CN108484474B - Luminescent material with aggregation-induced emission property and preparation and application thereof - Google Patents

Luminescent material with aggregation-induced emission property and preparation and application thereof Download PDF

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CN108484474B
CN108484474B CN201810299861.2A CN201810299861A CN108484474B CN 108484474 B CN108484474 B CN 108484474B CN 201810299861 A CN201810299861 A CN 201810299861A CN 108484474 B CN108484474 B CN 108484474B
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唐本忠
胡蓉蓉
李飞霞
赵祖金
秦安军
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of luminescent materials, and discloses a luminescent material with aggregation-induced emission properties, and preparation and application thereof. The molecular general formula of the luminescent material is shown as formula I, wherein R1And R2Are different or identical electron donating or electron withdrawing groups, R3And R4And is simultaneously hydrogen or methoxy. The luminescent material has stable structure, aggregation-induced emission property and good luminescent performance, and the crystalline fluorescence quantum efficiency can reach 20.7 percent at most; meanwhile, the preparation method of the luminescent material is simple to operate, mild in reaction condition and high in reaction yield; the material has the advantages of solid luminescence, low price of raw materials, reproducibility, easy realization of adjustment of light color by accessing different electron-donating groups and electron-withdrawing groups, and the like, is beneficial to large-scale popularization, and solves the problem of energy exhaustion. Meanwhile, the luminescent material has the property of mechanoluminescence, and can be used in the fields of anti-counterfeiting, real-time monitoring of pressure change and the like.

Description

Luminescent material with aggregation-induced emission property and preparation and application thereof
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a luminescent material with aggregation-induced emission properties, and a preparation method and application thereof.
Background
Compared with inorganic materials, the organic luminescent material has the advantages of large Stokes shift, easy adjustment of light color, flexibility, convenient preparation, renewable raw materials and the like. Based on these advantages, organic light emitting materials have been widely used in the fields of chemical sensing, biological imaging, fluorescent probes, and optoelectronics. However, conventional organic light emitting materials suffer from fluorescence quenching due to large planar structures, close intermolecular packing, and often due to pi-pi stacking. In practice, the light emitting materials such as organic light emitting diodes, nanoparticles, etc. are usually in the form of thin films or solid. The practical application of the conventional organic light emitting material is greatly limited.
Furthermore, mechanoluminescence refers to an emission spectrum under the action of ultrasonic oscillation, impulse, impact, bending, friction, fracture, tension or compression, etc., which is a special phenomenon of luminescence. In recent years, scientists have generated great interest in the phenomenon due to the huge application prospects of the mechanoluminescence materials in nondestructive detection of stress, detection of structural damage, display, illumination, anti-counterfeiting, biological imaging and the like. Although this phenomenon has been studied in a number of papers before, most of them have focused on transition metal elements or rare earth elements such as ZnS, MnS, Eu, and the like. Rare earth metals are expensive, and have limited resources and are not renewable. In addition, inorganic matters are difficult to realize the adjustment of light color, while organic matters have natural advantages in this respect, and the adjustment of light color can be realized only by introducing different substituents. If the luminescent material with both mechanoluminescence and aggregation induction property can be obtained, the application of the luminescent material is greatly expanded, and the luminescent material has important significance for long-term development of the luminescent material.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention provides a luminescent material with aggregation-induced emission property and a preparation method thereof. The luminescent material has stable structure, better luminescent performance in crystalline state and/or microcrystalline state and high fluorescence quantum efficiency. The luminescent material of the invention has simple preparation process, mild reaction condition and high yield, and simultaneously, the single crystal of the luminescent material is obtained by proper solvent culture. In addition, part of the luminescent material of the invention also has the characteristic of mechanoluminescence.
The invention also aims to provide application of the luminescent material with aggregation-induced emission property. The luminescent material with aggregation-induced emission property is applied to the fields of chemical sensing, photoelectricity, biological fluorescent probes and biological imaging. The luminescent material with photoluminescence in the luminescent material with aggregation induced luminescence property can also be applied in the fields of nondestructive stress detection, real-time pressure change monitoring, structural damage detection, display, illumination, anti-counterfeiting and the like.
The purpose of the invention is realized by the following scheme:
a luminescent material with aggregation-induced emission properties has a molecular general formula of formula I:
Figure BDA0001619505530000021
wherein R is1And R2Are different or identical electron-donating groups or electron-withdrawing groups and are respectively selected from one of the following structural formulas:
-H、-OCH3、-Br、-F、-CHO、-CN、
Figure BDA0001619505530000022
R3and R4And is simultaneously hydrogen or methoxy.
The luminescent material with aggregation-induced emission property is preferably one or more of the following structures:
R3and R4Simultaneously being hydrogen, R1And R2At the same time being-H, -F, -Br, -OCH3、CN；
Or R3And R4Simultaneously being hydrogen, R1And R2In a different sense, R1And R2Selected from-H, -F, -Br, -OCH3、CN、CHO、
Figure BDA0001619505530000023
One of the above two methods;
or R3And R4Simultaneously being methoxy, R1And R2Simultaneously is-H, -OCH3；
Or R3And R4Simultaneously being methoxy, R1And R2In a different sense, R1And R2Selected from-H, -OCH3One of them.
The luminescent material having aggregation-induced emission properties is more preferably a compound of formula II R1And R2Are all H, R3And R4Also simultaneously hydrogen:
Figure BDA0001619505530000031
the crystals of the compound of the formula II preferably have the space group Pna21The crystal of (4).
The luminescent material having aggregation-induced emission properties, more preferably a compound of formula III, R1And R2Are all F, R3And R4And simultaneously hydrogen:
Figure BDA0001619505530000032
the luminescent material with aggregation-induced emission properties is crystalline or microcrystalline.
The photoluminescence color of the luminescent material with the aggregation-induced emission property covers a yellow-green to red region (521-635 nm).
The preparation method of the luminescent material with aggregation-induced emission property is specifically divided into two types:
when R is1And R2Are identical and R3And R4When all H, the preparation method of the luminescent material comprises the following steps:
s1: 2-indolone and substituted benzophenone are subjected to a Kenao-Wencal condensation reaction to obtain a required luminescent material; substituted benzophenones are
Figure BDA0001619505530000033
When R is1And R2Is not identical or R3And R4When the methoxy groups are all methoxy groups, the preparation method of the luminescent material comprises the following steps:
p1: reacting a phenylpropanoic acid compound with thionyl chloride in an organic solvent to prepare a compound containing acyl chloride; after the reaction is finished, adding a compound containing acyl chloride into an organic solution of o-iodoaniline, and reacting at room temperature to obtain an acetyleneimine intermediate;
a phenylpropanoid compound with the structure
Figure BDA0001619505530000041
The structure of the alkynone imine intermediate is
Figure BDA0001619505530000042
P2: in an organic solvent and a catalytic system, reacting an acetylenic ketimine intermediate with aryl boric acid to obtain a luminescent material with aggregation-induced emission properties; the arylboronic acid has the structure
Figure BDA0001619505530000043
When R is1And R2Are identical and R3And R4When all H is H, in the preparation method, the solvent for reaction is a conventional organic solvent, preferably THF; the catalytic system required by the reaction comprises tetraisopropyl titanate (IV) and pyridine; the reaction is carried out in a protective gas atmosphere; the reaction time is 2-10 h; the molar ratio of the 2-indolone to the substituted benzophenone is 1: (1-1.2). After the reaction is finished, subsequent treatment is required, specifically, the solvent in the reaction product is removed, DCM/water extraction is adopted, the DCM layer is concentrated, and column chromatography separation and purification are carried out.
When R is1And R2Is not identical or R3And R4When both methoxy groups are present, the preparation method is that the organic solvent in the step P1 is a conventional organic solvent, preferably DCM; the organic solvent in the organic solution of o-iodoaniline is a conventional organic solvent, preferably THF; the room temperature reaction is carried out in a protective gas atmosphere; the reaction time at room temperature is 2-10 h; pyridine is required to be added for the reaction at room temperature;
when the acyl chloride-containing compound is prepared, the phenylpropanoic acid compound and thionyl chloride need to be mixed at low temperature, and then reflux reaction is carried out; the molar ratio of the phenylpropanoid compound to the thionyl chloride is 1: (2-4); the molar ratio of the phenylpropanoid compound to the o-iodoaniline is 1: (0.8-0.95).
The organic solvent in step P2 is a conventional organic solvent, preferably THF; the catalytic system comprises tetrakis (triphenylphosphine) palladium and cuprous thiophene-2-carboxylate; the reaction is carried out at room temperature, and the reaction is carried out in a protective gas atmosphere; the reaction time is 1-5 h; the molar ratio of the acetylenic ketimine intermediate to the arylboronic acid was 1: (2-3).
When R is1And R2Is not identical or R3And R4When both methoxy groups are present, the products of the reactions in steps P1 and P2 are purified by column chromatography.
The luminescent material (compound of formula II) with aggregation-induced emission properties of the present invention is a non-centrosymmetric crystal (space group Pna 2)1The crystal) can be excited to emit a fluorescence spectrum under the action of pressure, and the spectrum peak position of the fluorescence spectrum covers a yellow-green spectrum region, so that the fluorescence spectrum has better luminescence performance.
Figure BDA0001619505530000051
The crystals of the compound of the formula II preferably have the space group Pna21The crystal of (4).
The luminescent material with aggregation-induced emission property of the compound in the formula III also has the mechanoluminescence property, and the spectral peak position of the luminescent material covers a yellow-green spectral region, so that the luminescent material has better luminescence property.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the luminescent material has stable structure, aggregation-induced emission property and good luminescent performance, and the crystalline fluorescence quantum efficiency can reach 20.7 percent at most; meanwhile, the preparation method of the luminescent material is simple to operate, mild in reaction condition and high in reaction yield;
(2) the luminescent material with the aggregation-induced emission property has the advantages of solid-state luminescence, low raw material price, reproducibility, easy realization of light color adjustment by accessing different electron-donating groups and electron-withdrawing groups, and the like, is beneficial to large-scale popularization, and solves the problem of energy exhaustion;
(3) the luminescent material (compound of formula II (space group Pna 2)1The non-centrosymmetric crystal) and the compound of the formula III) are two yellow-green pure organic mechanoluminescence aggregation-induced luminescent materials, and the mechanoluminescence emission peaks are respectively positioned at 570nm and 587 nm; simultaneously with their powdersThe photoemission peak of the crystal corresponds to the crystal, and the crystal responds to mechanical force stimulation such as friction force, pressure, impact force and the like.
Drawings
FIG. 1 is an absorption spectrum of the aggregation-induced emission material prepared in examples 1 to 5 in a THF solution at a concentration of 10. mu. mol/L;
FIG. 2 is an emission spectrum of a crystal obtained by culturing the crystal according to example 6 in the luminescent material prepared in examples 1 to 5;
FIGS. 3(A) and (B) are graphs of spectra of the luminescent material INDO-DH prepared in example 1 and the luminescent material INDO-DF prepared in example 2 in different states, respectively; FIGS. 3(A) and (B) both include photoluminescence spectra of crystals, photoluminescence spectra of powders and photoluminescence spectra of crystals obtained by growing the crystals of the light-emitting material in the same manner as in example 6; in fig. 3(a), INDO-DH (a) -PL represents a photoluminescence emission spectrum of a type a crystal of the light-emitting material INDO-DH; INDO-DH (B) -PL represents the photoluminescence emission spectrum of the B-type crystal of the luminescent material INDO-DH; INDO-DH (A) -ML represents the force-induced emission spectrum of the type A crystal of INDO-DH; powder represents the photoluminescence emission spectrum measured when the type A crystals of INDO-DH were ground into Powder by means of a mortar; in FIG. 3(B), INDO-DF-PL represents the photoluminescence emission spectrum of the crystal of the light-emitting material INDO-DF; INDO-DF-ML represents the force-induced emission spectrum of the crystal of the luminescent material INDO-DF; powder denotes the photoluminescence emission spectrum of the crystal of the luminescent material INDO-DF as measured by grinding into Powder with a mortar.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available.
Example 1
Preparing an aggregation-induced emission material (INDO-DH) with a structural formula as follows:
Figure BDA0001619505530000061
the synthetic route is as follows:
Figure BDA0001619505530000062
2-Indolinone (1.07g,8m mol) and benzophenone (1.75g,9.6mmol) were dissolved in 50mL THF, followed by pyridine (1.3mL,16mmol), tetraisopropyl titanate (IV) (7.1mL,24mmol), and the mixture in N2The reaction was refluxed (60 ℃ C.) for 5H under protection, THF was dried on a vacuum rotary evaporator and then DCM/H was added2Dissolving O, extracting the filtrate for three times by using a Buchner funnel, taking DCM layer, concentrating, and performing column chromatography separation and purification to obtain yellow solid INDO-DH (aggregation-induced emission material) with the yield of 1.99g and the yield of 83.7%.
1H NMR(500MHz,CDCl3)(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)(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)
Example 2
Preparing an aggregation-induced emission material (INDO-DF), wherein the structural formula is as follows:
Figure BDA0001619505530000071
the synthetic route is as follows:
Figure BDA0001619505530000072
2-Indolinone (1.07g,8mmol) and 4,4' -difluorobenzophenone (2.09g,9.6mmol) were dissolved in 50mL THF, followed by pyridine (1.3mL,16mmol), tetraisopropyl titanate (IV) (7.1mL,24mmol), and the mixture was stirred in N2The reaction was refluxed for 5H under protection, THF was dried on a vacuum rotary evaporator and then DCM/H2Dissolving O and using a Buchner filterThe filtrate was extracted three times by funnel extraction, and after the DCM layer was concentrated, column chromatography separation and purification was carried out to obtain yellow solid indoo-DF (aggregation-induced emission material) with a yield of 2.44g and a yield of 91.7%.
1H NMR(500MHz,CDCl3)(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)(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).
Example 3
Preparing an aggregation-induced emission material (INDO-TOMe), wherein the structural formula is as follows:
Figure BDA0001619505530000081
the synthetic route is as follows:
Figure BDA0001619505530000082
(1) adding thionyl chloride (2.2mL,30mmol) into a solution of phenylpropargyl acid (1.46g,10mmol) in DCM (40mL) at 0 ℃ for reflux reaction for 5h, and removing the solvent by a rotary evaporator to obtain a yellow oily substance; then, the intermediate was added dropwise to a solution of pyridine (2.4mL,30mol) and o-iodoaniline (2.08g,9.5mmol) in THF (40mL), reacted at room temperature for 3 hours, then the reaction was stopped, concentrated and purified by column chromatography to give a white solid acetyleneimine intermediate f (2.62g) in 79.3% yield;
(2) the alkyneimine intermediate f (1.04g,3mmol) obtained in the reaction of (1), 3,4, 5-trimethoxyphenylboronic acid (1.27g, 6mmol), tetrakis (triphenylphosphine) palladium (346.7mg,0.3mmol), cuprous thiophene-2-carboxylate (1.14g,6mmol) and THF (40mL) were added under N2Reacting at room temperature for 3h under protection, and concentratingThen, the solid INDO-TOMe (aggregation-induced emission material) is obtained by column chromatography separation and purification, and the yield is 454mg and 39.0 percent.
1H NMR(500MHz,CDCl3)(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)(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(C24H21NO4Theoretical calculation of (M + H)+)＝388.1543).
Example 4
Preparing an aggregation-induced emission material (INDO-Cz), wherein the structural formula is as follows:
Figure BDA0001619505530000091
the synthetic route is as follows:
Figure BDA0001619505530000092
the alkyneimine intermediate f (1.04g,3mmol) obtained in the reaction (1) in example 3, 4- (9H-carbazol-9-yl) phenylboronic acid (1.72g, 6mmol), tetrakis (triphenylphosphine) palladium (346.7mg,0.3mmol), cuprous thiophene-2-carboxylate (1.14g,6mmol) and THF (40mL) were added to N2Reacting at room temperature for 3h under protection, concentrating, and purifying by column chromatography to obtain red solid INDO-Cz (aggregation-induced emission material) with yield of 1.02g and yield of 73.3%.
1H NMR(500MHz,CDCl3)(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,)(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).
Example 5
Preparing an aggregation-induced emission material (INDO-DOMe), wherein the structural formula is as follows:
Figure BDA0001619505530000101
the synthetic route is as follows:
Figure BDA0001619505530000102
2-Indolinone (2.66g,20mmol) and 4,4' -dimethoxybenzophenone (5.81g,24mmol) were dissolved in 100mL THF, followed by pyridine (3.2mL,40mmol), tetraisopropyl titanate (IV) (17.8mL,60mmol), and the mixture in N2Reaction at 60 ℃ for 5H under protection, rotary evaporation of THF in vacuo, and then DCM/H2Dissolving O, extracting the filtrate for three times by using a Buchner funnel, taking DCM layer, concentrating, and performing column chromatography separation and purification to obtain a golden yellow solid INDO-DOMe (aggregation-induced emission material), wherein the yield is 5.53g, and the yield is 77.3%.
1H NMR(500MHz,CDCl3)(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)(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(C23H19NO3Theoretical calculation of (M + H)+)＝358.1438).
Example 6
(one) growth of luminescent material crystal in example 1: the aggregation-inducing luminescent material INDO-DH of example 1 was grown by growing two types of single crystals under different experimental conditions, respectively, and named single crystal a (INDO-DH (a)) and single crystal B (INDO-DH (B)).
Single crystal a can be grown in two ways: (1) dissolving with good solvent dichloromethane, slowly adding a small amount of n-hexane, standing in a dark place until crystals slowly grow out of the solution, wherein the single crystal is rod-shaped; (2) dissolving with good solvent dichloromethane, slowly adding small amount of ethyl acetate, standing in dark place until crystals slowly grow out of the solution, and making single crystal into rod-shaped crystals. The space group of the single crystal A is Pna21。
The monocrystal B is prepared by dissolving INDO-DH with good solvent chloroform, adding n-hexane, shaking, standing in shade until crystal grows out of solution slowly. The space group is
Figure BDA0001619505530000112
Figure BDA0001619505530000111
(II) growth of luminescent material crystals in example 2: dissolving the luminescent material INDO-DF obtained in the example 2 by using a good solvent dichloromethane, slowly adding a small amount of n-hexane, standing in a dark place until crystals slowly grow out of the solution, wherein the single crystal is a blocky crystal with the space group of Pna21。
(third) growth of luminescent material crystal in example 3: the luminescent material indoo-TOMe obtained in example 3 was dissolved in a good solvent dichloromethane, then a small amount of n-hexane was slowly added, and the mixture was left to stand in a dark place until crystals slowly grown out of the solution, and the single crystal was bulk crystals. The space group is P121/n 1.
(fourth) growth of luminescent material crystal in example 4: luminescence obtained in example 4Dissolving the material INDO-Cz with a good solvent dichloromethane, slowly adding a small amount of n-hexane, standing in a dark place until crystals slowly grow out of the solution, wherein the shape of the single crystal is bulk crystal. The space group is
Figure BDA0001619505530000121
。
(V) growth of luminescent material crystals in example 5: the luminescent material INDO-DOMe obtained in the example 5 is firstly dissolved by good solvent dichloromethane, then a small amount of normal hexane is added, after uniform oscillation, the mixture is placed in a dark place and stands until crystals slowly grow out of the solution, and the shape of the single crystal is bulk crystal. The space group is
Figure BDA0001619505530000122
。
Example 7
The aggregation-induced emission materials prepared in examples 1 to 5 were dissolved in THF to obtain a THF solution of the aggregation-induced emission material, the concentration of which was 10. mu. mol/L. The absorption spectrum of the solution is shown in fig. 1. FIG. 1 shows absorption spectra of aggregation-induced emission materials prepared in examples 1 to 5 at a concentration of 10. mu. mol/L in THF solutions.
The aggregation-induced emission materials prepared in examples 1 to 5 were grown in the manner of crystals in example 6 to obtain respective crystals, and emission spectra of the crystals are shown in fig. 2. FIG. 2 is an emission spectrum of a crystal obtained by culturing the crystal according to example 6 in the luminescent material prepared in examples 1 to 5. The shoulder at 410nm in FIG. 1 was used as the excitation spectrum. As can be seen from the spectrum data of FIG. 2, the adjustment of the light color can be realized by accessing different substituents, and the light color realizes the regulation from green light to red light (521-635 nm). It is also noted that these luminescent materials, all of which have no emission spectrum detected in a solution, were measured in a single crystal state, demonstrating that they are crystallization-induced luminescent materials, i.e., aggregation-induced luminescent materials. The molecular example 5 has a quantum efficiency as high as 20.7% for the crystal obtained by the culture of example 6.
Example 8
The crystals obtained by culturing in example 6 were tested for their mechanoluminescence properties, and only the crystals of the luminescent material INDO-DH type A (INDO-DH (A)) and the crystals of the luminescent material INDO-DF had mechanoluminescence properties, and they were all non-centrosymmetric crystals. The mechanoluminescence spectrum of the above crystals was collected from the Acton SP2750 spectrometer using a liquid nitrogen cooled CCD (SPEC-10, Princeton) as a strong signal detector. FIGS. 3(A) and (B) are graphs of spectra of the luminescent material INDO-DH prepared in example 1 and the luminescent material INDO-DF prepared in example 2 in different states, respectively; FIGS. 3(A) and (B) both include photoluminescence spectra of crystals, photoluminescence spectra of powders and photoluminescence spectra of crystals obtained by growing the crystals of the light-emitting material in the same manner as in example 6; in fig. 3(a), INDO-DH (a) -PL represents a photoluminescence emission spectrum of a type a crystal of the light-emitting material INDO-DH; INDO-DH (B) -PL represents the photoluminescence emission spectrum of the B-type crystal of the luminescent material INDO-DH; INDO-DH (A) -ML represents the force-induced emission spectrum of the type A crystal of INDO-DH; powder represents the photoluminescence emission spectrum measured when the type A crystals of INDO-DH were ground into Powder by means of a mortar; in FIG. 3(B), INDO-DF-PL represents the photoluminescence emission spectrum of the crystal of the light-emitting material INDO-DF; INDO-DF-ML represents the force-induced emission spectrum of the crystal of the luminescent material INDO-DF; powder denotes the photoluminescence emission spectrum of the crystal of the luminescent material INDO-DF as measured by grinding into Powder with a mortar. When two glass slides clamping the crystal move relatively or are scraped by a spatula, the crystal emits yellow light with luminescence peaks respectively positioned at 570nm and 587nm under the condition of no ultraviolet lamp irradiation. The middle inset in FIG. 3(A) is a fluorescent picture of the INDO-DH (A) crystals without UV light when pressed with a spatula.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A luminescent material with aggregation-induced emission properties, characterized in that: the molecular general formula is shown as formula I:
Figure FDA0002564585880000011
wherein the content of the first and second substances,
R3and R4Simultaneously being hydrogen, R1And R2At the same time, -F, -Br, CN;
R3and R4Simultaneously being hydrogen, R1And R2In a different sense, R1And R2Selected from-H, -F, -Br, CN, CHO,
Figure FDA0002564585880000012
One of the above two methods;
R3and R4Simultaneously being methoxy, R1And R2Is simultaneously-OCH3；
R3And R4Simultaneously being methoxy, R1And R2In a different sense, R1And R2Selected from-H, -OCH3One of them.
2. The luminescent material having an aggregation-induced emission property according to claim 1, wherein: is a compound of formula III R1And R2Are all F, R3And R4And simultaneously hydrogen:
Figure FDA0002564585880000013
3. the luminescent material having an aggregation-induced emission property according to claim 1, wherein: the luminescent material with aggregation-induced emission properties is crystalline or microcrystalline.
4. The method for producing a luminescent material having an aggregation-induced emission property according to any one of claims 1 to 3, wherein: the method is specifically divided into two types:
when R is1And R2Are identical and R3And R4When all H, the preparation method of the luminescent material comprises the following steps:
s1: 2-indolone and substituted benzophenone are subjected to a Kenao-Wencal condensation reaction to obtain a required luminescent material; substituted benzophenones are
Figure FDA0002564585880000021
When R is1And R2Is not identical or R3And R4When the methoxy groups are all methoxy groups, the preparation method of the luminescent material comprises the following steps:
p1: reacting a phenylpropanoic acid compound with thionyl chloride in an organic solvent to prepare a compound containing acyl chloride; after the reaction is finished, adding a compound containing acyl chloride into an organic solution of o-iodoaniline, and reacting at room temperature to obtain an acetyleneimine intermediate;
a phenylpropanoid compound with the structure
Figure FDA0002564585880000022
The structure of the alkynone imine intermediate is
Figure FDA0002564585880000023
P2: in an organic solvent and a catalytic system, reacting an acetylenic ketimine intermediate with aryl boric acid to obtain a luminescent material with aggregation-induced emission properties;
the arylboronic acid has the structure
Figure FDA0002564585880000024
5. The method for producing a luminescent material having an aggregation-induced emission property according to claim 4, wherein: when R is1And R2Are identical and R3And R4When all H is H, in the preparation method, the solvent for reaction is a conventional organic solvent; catalytic system required for reactionComprising tetraisopropyl titanate (IV) and pyridine; the reaction is carried out in a protective gas atmosphere; the reaction time is 2-10 h; the molar ratio of the 2-indolone to the substituted benzophenone is 1: (1-1.2).
6. The method for producing a luminescent material having an aggregation-induced emission property according to claim 4, wherein: when R is1And R2Is not identical or R3And R4When the methoxy groups are all methoxy groups, in the preparation method, the organic solvent in the step P1 is a conventional organic solvent; the organic solvent in the organic solution of o-iodoaniline is conventional organic solvent THF; the room temperature reaction is carried out in a protective gas atmosphere; the reaction time at room temperature is 2-10 h;
when the acyl chloride-containing compound is prepared, the phenylpropanoic acid compound and thionyl chloride need to be mixed at low temperature, and then reflux reaction is carried out; the molar ratio of the phenylpropanoid compound to the thionyl chloride is 1: (2-4); the molar ratio of the phenylpropanoid compound to the o-iodoaniline is 1: (0.8-0.95);
the organic solvent in the step P2 is a conventional organic solvent; the catalytic system comprises tetrakis (triphenylphosphine) palladium and cuprous thiophene-2-carboxylate; the reaction is carried out at room temperature, and the reaction is carried out in a protective gas atmosphere; the reaction time is 1-5 h; the molar ratio of the acetylenic ketimine intermediate to the arylboronic acid was 1: (2-3).
7. Use of a luminescent material having aggregation-induced emission properties, wherein: the luminescent material with aggregation-induced emission property is applied to the fields of chemical sensing, photoelectricity, bioluminescent probes and biological imaging;
the molecular general formula of the luminescent material with the aggregation-induced emission property is shown as formula I:
Figure FDA0002564585880000031
wherein R is1And R2Are different or identical radicals, each being independently selectedOne from the following structural formulas:
-H、-OCH3、-Br、-F、-CHO、-CN、
Figure FDA0002564585880000032
R3and R4And is simultaneously hydrogen or methoxy.
8. Use of a luminescent material having aggregation-induced emission properties, wherein: the luminescent material with the aggregation-induced emission property is applied to the fields of nondestructive stress detection, real-time pressure change monitoring, structural damage detection, display, illumination and anti-counterfeiting;
the luminescent material with aggregation-induced emission properties is a compound of formula II:
Figure FDA0002564585880000033
the compound of formula II, the crystal of which has the space group Pna21The crystal of (4);
or the luminescent material with aggregation-induced emission properties is a compound of formula III:
Figure FDA0002564585880000041
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