CN103484103B - Aggregation-induced luminescent material and preparation method thereof - Google Patents
Aggregation-induced luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an aggregation-induced luminescent material and a preparation method thereof. The preparation method comprises the following steps: 1) adding iodine, an organic solvent and a sodium methoxide methanol solution into halobenzyl cyanide, and reacting for 3-4 hours to obtain a product 1; 2) adding an organic solvent and a sodium methoxide methanol solution into the product 1, and reacting for 2 hours to obtain a product 2; 3) proportionally adding potassium carbonate, acetone and halide into the product 2, and reacting for 5 hours to obtain a product 3; and 4) proportionally mixing the product 3, carbazole, inorganic alkali, CuI, 1,4-dioxane and cyclohexyl diamine, reacting for 12 hours, and purifying to obtain the target product N-substituted-3,4-di(4'-carbazolylphenyl)maleimide. The aggregation-induced luminescent material has the advantages of high heat stability, low cost, high solid fluorescence quantum efficiency, favorable biocompatibility and the like, and has wide application prospects in the fields of optical sensors, biomarkers, photoelectric devices and the like.
Description
Technical field
The present invention relates to a kind of gathering induced luminescence material and preparation method thereof, particularly contain gathering induced luminescence material of 4-carbazole phenyl maleimide and preparation method thereof.
Background technology
Most of luminous organic materials have stronger fluorescence under solution state, and in the time of state of aggregation, cause even quencher of fluorescent weakening (
phys.Chem., 1954,1,275), the application that this has limited to these materials to a great extent, therefore designs, synthesizes the compound strengthening at state of aggregation fluorescence and have far reaching significance.Calendar year 2001, it is luminous hardly in the time of dilute solution state that Tang Benzhong etc. (Tang, J.Mater.Chem., 2001,11,2974) find that thiophene is coughed up derivative, but send compared with hyperfluorescenceZeng Yongminggaoyingguang in the time of state of aggregation.They,, by luminous this abnormal phenomena called after aggregation inducing (Aggregation Induced Emission, AIE), have caused the very big concern of scientific circles.Afterwards, other material with this aggregation inducing luminescence phenomenon also gradually studied persons excavate.If polyhenylene acetylene is its 3.5 times (Deans, J.Am.Chem.Soc., 2000,122,8586) under solution state in the fluorescence quantum efficiency under state of aggregation; The quantum yield that polyphenylene ethylene is found its film is 8～10 times (Belton, Appl.Phys.Lett., 2001,78,1859) under its solution state; 1-cyano group-1,2-bis--(4 '-methyl biphenyl) ethene is luminous hardly in solution, but in the time of state of aggregation or solid film, luminous efficiency significantly improves (An, J.Am.Chem.Soc., 2002,124,14410).
The luminous organic material with the aggregation inducing characteristics of luminescence is the ideal material of the sensitive luminescent device of preparation high-performance, thereby this class material is subject to having broad application prospects in fields such as optical pickocff, biomarker and photoelectric devices.Along with the development of nanotechnology, organic nano material has been subject to many investigators' favor (Wang, J.Am.Chem.Soc., 2005,127,10350).Compare with inorganic nano-particle with noble metal nano particles, organic nano particle has more advantage, as lower in cost, easily modify and nanoparticle easily prepare.Utilize the fluorescent switch effect of aggregation inducing luminophor Micelle-like Nano-structure of Two, detect volatile organic matter (Kokado, Macromolecules, 2009,42,1418; Peterson, ACS Appl.Mater.Interfaces, 2011,3,1796); Utilize the aggregation inducing luminophor that electron donation is very strong can also detect the hazardous substance such as trotyl, picric acid, because the Photoinduced Electron occurring between the two shifts effectively quench fluorescence signal (Xu., Macromolecules, 2011,44,5089); The transformation that some aggregation inducing luminophors can dissolve-assemble in the time of suitable pH value, utilizes the principle of work of this sensitive procedures, can design fluorescent switch pH sensor (Lu, Langmuir, 2010,26,6838); The aggregate hybridized nanometer particle with organism with favorable compatibility also can be used for (Qin, Adv.Funct.Mater., 2012,22,771) such as biological in-vivo imaging, structure elucidation and detections.
Aryl maleimide derivatives has advantages of that because of it fluorescence intensity is high, chemical stability good, chemical structure is easily modified (Kaletas, J.Phys.Chem.A, 2005,109,6440; Yeh, Chem.Mater., 2006,18,832); Aspect photoelectric material, cause great concern.Maleimide itself is a stronger drawing electron group, introduces strong electron-donating group in its 3, No. 4 positions, can effectively reduce the optical band gap of material.As introduce the groups such as phenyl, thiophene and indoles and can effectively regulate the photochromic of maleimide, obtain strong green glow, orange light and red emission.But aryl maleimide often has stronger fluorescence in dilute solution, in strong solution, owing to having formed excimer between planar conjugate chromophoric group, thereby cause the generation of fluorescent quenching, i.e. concentration quenching effect.In addition, when aryl maleimide is used as the thin-film material of luminescent device, accumulation between molecule is tightr, between the aromatic nucleus of adjacent molecule, exist strong pi-pi accumulation effect, like this, aggregate in excited state can release energy and cause radiationless transition with the form such as thermal vibration, collision, thus the quenching of fluorescence of making, i.e. aggregation inducing quenching of fluorescence.Concentration quenching effect and aggregation inducing fluorescent quenching effect have limited the further application of aryl maleimide derivatives at photoelectric field to a great extent.
Summary of the invention
The object of this invention is to provide a kind of gathering induced luminescence material and preparation method thereof.The 4-carbazole phenyl that is about to have electron donation is incorporated on 3, No. 4 positions of maleimide.Utilize hole transport ability, photochemical stability and carrier mobility that carbazole group is high, improve luminous efficiency, simultaneously, the introducing of carbazole group, has increased the rigidity of molecular structure, has reduced the intermolecular strong interaction of state of aggregation and pi-pi accumulation effect, stop excimer to generate, inhibition concentration quenching effect and aggregation inducing fluorescent quenching effect, thus solid state fluorescence quantum yield can be improved, realize aggregation inducing luminous.
The chemical structural formula of a kind of gathering induced luminescence material provided by the invention is shown below:
Wherein R=CH
2cOOC (CH
3)
3, CH
2cOOH, CH
2c
6f
5, CH
2c
6h
5or C
nh
2n+1(n=1～12).
The quantum yield of gathering induced luminescence material in methylene dichloride is 0.01～0.07, and the quantum yield in acetone is 0.0005～0.005, and solid-state quantum yield is 0.10～0.78.
Gathering induced luminescence material of the present invention be by halobenzene acetonitrile through oxidative coupling, cyclization and substitution reaction, then under cuprous iodide catalysis, carry out with carbazole that Liv Ullmann linked reaction obtains.
The concrete preparation method of gathering induced luminescence material of the present invention is as follows:
1) preparation of two (4-halobenzene base) anti-maleic nitrile:
In 50ml two-neck bottle, add halobenzene acetonitrile, take out and fill with three times with nitrogen, the iodine adding under nitrogen protection, anhydrous organic solvent reinjects, at-78 DEG C of temperature, stir, slowly drip the previously prepared good methanol solution that contains 2mol/L sodium methylate, after dropwising, by ice-water bath hierarchy of control temperature of reaction, now solution colour deepens, and a large amount of light yellow solids are separated out, continue reaction 3～4 hours, after add 3～6% aqueous hydrochloric acids neutralizations, stopped reaction, suction filtration, with mixing solutions (v/v=1:2) washing of the methanol/water of ice, vacuum-drying, obtain two (4-halobenzene base) anti-maleic nitrile.
Described to halobenzene acetonitrile be selected from p-chlorobenzyl cyanide, to bromobenzylcyanide or to iodobenzene acetonitrile.
Described organic solvent is selected from ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or toluene.
Described is to add according to the ratio of 5mmol ︰ 2～6mmol ︰ 20ml ︰ 5～15ml to halobenzene acetonitrile, iodine, anhydrous organic solvent, methanol solution.
2) 3, the preparation of 4-bis-(4 '-halobenzene base) maleimide
In 50ml round-bottomed flask, add two (4-halobenzene base) anti-maleic nitrile, take out and fill with three times with nitrogen, under 25～50 DEG C of conditions and nitrogen protection, add anhydrous organic solvent, two (4-halobenzene base) anti-maleic nitrile is partly dissolved, add again the methanol solution (2mol/L) of previously prepared good sodium methylate, solution becomes clarification, and color is more and more darker, 2 hours reaction times; Be adjusted to neutrality with dilute hydrochloric acid, with dichloromethane extraction three times, then use respectively distilled water, saturated common salt water washing, anhydrous magnesium sulfate drying, filters, and revolves steaming, column chromatography is purified, obtain of the present invention 3,4-bis-(4 '-halobenzene base) maleimide.
Described organic solvent is selected from ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or toluene.
Described two (4-halobenzene base) anti-maleic nitrile, organic solvent, methanol solution are to add according to the ratio of 2mmol ︰ 10ml ︰ 3～7ml.
3) 3, the substitution reaction of 4-bis-(4 '-halobenzene base) maleimide
The round-bottomed flask that 3,4-bis-(4 '-halobenzene base) maleimide and salt of wormwood is placed in to 25ml, adds acetone, stirring at room temperature 30 minutes, solution colour progressively deepens, and adds halides, continue reaction after 5 hours, be extracted with ethyl acetate saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, recrystallization, obtain N-substituting group-3,4-bis-(4 '-halobenzene base) maleimide.
Described halides is selected from BrCH
2cOOC (CH
3)
3, ICH
2cOOH, BrCH
2c
6f
5, BrCH
2c
6h
5, ICH
3or BrC
nh
2n+1(n=2～12);
Described 3,4-bis-(4 '-halobenzene base) maleimide, salt of wormwood, acetone, halides are to add according to the ratio of 1mmol ︰ 1～3mmol ︰ 25ml ︰ 10ml.
4) N-substituting group-3, the preparation of 4-bis-(4 '-carbazole phenyl) maleimide:
In 10ml round-bottomed flask, add N-substituting group-3, 4-bis-(4 '-halobenzene base) maleimide, carbazole, mineral alkali, CuI, take out and fill with nitrogen three times, inject anhydrous 1, 4-dioxane, after stirring at room temperature 15min, injection ring hexanediamine fast, reflux 12 hours, after stopped reaction, filter out solid, filtrate dichloromethane extraction, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, obtain target compound N-of the present invention substituting group-3, 4-bis-(4 '-carbazole phenyl) maleimide, it is gathering induced luminescence material.
Described mineral alkali is selected from salt of wormwood, sodium hydroxide or potassium tert.-butoxide.
Described N-substituting group-3,4-bis-(4 '-halobenzene base) maleimide, carbazole, mineral alkali, CuI, anhydrous Isosorbide-5-Nitrae-dioxane, cyclohexanediamine are to add according to the ratio of 1mmol ︰ 2-10mmol ︰ 2-10mmol ︰ 0.4～1mmol ︰ 8ml ︰ 0.8～1.6mmol.
The gathering induced luminescence material that utilizes method of the present invention to prepare, the quantum yield in methylene dichloride is 0.01～0.07, and the quantum yield in acetone is 0.0005～0.005, and solid-state quantum yield is 0.10～0.78.
The advantages such as gathering induced luminescence material of the present invention has Heat stability is good, cost is low, solid state fluorescence quantum yield is high, good biocompatibility, it is at acetone, acetonitrile and N, luminous hardly in dinethylformamide isopolarity solvent, but send strong fluorescence after forming nanoparticle.Therefore, it has broad application prospects in fields such as optical pickocff, biomarker and photoelectric devices.
Brief description of the drawings
Fig. 1. N-tert.-butyl acetate of the present invention base-3,4-bis-(4 '-carbazole phenyl) maleimide gathering induced luminescence material chemical structural formula.
Fig. 2. water content is to N-tert.-butyl acetate base-3, the impact of the fluorescence quantum yield of 4-bis-(4 '-carbazole phenyl) maleimide nanoparticle.
Fig. 3. water content N-tert.-butyl acetate base-3 90% time, the electromicroscopic photograph of 4-bis-(4 '-carbazole phenyl) maleimide nanoparticle.
Embodiment
Following embodiment further illustrates of the present invention, instead of limits the scope of the invention.
Embodiment 1
1) preparation of two (4-bromophenyl) anti-maleic nitrile:
In 50ml two-neck bottle, add 0.98g to bromobenzylcyanide (5mmol), take out and fill with nitrogen three times, under nitrogen protection, add the iodine (2mmol) of 0.51g, the anhydrous diethyl ether of 20ml reinjects,-78 DEG C of stirrings, slowly drip the methanol solution (2mol/L) of the previously prepared good sodium methylate of 5ml, after dropwising, by ice-water bath hierarchy of control temperature of reaction, now solution colour deepens, and a large amount of light yellow solids are separated out, continue reaction 3 hours, after add 3% aqueous hydrochloric acid neutralization, stopped reaction, suction filtration, with mixing solutions (v/v=1:2) washing of the methanol/water of ice, vacuum-drying, obtain two (4-bromophenyl) anti-maleic nitrile,
2) 3, the preparation of 4-bis-(4 '-bromophenyl) maleimide
In 50ml round-bottomed flask, add two (4-bromophenyl) anti-maleic nitriles (2mmol) of 0.78g, take out and fill with nitrogen three times, add the anhydrous toluene of 10ml, reactant is partly dissolved, add again the methanol solution (2mol/L) of the previously prepared good sodium methylate of 3ml, solution becomes clarification, and color is more and more darker, 25 DEG C of reactions 2 hours, be adjusted to neutrality with dilute hydrochloric acid, with dichloromethane extraction three times, use respectively again distilled water, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, can obtain 3, 4-bis-(4 '-bromophenyl) maleimide,
3) 3, the substitution reaction of 4-bis-(4 '-bromophenyl) maleimide
By 3 of 0.41g, the salt of wormwood (1mmol) of 4-bis-(4 '-bromophenyl) maleimide (1mmol) and 0.13g is placed in the round-bottomed flask of 25ml, add the acetone of 10ml, stirring at room temperature 30 minutes, solution colour progressively deepens, add the bromo-acetic acid tert-butyl (1mmol) of 0.16ml, continue reaction after 5 hours, be extracted with ethyl acetate saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, recrystallization, obtain N-tert.-butyl acetate base-3,4-bis-(4 '-bromophenyl) maleimide;
4) N-tert.-butyl acetate base-3, the preparation of 4-bis-(4 '-carbazole phenyl) maleimide:
In 10ml round-bottomed flask, add N-tert.-butyl acetate base-3 of 0.52g, 4-bis-(4 '-bromophenyl) maleimide (1mmol), the carbazole (2mmol) of 0.33g, the salt of wormwood (2mmol) of 0.26g, the CuI (0.4mmol) of 76.18mg, take out and fill with nitrogen three times, inject anhydrous 1 of 8ml, 4-dioxane, after stirring at room temperature 15min, the 0.1ml cyclohexanediamine (0.8mmol) injecting fast, reflux 12 hours, after stopped reaction, filter out solid, filtrate dichloromethane extraction, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, obtain N-tert.-butyl acetate base-3, 4-bis-(4 '-carbazole phenyl) maleimide.Its structural formula as shown in Figure 1.Its quantum yield in methylene dichloride is 0.01, and the quantum yield in acetone is 0.0005, and solid-state quantum yield is 0.64.
Fig. 2 is N-tert.-butyl acetate base-3 prepared by the present embodiment, 4-bis-(the 4 '-carbazole phenyl) fluorescence quantum yield of maleimide nanoparticle and the graph of a relation of water content.As can be seen from the figure, the starting stage fluorescence quantum yield increasing in water content changes little, until water content is increased to 30%, fluorescence quantum yield starts to increase, and in the time that water content is 66%, reaches maximum value.
Fig. 3 is N-tert.-butyl acetate base-3 prepared by the present embodiment, the electromicroscopic photograph of 4-bis-(4 '-carbazole phenyl) maleimide nanoparticle in the time that water content is 90%.As can be seen from the figure, the nano-particles size heterogeneity of formation, particle diameter is between 15～250 nanometers.
Embodiment 2:
1) preparation of two (4-chloro-phenyl-) anti-maleic nitrile:
In 50ml two-neck bottle, add the p-chlorobenzyl cyanide (5mmol) of 0.76g, take out and fill with nitrogen three times, under nitrogen protection, add the iodine (3mmol) of 0.76g, the anhydrous tetrahydro furan of 20ml reinjects,-78 DEG C of stirrings, slowly drip the methanol solution (2mol/L) of the previously prepared good sodium methylate of 7ml, after dropwising, by ice-water bath hierarchy of control temperature of reaction, now solution colour deepens, and a large amount of light yellow solids are separated out, continue reaction 4 hours, after add 4% aqueous hydrochloric acid neutralization, stopped reaction, suction filtration, with mixing solutions (v/v=1:2) washing of the methanol/water of ice, vacuum-drying, obtain two (4-chloro-phenyl-) anti-maleic nitrile,
2) 3, the preparation of 4-bis-(4 '-chloro-phenyl-) maleimide
In 50ml round-bottomed flask, add two (4-chloro-phenyl-) anti-maleic nitriles (2mmol) of 0.60g, take out and fill with nitrogen three times, add 10ml anhydrous 1, 4-dioxane, reactant is partly dissolved, add again the methanol solution (2mol/L) of the previously prepared good sodium methylate of 4ml, solution becomes clarification, and color is more and more darker, 30 DEG C of reactions 2 hours, be adjusted to neutrality with dilute hydrochloric acid, with dichloromethane extraction three times, use respectively again distilled water, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, can obtain 3, 4-bis-(4 '-chloro-phenyl-) maleimide,
3) 3, the substitution reaction of 4-bis-(4 '-chloro-phenyl-) maleimide
By 3 of 0.32g, the salt of wormwood (1mmol) of 4-bis-(4 '-chloro-phenyl-) maleimide (1mmol) and 0.13g is placed in the round-bottomed flask of 25ml, add the acetone of 10ml, stirring at room temperature 30 minutes, solution colour progressively deepens, add the iodoacetic acid (1mmol) of 0.19g, continue reaction after 5 hours, be extracted with ethyl acetate saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, recrystallization, obtain N-acetic acid-3,4-bis-(4 '-chloro-phenyl-) maleimide;
4) N-acetic acid-3, the preparation of 4-bis-(4 '-carbazole phenyl) maleimide:
In 10ml round-bottomed flask, add N-acetic acid-3 of 0.38g, 4-bis-(4 '-chloro-phenyl-) maleimide (1mmol), the carbazole (4mmol) of 0.66g, the sodium hydroxide (2mmol) of 0.08g, the CuI (0.5mmol) of 0.1g, take out and fill with nitrogen three times, inject anhydrous 1 of 8ml, 4-dioxane, after stirring at room temperature 15min, the 0.12ml cyclohexanediamine (1.0mmol) injecting fast, reflux 12 hours, after stopped reaction, filter out solid, filtrate dichloromethane extraction, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, obtain N-acetic acid-3, 4-bis-(4 '-carbazole phenyl) maleimide.Its quantum yield in methylene dichloride is 0.02, and the quantum yield in acetone is 0.0007, and solid-state quantum yield is 0.56.
Embodiment 3:
1) preparation of two (4-iodophenyl) anti-maleic nitrile:
In 50ml two-neck bottle, add 1.22g to iodobenzene acetonitrile (5mmol), take out and fill with nitrogen three times, under nitrogen protection, add the iodine (4mmol) of 1.02g, anhydrous 1 of 20ml reinjects, 4-dioxane,-78 DEG C of stirrings, slowly drip the methanol solution (2mol/L) of the previously prepared good sodium methylate of 9ml, after dropwising, by ice-water bath hierarchy of control temperature of reaction, now solution colour deepens, and a large amount of light yellow solids are separated out, continue reaction 3 hours, after add 5% aqueous hydrochloric acid neutralization, stopped reaction, suction filtration, with mixing solutions (v/v=1:2) washing of the methanol/water of ice, vacuum-drying, obtain two (4-iodophenyl) anti-maleic nitrile,
2) 3, the preparation of 4-bis-(4 '-iodophenyl) maleimide
In 50ml round-bottomed flask, add two (4-iodophenyl) anti-maleic nitriles (2mmol) of 0.96g, take out and fill with nitrogen three times, add the anhydrous tetrahydrofuran (THF) of 10ml, reactant is partly dissolved, add again the methanol solution (2mol/L) of the previously prepared good sodium methylate of 5ml, solution becomes clarification, and color is more and more darker, 40 DEG C of reactions 2 hours, be adjusted to neutrality with dilute hydrochloric acid, with dichloromethane extraction three times, use respectively again distilled water, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, can obtain 3, 4-bis-(4 '-iodophenyl) maleimide,
3) 3, the substitution reaction of 4-bis-(4 '-iodophenyl) maleimide
By 3 of 0.50g, the salt of wormwood (1mmol) of 4-bis-(4 '-iodophenyl) maleimide (1mmol) and 0.13g is placed in the round-bottomed flask of 25ml, add the acetone of 10ml, stirring at room temperature 30 minutes, solution colour progressively deepens, add the bromobenzyl (1mmol) of 0.12ml, continue reaction after 5 hours, be extracted with ethyl acetate saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, recrystallization, obtain N-benzyl-3,4-bis-(4 '-iodophenyl) maleimide;
4) N-benzyl-3, the preparation of 4-bis-(4 '-carbazole phenyl) maleimide:
In 10ml round-bottomed flask, add N-benzyl-3 of 0.59g, 4-bis-(4 '-iodophenyl) maleimide (1mmol), the carbazole (6mmol) of 1g, the sodium tert-butoxide (2mmol) of 0.19g, the CuI (0.6mmol) of 0.11g, take out and fill with nitrogen three times, inject anhydrous 1 of 8ml, 4-dioxane, after stirring at room temperature 15min, the 0.15ml cyclohexanediamine (1.2mmol) injecting fast, reflux 12 hours, after stopped reaction, filter out solid, filtrate dichloromethane extraction, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, obtain N-benzyl-3, 4-bis-(4 '-carbazole phenyl) maleimide.Its quantum yield in methylene dichloride is 0.01, and the quantum yield in acetone is 0.0006, and solid-state quantum yield is 0.49.
Embodiment 4:
1) preparation of two (4-bromophenyl) anti-maleic nitrile:
In 50ml two-neck bottle, add 0.98g to bromobenzylcyanide (5mmol), take out and fill with nitrogen three times, under nitrogen protection, add the iodine (5mmol) of 1.27g, the anhydrous diethyl ether of 20ml reinjects,-78 DEG C of stirrings, slowly drip the methanol solution (2mol/L) of the previously prepared good sodium methylate of 11ml, after dropwising, by ice-water bath hierarchy of control temperature of reaction, now solution colour deepens, and a large amount of light yellow solids are separated out, continue reaction 4 hours, after add 6% aqueous hydrochloric acid neutralization, stopped reaction, suction filtration, with mixing solutions (v/v=1:2) washing of the methanol/water of ice, vacuum-drying, obtain two (4-bromophenyl) anti-maleic nitrile,
2) 3, the preparation of 4-bis-(4 '-bromophenyl) maleimide
In 50ml round-bottomed flask, add two (4-bromophenyl) anti-maleic nitriles (2mmol) of 0.78g, take out and fill with nitrogen three times, add the anhydrous toluene of 10ml, reactant is partly dissolved, add again the methanol solution (2mol/L) of the previously prepared good sodium methylate of 6ml, solution becomes clarification, and color is more and more darker, 50 DEG C of reactions 2 hours, be adjusted to neutrality with dilute hydrochloric acid, with dichloromethane extraction three times, use respectively again distilled water, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, can obtain 3, 4-bis-(4 '-bromophenyl) maleimide,
3) 3, the substitution reaction of 4-bis-(4 '-bromophenyl) maleimide
By 3 of 0.41g, the salt of wormwood (2mmol) of 4-bis-(4 '-bromophenyl) maleimide (1mmol) and 0.26g is placed in the round-bottomed flask of 25ml, add the acetone of 10ml, stirring at room temperature 30 minutes, solution colour progressively deepens, add the methyl iodide (2mmol) of 0.12ml, continue reaction after 5 hours, be extracted with ethyl acetate saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, recrystallization, obtain N-methyl-3,4-bis-(4 '-bromophenyl) maleimide;
4) N-methyl-3, the preparation of 4-bis-(4 '-carbazole phenyl) maleimide:
In 10ml round-bottomed flask, add N-methyl-3 of 0.42g, 4-bis-(4 '-bromophenyl) maleimide (1mmol), the carbazole (8mmol) of 1.32g, the salt of wormwood (4mmol) of 0.52g, the CuI (0.7mmol) of 133.3mg, take out and fill with nitrogen three times, inject anhydrous 1 of 8ml, 4-dioxane, after stirring at room temperature 15min, the 0.17ml cyclohexanediamine (1.4mmol) injecting fast, reflux 12 hours, after stopped reaction, filter out solid, filtrate dichloromethane extraction, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, obtain N-methyl-3, 4-bis-(4 '-carbazole phenyl) maleimide.Its quantum yield in methylene dichloride is 0.05, and the quantum yield in acetone is 0.002, and solid-state quantum yield is 0.23.
Embodiment 5:
1) preparation of two (4-chloro-phenyl-) anti-maleic nitrile:
In 50ml two-neck bottle, add the p-chlorobenzyl cyanide (5mmol) of 0.76g, take out and fill with nitrogen three times, under nitrogen protection, add the iodine (6mmol) of 1.52g, the anhydrous tetrahydro furan of 20ml reinjects,-78 DEG C of stirrings, slowly drip the methanol solution (2mol/L) of the previously prepared good sodium methylate of 13ml, after dropwising, by ice-water bath hierarchy of control temperature of reaction, now solution colour deepens, and a large amount of light yellow solids are separated out, continue reaction 3 hours, after add 4% aqueous hydrochloric acid neutralization, stopped reaction, suction filtration, with mixing solutions (v/v=1:2) washing of the methanol/water of ice, vacuum-drying, obtain two (4-chloro-phenyl-) anti-maleic nitrile,
2) 3, the preparation of 4-bis-(4 '-chloro-phenyl-) maleimide
In 50ml round-bottomed flask, add two (4-chloro-phenyl-) anti-maleic nitriles (2mmol) of 0.60g, take out and fill with nitrogen three times, add 10ml anhydrous 1, 4-dioxane, reactant is partly dissolved, add again the methanol solution (2mol/L) of the previously prepared good sodium methylate of 7ml, solution becomes clarification, and color is more and more darker, 25 DEG C of reactions 2 hours, be adjusted to neutrality with dilute hydrochloric acid, with dichloromethane extraction three times, use respectively again distilled water, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, can obtain 3, 4-bis-(4 '-chloro-phenyl-) maleimide,
3) 3, the substitution reaction of 4-bis-(4 '-chloro-phenyl-) maleimide
By 3 of 0.32g, the salt of wormwood (2mmol) of 4-bis-(4 '-chloro-phenyl-) maleimide (1mmol) and 0.26g is placed in the round-bottomed flask of 25ml, add the acetone of 10ml, stirring at room temperature 30 minutes, solution colour progressively deepens, add the PFBBR bromine (2mmol) of 0.28ml, continue reaction after 5 hours, be extracted with ethyl acetate saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, recrystallization, obtain N-PFBBR-3,4-bis-(4 '-chloro-phenyl-) maleimide;
4) N-PFBBR-3, the preparation of 4-bis-(4 '-carbazole phenyl) maleimide:
In 10ml round-bottomed flask, add N-PFBBR-3 of 0.50g, 4-bis-(4 '-chloro-phenyl-) maleimide (1mmol), the carbazole (10mmol) of 1.67g, the sodium hydroxide (4mmol) of 0.16g, the CuI (0.8mmol) of 0.15g, take out and fill with nitrogen three times, inject anhydrous 1 of 8ml, 4-dioxane, after stirring at room temperature 15min, the 0.20ml cyclohexanediamine (1.6mmol) injecting fast, reflux 12 hours, after stopped reaction, filter out solid, filtrate dichloromethane extraction, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, obtain N-PFBBR-3, 4-bis-(4 '-carbazole phenyl) maleimide.Its quantum yield in methylene dichloride is 0.07, and the quantum yield in acetone is 0.001, and solid-state quantum yield is 0.34.
Embodiment 6:
1) preparation of two (4-iodophenyl) anti-maleic nitrile:
In 50ml two-neck bottle, add 1.22g to iodobenzene acetonitrile (5mmol), take out and fill with nitrogen three times, under nitrogen protection, add the iodine (2mmol) of 0.51g, anhydrous 1 of 20ml reinjects, 4-dioxane,-78 DEG C of stirrings, slowly drip the methanol solution (2mol/L) of the previously prepared good sodium methylate of 15ml, after dropwising, by ice-water bath hierarchy of control temperature of reaction, now solution colour deepens, and a large amount of light yellow solids are separated out, continue reaction 4 hours, after add 3% aqueous hydrochloric acid neutralization, stopped reaction, suction filtration, with mixing solutions (v/v=1:2) washing of the methanol/water of ice, vacuum-drying, obtain two (4-iodophenyl) anti-maleic nitrile,
2) 3, the preparation of 4-bis-(4 '-iodophenyl) maleimide
In 50ml round-bottomed flask, add two (4-iodophenyl) anti-maleic nitriles (2mmol) of 0.96g, take out and fill with nitrogen three times, add the anhydrous tetrahydrofuran (THF) of 10ml, reactant is partly dissolved, add again the methanol solution (2mol/L) of the previously prepared good sodium methylate of 3ml, solution becomes clarification, and color is more and more darker, 30 DEG C of reactions 2 hours, be adjusted to neutrality with dilute hydrochloric acid, with dichloromethane extraction three times, use respectively again distilled water, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, can obtain 3, 4-bis-(4 '-iodophenyl) maleimide,
3) 3, the substitution reaction of 4-bis-(4 '-iodophenyl) maleimide
By 3 of 0.50g, the salt of wormwood (2mmol) of 4-bis-(4 '-iodophenyl) maleimide (1mmol) and 0.26g is placed in the round-bottomed flask of 25ml, add the acetone of 10ml, stirring at room temperature 30 minutes, solution colour progressively deepens, add the iodohexane (2mmol) of 0.30ml, continue reaction after 5 hours, be extracted with ethyl acetate saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, recrystallization, obtain N-hexyl-3,4-bis-(4 '-iodophenyl) maleimide;
4) N-hexyl-3, the preparation of 4-bis-(4 '-carbazole phenyl) maleimide:
In 10ml round-bottomed flask, add N-hexyl-3 of 0.58g, 4-bis-(4 '-iodophenyl) maleimide (1mmol), the carbazole (2mmol) of 0.33g, the sodium tert-butoxide (4mmol) of 0.38g, the CuI (0.9mmol) of 0.17g, take out and fill with nitrogen three times, inject anhydrous 1 of 8ml, 4-dioxane, after stirring at room temperature 15min, the 0.15ml cyclohexanediamine (1.2mmol) injecting fast, reflux 12 hours, after stopped reaction, filter out solid, filtrate dichloromethane extraction, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, obtain N-hexyl-3, 4-bis-(4 '-carbazole phenyl) maleimide.Its quantum yield in methylene dichloride is 0.06, and the quantum yield in acetone is 0.005, and solid-state quantum yield is 0.44.
Claims (10)
1. a gathering induced luminescence material, is characterized in that chemical structural formula is as follows:
Wherein: R=CH
2cOOC (CH
3)
3, CH
2cOOH, CH
2c
6f
5, CH
2c
6h
5or C
nh
2n+1, wherein n=1～12.
2. a preparation method for gathering induced luminescence material, is characterized in that preparation method is as follows:
1) preparation of two (4-halobenzene base) anti-maleic nitrile:
In 50ml two-neck bottle, add halobenzene acetonitrile, take out and fill with three times with nitrogen, the iodine adding under nitrogen protection, anhydrous organic solvent reinjects, at-78 DEG C of temperature, stir, slowly drip the previously prepared good methanol solution that contains 2mol/L sodium methylate, after dropwising, by ice-water bath hierarchy of control temperature of reaction, now solution colour deepens, and a large amount of light yellow solids are separated out, continue reaction 3～4 hours, after add 3～6% aqueous hydrochloric acids neutralizations, stopped reaction, suction filtration, with the mixing solutions washing of the methanol/water of the ice of v/v=1:2, vacuum-drying, obtain two (4-halobenzene base) anti-maleic nitrile,
2) 3, the preparation of 4-bis-(4 '-halobenzene base) maleimide
In 50ml round-bottomed flask, add two (4-halobenzene base) anti-maleic nitrile, take out and fill with three times with nitrogen, under 25～50 DEG C of conditions and nitrogen protection, add anhydrous organic solvent, two (4-halobenzene base) anti-maleic nitrile is partly dissolved, add again the methanol solution (2mol/L) of previously prepared good sodium methylate, solution becomes clarification, and color is more and more darker, 2 hours reaction times; Be adjusted to neutrality with dilute hydrochloric acid, with dichloromethane extraction three times, then use respectively distilled water, saturated common salt water washing, anhydrous magnesium sulfate drying, filters, and revolves steaming, and column chromatography is purified, and obtains 3,4-bis-(4 '-halobenzene base) maleimide;
3) 3, the substitution reaction of 4-bis-(4 '-halobenzene base) maleimide
The round-bottomed flask that 3,4-bis-(4 '-halobenzene base) maleimide and salt of wormwood is placed in to 25ml, adds acetone, stirring at room temperature 30 minutes, solution colour progressively deepens, and adds halides, continue reaction after 5 hours, be extracted with ethyl acetate saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, recrystallization, obtain N-substituting group-3,4-bis-(4 '-halobenzene base) maleimide;
4) N-substituting group-3, the preparation of 4-bis-(4 '-carbazole phenyl) maleimide:
In 10ml round-bottomed flask, add N-substituting group-3,4-bis-(4 '-halobenzene base) maleimide, carbazole, mineral alkali, CuI, takes out and fills with nitrogen three times, injects anhydrous 1,4-dioxane, after stirring at room temperature 15min, injection ring hexanediamine, refluxes 12 hours fast, after stopped reaction, filter out solid, filtrate dichloromethane extraction, saturated common salt water washing, anhydrous magnesium sulfate drying, filter, revolve steaming, column chromatography is purified, and obtains target compound N-substituting group-3,4-bis-(4 '-carbazole phenyl) maleimide, i.e. gathering induced luminescence material.
3. the preparation method of a kind of gathering induced luminescence material according to claim 2, is characterized in that organic solvent is selected from ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or toluene.
4. the preparation method of a kind of gathering induced luminescence material according to claim 2, it is characterized in that described to halobenzene acetonitrile be selected from p-chlorobenzyl cyanide, to bromobenzylcyanide or to iodobenzene acetonitrile.
5. the preparation method of a kind of gathering induced luminescence material according to claim 2, described in it is characterized in that is to add according to the ratio of 5mmol ︰ 2～6mmol ︰ 20ml ︰ 5～15ml to halobenzene acetonitrile, iodine, organic solvent, methanol solution.
6. the preparation method of a kind of gathering induced luminescence material according to claim 2, is characterized in that described two (4-halobenzene base) anti-maleic nitrile, organic solvent, methanol solution are to add according to the ratio of 2mmol ︰ 10ml ︰ 3～7ml.
7. the preparation method of a kind of gathering induced luminescence material according to claim 2, is characterized in that described halides is selected from BrCH
2cOOC (CH
3)
3, ICH
2cOOH, BrCH
2c
6f
5, BrCH
2c
6h
5, ICH
3or BrC
nh
2n+1, wherein n=2～12.
8. the preparation method of a kind of gathering induced luminescence material according to claim 2, described in it is characterized in that 3,4-bis-(4 '-halobenzene base) maleimide, salt of wormwood, acetone, halides are to add according to the ratio of 1mmol ︰ 1～3mmol ︰ 25ml ︰ 10ml.
9. the preparation method of a kind of gathering induced luminescence material according to claim 2, is characterized in that described mineral alkali is selected from salt of wormwood, sodium hydroxide or potassium tert.-butoxide.
10. the preparation method of a kind of gathering induced luminescence material according to claim 2, it is characterized in that described N-substituting group-3,4-bis-(4 '-halobenzene base) maleimide, carbazole, mineral alkali, CuI, anhydrous Isosorbide-5-Nitrae-dioxane, cyclohexanediamine are to add according to the ratio of 1mmol ︰ 2-10mmol ︰ 2-10mmol ︰ 0.4～1mmol ︰ 8ml ︰ 0.8～1.6mmol.
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