CN107573489A - A kind of polymer semiconductor containing double pyridine oxadiazole derivative acceptors and preparation method and application - Google Patents

A kind of polymer semiconductor containing double pyridine oxadiazole derivative acceptors and preparation method and application Download PDF

Info

Publication number
CN107573489A
CN107573489A CN201710654172.4A CN201710654172A CN107573489A CN 107573489 A CN107573489 A CN 107573489A CN 201710654172 A CN201710654172 A CN 201710654172A CN 107573489 A CN107573489 A CN 107573489A
Authority
CN
China
Prior art keywords
polymer
compound
acceptors
oxadiazole derivative
containing double
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710654172.4A
Other languages
Chinese (zh)
Other versions
CN107573489B (en
Inventor
陈华杰
朱春光
郑丽萍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiangtan University
Original Assignee
Xiangtan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiangtan University filed Critical Xiangtan University
Priority to CN201710654172.4A priority Critical patent/CN107573489B/en
Publication of CN107573489A publication Critical patent/CN107573489A/en
Application granted granted Critical
Publication of CN107573489B publication Critical patent/CN107573489B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention belongs to polymer semiconducting material field, discloses a kind of polymer semiconductor containing double pyridine oxadiazole derivative acceptors and preparation method and application.Shown in the structure of the polymer semiconductor such as formula (I).Preparation method includes：The alkylthrophene of (1) 2 tributyl tinbase 4 prepares intermediate a with dibromo benzothia (oxa) diazol derivatives reaction；(2) compound a and double butyl tin b react to obtain compound c；(3) compound c and N bromo-succinimides are reacted to obtain M1；(4) M1 and (E)-bis- 1,2-(tri-n-butyl tin base) ethene carry out palladium catalysed cross coupling reaction, obtain final product.The synthetic route of the present invention is simple efficiently, raw material is easy to get, cost is cheap, universality is high and reproducible, obtains prominent bipolar transmission characteristic by field-effect transistor prepared by active layer of the polymer semiconductor of the present invention, has wide market prospects.

Description

A kind of polymer semiconductor containing double pyridine oxadiazole derivative acceptors and preparation method thereof With application
Technical field
The invention belongs to polymer semiconducting material field, is related to a kind of polymer containing double pyridine oxadiazole derivative acceptors Semiconductor and preparation method and application.
Background technology
Bipolar Polymer semi-conducting material can simplify the preparation technology of bipolarity logical complement circuit, reduction is configured to This, but such material the is faced with challenge such as mobility is low, carrier transport is uneven and construction unit is rare.At present, Gao Qian Shifting rate Bipolar Polymer semi-conducting material is mainly formed by pyrrolo-pyrrole-dione and isoindigo derivative cell formation, and only The hole and electron mobility for having a small number of polymer semiconducting materials can be simultaneously more than 4.0cm2/V s (J.Am.Chem.Soc.,2013,135,9540；Chem.Mater.,2014,26,6963；Adv.Mater.,2015,27, 4963).Therefore, new layout strategy is explored, seeks new construction unit and is still one of the effective ways for solving these problems.
Pyridine oxadiazole derivative is a kind of rich hetero atom, the electron acceptor unit that electron affinity is strong, coplanarity is good, quilt Be widely used in exploitation p-type organic molecule and polymer semiconducting material (J.Am.Chem.Soc., 2013,135,2298； J.Am.Chem.Soc.,2012,134,20609).The compound semiconductor material however, electron-transporting type pyridine oxadiazole derivative is birdsed of the same feather flock together Material has no report.Therefore, new electron-transporting type pyridine oxadiazole derivative is developed to birds of the same feather flock together compound semi-conducting material and research Its TFT device performance has great importance.
The content of the invention
It is an object of the invention to provide a kind of polymer semiconducting material and its system containing double pyridine oxadiazole derivative acceptors Preparation Method and application.Present invention solves the technical problem that be to provide a kind of compound, polymer and polymer semiconducting material, The polymer semiconducting material mobility is higher；Present invention also offers a kind of polymerization object field for having the polymer semiconductor Effect transistor.
A kind of polymer semiconductor containing double pyridine oxadiazole derivative acceptors, for general formula of molecular structure shown in formula (I) Polymer：
In the formula (I), the R is the straight chained alkyl that the total number of carbon atoms is 6-16 or the side chain that the total number of carbon atoms is 8-30 Any one in alkyl；
Ar is following three kinds of situations：It is not present, carbon-carbon double bond or triple carbon-carbon bonds；
X is oxygen atom, sulphur atom, selenium atom or tellurium atom；
N is 10-300 integer.
In the formula (I), n is 10-300 integer, preferably 50-150 integer, more preferably 100.
The straight chained alkyl that described the total number of carbon atoms is 6-16 concretely n-hexyl, n-heptyl, n-octyl, n-nonyl, just Decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base or n-hexadecyl, but not It is limited to this；Wherein, the branched alkyl concretely 2- ethylhexyls that described the total number of carbon atoms is 8-30,2- butyl hexyl, 2- oneself Base octyl group, 4- hexyls decyl, 3- hexyls undecyl, 2- octyl-decyls, 2- octyldodecyls, 3- octyl groups tridecyl, 2- Decyl dodecyl, 2- decyls myristyl, 3- decyls pentadecyl, 2- dodecyls cetyl, 4- octyl groups myristyl, 4- decyls cetyl, 4- hexyls decyl, 4- octyldodecyls, 4- decyls myristyl or 4- dodecyl cetyls, But not limited to this；
It is furthermore preferred that polymer semiconductor shown in the formula (I) is specifically as follows polymer P BPTV or PBPT2V：
In the PBPTV and PBPT2V, n definition is identical with the definition in formula (I).N concretely 10-300 integer, It more specifically can be 50-150 integer, most specifically can be 100.
The inventive concept total as one, the present invention also provide a kind of above-mentioned poly- containing double pyridine oxadiazole derivative acceptors The preparation method of compound semiconductor, this method comprise the following steps：
(1) 2- tributyls tinbase -4- alkylthrophenes react with dibromo benzothia (oxa) diazol derivatives, obtain intermediate a, the 2- The structural formula of tributyl tinbase -4- alkylthrophenes is：
Wherein, in the branched alkyl that the R is the straight chained alkyl of the total number of carbon atoms 6-16 or the total number of carbon atoms is 8-30 Any one；
The dibromo benzothia (oxa) diazol derivatives structural formula is：
Wherein, the X is oxygen atom, sulphur atom, selenium atom or tellurium atom；
The structural formula of the intermediate a is：
Wherein, in the branched alkyl that the R is the straight chained alkyl of the total number of carbon atoms 6-16 or the total number of carbon atoms is 8-30 Any one；
(2) under nitrogen protection, midbody compound a and compound b is subjected to palladium catalysed cross coupling reaction, obtains compound c；The structural formula of the compound b is：
Wherein, the Ar is carbon-carbon single bond, double or triple bonds；
The structural formula of the midbody compound c is：
Wherein, in the branched alkyl that the R is the straight chained alkyl of the total number of carbon atoms 6-16 or the total number of carbon atoms is 8-30 Any one；The Ar is carbon-carbon single bond, double or triple bonds；The X is oxygen atom, sulphur atom, selenium atom or tellurium atom；
(3) under nitrogen protection, midbody compound c and N- bromo-succinimide are subjected to electrophilic reaction, obtain list Body Formula M1, its structural formula are：
Wherein, in the branched alkyl that the R is the straight chained alkyl of the total number of carbon atoms 6-16 or the total number of carbon atoms is 8-30 Any one；The Ar is carbon-carbon single bond, double or triple bonds；The X is oxygen atom, sulphur atom, selenium atom or tellurium atom；
(4) under inert gas shielding, by shown in monomer shown in formula M1 and (E)-bis- 1,2-(tri-n-butyl tin base) ethene Monomer is placed in progress palladium chtalyst coupling polymerization reaction in solvent, and reaction is finished to obtain polymer shown in the formula (I), that is, contained The polymer semiconductor of double pyridine oxadiazole derivative acceptors.
Preferably, the preparation method of the above-mentioned polymer semiconducting material containing double pyridine oxadiazole derivative acceptors, described in it The concrete operations of step (1) are：Under nitrogen protection, 2- tributyl tinbase -4- alkylthrophenes, dibromo benzo are added into there-necked flask Oxadiazole derivative (commercially available), double (triphenyl phosphorus) palladium chloride catalyst and toluene solvant, return stirring reaction 1-10 are small Shi Hou, room temperature is cooled to, is extracted using dichloromethane, organic phase is dried with magnesium sulfate, is spin-dried for solvent and is obtained crude product, using silica gel Chromatographic column purifies to obtain oily liquids a；The wherein reaction raw materials mol ratio that feeds intake is dibromo benzothia (oxa) diazol derivatives：2- tributyls Tinbase -4- alkylthrophenes：Double (triphenyl phosphorus) palladium chloride=1：1–2：0.01-0.1, it is preferably in a proportion of 1：1.2：0.05.
Preferably, the preparation method of the above-mentioned polymer semiconducting material containing double pyridine oxadiazole derivative acceptors, described in it The concrete operations of step (2) are：Under nitrogen protection, midbody compound a, compound b, four (triphenyls are added into there-necked flask Phosphine) palladium catalyst and toluene solvant, after return stirring reacts 10-72 hours, room temperature is cooled to, is extracted using dichloromethane, is had Machine is mutually dried with anhydrous magnesium sulfate, is spin-dried for solvent and is obtained crude product, and red oil c is purified to obtain using silica gel chromatographic column；Wherein The reaction raw materials mol ratio that feeds intake is compound b：Midbody compound a：Tetrakis triphenylphosphine palladium=1：2.0–6.0：0.01– 0.1.Wherein, preferred reaction time is 24 hours, and preferably ingredient proportion is 1：3：0.05.
Preferably, the preparation method of the above-mentioned polymer semiconducting material containing double pyridine oxadiazole derivative acceptors, described in it The concrete operations of step (3) are：Under nitrogen protection, chloroform and compound c are added into there-necked flask, is placed on ice bath In, N- bromo-succinimides are slowly added into reaction bulb in batches, after reaction being stirred at room temperature 5-24 hours, using dichloro Methane is extracted, and organic phase is dried with anhydrous magnesium sulfate, is spin-dried for solvent and obtains crude product, and target product is purified to obtain using silica gel chromatographic column M1；The wherein reaction raw materials mol ratio that feeds intake is compound c：N- bromo-succinimide=1：2.0–3.0.Wherein, preferably instead It is 8 hours between seasonable, preferably ingredient proportion is 1：2.5.
Preferably, the preparation method of the above-mentioned polymer semiconducting material containing double pyridine oxadiazole derivative acceptors, described in it The concrete operations of step (4) are：Nitrogen protection under, into there-necked flask add M1, (E)-bis- 1,2-(tri-n-butyl tin base) ethene, Solvent and palladium catalyst, after 100-150 DEG C of return stirrings react 10-72 hours, room temperature is cooled to, reaction solution is fallen into methanol In, filter, collect blue brown solid, then subject polymer is purified using cable type extractor according, it is spin-dried for solvent and obtains the black of gold lustre Color solid；The wherein reaction raw materials mol ratio that feeds intake is compound M1：(E)-bis- 1,2-(tri-n-butyl tin base) ethene：Palladium is urged Agent=1：1.0–1.5：0.01–0.1.Wherein, preferable reaction temperature is 120 DEG C；Preferred reaction time is 48 hours；It is preferred that throw Material is than being 1：1：0.05.The palladium catalyst is selected from tetrakis triphenylphosphine palladium, palladium, two (triphenylphosphine) palladium chlorides and three At least one of (dibenzalacetone) two palladium, preferably two (triphenyl phosphorus) palladium chlorides；The solvent is selected from toluene, diformazan At least one of benzene, methyl naphthalene, chlorobenzene, dichloro-benzenes, dichloronaphtalene, trichloro-benzenes, chloronaphthalene and tetrahydrofuran, preferably chlorobenzene.
The inventive concept total as one, the present invention also provide shown in a kind of above-mentioned formula (I) any one and contain double pyridines Application of the polymer semiconducting material of oxadiazole derivative acceptor in film F ET devices are prepared.In addition, with the formula (I) Suo Shi Polymer containing double pyridine oxadiazole derivative acceptors falls within the guarantor of the present invention for the film F ET devices of organic semiconductor active layer Protect scope.
The present invention devises the serial polymer containing double pyridine oxadiazole derivative acceptors using isotactic amboceptor strategy and partly led Body material, it is intended to obtain electron transport property.Its main design thought is as follows：1) single electron acceptor, double electron acceptor are compared The short of electricity density of polymer repeat unit can be strengthened, improve the electron affinity of strand；2) using chemical method control pyridine The relative position of nitrogen, the polymer molecule skeleton of regio-regular can be built, can so improve the assembling energy of polymer molecule interchain Power and carrier mobility；3) the rich heteroatomic big pi-conjugated skeleton of structure, can strengthen the π-π interactions of molecule interchain, improve Carrier mobility.Research shows：In atmosphere, with double pyridine oxadiazole derivative acceptor based polyalcohol semiconductor materials of the present invention Expect that the top-gated FET device for organic semiconductor active layer shows the bipolarity charge transmission of superelevation, its highest hole and Electron mobility is respectively 6.87cm2/ V s and 8.49cm2/ V s, such polymer semiconducting material is fully illustrated bipolar Property the organic electronic device such as reverser, logic circuit and bipolarity field-effect light emitting diode in there is wide market before Scape.
The advantage of the invention is that：
1st, synthetic method of the invention has that universality is strong, synthetic route is brief efficiently, development cost is cheap, synthetic yield The advantages that high, reaction raw materials are easy to get, other can also be promoted the use of with the amplification synthesis and production in popularization and application industry The synthesis of all kinds of polymer semiconductors containing double pyridine oxadiazole derivative acceptors.
2nd, such polymer molecule backbone of the invention has rich heteroatomic big pi-conjugated skeleton, can strengthen molecule interchain π-π interaction, improve carrier mobility.
3rd, polymer semiconducting material of the invention contains the double electron acceptor unit of strong electron-withdrawing power, can strengthen polymerization The short of electricity density of thing repeat unit, the electron affinity of strand is improved, obtains high electron mobility.
4th, the present invention is precisely controlled the relative position of pyridine nitrogen using chemical method, can build the polymer point of regio-regular Sub- skeleton, it can so improve the assembling ability and carrier mobility of polymer molecule interchain.
5th, double pyridine oxadiazole derivative acceptors birds of the same feather flock together compound semiconductor in film F ET devices, showing shown in the present invention Go out excellent bipolarity charge transmission, its highest hole and electron mobility are respectively 6.87cm2/ V s and 8.49cm2/V s.Meanwhile such FET device shows excellent stability under damp atmosphere environment, such polymer is fully shown Semi-conducting material has in the organic electronic devices such as bipolarity reverser, logic circuit and bipolarity field-effect light emitting diode There are wide market prospects.
Brief description of the drawings
Fig. 1 is that the polymer P BPTV containing double pyridine oxadiazole derivative acceptors obtained by prepared by the embodiment of the present invention 1 is molten in chlorobenzene The absorption spectrum of solid film on liquid and quartz plate.
Fig. 2 is that the embodiment of the present invention 2 prepares polymer P BPT2V of the gained containing double pyridine oxadiazole derivative acceptors in chlorobenzene The absorption spectrum of solid film on solution and quartz plate.
Fig. 3 be with the embodiment of the present invention prepare polymer P BPTV of the gained containing double pyridine oxadiazole derivative acceptors or PBPT2V is the structural representation of the FET device of organic active semiconductor layer.
Fig. 4 is to prepare polymer P BPTV of the gained containing double pyridine oxadiazole derivative acceptors to be organic using the embodiment of the present invention 1 The output characteristic curve figure of the FET device of active semiconducting layer.
Fig. 5 is to prepare polymer P BPTV of the gained containing double pyridine oxadiazole derivative acceptors to be organic using the embodiment of the present invention 1 The transfer characteristic curve figure of the FET device of active semiconducting layer.
Fig. 6 is to prepare polymer P BPT2V of the gained containing double pyridine oxadiazole derivative acceptors to have using the embodiment of the present invention 2 The output characteristic curve figure of the FET device of machine active semiconducting layer.
Fig. 7 is to prepare polymer P BPT2V of the gained containing double pyridine oxadiazole derivative acceptors to have using the embodiment of the present invention 2 The transfer characteristic curve figure of the FET device of machine active semiconducting layer.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute It is conventional method unless otherwise instructed to state method.The raw material can obtain from open commercial sources unless otherwise instructed. Bromo- [1,2,5] thiadiazoles of reaction substrate 4,7- bis- used simultaneously [3,4-c] pyridine and (E)-bis- 1,2-(three in following embodiments Normal-butyl tinbase) ethene all commercially obtains, and remaining reaction dissolvent and catalyst used commercially obtain.
Specific embodiment 1
A kind of polymer semiconductor of the invention containing double pyridine oxadiazole derivative acceptors, specially chemical constitution are PBPTV polymer semiconducting material, its synthetic route are as follows：
(1) chemical structural formula is the synthesis of a intermediate：Under nitrogen protection, tributyl-[4- (2- are added into there-necked flask Decyl myristyl) thiophene -2- bases] alkane tin (5.8g, 8.2mmol), bromo- [1,2,5] thiadiazoles of 4,7- bis- simultaneously [3,4-c] pyridine (2.0g, 6.8mmol), double (triphenyl phosphorus) palladium chloride (0.24g, 0.34mmol) catalyst, 70mL toluene solvants.Backflow 4 After hour, room temperature is cooled to.Extracted using dichloromethane, organic phase is dried with magnesium sulfate, is spin-dried for solvent and is obtained crude product.Then adopt With silica gel chromatographic column purify the bromo- 4- of target product 7- (4- (2- decyls myristyl) thiophene -2- bases)-[1,2,5] thiazole [3, 4-c] pyridine, yield=85%.
Structural characterization data are as follows,
1H NMR(400MHz,CDCl3),δ(ppm):8.66(s,1H),8.53(s,1H),7.24(s,1H),2.65–2.64 (d,2H),1.70(br,1H),1.30–1.24(m,40H),0.89-0.85(m,6H)；MALDI-TOF-MS:M/z=636.19 (M+).
From the foregoing, it will be observed that the compound structure is correct, for the bromo- 4- of shown compound 7- (4- (2- decyls myristyl) thiophene- 2- yls)-[1,2,5] thiazole [3,4-c] pyridine.
(2) chemical structural formula is the synthesis of c intermediate：Under nitrogen protection, compound b (positive six is added into there-necked flask Dibutyltin dilaurate) (0.33g, 0.54mmol), compound a (1.03g, 1.62mmol), tetrakis triphenylphosphine palladium catalyst (0.03g, 0.03mmol) and toluene solvant.After backflow 24 hours, room temperature is cooled to.Extracted using dichloromethane, organic phase anhydrous slufuric acid Magnesium is dried, and is spin-dried for solvent and is obtained crude product.Target product 4,4 '-bis- (4- (2- decyl tetradecanes are purified to obtain using silica gel chromatographic column Base) thiophene -2- bases)-two [1,2,5] thiazole [3,4-c] pyridines, yield=60%.
Structural characterization data are as follows,
1H NMR(400MHz,CDCl3),δ(ppm):9.44(s,2H),8.63(s,2H),7.25(s,2H),2.69-2.67 (d,4H),1.74(br,2H),1.33–1.25(m,80H),0.87-0.85(t,12H)；MALDI-TOF-MS:M/z= 1110.39(M+).
From the foregoing, it will be observed that the compound structure is correct, for shown compound 4,4 '-bis- (4- (2- decyls myristyl) thiophene- 2- yls)-two [1,2,5] thiazole [3,4-c] pyridines.
(3) chemical structural formula is the synthesis of M1 monomer：Under nitrogen protection, 20mL chloroform is added into there-necked flask With compound c (0.35g, 0.3mmol).Be placed in ice bath, with syringe will dissolved with N- bromo-succinimides (NBS, 0.14g, 0.8mmol) N, N'- dimethylformamides (DMF) solution 4mL is slowly added into reaction.Rear room temperature is dripped to stir After mixing reaction 8 hours, extracted using dichloromethane, organic phase is dried with anhydrous magnesium sulfate, is spin-dried for solvent and is obtained crude product.Using silicon Glue chromatographic column purify target product 4,4 '-bis- (the bromo- 4- of 5- (2- decyls myristyl) thiophene -2- bases) -7,7 '-two [1,2, 5] thiazole [3,4-c] pyridine, yield=90%.
Structural characterization data are as follows,
1H NMR(400MHz,CDCl3),δ(ppm):9.42(s,2H),8.44(s,2H),2.63–2.61(d,4H),1.80 (br,2H),1.34–1.24(m,80H),0.88–0.85(t,12H)；MALDI-TOF-MS:M/z=1267.11 (M+).
It is comonomer compounds 4,4 ' shown in formula M1 used in embodiment 1-bis- from the foregoing, it will be observed that the compound structure is correct (the bromo- 4- of 5- (2- decyls myristyl) thiophene -2- bases) -7,7 '-two [1,2,5] thiazole [3,4-c] pyridines.
(4) chemical structural formula is the synthesis of polymer P BPTV shown in formula (I)：Under nitrogen protection, toward 25mL there-necked flask In, sequentially add monomeric compound 4,4 ' shown in formula M1-bis- (the bromo- 4- of 5- (2- decyls myristyl) thiophene-2- bases)-7,7 '- Two [1,2,5] thiazole [3,4-c] pyridines (152mg, 0.12mmol), (E)-bis- 1,2-(tri-n-butyl tin base) ethene (73mg, 0.12mmol), two (triphenyl phosphorus) palladium chlorides (4mg, 0.006mmol) and chlorobenzene (5mL) are added in reaction bulb, in argon gas Middle progress freezing-pumping-thaw cycles deoxygenation three times, reactant mixture is then heated to 120 DEG C of reaction 48h.After cooling, add Enter 200mL methanol, stir 2h at room temperature, filter.Obtained polymer loads apparatus,Soxhlet's extracting.First with methanol, acetone, just Hexane extraction removes small molecule and catalyst to colourless, then is extracted with chloroform to obtain final product, yield=80%.
The structural characterization data of resulting polymers are as follows：
Molecular weight characterization data are as follows：Weight average molecular weight is 50.6kDa, number-average molecular weight 22.7kDa, polymer molecule It is 2.23 to measure profile exponent.
Elementary analysis (%) calculates (C68H106N6S4)n:C,71.90；H,9.41；N,7.40；Measure:C,71.80；H, 9.38；N,7.46.
From the foregoing, it will be observed that the product structure is correct, it is polymer P BPTV shown in formula (I).
Specific embodiment 2
A kind of polymer semiconductor of the invention containing double pyridine oxadiazole derivative acceptors, specially chemical constitution are PBPT2V polymer semiconducting material, its synthetic route are as follows：
(1) chemical structural formula is the synthesis of a intermediate：Synthesized with reference to the synthetic method of above-described embodiment 1.
(2) chemical structural formula is the synthesis of c intermediate：Under nitrogen protection, added into there-necked flask compound b [(E)- Double (tributyl tinbase) ethene of 1,2-] (0.56g, 0.92mmol), compound a (1.75g, 2.76mmol), four (triphenylphosphines) Palladium catalyst (0.053g, 0.046mmol) and toluene solvant.After backflow 24 hours, room temperature is cooled to.Extracted using dichloromethane Take, organic phase is dried with anhydrous magnesium sulfate, is spin-dried for solvent and is obtained crude product.Target product (E) -1 is purified to obtain using silica gel chromatographic column, Double (4-4- (2- decyls myristyl) thiophene -2- bases)-[1,2,5] thiazole [3, the 4-c] pyridin-7-yls of 2-) ethene, yield= 80%.
Structural characterization data are as follows,
1H NMR(400MHz,CDCl3),δ(ppm):8.67(s,2H),8.57(s,2H),8.54(s,2H),7.22(s, 2H),2.66-2.65(d,4H),1.72(br,2H),1.32–1.25(m,80H),0.89-0.85(t,12H)；MALDI-TOF- MS:M/z=1136.51 (M+).
From the foregoing, it will be observed that the compound structure is correct, it is double (4-4- (the 2- decyl tetradecanes of midbody compound (E) -1,2- Base) thiophene -2- bases)-[1,2,5] thiazole [3,4-c] pyridin-7-yl) ethene.
(3) chemical structural formula is the synthesis of M1 intermediate：Under nitrogen protection, 20mL three chloromethanes are added into there-necked flask Alkane and compound c (0.50g, 0.44mmol).It is placed in ice bath, will be dissolved with N- bromo-succinimides with syringe The N of (0.20g, 1.10mmol), N '-dimethyl formamide solution 4mL are slowly added into reaction.8 are reacted at room temperature after dripping After hour, extracted using dichloromethane, organic phase is dried with anhydrous magnesium sulfate, is spin-dried for solvent and is obtained crude product.Using silica gel chromatograph Post purifies to obtain double (4- (the bromo- 4- of 5- (2- decyls myristyl) thiophene -2- bases)-[1,2,5] thiazoles of target product (E) -1,2- [3,4-c] pyridin-7-yl) ethene, yield=88%.
Structural characterization data are as follows,
1H NMR(400MHz,CDCl3),δ(ppm):8.47(s,2H),8.30(s,2H),8.26(s,2H),2.54-2.52 (d,4H),1.75(br,2H),1.31-1.24(m,80H),0.88-0.85(t,12H)；MALDI-TOF-MS:M/z= 1293.38(M+).
From the foregoing, it will be observed that the compound structure is correct, being comonomer compounds (E) shown in formula M1-1,2- pairs, ((5- is bromo- by 4- 4- (2- decyls myristyl) thiophene -2- bases)-[1,2,5] thiazole [3,4-c] pyridin-7-yl) ethene.
(4) chemical structural formula is the synthesis of polymer P BPT2V shown in formula (I)：Into 25mL there-necked flask, sequentially add Double (4- (the bromo- 4- of 5- (2- decyls myristyl) thiophene -2- bases)-[1,2,5] thiazoles of -1,2- of monomeric compound (E) shown in formula M1 [3,4-c] pyridin-7-yl) ethene (259mg, 0.2mmol), (E)-bis- 1,2-(tri-n-butyl tin base) ethene (121mg, 0.2mmol), two (triphenyl phosphorus) palladium chlorides (7mg, 0.01mmol) and chlorobenzene (5mL) are added in reaction bulb, in argon gas Freezing-pumping-thaw cycles deoxygenation three times is carried out, reactant mixture is then heated to 120 DEG C of reaction 48h.After cooling, add 200mL methanol, 2h is stirred at room temperature, filter.Obtained polymer loads apparatus,Soxhlet's extracting.First with methanol, acetone, just oneself Alkane is extracted to colourless, removes small molecule and catalyst, then is extracted with chloroform to obtain final product, yield=92%.
The structural characterization data of resulting polymers are as follows：
Molecular weight characterization data are as follows：Weight average molecular weight is 52.2kDa, number-average molecular weight 20.9kDa, polymer molecule It is 2.50 to measure profile exponent.
Elementary analysis (%) calculates (C70H108N6S4)n:C,72.36；H,9.37；N,7.23；Measure:C,72.18；H, 9.28；N,7.21.
From the foregoing, it will be observed that the product structure is correct, it is polymer P BPT2V shown in formula (I).
Above-described embodiment 1 and 2 prepares resulting polymers PBPTV and PBPT2V spectral quality and thin film field-effect crystal The measure of pipe property：
(1) polymer P BPTV and PBPT2V absorption spectra property
Fig. 1 is ultraviolet-visible-near-infrared absorption spectrum of polymer P BPTV films on chlorobenzene solution and quartz plate.By Fig. 1 understands that polymer P BPTV solution and film show wide absorption region, and its film absorption absorption maximum sideband value is all For 865nm or so, corresponding optical band gap is that (optical band gap is according to formula E by 1.43eVg=1240/ λ is calculated, wherein EgFor optics Band gap, λ are film absorption absorption maximum sideband value).
Fig. 2 is ultraviolet-visible-near-infrared absorption spectrum of polymer P BPT2V films on chlorobenzene solution and quartz plate. As shown in Figure 2, polymer P BPT2V solution and film show wide absorption region, its film absorption absorption maximum sideband value All it is 867nm or so, corresponding optical band gap is that (optical band gap is according to formula E by 1.43eVg=1240/ λ is calculated, wherein EgFor light Band gap is learned, λ is film absorption absorption maximum sideband value).
(2) polymer P BPTV and PBPT2V TFT performance measurement
The present invention is using the characteristic of semiconductor of top-gated bottom contact (TGBC) device architecture Study Polymer Melts film, its device junction Structure schematic diagram is as shown in Figure 3.Its detailed device configuration program reference literature completes (Adv.Mater., 2017,29,1602410). Using highly doped silicon chip as substrate, silica is as insulating barrier (300nm)；By photoetching process prepare golden (Au) source/ Drain electrode source electrode and drain electrode (gold/titanium, 30nm/5nm).The channel width (W) of FET device is 1400 μm, channel length (L) For 5 μm.After substrate first passes through oxygen plasma processing 5 minutes, acetone, deionized water and ethanol cleaning are passed sequentially through.Then exist Under vacuum, with octadecyl trichlorosilane alkane (OTS) to SiO2Surface of insulating layer is modified, the substrate for then modifying OTS (OTS-Treated SiO2Substrate 60 DEG C of vacuum drying oven) is positioned over to be dried.In nitrogen box, semiconductor active Layer (Polymer Semiconductors) is prepared by-the 15mg/mL of spin coating 8 polymer dichlorobenzene solution, and film sample exists 180 DEG C of annealing 10min in nitrogen box.The active layer by embodiment 1 or the gained ownership formula of embodiment 2 (I) copolymer p BPTV and PBPT2V is formed.Then, film sample is annealed in blanket of nitrogen (180 DEG C) processing.Then, spin coating 80mg/mL is passed through Polymethyl methacrylate (PMMA) butyl acetate solution prepare polymethyl methacrylate (PMMA, about 1150nm) dielectric Layer, PMMA used weight average molecular weight is 996kDa, and dielectric constant k is about 2.17.Then, whole device is placed in 80 DEG C true 30 minutes are toasted in empty drying box to remove butyl acetate solvent.Finally, a layer thickness about 100nm is deposited on PMMA dielectric layers Aluminium (Al) as gate electrode.In atmosphere, FETs semiconductor is measured using Keithley 4200SCS semi-conductor test instruments Characteristic, its typical case's output and transfer curve are as shown in Fig. 4-7.Wherein, the hole of its saturation region and electron mobility can be by following Equation is calculated：IDS=(W/2L) Ciμ(VG–VT)2(saturation region, VDS=VG–VT).Wherein, IDSFor drain current, μ is current-carrying Transport factor, VGFor grid voltage, VTFor threshold voltage, CiFor the body capacitance that insulate.
Fig. 4 is to prepare polymer P BPTV of the gained containing double pyridine oxadiazole derivative acceptors as organic active half using embodiment 1 The output characteristic curve figure of the FET device of conductor layer, it is shown that good linear zone and saturation region, illustrate PBPTV based fet devices With good field-effect performance of control.
Fig. 5 is to prepare polymer P BPTV of the gained containing double pyridine oxadiazole derivative acceptors as organic active half using embodiment 1 Transfer characteristic curve of the FET device of conductor layer when source-drain voltage is ± 100V.The device shows good bipolarity device Part performance, its hole and electron mobility are respectively 6.87 and 8.49cm2/V s。
Fig. 6 is to prepare polymer P BPT2V of the gained containing double pyridine oxadiazole derivative acceptors as organic active using embodiment 2 The output characteristic curve of the FET device of semiconductor layer, it is shown that good linear zone and saturation region, illustrate PBPT2V based fet devices Part has good field-effect performance of control.
Fig. 7 is to prepare polymer P BPT2V of the gained containing double pyridine oxadiazole derivative acceptors as organic active using embodiment 2 Transfer characteristic curve of the FET device of semiconductor layer when source-drain voltage is ± 100V.The device shows good bipolarity Device performance, its hole and electron mobility are respectively 1.99 and 0.35cm2/V s。
In addition, gained result of study confirms：Double pyridine oxadiazole derivative acceptor base polymerizations shown in formula (I) provided by the invention Thing semiconductor is the bipolarity conjugated polymer of a kind of excellent combination property；The hole of superelevation and electron mobility depend on such Polymer semiconducting material has big copline skeleton, the effect of strong hetero atom, the molecule chain backbone of isotactic and good solution Processing characteristics.The advantages such as preparation method provided by the present invention is easy and effective, raw material is easy to get and generalization is strong.By changing not Same hydrotropy alkyl chain, hetero atom substitution and conjugated bridging element bridging, double pyridines two of the excellent combination property of series can be prepared Zole derivatives acceptor based polyalcohol semi-conducting material, this is for studying between Bipolar Polymer semiconductor structure and performance Had very important significance in association, have to the high performance Bipolar Polymer semi-conducting material of Future Development and instruct to anticipate Justice.

Claims (10)

  1. A kind of 1. polymer semiconductor containing double pyridine oxadiazole derivative acceptors, it is characterised in that：Polymer semiconductor's tool There is the general formula of molecular structure shown in formula (I)；
    In the formula (I), the R is the straight chained alkyl that the total number of carbon atoms is 6-16 or the branched alkyl that the total number of carbon atoms is 8-30 In any one；
    Ar is following three kinds of situations：It is not present, carbon-carbon double bond or triple carbon-carbon bonds；
    X is oxygen atom, sulphur atom, selenium atom or tellurium atom；
    N is 10-300 integer.
  2. 2. the polymer semiconductor according to claim 1 containing double pyridine oxadiazole derivative acceptors, it is characterised in that：It is described In formula (I), n be 50-150 integer, more preferably 100.
  3. 3. the polymer semiconductor according to claim 1 or 2 containing double pyridine oxadiazole derivative acceptors, it is characterised in that： The straight chained alkyl that described the total number of carbon atoms is 6-16 is n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane Base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base or n-hexadecyl；Described the total number of carbon atoms be 8- 30 branched alkyl is 2- ethylhexyls, and 2- butyl hexyl, 2- hexyls octyl group, 4- hexyls decyl, 3- hexyls undecyl, 2- are pungent Base decyl, 2- octyldodecyls, 3- octyl groups tridecyl, 2- decyls dodecyl, 2- decyls myristyl, 3- decyls 15 Alkyl, 2- dodecyls cetyl, 4- octyl groups myristyl, 4- decyls cetyl, 4- hexyls decyl, 4- octyldodecyls Base, 4- decyls myristyl or 4- dodecyl cetyls；
    Polymer semiconductor shown in the formula (I) is specially polymer shown in following PBPTV or PBPT2V：
  4. A kind of 4. system of polymer semiconductor containing double pyridine oxadiazole derivative acceptors as any one of claim 1-3 Preparation Method, it is characterised in that including following synthesis step：
    (1) 2- tributyls tinbase -4- alkylthrophenes react with dibromo benzothia (oxa) diazol derivatives, obtain intermediate a, the fourths of 2- tri- The structural formula of base tinbase -4- alkylthrophenes is：
    Wherein, R definition is identical with the definition in claim 1-3；
    The dibromo benzothia (oxa) diazol derivatives structural formula is：
    Wherein, the X is oxygen atom, sulphur atom, selenium atom or tellurium atom；
    The structural formula of the intermediate a is：
    Wherein, R definition is identical with the definition in claim 1-3；
    (2) under nitrogen protection, midbody compound a and compound b is subjected to palladium catalysed cross coupling reaction, obtains compound c；Institute The structural formula for stating compound b is：
    Wherein, Ar definition is identical with the definition in claim 1；
    The structural formula of the midbody compound c is：
    Wherein, in the midbody compound c, R, Ar and X definition are identical with the definition in claim 1-3；
    (3) under nitrogen protection, midbody compound c and N- bromo-succinimide are subjected to electrophilic reaction, obtain singulation Compound formula M1, its structural formula are：
    (4) under inert gas shielding, by monomer shown in formula M1 and (E)-bis- 1,2-(tri-n-butyl tin base) monomers shown in ethene It is placed in solvent and carries out palladium catalysed cross coupling reaction, reaction finishes to obtain polymer shown in the formula (I), that is, obtains containing double pyridines two The polymer semiconductor of Zole derivatives acceptor.
  5. 5. the preparation method of the polymer semiconductor according to claim 4 containing double pyridine oxadiazole derivative acceptors, it is special Sign is：The concrete operations of the step (1) are：Under nitrogen protection, 2- tributyl tinbase -4- alkyl thiophenes are added into there-necked flask Fen, dibromo benzothia (oxa) diazol derivatives, double (triphenyl phosphorus) palladium chloride catalyst and toluene solvant, return stirring reaction 1-10 are small Shi Hou, room temperature is cooled to, is extracted using dichloromethane, organic phase is dried with magnesium sulfate, is spin-dried for solvent and is obtained crude product, using silica gel Chromatographic column purifies to obtain oily liquids a；The wherein reaction raw materials mol ratio that feeds intake is dibromo benzothia (oxa) diazol derivatives：2- tributyls Tinbase -4- alkylthrophenes：Double (triphenyl phosphorus) palladium chloride=1：1–2：0.01–0.1.
  6. 6. the preparation method of the polymer semiconductor according to claim 4 containing double pyridine oxadiazole derivative acceptors, it is special Sign is：The concrete operations of the step (2) are：Under nitrogen protection, midbody compound a, compound are added into there-necked flask B, tetrakis triphenylphosphine palladium catalyst and toluene solvant, after return stirring reacts 10-72 hours, room temperature is cooled to, using dichloro Methane is extracted, and organic phase is dried with anhydrous magnesium sulfate, is spin-dried for solvent and obtains crude product, and Red oil is purified to obtain using silica gel chromatographic column Liquid c；The wherein reaction raw materials mol ratio that feeds intake is compound b：Midbody compound a：Tetrakis triphenylphosphine palladium=1：2.0– 6.0：0.01–0.1.
  7. 7. the preparation method of the polymer semiconductor according to claim 4 containing double pyridine oxadiazole derivative acceptors, it is special Sign is：The concrete operations of the step (3) are：Under nitrogen protection, chloroform and compound c are added into there-necked flask, will It is placed in ice bath, and N- bromo-succinimides are slowly added into reaction bulb in batches, reaction is stirred at room temperature 5-24 hours Afterwards, extracted using dichloromethane, organic phase is dried with anhydrous magnesium sulfate, is spin-dried for solvent and is obtained crude product, is carried using silica gel chromatographic column It is pure to obtain target product M1；The wherein reaction raw materials mol ratio that feeds intake is compound c：N- bromo-succinimide=1：2.0– 3.0。
  8. 8. the preparation method of the polymer semiconductor according to claim 4 containing double pyridine oxadiazole derivative acceptors, it is special Sign is：The concrete operations of the step (4) are：Under nitrogen protection, M1, (E)-bis- 1,2-(three positive fourths are added into there-necked flask Base tinbase) ethene, solvent and palladium catalyst, after 100-150 DEG C of return stirrings react 10-72 hours, room temperature is cooled to, will be reacted Liquid is fallen in methanol, is filtered, and collects blue brown solid, then purifies subject polymer using cable type extractor according, is spin-dried for solvent and is obtained The black solid of gold lustre；The wherein reaction raw materials mol ratio that feeds intake is compound M1：(E)-bis- 1,2-(tri-n-butyl tins Base) ethene：Palladium catalyst=1：1.0–1.5：0.01–0.1；The palladium catalyst is selected from tetrakis triphenylphosphine palladium, palladium, two At least one of (triphenylphosphine) palladium chloride and three (dibenzalacetone) two palladium；The solvent be selected from toluene, dimethylbenzene, At least one of methyl naphthalene, chlorobenzene, dichloro-benzenes, dichloronaphtalene, trichloro-benzenes, chloronaphthalene and tetrahydrofuran.
  9. 9. a kind of polymer semiconductor containing double pyridine oxadiazole derivative acceptors as any one of claim 1-3 or Polymer semiconductor containing double pyridine oxadiazole derivative acceptors made from preparation method as any one of claim 4-8 Application in thin polymer film FET device is prepared.
  10. 10. application according to claim 9, it is characterised in that the application includes preparing with described containing double pyridine diazole The polymer semiconductor of derivative acceptor is the thin polymer film FET device of organic semiconductor active layer.
CN201710654172.4A 2017-08-03 2017-08-03 Polymer semiconductor containing bispyridazole derivative receptor and preparation method and application thereof Active CN107573489B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710654172.4A CN107573489B (en) 2017-08-03 2017-08-03 Polymer semiconductor containing bispyridazole derivative receptor and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710654172.4A CN107573489B (en) 2017-08-03 2017-08-03 Polymer semiconductor containing bispyridazole derivative receptor and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107573489A true CN107573489A (en) 2018-01-12
CN107573489B CN107573489B (en) 2019-12-27

Family

ID=61034248

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710654172.4A Active CN107573489B (en) 2017-08-03 2017-08-03 Polymer semiconductor containing bispyridazole derivative receptor and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN107573489B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110128631A (en) * 2019-02-18 2019-08-16 湘潭大学 Super low band-gap conjugated polymer of D-A type and the preparation method and application thereof
CN111233898A (en) * 2020-03-09 2020-06-05 湘潭大学 Organic small molecule conjugated material containing isotactic bipyridine thiadiazole receptor and preparation method and application thereof
CN112280008A (en) * 2019-07-24 2021-01-29 华南协同创新研究院 Bridged asymmetric benzodiazole and/or pyridine diazole birceptor polymer semiconductor and preparation method and application thereof
CN114409682A (en) * 2022-02-14 2022-04-29 中国科学院化学研究所 Triazole pyridine receptor with positioning effect, polymer thereof and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120322966A1 (en) * 2011-06-17 2012-12-20 Bazan Guillermo C Regioregular pyridal[2,1,3]thiadiazole pi-conjugated copolymers for organic semiconductors
CN105384918A (en) * 2015-12-15 2016-03-09 中国科学院化学研究所 Azaisoindigo polymer and its preparation method and use
CN105820316A (en) * 2016-04-28 2016-08-03 湘潭大学 Heteroatom substituted naphthalimide polymer semiconductor as well as preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120322966A1 (en) * 2011-06-17 2012-12-20 Bazan Guillermo C Regioregular pyridal[2,1,3]thiadiazole pi-conjugated copolymers for organic semiconductors
CN105384918A (en) * 2015-12-15 2016-03-09 中国科学院化学研究所 Azaisoindigo polymer and its preparation method and use
CN105820316A (en) * 2016-04-28 2016-08-03 湘潭大学 Heteroatom substituted naphthalimide polymer semiconductor as well as preparation method and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110128631A (en) * 2019-02-18 2019-08-16 湘潭大学 Super low band-gap conjugated polymer of D-A type and the preparation method and application thereof
CN110128631B (en) * 2019-02-18 2021-10-08 湘潭大学 D-A type ultralow band gap conjugated polymer and preparation method and application thereof
CN112280008A (en) * 2019-07-24 2021-01-29 华南协同创新研究院 Bridged asymmetric benzodiazole and/or pyridine diazole birceptor polymer semiconductor and preparation method and application thereof
CN112280008B (en) * 2019-07-24 2022-12-20 东莞伏安光电科技有限公司 Bridged asymmetric benzodiazole and/or pyridine diazole birceptor polymer semiconductor and preparation method and application thereof
CN111233898A (en) * 2020-03-09 2020-06-05 湘潭大学 Organic small molecule conjugated material containing isotactic bipyridine thiadiazole receptor and preparation method and application thereof
CN111233898B (en) * 2020-03-09 2021-05-11 湘潭大学 Organic small molecule conjugated material containing isotactic bipyridine thiadiazole receptor and preparation method and application thereof
CN114409682A (en) * 2022-02-14 2022-04-29 中国科学院化学研究所 Triazole pyridine receptor with positioning effect, polymer thereof and application thereof

Also Published As

Publication number Publication date
CN107573489B (en) 2019-12-27

Similar Documents

Publication Publication Date Title
CN107573489A (en) A kind of polymer semiconductor containing double pyridine oxadiazole derivative acceptors and preparation method and application
Qian et al. Family of diazapentalene chromophores and narrow-band-gap polymers: synthesis, halochromism, halofluorism, and visible–near infrared photodetectivity
CN102510851B (en) Methanofullerene derivative and use its electrooptical device
EP2626375B1 (en) Semiconductor materials prepared from dithienylvinylene copolymers
CN105601662A (en) Compound used for forming high-molecular compound
Sun et al. Synthetically controlling the optoelectronic properties of dithieno [2, 3-d: 2′, 3′-d′] benzo [1, 2-b: 4, 5-b′] dithiophene-alt-diketopyrrolopyrrole-conjugated polymers for efficient solar cells
KR20100017463A (en) Organic semiconductors
An et al. Synthesis and transistor properties of asymmetric oligothiophenes: relationship between molecular structure and device performance
Higashihara et al. Synthesis of thiophene-based π-conjugated polymers containing oxadiazole or thiadiazole moieties and their application to organic photovoltaics
Vollbrecht et al. Liquid crystalline dithienothiophene derivatives for organic electronics
EP3135726A1 (en) Composition and polymer compound, and organic semiconductor element containing said composition and said polymer compound
Kawabata et al. Synthesis of soluble dinaphtho [2, 3-b: 2′, 3′-f] thieno [3, 2-b] thiophene (DNTT) derivatives: One-step functionalization of 2-bromo-DNTT
Aguiar et al. Synthesis, characterization and application of meso-substituted fluorinated boron dipyrromethenes (BODIPYs) with different styryl groups in organic photovoltaic cells
CN110128631A (en) Super low band-gap conjugated polymer of D-A type and the preparation method and application thereof
CN109970768A (en) Based on ten unitary condensed ring plane kernel D (A-Ar) of carbazole2Type organic photoelectric compound and preparation method and application
JP2013235903A (en) Organic thin-film solar cell and composition used for the same
Ohshita et al. Synthesis of bis (diarylphosphino) dithienosilole derivatives as novel photo-and electroluminescence materials
Krebs et al. Antibatic photovoltaic response in zinc-porphyrin-linked oligothiophenes
Bianchi et al. Synthesis of dithienocyclohexanones (DTCHs) as a family of building blocks for π-conjugated compounds in organic electronics
Zhang et al. Fast construction of dianthraceno [a, e] pentalenes for OPV applications
Ding et al. Benzothiophene and benzosulfone fused pyrazino [2, 3-g] quinoxaline: Synthesis and semiconducting properties
Park et al. A new class of organic semiconductors for solution processed OTFTs: Synthesis and characterization of pyrrolo–perylene derivatives with different end groups
Li et al. A comparative study of diketopyrrolopyrrole and isoindigo based polymers for organic photovoltaic applications
Miguel et al. Regiochemical effects of sulfur oxidation on the electronic and solid-state properties of planarized oligothiophenes containing thieno [3, 2-b] thiophene units
Yan et al. Design, synthesis and photophysical properties of ADADA small molecules for photovoltaic application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant