CN103922915A - Bis-pyrene type compound with piezochromic property and preparation method and application thereof - Google Patents
Bis-pyrene type compound with piezochromic property and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000004528 spin coating Methods 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000003860 storage Methods 0.000 claims abstract description 15
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims abstract description 7
- 238000006266 etherification reaction Methods 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 238000010992 reflux Methods 0.000 claims description 25
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- 229940125782 compound 2 Drugs 0.000 claims description 18
- 229940126214 compound 3 Drugs 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 150000003220 pyrenes Chemical class 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 229940125904 compound 1 Drugs 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- -1 pyrene compound Chemical class 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 230000007480 spreading Effects 0.000 claims description 8
- 238000003892 spreading Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 235000015320 potassium carbonate Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 6
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000010409 thin film Substances 0.000 abstract description 6
- 238000003403 chloroformylation reaction Methods 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229940125898 compound 5 Drugs 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 235000011194 food seasoning agent Nutrition 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002120 nanofilm Substances 0.000 description 4
- 0 *Oc1cc(C(N)=O)cc(C(N)=O)c1 Chemical compound *Oc1cc(C(N)=O)cc(C(N)=O)c1 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- SYKMYTRHAFFXBI-UHFFFAOYSA-N C[O](C(c1cc(C([O](C)=C)=O)cc([O]#C)c1)=O)=C Chemical compound C[O](C(c1cc(C([O](C)=C)=O)cc([O]#C)c1)=O)=C SYKMYTRHAFFXBI-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Abstract
The invention discloses a bis-pyrene type compound with piezochromic property and a preparation method and application thereof. The compound has the structure as shown in general formula (I), and the preparation is completed by four-step conventional reactions, namely etherification reaction, hydrolysis reaction, chloroformylation reaction and Friedel-Crafts acylation reaction. The bis-pyrene type compound disclosed by the invention can be used for preparing a thin film in a spin-coating way, and the thin film has piezochromic luminescent property with high repeatability, high contrast and high sensitivity and can be used for information storage.
Description
Technical field
The present invention relates to a kind of two pyrene compounds, preparation method and application thereof with piezallochromy character.
Background technology
Organic molecule pressure causes fluorescence off-color material and has suitable extensive use, it not only can be used as sensor, information display and storer etc. and is applied in display screen, register, and it is also widely used in multiple emerging field, such as secret letter paper, glo-stick etc.Along with the reach of science and social progress, people press the demand that causes fluorescence off-color material further to increase to having the organic molecule of special purpose, and the organic molecule with specific function that therefore exploitation makes new advances is pressed and caused fluorescence colour change function material and have great importance.
Organic molecule fluorescent material has the advantages such as highly sensitive, selectivity good, the time of response is short, can directly observe as fluorescent optical sensor.Therefore, in recent years, the research of the fluorescent optical sensor detecting about heavy metal ion and transition metal ion has been subject to scientist's extensive concern.Various fluorescent molecular probes highly sensitive to metal ion, that selectivity is good are in the news in succession.If cause fluorescence off-color material as optical pickocff or storer with pressing, must meet two conditions: the one, obvious fluorescence color changes, and the 2nd, obvious Strength Changes.
Nearly 2 years, there is correlative study report, as professor Pei (J.Luo, L.Y.Li, Y.L.Song and J.Pei, Chem.Eur.J., 2011, 17, 10515-10519) with professor Piao (S.J.Yoon, J.W.Chung, J.Gierschner, K.S.Kim, M.G.Choi, D.Kim and S.Y.Park, J.Am.Chem.Soc., 2010, 132, 13675-13683) design respectively, prepare the compacting fluorescence off-color material based on donor-receiver principle, Tang Benzhong (J.Wang, J.Mei, R.R.Hu, J.Z.Sun, A.J.Qin and B.Z.Tang, J.Am.Chem.Soc., 2012, 134, 9956-9966) the aggregation inducing light emitting molecule of high-contrast etc. has been synthesized in design.But the pressure of this class causes still rareness very of fluorescence off-color material.
Summary of the invention
For the deficiency of prior art, one of object of the present invention is to provide a kind of two pyrene compounds with piezallochromy character, and it has good optical stability, high performance reproducibility, and high-contrast and high susceptibility can be used for information storage aspect.
In order to achieve the above object, the present invention has adopted following technical scheme:
Two pyrene compounds with piezallochromy character, it has the structure shown in logical formula I:
In formula, R is selected from C
nh
2n+1, (CH
2cH
2o)
ncH
3, (CH
2cH
2o)
ncH
2cH
3or
in any one;
R
1be selected from C
nh
2n+1, (CH
2cH
2o)
ncH
3or (CH
2cH
2o)
ncH
2cH
3in any one;
N is any nature of 2～12.
Described n is for example 2,3,4,5,6,7,8,9,10 or 11.
Two of object of the present invention is to provide a kind of preparation method of two pyrene compounds with piezallochromy character as above, and described method comprises the steps:
(1) etherification reaction of compound 1: add the salt of wormwood of compound 1, acetone, 1～4 equivalent, the compound R-Br of 1～4 equivalent in reaction vessel, after heating reflux reaction 12～24 hours, the concentrated crude product that obtains, through column chromatography for separation, with methylene dichloride/sherwood oil mixed solvent wash-out, evaporating solvent obtains white solid compound 2;
(2) hydrolysis reaction of compound 2: to the potassium hydroxide that adds ethanol, water, compound 2 and 1～4 equivalent in reaction vessel, reflux 2～10 hours, adds acid for adjusting pH to 2～4 after cooling, filters and obtains white solid compound 3;
(3) acyl chloride reaction of compound 3: the chloride reagent that adds 2～5 equivalents in reaction vessel, under room temperature, drip wherein compound 3 and catalyzer DMF(N, dinethylformamide) mixing solutions, be warmed up to 40～60 DEG C of insulations 2～4 hours, excessive chloride reagent is removed in distillation, obtains compound 4;
(4) friedel-crafts acylation of compound 4: pyrene is dissolved in dithiocarbonic anhydride, and be placed in reaction vessel, add the compound 4 of 1～4 equivalent to it, then be cooled to 0～5 DEG C, add aluminum chloride, reflux 12～18 hours, after product is cooling, pour in frozen water and stir 2～5 hours, with dichloromethane extraction, after organic phase dry filter, obtain thick product, further, through column chromatography for separation, with methylene dichloride and sherwood oil mixed solvent wash-out, evaporating solvent obtains having two pyrene compounds of piezallochromy character;
R is selected from C
nh
2n+1, (CH
2cH
2o)
ncH
3, (CH
2cH
2o)
ncH
2cH
3or
in any one;
R
1be selected from C
nh
2n+1, (CH
2cH
2o)
ncH
3or (CH
2cH
2o)
ncH
2cH
3in any one;
N is 2～12 random natural number.
The add-on of the described salt of wormwood of step (1) is 1～4 equivalent, for example 1.1 equivalents, 1.3 equivalents, 1.5 equivalents, 1.7 equivalents, 1.9 equivalents, 2.1 equivalents, 2.3 equivalents, 2.5 equivalents, 2.7 equivalents, 2.9 equivalents, 3.1 equivalents, 3.3 equivalents, 3.5 equivalents, 3.7 equivalents or 3.9 equivalents.
The add-on of the described compound R-Br of step (1) is 1～4 equivalent, for example 1.1 equivalents, 1.3 equivalents, 1.5 equivalents, 1.7 equivalents, 1.9 equivalents, 2.1 equivalents, 2.3 equivalents, 2.5 equivalents, 2.7 equivalents, 2.9 equivalents, 3.1 equivalents, 3.3 equivalents, 3.5 equivalents, 3.7 equivalents or 3.9 equivalents.
The described back flow reaction of step (1) 12～24 hours, for example 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 16.5 hours, 17 hours, 17.5 hours, 18 hours, 18.5 hours, 19 hours, 19.5 hours, 20 hours, 20.5 hours, 21 hours, 21.5 hours, 22 hours, 22.5 hours, 23 hours or 23.5 hours.
Preferably, step (1) rotary evaporation solvent.
Step (1) adopts the mixed solvent of methylene dichloride and sherwood oil to carry out wash-out as eluent, preferably, described in step (1), the volume ratio of methylene dichloride and sherwood oil is 1:10～10:1, for example 1:9,1:8,1:7,1:6,1:5,1:4,1:3,1:2,1.4:1,1.8:1,2.2:1,2.6:1,3:1,3.4:1,3.8:1,4.2:1,4.6:1,5:1,5.4:1,5.8:1,6.2:1,6.6:1,7:1,7.4:1 or 7.8:1, preferably 1:1～8:1.
The add-on of the described potassium hydroxide of step (2) is 1～4 equivalent, for example 1.1 equivalents, 1.3 equivalents, 1.5 equivalents, 1.7 equivalents, 1.9 equivalents, 2.1 equivalents, 2.3 equivalents, 2.5 equivalents, 2.7 equivalents, 2.9 equivalents, 3.1 equivalents, 3.3 equivalents, 3.5 equivalents, 3.7 equivalents or 3.9 equivalents.
The time of the described reflux of step (2) is 2～10 hours, for example 2.4 hours, 2.8 hours, 3.2 hours, 3.6 hours, 4 hours, 4.4 hours, 4.8 hours, 5.2 hours, 5.6 hours, 6 hours, 6.4 hours, 6.8 hours, 7.2 hours, 7.6 hours, 8 hours, 8.4 hours, 8.8 hours, 9.2 hours or 9.6 hours.
Step (2) adds acid for adjusting pH to 2～4 with the alkali in neutralization reaction system, for example, regulate pH to 2.2,2.4,2.6,2.8,3,3.2,3.4,3.6 or 3.8.
Preferably, described in step (2), acid is hydrochloric acid, and the concentration of described hydrochloric acid is 1～5M, for example 1.3M, 1.6M, 1.9M, 2.2M, 2.5M, 2.8M, 3.1M, 3.4M, 3.6M, 3.9M, 4.2M, 4.5M or 4.8M.
The exemplary described reaction vessel of step (3) is as being equipped with thermometer, dropping funnel, reflux exchanger (with HCl and SO
2absorption unit) there-necked flask.
The add-on of the described chloride reagent of step (3) is 2～5 equivalents, for example 2.2 equivalents, 2.5 equivalents, 2.8 equivalents, 3.1 equivalents, 3.4 equivalents, 3.7 equivalents, 4 equivalents, 4.3 equivalents, 4.6 equivalents or 4.9 equivalents.
Preferably, the described chloride reagent of step (3) is that thionyl chloride is or/and phosphorus pentachloride.
Described in step (3), be warmed up to 40～60 DEG C, for example, be warmed up to 41 DEG C, 42 DEG C, 43 DEG C, 44 DEG C, 45 DEG C, 46 DEG C, 47 DEG C, 48 DEG C, 49 DEG C, 50 DEG C, 51 DEG C, 52 DEG C, 53 DEG C, 54 DEG C, 55 DEG C, 56 DEG C, 57 DEG C, 58 DEG C or 59 DEG C.
The described insulation of step (3) 2～4 hours, for example, be incubated 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours, 3 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours or 3.9 hours.
Preferably, the described distillation of step (3) is underpressure distillation.
The add-on of the described compound 4 of step (4) is 1～4 equivalent, for example 1.1 equivalents, 1.3 equivalents, 1.5 equivalents, 1.7 equivalents, 1.9 equivalents, 2.1 equivalents, 2.3 equivalents, 2.5 equivalents, 2.7 equivalents, 2.9 equivalents, 3.1 equivalents, 3.3 equivalents, 3.5 equivalents, 3.7 equivalents or 3.9 equivalents.
Preferably, step (4) is cooled to 0～5 DEG C in ice bath, for example 0.4 DEG C, 0.8 DEG C, 1.2 DEG C, 1.6 DEG C, 2 DEG C, 2.4 DEG C, 2.8 DEG C, 3.2 DEG C, 3.6 DEG C, 4 DEG C, 4.4 DEG C or 4.8 DEG C.
The described reflux of step (4) 12～18 hours, for example 12.4 hours, 12.8 hours, 13.2 hours, 13.6 hours, 14 hours, 14.4 hours, 14.8 hours, 15.2 hours, 15.6 hours, 16 hours, 16.4 hours, 16.8 hours, 17.2 hours or 17.6 hours.
After step (4) is cooling by product, pours in frozen water and stir 2～5 hours with dissolved salt, for example 2.3 hours, 2.6 hours, 2.9 hours, 3.2 hours, 3.5 hours, 3.8 hours, 4.1 hours, 4.4 hours, 4.7 hours or 4.9 hours.
Preferably, step (4) obtains thick product after by anhydrous magnesium sulfate or Calcium Chloride Powder Anhydrous dry filter.
Step (4) adopts the mixed solvent of methylene dichloride and sherwood oil to carry out wash-out as eluent, preferably, the volume ratio of step (4) methylene dichloride and sherwood oil is 1:10～10:1, for example 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1.4:1, 1.8:1, 2.2:1, 2.6:1, 3:1, 3.4:1, 3.8:1, 4.2:1, 4.6:1, 5:1, 5.4:1, 5.8:1, 6.2:1, 6.6:1, 7:1 or 7.8:1, preferably 5:1～10:1, for example 5.3:1, 5.6:1, 5.9:1, 6.2:1, 6.5:1, 6.8:1, 7.1:1, 7.4:1, 7.7:1, 8:1, 8.3:1, 8.6:1, 8.9:1, 9.2:1, 9.5:1 or 9.8:1.
Preferably, step (4) rotary evaporation solvent.
The synthetic line figure of two pyrene compounds with piezallochromy character of the present invention is as shown below:
Three of object of the present invention is to provide a kind of preparation method of two pyrene compound films with piezallochromy character, comprises the steps:
(1) solution of preparing two pyrene compounds with piezallochromy character as above is spin coating liquid;
(2) substrate is fixed on spin coating instrument, spin coating drop is added on substrate, spin coating makes spin coating liquid uniform spreading generate film, and room temperature is placed and made it dry;
(3) optionally, repeat above-mentioned spin coating step;
(4) vacuum-drying, obtains having two pyrene compound films of piezallochromy character.
Preferably, described substrate is selected from silica glass, ito glass, Calcium Fluoride (Fluorspan) glass, silicon chip, PDMS or is fixed on any one in the paper on silica glass.
Preferably, in the time that described substrate is silica glass, ito glass or Calcium Fluoride (Fluorspan) glass, described substrate is carried out to following pre-treatment:
Utilize washing composition to clean in silica glass, ito glass or Calcium Fluoride (Fluorspan) glass and clean with deionized water, the sodium hydroxide solution that is placed in 40wt% boils, and taking-up is cleaned and soaks, then drying at room temperature with deionized water.
Preferably, first, with rotating speed spin coating 5～10s of 400～600rpm, then with rotating speed spin coating 40～60s of 2500～3000rpm, make spin coating liquid uniform spreading generate film.
Preferably, the described vacuum drying time is 6～10 hours, for example 6.3 hours, 6.6 hours, 6.9 hours, 7.2 hours, 7.5 hours, 7.8 hours, 8.1 hours, 8.4 hours, 8.7 hours, 9 hours, 9.3 hours, 9.6 hours or 9.9 hours.Described vacuum-drying can be carried out in vacuum drying oven.
As wish is coated with multilayer film, can be after drying at room temperature, repeat above-mentioned spin coating step with film again, repeated multiple times after, then vacuum-drying, can multilayer has two pyrene compound films of piezallochromy character.
Four of object of the present invention is to provide a kind of purposes of two pyrene compounds with piezallochromy character as above, and it is for information storage.
Compared with the prior art, the present invention has following beneficial effect:
Of the present invention pair of pyrene compound film has good compacting fluorescence color shifting properties, can under pressure, change fluorescence color and intensity, under solvent atmosphere, quickly recover to original state, can be for information recording and storage, and also such process has recyclability.
Provided by the present invention pair of pyrene compound is two pyrene compounds of conjugated structure, its advantage be this compounds to external world pressure make response.Piezochromic material of the present invention has good optical stability, high performance reproducibility, and high-contrast and high susceptibility are being with a wide range of applications aspect information storage.
Brief description of the drawings
Fig. 1 be molecule described in embodiment 1 nuclear magnetic spectrum (
1h NMR);
Fig. 2 is the emmission spectrum that described in embodiment 1, molecular press causes fluorescence variable color, before solid line representative friction, after dotted line representative friction;
Fig. 3 is molecular film described in embodiment 1 and information storage application photo thereof, before friction, is blue (in Fig. 3, appearing dimmed), is green (in Fig. 3, being shown as white) after friction;
Fig. 4 be molecule described in embodiment 2 nuclear magnetic spectrum (
1h NMR);
Fig. 5 is the emmission spectrum that described in embodiment 2, molecular press causes fluorescence variable color, before solid line representative friction, after dotted line representative friction;
Fig. 6 is molecular film described in embodiment 2 and information storage application photo thereof, before friction, is blue (in Fig. 6, appearing dimmed), record " CN " letter (figure is shown as white) after friction.
Fig. 7 be molecule described in embodiment 3 nuclear magnetic spectrum (
1h NMR);
Fig. 8 is the emmission spectrum that described in embodiment 3, molecular press causes fluorescence variable color, before solid line representative friction, after dotted line representative friction;
Fig. 9 is the XRD data of molecular film described in embodiment 3 before and after friction, before line representative friction above, after line representative friction below;
Figure 10 be molecule described in embodiment 4 nuclear magnetic spectrum (
1h NMR);
Figure 11 is the emmission spectrum that described in embodiment 4, molecular press causes fluorescence variable color, before solid line representative friction, after dotted line representative friction;
Figure 12 is the XRD data of molecular film described in embodiment 4 before and after friction, before line representative friction above, after line representative friction below;
Embodiment
Further illustrate technical scheme of the present invention below by embodiment.
Embodiment 1
Taking R structure as C
12h
25for example
1. the synthetic method of compound:
The etherification reaction of compound 1: add 10mmol compound 1 (2.38g), acetone (100mL), 10mmol salt of wormwood (1.37g), compound 10mmol C in there-necked flask
12h
25br (2.49g), heating reflux reaction, after 12 hours, concentrates and obtains crude product, through column chromatography for separation, with methylene dichloride/sherwood oil (volume ratio 2:1) mixed solvent wash-out, rotary evaporation solvent obtains white solid compound 2 (3.07g, productive rate: 75.6%).
The hydrolysis reaction of compound 2: add 30mL ethanol, 60mL water, 5mmol compound 2 (2.03g) and 10mmol potassium hydroxide (0.56g) in there-necked flask, reflux 5 hours, cooling rear dropping 1M hydrochloric acid is to pH=3, filtration obtains white solid compound 3 (1.65g, productive rate: 94.3%).
The acyl chloride reaction of compound 3: thermometer, dropping funnel, reflux exchanger are being housed (with HCl and SO
2absorption unit) there-necked flask in add the thionyl chloride (5.95g) of 50mmol, in dropping funnel, add the mixing solutions of 10mmol compound 3 (3.5g) and catalyzer DMF (0.2mL), after at room temperature dropwising, be warmed up to 50 DEG C of insulations 2 hours, underpressure distillation is removed excessive thionyl chloride and is obtained compound 4 (3.65g, productive rate: 94.3%).
The friedel-crafts acylation of compound 4: 10mmol pyrene (2g) is dissolved in 30mL dithiocarbonic anhydride, and be placed in there-necked flask, add the compound 4(1.94g of 5mmol) after, in ice bath, be cooled to 0 degree, add aluminum chloride, reflux 12 hours, after product is cooling, pour in frozen water and stir 2 hours, with dichloromethane extraction, organic phase obtains thick product after filtering by anhydrous magnesium sulfate drying, further through column chromatography for separation, with methylene dichloride/sherwood oil (volume ratio 8:1) mixed solvent wash-out, rotary evaporation solvent obtains white solid compound 5 (2.67g, productive rate: 74.5%), there are two pyrene compounds of piezallochromy character.
2. pair pyrene compound method for manufacturing thin film
To be fixed on paper on silica glass as substrate, this substrate is fixed on spin coating instrument, will prepare the DMSO solution (10 of compound 5
-4m) drip on substrate, with different rotating speeds spin coating, (rotation is when coated film, low rate start stage speed of rotation fixes on 400rpm, time is 5s, high speed rotating speed can fix on 2500rpm, time is 40s), spin coating liquid uniform spreading generate film room temperature is placed and made its seasoning, then put into vacuum drying oven dry 10 hours.After seasoning, film again, finally puts into vacuum drying oven for three times dry repeatedly.
3. compacting color change information storage
Spin coating is had to the paper of film as the carrier of information storage, use metal bar to carry out information recording as " pen ".Firmly write on paper with metal bar, the place that metal bar streaks presents green fluorescence pattern under ultra violet lamp, and the background color of paper film itself is blue.And whole paper film presents yellow under ordinary light, can't see any information.
Embodiment 2
Taking R structure as C
3h
7for example
The etherification reaction of compound 1: add 10mmol compound 1 (2.38g), acetone (100mL), 10mmol salt of wormwood (1.37g), compound 10mmol C in there-necked flask
12h
25br (1.23g), heating reflux reaction, after 12 hours, concentrates and obtains crude product, through column chromatography for separation, with methylene dichloride/sherwood oil (volume ratio 3:1) mixed solvent wash-out, rotary evaporation solvent obtains white solid compound 2 (2.04g, productive rate: 73.0%).
The hydrolysis reaction of compound 2: add 30mL ethanol, 60mL water, 5mmol compound 2 (1.42g) and 10mmol potassium hydroxide (0.56g) in there-necked flask, reflux 5 hours, cooling rear dropping 1M hydrochloric acid is to pH=3, filtration obtains white solid compound 3 (1.08g, productive rate: 96.4%).
The acyl chloride reaction of compound 3: thermometer, dropping funnel, reflux exchanger are being housed (with HCl and SO
2absorption unit) there-necked flask in add the thionyl chloride (5.95g) of 50mmol, in dropping funnel, add the mixing solutions of 10mmol compound 3 (2.24g) and catalyzer DMF (0.2mL), after at room temperature dropwising, be warmed up to 50 DEG C of insulations 2 hours, underpressure distillation is removed excessive thionyl chloride and is obtained compound 4 (2.46g, productive rate: 94.2%).
The friedel-crafts acylation of compound 4: 10mmol pyrene (2g) is dissolved in 30mL dithiocarbonic anhydride, and be placed in there-necked flask, add the compound 4(1.31g of 5mmol) after, in ice bath, be cooled to 0 degree, add aluminum chloride, reflux 12 hours, after product is cooling, pour in frozen water and stir 2 hours, with dichloromethane extraction, organic phase obtains thick product after filtering by anhydrous magnesium sulfate drying, further through column chromatography for separation, with methylene dichloride/sherwood oil (volume ratio 9:1) mixed solvent wash-out, rotary evaporation solvent obtains white solid compound 5 (2.10g, productive rate: 71.0%).
2. pair pyrene compound method for manufacturing thin film
To be fixed on paper on silica glass as substrate, this substrate is fixed on spin coating instrument, will prepare the DMSO solution (10 of compound 5
-4m) drip on substrate, with different rotating speeds spin coating, (rotation is when coated film, low rate start stage speed of rotation fixes on 400rpm, time is 5s,, high speed rotating speed can fix on 2500rpm, and the time is 40s), spin coating liquid uniform spreading generate film room temperature is placed and made its seasoning, then put into vacuum drying oven dry 10 hours.After seasoning, film again, finally puts into vacuum drying oven for three times dry repeatedly.
3. compacting color change information storage:
Spin coating is had to the paper of film as the carrier of information storage, use metal bar to carry out information recording as " pen ".Firmly write on paper with metal bar, the place that metal bar streaks presents green fluorescence pattern under ultra violet lamp, and the background color of paper film itself is blue.And whole paper film presents yellow under ordinary light, can't see any information.
Embodiment 3
Taking R structure as (CH
2cH
2o)
2cH
3for example
The etherification reaction of compound 1: add 10mmol compound 1 (2.38g), acetone (100mL), 10mmol salt of wormwood (1.37g), compound 10mmol Br (CH in there-necked flask
2cH
2o)
2cH
3(1.81g), heating reflux reaction, after 12 hours, concentrates and obtains crude product, through column chromatography for separation, with methylene dichloride/sherwood oil (volume ratio 3:1) mixed solvent wash-out, rotary evaporation solvent obtains white solid compound 2 (2.13g, productive rate: 71.0%).
The hydrolysis reaction of compound 2: add 30mL ethanol, 60mL water, 5mmol compound 2 (1.58g) and 10mmol potassium hydroxide (0.56g) in there-necked flask, reflux 5 hours, cooling rear dropping 1M hydrochloric acid is to pH=3, filtration obtains white solid compound 3 (1.21g, productive rate: 94.4%).
The acyl chloride reaction of compound 3: thermometer, dropping funnel, reflux exchanger are being housed (with HCl and SO
2absorption unit) there-necked flask in add the thionyl chloride (5.95g) of 50mmol, in dropping funnel, add the mixing solutions of 10mmol compound 3 (2.42g) and catalyzer DMF (0.2mL), after at room temperature dropwising, be warmed up to 50 DEG C of insulations 2 hours, underpressure distillation is removed excessive thionyl chloride and is obtained compound 4 (2.56g, productive rate: 96.1%).
The friedel-crafts acylation of compound 4: 10mmol pyrene (2g) is dissolved in 30mL dithiocarbonic anhydride, and be placed in there-necked flask, add the compound 4(1.45g of 5mmol) after, in ice bath, be cooled to 0 degree, add aluminum chloride, reflux 12 hours, after product is cooling, pour in frozen water and stir 2 hours, with dichloromethane extraction, organic phase obtains thick product after filtering by anhydrous magnesium sulfate drying, further through column chromatography for separation, with methylene dichloride/sherwood oil (volume ratio 9:1) mixed solvent wash-out, rotary evaporation solvent obtains white solid compound 5 (2.03g, productive rate: 67.2%).
2. pair pyrene compound method for manufacturing thin film
To be fixed on paper on silica glass as substrate, this substrate is fixed on spin coating instrument, will prepare the DMSO solution (10 of compound 5
-4m) drip on substrate, with different rotating speeds spin coating, (rotation is when coated film, low rate start stage speed of rotation fixes on 400rpm, time is 5s,, high speed rotating speed can fix on 2500rpm, and the time is 40s), spin coating liquid uniform spreading generate film room temperature is placed and made its seasoning, then put into vacuum drying oven dry 10 hours.After seasoning, film again, finally puts into vacuum drying oven for three times dry repeatedly.
3. compacting optically variable films structural changes:
Spin coating is had to the paper of film as the carrier of information storage, use metal bar to carry out information recording as " pen ".Firmly write on paper with metal bar, the place that metal bar streaks presents green fluorescence pattern under ultra violet lamp, and the background color of paper film itself is blue.And whole paper film presents yellow under ordinary light, can't see any information, this variation is determined by molecule arranging structure.
Embodiment 4
Taking R structure as (CH
2cH
2o)
12cH
3for example
The etherification reaction of compound 1: add 10mmol compound 1 (2.38g), acetone (100mL), 10mmol salt of wormwood (1.37g), compound 10mmol Br (CH in there-necked flask
2cH
2o)
12cH
3(6.23g), heating reflux reaction, after 12 hours, concentrates and obtains crude product, through column chromatography for separation, with methylene dichloride/sherwood oil (volume ratio 3:1) mixed solvent wash-out, rotary evaporation solvent obtains white solid compound 2 (5.04g, productive rate: 63.0%).
The hydrolysis reaction of compound 2: add 30mL ethanol, 60mL water, 5mmol compound 2 (3.92g) and 10mmol potassium hydroxide (0.56g) in there-necked flask, reflux 5 hours, cooling rear dropping 1M hydrochloric acid is to pH=3, filtration obtains white solid compound 3 (3.58g, productive rate: 93.2%).
The acyl chloride reaction of compound 3: thermometer, dropping funnel, reflux exchanger are being housed (with HCl and SO
2absorption unit) there-necked flask in add the thionyl chloride (5.95g) of 50mmol, in dropping funnel, add the mixing solutions of 10mmol compound 3 (7.24g) and catalyzer DMF (0.2mL), after at room temperature dropwising, be warmed up to 50 DEG C of insulations 2 hours, underpressure distillation is removed excessive thionyl chloride and is obtained compound 4 (7.35g, productive rate: 92.5%).
The friedel-crafts acylation of compound 4: 10mmol pyrene (2g) is dissolved in 30mL dithiocarbonic anhydride, and be placed in there-necked flask, add the compound 4(3.80g of 5mmol) after, in ice bath, be cooled to 0 degree, add aluminum chloride, reflux 12 hours, after product is cooling, pour in frozen water and stir 2 hours, with dichloromethane extraction, organic phase obtains thick product after filtering by anhydrous magnesium sulfate drying, further through column chromatography for separation, with methylene dichloride/sherwood oil (volume ratio 9:1) mixed solvent wash-out, rotary evaporation solvent obtains white solid compound 5 (4.23g, productive rate: 70.2%).
2. pair pyrene compound method for manufacturing thin film
To be fixed on paper on silica glass as substrate, this substrate is fixed on spin coating instrument, will prepare the DMSO solution (10 of compound 5
-4m) drip on substrate, with different rotating speeds spin coating, (rotation is when coated film, low rate start stage speed of rotation fixes on 400rpm, time is 5s,, high speed rotating speed can fix on 2500rpm, and the time is 40s), spin coating liquid uniform spreading generate film room temperature is placed and made its seasoning, then put into vacuum drying oven dry 10 hours.After seasoning, film again, finally puts into vacuum drying oven for three times dry repeatedly.
3. compacting color change information storage:
Spin coating is had to the paper of film as the carrier of information storage, use metal bar to carry out information recording as " pen ".Firmly write on paper with metal bar, the place that metal bar streaks presents green fluorescence pattern under ultra violet lamp, and the background color of paper film itself is blue.And whole paper film presents yellow under ordinary light, can't see any information, this variation is determined by molecule arranging structure.
Applicant's statement, the present invention illustrates detailed structure of the present invention and method by above-described embodiment, but the present invention is not limited to above-mentioned detailed structure and method, does not mean that the present invention must rely on above-mentioned detailed structure and method could be implemented.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. two pyrene compounds with piezallochromy character, is characterized in that, it has the structure shown in logical formula I:
In formula, R is selected from C
nh
2n+1, (CH
2cH
2o)
ncH
3, (CH
2cH
2o)
ncH
2cH
3or
in any one;
R
1be selected from C
nh
2n+1, (CH
2cH
2o)
ncH
3or (CH
2cH
2o)
ncH
2cH
3in any one;
N is any nature of 2～12.
2. a preparation method for two pyrene compounds with piezallochromy character as claimed in claim 1, is characterized in that, described method comprises the steps:
(1) etherification reaction of compound 1: add the salt of wormwood of compound 1, acetone, 1～4 equivalent, the compound R-Br of 1～4 equivalent in reaction vessel, after heating reflux reaction 12～24 hours, the concentrated crude product that obtains, through column chromatography for separation, with methylene dichloride/sherwood oil mixed solvent wash-out, evaporating solvent obtains white solid compound 2;
(2) hydrolysis reaction of compound 2: to the potassium hydroxide that adds ethanol, water, compound 2 and 1～4 equivalent in reaction vessel, reflux 2～10 hours, adds acid for adjusting pH to 2～4 after cooling, filters and obtains white solid compound 3;
(3) acyl chloride reaction of compound 3: the chloride reagent that adds 2～5 equivalents in reaction vessel, under room temperature, drip wherein compound 3 and catalyzer DMF(N, dinethylformamide) mixing solutions, be warmed up to 40～60 DEG C of insulations 2～4 hours, excessive chloride reagent is removed in distillation, obtains compound 4;
(4) friedel-crafts acylation of compound 4: pyrene is dissolved in dithiocarbonic anhydride, and be placed in reaction vessel, add the compound 4 of 1～4 equivalent to it, then be cooled to 0～5 DEG C, add aluminum chloride, reflux 12～18 hours, after product is cooling, pour in frozen water and stir 2～5 hours, with dichloromethane extraction, after organic phase dry filter, obtain thick product, further, through column chromatography for separation, with methylene dichloride and sherwood oil mixed solvent wash-out, evaporating solvent obtains having two pyrene compounds of piezallochromy character;
R is selected from C
nh
2n+1, (CH
2cH
2o)
ncH
3, (CH
2cH
2o)
ncH
2cH
3or
in any one;
R
1be selected from C
nh
2n+1, (CH
2cH
2o)
ncH
3or (CH
2cH
2o)
ncH
2cH
3in any one;
N is 2～12 random natural number.
3. method as claimed in claim 2, is characterized in that, step (1) rotary evaporation solvent;
Preferably, described in step (1), the volume ratio of methylene dichloride and sherwood oil is 1:10～10:1, preferably 1:1～8:1.
4. method as claimed in claim 2 or claim 3, is characterized in that, the described chloride reagent of step (3) is that thionyl chloride is or/and phosphorus pentachloride;
Preferably, the described distillation of step (3) is underpressure distillation.
5. the method as described in one of claim 2-4, is characterized in that, step (4) is cooled to 0～5 DEG C in ice bath;
Preferably, step (4) obtains thick product after by anhydrous magnesium sulfate or Calcium Chloride Powder Anhydrous dry filter.
6. the method as described in one of claim 2-5, is characterized in that, the volume ratio of step (4) methylene dichloride and sherwood oil is 1:10～10:1, preferably 5:1～10:1;
Preferably, step (4) rotary evaporation solvent.
7. a preparation method with two pyrene compound films of piezallochromy character, is characterized in that, described method comprises the steps:
(1) solution of preparing two pyrene compounds with piezallochromy character claimed in claim 1 is spin coating liquid;
(2) substrate is fixed on spin coating instrument, spin coating drop is added on substrate, spin coating makes spin coating liquid uniform spreading generate film, and room temperature is placed and made it dry;
(3) optionally, repeat above-mentioned spin coating step;
(4) vacuum-drying, obtains having two pyrene compound films of piezallochromy character.
8. method as claimed in claim 7, is characterized in that, described substrate is selected from silica glass, ito glass, Calcium Fluoride (Fluorspan) glass, silicon chip, PDMS or is fixed on any one in the paper on silica glass;
Preferably, in the time that described substrate is silica glass, ito glass or Calcium Fluoride (Fluorspan) glass, described substrate is carried out to following pre-treatment:
Utilize washing composition to clean in silica glass, ito glass or Calcium Fluoride (Fluorspan) glass and clean with deionized water, the sodium hydroxide solution that is placed in 40wt% boils, and taking-up is cleaned and soaks, then drying at room temperature with deionized water.
9. method as claimed in claim 7 or 8, is characterized in that, first, with rotating speed spin coating 5～10s of 400～600rpm, then with rotating speed spin coating 40～60s of 2500～3000rpm, makes spin coating liquid uniform spreading generate film;
Preferably, the described vacuum drying time is 6～10 hours.
10. a purposes for two pyrene compounds with piezallochromy character as claimed in claim 1, is characterized in that, it is for information storage.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749518A (en) * | 2016-11-10 | 2017-05-31 | 国家纳米科学中心 | A kind of polypeptide nano material containing double pyrenyl groups and its preparation method and application |
| CN108470852A (en) * | 2018-04-10 | 2018-08-31 | 南京邮电大学 | A kind of preparation method of modifying interface perovskite solar cell |
| CN108947933A (en) * | 2018-08-17 | 2018-12-07 | 天津师范大学 | The diethyl terephthalate class compound and preparation method and purposes of power mutagens color |
| CN110564414A (en) * | 2019-10-08 | 2019-12-13 | 河北工业大学 | Preparation method of carbon dots with adjustable force-induced fluorescence color |
| CN115171526A (en) * | 2022-06-17 | 2022-10-11 | 昆山国显光电有限公司 | Display panel and method for determining stress generation area of display panel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010038252A2 (en) * | 2008-10-02 | 2010-04-08 | Università Degli Studi Di Roma La Sapienza | Carbonyl derivatives having a c3 symmetry, their preparation and uses thereof |
| CN101460588B (en) * | 2006-05-31 | 2013-05-08 | 默克专利有限公司 | New materials for organic electroluminescent devices |
-
2014
- 2014-04-14 CN CN201410147961.5A patent/CN103922915B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101460588B (en) * | 2006-05-31 | 2013-05-08 | 默克专利有限公司 | New materials for organic electroluminescent devices |
| WO2010038252A2 (en) * | 2008-10-02 | 2010-04-08 | Università Degli Studi Di Roma La Sapienza | Carbonyl derivatives having a c3 symmetry, their preparation and uses thereof |
Non-Patent Citations (2)
| Title |
|---|
| LEI WANG ET AL.: "Supramolecular Nano-Aggregates Based on Bis(Pyrene) Derivatives for Lysosome-Targeted Cell Imaging", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》, vol. 117, 26 November 2013 (2013-11-26), pages 26811 - 26820 * |
| 陈莹等: "一种基于二芘基苯的高效有机固态蓝色荧光化合物", 《有机化学研究简报》, 31 December 2012 (2012-12-31), pages 589 - 592 * |
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| CN106749518A (en) * | 2016-11-10 | 2017-05-31 | 国家纳米科学中心 | A kind of polypeptide nano material containing double pyrenyl groups and its preparation method and application |
| CN106749518B (en) * | 2016-11-10 | 2021-01-01 | 国家纳米科学中心 | Polypeptide nano material containing pyrene group and preparation method and application thereof |
| CN108470852A (en) * | 2018-04-10 | 2018-08-31 | 南京邮电大学 | A kind of preparation method of modifying interface perovskite solar cell |
| CN108947933A (en) * | 2018-08-17 | 2018-12-07 | 天津师范大学 | The diethyl terephthalate class compound and preparation method and purposes of power mutagens color |
| CN108947933B (en) * | 2018-08-17 | 2022-12-13 | 天津师范大学 | Force-induced color-changing diethyl terephthalate compound, preparation method and application thereof |
| CN110564414A (en) * | 2019-10-08 | 2019-12-13 | 河北工业大学 | Preparation method of carbon dots with adjustable force-induced fluorescence color |
| CN110564414B (en) * | 2019-10-08 | 2022-03-01 | 河北工业大学 | Preparation method of carbon dots with adjustable force-induced fluorescence color |
| CN115171526A (en) * | 2022-06-17 | 2022-10-11 | 昆山国显光电有限公司 | Display panel and method for determining stress generation area of display panel |
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