CN104496933B - A kind of photosensitive chirality macrocycle molecule and its production and use - Google Patents
A kind of photosensitive chirality macrocycle molecule and its production and use Download PDFInfo
- Publication number
- CN104496933B CN104496933B CN201410668224.XA CN201410668224A CN104496933B CN 104496933 B CN104496933 B CN 104496933B CN 201410668224 A CN201410668224 A CN 201410668224A CN 104496933 B CN104496933 B CN 104496933B
- Authority
- CN
- China
- Prior art keywords
- chirality
- photosensitive
- macrocycle molecule
- preparation
- molecule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 C1OCCOc(ccc2c3cccc2)c3-c(c(cccc2)c2cc2)c2OCCOCCOc2ccccc2N*c(cccc2)c2OC1 Chemical compound C1OCCOc(ccc2c3cccc2)c3-c(c(cccc2)c2cc2)c2OCCOCCOc2ccccc2N*c(cccc2)c2OC1 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of photosensitive chirality macrocycle molecule and its production and use, belong to light responsive material preparation field, the preparation method of this photosensitive chirality macrocycle molecule, use following step: a) by oligomeric ethylene glycol, NaOH and p-methyl benzene sulfonic chloride under an inert atmosphere, in tetrahydrofuran solvent reaction obtain intermediate 1；B) being dissolved in N N-dimethylformamide solvent by described intermediate 1, o-dihydroxy azobenzene, cesium carbonate and dibenzo 18 hat six, reaction obtains intermediate 2 under an inert atmosphere；C) being dissolved in N N-dimethylformamide solvent by described intermediate 2, chiral binaphthyl phenolic compound, cesium carbonate and dibenzo 18 hat six, reaction obtains target product in an inert atmosphere.The photosensitive chirality macrocycle molecule of the present invention is easily-synthesized, good stability, has the ability of selective complexation chirality ammonium salt, and can be realized complexing and the release of chirality ammonium salt by azo cis-trans isomerism behavior.
Description
Technical field
The present invention relates to a kind of photosensitive chirality macrocycle molecule and its preparation method and application, belong to light responsive material system
Standby field.
Background technology
Azo-compound is the organic compound that a class is important, is widely used for dyestuff and analytical reagent.Azo
Compound regulates and controls at optical storage material, nonlinear optical material, liquid crystal material, biologically active light, nanometer material
There is important using value in the fields such as material.Compound containing azobenzene becomes with its distinctive photoresponse character
One Disciplinary Frontiers of functional material research, shows vast potential for future development.Dinaphthalenes compounds is in recent years
Study the more biaryl aroma compounds with axle asymmetric nature.Naphthalene nucleus itself does not has chirality, but when two naphthalenes
Ring is connected at 1, and after 2,2 ' positions introduce two substituents, has just become a chirality with C2 axle
Compound.On the one hand, the volume of two naphthalene nucleus makes more greatly its space structure have rigidity；On the other hand, two
Having certain rotation leeway between individual ring, thus have certain toughness, this also allows for it becomes asymmetric
Chiral source excellent in synthesis.Seldom there is a kind of molecule can be controlled the complexing power of molecule by illumination at present.
Therefore, those skilled in the art is devoted to develop and a kind of new has illumination response, the adjustable light of chirality size
Quick chirality macrocycle molecule, makes its distortion constant in liquid crystal change by the change of illumination wavelength, controls opponent
The complexing of property ammonium salt and release.
Summary of the invention
It is desirable to provide a kind of photosensitive chirality macrocycle molecule and preparation method thereof and purposes, the light of the present invention rings
Answering chirality macrocycle molecule Heat stability is good, be readily synthesized, structure is prone to modify and cutting, and speed of photoresponse is fast,
The recognition capability of chiral ammonium radical ion is stronger.
The photosensitive chirality macrocycle molecule of the present invention, has a following general structural formula:
In formula, R1Selected from-H ,-CH3、-CF3、-F、-NO2、-OCH3Or-COOCH3；N is for being not more than
The positive integer of 10, preferably n are not more than 5.
The invention also discloses the preparation method of this photosensitive chirality macrocycle molecule, it uses following step:
A), by oligomeric ethylene glycol, NaOH and p-methyl benzene sulfonic chloride under an inert atmosphere, in tetrahydrofuran solvent
8-12h is stirred at room temperature, purifies washing and obtain intermediate 1 after drying；
B), described intermediate 1, o-dihydroxy azobenzene, cesium carbonate and dibenzo 18 hat six is dissolved in N-N bis-
In NMF solvent, under an inert atmosphere, it is heated to reflux 10-15h, separates, wash and dried
To intermediate 2；
C), described intermediate 2, chiral binaphthyl phenolic compound, cesium carbonate and dibenzo 18 hat six is dissolved in N-N
In solvent dimethylformamide, in an inert atmosphere, stirring reaction 60-80h under room temperature, separate, wash also
Obtain target product after drying.
The mol ratio of the described oligomeric ethylene glycol of step a), NaOH and p-methyl benzene sulfonic chloride is preferably 1:
2-2.3:2-2.3, more preferably 1:2.2:2.2.
The described intermediate of step b) 1, o-dihydroxy azobenzene, cesium carbonate and dibenzo 18 hat six mole
Ratio preferably 3-3.4:1:3-3.4:0.3-0.35, more preferably 3:1:3:0.3.
The described dried employing silica gel column chromatography of step b) is vacuum dried again, flowing during described silica gel column chromatography
It is preferably n-hexane: ethyl acetate=4:1 (v/v) mutually.
Described in step c), the structural formula of chiral binaphthyl phenolic compounds is:
R in formula1Selected from-H ,-CH3、-CF3、-F、-NO2、-OCH3Or-COOCH3。
The described intermediate of step c) 2, chiral binaphthyl phenolic compound, cesium carbonate and dibenzo 18 hat six
Mol ratio is preferably 1:1-1.2:3-3.3:0.3-0.32, more preferably 1:1.1:3:0.3.
The described dried employing silica gel column chromatography of step c) is vacuum dried to obtain target product, described silica gel column layer again
Flowing during analysis is n-hexane mutually: ethyl acetate=3:2 (v/v).
Inert atmosphere described above can be nitrogen, argon gas, helium, neon etc..
The purposes of photosensitive chirality macrocycle molecule of the present invention, it can be used for being complexed chirality ammonium ion and by illumination ripple
Long and intensity controls complexing and the release of chirality ammonium salt, can be used for the reversible tune of the pitch to cholesteryl liquid crystal
Joint.
The synthetic route of light-sensitive catalyst agent of the present invention is as follows:
The photosensitive chirality macrocycle molecule of the present invention can be complexed chirality ammonium ion and can be controlled by illumination wavelength and intensity
The complexing of chirality ammonium salt processed and release.Specifically comprise the following steps that
Photosensitive chirality macrocycle molecule is made into concentration is 2 × 10-5The tetrahydrofuran solution of mol/L, heats 8
H, irradiates with the ultraviolet light of 365nm, measures the ultraviolet-visible absorption spectroscopy of different exposure time solution until light
Spectrum is not changing, and adds the chirality ammonium salt solution of variable concentrations in solution, measures the UV, visible light of solution
Absorption spectrum, when ammonium salt concentration and photosensitive chirality macrocycle molecule concentration reach to balance than during equal to 0.76.440
Under the radiation of visible light of nm, measure the ultraviolet-visible absorption spectroscopy of different exposure time solution until spectrum does not exists
Change, in solution, add the chirality ammonium salt solution of variable concentrations, measure the ultravioletvisible absorption light of solution
Spectrum, when ammonium salt concentration and photosensitive chirality macrocycle molecule concentration reach balance than during equal to 0.36, macrocyclic structure
Change causes the complexing power of the chiral ammonium salt of this molecule to there occurs change.
The present invention photosensitive chirality macrocycle molecule has cis-trans isomerism, and the dinaphthalene chirality size of two kinds of isomers is not
With, the pitch of adjustable cholesteric liquid crystal, specifically comprise the following steps that
The photosensitive chiral molecules of 0.002g is added in 0.100g liquid crystal, after heating reaches clearing point process 1 hour,
Injecting in wedged liquid crystal cell of α=0.01 °, measuring 365nm illumination 140s pitch with petrographic microscope is 1689
μm, uses 300 seconds pitch of 440nm illumination instead and becomes 2356 μm, and this process quickly responds and reversible.
The beneficial effects of the present invention is:
The light using different wave length irradiates photosensitive macrocycle molecule, can achieve the complexing of chiral ammonium radical ion with
Release and the reversible regulation of pitch to cholesteryl liquid crystal.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 photosensitive azo chiral ring molecule1H NMR(600M Hz,CD3OD)
Spectrogram.
Fig. 2 is the embodiment of the present invention 1 photosensitive azo chiral ring molecule13C NMR (150M Hz, CDCl3)
Spectrogram.
Fig. 3 is circular dichroism spectrogram in the embodiment of the present invention 2.
Fig. 4 is the embodiment of the present invention 2 photosensitive azo chiral molecules, and the 365nm uv-exposure time is purple to solution
The impact of outer visible ray spectrogram.
Fig. 5 is that adulterate in the embodiment of the present invention 3 cholesteric liquid crystal of photosensitive azo chiral ring molecule is in angle
Petrographic microscope (POM) figure of shooting in the wedge shape box of 0.01 °, exposes 365nm ultraviolet light 140s and 440
Pitch 1689 μm of nm visible ray 160s refraction of light path generation and 2356 μm, middle graph is for just having loaded wedge shape
Pitch after in liquid crystal cell is 2065 μm.
Fig. 6 is that the embodiment of the present invention 2 photosensitive azo molecules solution adds variable concentrations chirality ammonium radical ion solution
Ultraviolet-visible spectrogram, and the relation of concentration and absorbance；A) under 365nm illumination, different chirality ammonium salts
The complex compound ultra-violet absorption spectrum of concentration；B) under 365nm illumination, the impact of Subjective and Objective concentration comparison absorbance；
C) under 440nm illumination, the complex compound ultra-violet absorption spectrum of different chirality ammonium salt concentration；D) under 440nm illumination,
The impact of Subjective and Objective concentration comparison absorbance.
Fig. 7 is 1H NMR (300MHz, the CDCl3) spectrogram of intermediate 1 described in embodiment 1.
Fig. 8 is the infrared spectrum of intermediate 2 described in embodiment 1.
Detailed description of the invention
Following embodiment is to further illustrate to explain as to the technology of the present invention content for present invention
Releasing, but the flesh and blood of the present invention is not limited in described in following embodiment, those of ordinary skill in the art can
With and any simple change based on true spirit should be known or replace and all should belong to the present invention and wanted
The protection domain asked.
The preparation of embodiment 1:R type dinaphthalene photosensitive chirality macrocycle molecule
A). by diethylene glycol 5.000g (0.0472mol), NaOH 4.774g (0.1038mol) and to Methyl benzenesulfonyl
Chlorine 19.72g (0.1038mol) is dissolved in 40ml oxolane under nitrogen protection, and 10h is stirred at room temperature,
Being recrystallized in distilled water by product, washing also obtains white solid powder intermediate 1 after drying, its structural formula
As follows:
Nuclear-magnetism spectrum such as Fig. 7,1H NMR (300MHz, CDCl3) data: δ (ppm) 2.428 (s, 6H), 3.588 (t,
J=4.8Hz, 4H), 4.035 (t, J=4.8Hz, 4H), 7.319 (d, J=8.1Hz, 4H), 7.774 (d, J=8.1Hz,
4H)。
B). take described intermediate 1 5.8g (0.014mol), o-dihydroxy azobenzene 1g (0.0047mol), cesium carbonate 4.56
G (0.014mol) and dibenzo 18 hat six 0.504g (0.0014mol) are dissolved in 50ml N, N-dimethyl formyl
In amine, under nitrogen atmosphere, stirring 13h at 80 DEG C, reaction adds ethyl acetate, successively with saturated after terminating
Ammonium chloride solution, saturated sodium bicarbonate solution and saturated nacl aqueous solution wash 2-3 time, add anhydrous sodium sulfate
Crocus solid intermediate 2 is obtained after dried silica gel column chromatography (n-hexane: ethyl acetate=4:1) vacuum drying,
Its structural formula is as follows:
Can be seen that by infrared spectrum 8 peak of 3002 is aromatic ring frame hydrogen stretching vibration, 2940 and 2862 are
Methyl hydrogen stretching vibration, 1610 peaks are the vibration of nitrogen nitrogen double bond, and 1539 and 1477 is aromatic ring frame vibration.Infrared
IR (KBr): 3002,2940,2862,1610,1539,1477,786cm-1；
C). by described intermediate 2 0.1g (0.00016mol), R-1,1'-union-2-naphthol 0.05g (0.000176mol), carbon
Acid caesium 0.156g (0.00048mol) and dibenzo 18 hat six 0.0172g (0.000048mol) are dissolved in 200
In the DMF of ml, under nitrogen atmosphere, stirring reaction 72h under room temperature, reaction end subtracts
Pressure removes solvent, adds ethyl acetate, successively with saturated ammonium chloride solution, saturated sodium bicarbonate solution and saturated
Sodium chloride solution washs 2-3 time, adds anhydrous sodium sulfate dried silica gel column chromatography (n-hexane: ethyl acetate
=3:2, v/v), obtain Chinese red solid target compound after vacuum drying, its structural formula is as follows:
Fig. 1 provides the proton nmr spectra of this material:1H–NMR(600MHz,CD3OD,25℃):δ(ppm)
3.62-3.66 (m, 3H), 3.85 (t, 5H, J=4.2Hz), 3.98-4.06 (m, 3H), 4.22 (t, 5H, J=4.2Hz),
6.72 (d, 2H, J=6Hz, Ar), 6.77 (t, 2H, J=7.8Hz, Ar), 6.95 (d, 2H, J=7.8Hz, Ar),
7.11 (t, 2H, J=7.8Hz, Ar), 7.16 (t, 3H, J=7.8Hz, Ar), 7.21 (d, 3H, J=7.8Hz, Ar), 7.40
(t, 3H, J=4.8Hz, Ar), 7.7 (d, 3H, J=7.8Hz, Ar).Wherein 3.62-4.22 is 16 hydrogen of alkoxy chain,
6.72-7.70 is 20 hydrogen of phenyl ring, is methylene chloride near δ 5.2, is solvent methanol near δ 3.3,
It is water near δ 1.5, is petroleum ether near δ 0.8 and δ 1.25.
Fig. 2 provides this compound carbon-13 nmr spectra:13C NMR(150MHz,CDCl3,25℃):δ155.9,
151.3,147.1,146.7,133.9,131.1,126.0,125.0,123.6,122.8,120.7,
116.7,74.6,73.5,72.3,71.1.This compound is carried out mass spectral analysis EI-MS:m/z=641
[M+H]+, corresponding theoretical molecular is 640.
Embodiment 2: photoresponse complexing and the release of chiral ammonium salt
Taking target product 2mg and being made into concentration is 2 × 10-5The tetrahydrofuran solution of mol/L, by this solution 55 DEG C
Dark processing 8h, exposes under 365nm illumination, measures circular dichroism spectra and the purple of material under different exposure time
Outer visible spectrum, in Fig. 3, square line is the circular dichroism spectrogram of solution after long-time 365nm uv-exposure,
Open triangles line is the circular dichroism spectrogram of solution after long-time 440nm exposes, it can be seen that after different illumination
The CD signal of molecule changes, and chirality changes, the ultraviolet-visible under different light application times in Fig. 4
Spectrogram line marks the most in the drawings, along with the UV absorption at the increase 365nm of time for exposure reduces, and 440nm
The UV absorption at place increases, and illustrates that this molecule has the character of illumination response, adds different dense in reaction mixture
The ALANINE ethyl ester salting liquid of degree measures the uv-vis spectra of complex solution, when ammonium salt concentration and light
Quick chirality macrocycle molecule concentration reaches balance than during equal to 0.76；On carrying out equally under 440nm visible ray shines
State operation, when ammonium salt concentration and photosensitive chirality macrocycle molecule concentration reach to balance than during equal to 0.36.This enforcement
In example, the structural formula of ALANINE carbethoxy hydrochloride is as follows:
Embodiment 3: the change of cholesteric liquid crystal distortion power constant
Take 0.1g liquid crystal and add 0.002g target product, thermal station is heated to the clearing point of liquid crystal, constant temperature 1
H makes it join after being sufficiently mixed in wedged liquid crystal cell.This wedged liquid crystal cell is seen under petrographic microscope
Examining, the pitch length measuring liquid crystal is 2065 μm.Wheel uses the light liquid like this of 365nm and 440nm instead respectively
Brilliant device, measuring pitch length is 1689 μm and 2356 μm such as Fig. 5.
The preparation of embodiment 4:S type dinaphthalene photosensitive chirality macrocycle molecule
A). by diethylene glycol 5.000g (0.0472mol), NaOH 4.774g (0.1038mol) and to Methyl benzenesulfonyl
Chlorine 19.72g (0.1038mol) is dissolved in 40ml oxolane under nitrogen protection, and 10h is stirred at room temperature,
Being recrystallized in distilled water by product, washing also obtains white solid powder intermediate 1 after drying, and structural formula is such as
Under:
B). take described intermediate 1 5.8g (0.014mol), o-dihydroxy azobenzene 1g (0.0047mol), cesium carbonate 4.56
G (0.014mol) and dibenzo 18 hat six 0.504g (0.0014mol) are dissolved in 50ml N, N-dimethyl formyl
In amine, under nitrogen atmosphere, stirring 13h at 80 DEG C, reaction adds ethyl acetate, successively with saturated after terminating
Ammonium chloride solution, saturated sodium bicarbonate solution and saturated nacl aqueous solution wash 2-3 time, add anhydrous sodium sulfate
Crocus solid intermediate 2 is obtained after dried silica gel column chromatography (n-hexane: ethyl acetate=4:1) vacuum drying,
Structural formula is as follows:
C). by described intermediate 2 0.1g (0.00016mol), S-1,1'-union-2-naphthol 0.05g (0.000176mol),
Cesium carbonate 0.156g (0.00048mol) and dibenzo 18 hat six 0.0172g (0.000048mol) are dissolved in 200
In the DMF of ml, under nitrogen atmosphere, stirring reaction 72h under room temperature, reaction end subtracts
Pressure removes solvent, adds ethyl acetate, successively with saturated ammonium chloride solution, saturated sodium bicarbonate solution and saturated
Sodium chloride solution washs 2-3 time, adds anhydrous sodium sulfate dried silica gel column chromatography (n-hexane: ethyl acetate
=3:2), obtain Chinese red solid target compound after vacuum drying, its structural formula is as follows:
Embodiment 5: photoresponse complexing and the release of chiral ammonium salt
Taking target product 2mg and being made into concentration is 2 × 10-5The tetrahydrofuran solution of mol/L, by this solution 55 DEG C
Dark processing 8h, exposes under 365nm illumination, measures the ultraviolet-visible of material under different exposure time
Spectrum and circular dichroism spectra, the ALANINE ethyl ester salting liquid adding variable concentrations in reaction mixture measures network
The uv-vis spectra of polymer solution, when ammonium salt concentration and photosensitive chirality macrocycle molecule concentration ratio are during equal to 0.56
Reach balance；Aforesaid operations is carried out equally, when ammonium salt concentration is big with photosensitive chirality under 440nm visible ray shines
Toroidal molecule concentration reaches balance than during equal to 0.87.
Embodiment 6: the change of cholesteric liquid crystal distortion power constant
Take 0.1g liquid crystal and add 0.002g S type photosensitive chirality macrocycle molecule, thermal station is heated to the clear of liquid crystal
Bright spot, constant temperature 1h makes it join after being sufficiently mixed in wedged liquid crystal cell.By this wedged liquid crystal cell at polarisation
Basis of microscopic observation, measures pitch length 2002 μm formed.Wheel uses 365nm's and 440nm instead respectively
Light liquid crystal device like this, measuring pitch length is 1840 μm and 2331 μm.
Claims (10)
1. a photosensitive chirality macrocycle molecule, has a following general structural formula:
In formula, R1Selected from-H ,-CH3、-CF3、-F、-NO2、-OCH3Or-COOCH3；N is for being not more than
The positive integer of 10.
2. the preparation method of photosensitive chirality macrocycle molecule described in claim 1, comprises the following steps:
A), by oligomeric ethylene glycol, NaOH and p-methyl benzene sulfonic chloride under an inert atmosphere, in tetrahydrofuran solvent
8-12h is stirred at room temperature, purifies washing and obtain intermediate 1 after drying；
B), described intermediate 1, o-dihydroxy azobenzene, cesium carbonate and dibenzo-18-crown-6 (DB18C6) are dissolved in N,
In dinethylformamide solvent, under an inert atmosphere, it is heated to reflux 10-15h, separates, wash and be dried
After obtain intermediate 2；
C), described intermediate 2, chiral binaphthyl phenolic compound, cesium carbonate and dibenzo-18-crown-6 (DB18C6) are dissolved in
In DMF solvent, in an inert atmosphere, stirring reaction 60-80h under room temperature, separate,
Washing also obtains target product after drying.
The preparation method of photosensitive chirality macrocycle molecule the most as claimed in claim 2, it is characterised in that step a) is described
The mol ratio of oligomeric ethylene glycol, NaOH and p-methyl benzene sulfonic chloride is 1:2-2.3:2-2.3.
The preparation method of photosensitive chirality macrocycle molecule the most as claimed in claim 2, it is characterised in that step b) is described
The mol ratio of intermediate 1, o-dihydroxy azobenzene, cesium carbonate and dibenzo-18-crown-6 (DB18C6) is 3-3.4:1:
3-3.4:0.3-0.35.
The preparation method of photosensitive chirality macrocycle molecule the most as claimed in claim 2, it is characterised in that step b) is described
Dried employing silica gel column chromatography is vacuum dried again, and flowing during described silica gel column chromatography is n-hexane mutually: acetic acid
Ethyl ester=4:1.
The preparation method of photosensitive chirality macrocycle molecule the most as claimed in claim 2, it is characterised in that step c) is described
The structural formula of chiral binaphthyl phenolic compounds is:
R in formula1Selected from-H ,-CH3、-CF3、-F、-NO2、-OCH3Or-COOCH3。
The preparation method of photosensitive chirality macrocycle molecule the most as claimed in claim 2, it is characterised in that step c) is described
The mol ratio of intermediate 2, chiral binaphthyl phenolic compound, cesium carbonate and dibenzo-18-crown-6 (DB18C6) is 1:1-1.2:
3-3.3:0.3-0.32.
The preparation method of photosensitive chirality macrocycle molecule the most as claimed in claim 2, it is characterised in that step c) is described
Dried employing silica gel column chromatography is vacuum dried to obtain target product again, and flowing during described silica gel column chromatography is just mutually
Hexane: ethyl acetate=3:2.
9. the purposes of the photosensitive chirality macrocycle molecule prepared any one of claim 2-8, it is characterised in that use
In being complexed chirality ammonium ion and being controlled complexing and the release of chirality ammonium salt by illumination wavelength and intensity.
10. the purposes of the photosensitive chirality macrocycle molecule prepared any one of claim 2-8, it is characterised in that use
Reversible regulation in the pitch to cholesteryl liquid crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410668224.XA CN104496933B (en) | 2014-11-20 | 2014-11-20 | A kind of photosensitive chirality macrocycle molecule and its production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410668224.XA CN104496933B (en) | 2014-11-20 | 2014-11-20 | A kind of photosensitive chirality macrocycle molecule and its production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104496933A CN104496933A (en) | 2015-04-08 |
| CN104496933B true CN104496933B (en) | 2016-08-17 |
Family
ID=52938407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410668224.XA Active CN104496933B (en) | 2014-11-20 | 2014-11-20 | A kind of photosensitive chirality macrocycle molecule and its production and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104496933B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619378B (en) * | 2016-07-14 | 2019-07-30 | 京东方科技集团股份有限公司 | Chipal compounds and liquid crystal material and preparation method thereof, display device |
| CN106833680B (en) * | 2017-01-03 | 2020-12-18 | 复旦大学 | Photoresponse tristable chiral molecular material and preparation method and application thereof |
| CN107903916B (en) * | 2017-11-29 | 2020-12-11 | 北京化工大学 | Application of cholesteric liquid crystal composition in ultraviolet light detection and ultraviolet light detector |
| CN109001930B (en) * | 2018-07-13 | 2021-11-02 | 华南师范大学 | Electric response infrared reflection device and preparation method thereof |
| CN109810129B (en) * | 2019-02-14 | 2021-06-11 | 合肥工业大学 | Annular photosensitive chiral molecule of binaphthylazobenzene and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005200310A (en) * | 2004-01-13 | 2005-07-28 | Nagaoka Univ Of Technology | Phthalocyanine derivative having crown ether ring in molecule and intermediate therefor |
| CN102495494A (en) * | 2011-12-06 | 2012-06-13 | 北京科技大学 | Method for regulating and controlling liquid crystal reflected color by using reversibility of azobenzene |
| CN102675612A (en) * | 2012-05-28 | 2012-09-19 | 齐齐哈尔大学 | Synthesis of novel chiral polyester containing binaphthyl and application thereof to molecular recognition |
-
2014
- 2014-11-20 CN CN201410668224.XA patent/CN104496933B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104496933A (en) | 2015-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104496933B (en) | A kind of photosensitive chirality macrocycle molecule and its production and use | |
| Deng et al. | A novel type of optically active helical polymers: Synthesis and characterization of poly (N‐propargylureas) | |
| CN106117301B (en) | One kind has arylamine class lung cancer marker the preparation and application of the fluorescent chemicals and its fluorescence sense film of sensing function | |
| CN109988560A (en) | A kind of hydrazine fluorescence probe of novel coumarin derivative | |
| CN102174131A (en) | Rubber with fluorescence response to pH value and preparation method thereof | |
| Li et al. | AIE-based fluorescent boronate probe and its application in peroxynitrite imaging | |
| Ghosh et al. | Ultrafast and nanomolar level detection of H 2 S in aqueous medium using a functionalized UiO-66 metal–organic framework based fluorescent chemosensor | |
| Hasegawa et al. | Chiroptical properties of 1, 3-diphenylallene-anchored tetrathiafulvalene and its polymer synthesis | |
| Mao et al. | An “off–on” fluorescence probe for chromium (III) ion determination in aqueous solution | |
| CN103242526A (en) | Preparation method of photoresponse type hyperbranched zinc phthalocyanine polymer | |
| CN114591632A (en) | Azaindole-hemicyanine dye, and synthesis method and application thereof | |
| Liu et al. | Synthesis and properties of optically active 6, 6′-didodecyl-1, 1′-binaphthyl-phthalocyanine linked through crown ether units | |
| CN109232594B (en) | Spiropyran-bipyridine derivative and naked eye detection of copper (II) by spiropyran-bipyridine derivative | |
| CN101666748A (en) | New method for detecting TNT in water phase by fluorescence | |
| Wang et al. | Yb (III)-based MOFs with different bulky backbone ligands for optical detection and degradation of organic molecules in wastewater | |
| CN113896736B (en) | Aryl-substituted spirooxazine photochromic compound and preparation method and application thereof | |
| CN108456215B (en) | controlled-release singlet oxygen endoperoxide and preparation and application thereof | |
| Tang et al. | A dual-channel sensor for Hg 2+ based on a diarylethene with a rhodamine B unit | |
| CN105968130B (en) | Two pyrroles's methine derivatives and preparation method thereof are complexed containing double center boron fluorides of carbazole and bridge linkage group in a kind of middle position | |
| CN111410624B (en) | Asymmetric naphthalene-pyrrole hybrid diarylethene compound and application thereof | |
| Kicková et al. | A chiroptical binaphthopyran switch: amplified CD response in a polystyrene film | |
| JP4545370B2 (en) | Chiral sensor | |
| CN100582193C (en) | Bifunctional photochromic compound with aromatic azo group and spirooxazine group and synthesis method and application thereof | |
| CN110845495A (en) | Triplet photosensitizers and methods of synthesis | |
| Chen et al. | Thiophenic silicon phthalocyanines: synthesis, characterization, and photophysical properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210105 Address after: 245000 No.50, Meilin Avenue, Huangshan Economic Development Zone, Huangshan City, Anhui Province Patentee after: Huangshan Development Investment Group Co.,Ltd. Address before: 230009 No. 193, Tunxi Road, Hefei, Anhui Patentee before: Hefei University of Technology |