CN108003859B - A kind of piezallochromy fluorescent molecule and its preparation method and application - Google Patents
A kind of piezallochromy fluorescent molecule and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of piezallochromy fluorescent molecule and its preparation method and application.Piezallochromy fluorescent molecule provided by the invention has aggregation-induced emission property, and under pressure, compound is changed into amorphous state by original crystalline state, changes the accumulation mode in the case of its solid-state, and then cause the variation of emission spectrum；Compound is changed into crystalline state from amorphous state again after stifling, has piezallochromy performance.The experimental results showed that piezallochromy fluorescent molecule provided by the invention has good dissolubility in dimethyl sulfoxide, and almost do not dissolve in methylene chloride, Micelle-like Nano-structure of Two can be formed, there is aggregation-induced emission characteristic.In addition solid luminescence color is from green-yellow light to orange light, after the effect of pressure, solid luminescence color change can be clearly observed under 365nm ultraviolet lamp, while can restore original luminescent color in the case where methanol steam is stifling.
Description
Technical field
The present invention relates to photoelectric functional material technology field, in particular to a kind of piezallochromy fluorescent molecule and its preparation side
Method and application.
Background technique
In recent years, fluorescent molecule is extensive due to having in fields such as oled light electrical part, biosensor, information securities
Application value has caused the strong interest of vast research works.However, conventional fluorescent compound presents in the solution
High luminous efficiency shows as fluorescence intensity in coherent condition and weakens or even be quenched, and here it is common aggregation inducing fluorescence
Quenching effect (aggregation caused quenching, ACQ).In view of fluorescent material usually with aggregation or solid film shape
Formula uses, and ACQ phenomenon seriously limits the application prospect of fluorescent material under specific circumstances.
2001, Tang Benzhong academician seminar reported a kind of molecule with propeller arrangement, they have existing with ACQ
As opposite luminescent behavior: fluorescence is very weak in the solution or does not shine for such molecule, but in solid-state or coherent condition, then produces
Raw strong fluorescence.They this phenomenon be named as aggregation-induced emission (aggregation-induced emission,
AIE) phenomenon.AIE phenomenon and traditional ACQ phenomenon are just the opposite, can further widen organic fluorescence using this new features
Application of the compound in solid or coherent condition field.In addition, since most of molecules with AIE property have point of distortion
Sub- conformation leads to its packing of molecules relative loose, and after being stimulated by power, intramolecular action power changes, and leads to molecule
Accumulation mode changes, so that material becomes another orderly or partial order, disordered structure, material from a kind of ordered structure
The photophysical property of material changes therewith, i.e. piezallochromy property.Then after the processing such as heating, solvent be stifling, the heap of molecule
Product mode can revert to original, the invertibity of realization fluorescence color variation.Fluorescent material with piezallochromy property is one
The novel intellectual material of kind, it has very extensive in fields such as strain gauge, information storage, fluorescent switch and luminescent devices
Application.
2014 Nian Liurui seminars, which report, introduces bowl-shape phenthazine molecule using fluorine boron complexes as core as power supply
Sub- substituent group, the compound present AIE characteristic.In addition under pressure, shining for compound becomes red from yellow,
Under methylene chloride steam, luminescent color can be restored to initial yellow (Chem.Commun., 2014,50,12951-
12954).You seminar in 2016 reports with [1,2,4] triazolone-[1,5-a] pyrimidine as parent, introduces respectively different
It is adjustable to realize luminescent color for substituent group, at the same obtain a series of piezochromic materials (J.Am.Chem.Soc.2016,
138,12803-12812).But up to the present it has been reported that the luminescent material with piezallochromy property it is also seldom.
Summary of the invention
The purpose of the present invention is to provide a kind of piezallochromy fluorescent molecules and its preparation method and application.The present invention provides
Piezallochromy fluorescent molecule have aggregation-induced emission characteristic and piezallochromy characteristic.
The present invention provides a kind of piezallochromy fluorescent molecules, have chemical structure shown in Formulas I:
A in the Formulas I-For acid ion；
R is group shown in R1 or R3 in the Formulas I:
Preferably, the acid ion includes chloride ion, sulfate ion, acetate ion or trifluoroacetic acid radical ion.
The present invention provides a kind of preparation methods of piezallochromy fluorescent molecule described in above-mentioned technical proposal, including following step
It is rapid:
(1) 1,1,3,3- tetramethoxy propane, arylamine and organic solvent are mixed, obtains mixed solution；The aryl
Amine is aniline or para-bromoaniline；
(2) mixed solution that the step (1) obtains is cooled to -5~5 DEG C, acid solution is added dropwise, be hydrolyzed and nucleophilic
Addition reaction obtains piezallochromy fluorescent molecule.
Preferably, organic solvent includes one of methanol, ethyl alcohol, acetonitrile and tetrahydrofuran or more in the step (1)
Kind.
Preferably, the acid in the step (2) in acid solution and the molar ratio of 1,1,3,3- tetramethoxy propane be (1~
4):1。
Preferably, the rate being added dropwise in the step (2) is 0.25~0.4mL/min.
Preferably, the mass concentration of the acid solution is 30~40%.
Preferably, the acid solution includes the aqueous solution of one of hydrochloric acid, sulfuric acid, acetic acid and trifluoroacetic acid.
The present invention provides the applications of piezallochromy fluorescent molecule described in above-mentioned technical proposal, press described in claim 1
Mutagens color fluorescent molecule forms confidential information to be added.
Preferably, described to be encrypted as by carrying out the encryption that information is realized in pressurization to the piezallochromy fluorescent molecule；Institute
Decryption is stated as by carrying out the stifling decryption for realizing information of steam to the piezallochromy fluorescent molecule.
The present invention provides a kind of piezallochromy fluorescent molecules, have chemical structure shown in Formulas I:
A in the Formulas I-For acid ion；
R is group shown in R1 or R3 in the Formulas I:
Piezallochromy fluorescent molecule provided by the invention has aggregation-induced emission property, and the principle of piezallochromy, which is derived from, divides
Transformation between sub- crystalline state and amorphous state.The present invention results in chemical combination by the arylamine in molecular end introducing different structure
Object is in solid-state with different accumulation modes, and compound is crystalline state in solid-state, and under pressure, compound is by original
Crystalline state is changed into amorphous state, changes the accumulation mode in the case of its solid-state, and then causes the variation of emission spectrum；Smoked
Compound is changed into crystalline state from amorphous state again after steaming, has piezallochromy performance.The experimental results showed that pressure provided by the invention
Mutagens color fluorescent molecule has good dissolubility in dimethyl sulfoxide, and does not almost dissolve in methylene chloride, can be formed
Micelle-like Nano-structure of Two has aggregation-induced emission characteristic.In addition solid luminescence color is from green-yellow light to orange light, in the effect of pressure
Afterwards, can be apparent under 365nm ultraviolet lamp observe solid luminescence color change, while can be in the case where methanol steam is stifling
Restore original luminescent color.
Also, piezallochromy fluorescent molecule provided by the invention, which is repeated as many times, grinds and fumigates, aggregation-induced emission
It can illustrate that the anti-fatigue performance of compound is more excellent with piezallochromy performance there is no apparent decay.
In addition, the preparation method synthesis step of piezallochromy fluorescent molecule provided by the invention is short, yield it is higher (55~
83%), raw material is cheap, and overall cost is low.
Detailed description of the invention
Fig. 1 be in the embodiment of the present invention 1~2 and comparative example 1~3 compound in dimethyl sulphoxide solution it is ultraviolet-
Visible absorption spectra；
Fig. 2 is the preferred configuration of compound ground state in the embodiment of the present invention 1~2 and comparative example 1~3, and highest occupies rail
The Cloud Distribution in road and lowest unoccupied molecular orbital；
Fig. 3 be in the embodiment of the present invention 1~2 and comparative example 1~3 compound in the transmitting light of dimethyl sulphoxide solution
Spectrum；
Fig. 4 is the emission spectrum of compound solid state in the embodiment of the present invention 1~2 and comparative example 1~3；
Fig. 5 is piezallochromy fluorescent molecule in the embodiment of the present invention 1 in dimethyl sulfoxide-methylene chloride mixed system
The relative intensity figure of emission spectrum and transmitting；
Fig. 6 is piezallochromy fluorescent molecule in comparative example 1 of the present invention in dimethyl sulfoxide-methylene chloride mixed system
The relative intensity figure of emission spectrum and transmitting；
Fig. 7 is piezallochromy fluorescent molecule in the embodiment of the present invention 2 in dimethyl sulfoxide-methylene chloride mixed system
The relative intensity figure of emission spectrum and transmitting；
Fig. 8 is piezallochromy fluorescent molecule in comparative example 2 of the present invention in dimethyl sulfoxide-methylene chloride mixed system
The relative intensity figure of emission spectrum and transmitting；
Fig. 9 be comparative example 3 of the present invention in emission spectrum of the compound in dimethyl sulfoxide-methylene chloride mixed system with
The relative intensity figure of transmitting；
Figure 10 is the fluorescence spectrum of the grinding of piezallochromy fluorescent molecule and the stifling front and back of methanol in the embodiment of the present invention 1 and 2；
Figure 11 is the wavelength change that piezallochromy fluorescent molecule circular grinding and methanol are fumigated in the embodiment of the present invention 1 and 2；
Figure 12 is that original, the X under grinding and stifling situation is penetrated piezallochromy fluorescent molecule in the embodiment of the present invention 1 and 2
Ray diffraction diagram；
Figure 13 is the information encrypt-decrypt schematic diagram of piezallochromy fluorescent molecule in the embodiment of the present invention 1.
Specific embodiment
The present invention provides a kind of piezallochromy fluorescent molecules, have chemical structure shown in Formulas I:
A in the Formulas I-For acid ion；
R is one of group shown in R1 or R3 in the Formulas I:
Piezallochromy fluorescent molecule provided by the invention has aggregation-induced emission property, and under pressure, changes
It closes object and amorphous state is changed by original crystalline state, change the accumulation mode in the case of its solid-state, and then cause transmitting light
The variation of spectrum；Compound is changed into crystalline state from amorphous state again after stifling, has piezallochromy performance.
The present invention provides a kind of preparation methods of piezallochromy fluorescent molecule described in above-mentioned technical proposal, including following step
It is rapid:
(1) 1,1,3,3- tetramethoxy propane, arylamine and organic solvent are mixed, obtains mixed solution；The aryl
Amine is aniline or para-bromoaniline；
(2) mixed solution that the step (1) obtains is cooled to -5~5 DEG C, acid solution is added dropwise, be hydrolyzed and nucleophilic
Addition reaction obtains piezallochromy fluorescent molecule.
The present invention mixes 1,1,3,3- tetramethoxy propane, arylamine and organic solvent, obtains mixed solution.In this hair
In bright, the arylamine is aniline or para-bromoaniline.In the present invention, it when the arylamine is aniline and para-bromoaniline, obtains
Product respectively correspond the compound that R in Formulas I is R1 and R3.The present invention is to the 1,1,3,3- tetramethoxy propane and arylamine
Ratio there is no special restriction, be adjusted according to chemical equation.
In the present invention, the organic solvent is preferably polar organic solvent, more preferably include methanol, ethyl alcohol, acetonitrile and
One of tetrahydrofuran is a variety of, more preferably ethyl alcohol.The present invention does not have special restriction to the dosage of the organic solvent,
Reaction raw materials can be made to dissolve.In the present invention, the organic solvent and 1, the mass ratio of 1,3,3- tetramethoxy propane
Preferably (10~20): 1, more preferably (14~16): 1.
The operation that the present invention mixes the 1,1,3,3- tetramethoxy propane, arylamine and organic solvent is not special
It limits, using the technical solution well known to those skilled in the art for preparing mixed solution.
After obtaining mixed solution, the mixed solution is cooled to -5~5 DEG C by the present invention, and acid solution is added dropwise, is hydrolyzed
And nucleophilic addition, obtain piezallochromy fluorescent molecule.In the present invention, the mixed solution is preferably cooled to -3~3 DEG C,
More preferably 0 DEG C.In the present invention, the cooling provides suitable temperature condition for sequential hydrolysis and nucleophilic addition.
In the present invention, the acid in the acid solution and the molar ratio of 1,1,3,3- tetramethoxy propane be preferably (1~
4): 1, more preferably (2~3): 1.In the present invention, the mass concentration of the acid solution is preferably 30~40%, more preferably
32~38%, most preferably 34~36%.In the present invention, the acid solution preferably includes hydrochloric acid, sulfuric acid, acetic acid and trifluoro second
The aqueous solution of one of acid.In the present invention, the hydrochloric acid, sulfuric acid, acetic acid and trifluoroacetic acid respectively correspond A in Formulas I-For chlorine
Ion, sulfate ion, acetate ion and trifluoroacetic acid radical ion compound.In the present invention, the acid solution plus
Enter to hydrolyze and providing acid reaction environment with nucleophilic addition, and be capable of providing acid ion, forms stable salt.
In the present invention, the rate of the dropwise addition of the acid solution is preferably 0.25~0.4mL/min, more preferably 0.27~
0.35mL/min, most preferably 0.3mL/min.In the present invention, the dropwise addition can control the speed of hydrolysis, reduce by-product
Production.
In the present invention, the hydrolysis and nucleophilic addition successively carry out step by step, and 1,1,3,3- tetramethoxy propane exists
Acid solution be added dropwise during hydrolysis obtains malonaldehyde, then with arylamine nucleophilic addition.
After the completion of hydrolysis and nucleophilic addition, product of the present invention preferably by the hydrolysis and nucleophilic addition is carried out
It is separated by solid-liquid separation, obtains piezallochromy fluorescent molecule.The not special restriction of operation of the present invention to the separation of solid and liquid, using this
The operation being separated by solid-liquid separation known to the technical staff of field.In the present invention, the separation of solid and liquid preferably successively includes filtering
And drying.The present invention does not have special restriction to the filtering and dry technical solution, using known to those skilled in the art
Filtering and drying technical solution.
The present invention also provides the applications of piezallochromy fluorescent molecule described in above-mentioned technical proposal, with above-mentioned technical proposal institute
It states piezallochromy fluorescent molecule and forms confidential information to be added.The present invention is preferably by pressurizeing to the piezallochromy fluorescent molecule
The encryption for realizing information, by carrying out the stifling decryption for realizing information of steam to the piezallochromy fluorescent molecule.
In the present invention, the application of the piezallochromy fluorescent molecule preferably includes: using and contains piezallochromy fluorescent molecule
Solution confidential information to be added is stamped on the paper of yellow, obtain the paper with encryption information；By described with encryption information
Paper is fumigated in the steam of easy volatile solvent.
Confidential information to be added is preferably stamped on the paper of yellow with the solution containing piezallochromy fluorescent molecule by the present invention, is obtained
To the paper for having encryption information.In the present invention, the solvent in the solution containing piezallochromy fluorescent molecule is preferably two
Methyl sulfoxide.The present invention does not have special restriction to the concentration of solution and the pressure of coining of the piezallochromy fluorescent molecule,
It can guarantee that information completely develops the color.
In the present invention, the paper of the yellow and it is pressurized after piezallochromy fluorescent molecule luminous face in the UV lamp
Color is identical, can hide the encryption information of piezallochromy fluorescent molecule formation.
When needing to decrypt, the present invention preferably fumigates the paper with encryption information in the steam of easy volatile solvent.
In the present invention, the easy volatile solvent is preferably one of methanol, ethyl alcohol, acetone, tetrahydrofuran and acetonitrile or a variety of.?
In the present invention, the stifling pressure is preferably the vapour pressure of easy volatile solvent at normal temperature.In the present invention, described stifling
Time is preferably 5~20min, more preferably 10~15min.In the present invention, the piezallochromy fluorescent molecule is after stifling
Restoring its original color in the UV lamp shows encryption information different from the yellow of paper.
In order to further illustrate the present invention, below with reference to embodiment to piezallochromy fluorescent molecule provided by the invention and its
Preparation method and application are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1:
The synthesis of N- ((1E) -3- (phenyl imido) propyl- 1- alkene -1- base) anilinechloride (N1), reaction equation are as follows:
1,1,3,3- tetramethoxy propane 3.284g (0.02mol, 1eq.), aniline are added in bis- mouthfuls of flasks of 100mL
3.720g (0.04mol, 2eq.) and 50ml dehydrated alcohol, stirring are completely dissolved rear solution and are cooled to 0 DEG C, use constant pressure funnel
4ml concentrated hydrochloric acid is slowly added dropwise in 15 minutes, is added dropwise and continues that 1~2h is stirred at room temperature, there is yellow solid precipitation, filters,
Vacuum drying obtains crocus product, yield 55% after water and ethyl alcohol wash filter cake 3 times respectively.
Testing result: 1H NMR δ 12.70 (s, 2H), 8.925 (d, J=6.0Hz, 2H), 7.43-7.50 (m, 8H), 7.25
(t, J=4.0Hz, 2H), 6.51 (t, J=12Hz, 1H),
Elemental analysis: packet type C15H15ClN2。
Calculated value: C, 69.63；H,5.84；N,10.83.
Actual measured value: C, 69.60；H,5.87；N,10.82.
High resolution mass spectrum: quasi-molecular ions calculated value [M-Cl-]:223.1229。
Measured value: 223.1230.
Comparative example 1:
The synthesis of 4- methyl-N- ((1E) -3- (to toluene imido grpup) propyl- 1- alkene -1- base) anilinechloride (N2), reaction
Equation is as follows:
Process is same as embodiment 1, and reactant aniline is only changed to para-totuidine, and vacuum drying obtains yellow product, receives
Rate is 79%.
Testing result: 1H NMR δ 12.55 (d, J=8.0Hz, 2H), 8.79 (q, J=12Hz, J=4.0Hz, 2H), 7.29
(q, J=8Hz, J=4.0Hz, 8H), 6.43 (t, J=8.0Hz, 1H), 2.31 (s, 6H),
Elemental analysis: molecular formula C17H19ClN2。
Calculated value: C, 71.19；H,6.68；N,9.77.
Actual measured value: C, 71.13；H,6.64；N,9.71.
High resolution mass spectrum: quasi-molecular ions calculated value [M-Cl-]:251.1543。
Measured value: 251.1545.
Embodiment 2:
The synthesis of the bromo- N- of 4- ((1E) -3- ((4- bromobenzene) imido grpup) propyl- 1- alkene -1- base) anilinechloride (N3), reaction
Equation is as follows:
Process is same as embodiment 1, and reactant aniline is only changed to para-bromoaniline, and vacuum drying obtains yellow product, receives
Rate is 83%.
Testing result: 1H NMR δ 12.74 (s, 2H), 8.815 (d, J=6.0Hz, 2H), 7.70 (d, J=4.0Hz, 4H),
7.37 (d, J=4.0Hz, 4H), 6.51 (t, J=12Hz, 1H).
Elemental analysis: molecular formula C15H13Br2ClN2。
Calculated value: C, 43.25；H,3.15；N,6.73.
Actual measured value: C, 43.29；H,3.13；N,6.70.
High resolution mass spectrum: quasi-molecular ions calculated value [M-Cl-]:380.9440。
Measured value: 380.9436.
Comparative example 2:
The synthesis of 4- nitro-N- ((1E) -3- ((4- nitrobenzene) imido grpup) propyl- 1- alkene -1- base) anilinechloride (N4),
Reaction equation is as follows:
Process is same as embodiment 1, and reactant aniline is only changed to paranitroanilinum, and vacuum drying obtains yellow product,
Yield is 65%.
Testing result: 1H NMR δ 13.43 (s, 2H), 9.075 (d, J=6.0Hz, 2H), 8.385 (d, J=6.0Hz,
4H), 7.645 (d, J=6.0Hz, 4H), 6.72 (t, J=12Hz, 1H).
Elemental analysis: molecular formula C15H13ClN4O4。
Calculated value: C, 51.66；H,3.76；N,16.07.
Actual measured value: C, 51.69；H,3.78；N,16.02.
High resolution mass spectrum: quasi-molecular ions calculated value [M-Cl-]:313.0937。
Measured value: 313.0932.
Comparative example 3:
The synthesis of N- ((1E) -3- (naphthalene -1- imido grpup) propyl- 1- alkene -1- base) naphthalene -1- amine hydrochlorate (N5), reactional equation
Formula is as follows:
Process is same as embodiment 1, and reactant aniline is only changed to naphthalidine, and vacuum drying obtains crocus product, receives
Rate is 78%.
Testing result: 1H NMR δ 12.90 (s, 2H), 8.83 (t, J=12.0Hz, 2H), 8.43 (d, J=4.0Hz, 2H),
8.03 (t, J=4.0Hz, 2H), 7.94 (d, J=4.0Hz, 2H), 7.62-7.71 (m, 8H), 7.15 (t, J=12Hz, 1H).
Elemental analysis: molecular formula C23H19ClN2。
Calculated value: C, 76.98；H,5.34；N,7.81.
Actual measured value: C, 76.91；H,5.39；N,7.82.
High resolution mass spectrum: quasi-molecular ions calculated value [M-Cl-]:323.1543。
Measured value: 323.1549.
Embodiment 3
The uv-visible absorption spectra of 1~N5 of compound N is tested
Using dimethyl sulfoxide as solvent, it is 1 × 10 that 1~N5 of compound N is made into concentration respectively-5The solution of mol/L.In room
Under the conditions of temperature, using TU-1900UV type ultraviolet-visible photometer, with the quartz colorimetric utensil of 1cm, 200~600nm wave band into
The scanning of row ultra-violet absorption spectrum measures uv-visible absorption spectra of the 1~N5 of compound N in dimethyl sulphoxide solution, test
The result is shown in Figure 1.The dimethyl sulphoxide solution of these compounds all shows stronger absorption in ultraviolet-visible light area, in conjunction with compared with
Strong molar absorption coefficient, the absorption peak of no fine structure and certain solvation effect can be attributed to 1 π, π * transition
Mix certain Intramolecular electron transfer (ICT).
Embodiment 4
Compound N 1~N5 quantum chemical method
In order to understand compound N 1~N5 ground state electron property in depth, optimize to obtain energy most using 09 Gauss program
After low space conformation, the calculating of density functional theory (DFT) is carried out to 1~N5 of compound N with B3LYP/6-31g (d) unit.
Fig. 2 illustrates that the right side of the compound in addition to N5, other compounds is almost coplanar, and the aromatic rings on the left side and principal plane
There are certain distortions.Two naphthalene nucleus and middle section in 5 molecule of compound N are all made of the space conformation of distortion.In addition,
Influence of the dihedral angle by distinct fragrance ring is observed in the optimized geometries of these molecules.With NO2Substituted compound
The dihedral angle of N4 is 40.5 °, all bigger than the dihedral angle of other compounds.Additionally due to approximate coplanar steric configuration, chemical combination
Almost delocalization is in entire molecule for π-electronics of the highest occupied molecular orbital of object N1-N4 and lowest unoccupied molecular orbital, and corresponding to be, N5 is most
High occupied orbital and lowest unoccupied molecular orbital distribution are mainly distributed on two naphthalene nucleus, therefore are observed that some electric charge transfers are special
Property.
Embodiment 5
The emission spectrum of 1~N5 of compound N is tested
Using dimethyl sulfoxide as solvent, it is 1 × 10 that 1~N5 of compound N, which is made into concentration,-5The solution of mol/L.In room temperature item
Under part, transmitting light of the 1~N5 of Hitachi F-4600 fluorescence spectrophotometer measurement compound N in dimethyl sulphoxide solution is used
Spectrum, test result are shown in Fig. 3.The transmitting of all compounds is respectively positioned on blue green light region.Wherein compound N 1~N4 is in the solution
Variation in emission wavelength is little, illustrate it is different for electron-withdrawing group in phenyl ring up conversion, be not significantly affected by compound molten
Emission level in liquid.The launch wavelength of compound N 5 has apparent red shift with respect to other several compounds, this may be due to big
Conjugated system existing for reason.
Embodiment 6
The solid-state emission spectrum of 1~N5 of compound N is tested
At room temperature, compound N 1~N5 solid powder is added in solid sample slot, is excited and is surveyed with 360nm wavelength
The solid emissive spectrum of compound is tried, test result is shown in Fig. 4.The transmitting of all compounds is located at yellow green to orange-yellow region.
Compared with liquid transmitting, the emission spectrum and substituent group of compound have very big relationship.The emission peak of 1~N5 of compound N is distinguished
Positioned at 561nm, 549nm, 593nm, 531nm and 622nm, 580nm.
Embodiment 7
The aggregation inducing emission spectrum of 1~N5 of compound N is tested
1~N5 of compound N has good dissolubility in dimethyl sulfoxide, while almost not dissolving in methylene chloride,
Therefore we select dimethyl sulfoxide-dichloromethane system test compound aggregation inducing emission characteristic.Respectively by compound
Different volumes are dissolved or dispersed in than in mixed dimethyl sulfoxide-methylene chloride liquid, using Hitachi's F-4600 fluorescence spectrophotometer
Photometer tests the emissive porwer of mixed system, as a result sees Fig. 5-9.As seen from the figure, such compound all has certain aggregation
Induced luminescence property.
Embodiment 8
The fluorescence spectrum of compound N 1 and N3 grinding and stifling front and back
Compound N 1 and the N3 emission spectrum before and after pressure effect and solvent are stifling are shown in Figure 10, and compound N 1 and N3 are placed in
In agate mortar, solid is firmly ground, until them, the luminescent color under 365nm ultraviolet lamp becomes yellow green and yellow respectively,
Solid sample collection after grinding is added in solid sample slot, solid emissive spectrum after test grinding, it can be found that grinding
Solid emissive peak position afterwards is converted near 518nm and 552nm by original 561nm and 593nm respectively.Then after grinding
Solid sample be put into the steam atmosphere of methanol, observe after its color is restored to initial conditions and test its solid emissive spectrum,
Solid emissive peak position is nearby restored to 561nm and 593nm by 518nm and 552nm again as the result is shown.Two compounds are in pressure
Under the action of steam, the movement of launch wavelength about 40nm may be implemented.In addition as shown in figure 11, grinding and stifling experiment can
To be repeated as many times there is no apparent decay, illustrate that the anti-fatigue performance of compound is more excellent.
Embodiment 9
Compound N 1 and N3 grinding and it is stifling under powder x-ray diffraction
Compound N 1 and N3 is original, and sample stifling again carries out powder x-ray diffraction, original chemical combination after grinding and grinding
Object N1 and N3 show it is many point and thin diffraction maximum, illustrate that their solid is crystalline state, after being fully ground almost without
Apparent diffraction maximum illustrates that their solid is amorphous state.Under pressure, compound is changed into nothing by original crystalline state
Shape state, changes the accumulation mode in the case of its solid-state, and then cause the variation of emission spectrum.In addition the chemical combination after stifling
Object presents many diffraction maximums again, illustrates in the case where solvent is stifling, and compound is changed into crystalline state from amorphous state again.This illustrate N1 and
The piezallochromy reason of N3 compound derives from the unbodied transformation of crystal-.
Embodiment 10
Using the piezallochromy of compound N 1 and the property of gas-discoloration, a kind of promising data storage material is developed
Material is encrypted and is decrypted for information.Encryption and decryption schematic diagram are as shown in figure 13.Select dyestuff (E) -4- (4- (diethyl) benzene
Methylene) benzoic acid offer background colour.Filter paper is impregnated 10 minutes in the dichloromethane solution of dyestuff, after being dried at room temperature for
The paper of a yellow is obtained, which issues green-yellow light under ultraviolet light.In encrypting stage, with containing alphabetical " NJTECH " seal
Special " ink " methanol solution has been dipped in (containing compound N 1, concentration 10-4Mol/L), upper letter is covered on the filter paper of yellow
" NJTECH ", after dry, under natural light and 365nm ultraviolet lamp, due to color is similar, be invisible to the naked eye any word
Mother, this shows that data encryption is completed.In decryption phase, filter paper is exposed to a period of time in methanol steam, in 365nm ultraviolet light
According to it is lower it will be clear that character " NJTECH " yellow emission.These the result shows that compound N 1 in data security protecting side
Face has potential application.
As can be seen from the above Examples and Comparative Examples, piezallochromy fluorescent molecule provided by the invention has aggregation inducing
Luminosity, and under pressure, compound is changed into amorphous state by original crystalline state, in the case of changing its solid-state
Accumulation mode, and then cause the variation of emission spectrum；Compound is changed into crystalline state from amorphous state again after stifling, has
Piezallochromy performance.
The above is only a preferred embodiment of the present invention, it is not intended to limit the present invention in any form.It should
It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make
Dry improvements and modifications, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (2)
1. a kind of application of piezallochromy fluorescent molecule in information encrypt-decrypt, which is characterized in that the piezallochromy fluorescence
Molecule forms confidential information to be added；
The piezallochromy fluorescent molecule has chemical structure shown in Formulas I:
A- is acid ion in the Formulas I；
R is group shown in R1 or R3 in the Formulas I:
The acid ion includes chloride ion, sulfate ion, acetate ion or trifluoroacetic acid radical ion.
2. application according to claim 1, which is characterized in that described to be encrypted as by the piezallochromy fluorescent molecule
Carry out the encryption that information is realized in pressurization；The decryption is steam is stifling to realize letter by carrying out to the piezallochromy fluorescent molecule
The decryption of breath.
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