CN108484474A - Luminescent material with aggregation-induced emission property and its preparation and application - Google Patents
Luminescent material with aggregation-induced emission property and its preparation and application Download PDFInfo
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Abstract
The invention belongs to the technical field of luminescent material, the luminescent material with aggregation-induced emission property and its preparation and application are disclosed.The luminescent material, general molecular formula are Formulas I, wherein R1And R2For similar and different electron or electron-withdrawing group, R3And R4It is hydrogen or methoxyl group simultaneously.The luminescent material structure of the present invention is stablized, and there is aggregation-induced emission property, good luminous performance, crystalline state fluorescence quantum efficiency to reach as high as 20.7%；The luminescent material preparation method of the present invention is easy to operate simultaneously, and reaction condition is mild, and reaction yield is high；With solid luminescent, low in raw material price is renewable, the advantages that by accessing the photochromic adjusting easy to implement of different supplied for electronic and electron-withdrawing group, is conducive to large-scale promotion, solves the problems, such as lack of energy.The luminescent material of the present invention has the property of mechanoluminescence simultaneously, can be used for the fields such as anti-fake, monitoring pressure in real time variation.
Description
Technical field
The invention belongs to the technical field of luminescent material, more particularly to a kind of luminous material with aggregation-induced emission property
Material and the preparation method and application thereof.
Background technology
Luminous organic material has Stokes shift big, photochromic to can easily be accommodated, bendable for inorganic material
The advantages that song facilitates preparation, and raw material is renewable.Based on these advantages, luminous organic material has been widely used in chemistry
Sensing, bio-imaging, fluorescence probe and photoelectric field.However, conventional organic luminescence material is divided due to big planar structure
It is tightly packed between son, usually since pi-pi accumulation acts on, lead to fluorescent quenching.And such as Organic Light Emitting Diode in practical application,
The luminescent material of nano particle etc. usually exists with film or solid-state form again.Therefore conventional organic luminescence material limits significantly
Its practical application.
In addition, mechanoluminescence refers in works such as supersonic oscillations, pulse, impact, bending, friction, fracture, stretching or compressions
With lower emission spectrum, it is a kind of special luminescence phenomenon.In recent years, since mechanoluminescence material is in lossless detection stress, knot
The huge applications foreground that detection that structure destroys, display, illumination, anti-fake and bio-imaging etc. are shown, scientists pair
This phenomenon produces great interest.Although having there is many articles to have studied this phenomenon, most of they before this
Concentrate on transition metal element or rare earth element such as ZnS, MnS, Eu etc. metals.Rare earth metal is expensive, and resource has
Limit, it is non-renewable.In addition, inorganic matter is difficult to realize photochromic adjusting, and organic matter has natural advantage in this respect, need to only draw
Enter different substituent groups, can be achieved with photochromic regulation and control.If can obtain not only with mechanoluminescence but also with aggregation inducing property
Luminescent material, this will greatly expand luminescent material application, be of great significance to the long term growth of luminescent material.
Invention content
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of with aggregation
The luminescent material and preparation method thereof of induced luminescence property.The luminescent material structure of the present invention is stablized, in crystalline state and/or crystallite state
With preferable luminescent properties, fluorescence quantum efficiency is high.The luminescent material preparation process of the present invention is simple, reaction condition temperature
With, yield height, while its monocrystalline is obtained by solvent culture appropriate.In addition, the part luminescent material of the present invention also has power
The characteristics of photoluminescence.
Another object of the present invention is to provide the application of the above-mentioned luminescent material with aggregation-induced emission property.The tool
There is the luminescent material of aggregation-induced emission property in chemical sensitisation, photoelectric field, biological fluorescent labeling and bio-imaging field
Application.The luminescent material with mechanoluminescence can also be lossless in the luminescent material with aggregation-induced emission property
Detect the application in the fields such as stress, monitoring pressure in real time variation, the detection of structure destruction, display, illumination, anti-fake.
The purpose of the present invention is realized by following proposal：
It is Formulas I that one kind, which has the luminescent material of aggregation-induced emission property, general molecular formula,：
Wherein, R1And R2For similar and different electron or electron-withdrawing group, one be respectively selected from following structural
Kind：
-H、-OCH3、-Br、-F、-CHO、-CN、
R3And R4It is hydrogen or methoxyl group simultaneously.
The luminescent material with aggregation-induced emission property, preferably with more than one in lower structure：
R3And R4It is hydrogen, R simultaneously1And R2It is simultaneously-H ,-F ,-Br ,-OCH3、CN；
Or R3And R4It is hydrogen, R simultaneously1And R2Difference, R1And R2Selected from-H ,-F ,-Br ,-OCH3、CN、CHO、Middle one kind；
Or R3And R4It is methoxyl group, R simultaneously1And R2It is-H ,-OCH simultaneously3；
Or R3And R4It is methoxyl group, R simultaneously1And R2Difference, R1And R2Selected from-H ,-OCH3Middle one kind.
The luminescent material with aggregation-induced emission property, the more preferably compound of Formula II, R1And R2All it is H, R3
And R4Also it is hydrogen simultaneously：
The compound of the Formula II, crystal are preferably that space group is Pna21Crystal.
The luminescent material with aggregation-induced emission property, the more preferably compound of formula III, R1And R2All it is F,
R3And R4It is hydrogen simultaneously：
The luminescent material with aggregation-induced emission property is crystalline state or crystallite state.
The luminescent material with aggregation-induced emission property of the present invention, photoluminescent color cover yellow green to red
Light region (521-635nm).
The preparation method of the luminescent material with aggregation-induced emission property, is specifically divided into two kinds：
Work as R1And R2Identical and R3And R4When being H, the preparation method of luminescent material includes the following steps：
S1：2- indolones and substituted benzophenone are obtained into required luminous material by Borneo camphor-Wen Gaier condensation reactions
Material；Substituted benzophenone is
Work as R1And R2It differs or R3And R4When being methoxyl group, the preparation method of luminescent material includes the following steps：
P1：In organic solvent, phenyl-allylene acid compounds are reacted with thionyl chloride, prepares the chemical combination containing acyl chlorides
Object；After having reacted, the compound containing acyl chlorides is added in the organic solution of adjacent Iodoaniline, room temperature reaction obtains in acetylenic ketone imines
Mesosome；
Phenyl-allylene acid compounds, structure areThe structure of acetylenic ketone imine intermediate is
P2：In organic solvent and catalyst system and catalyzing, by acetylenic ketone imine intermediate and aromatic yl acid reaction, obtaining has aggregation
The luminescent material of induced luminescence property；The structure of aryl boric acid is
Work as R1And R2Identical and R3And R4When being H, in preparation method, the solvent of reaction is conventional organic solvent, excellent
It is selected as THF；Catalyst system and catalyzing needed for reaction includes tetraisopropyl titanate (IV) and pyridine；The reaction is in protective gas atmosphere
Lower progress；The time of reaction is 2~10h；The molar ratio of 2- indolones and substituted benzophenone is 1：(1~1.2).It has reacted
Cheng Hou need to carry out solvent in subsequent processing, in particular to removal reaction product, be extracted using DCM/ water, DCM layers be concentrated, into
Row pillar layer separation purifies.
Work as R1And R2It differs or R3And R4When being methoxyl group, in preparation method, organic solvent is conventional in step P1
Organic solvent, preferably DCM；Organic solvent is conventional organic solvent, preferably THF in the organic solution of adjacent Iodoaniline；It is described
Room temperature reaction carries out under protective gas atmosphere；The time of room temperature reaction is 2~10h；Pyridine need to be added in room temperature reaction；
Compound containing acyl chlorides in the preparation, needs first at low temperature to mix phenyl-allylene acid compounds with thionyl chloride
It closes, then carries out back flow reaction；The molar ratio of phenyl-allylene acid compounds and thionyl chloride is 1：(2~4)；Phenyl-allylene acids
The molar ratio for closing object and adjacent Iodoaniline is 1：(0.8~0.95).
Organic solvent is conventional organic solvent, preferably THF in step P2；The catalyst system and catalyzing includes four (triphenylphosphines)
Palladium and thiophene-2-carboxylic acid are cuprous；The reaction carries out at ambient temperature, and the reaction carries out under protective gas atmosphere；
The time of reaction is 1~5h；Acetylenic ketone imine intermediate and the molar ratio of aryl boric acid are 1：(2~3).
Work as R1And R2It differs or R3And R4When being methoxyl group, the product reacted in step P1 and P2 need to use column chromatography
Separating-purifying.
The luminescent material (compound of Formula II) with aggregation-induced emission property of the present invention is non-centrosymmetry when it
Crystal (space group Pna21Crystal), can excite send out fluorescence spectrum under the effect of the pressure, the covering of spectrum peak position is yellow
Green light spectrum area has preferable luminescent properties.
The compound of the Formula II, crystal are preferably that space group is Pna21Crystal.
The luminescent material with aggregation-induced emission property of the formula III compound of the present invention is also with mechanoluminescence
Matter, spectrum peak position cover yellow-green spectrum region, have preferable luminescent properties.
Compared with the existing technology, the present invention has the advantage that and advantageous effect：
(1) luminescent material structure of the invention is stablized, and has aggregation-induced emission property, good luminous performance, crystalline state fluorescence
Quantum efficiency reaches as high as 20.7%；The luminescent material preparation method of the present invention is easy to operate simultaneously, and reaction condition is mild, reaction
Yield is high；
(2) for the luminescent material with aggregation-induced emission property of the invention with solid luminescent, low in raw material price can
Regeneration the advantages that by accessing the photochromic adjusting easy to implement of different supplied for electronic and electron-withdrawing group, is conducive to large-scale promotion,
Solves the problems, such as lack of energy；
(3) luminescent material (Formula II compound (space group Pna2 of the invention1Noncentrosymmetric crystal) and formula III
Compound) be two kinds of yellowish green organic mechanoluminescences of colour purity gathering induced luminescence material, power cause emission peak be located at 570nm
And 587nm；Corresponding with the photic emission peak of their powder simultaneously, crystal is to mechanical forces such as frictional force, pressure, impact forces
Stimulation has response.
Description of the drawings
Fig. 1 is the gathering induced luminescence material for preparing of Examples 1 to 5 in THF solution, suction when a concentration of 10 μm of ol/L
Receive spectrum；
Fig. 2 is the hair for the crystal that luminescent material prepared by Examples 1 to 5 is obtained according to the mode of the culture crystal of embodiment 6
Penetrate spectrum；
Fig. 3 (A) and (B) are respectively luminescent material INDO-DH prepared by embodiment 1 and luminescent material prepared by embodiment 2
Spectrograms of the INDO-DF under different conditions；Fig. 3 (A) and (B) include the side that luminescent material grows crystal according to embodiment 6
The photoluminescence spectra for the crystal that formula obtains, the photoluminescence spectra of powder and the mechanoluminescence spectrum of crystal；In Fig. 3 (A),
INDO-DH (A)-PL indicates the photoluminescence spectra of the A type crystal of luminescent material INDO-DH；INDO-DH (B)-PL indicates to shine
The photoluminescence spectra of the Type B crystal of material INDO-DH；INDO-DH (A)-ML indicates that the power of the A type crystal of INDO-DH causes hair
Penetrate spectrum；Powder indicates the photoluminescence spectra that the A type crystal of INDO-DH is measured by mortar grinder in powder；In Fig. 3
(B) in, INDO-DF-PL indicates the photoluminescence spectra of the crystal of luminescent material INDO-DF；INDO-DF-ML indicates the material that shines
Expect that the power of the crystal of INDO-DF causes emission spectrum；Powder indicates that the crystal of luminescent material INDO-DF passes through mortar grinder into powder
Its photoluminescence spectra that end measures.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.Material involved in the following example can be obtained from commercial channel.
Embodiment 1
The preparation of gathering induced luminescence material (INDO-DH), structural formula are：
Synthetic route is as follows：
2- indolones (1.07g, 8m mol) and benzophenone (1.75g, 9.6mmol) are dissolved in 50mLTHF, then added
Enter pyridine (1.3mL, 16mmol), tetraisopropyl titanate (IV) (7.1mL, 24mmol), mixed liquor is in N2Reflux (60 under protection
DEG C) reaction 5h, THF is spin-dried for vacuum rotary evaporator, then uses DCM/H2O dissolves and extracts filtrate extraction with Buchner funnel
Three times, after taking DCM layers of concentration, pillar layer separation purification is carried out, yellow solid INDO-DH (gathering induced luminescence material) is obtained,
Yield is 1.99g, yield 83.7%.
1H NMR(500MHz,CDCl3)δ(TMS,ppm):8.11(s,1H),7.41-7.45(m,3H),7.35-7.38(m,
5H), 7.30-7.33 (m, 2H), 7.08 (t, J=7.7Hz, 1H), 6.72 (d, J=7.6Hz1H), 6.64 (t, J=7.7Hz,
1H), 6.37 (d, J=7.8Hz, 1H)
13C NMR(126MHz,CDCl3)δ(TMS,ppm):168.07,155.14,141.34,140.39,139.71,
130.32,129.38,129.27,128.95,128.74,127.80,124.17,123.42,121.34,109.35.
HRMS(TOF LD+)：M/z=298.1243 (C21H15NO, theoretical calculation (M+H+)=298.1226)
Embodiment 2
The preparation of gathering induced luminescence material (INDO-DF), structural formula are：
Synthetic route is as follows：
2- indolones (1.07g, 8mmol) and 4,4 '-difluoro benzophenones (2.09g, 9.6mmol) are dissolved in 50mLTHF
In, pyridine (1.3mL, 16mmol) is then added, tetraisopropyl titanate (IV) (7.1mL, 24mmol), mixed liquor is in N2Under protection
THF is spin-dried for vacuum rotary evaporator, then uses DCM/H by back flow reaction 5h2O dissolves and extracts filtrate extraction with Buchner funnel
It takes three times, after taking DCM layers of concentration, carries out pillar layer separation purification, obtain yellow solid INDO-DF (aggregation-induced emission materials
Material), yield 2.44g, yield 91.7%.
1H NMR(500MHz,CDCl3)δ(TMS,ppm):7.64(s,1H),7.38-7.37(m,4H),7.13(m,3H),
7.04 (t, J=8.7Hz, 2H), 6.78 (d, J=7.8Hz, 1H), 6.70 (t, J=7.7Hz, 1H), 6.44 (d, J=7.8Hz,
1H).
13C NMR(126MHz,CDCl3)δ(TMS,ppm):168.46,168.45,164.56,164.42,162.57,
162.43,152.39,140.68,137.09,137.06,135.44,135.42,132.77,132.70,131.81,131.75,
129.00,124.87,123.84,123.08,121.38,116.29,116.11,115.05,114.87,109.77.
HRMS(TOF LD+)：M/z=333.0963 (C21H13F2NO, theoretical calculation (M)=333.0965)
Embodiment 3
The preparation of gathering induced luminescence material (INDO-TOMe), structural formula are：
Synthetic route is as follows：
At (1) 0 DEG C, thionyl chloride (2.2ml, 30mmol) is added to the DCM of phenylpropiolic acid (1.46g, 10mmol)
Back flow reaction 5h in (40mL) solution obtains yellow oil after being walked solvent rotation with Rotary Evaporators；Then it is added dropwise
Enter into pyridine (2.4ml, 30mol) and THF (40mL) solution of adjacent Iodoaniline (2.08g, 9.5mmol), after reacting at room temperature 3h
Stop reaction, is purified by pillar layer separation after concentration, obtain white solid acetylenic ketone imine intermediate f (2.62g), yield is
79.3%；
(2) by (1) acetylenic ketone imine intermediate f obtained by the reaction (1.04g, 3mmol), 3,4,5- trimethoxy phenyl boric acids
(1.27g, 6mmol), tetrakis triphenylphosphine palladium (346.7mg, 0.3mmol), thiophene-2-carboxylic acid cuprous (1.14g, 6mmol) and
THF (40mL) is in N2Under protection, 3h is reacted at room temperature, is purified by pillar layer separation after concentration, obtains yellow solid INDO-TOMe
(gathering induced luminescence material), yield 454mg, yield 39.0%.
1H NMR(500MHz,CDCl3)δ(TMS,ppm):7.90 (s, 1H), 7.45-7.33 (m, 5H), 7.11 (t, J=
7.7Hz, 1H), 6.75 (dd, J=7.8,1.9Hz, 1H), 6.71 (t, J=7.7Hz, 1H), 6.56 (d, J=7.8Hz, 1H),
6.52(s,2H),3.94(s,3H),3.75(s,6H).
13C NMR(126MHz,CDCl3)δ(TMS,ppm):168.28,154.93,153.62,140.43,139.36,
138.95,136.46,130.41,129.46,128.77,127.79,124.09,123.54,121.41,109.46,106.67,
61.12,56.28.
HRMS(TOF LD+)：M/z=388.1545 (C24H21NO4, theoretical calculation (M+H+)=388.1543)
Embodiment 4
The preparation of gathering induced luminescence material (INDO-Cz), structural formula are：
Synthetic route is as follows：
By (1) in embodiment 3 acetylenic ketone imine intermediate f (1.04g, 3mmol) obtained by the reaction, 4- (9H- carbazole -9- bases)
Phenyl boric acid (1.72g, 6mmol), tetrakis triphenylphosphine palladium (346.7mg, 0.3mmol), thiophene-2-carboxylic acid it is cuprous (1.14g,
6mmol) and THF (40mL) is in N2Under protection, 3h is reacted at room temperature, is purified by pillar layer separation after concentration, obtains red solid
INDO-Cz (gathering induced luminescence material), yield 1.02g, yield 73.3%.
1H NMR(500MHz,CDCl3)δ(TMS,ppm):8.17 (d, J=7.6Hz, 2H), 7.71 (s, 1H), 7.67 (d, J
=7.4Hz, 2H), 7.58 (d, J=8.5Hz, 2H), 7.53 (d, J=8.2Hz, 2H), 7.49-7.40 (m, 7H), 7.36-7.30
(t, 2H), 7.16 (td, J=7.7,1.1Hz, 1H), 6.81 (d, J=7.7Hz, 1H), 6.77 (td, J=7.7,1.0Hz, 1H),
6.62 (d, J=7.8Hz, 1H)
13C NMR(126MHz,)δ(TMS,ppm):168.03,154.12,140.73,140.63,140.20,139.63,
138.85,131.37,130.61,129.73,129.26,128.20,127.34,126.30,124.99,124.20,123.86,
123.47,121.68,120.66,120.55,109.92,109.74.
HRMS(TOF LD+)：M/z=462.1720 (C33H22N2O, theoretical calculation (M)=462.1732)
Embodiment 5
The preparation of gathering induced luminescence material (INDO-DOMe), structural formula are：
Synthetic route is as follows：
2- indolones (2.66g, 20mmol) and 4,4'- dimethoxy-benzophenones (5.81g, 24mmol) are dissolved in
In 100mLTHF, pyridine (3.2mL, 40mmol), tetraisopropyl titanate (IV) (17.8mL, 60mmol), mixed liquor is then added
In N2Lower 60 DEG C of reactions 5h is protected, THF is spin-dried for vacuum rotary evaporator, then uses DCM/H2O is dissolved and is taken out with Buchner funnel
It takes filtrate extraction three times, after taking DCM layers of concentration, carries out pillar layer separation purification, obtain bright yellow solid INDO-DOMe (aggregations
Induced luminescence material), yield 5.53g, yield 77.3%.
1H NMR(500MHz,CDCl3)δ(TMS,ppm):7.80 (s, 1H), 7.30 (d, J=8.8Hz, 2H), 7.26 (d, J
=8.8Hz, 2H), 7.08 (td, J=7.7,1.0Hz, 1H), 6.94 (d, J=8.8Hz, 2H), 6.87 (d, J=8.9Hz, 2H),
6.79 (d, J=7.7Hz, 1H), 6.69 (t, J=7.7Hz, 1H), 6.55 (d, J=7.8Hz, 1H), 3.89 (s, 3H), 3.85
(s,3H).
13C NMR(126MHz,CDCl3)δ(TMS,ppm):168.72,161.09,160.83,155.62,139.89,
133.75,133.16,132.13,132.07,127.89,125.05,122.69,121.10,114.11,113.11,109.39,
55.38,55.28.
HRMS(TOF LD+)：M/z=358.1469 (C23H19NO3, theoretical calculation (M+H+)=358.1438)
Embodiment 6
(1) in embodiment 1 luminescent material crystal growth：By the gathering induced luminescence material INDO-DH in embodiment 1,
By growing two kinds of monocrystalline respectively under varying experimental conditions, it is respectively designated as monocrystalline A (INDO-DH (A)) and list
Brilliant B (INDO-DH (B)).
Two ways culture may be used in monocrystalline A：(1) first good solvent dichloromethane is used to dissolve, be then slowly added few
The n-hexane of amount is placed on the place's of being protected from light standing, until there is crystal slowly to grow from solution, monocrystalline shape is rhabdolith；(2)
First good solvent dichloromethane is used to dissolve, a small amount of ethyl acetate is then slowly added, the place's of being protected from light standing is placed on, until there is crystal
It slowly grows from solution, monocrystalline is similarly rhabdolith.The space group of monocrystalline A is Pna21。
Monocrystalline B is then to be added n-hexane by first being dissolved INDO-DH with good solvent chloroform, after shaken well, is placed in
The cool place place of being protected from light is stood, until there is crystal slowly to grow from solution.Its space group is
(2) in embodiment 2 luminescent material crystal growth：The luminescent material INDO-DF that will be obtained in embodiment 2, is first used
Good solvent dichloromethane dissolve, a small amount of n-hexane is then slowly added, be placed on the place of being protected from light standing, up to have crystal slowly from
It grows in solution, monocrystalline shape is bulk crystals, space group Pna21。
(3) in embodiment 3 luminescent material crystal growth：The luminescent material INDO-TOMe that will be obtained in embodiment 3, first
It is dissolved with good solvent dichloromethane, a small amount of n-hexane is then slowly added, the place's of being protected from light standing is placed on, until there is crystal slow
It grows from solution, monocrystalline shape is bulk crystals.Its space group is P1 21/n 1.
(4) in embodiment 4 luminescent material crystal growth：The luminescent material INDO-Cz that will be obtained in embodiment 4, is first used
Good solvent dichloromethane dissolve, a small amount of n-hexane is then slowly added, be placed on the place of being protected from light standing, up to have crystal slowly from
It grows in solution, monocrystalline shape is bulk crystals.Its space group is。
(5) in embodiment 5 luminescent material crystal growth：The luminescent material INDO-DOMe that will be obtained in embodiment 5, first
It is dissolved with good solvent dichloromethane, is then added a small amount of n-hexane, after shaken well, the place of being protected from light standing is placed on, up to there is crystalline substance
Body slowly grows from solution, and monocrystalline shape is bulk crystals.Its space group is。
Embodiment 7
Gathering induced luminescence material prepared by Examples 1 to 5 is dissolved in THF, the THF for obtaining gathering induced luminescence material is molten
Liquid, a concentration of 10 μm of ol/L.The abosrption spectrogram of the solution is as shown in Figure 1.Fig. 1 is aggregation inducing prepared by Examples 1 to 5
Luminescent material is in THF solution, absorption spectrum when a concentration of 10 μm of ol/L.
Gathering induced luminescence material prepared by Examples 1 to 5 obtains respective according to the growth pattern of crystal in embodiment 6
The launching light spectrogram of crystal, crystal is as shown in Figure 2.Fig. 2 is that luminescent material prepared by Examples 1 to 5 cultivates crystalline substance according to embodiment 6
The emission spectrum for the crystal that the mode of body obtains.Use the acromion of 410nm in Fig. 1 as excitation spectrum.From the spectroscopic data of Fig. 2
As can be seen that photochromic adjusting may be implemented by accessing different substituent groups, it is photochromic to realize the (521- from green light to feux rouges
Regulation and control 635nm).It is otherwise noted that these luminescent materials, can't detect emission spectrum in the solution, and in list
Under crystalline state spectrum is all measured, it was demonstrated that they are the material for crystallizing induced luminescence, i.e. gathering induced luminescence material.Embodiment
Molecule in 5 cultivates obtained crystal by embodiment 6, and quantum efficiency is up to 20.7%.
Embodiment 8
The crystal cultivated in embodiment 6 is tested into its mechanoluminescence property, only the A types of luminescent material INDO-DH
The crystal of crystal (INDO-DH (A)) and luminescent material INDO-DF have the property of mechanoluminescence, and they are all non-central
Symmetrical crystal.The mechanoluminescence spectrum of above-mentioned crystal is using the CCD (SPEC-10, Princeton) of liquid nitrogen cooling as strong letter
Number detector is collected from the spectrometer of Acton SP2750.Fig. 3 (A) and (B) are respectively luminescent material prepared by embodiment 1
The spectrogram of luminescent material INDO-DF prepared by INDO-DH and embodiment 2 under different conditions；Fig. 3 (A) and (B) include hair
The photoluminescence spectra of crystal that luminescent material obtains in such a way that embodiment 6 grows crystal, the photoluminescence spectra of powder and
The mechanoluminescence spectrum of crystal；In Fig. 3 (A), INDO-DH (A)-PL indicates the photic of the A type crystal of luminescent material INDO-DH
Emission spectrum；INDO-DH (B)-PL indicates the photoluminescence spectra of the Type B crystal of luminescent material INDO-DH；INDO-DH(A)-
ML indicates that the power of the A type crystal of INDO-DH causes emission spectrum；Powder indicates that the A type crystal of INDO-DH is in by mortar grinder
The photoluminescence spectra that powder measures；In Fig. 3 (B), INDO-DF-PL indicates the photic hair of the crystal of luminescent material INDO-DF
Penetrate spectrum；INDO-DF-ML indicates that the power of the crystal of luminescent material INDO-DF causes emission spectrum；Powder indicates luminescent material
The crystal of INDO-DF passes through its photoluminescence spectra that mortar grinder is measured at powder.When two load glass for accompanying above-mentioned crystal
When piece relatively moves, or when being scraped with spatula, crystal launches glow peak point in the case of no ultra violet lamp
Not Wei Yu 570nm and 587nm yellow light.When intermediate illustration is that INDO-DH (A) crystal is pressed with spatula in Fig. 3 (A), crystal
Fluorescence picture in the case of no ultra violet lamp.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. one kind has the luminescent material of aggregation-induced emission property, it is characterised in that：Its general molecular formula is Formulas I：
Wherein, R1And R2For similar and different electron or electron-withdrawing group, the one kind being respectively selected from following structural：
-H、-OCH3、-Br、-F、-CHO、-CN、
R3And R4It is hydrogen or methoxyl group simultaneously.
2. the luminescent material with aggregation-induced emission property according to claim 1, it is characterised in that：For following structuring
Close object：
R3And R4It is hydrogen, R simultaneously1And R2It is simultaneously-H ,-F ,-Br ,-OCH3、CN；
R3And R4It is hydrogen, R simultaneously1And R2Difference, R1And R2Selected from-H ,-F ,-Br ,-OCH3、CN、CHO、In one
Kind；
R3And R4It is methoxyl group, R simultaneously1And R2It is-H ,-OCH simultaneously3；
R3And R4It is methoxyl group, R simultaneously1And R2Difference, R1And R2Selected from-H ,-OCH3Middle one kind.
3. the luminescent material with aggregation-induced emission property according to claim 1, it is characterised in that：For the chemical combination of Formula II
Object, R1And R2All it is H, R3And R4Also it is hydrogen simultaneously：
The compound of the Formula II, crystal are that space group is Pna21Crystal.
4. the luminescent material with aggregation-induced emission property according to claim 1, it is characterised in that：For the change of formula III
Close object, R1And R2All it is F, R3And R4It is hydrogen simultaneously：
5. the luminescent material with aggregation-induced emission property according to claim 1, it is characterised in that：It is described that there is aggregation
The luminescent material of induced luminescence property is crystalline state or crystallite state.
6. special according to the preparation method of the luminescent material with aggregation-induced emission property described in any one of Claims 1 to 5
Sign is：It is specifically divided into two kinds：
Work as R1And R2Identical and R3And R4When being H, the preparation method of luminescent material includes the following steps：
S1：2- indolones and substituted benzophenone are obtained into required luminescent material by Borneo camphor-Wen Gaier condensation reactions；It takes
The benzophenone in generation is
Work as R1And R2It differs or R3And R4When being methoxyl group, the preparation method of luminescent material includes the following steps：
P1：In organic solvent, phenyl-allylene acid compounds are reacted with thionyl chloride, prepares the compound containing acyl chlorides；
After having reacted, the compound containing acyl chlorides is added in the organic solution of adjacent Iodoaniline, room temperature reaction obtains among acetylenic ketone imines
Body；
Phenyl-allylene acid compounds, structure areThe structure of acetylenic ketone imine intermediate is
P2：In organic solvent and catalyst system and catalyzing, by acetylenic ketone imine intermediate and aromatic yl acid reaction, obtaining has aggregation inducing
The luminescent material of luminosity；
The structure of aryl boric acid is
7. the preparation method of the luminescent material with aggregation-induced emission property according to claim 5, it is characterised in that：When
R1And R2Identical and R3And R4When being H, in preparation method, the solvent of reaction is conventional organic solvent；Urging needed for reaction
Change system includes tetraisopropyl titanate (IV) and pyridine；The reaction carries out under protective gas atmosphere；The time of reaction is 2
~10h；The molar ratio of 2- indolones and substituted benzophenone is 1：(1~1.2).
8. the preparation method of the luminescent material with aggregation-induced emission property according to claim 5, it is characterised in that：When
R1And R2It differs or R3And R4When being methoxyl group, in preparation method, organic solvent is conventional organic solvent in step P1；
Organic solvent is conventional organic solvent THF in the organic solution of adjacent Iodoaniline；The room temperature reaction is under protective gas atmosphere
It carries out；The time of room temperature reaction is 2~10h；
Compound containing acyl chlorides in the preparation, needs first at low temperature to mix phenyl-allylene acid compounds with thionyl chloride,
Then back flow reaction is carried out；The molar ratio of phenyl-allylene acid compounds and thionyl chloride is 1：(2~4)；Phenyl-allylene acids chemical combination
The molar ratio of object and adjacent Iodoaniline is 1：(0.8~0.95)；
Organic solvent is conventional organic solvent in step P2；The catalyst system and catalyzing includes pyridine, tetrakis triphenylphosphine palladium and thiophene-
2- carboxylic acids are cuprous；The reaction carries out at ambient temperature, and the reaction carries out under protective gas atmosphere；The time of reaction
For 1~5h；Acetylenic ketone imine intermediate and the molar ratio of aryl boric acid are 1：(2~3).
9. the application of the luminescent material with aggregation-induced emission property according to claim 1, it is characterised in that：The tool
There is the luminescent material of aggregation-induced emission property in chemical sensitisation, photoelectric field, biological fluorescent labeling and bio-imaging field
Application.
10. according to the application of claim 3 or 4 luminescent materials with aggregation-induced emission property, it is characterised in that：Institute
State the inspection that the luminescent material with aggregation-induced emission property is destroyed in lossless detection stress, monitoring pressure in real time variation, structure
It surveys, display, illuminate, the application of anti-counterfeit field.
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