CN110590845A - Organic semiconductor design, analysis and screening method for adjusting thermodynamic property based on alkyl chain - Google Patents
Organic semiconductor design, analysis and screening method for adjusting thermodynamic property based on alkyl chain Download PDFInfo
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- CN110590845A CN110590845A CN201910948252.XA CN201910948252A CN110590845A CN 110590845 A CN110590845 A CN 110590845A CN 201910948252 A CN201910948252 A CN 201910948252A CN 110590845 A CN110590845 A CN 110590845A
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000012216 screening Methods 0.000 title claims abstract description 13
- 238000004458 analytical method Methods 0.000 title claims abstract description 12
- 238000013461 design Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000002411 thermogravimetry Methods 0.000 claims description 4
- 238000005481 NMR spectroscopy Methods 0.000 claims description 3
- 150000003577 thiophenes Chemical class 0.000 claims description 3
- 238000002441 X-ray diffraction Methods 0.000 claims description 2
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 2
- 238000012932 thermodynamic analysis Methods 0.000 claims 1
- 238000005457 optimization Methods 0.000 abstract description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 8
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 8
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000646 scanning calorimetry Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention belongs to the technical field of semiconductor design, and particularly relates to an organic semiconductor design, analysis and screening method for adjusting thermodynamic properties based on alkyl chains. The method of the invention provides a basis for material design, performance optimization and high-performance semiconductor material screening.
Description
Technical Field
The invention belongs to the field of semiconductor design, and particularly relates to an organic semiconductor design, analysis and screening method for adjusting thermodynamic performance based on an alkyl chain.
Background
The organic semiconductor material has the characteristics of strong design, outstanding material performance and the like, and has wide application prospects in the fields of flexible electronics, wearable equipment development and the like. The introduction of alkyl chain in the semiconductor material changes the solubility of the material, introduces parity effect, adjusts molecular arrangement by liquid crystal performance and finally causes the change of the thermodynamic performance of the material. The invention utilizes the point, analyzes the thermodynamic property of semiconductor molecules containing alkyl chains with different lengths through thermodynamics and related characterization, and provides a basis for material design, performance optimization and high-performance semiconductor material screening.
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a method for screening semiconductor materials with alkyl chains of different lengths.
Means for solving the technical problem
Aiming at the problems, the invention provides an organic semiconductor design, analysis and screening method for adjusting thermodynamic property based on an alkyl chain.
According to one embodiment of the invention, an organic semiconductor design, analysis and screening method for adjusting thermodynamic properties based on alkyl chains is provided, which comprises the following steps of modifying alkyl chain structures with different lengths in the organic semiconductor material structure, then carrying out thermodynamic property analysis on the material, and carrying out screening on the material according to the thermodynamic properties.
An embodiment is, wherein the thermodynamic property analysis includes, but is not limited to, thermogravimetric analysis, differential scanning calorimetry analysis.
An embodiment is wherein the thermodynamic property analysis is further combined with nuclear magnetic resonance, X-ray diffraction analysis.
In one embodiment, the alkyl chain carbon chain length is 3 to 11.
According to a second aspect of the present invention, there is provided a thiophene derivative BTBT-Cn-P having the structure:
wherein n is 3 to 11.
The invention has the advantages of
The screening method disclosed by the invention analyzes the thermodynamic performance of semiconductor molecules containing alkyl chains with different lengths through thermodynamics and related characterization, and provides a basis for material design, performance optimization and high-performance semiconductor material screening.
Further features of the present invention will become apparent from the following description of exemplary embodiments.
Drawings
FIG. 1 is a schematic diagram of the synthetic route in example 1.
FIG. 2 is a graph showing the results of example 2 on BTBT-Cn-P(n＝3-11)，31And P NMR characterization.
FIG. 3 is BTBT-C in example 3n-thermogravimetric analysis characterization of P (n-3-11) material.
FIG. 4 shows the results of the scanning calorimetry performed on the material in example 4.
Detailed Description
One embodiment of the present disclosure will be specifically described below, but the present disclosure is not limited thereto.
Example 1: benzo [ b ] s with alkyl chains of different lengths]Benzo [4,5 ]]Thieno [2,3-d ]]Thiophene derivative BTBT-Cn-P (n-3-11) design and synthesis
The BTBT semiconductor core is connected with phosphoric acid through an alkyl chain with the length of 3-11, and the coupling degree of a BTBT group and a phosphoric acid group is adjusted through alkyl chains with different lengths, so that the performance optimization of the material is realized. The synthesis method comprises the following steps: to a solution of compound 1-n (n ═ 3-11, 0.168mmol) in 1mL of dichloromethane was added dropwise TMSBr (0.3mL), and the mixture was stirred at room temperature overnight. Then 2mL of methanol is added into the system and stirring is continued for 2h, and the product is dried by solvent extraction and recrystallized to obtain the product as a white solid. The characterization was as follows:
C3PA–BTBT:1H NMR(d-THF,500MHz,ppm,40℃):δ7.95(d,1H,J＝8.0Hz), 7.87(d,1H,J＝7.8Hz),7.82(s,1H),7.79(d,1H,J＝8.1Hz),7.39(m,2H),7.32(d, 1H,J＝8.3Hz),2.88(t,2H,J＝7.2Hz),2.00(m,2H),1.30(m,2H)；31P NMR(d-THF, 200MHz,ppm):δ31.44.EI-MS:Calcd.for[M-H]-:361.012747.Found: 361.012749.
C4PA–BTBT:1H NMR(d-THF,500MHz,ppm,40℃):δ7.96(d,1H,J＝7.8Hz), 7.87(d,1H,J＝7.1Hz),7.80(m,2H),7.41(m,2H),7.32(d,1H,J＝8.4Hz),2.80(t, 2H,J＝7.7Hz),1.83(m,4H),1.31(m,2H)；31P NMR(d-THF,200MHz,ppm):δ 31.50.EI-MS:Calcd.for[M-H]-:375.028397.Found:375.027394.
C5PA–BTBT:1H NMR(d-THF,500MHz,ppm,40℃):δ7.95(d,1H,J＝7.9Hz), 7.87(d,1H,J＝7.6Hz),7.80(m,2H),7.40(m,2H),7.30(d,1H,J＝9.2Hz),2.78(t, 2H,J＝7.7Hz),1.67(m,6H),1.50(m,2H)；31P NMR(d-THF,200MHz,ppm):δ 32.03.EI-MS:Calcd.for[M-H]-:389.044047.Found:389.044994.
C6PA–BTBT:1H NMR(d-THF,500MHz,ppm,40℃):δ7.95(d,1H,J＝8.0Hz), 7.87(d,1H,J＝7.2Hz),7.80(m,2H),7.41(m,2H),7.30(d,1H,J＝8.1Hz),2.78(m, 2H),1.62(m,2H),1.31(m,8H)；31P NMR(d-THF,200MHz,ppm):δ32.06.EI-MS: Calcd.for[M-H]-:403.059697.Found:403.059647.
C7PA–BTBT:1H NMR(d-THF,500MHz,ppm,40℃):δ7.95(d,1H,J＝8.0Hz), 7.87(d,1H,J＝7.5Hz),7.80(m,2H),7.41(m,2H),7.31(d,1H,J＝8.2Hz),2.78(t, 2H,J＝7.6Hz),1.62(m,4H),1.31(m,8H)；31P NMR(d-THF,200MHz,ppm):δ 32.03.EI-MS:Calcd.for[M-H]-:417.075347.Found:417.076116.
C8PA–BTBT:1H NMR(d-THF,500MHz,ppm,40℃):δ7.95(d,1H,J＝8.0Hz), 7.88(d,1H,J＝7.6Hz),7.80(m,2H),7.41(m,2H),7.30(d,1H,J＝7.9Hz),2.78(t, 2H,J＝7.6Hz),1.61(m,4H),1.31(m,10H)；31P NMR(d-THF,200MHz,ppm):δ 32.05.EI-MS:Calcd.for[M-H]-:431.090989.Found:431.091066.
C9PA–BTBT:1H NMR(d-THF,500MHz,ppm,40℃):δ7.95(d,1H,J＝8.0Hz), 7.88(d,1H,J＝7.6Hz),7.80(m,2H),7.41(m,2H),7.31(d,1H,J＝7.9Hz),2.78(t, 2H,J＝7.6Hz),1.60(m,4H),1.31(m,12H)；31P NMR(d-THF,200MHz,ppm):δ 32.02.EI-MS:Calcd.for[M-H]-:445.106648.Found:445.106766.
C10PA–BTBT:1H NMR(d-THF,500MHz,ppm,40℃):δ7.95(d,1H,J＝8.0Hz), 7.88(d,1H,J＝7.6Hz),7.80(m,2H),7.41(m,2H),7.30(d,1H,J＝8.1Hz),2.78(t, 2H,J＝7.6Hz),1.61(m,4H),1.31(m,14H)；31P NMR(d-THF,200MHz,ppm):δ 32.03.EI-MS:Calcd.for[M-H]-:459.122298.Found:459.122675.
C11PA–BTBT:1H NMR(d-THF,500MHz,ppm,40℃):δ7.95(d,1H,J＝7.9Hz), 7.88(d,1H,J＝7.5Hz),7.80(m,2H),7.41(m,2H),7.30(d,1H,J＝7.8Hz),2.78(t, 2H,J＝7.7Hz),1.60(m,4H),1.31(m,16H)；31P NMR(d-THF,200MHz,ppm):δ 32.04.ESI-MS:Calcd.for[M+H]+:475.15250.Found:475.15220.
example 2: BTBT-Cn-P(n＝3-11)，31P NMR characterization
For BTBT-Cn-P (n-3-11) is carried out31P NMR characterization, as shown in fig. 2, found that when n ═ 3-4, the phosphorus element chemical shift was low, indicating that when the alkyl chain length was 3 and 4, the BTBT conjugated group had greater coupling strength to the P element, and the material exhibited significant rigidity and was not easily processed.
Example 3:
as shown in FIG. 3, BTBT-CnThe thermal weight loss analysis of the-P (n-3-11) material is characterized in that the thermal weight loss curve shows that the material begins to lose weight above 180 ℃, the stability of the material is good, materials with different alkyl chain lengths in the DTG curve show thermodynamic difference, the first peak of the DTG is subjected to temperature statistics, good parity is shown, and the DTG thermodynamic performance shows a negative correlation relation along with the increase of the alkyl chain length.
Example 4: BTBT-CnThermogravimetric analysis characterization of P (n-3-11) material
Watch 1
Note that: the heating and cooling rates are both 10 ℃/min; cr is crystalline phase; IL is an amorphous phase; LC is a liquid crystal phase; LC1 liquid crystal phase 1; cr (chromium) componentmetaMetastable state.
The results of the scanning calorimetry test on the material are shown in FIG. 4, and the results are shown in Table I. The first temperature rising and reducing process is omitted, and the second temperature rising and reducing process is analyzed to find that when the length of an alkyl chain is 3 and 4, the coupling strength of the semiconductor core BTBT and the polar functional group phosphate group is high, the material basically has no any thermodynamic change, and the material is not a good organic semiconductor material; when the length of the alkyl chain is 5-7, the coupling of the semiconductor core BTBT and the polar functional group phosphate group is properly weakened, a pair of melting peak and cooling peak is basically shown, and the material thermal annealing is carried out at a temperature slightly lower than the temperature of the melting peak; when the alkyl chain length is 8-11, the influence of the alkyl chain gradually exceeds that of a semiconductor and a polar phosphate group, and the material has good liquid crystal performance.
The present invention is not limited to the above embodiments, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. A method for designing, analyzing and screening an organic semiconductor based on alkyl chain adjustment thermodynamic performance is characterized in that alkyl chain structures with different lengths are modified in an organic semiconductor material structure, then thermodynamic performance analysis is carried out on the material, and the material is screened according to the thermodynamic performance.
2. The method of claim 1, wherein the thermodynamic property analysis includes, but is not limited to, thermogravimetric analysis, differential scanning calorimetry analysis.
3. The method of claim 2, wherein the thermodynamic analysis is further combined with nuclear magnetic resonance, X-ray diffraction analysis.
4. The method of any one of claims 1-3, wherein the alkyl chain carbon chain length is 3-11.
5. A thiophene derivative having the structure:
wherein n is 3 to 11.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114965393A (en) * | 2022-04-29 | 2022-08-30 | 山东理工大学 | Method for detecting nitro-aromatic hydrocarbon pollutants by using pyrenyl derivatives |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103140493A (en) * | 2010-07-21 | 2013-06-05 | 赫劳斯贵金属有限两和公司 | Semiconductors based on substituted [1]benzothieno[3,2-b] [1]-benzothiophenes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103140493A (en) * | 2010-07-21 | 2013-06-05 | 赫劳斯贵金属有限两和公司 | Semiconductors based on substituted [1]benzothieno[3,2-b] [1]-benzothiophenes |
Non-Patent Citations (1)
| Title |
|---|
| THOMAS SCHMALTZ等: ""Effect of Structure and Disorder on the Charge Transport in Defined Self-Assembled Monolayers of Organic Semiconductors"", 《ACS NANO》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114965393A (en) * | 2022-04-29 | 2022-08-30 | 山东理工大学 | Method for detecting nitro-aromatic hydrocarbon pollutants by using pyrenyl derivatives |
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Application publication date: 20191220 |