CN103242360A - Linear soluble sulfur atom-containing pentaphene derivatives as well as preparation method and application thereof - Google Patents
Linear soluble sulfur atom-containing pentaphene derivatives as well as preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 35
- 125000004434 sulfur atom Chemical group 0.000 title abstract description 35
- 150000002970 pentaphenes Chemical class 0.000 title abstract 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 230000005669 field effect Effects 0.000 claims abstract description 21
- 239000004065 semiconductor Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 11
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 claims description 11
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 11
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Substances CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 9
- 229940043279 diisopropylamine Drugs 0.000 claims description 9
- 239000011630 iodine Substances 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 14
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 46
- 150000002964 pentacenes Chemical class 0.000 description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 229930192474 thiophene Natural products 0.000 description 24
- 239000000377 silicon dioxide Substances 0.000 description 15
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 14
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- 125000002346 iodo group Chemical group I* 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- KZGWPHUWNWRTEP-UHFFFAOYSA-N ethynyl-tri(propan-2-yl)silane Chemical group CC(C)[Si](C#C)(C(C)C)C(C)C KZGWPHUWNWRTEP-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000005582 pentacene group Chemical group 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
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- 238000004776 molecular orbital Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- -1 tetrabutyl ammonium hexafluorophosphate Chemical compound 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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Abstract
The invention discloses novel soluble sulfur atom-containing pentaphene derivatives as well as a preparation method and application thereof. The structural formula of the sulfur atom-containing pentaphene derivatives is shown in the formula 1-1 or 1-2. A synthetic route provided by the invention is simple and efficient; the materials are simple and easily available; a synthetic method has universality and can be popularized and applied to the synthesis of the sulfur atom-containing pentaphene derivatives containing various substituent groups. The compounds have larger pi-conjugate planes and can be used for preparing a high-mobility OFET (Organic Field Effect Transistor) apparatus by virtue of a solution method due to good solubility of the compounds. The compound has low highest occupied molecular orbital energy level (HOMO) and good stability in air, and is beneficial to obtaining the OFET apparatus which has a high mobility and a high switch ratio and is stable in air. According to the embodiment of the invention, OFET is prepared from the linear soluble sulfur atom-containing pentaphene derivative mixture ADT-TES serving as an organic semiconductor layer, wherein the OFET has high mobility (mu) and high switch ratio, the highest mu is 2.3*10<-4>cm<2>V<-1>s<-1>, the switch ratio is larger than 104, and therefore, the linear soluble sulfur atom-containing pentaphene derivatives have a certain application prospect in OFET.
Description
Technical field
The present invention relates to a kind of pentacene derivative and preparation method thereof and application of linear solubility sulfur atom-containing.
Background technology
Organic field effect tube (Organic Field-effect Transistors, be called for short OFETs) be the basic parts of developing big area of future generation, flexible electronic device, correlative study relates to chemistry, physics and materialogy, multi-door subject such as electronics, people's extensive concern (Mas-Torrent, M. have been caused; Rovira, C.Chem.Soc.Rev.2008,37,827.Voss, D.Nature2000,407,442; Katz, H.E.Chem.Mater.2004,16,4748; Zaumseil, J.; Sirringhaus, H.Chem.Rev.2007,107,1296; Wen, Y.; Liu, Y.Adv.Mater.2010,22,1331; Guo, Y.; Yu, G.; Liu, Y.Adv.Mater.2010,22,4427), become one of forward position research hot fields.The OFET device is at smart card, sensor, and electronic radio frequency tags, large screen display, unicircuit, Electronic Paper etc. have huge application potential.In view of OFET device good prospects for application is arranged, famous research institution, university and transnational company all dropped into a large amount of energy exploitation high-performance, the organic semiconductor material of high stability both at home and abroad in the last few years.Domestic many colleges and universities and scientific research institutions, such as Tsing-Hua University, Peking University, South China Science ﹠ Engineering University, Wuhan University, Jilin University, Shandong University, Zhejiang University, Beijing Jiaotong University, Shanghai Communications University, institute should be changed in Chinese Academy of Sciences Changchun, physics and chemistry institute of the Chinese Academy of Sciences, the organic institute in Chinese Academy of Sciences Shanghai, Suzhou nanometer institute of the Chinese Academy of Sciences, the unit of waiting of chemistry institute of Microelectronics Institute of the Chinese Academy of Sciences and the Chinese Academy of Sciences has successively carried out the organic field effect tube material and has synthesized the research that reaches related device, and the performance of present high performance organic field effect tube can compare favourably with the amorphous silicon of widespread use is transistorized.
The organic semiconductor material that is used for field-effect transistor generally all has bigger pi-conjugated two dimensional structure.Although emerging in large numbers of a large amount of good molecule organic semiconductor materials arranged at present, since material, the stability of device, the difficulty or ease of device preparation etc. problem, explore and find high-performance, stable, but the semiconductor material that solution method is handled still has very important meaning.Because thiophenes has good conjugacy and stronger Intermolecular Forces, such as S ... S and CH ... π effect etc., the thiophene-based material has become one of the research focus in this field (Xiao, K.; Liu, Y.; Qi, T.; Zhang, W.; Wang, F.; Gao, J.; Qiu, W.; Ma, Y.; Cui, G.; Chen, S.; Zhan, X.; Yu, G.; Qin, J.; Hu, W.; Zhu, D.J.Am.Chem.Soc.2005,127,13281.Minemawari.H.; Yamda.T.; Matsui.H.; Tsutsumi.J.; Haas.S.; Chiba.R.; Kumai.R.; Hasegawa.T.Nature2011,475,364).Has the linear molecule of bigger pi-conjugated two dimensional structure because good solid-state accumulation mode, very be suitable as the semiconductor material that solution method prepares field-effect transistor, also be subjected to increasing concern (Wang C, Dong H, Hu W, Liu Y, Zhu D.Chem Rev.2012,112,2208; Yamamoto, T.; Takimiya, K.J.Am.Chem.Soc.2007,129,2224.Minemawari, H.; Yamda, T.; Matsui, H.; Tsutsumi, J.; Haas, S.; Chiba, R.; Kumai, R.; Hasegawa, T.Nature2011,475,364; Y.Guo, C.Du, G.Yu, C.Di, S.Jiang, H.Xi, J.Zheng, S.Yan, C.Yu, W.Hu, Y.Liu.Adv.Funct.Mater.2010,20,1019).
Summary of the invention
The pentacene derivative and preparation method thereof and application that the purpose of this invention is to provide a kind of novel soluble sulfur atom-containing.
The structural formula of the pentacene derivative of solubility sulfur atom-containing provided by the present invention is suc as formula shown in I-1 or the formula I-2,
Formula I-1
Formula I-2
In formula I-1 and the formula I-2, R is straight or branched alkane.
Above-mentioned compound, described R can be C
1～C
20Straight or branched alkane.
The invention provides the preparation method of compound shown in the formula I-1, may further comprise the steps:
(1) under rare gas element, compound, n-Butyl Lithium and iodine react shown in the formula II-1, namely obtain compound shown in the formula III-1;
Formula II-1 formula III-1
(2) compound, N shown in the formula III-1, compound reacts under the katalysis of triphenylphosphine palladium chloride and cuprous iodide shown in N-diisopropylamine and the formula IV, namely obtains compound shown in the formula I-1;
The formula IV
In the formula IV, R is straight or branched alkane.
Among the above-mentioned preparation method, in the step (1), the molar ratio of compound and described n-Butyl Lithium can be 1:2～12 shown in the formula II-1, as 1:3;
The ingredient proportion of compound and described iodine can be 1:2～12 shown in the formula II-1, as 1:3;
The temperature of reaction of described reaction can be-78～20 ℃, and the reaction times can be 1～36 hour.
Among the above-mentioned preparation method, in the step (1), the solvent of described reaction can be tetrahydrofuran (THF) or ether.
Among the above-mentioned preparation method, in the step (2), the mole that feeds intake of compound shown in the formula III-1 and described triphenylphosphine palladium chloride can be 1:0.1～0.005, as 1:0.007;
Compound shown in the III-1 and described N, the molar ratio of N-diisopropylamine can be 1:2～20, as 1:14;
The molar ratio of compound can be 1:2～10 shown in compound shown in the III-1 and the formula IV;
Compound shown in the formula III-1 and described cuprous iodide molar ratio can be 1:0.2～0.01, as 1:0.052;
The temperature of reaction of described reaction can be 40～80 ℃.
The solvent of described reaction can be tetrahydrofuran (THF) or 1,4-dioxane.
The present invention also provides the preparation method of compound shown in the formula I-2, may further comprise the steps:
(1) under rare gas element, compound, n-Butyl Lithium and iodine react shown in the formula II-2, namely obtain compound shown in the formula III-2;
Formula II-2 formula III-2
(2) compound, N shown in the formula III-2, compound reacts under the katalysis of triphenylphosphine palladium chloride and cuprous iodide shown in N-diisopropylamine and the formula IV, namely obtains compound shown in the formula I-2;
The formula IV
In the formula IV, R is straight or branched alkane.
Among the above-mentioned preparation method, in the step (1), the molar ratio of compound and described n-Butyl Lithium can be 1:2～12 shown in the formula II-2, as 1:3;
The ingredient proportion of compound and described iodine can be 1:2～12 shown in the formula II-2, as 1:3;
The temperature of reaction of described reaction can be-78～20 ℃, and as-20 ℃ or-78 ℃, the reaction times can be 1～36 hour.
Among the above-mentioned preparation method, in the step (1), the solvent of described reaction can be tetrahydrofuran (THF) or ether.
Among the above-mentioned preparation method, in the step (2), the mole that feeds intake of compound shown in the formula III-2 and described triphenylphosphine palladium chloride can be 1:0.1～0.005,1:0.007;
Compound shown in the III-2 and described N, N-diisopropylamine molar ratio can be 1:2～20, as 1:14;
The molar ratio of compound can be 1:2～10 shown in compound shown in the III-2 and the formula IV, as 1:6.7;
Compound shown in the formula III-2 and described cuprous iodide molar ratio can be 1:0.2～0.01, as 1:0.052;
The temperature of reaction of described reaction can be 40～80 ℃.
The solvent of described reaction is tetrahydrofuran (THF) or 1,4-dioxane.
The application of compound shown in formula I-1 or the formula I-2 in the preparation organic field effect tube also further is provided among the present invention.
The present invention also provides a kind of organic field effect tube, and its organic semiconductor layer is made by compound shown in formula I-1 or the formula I-2.
The present invention has following advantage:
1, synthetic route is succinctly efficient; Raw material is simple and easy to; Synthetic method has universality, can promote the use of the pentacene derivative that contains various substituent linear solubility sulfur atom-containing synthetic in;
2, this compounds is to have bigger pi-conjugated plane, and well solvability can be used for the OFET device that solution method prepares high mobility;
3, this compounds has the highest lower molecular orbital energy level (HOMO) that takies, and good stability in the air is conducive to obtain the OFET device of high mobility stable in the air and high on-off ratio;
4, be that higher (μ is up to 2.3 * 10 for the mobility (μ) of OFET of organic semiconductor layer preparation and on-off ratio with the pentacene deriving mixture ADT-TES of the linear solubility sulfur atom-containing of embodiments of the invention
-4Cm
2V
-1s
-1, on-off ratio is greater than 10
4), in OFET, have certain application prospect.
Description of drawings
Fig. 1 is the synthetic route chart of the pentacene derivative of linear solubility sulfur atom-containing provided by the invention.
Fig. 2 is the synthetic route chart of the pentacene derivative ADT-TES of the linear solubility sulfur atom-containing of embodiment 1 preparation.
Fig. 3 is the synthetic route chart of the pentacene derivative ADT-TPS of the linear solubility sulfur atom-containing of embodiment 2 preparations.
Fig. 4 is that the pentacene derivative ADT-TES of the linear solubility sulfur atom-containing of embodiment 1 preparation gained is at the uv-visible absorption spectra of dichloromethane solution neutralized film.
Fig. 5 is that the pentacene derivative ADT-TPS of the linear solubility sulfur atom-containing of embodiment 2 preparation gained is at the uv-visible absorption spectra of dichloromethane solution neutralized film.
Fig. 6 is embodiment 1 and the pentacene derivative ADT-TPS of the linear solubility sulfur atom-containing of 2 preparation gained and the thermogravimetric curve of ADT-TPS.
Fig. 7 is embodiment 1 and the pentacene derivative ADT-TPS of the linear solubility sulfur atom-containing of 2 preparation gained and the cyclic voltammetry curve of ADT-TPS.
Fig. 8 is the structural representation of the organic field effect tube of semiconductor layer for the pentacene derivative ADT-TES of the linear solubility sulfur atom-containing of embodiment 1 preparation gained.
Fig. 9 is the output characteristic curve figure of the organic field effect tube of semiconductor layer for the pentacene derivative ADT-TES of the linear solubility sulfur atom-containing of embodiment 1 preparation gained.
Figure 10 is the transfer characteristic curve figure of the organic field effect tube of semiconductor layer for the pentacene derivative ADT-TES of the linear solubility sulfur atom-containing of embodiment 1 preparation gained.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Embodiment 1, two (the silica-based ethynyl of triethyl) anthra [2,3-b:6,7-b'] two thiophene of preparation 2,8-and two (the silica-based ethynyl of triethyl) anthra [2,3-b:7,6-b'] two thiophene of 2,8-
The synthetic route chart that present embodiment prepares ADT-TES as shown in Figure 2
(1) preparation 2,8-, two iodo anthras [2,3-b:6,7-b'] two thiophene and anthra [2,3-b:7,6-b'] two thiophene
(single compounds process for production thereof is with reference to Tylleman, B. with anthra [2,3-b:6,7-b'] two thiophene and anthra [2,3-b:7,6-b'] two thiophene mixture; Vande Velde, C.; Balandier, J.; Stas, S.; Sergeyev, S.; Geerts, Y.Org.Lett., 2011.13,5208; . (d) Lehnherr, D.; Waterloo, A.; Goetz, K.; Payne, M.; Hampel, F.; Anthony, J.; Jurchescu, O.; Tykwinski, R.Org.Lett., 2012.14,3660. (e) Mamada, M.; Minamiki, T.; Katagiri, H.; Tokito.S.Org.Lett., 2012.14,4062.Preparation process of mixture is with reference to Laquindanum, J.; Katz, H.; Lovinger, A.J.Am.Chem.Soc.1998,120,66) in dry tetrahydrofuran (100 milliliters) solution of (0.93 gram, 3.2 mmoles), slowly drip 1.6 moles every liter n-Butyl Lithium (6.0 milliliters, 9.6 mmoles) at-78oC.Continue stirring reaction after one hour, reaction system slowly is warming up to-20 ° of C, continues to stir after one hour, and this reaction system is cooled to-78 ° of C again, adds iodine (2.54 grams, 10 mmoles).System slowly is warming up to room temperature after-78 ° of C react 30 minutes.The go out reaction and remove remaining iodine with sodium sulfite aqueous solution of Yong Shui temper.Filter, be directly used in the next step after the red solid drying that obtains.Obtain product 1.6 grams, 92%.
The structural characterization data are as follows:
High resolution mass spectrum (MALDI-TOF): theoretical value: 541.8157; Measured value: 541.8163.
(2) two (the silica-based ethynyl of triethyl) anthra [2,3-b:6,7-b'] two thiophene of preparation 2,8-and two (the silica-based ethynyl of triethyl) anthra [2,3-b:7,6-b'] two thiophene mixture (ADT-TES, namely in the formula I, R is ethyl) of 2,8-
2 of the step that makes progress preparation, 8-two iodo anthras [2,3-b:6,7-b'] two thiophene and anthra [2,3-b:7,6-b'] (270 milligrams in two thiophene, 0.50 add triphenylphosphine palladium chloride (2.5 milligrams) in mixture mmole), add N again with behind the inert gas replacement three times then behind cuprous iodide (5.0 milligrams) and the 50 milliliters of anhydrous tetrahydro furans, N-diisopropylamine (1.0 milliliters), the silica-based acetylene of triethyl (0.8 milliliter), in this reaction system, mixture and the triphenylphosphine palladium chloride mole that feeds intake can be 1:0.007, mixture and N, N-diisopropylamine molar ratio can be 1:14, the mol ratio of mixture and cuprous iodide is 1:0.052, and the mol ratio of mixture and the silica-based acetylene of triethyl is 1:6.7, and the reacting by heating system continued to stir 48 hours to refluxing.With the reaction of going out of chlorination aqueous ammonium temper, extract with 80 milliliters of methylene dichloride (70 * 3 milliliters) after the cooling room temperature, mistake post behind the anhydrous sodium sulfate drying, eluent is sherwood oil and methylene dichloride, obtains 100 milligrams of red product, yield 52%.
The structural characterization data are as follows:
High resolution mass spectrum (MALDI-TOF): theoretical value: 566.1954; Measured value: 566.1961.
Nucleus magnetic hydrogen spectrum and carbon spectrum:
1H NMR (400MHz, CDCl3, δ) 8.69-8.48 (m, 2H), 8.37 (s, 2H), 8.35 (s, 2H), 7.49 (s, 2H), 1.11 (tt, J=8.0Hz, 18H), 0.77 (q, J=8.0Hz, 12H).
13C NMR (100MHz, CDCl3, δ) 138.8,138.6,138.1,137.8,129.9,129.6,129.3,129.0,125.6,125.1,124.9,122.2,119.6,101.0,99.0,7.5,4.3.
As from the foregoing, this compound structure is correct, is the mixture of two (the silica-based ethynyl of triethyl) anthra [2,3-b:6,7-b'] two thiophene of 2,8-and two (the silica-based ethynyl of triethyl) anthra [2,3-b:7,6-b'] two thiophene of 2,8-.
Embodiment 2, two (the silica-based ethynyl of triisopropyl base) anthra [2,3-b:6,7-b'] two thiophene of preparation 2,8-and two (the silica-based ethynyl of triethyl) anthra [2,3-b:7,6-b'] two thiophene of 2,8-
The synthetic route chart that present embodiment prepares ADT-TES as shown in Figure 3
(1) prepares 2,8-, two iodo anthras [2,3-b:6,7-b'] two thiophene and anthra [2,3-b:7,6-b'] two thiophene according to the method among the embodiment 1.
(2) two (the silica-based ethynyl of triisopropyl base) anthra [2,3-b:6,7-b'] two thiophene of preparation 2,8-and two (the silica-based ethynyl of triethyl) anthra [2,3-b:7,6-b'] two thiophene mixture (ADT-TPS, namely in the formula I, R is the sec.-propyl base) of 2,8-
To 2 of preparation, 8-two iodo anthras [2,3-b:6,7-b'] two thiophene and anthra [2,3-b:7,6-b'] (270 milligrams in two thiophene, 0.50 add triphenylphosphine palladium chloride (2.5 milligrams) in mixture mmole), add N again with behind the inert gas replacement three times then behind cuprous iodide (5.0 milligrams) and the 50 milliliters of anhydrous tetrahydro furans, N-diisopropylamine (1.0 milliliters), triisopropylsilyl acetylene (0.8 milliliter), in this reaction system, mixture and the triphenylphosphine palladium chloride mole that feeds intake can be 1:0.007, mixture and N, the N-diisopropylamine mole that feeds intake can be 1:14, the mol ratio of mixture and cuprous iodide is 1:0.052, and the mol ratio of mixture and triisopropylsilyl acetylene is 1:6.7, and the reacting by heating system continued to stir 48 hours to refluxing.With the reaction of going out of chlorination aqueous ammonium temper, extract with 80 milliliters of methylene dichloride (70 * 3 milliliters) after the cooling room temperature, mistake post behind the anhydrous sodium sulfate drying, eluent is sherwood oil and methylene dichloride, obtains 100 milligrams of red product, yield 52%.
The structural characterization data are as follows:
High resolution mass spectrum (MALDI-TOF): theoretical value: 650.2893; Measured value: 650.2899.
Nucleus magnetic hydrogen spectrum and carbon spectrum:
1H NMR (400MHz, CDCl
3, δ) 8.71-8.51 (m, 2H), 8.38 (s, 2H), 8.36 (s, 2H), 7.50 (s, 2H), 1.17-1.16 (m, 42H).
13C NMR (100MHz, CDCl3, δ) 138.9,138.7,138.1,137.8,129.9,129.6,129.3,128.8,125.6,125.2,125.1,122.2,119.6,100.3,99.8,18.7,11.3.
As from the foregoing, this compound structure is correct, is the mixture of two (triisopropylsilyl ethynyl) anthra [2,3-b:6,7-b'] two thiophene of 2,8-and two (triisopropylsilyl ethynyl) anthra [2,3-b:7,6-b'] two thiophene of 2,8-.
The mensuration of the spectral quality of the pentacene derivative of embodiment 3, linear solubility sulfur atom-containing, electrochemical properties, field-effect transistor character
(1) spectrum property of the pentacene derivative ADT-TES of linear solubility sulfur atom-containing and ADT-TPS
Fig. 4 is that the pentacene derivative ADT-TES of linear solubility sulfur atom-containing of embodiment 1 preparation is at the ultraviolet-visible absorption spectroscopy of dichloromethane solution neutralized film.
As shown in Figure 4, the maximum absorption peak position of the pentacene derivative ADT-TES of linear solubility sulfur atom-containing in methylene dichloride is 520 nanometers, absorption maximum absorption band in film is red shift to 540 nanometer then, calculates optical band gap and be 2.30 electron-volts that (optical band gap is according to formula E
g=1240/ λ calculates, wherein E
gBe optical band gap, λ is the cut off value of ultraviolet absorption curve).
Fig. 5 is that the pentacene derivative ADT-TPS of linear solubility sulfur atom-containing of embodiment 5 preparation is at the ultraviolet-visible absorption spectroscopy of dichloromethane solution neutralized film.
As shown in Figure 5, the maximum absorption peak position of the pentacene derivative ADT-TES of linear solubility sulfur atom-containing in methylene dichloride is 520 nanometers, absorption maximum absorption band in film is red shift to 545 nanometer then, and calculating optical band gap is 2.28 electron-volts.
(2) thermal property of the pentacene derivative ADT-TES of linear solubility sulfur atom-containing and ADT-TPS
Fig. 6 is embodiment 1 and the pentacene derivative ADT-TES of the 2 linear solubility sulfur atom-containing that prepare and the thermogravimetric curve of ADT-TPS.As shown in Figure 6, ADT-TES and ADT-TPS have good calorifics stability, and its decomposition temperature is all greater than 400 degrees centigrade.
(3) chemical property of the pentacene derivative ADT-TES of linear solubility sulfur atom-containing and ADT-TPS
Fig. 7 is the pentacene derivative ADT-TES of linear solubility sulfur atom-containing and the cyclic voltammetry curve of ADT-TPS.
Electrolyzer adopts three-electrode system, and platinum is working electrode, and platinum filament is counter electrode, and silver/silver chloride is reference electrode, and tetrabutyl ammonium hexafluorophosphate is as supporting electrolyte.The condition of cyclic voltammetric is: sweep limit is-1.6～1.3 volts (vs.Ag/AgCl), and scanning speed is 100 millivolts of per seconds.
Electro-chemical test shows that its initial oxidation current potential is about 0.78 volt, estimate the HOMO(highest occupied molecular orbital energy level of ADT-TES and ADT-TPS thus) energy level is-5.18 electron-volts, its initial reduction potential is estimated the minimum not occupied orbital of the LUMO(energy level of ADT-TES thus about-1.20 volts) energy level is-3.20 electron-volts.
(4) field-effect transistor performance of the pentacene derivative ADT-TES of linear solubility sulfur atom-containing
Fig. 8 is the structural representation of the organic field effect tube constructed, as shown in the figure, adopt highly doped silicon chip as substrate and gate electrode, the silicon-dioxide of 300 nanometer thickness is as insulation layer, (OTS) modifies silica sphere with the octadecyl trichlorosilicane, pentacene derivative ADT-TES is semiconductor layer, and gold is source electrode and drain electrode (adopting the Vacuum Coating method preparation).The chloroform soln of the pentacene derivative ADT-TES of sulfur atom-containing (10 milligrams/every milliliter) is coated on the silica sphere of being modified by OTS with the method for getting rid of film.
At room temperature use Hewlett-Packard (HP) 4140B semi-conductor test instrument to measure the electrical property of prepared OFET device.
Determine two key parameters of the performance of OFET to be: the on-off ratio (I of mobility of charge carrier rate (μ) and device
On/ I
Off).Mobility refers to: under unit electric field, (unit is cm to the average drift velocity of current carrier
2V
-1s
-1), it has reflected hole or the transfer ability of electronics in semi-conductor under electric field.On-off ratio is defined as: the ratio of the electric current of transistor under "On" state and "Off" state, it has reflected the quality of devices switch performance.For a high performance field-effect transistor, its mobility and on-off ratio should be high as much as possible.
Fig. 7 be based on pentacene derivative ADT-TES prepared without the FET device of anneal different grid voltage V when the room temperature
GOutput characteristic curve under (0 Dao – 100V).Output characteristic curve has shown better linearity district and saturation region, illustrates that the OFET device based on pentacene derivative ADT-TES has the regulation and control of field-effect preferably performance.
Fig. 8 for based on pentacene derivative ADT-TES prepared be – 100V without the FET device of anneal drain-source voltage when the room temperature time transfer characteristic curve.The mobility that can be calculated field-effect transistor by the data among the figure is 2.3 * 10
-4Cm
2V
-1s
-1With on-off ratio be 10
4(seeing Table 1).
Carrier mobility can be drawn by Equation for Calculating:
I
DS=(W/2L) C
iμ (V
G– V
T)
2(saturation region, V
DS=V
G– V
T)
Wherein, I
DSBe drain current, μ is carrier mobility, V
GBe grid voltage, V
TBe threshold voltage, W is channel width, and L is channel length, C
iBe isolator electric capacity (C
i=7.5 * 10
-9Every square centimeter of method).Utilize (I
DS, sat)
1/2To V
GMapping, and do linear regression, the slope of the tropic is extrapolated carrier mobility (μ) thus, tries to achieve V by the section of the tropic and X-axis
TMobility can calculate according to the slope of formula from transition curve.On-off ratio can be drawn by the maximum value of Fig. 7 right side source-drain current ratio with minimum value.
Be that semiconductor layer has been made a lot of organic field effect tube devices with pentacene derivative ADT-TES, in these devices, wherein the highest mobility is up to 2.3 * 10 when testing without the anneal room temperature
-4Cm
2V
-1s
-1, on-off ratio is greater than 10
4All experimental results show that the pentacene derivative of such linear solubility sulfur atom-containing is promising organic semiconductor material.
Table 1 is based on the FET device performance of compd A DT-TES
This material that the present invention is not limited to report, change different substituting groups and can obtain a series of novel organic semi-conductor material, and the synthetic method that the present invention provides is succinctly efficient, this is very helpful for the structure of research organic semiconductor material and the relation of performance, can further instruct the design of high performance material with synthetic.
Claims (9)
1. compound shown in formula I-1 or the formula I-2,
Formula I-1
Formula I-2
In formula I-1 and the formula I-2, R is straight or branched alkane.
2. compound according to claim 1, it is characterized in that: described R is C
1～C
20Straight or branched alkane.
3. the preparation method of compound shown in the formula I-1 may further comprise the steps:
(1) under rare gas element, compound, n-Butyl Lithium and iodine react shown in the formula II-1, namely obtain compound shown in the formula III-1;
Formula II-1 formula III-1
(2) compound, N shown in the formula III-1, compound reacts under the katalysis of triphenylphosphine palladium chloride and cuprous iodide shown in N-diisopropylamine and the formula IV, namely obtains compound shown in the formula I-1;
The formula IV
In the formula IV, R is straight or branched alkane.
4. the preparation method of compound shown in the formula I-2 may further comprise the steps:
(1) under rare gas element, compound, n-Butyl Lithium and iodine react shown in the formula II-2, namely obtain compound shown in the formula III-2;
Formula II-2 formula III-2
(2) compound, N shown in the formula III-2, compound reacts under the katalysis of triphenylphosphine palladium chloride and cuprous iodide shown in N-diisopropylamine and the formula IV, namely obtains compound shown in the formula I-2;
The formula IV
In the formula IV, R is straight or branched alkane.
5. according to claim 3 or 4 described methods, it is characterized in that: in the step (1), the molar ratio of compound and described n-Butyl Lithium is 1:2～12 shown in compound shown in the formula II-1 or the formula II-2;
The ingredient proportion of compound and described iodine is 1:2～12 shown in compound shown in the formula II-1 or the formula II-2;
The temperature of reaction of described reaction is-78～20 ℃, and the reaction times is 1～36 hour.
6. according to each described method among the claim 3-5, it is characterized in that: in the step (1), the solvent of described reaction is tetrahydrofuran (THF) or ether.
7. according to each described method among the claim 3-5, it is characterized in that: in the step (2), the mole that feeds intake of compound and described triphenylphosphine palladium chloride shown in compound shown in the formula III-1 or the formula III-2 is 1:0.1～0.005;
The molar ratio of compound and described cuprous iodide is 1:0.2～0.01 shown in compound shown in the formula III-1 or the formula III-2;
Compound and described N shown in III-1 or the formula III-2, the molar ratio of N-diisopropylamine is 1:2～20;
The molar ratio of compound shown in compound and the formula IV is 1:2～10 shown in III-1 or the formula III-2;
The temperature of reaction of described reaction is 40～80 ℃.
The solvent of described reaction is tetrahydrofuran (THF) or 1,4-dioxane.
8. the application of compound shown in formula I-1 or the formula I-2 in the preparation organic field effect tube.
9. organic field effect tube, its feature then is: its organic semiconductor layer is made by compound shown in formula I-1 or the formula I-2.
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