CN102875398B - Application of triphenylamine derivative as reversible force stimulus fluorescent switch material - Google Patents
Application of triphenylamine derivative as reversible force stimulus fluorescent switch material Download PDFInfo
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- CN102875398B CN102875398B CN201210192638.0A CN201210192638A CN102875398B CN 102875398 B CN102875398 B CN 102875398B CN 201210192638 A CN201210192638 A CN 201210192638A CN 102875398 B CN102875398 B CN 102875398B
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- triphenylamine derivative
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- fluorescent switch
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- 239000000463 material Substances 0.000 title claims abstract description 33
- 125000006617 triphenylamine group Chemical group 0.000 title claims abstract description 29
- 230000002441 reversible effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000004936 stimulating effect Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention discloses application of a triphenylamine derivative as a reversible force stimulus fluorescent switch material. The structure formula of the triphenylamine derivative is as shown in formula (1); the force stimulus response fluorescent switching performance of the triphenylamine derivative has the characteristics of high contrast, self-restoring capability and good circularity. The triphenylamine derivative (1) is convenient in preparation device, and can be applied to the field of fluorescent switches, sensors, storage, fake resistance, display and the like as the reversible force stimulus fluorescent switch material.
Description
(1) technical field
The present invention relates to a kind of triphenylamine derivative stimulates the application of fluorescent switch material as reversible power, be applicable to the fields such as fluorescent switch, sensor, false proof, storage and demonstration.
(2) background technology
The phenomenon that fluorescence color changes in the time that material is applied in mechanical force is called piezallochromy phenomenon, and the material with piezallochromy phenomenon at least has stable state or the metastable state accumulation mode of two kinds of impacts that are stressed.After the power that is being subject to stimulates, intramolecular action power changes, and causes packing of molecules mode to change, make material from a kind of ordered structure become another kind of in order or partial order, disordered structure, the photophysical property of material changes thereupon.Then, after heating, solvent etc. are processed, it is original that the accumulation mode of molecule can revert to, and realizes the reversibility that fluorescence color changes.At present mainly concentrate on these several classes of small molecules, oligopolymer, liquid crystal and doped polymer to thering is the research of piezallochromy phenomenon, the state scientists such as the U.S., Japan after deliberation relatively go deep into.
(the J.Am.Chem.Soc. such as Yasuhiko Sagara, 2007, the pyrene derivatives that 129:1520-1521) synthesizes and found to have four N-hexyl paraphenylene terephthalamide bases to form, in the time that the power that is subject to stimulates, material becomes green fluorescence by blue-fluorescence originally, after heating, can again become blue-fluorescence.This is due to the variation of the variation of torsion(al)angle between phenyl ring between molecule and pyrene ring and the ratio of clustered pattern and hydrogen bond, finally makes the fluorescence color of material change.
(the Asian J.Chem. such as Chi Zhenguo, 2011,6 (3): 808-811) synthesized tetraphenyl ethylene derivative, in the time that material is subject to power stimulation, the fluorescence color of solid has become yellow by original green, reverts to original strong green fluorescence after heat treated.This is because the space steric effect between aromatic ring makes all or part of space structure distortion of molecule.Because the space structure of distortion makes pi-pi bond reaction force attenuation, after forces are applied, molecular conformation complanation or molecular slippage, increase conjugated degree, and fluorescence color changes.
But the reversible piezochromic phenomenon of report is mainly the material fluorescence color transformation under External Force Acting at present, and the variation of rare fluorescence intensity; In addition, realize reversible temperature and be generally greater than 100 ° of C, (J.Am.Chem.Soc.2010,132,13675 – 13683) will limit the application of this type of material so greatly.Under external force stimulates, realize opening and recovering voluntarily within a certain period of time of fluorescence, in actual life, have using value widely.
(3) summary of the invention
The object of this invention is to provide a kind of triphenylamine derivative stimulates the application of fluorescent switch material as reversible power, this material under external force stimulates from be converted to hyperfluorescenceZeng Yongminggaoyingguang emission state without fluorescent emission, have contrast gradient high, can recover voluntarily, feature that cyclicity is good.
The invention provides the triphenylamine derivative shown in a kind of formula (I), this compound causes that because accumulation mode changes fluorescence intensity change presents reversible power stimuli responsive Enhancement of Fluorescence stressed in the situation that, external force stimulate under from be converted to hyperfluorescenceZeng Yongminggaoyingguang emission state without fluorescent emission, through the post-stimulatory material of external force can return to before not stressed without fluorescence state, stimulate fluorescent switch material therefore can be used as reversible power
The preparation of triphenylamine derivative of the present invention (I) can reference (Chem.Lett., 2011,40 (9), 1036-1038).
Described triphenylamine derivative has the characteristic that contrast gradient is high in the time stimulating fluorescent switch material as reversible power: after pressure is 2MPa-10MPa effect, triphenylamine derivative shown in described formula I under ultraviolet lamp by becoming very bright blue-fluorescence without fluorescence before not pressing, fluorescence quantum efficiency reaches 12.3%, exceedes (0.4%) before not exerting pressure 30 times.
Described triphenylamine derivative is in the time stimulating fluorescent switch material as reversible power, can recover voluntarily in several ways, such as after the pressure-acting of 2MPa-10MPa, triphenylamine derivative shown in formula I under ultraviolet lamp by becoming blue-fluorescence without fluorescence before not pressing, again described material is placed in to room temperature (20-25 DEG C) 0.5h-3h, or be placed in 120 ~ 60 ° of C thermostat container 0.5 ~ 2min, before described material can return to voluntarily and originally not exert pressure under ultraviolet lamp without fluorescence; Or, material after stressed is placed in to organic vapor and places 5s-5min, before described material also can return to and originally not exert pressure under ultraviolet lamp without fluorescence, described organic solvent can be methyl alcohol, ethanol, normal hexane, sherwood oil, ethyl acetate, acetone, toluene etc.; Again or organic solvent is dripped to 1-5 drip on the material after stressed, after solvent evaporates, described material under ultraviolet lamp, also return to before the application of force not without fluorescence.
In addition, when described triphenylamine derivative stimulates fluorescent switch material as reversible power, also there is the feature that cyclicity is good: stimulate in the power through 5-30 time-certainly recover, after circulation, still to there is good switch.
Reversible power stimulation fluorescent switch material of the present invention can be specifically for preparing reversible power stimuli responsive fluorescent switch device.Crystalline solid or the powder solid of described triphenylamine derivative (I), can in substrate, apply by film technique triphenylamine derivative (I) film mode or make the fluorescent switch device with power stimuli responsive performance by the mode that triphenylamine derivative (I) is doped in the polymkeric substance such as polymethylmethacrylate.
Compared with prior art, beneficial effect of the present invention is: the organic molecule that the invention provides a kind of power of having stimuli responsive fluorescent switch performance---triphenylamine derivative (I), its power stimuli responsive fluorescent switch performance have contrast gradient high, can recover voluntarily, feature that cyclicity is good.Described triphenylamine derivative (I) stimulates fluorescent switch material fabricate devices convenient as reversible power, can be applicable to the fields such as fluorescent switch, sensor, storage, false proof and demonstration.
(4) brief description of the drawings
Fig. 1 is crystal powder in the embodiment of the present invention 1 (I) photo under ultraviolet lamp before and after the application of force, (a) be the fluorescence that does not pass through external force excitor substance, (b) being the fluorescence of the material after External Force Acting, is (c) to mark "+" shape on the material not stimulating through external force;
Fig. 2 is that crystal powder in the embodiment of the present invention 2 (I) application of force is placed on the fluorescence spectrum in different time in room temperature;
Fig. 3 is that the power of triphenylamine derivative in the embodiment of the present invention 4 (I) stimulate-is recovered cycle performance certainly;
Fig. 4 be in the embodiment of the present invention 5, adulterate triphenylamine derivative (I) polymeric film power stimulation-solvent vapo(u)r recover cycle performance.
(5) embodiment
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited to this:
Each embodiment of the present invention for the reactive force of triphenylamine derivative (I) or fluorescent switch device all at 2 ~ 10MPa.
Embodiment 1
Getting triphenylamine derivative crystal powder (I) 0.1g spreads on quartz plate or is placed in mortar, under ultraviolet lamp, do not show fluorescence, when being subject to, key is scraped shearing force or pestle is made the very strong blue-fluorescence of used time appearance, removes external force, and part of the force still keeps strong blue-fluorescence.Use ethanol or sherwood oil to process the sample after stressed, fluorescence intensity dimmed and return to before stressed without fluorescence state.
Embodiment 2
0.1g triphenylamine derivative crystal powder (I) is spread on quartz plate, with key scrape fully press after its fluorescence obviously strengthen, be placed under room temperature after 3h its fluorescence obviously dimmed, almost can't see fluorescence.
Embodiment 3
It is 10 that triphenylamine derivative crystal powder (I) is made into concentration
-4the tetrahydrofuran solution of mol/L, is then added drop-wise to above-mentioned solution on filter paper, is placed in baking oven and dries, and on filter paper, scrapes and writes or symbol with key.Under ultraviolet lamp, write or the place of symbol becomes strong blue-fluorescence.Above-mentioned sample is put in 80 DEG C of baking ovens and is reverted to without fluorescence after 1min.
Embodiment 4
By triphenylamine derivative (I) spin-coating film on quartz plate, fully to press rear fluorescence and obviously strengthen, fluorescence quantum efficiency reaches 12.3%.Then on quartz plate, drip 3 of methyl alcohol, fluorescence intensity obviously declines, almost without fluorescence.Repeatedly exert pressure and drip after solvent 5-30 time, finding that it still has good fluorescent switch performance.
Embodiment 5
Taking chloroform as solvent, by triphenylamine derivative (I) by solution blending in polymethylmethacrylate (triphenylamine derivative I is 20wt% with respect to the weight percentage of polymethylmethacrylate), and be spun in substrate of glass, the doped polymer film obtaining after solvent evaporates does not show fluorescence under ultraviolet lamp.In the time being subject to stretching, extruding or shearing force, occur very strong blue-fluorescence, remove after external force, part of the force still keeps strong blue-fluorescence.Film is placed in to methylene dichloride atmosphere fluorescence intensity and reduces, show hardly fluorescence.Power stimulation-solvent vapo(u)r recovers can be through repeatedly circulation.
Claims (2)
1. the triphenylamine derivative shown in formula (I) stimulates the application of fluorescent switch material as a kind of reversible power,
2. application as claimed in claim 1, is characterized in that: described reversible power stimulates fluorescent switch material for the preparation of the fluorescent switch device with power stimuli responsive performance.
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| CN104003886B (en) * | 2013-02-25 | 2015-11-25 | 北京师范大学 | Many nitros replace preparation and the application thereof of tetraphenylethylene compound |
| CN105175583B (en) * | 2015-08-09 | 2017-06-13 | 同济大学 | Acetophenones light trigger, preparation method and applications of one class with biphenyl as conjugated structure |
| CN105567217B (en) * | 2015-12-15 | 2017-12-01 | 华南理工大学 | A kind of more stimuli responsive organic molecule luminescent materials and preparation and application |
| CN110117253A (en) * | 2018-02-05 | 2019-08-13 | 三峡大学 | A kind of organic fluorescent dye with piezallochromy characteristic, preparation method and applications |
| CN112939794B (en) * | 2021-02-24 | 2022-07-29 | 温州大学 | Phosphorescent emitting material with high quantum yield, and preparation method and application thereof |
| CN114634546B (en) * | 2022-03-22 | 2023-07-28 | 湖州学院 | High-luminous-power electrochromic material from red to near infrared and preparation method thereof |
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Non-Patent Citations (5)
| Title |
|---|
| JP特开2004-203765A 2004.07.22 |
| Material Design for Piezochromic Luminescence: Hydrogen-Bond-Directed Assemblies of a Pyrene Derivative;Yoshimitsu Sagara et al;《J. AM. CHEM. SOC.》;20070124;第129卷(第6期);1520-1521 * |
| Multistimuli Two-Color Luminescence Switching via Different Slip-Stacking of Highly Fluorescent Molecular Sheets;Seong-Jun Yoon et al;《J. AM. CHEM. SOC.》;20100914;第132卷(第39期);13675–13683 * |
| Seong-Jun Yoon et al.Multistimuli Two-Color Luminescence Switching via Different Slip-Stacking of Highly Fluorescent Molecular Sheets.《J. AM. CHEM. SOC.》.2010,第132卷(第39期),13675–13683. |
| Yoshimitsu Sagara et al.Material Design for Piezochromic Luminescence: Hydrogen-Bond-Directed Assemblies of a Pyrene Derivative.《J. AM. CHEM. SOC.》.2007,第129卷(第6期),1520-1521. |
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