CN106008558B - The polycyclic aromatic hydrocarbon organic semiconducting materials of one kind based on thiadiazoles and preparation method thereof and in photoelectric device application - Google Patents
The polycyclic aromatic hydrocarbon organic semiconducting materials of one kind based on thiadiazoles and preparation method thereof and in photoelectric device application Download PDFInfo
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Abstract
Polycyclic aromatic hydrocarbon organic semiconducting materials and preparation method thereof the invention discloses one kind based on thiadiazoles, structure can be indicated by logical formula (I).Wherein Ar indicates aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.Hete rocyclic derivatives of the invention can activate coupling reaction, Sonogashira coupling reaction, PtCl by Suzuki coupling reaction, C-H2Catalytic cyclization reaction and Scholl reaction synthesis.Polycyclic aromatic hydrocarbon derivative of the invention not only has excellent dissolubility and thermal stability, and has excellent pi-conjugated skeleton, and it is the good organic semiconducting materials of performance that the increase of pi-conjugated system, which is conducive to improve corresponding device performance,.
Description
Technical field
Polycyclic aromatic hydrocarbon organic semiconducting materials preparation method and its photoelectric device the present invention relates to one kind based on thiadiazoles
Using specifically including preparation method and photoelectric device application field.
Background technique
For a long time, it has been recognized that organic matter is nonconducting, therefore it is used as insulating materials until 1954 extensively
Year, electrically conductive (the conductivity about 0.1S of aromatic series carbon hydrate of Japanese Scientists Japanese red pine, well head et al. discovery doping chlorine
cm-1) after, it has been put forward for the first time this concept of organic semiconductor.1977, Americanized scholar M.MacDiarmid, American Physical
Family Alan J.Heeger Japanese chemists Shirakawa has found highly conductive polyacetylene, and the great discovery of this makes this three science
Family obtains Nobel chemistry Prize in 2000, has pulled open the prelude of organic semiconductor research since then.Organic semiconducting materials are made
The new material developed and produced for next-generation electronic device starts to be concerned.
The appearance of organic semiconducting materials is not accidental, but inevitable.Since nineteen fifties, silicon, germanium,
The inorganic semiconductor materials such as GaAs almost occupy entire electronics and information industry, however as constantly mentioning for the level of IT application
Height, in order to meet the needs of people, the performance of electronic product needs to be continuously improved, this core for just needing development function more powerful
Piece, and on the basis of considering practical and attractive, it is desirable to the continuous diminution of electronic component, integrated level is continuously improved, when response
Between constantly shorten.And the Electronic Performance development of inorganic material has been approached the limit, continues to reduce size, reduces cost, improves performance
Deng all extremely difficult, so far inorganic semiconductor material can not meet the demand of application field.Organic semiconducting materials have
It is excellent that raw material is easy to get, is cheap, is light-weight, preparation process is simple, environmental stability is good and can be fabricated to large area flexible device etc.
Point.Therefore, the appearance of organic semiconducting materials just in time, largely breaches the hair of inorganic material theory and technology
Bottleneck is opened up, the new direction of electronic information technology development is become.
With the research that deepens continuously to organic semiconducting materials, the application field of organic semiconducting materials constantly expands,
Wherein Organic Light Emitting Diode, organic field effect tube, organic solar batteries are developed rapidly, and gradually move towards quotient
Industry.And in organic semiconducting materials, conjugation heterocycle organic semiconducting materials rely on excellent optical characteristics and electrology characteristic
Characteristic becomes the research emphasis of photoelectric material in recent years.
Diazosulfide (BT) group is strong electron-withdrawing group group, be a kind of high efficiency, high chemical stability it is famous glimmering
Light blob is applied in D-A conjugated compound frequently as receptor unit, by adjusting molecule front rail to the interaction between receptor
Road and spectral region.Compound containing BT often can obtain orderly crystal structure, this is primarily due to its higher polarization characteristic
So as to cause the reinforcement for contacting this kind of intermolecular interaction that interacts with π-π as hetero atom, these characteristics are for Organic Electricity
It is vital that son, which is learned,.
Summary of the invention
Goal of the invention: developing one kind has high conjugated degree, and high mobility, stability, film forming, dissolubility etc. are excellent
Point, and prepare the easy low-cost conjugation heterocycle organic semiconducting materials based on thiadiazoles.
Technical solution: the preparation method of a kind of polycyclic aromatic hydrocarbon organic semiconducting materials based on thiadiazoles of the invention,
Structure can be indicated by logical formula (I):
Wherein Ar indicates one of aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
In formula (I) general formula, aryl or substituted aryl be benzene, naphthalene, anthracene, pyrene, one of fluorenes；Heterocyclic aryl takes
For one of derivative that heterocyclic aryl is thiophene, benzothiophene, carbazole, fluorenes etc., these groups can also pass through some alkyl
Chain or oxyalkyl chain are modified.
Preparation method includes following synthesis step:
(a) first with 5,6- dibromo diazosulfide for initial feed, the then boric acid with Ar or with Ar group, boron
Ester, tin reagent etc. derivative react to obtain under the action of palladium catalyst one kind such as formula (1) compound represented；
(b) formula (1) compound represented is dissolved in suitable organic solvent, by Sonogashira coupling reaction, in palladium
Catalyst, cuprous iodide, triphenylphosphine, diisopropylamine, existing for trimethylsilyl acetylene under the conditions of formula (1) compound represented
On bromine become trimethylsilyl acetylene base to get to one kind such as formula (2) compound represented；
(c) formula (2) compound represented is dissolved in suitable organic solvent, under the conditions of existing for a large amount of methanol and alkali,
Stirring at normal temperature 5 hours, a kind of compound as represented by formula (3) can be obtained；
(d) ratio of formula (1) compound represented and formula (3) compound represented 1:1 in molar ratio are dissolved in suitably
Organic solvent, by Sonogashira coupling reaction, the item existing for palladium catalyst, cuprous iodide, triphenylphosphine, triethylamine
It is reacted 12 hours under part, the compound of a kind of coupling of the alkynes as shown in formula (4) can be obtained；
(e) compound that alkynes shown in formula (4) is coupled is dissolved in suitable organic solvent, in platinous chloride or dichloride
For gold as under conditions of catalyst, 80~120 DEG C of reactions become unilateral six to get to the acetylene bond as represented by formula (5) in 24 hours
The compound of member ring；
(f) compound as represented by formula (6) is dissolved in suitable organic solvent, is added dropwise under room temperature into mixed liquor molten
There is the nitromethane of ferric trichloride, is monitored by TLC plate until consumption of raw materials is completely to get to as general formula (1) is represented
Compound.
Conjugation heterocycle organic semiconducting materials and preparation method thereof of the one kind described in step (a) based on diazosulfide,
It is characterized in that palladium catalyst described in step a is tetrakis triphenylphosphine palladium, palladium acetate, dichloro two (triphenylphosphine) palladium etc.；It is described
Organic solvent be tetrahydrofuran, toluene, n,N-Dimethylformamide, n,N-dimethylacetamide etc..
Step (b) organic solvent is new steaming anhydrous tetrahydro furan, toluene etc..
Step (c) organic solvent is common tetrahydrofuran, toluene etc. (do not need anhydrous, super dry), and the alkali can
To be potassium hydroxide, sodium hydroxide, potassium carbonate etc..
Organic solvent described in step (d) is new steaming anhydrous tetrahydro furan, toluene etc..
Organic solvent described in step (e) is generally newly to steam dry toluene.
Organic solvent described in step (f) is anhydrous methylene chloride, chloroform etc..
The utility model has the advantages that compared with prior art, a kind of polycyclic aromatic hydrocarbon organic semiconductor material based on thiadiazoles of the invention
Preparation method for material and its photoelectric device application.Coupling reaction, Sonogashira coupling are activated by Suzuki coupling reaction, C-H
Reaction, PtCl2Catalytic cyclization reaction and Scholl reaction, it is easy to operate, by-product is few, is easily isolated；By using 5,6- bis-
Bromine diazosulfide is raw material, ensure that the presence that strong electron-withdrawing group is rolled into a ball in system, guarantees in the case where enhancing conjugated system
The stability of molecule.And diazosulfide group is good chromophore, increases it in the application of photoelectric field.Structure
In use 5,6- dibromo diazosulfide be raw material, ensure that the stability of material, bigger conjugation constructed using a variety of Ar
System, and flexible alkyl chains appropriate are introduced, the dissolubility of material is improved, the organic semiconductor material haveing excellent performance is obtained
Material.And the raw material used is 5,6- dibromo diazosulfide, is to be made by simple o-phenylenediamine, o-phenylenediamine is inexpensively easy
, be conducive to industrialization production in this way.
The present invention has obtained a kind of polycyclic aromatic hydrocarbon organic semiconducting materials based on thiadiazoles, passes through nuclear magnetic resonance, mass spectrum
Etc. test methods compound structure is characterized.Then the side such as ultraviolet and fluorescence spectrum, cyclic voltammetric, thermogravimetric analysis is utilized
To their optical physics, electrochemical properties and thermal stability study and have been applied to field effect transistor method.
Multiring aromatic hydrocarbon organic semiconducting materials based on thiadiazoles of the invention are with stability is good, dissolubility is good, moves
The advantages that shifting rate is high, synthesis technology is simple, low in cost is a kind of to be widely used the excellent organic semiconducting materials of performance.
Detailed description of the invention
In Fig. 1 embodiment 1, the MADLI-TOF of D6-C12BBT schemes.
In Fig. 2 embodiment 2, thermogravimetric analysis (DTG) curve of D6-C8BBT.
In Fig. 3 embodiment 2, the differential scanning amount of D6-C8BBT controls (DSC) curve.
The FET device curve of output of Fig. 4 .D6-C8BBT.
The FET device transfer curve of Fig. 5 .D6-C8BBT
Specific embodiment
It the following examples are further illustrations of the invention, is not limitation of the present invention.
Embodiment 1:
100mL reaction tube is taken, is added 5,6- dibromo diazosulfide (2.94g, 10mmol), 2- dodecylthiophene
(2.77g, 11mmol), potassium carbonate (1.66g, 12mmol), trimethylace tonitric (306mg, 3mmol), 5% catalyst acetic acid
Palladium vacuumizes bulging nitrogen, injects the anhydrous n,N-dimethylacetamide of 30mL with syringe, makes within stirring at normal temperature 1 minute it sufficiently molten
It solves, is reacted 4 hours under the conditions of 110 DEG C.It is extracted with ethyl acetate after reaction, saturated common salt water stratification of adding some points becomes apparent from.With
Anhydrous sodium sulfate is dry, obtains crude product, column chromatography, petroleum ether/methylene chloride (8:1) after solvent is removed under reduced pressure.Obtain product
1a (2.79g, 60%), pale yellow oily liquid.1H NMR(400MHz,CDCl3)δ(ppm):8.40(s,1H),8.08(s,
1H), 7.19 (d, J=3.6Hz, 1H), 6.82 (d, J=3.6Hz, 1H), 2.87 (t, J=7.6Hz, 2H), 1.74 (dt, J=
15.3,7.6Hz, 2H), 1.26 (s, 18H), 0.88 (t, J=6.8Hz, 3H)13C NMR(100MHz,CDCl3)δ(ppm):
154.14,153.69,148.41,137.44,137.01,128.91,126.36,125.20,124.32,122.31,31.93,
31.63,30.18,29.69,29.66,29.57,29.37,29.20,22.71,14.14.
50mL reaction tube is taken, is added 1a (465mg, 1mmol), 10mL is extracted with syringe and newly steams tetrahydrofuran and 10mL bis-
Isopropylamine be added reaction tube, stirring at normal temperature, and use long syringe needle air-blowing five minutes, after five minutes snare drum gas side be successively spaced 1 minute add
Enter triphenylphosphine (26.2mg, 0.1mmol), cuprous iodide (19mg, 0.1mmol), catalyst bis-triphenylphosphipalladium palladium dichloride
(35mg, 0.05mmol), gets up to guarantee the inside nitrogen environment bottle seal after adding, and extracts trimethylsilyl acetylene with syringe
(196mg, 2mmol) squeezes into reaction tube, reacts overnight under the conditions of 55 DEG C.It is extracted with ethyl acetate after reaction, with anhydrous sulphur
Sour sodium is dry, obtains crude product, column chromatography, petroleum ether/methylene chloride (4:1) after solvent is removed under reduced pressure.Obtain product 2a
(433mg, 90%), yellow liquid.1H NMR(400MHz,CDCl3)δ(ppm):8.22(s,1H),8.05(s,1H),7.55(d,
J=3.6Hz, 1H), 6.80 (d, J=3.6Hz, 1H), 2.86 (t, J=7.6Hz, 2H), 1.73 (dt, J=15.1,7.5Hz,
2H), 1.23 (s, 18H), 0.88 (t, J=Hz, 3H), 0.27 (s, 9H)；13C NMR(100MHz,CDCl3)δ(ppm):
154.50,153.19,148.19,137.41,137.07,128.41,126.70,124.56,123.91,119.71,103.62,
102.83,31.93,31.69,30.25,29.68,29.66,29.65,29.57,29.39,29.36,29.17,22.70,
14.12,1.03.
100mL single port bottle is taken, 2a (960mg, 2mmol) and potassium hydroxide (1g, 18mmol) is added, beyond the Great Wall rubber stopper, is taken out
Vacuum plugs nitrogen ball, squeezes into 20mL tetrahydrofuran and 20mL methanol with syringe, and stirring at normal temperature 5 hours.It uses after reaction
Ethyl acetate extraction, it is dry with anhydrous sodium sulfate, crude product, column chromatography, petroleum ether/methylene chloride are obtained after solvent is removed under reduced pressure
(4:1).Obtain product 3a (780mg, 95%), yellow solid.1H NMR(400MHz,CDCl3)δ(ppm):8.28(s,1H),
8.06 (s, 1H), 7.54 (d, J=3.6Hz, 1H), 6.82 (d, J=3.6Hz, 1H), 3.44 (s, 1H), 2.86 (t, J=
7.6Hz, 2H), 1.73 (dt, J=15.2,7.5Hz, 2H), 1.26 (s, 18H), 0.88 (t, J=6.8Hz, 3H)13CNMR
(100MHz,CDCl3)δ(ppm):154.64,153.08,148.27,137.22,136.99,128.43,127.57,124.86,
123.01,120.13,84.52,82.34,31.94,31.62,30.23,29.69,29.67,29.58,29.39,29.37,
29.20,22.71,14.14.
Take 50mL reaction tube, be added product 1a (465mg, 1mmol), with syringe extract 10mL newly steam tetrahydrofuran and
Reaction tube, stirring at normal temperature is added in 10mL triethylamine, and is roused nitrogen five minutes with long syringe needle, and snare drum gas side is successively spaced 1 after five minutes
Triphenylphosphine (26.2mg, 0.1mmol) is added in minute, cuprous iodide (19mg, 0.1mmol), catalyst bi triphenyl phosphine dichloride
Change palladium (35mg, 0.05mmol), 3a (450mg, 1.1mmol) plugs 70 DEG C of conditions of nitrogen ball bottle seal after adding
Lower reaction is overnight.It is extracted with dichloromethane after reaction, it is dry with anhydrous sodium sulfate, it is slightly produced after solvent is removed under reduced pressure
Object, column chromatography, petroleum ether/methylene chloride (1:1).Target product 4a (475mg, 60%) is obtained, is yellow solid.1H NMR
(400MHz,CDCl3) δ (ppm): 8.24 (d, J=0.6Hz, 2H), 8.11 (d, J=0.5Hz, 2H), 7.48 (d, J=3.6Hz,
2H), 6.86 (d, J=3.6Hz, 2H), 2.89 (t, J=7.6Hz, 4H), 1.76 (dt, J=15.3,7.6Hz, 4H), 1.42
(dd, J=15.4,7.1Hz, 4H), 1.25 (s, 32H), 0.87 (t, J=4.8Hz, 6H)；13C NMR(100MHz,CDCl3)δ
(ppm):154.70,153.26,148.65,137.39,136.98,128.29,126.23,124.91,123.78,120.08,
95.23,31.93,31.75,30.33,29.69,29.67,29.58,29.39,29.37,29.27,22.70,14.13.
50mL reaction tube is taken, is added 4a (398mg, 0.5mmol), 10mL is extracted with syringe and is newly steamed toluene and be added and reacted
Pipe, stirring at normal temperature, and with long syringe needle drum nitrogen five minutes, after five minutes snare drum gas side addition catalyst platinous chloride (13mg,
0.05mmol), continue to rouse nitrogen after adding, bottle seal is got up after 2 minutes, plugs nitrogen ball, under the conditions of 90 DEG C, 24 is small
When.It is extracted with dichloromethane after reaction, it is dry with anhydrous sodium sulfate, crude product is obtained after solvent is removed under reduced pressure, column chromatographs,
Petroleum ether/methylene chloride (1:1).Product 5a (235mg, 60%) is obtained, is orange solids.1H NMR(400MHz,CDCl3)δ
(ppm):8.72(s,1H),8.63(s,1H),8.24(s,1H),8.15(s,1H),7.78(s,1H),6.62(s,1H),6.61
(d, J=3.6Hz, 1H), 6.36 (d, J=3.6Hz, 1H), 2.78 (t, J=7.6Hz, 2H), 2.58 (t, J=7.5Hz, 2H),
1.67-1.59 (m, 2H), 1.48-1.41 (m, 2H), 1.30-1.17 (m, 36H), 0.87 (td, J=6.8,2.2Hz, 6H)
.13CNMR(100MHz,CDCl3)δ(ppm):154.75,153.88,153.02,152.44,147.92,147.30,141.34,
138.24,137.55,136.79,136.39,134.95,132.89,130.41,127.87,126.57,124.53,122.74,
122.29,120.68,119.96,112.70,31.93,31.48,31.43,30.60,29.91,29.66,29.54,29.37,
29.28,29.01,28.82,22.70,14.13.
100mL two-mouth bottle is taken, is added 5a (80mg, 0.1mmol), is added 40mL methylene chloride and be completely dissolved, is claimed
Ferric trichloride (81mg, 0.5mmol) is taken to be dissolved in the nitromethane of 0.8mL, to two-mouth bottle drum nitrogen, snare drum nitrogen side is slow
Liquor ferri trichloridi is added dropwise, TLC point board monitoring after raw material has reacted, adds 25mL methanol quenching reaction.Reaction solution methylene chloride
Extraction, it is dry with anhydrous sodium sulfate, crude product, column chromatography are obtained after solvent is removed under reduced pressure, petroleum ether/methylene chloride (2:1) obtains
To 24mg product D6-C12TBT, yield 30% is red solid.1H NMR(400MHz,CDCl3)δ(ppm):9.26(s,2H),
7.82 (s, 2H), 7.26 (s, 2H), 3.02 (t, J=7.5Hz, 4H), 1.90-1.70 (m, 4H), 1.25 (s, 36H), 0.85 (t,
J=6.9Hz, 6H)
Embodiment 2:
100mL reaction tube is taken, is added 5,6- dibromo diazosulfide (1.47g, 5mmol), 3,4- bis- octyloxy phenyl boric acids
Ester (2.53g, 5.5mmol), cesium carbonate (2.44g, 7.5mmol) add new steaming toluene 20mL, water 2mL, and stirring at normal temperature 5 is divided
Clock rouses nitrogen while stirring, is eventually adding catalyst tetra-triphenylphosphine palladium (60mg, 0.05mmol), and last capping pipe is inserted
Upper nitrogen ball reacts 12 hours under the conditions of 90 DEG C.It is extracted with ethyl acetate after reaction, saturated common salt water stratification of adding some points is brighter
It is aobvious.It is dry with anhydrous sodium sulfate, crude product, column chromatography, petroleum ether/methylene chloride (4:1) are obtained after solvent is removed under reduced pressure.It obtains
Product 1b (2.19g, 80%), pale yellow waxy solid.1H NMR(400MHz,CDCl3)δ(ppm):8.40(s,1H),7.95
(s, 1H), 6.97 (dd, J=6.8,5.0Hz, 3H), 4.07 (t, J=5.3Hz, 2H), 4.04 (t, J=5.4Hz, 2H), 1.91-
1.80(m,4H),1.52–1.27(m,20H),0.91–0.86(m,6H).13C NMR(100MHz,CDCl3)δ(ppm):
154.21,153.89,149.48,148.38,143.83,132.47,126.98,124.74,122.15,121.65,115.57,
112.89,69.46,69.19,31.85,31.83,29.41,29.40,29.31,29.29,26.09,26.04,22.69,
22.68,14.12,14.11.
Or take 50mL reaction tube, be added product 1b (547mg, 1mmol), with syringe extract 10mL newly steam tetrahydrofuran and
10mL diisopropylamine is added reaction tube, stirring at normal temperature, and with long syringe needle air-blowing five minutes, snare drum gas side was successively spaced 1 after five minutes
Triphenylphosphine (26.2mg, 0.1mmol) is added in minute, cuprous iodide (19mg, 0.1mmol), catalyst bi triphenyl phosphine dichloride
Change palladium (35mg, 0.05mmol), bottle seal is got up to guarantee the inside nitrogen environment after adding, extracts trimethyl silicane with syringe
Acetylene (196mg, 2mmol) squeezes into reaction tube, reacts overnight under the conditions of 55 DEG C.It is extracted with ethyl acetate after reaction, with nothing
Aqueous sodium persulfate is dry, obtains crude product, column chromatography, the analysis separation of petroleum ether/methylene chloride (4:1) layer column after solvent is removed under reduced pressure.
Obtain product 2b (507mg, 90%), yellow liquid.1H NMR(400MHz,CDCl3)δ(ppm):8.23(s,1H),7.92(s,
1H), 7.17 (dq, J=4.0,2.1Hz, 2H), 6.94 (d, J=8.8Hz, 1H), 4.05 (dd, J=15.6,6.7Hz, 4H),
1.85 (dt, J=15.3,4.7Hz, 4H), 1.50-1.26 (m, 20H), 0.88 (q, J=6.8Hz, 6H), 0.16 (s, 9H)13C
NMR(100MHz,CDCl3)δ(ppm):154.59,153.35,149.31,148.57,144.60,131.80,125.95,
124.88,122.21,120.50,115.31,113.23,103.75,101.98,69.38,69.30,31.87,31.85,
29.43,29.40,29.32,26.12,26.08,22.70,14.14,-0.33.
100mL single port bottle is taken, compound 2b (1.13g, 2mmol) and potassium hydroxide (1g, 18mmol) is added, beyond the Great Wall rubber
Plug, vacuumizes, plugs nitrogen ball, squeezes into 20mL tetrahydrofuran and 20mL methanol with syringe, and stirring at normal temperature 5 hours.Reaction knot
It is extracted with ethyl acetate after beam, it is dry with anhydrous sodium sulfate, crude product, column chromatography, petroleum ether/bis- are obtained after solvent is removed under reduced pressure
Chloromethanes (4:1).Obtain product 3b (885mg, 90%), yellow solid.1H NMR(400MHz,CDCl3)δ(ppm):8.29(s,
1H), 7.94 (s, 1H), 7.20 (d, J=2.1Hz, 1H), 7.15 (dd, J=8.3,2.1Hz, 1H), 6.96 (d, J=8.3Hz,
1H), 4.06 (td, J=6.6,4.6Hz, 4H), 3.28 (s, 1H), 1.92-1.80 (m, 4H), 1.52-1.27 (m, 20H), 0.89
(q, J=6.8Hz, 6H)13C NMR(100MHz,CDCl3)δ(ppm):154.73,153.26,149.51,148.40,
144.49,131.44,126.87,123.91,122.05,120.76,115.38,112.99,83.87,82.42,69.37,
69.16,31.85,29.42,29.32,26.10,26.08,22.70,14.13.
Take 50mL reaction tube, be added product 1b (547mg, 1mmol), with syringe extract 10mL newly steam tetrahydrofuran and
Reaction tube, stirring at normal temperature is added in 10mL triethylamine, and is roused nitrogen five minutes with long syringe needle, and snare drum gas side is successively spaced 1 after five minutes
Triphenylphosphine (26.2mg, 0.1mmol) is added in minute, cuprous iodide (19mg, 0.1mmol), catalyst bi triphenyl phosphine dichloride
Change palladium (35mg, 0.05mmol), compound 3b (541mg, 1.1mmol) plugs nitrogen ball 70 bottle seal after adding
It is reacted overnight under the conditions of DEG C.It is extracted with dichloromethane after reaction, it is dry with anhydrous sodium sulfate, it is obtained after solvent is removed under reduced pressure
Crude product, column chromatography, petroleum ether/methylene chloride (1:1).Product 4b (574mg, 60%) is obtained, is yellow solid.1H NMR
(400MHz,CDCl3) δ (ppm): 8.04 (s, 2H), 7.96 (s, 2H), 7.19 (d, J=2.1Hz, 2H), 7.17 (dd, J=
8.2,2.1Hz, 2H), 6.97 (d, J=8.2Hz, 2H), 4.10 (t, J=6.6Hz, 4H), 4.00 (t, J=6.7Hz, 4H),
1.93-1.85 (m, 4H), 1.82-1.74 (m, 4H), 1.47-1.14 (m, 40H), 0.86 (dd, J=14.3,7.2Hz, 12H)
.13C NMR(100MHz,CDCl3)δ(ppm):154.77,153.36,149.65,148.73,144.18,131.53,125.72,
124.55,122.22,120.67,115.35,113.17,94.97,69.54,69.38,31.87,31.78,29.46,29.38,
29.34,29.25,26.12,26.04,22.70,22.66,14.12,14.10.
50mL reaction tube is taken, is added 4b (479mg, 0.5mmol), 10mL is extracted with syringe and is newly steamed toluene and be added and reacted
Pipe, stirring at normal temperature, and with long syringe needle drum nitrogen five minutes, after five minutes snare drum gas side addition catalyst platinous chloride (13mg,
0.05mmol), continue to rouse nitrogen after adding, bottle seal is got up after 2 minutes, plugs nitrogen ball, under the conditions of 90 DEG C, 24 is small
When.It is extracted with dichloromethane after reaction, it is dry with anhydrous sodium sulfate, crude product is obtained after solvent is removed under reduced pressure, column chromatographs,
Petroleum ether/methylene chloride (1:1).Product 5b (239mg, 50%) is obtained, is orange solids.1H NMR(400MHz,CDCl3)δ
(ppm):9.08(s,1H),8.41(s,1H),8.18(s,1H),8.15(s,1H),8.02(s,1H),7.62(s,1H),6.95
(dd, J=8.3,2.1Hz, 1H), 6.78 (s, 1H), 6.72 (d, J=2.0Hz, 1H), 6.63 (d, J=8.4Hz, 1H), 4.21
(t, J=6.6Hz, 2H), 3.79 (q, J=6.9Hz, 4H), 3.20 (dd, J=16.0,7.0Hz, 1H), 3.06-2.93 (m,
1H), 1.98-1.87 (m, 2H), 1.76-1.48 (m, 8H), 1.28 (d, J=27.0Hz, 32H), 1.13-0.92 (m, 6H),
0.92–0.79(m,12H).13C NMR(100MHz,CDCl3)δ(ppm):154.95,154.00,153.37,152.55,
149.94,149.48,148.62,147.97,143.90,142.13,139.43,133.26,132.19,126.94,126.01,
124.11,122.90,121.45,121.11,118.56,114.33,112.91,110.40,106.84,69.24,69.04,
68.90,68.65,31.86,31.80,31.76,29.71,29.46,29.35,29.33,29.27,29.21,29.13,
29.07,28.76,26.12,26.05,25.91,25.50,22.71,22.68,22.64,14.13,14.08.
100mL two-mouth bottle is taken, is added 5b (96mg, 0.1mmol), is added 40mL methylene chloride and be completely dissolved, is claimed
Ferric trichloride (50mg, 0.3mmol) is taken to be dissolved in the nitromethane of 0.5mL, to two-mouth bottle drum nitrogen, snare drum nitrogen side is slow
Liquor ferri trichloridi is added dropwise, continues stirring 10 minutes after dripping, TLC point board monitoring after raw material has reacted, adds 25mL methanol to quench
It goes out reaction.Reaction solution is extracted with dichloromethane, dry with anhydrous sodium sulfate, obtains crude product after solvent is removed under reduced pressure, and column chromatographs,
Petroleum ether/methylene chloride (2:1), obtains 76mg product D6-C8BBT, and yield 80% is red solid.1H NMR(400MHz,
CDCl3) δ (ppm): 9.04 (s, 2H), 8.88 (s, 2H), 7.81 (s, 2H), 7.78 (s, 2H), 4.28 (t, J=6.5Hz, 4H),
4.05 (t, J=6.6Hz, 4H), 2.07-1.95 (m, 4H), 1.93-1.79 (m, 4H), 1.53-1.44 (m, 8H), 1.43-1.20
(m, 32H), 0.92 (t, J=6.8Hz, 6H), 0.87 (t, J=6.9Hz, 6H)13C NMR(100MHz,CDCl3)δ(ppm):
152.78,152.20,149.17,148.36,132.86,130.29,127.43,123.64,123.51,118.52,113.58,
111.23,107.41,69.16,68.89,31.95,31.85,29.70,29.60,29.46,29.44,29.35,29.25,
26.33,26.16,22.77,22.70,14.17,14.12.
Carry out characterization test and photoelectric device application to D6-C8BBT: as shown in Figure 1, the molecular weight of D6-C8BBT can be by base
The confirmation of matter auxiliary spark excitation flight time mass spectrum.As shown in Fig. 2, thermogravimetric analysis shows that D6-C8BBT has in a nitrogen atmosphere is more than
380 degree of thermal decomposition temperature reflects the good thermal stability of D6-C8BBT.As shown in figure 3, scanning differential thermal analysis shows D6-
C8BBT has good phase transformation crystallinity.It is revolved using D6-C8BBT as active layer through 9 mg/ml chloroformic solution 1500rpm/min
The FET device for applying preparation is shown more than 0.17cm2/(Vs)-1Mobility, curve of output and transfer curve
It is as shown in Figure 4 and Figure 5 respectively.
Claims (8)
1. a kind of polycyclic aromatic hydrocarbon organic semiconducting materials based on thiadiazoles, it is characterised in that the material is following formula (I) general formula
Compound:
Wherein, R is one of C1-C24 straight chained alkyl, branched alkyl.
2. polycyclic aromatic hydrocarbon organic semiconducting materials preparation method of the one kind based on thiadiazoles described in claim 1, feature exist
In, including following synthesis step:
A. first with 5,6- dibromo diazosulfide shown in formula (1) for initial feed, then with Ar or with Ar group
Boric acid, boron ester, tin reagent react to obtain formula (2) compound represented under the action of palladium catalyst；
B. formula (2) compound represented is dissolved in suitable organic solvent, by Sonogashira coupling reaction, in palladium chtalyst
Agent, cuprous iodide, triphenylphosphine, diisopropylamine, existing for trimethylsilyl acetylene under the conditions of in formula (2) compound represented
Bromine becomes trimethylsilyl acetylene base, obtains formula (3) compound represented；
C. formula (3) compound represented is dissolved in suitable organic solvent, under the conditions of existing for the methanol and alkali, stirring at normal temperature 5
Hour, obtain compound represented by formula (4)；
D. the ratio of formula (2) compound represented and formula (4) compound represented 1:1 in molar ratio are dissolved in suitable organic molten
Agent, it is anti-under the conditions of existing for palladium catalyst, cuprous iodide, triphenylphosphine, the triethylamine by Sonogashira coupling reaction
It answers 12 hours, obtains the compound of the coupling of alkynes shown in (5)；
E. the compound that alkynes shown in formula (5) is coupled is dissolved in suitable organic solvent, made in platinous chloride or gold dichloride
Under conditions of catalyst, 80~120 DEG C of reactions become unilateral hexatomic ring to get to the acetylene bond as represented by formula (6) in 24 hours
Compound；
F. the compound as represented by formula (6) is dissolved in suitable organic solvent, is added dropwise into mixed liquor dissolved with three under room temperature
The nitromethane of iron chloride is monitored by TLC plate until consumption of raw materials is led to represented by formula (I) to get to target completely
Compound.
3. the preparation side of a kind of conjugation heterocycle organic semiconducting materials based on diazosulfide according to claim 2
Method, it is characterised in that palladium catalyst described in step a is tetrakis triphenylphosphine palladium, palladium acetate, dichloro two (triphenylphosphine) palladium；It is described
Organic solvent be tetrahydrofuran, toluene, n,N-Dimethylformamide, any or mixture in n,N-dimethylacetamide.
4. the preparation side of a kind of conjugation heterocycle organic semiconducting materials based on diazosulfide according to claim 2
Method, it is characterised in that organic solvent described in step b be it is new steam anhydrous tetrahydro furan, any or mixture in toluene.
5. the preparation side of a kind of conjugation heterocycle organic semiconducting materials based on diazosulfide according to claim 2
Method, it is characterised in that organic solvent described in step c is common tetrahydrofuran, toluene, and the alkali is potassium hydroxide, hydroxide
Any or mixture in sodium, potassium carbonate.
6. the preparation side of a kind of conjugation heterocycle organic semiconducting materials based on diazosulfide according to claim 2
Method, it is characterised in that organic solvent described in step d be it is new steam anhydrous tetrahydro furan, any or mixture in toluene.
7. the preparation side of a kind of conjugation heterocycle organic semiconducting materials based on diazosulfide according to claim 2
Method, it is characterised in that organic solvent described in step e is new steaming dry toluene.
8. the preparation side of a kind of conjugation heterocycle organic semiconducting materials based on diazosulfide according to claim 2
Method, it is characterised in that organic solvent described in step f is anhydrous methylene chloride, any or mixture in chloroform.
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