube when the different annealing temperature.Can find out that the film thermal treatment temp has a significant impact device performance.This shows, based on the device of 3a-c in room temperature or lower annealing temperature (80 ℃) has different transport propertys, and the gradually rising with annealing temperature, their device performance shows different variation tendencies, this mainly comes from them and has different alkyl substituents, thus affected the arrangement mode of molecule in film with and variation with temperature trend.
Claims (25)
1. the compound that has following general formula I:
Formula I
Wherein,
W, identical or different, represent independently electron-withdrawing group, prerequisite is that at least one W represents cyano group;
A, identical or different, be independently selected from hydrogen and monovalence electron-withdrawing group;
X, identical or different, be independently selected from hydrogen and monovalence electron-withdrawing group;
D, identical or different, represent the heteroatoms of VIA family element;
G represents the heteroatoms of VA family element, or represents G '-Y ', and wherein G ' represents the heteroatoms of IVA family element;
Y and Y ', identical or different, be independently selected from hydrogen and monovalence solubility group;
Z, identical or different, be independently selected from hydrogen, monovalence electron-withdrawing group and monovalence solubility group;
M, identical or different, represent independently 0 to 8 integer;
N, identical or different, represent independently 1 to 4 integer.
2. according to claim 1 compound, wherein the monovalence electron-withdrawing group is independently selected from cyano group, halogen, C
2-C
60Carboxylicesters, it is chosen wantonly and is substituted, C
2-C
60Acyl group, it is chosen wantonly and is substituted, C
1-C
60Perhalogenation alkyl, C
1-C
60Perhalogenation mix alkyl, C
1-C
60Partially halogenated alkyl and C
1-C
60Partially halogenated assorted alkyl.
3. according to claim 1 and 2 compound, wherein monovalence solubility group is independently selected from, C
1-C
60Alkyl and assorted alkyl, its optional being substituted is preferably selected from: alkyl, assorted alkyl, acyl group, assorted acyl group, alkyl acyl, assorted alkyl acyl and the assorted acyl group of alkyl.
4. according to each compound of aforementioned claim, wherein each W represents cyano group.
5. according to each compound of aforementioned claim, wherein each A and each X represent hydrogen atom.
6. according to each compound of aforementioned claim 1-4, wherein each A represents electron-withdrawing group and each X represents hydrogen atom.
7. according to each compound of aforementioned claim, wherein Y and Y ' represent the solubility group, preferably, and the optional C that replaces
1-C
60Alkyl, more preferably C
2-C
30Alkyl.
8. according to each compound of aforementioned claim, wherein each D represention oxygen atom.
9. according to each compound of aforementioned claim, wherein G represents the heteroatoms of VA family element.
10. according to claim 9 compound, wherein G represents nitrogen-atoms.
11. according to each compound of aforementioned claim 1-8, wherein G represents Si-Y '.
12. according to each compound of aforementioned claim, wherein each m is greater than 0, each Z represents hydrogen atom.
13. according to each compound of aforementioned claim 1-11, wherein each m equals 0.
14. according to each compound of aforementioned claim, it has following general formula (II):
Formula (II)
15. compound according to claim 14, it is:
16. according to each the isomer of compound of aforementioned claim.
17. isomer according to claim 16, it has following general formula (III):
Formula (III)
18. isomer according to claim 16, it has following general formula (IV):
19. comprise according to aforementioned claim 1-15 each compound and the mixture of at least a its isomer.
20. mixture according to claim 19, it comprises (i) compound according to claim 14, and (ii) or the isomer of the isomer of claim 17 or claim 18 or this two kinds of isomer.
21. preparation claim each compound of 1-15 or according to claim 16-18 each isomer or the method for the mixture of claim 19 or 20, it comprises the steps A:
With at least a Compound C 1 with following formula
With at least a Compound C 2 reactions with following formula
Wherein, T represents halogen atom, preferred Br,
Wherein, A, X, D, G, Y, Z, W and m state as defined above claim each.
22. method according to claim 21, it further comprised step B before steps A, carry out following reaction:
Wherein, T represents halogen atom, preferred Br,
X ' represents (valence number of G)-1, for example, and 1,2,3 or 4,
Wherein, A, X, D, G, Y, Z and W state as defined above claim each.
23. method according to claim 22, it further comprised step C before step B, carry out following reaction:
Wherein, T represents halogen atom, preferred Br,
Wherein, A, X, D, G, Y, Z and W state as defined above claim each.
24. each method of claim 21-23, wherein the product of steps A is according to claim 19 or 20 mixture, described method and then steps A further comprises step I, with each compound isomer separation at least a with it according to claim 1-15.
25. organic semiconductor equipment, organic field effect tube OFET especially, it comprises according to claim 1-15 each compound or each isomer or the mixture of claim 19 or 20 or the compound, isomer or the mixtures that prepare of method according to claim 21-24 according to claim 16-18.
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