CN106518872B - A kind of aggregation inducing red-luminescing material and preparation method thereof - Google Patents
A kind of aggregation inducing red-luminescing material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of aggregation inducing red-luminescing material and preparation method thereof, which has the general structure as shown in [I] formula.Aggregation inducing red-luminescing material of the present invention uses the benzophenone derivates on the positions 4- with substituent group to synthesize the tetraphenylethylene derivative for carrying hydroxyl under the catalysis of zinc powder and titanium tetrachloride with 4- dihydroxy benaophenonels when preparation first；Then organic amine and tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides of 1,6,7,12- is used to synthesize tetrachloro imide derivative；Final product is finally prepared by Williamson reactions using above two intermediate.The preparation method mild condition of aggregation inducing red-luminescing material provided by the invention, the advantages that simple for process, used cost of material is cheap.
Description
Technical field
The invention belongs to organic gathering induced luminescence material technical field more particularly to a kind of aggregation inducing red-luminescing materials
And preparation method thereof.
Background technology
Organic red light material is often the plane molecule or band that big π organic red light materials are often big Pi-conjugated systems
The pi-conjugated molecule for having push-and-pull electron group, such as fused ring compound, derivatives of porphyrin, pyrans nitrile (DCM) class dyestuff, two pyrrole of fluorine boron
Cough up (BODIPY) analog derivative and the dyestuff etc. based on diazosulfide.Although these molecules send out very strong glimmering in the solution
Light, however under coherent condition or solid-state, due to pi-pi accumulation effect or dipole-dipole effect strong between molecule, it is easy to shape
At the exciplex (exciplex) between the excimer (excimer) or different molecular between same molecules, to lead
The decline of cause fluorescence intensity (Nature, 1999,397,121-128；Science, 1994,265,765-768), this phenomenon is
" aggregation fluorescent quenching " (ACQ).Serious ACQ effects greatly limit red light material and are preparing organic red light diode, chemistry
With the application in the multiple fields such as biosensor.Red light material usually needs to mix to solve when such as preparing red diodes
ACQ problems, and it is very rambunctious to adulterate, and is on the one hand another party because doping molecule tends to assemble over time
Face optimum doping concentration is often very low and effective doping concentration narrow range, and therefore, the OLEDs of doping is difficult mass production；
It is set to tend to assemble in water environment in biochemistry detection and bio-imaging field, the hydrophobic property of fluorogen, since ACQ is imitated
Fluorescence signal should be caused significantly to decline even to disappear, therefore fluorogen must be controlled in low strength range in use
It is interior, make fluorescence signal weak in this way, reduces the accuracy of analysis.
2001, Tang Benzhong professors seminar find a kind of phenomenon of abnormality (Chem.Commun.2001,18,1740-
1741)：1- methyl-1s, five phenyl Siloles of 2,3,4,5- hardly shine in weak solution；And it is a certain amount of when being added
Poor solvent after, molecule starts to assemble and generate precipitation, and suspension sends out strong fluorescence.Tang seminars are by this phenomenon
It is named as " aggregation-induced emission " (AIE).In-depth study is passed through by Tang seminars, it is proposed that Internal Rotations of Molecules is limited (RIR)
Mechanism.RIR mechanism can be described as：Phenyl in weak solution in AIE molecules consumes excitation around rotating freely for singly-bound
State energy, leads to non-radiative decay, and AIE molecules Weak-luminescence is as a result made not shine even；And in coherent condition or solid-state, due to
Intermolecular tightly packed, the rotation of intramolecular phenyl is restricted, and non-radiative decay channel is suppressed, to make AIE points
Sub- strong luminescence.This new material is widely used in the fields such as opto-electronic device, biology/chemical sensitisation and bio-imaging
(Chem.Commun.2009,4332-4353；Chem.Soc.Rev.2011,40,5361-5388；Adv.Mater.2014,26,
5429-5479)。
The unique luminescent properties of kind, cause the great interest of researcher, more and more AIE molecules are synthesized.Especially
It has been since AIE molecules tetraphenylethylene (TPE) that is convenient from synthesis in 2007, being easy to modify is reported
(Appl.Phys.Lett.2007,91,011111-011113) emerges the largely AIE molecules based on TPE
(Chem.Commun.2009,4332-4353；Chem.Soc.Rev.2011,40,5361-5388).However, AIE points of major part
Son is blue light-emitting or green light, exploitation AIE red light materials be there is an urgent need for.
Invention content
The object of the present invention is to provide a kind of aggregation inducing red-luminescing materials, solve asking for organic red light material aggregation quenching
Topic.Material prepared by the present invention has the rubescent optical property of apparent aggregation inducing.The luminescent material is suitable for preparing organic electroluminescence
Emitting layer material in luminescent material device is applied to chemical/biological sensors or as glimmering as stimuli responsive functional material
Light probe is applied to bio-imaging field.
The present invention provides a kind of preparation method of aggregation inducing red-luminescing material in turn, and this method is directed to existing aggregation
Induce the synthesis difficulty of red-luminescing material big, severe reaction conditions (anhydrous and oxygen-free needs to use inflammable butyl lithium etc.), cost
The problems such as high (raw material, noble metal catalyst are expensive), invent that a kind of experimental raw is cheap and easy to get, the mild preparation of reaction condition
The method of aggregation inducing red-luminescing material.
To achieve the above object, the technical solution used in the present invention is：The rubescent optical molecule of aggregation inducing has such as [I] institute
The structural formula shown：
Wherein, R1For C1~C12Straight chained alkyl, branched alkyl or cyclic alkyl, R2For-H ,-CH3Or-OCnH2n+1, n=1~
12。
The present invention provides a kind of method of synthesis above-mentioned substance, and step is：
(1) by benzophenone derivates and 4- dihydroxy benaophenonels that substituent group is carried on the positions 4- according to molar ratio be 1~
1.5：1 ratio is put into three-necked flask, and it is 4~6 to add with 4- dihydroxy benaophenonel molar ratios:1 catalyst zinc powder, so
Solvents tetrahydrofurane is added in vacuum nitrogen gas afterwards afterwards repeatedly for three times, then under the conditions of ice-water bath, is slowly added to and 4- hydroxyls
Benzophenone molar ratio is 2~3:1 catalyst titanium tetrachloride, is subsequently agitated for 0.5~1h, then at 65~85 DEG C stirring 12~
36h obtains the tetraphenylethylene derivative with hydroxyl after separating-purifying；
(2) under inert gas protection, by organic amine and 1,6,7,12- tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides according to
Molar ratio is 2~6:1 ratio is put into three-necked flask, and solvent A, 100~150 DEG C of 12~36h of reaction, separating-purifying is then added
After obtain 1,6,7,12- tetrachloro imide derivatives；
(3) under inert gas protection, by the tetraphenylethylene derivative with hydroxyl obtained by step (3), step (4) institute
It is 4~6 that 1,6,7,12- tetrachloros imide derivative and potassium carbonate, which are obtained, according to molar ratio:1:4~6 ratio is added to three
In mouth flask, solvent N-methyl pyrilidone is then added, 24~48h is stirred at 80~90 DEG C, structure is obtained after separating-purifying
Formula aggregation inducing red-luminescing material as shown in [I].
Further, the benzophenone derivates with substituent group are 4- methyl benzophenones, 4- methoxyl groups on the positions 4-
Benzophenone, 4- oxethyl-diphenyl-ketones, 4- positive hexyloxies benzophenone, 4- oxy-octyl benzophenones or 4- n-dodecane oxygen
One kind in base benzophenone.
Further, the 4- oxethyl-diphenyl-ketones, 4- positive hexyloxies benzophenone, 4- oxy-octyl benzophenones, 4-
Positive 12-alkoxy benzophenone is obtained by following methods：
It is 1~2 by molar ratio:1 bromoalkane and 4- dihydroxy benaophenonels is added in three-necked flask, and solvent acetone is added
Afterwards, it is 1~2 to add with 4- dihydroxy benaophenonel molar ratios:1 potassium carbonate then heats to 50~60 DEG C and continues stirring 12
~4- oxethyl-diphenyl-ketones, 4- positive hexyloxies benzophenone, 4- n-octyloxy hexichol first are respectively obtained for 24 hours, after separating-purifying
Ketone or 4- positive 12-alkoxy benzophenones；
Separating-purifying includes：
Wait for that reaction stops postcooling to room temperature, filtrate is collected in filtering, and rotation solvent evaporated obtains crude product, with volume ratio
It is 30~60：1 petroleum ether and the mixed liquor of ethyl acetate are eluant, eluent, SiO2For stationary phase, column chromatography for separation purifies to obtain the final product.
Further, when the bromoalkane is chosen for bromic ether, bromo n-hexane, n-octane bromide or bromo positive ten respectively
When a kind of in dioxane, the 4- benzophenone derivates with alkoxy are respectively the just own oxygen of 4- oxethyl-diphenyl-ketones, 4-
Base benzophenone, 4- oxy-octyl benzophenones or 4- positive 12-alkoxy benzophenones.
Further, the organic amine is cyclohexylamine, n-butylamine, n-hexylamine, n-octyl amine, n-dodecylamine, isopropylamine or 2- second
One kind in base hexylamine.
Further, the solvent A is one kind in cyclohexylamine, water, quinoline or imidazoles.
Further, in the step (3), the separating-purifying of the tetraphenylethylene derivative with hydroxyl includes：
Waiting for that reaction stops postcooling to room temperature, reaction system is adjusted to neutrality by the dilute hydrochloric acid that a concentration of 1mol/L is added,
Then three times with dichloromethane extraction, collected organic layer is dried with anhydrous magnesium sulfate, and rotation solvent evaporated obtains crude product, with
Volume ratio is 20~60：1 petroleum ether and the mixed liquor of ethyl acetate are eluant, eluent, SiO2For stationary phase, column chromatography for separation carries
It is pure to obtain the tetraphenylethylene derivative with hydroxyl.
Further, in the step (4), the separating-purifying of 1,6,7,12- tetrachloro imide derivative includes：
It waits for being cooled to room temperature after reaction, is adjusted to neutrality reaction system with the KOH solution of a concentration of 1mol/L, it is quiet
After setting for 24 hours, filtering is dried to obtain crude product, and it is 1~3 then to use volume ratio：1 dichloromethane and the mixed liquor of petroleum ether are
Eluant, eluent, SiO2For stationary phase, column chromatography for separation obtains 1,6,7,12- tetrachloro imide derivatives.
Further, in the step (5), the separating-purifying of the rubescent optical molecule of aggregation inducing includes：
It after reaction stops, being cooled to room temperature, pours into beaker, after the hydrochloric acid to acidity of a concentration of 1mol/L is added, stand
For 24 hours, it filters, vacuum drying obtains crude product, and it is 1~3 then to use volume ratio：1 petroleum ether and the mixed liquor of dichloromethane are
Eluant, eluent, SiO2For stationary phase, column chromatography for separation purification, it is 20~30 further to use volume ratio：1 methanol and dichloromethane weight
Crystallization and purification obtains the aggregation inducing red-luminescing material after dry.
The material has the property that aggregation inducing glows：The rubescent optical molecule of aggregation inducing is in the collected state and solid-like
Launch wavelength is all higher than 600nm under state.Coherent condition refer to the rubescent optical molecule of aggregation inducing be dispersed in volume ratio be 1：7~
9 tetrahydrofuran and the in the mixed solvent of water.The rubescent optical molecule of aggregation inducing does not shine in tetrahydrofuran, in water/tetrahydrochysene furan
In the mixed solvent of muttering is gradually increased with the fluorescence intensity that increases of water content, when the volume fraction of water is more than or equal to 70%, hair
Go out stronger feux rouges；Also emit stronger feux rouges in the solid state.
Compared with prior art, the beneficial effects of the present invention are：
The preparation method of the rubescent optical molecule of aggregation inducing provided by the present invention has experimental raw cheap and easy to get, reacts item
The advantages that part is mild, and experimental procedure is simple and practicable.The rubescent optical molecule of aggregation inducing of the present invention in good solvent hardly
It shines, Fluorescence Increasing under coherent condition or under solid-state can be used for bio-imaging.
Description of the drawings
Fig. 1 is N prepared by the embodiment of the present invention 1, [4- (the 1,2,2- triphenylethylenes of N- di-n-butyls -1,6,7,12- four
Base) phenoxy group] -3,4,9,10- acid imides are continuously increased the fluorescent emission of water content in tetrahydrofuran and water mixed solvent
Spectrogram (10-5mol·L-1)。
Fig. 2 is N prepared by the embodiment of the present invention 1, [4- (the 1,2,2- triphenylethylenes of N- di-n-butyls -1,6,7,12- four
Base) phenoxy group] -3,4,9,10- acid imides are continuously increased the fluorescent emission of water content in tetrahydrofuran and water mixed solvent
Strength Changes figure (10-5mol·L-1)。
Fig. 3 is N prepared by the embodiment of the present invention 1, [4- (the 1,2,2- triphenylethylenes of N- di-n-butyls -1,6,7,12- four
Base) phenoxy group] -3,4,9,10- acid imide solid powders fluorescence spectra.
Specific implementation mode
It is further illustrated the present invention below by specific embodiment, it should be noted that the embodiment is not as to this hair
Bright limitation.
The present invention provides a kind of method of synthesis aggregation inducing red-luminescing material, and this approach includes the following steps：
(1) using the benzophenone derivates with substituent group on the benzophenone of 4- hydroxyls and the positions 4- as raw material, in tetrachloro
Change under titanium and zinc powder catalysis, carry out McMurry reactions, prepares the tetraphenylethylene derivative with hydroxyl, specially：
By the benzophenone derivates with substituent group on the positions 4-, (benzophenone derivates with substituent group are on the positions 4-
4- methyl benzophenones, 4- methoxy benzophenones, 4- oxethyl-diphenyl-ketones, 4- positive hexyloxies benzophenone, the just pungent oxygen of 4-
One kind in base benzophenone or 4- positive 12-alkoxy benzophenones) with 4- dihydroxy benaophenonels according to molar ratio be 1~
1.5：1 ratio is put into three-necked flask, and it is 4~6 to add with 4- dihydroxy benaophenonel molar ratios:1 catalyst zinc powder, so
Solvents tetrahydrofurane is added in vacuum nitrogen gas afterwards afterwards repeatedly for three times, then under the conditions of ice-water bath, is slowly added to and 4- hydroxyls
Benzophenone molar ratio is 2~3:1 catalyst titanium tetrachloride, is subsequently agitated for 0.5~1h, then at 65~85 DEG C stirring 12~
36h obtains the tetraphenylethylene derivative with hydroxyl after separating-purifying.
Separating-purifying includes：
Waiting for that reaction stops postcooling to room temperature, reaction system is adjusted to neutrality by the dilute hydrochloric acid that a concentration of 1mol/L is added,
Then three times with dichloromethane extraction, collected organic layer is dried with anhydrous magnesium sulfate, and rotation solvent evaporated obtains crude product, with
Volume ratio is 20~60：1 petroleum ether and the mixed liquor of ethyl acetate are eluant, eluent, SiO2For stationary phase, column chromatography for separation carries
It is pure to obtain the tetraphenylethylene derivative with hydroxyl.
Wherein on the positions 4- in the benzophenone derivates with substituent group, 4- oxethyl-diphenyl-ketones, 4- positive hexyloxies two
Benzophenone, 4- oxy-octyl benzophenones, 4- positive 12-alkoxy benzophenones are obtained by following methods：
It is 1~2 by molar ratio:1 bromoalkane (bromic ether, bromo n-hexane, n-octane bromide or N-dodeeyl bromide
In one kind) and 4- dihydroxy benaophenonels be added three-necked flask in, be added solvent acetone after, add and 4- dihydroxy benaophenonels
Molar ratio is 1~2:1 potassium carbonate then heats to 50~60 DEG C and continues stirring 12~obtain 4- bands for 24 hours, after separating-purifying
There are benzophenone derivates (4- oxethyl-diphenyl-ketones, 4- positive hexyloxies benzophenone, the 4- n-octyloxy hexichol first of alkoxy
Ketone or 4- positive 12-alkoxy benzophenones)；
Separating-purifying includes：
Wait for that reaction stops postcooling to room temperature, filtrate is collected in filtering, and rotation solvent evaporated obtains crude product, with volume ratio
It is 30~60：1 petroleum ether and the mixed liquor of ethyl acetate are eluant, eluent, SiO2For stationary phase, column chromatography for separation purifies to obtain
4- benzophenone derivates (4- oxethyl-diphenyl-ketones, 4- positive hexyloxies benzophenone, the 4- n-octyloxies for carrying alkoxy
Benzophenone or 4- positive 12-alkoxy benzophenones).
(2) with 1,6,7,12- tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides and organic amine are raw material, and it is anti-to carry out imidizate
It answers, prepares 1,6,7,12- tetrachloro imide derivatives, specially：
Under inert gas protection, by organic amine (cyclohexylamine, n-butylamine, n-hexylamine, n-octyl amine, n-dodecylamine, isopropylamine
Or one kind in 2 ethyl hexylamine) with tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides of 1,6,7,12- according to molar ratio be 2~6:1
Ratio is put into three-necked flask, then addition solvent A (one kind in cyclohexylamine, water, quinoline or imidazoles), anti-at 100~150 DEG C
12~36h is answered, 1,6,7,12- tetrachloro imide derivatives are obtained after separating-purifying.
Separating-purifying includes：
It waits for being cooled to room temperature after reaction, is adjusted to neutrality reaction system with the KOH solution of a concentration of 1mol/L, it is quiet
After setting for 24 hours, filtering is dried to obtain crude product, and it is 1~3 then to use volume ratio：1 dichloromethane and the mixed liquor of petroleum ether are
Eluant, eluent, SiO2For stationary phase, column chromatography for separation obtains 1,6,7,12- tetrachloro imide derivatives.
(3) the tetraphenylethylene derivative and 1,6,7,12- tetrachloro imide derivatives for carrying hydroxyl carry out
Williamson reacts, preparation such as structural formula aggregation inducing red-luminescing material as shown in [I], specially：
Under inert gas protection, tetraphenylethylene derivative, the step 2) gained 1 of hydroxyl will be carried obtained by step 1),
6,7,12- tetrachloros imide derivative and potassium carbonate are 4~6 according to molar ratio:1:4~6 ratio is added to three mouthfuls of burnings
In bottle, solvent N-methyl pyrilidone is then added, 24~48h is stirred at 80~90 DEG C, structural formula is obtained such as after separating-purifying
Aggregation inducing red-luminescing material shown in [I].
Separating-purifying includes：
It after reaction stops, being cooled to room temperature, pours into beaker, after the hydrochloric acid to acidity of a concentration of 1mol/L is added, stand
For 24 hours, it filters, vacuum drying obtains crude product, and it is 1~3 then to use volume ratio：1 petroleum ether and the mixed liquor of dichloromethane are
Eluant, eluent, SiO2For stationary phase, column chromatography for separation purification, it is 20~30 further to use volume ratio：1 methanol and dichloromethane weight
Crystallization and purification obtains the aggregation inducing red-luminescing material after dry.
Embodiment 1
In a preferred technical solution of the invention, R1For normal-butyl, R2For-H.
(1) synthesis of intermediate 1- (4- hydroxy phenyls) -1,2,2- triphenylethylenes.It is added in 250mL round-bottomed flasks
4- dihydroxy benaophenonels (1.9g, 10mmol), benzophenone (2.2g, 12mmol), Zn powder (2.9g, 44mmol).It vacuumizes and changes
Nitrogen three times after, be added 80mL tetrahydrofurans.After being cooled to 0 DEG C, it is slowly added to TiCl4(4.2g, 22mmol), is subsequently agitated for
1h.Then at 70 DEG C, stirring for 24 hours, after being cooled to room temperature, is added 80mL dilute hydrochloric acid (1mol/L), is adjusted to neutrality, DCM extractions three
Secondary, collected organic layer, anhydrous magnesium sulfate drying is spin-dried for solvent and obtains crude product, with volume ratio for 20:1 petroleum ether and acetic acid
The mixture of ethyl ester is leacheate, SiO2For stationary phase, column chromatography for separation obtains white solid 0.8g, yield 47%.
(2) the four chloro- imido synthesis of 3,4,9,10- of intermediate N, N- di-n-butyl -1,6,7,12-.By 5g
(9.5mmol) 1,6,7,12- tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides, 100mL water, 2.8g (38mmol) n-butylamine are added
Into 250mL three-necked flasks, under nitrogen protection, 100 DEG C of reaction 20h.It is cooled to room temperature after reaction, filters, be used in combination 5%
KOH solution (1mol/L) is washed four times, and neutrality is then washed to, and after standing for 24 hours, is filtered, dry crude product is with volume ratio
1：1 dichloromethane and the mixed liquor of petroleum ether are leacheate, SiO2For stationary phase, column chromatography for separation obtains product 2.7g, yield
45%.
(3) the rubescent optical molecule N of aggregation inducing, N- di-n-butyls -1,6,7,12- four [4- (1,2,2- triphenyl vinyls)
Phenoxy group] the imido synthesis of -3,4,9,10-
By 0.2g (0.3mmol) N, N- di-n-butyl -1,6,7,12- tetra- chloro- 3,4,9,10- acid imides, 0.5g
(1.5mmol) 1- (4- hydroxy phenyls) -1,2,2- triphenylethylenes, 0.2g (1.5mmol) potassium carbonate, N-Methyl pyrrolidone
50mL is added in 250mL three-necked flasks, and 36h is stirred at 85 DEG C and is cooled to room temperature, pours into beaker after reaction stops, being added
After (1mol/L) hydrochloric acid to acidity, stand for 24 hours, filtering, vacuum drying crude product, with volume ratio for 3:1 petroleum ether and two
The mixture of chloromethanes is leacheate, SiO2For stationary phase, column chromatography for separation further uses volume ratio for 30:1 dichloromethane
It is purified with recrystallizing methanol, obtains red powder solid 0.45g, yield 80%.
N manufactured in the present embodiment, N- di-n-butyl -1,6,7,12- four [4- (1,2,2- triphenyl vinyls) phenoxy group] -
3,4,9,10- acid imides have typical aggregation-induced emission performance.N, N- di-n-butyl -1,6,7,12- tetra- [4- (1,2,
2- triphenyl vinyls) phenoxy group] -3,4,9,10- acid imides hardly shine in tetrahydrofuran, with poor solvent water
Be continuously added, molecular aggregates, fluorescence enhances rapidly after water content is more than 50% (volume fraction of water), works as water content
Its fluorescence is most strong when being 90%, and emission peak is located at 627nm at this time.[4- (the 1,2,2- triphens of N, N- di-n-butyl -1,6,7,12- four
Base vinyl) phenoxy group] -3,4,9,10- acid imides water/tetrahydrofuran in the mixed solvent maximum fluorescence intensity curve also
Embody this property：Under the same conditions, fluorescence intensity of the compound in tetrahydrofuran only has 7, when water content is low
When 40%, fluorescence intensity change is little, and after water content reaches 50%, fluorescence intensity significantly increases, when water content reaches
When 90%, fluorescence intensity has reached 120, is its 17.1 in tetrahydrofuran times.Fig. 1 is N prepared by embodiment, bis- positive fourths of N-
Base -1,6,7,12- four [4- (1,2,2- triphenyl vinyls) phenoxy group] -3,4,9,10- acid imides are in different composition water/tetra-
Fluorescence spectrum (solution concentration 10 in hydrogen tetrahydrofuran solution-5Mol/L, percentage is water body shared in mixed solution in figure
Fraction).Fig. 2 is N, N- di-n-butyls -1,6,7,12- four [4- (1,2,2- triphenyl vinyls) phenoxy group] -3,4,9,10-
Fluorescence intensity curves (solution concentration 10 of the acid imide in different composition water/tetrahydrofuran solutions-5Mol/L, percentage in figure
Than for water volume fraction shared in mixed solution).
N manufactured in the present embodiment, N- di-n-butyl -1,6,7,12- four [4- (1,2,2- triphenyl vinyls) phenoxy group] -
3,4,9,10- acid imides emit stronger feux rouges, maximum emission wavelength 646nm in the solid state.Fig. 3 is embodiment system
Standby N, N- di-n-butyl -1,6,7,12- four [4- (1,2,2- triphenyl vinyls) phenoxy group] -3,4,9,10- acid imides
The fluorescence spectrum of solid powder.
Embodiment 2
In presently preferred technical solution, R1For cyclohexyl, R2For-CH3。
(1) synthesis of intermediate 4- (1,2- diphenyl -2- p-methylphenyls vinyl) phenol.In 250mL round-bottomed flasks
Addition 4- dihydroxy benaophenonels (1.9g, 10mmol), 4- methyl benzophenones (2.9g, 15mmol), Zn powder (3.9g,
60mmol).Vacuum and exchange nitrogen three times after, be added 80mL tetrahydrofurans.After being cooled to 0 DEG C, it is slowly added to TiCl4(5.7g,
30mmol), it is subsequently agitated for 0.8h.Then 36h is stirred at 65 DEG C, and after being cooled to room temperature, 80mL dilute hydrochloric acid (1mol/L) is added, adjusts
Section is to neutrality, and DCM is extracted three times, collected organic layer, and anhydrous magnesium sulfate drying is spin-dried for solvent and obtains crude product, is with volume ratio
40:1 petroleum ether and the mixture of ethyl acetate are leacheate, SiO2For stationary phase, column chromatography for separation obtains white solid
0.76g, yield 42%.
2) the four chloro- imido synthesis of 3,4,9,10- of intermediate N, N- dicyclohexyl -1,6,7,12-.By 5g
(9.5mmol) 1,6,7,12- tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides, 1.9g (19mmol) cyclohexylamine are added to 250mL tri-
In mouth flask, 80mL cyclohexylamine is then added as reaction dissolvent (cyclohexylamine is both reactant and solvent), nitrogen protection
Under, 135 DEG C of reactions are for 24 hours.It is cooled to room temperature, filters after reaction, 5%KOH solution (1mol/L) washing four times is used in combination, then
It is washed to neutrality, after standing for 24 hours, filtering, dry crude product, with volume ratio for 3：The mixed liquor of 1 dichloromethane and petroleum ether
For leacheate, SiO2For stationary phase, column chromatography for separation obtains product 5.9g, yield 90%.
(3) [(1,2- diphenyl -2- are to toluene by 4- by the rubescent optical molecule N of aggregation inducing, N- dicyclohexyls -1,6,7,12- four
Base vinyl) phenoxy group] the imido synthesis of -3,4,9,10-
By 0.21g (0.3mmol) N, N- dicyclohexyl -1,6,7,12- tetra- chloro- 3,4,9,10- acid imides, 0.54g
(1.5mmol) 4- (1,2- diphenyl -2- p-methylphenyls vinyl) phenol, 0.21g (1.5mmol) potassium carbonate, N- methylpyrroles
Alkanone 50mL is added in 250mL three-necked flasks, and 48h is stirred at 80 DEG C and is cooled to room temperature, pours into beaker after reaction stops,
After (1mol/L) hydrochloric acid to acidity is added, stand for 24 hours, filtering, vacuum drying crude product, with volume ratio for 1:1 petroleum ether
Mixture with dichloromethane is leacheate, SiO2For stationary phase, column chromatography for separation further uses volume ratio for 25:1 dichloro
Methane and recrystallizing methanol purification, obtain red powder solid 0.42g, yield 71%.
Embodiment 3
In presently preferred technical solution, R1For 2- ethylhexyls, R2For-OCH3。
(1) synthesis of intermediate 4- (2- (4- methoxyphenyls) -1,2- diphenylacetylenes) phenol.In 250mL round bottoms
4- dihydroxy benaophenonels (1.9g, 10mmol), 4- methoxy benzophenones (2.1g, 10mmol), Zn powder are added in flask
(2.6g,40mmol).Vacuum and exchange nitrogen three times after, be added 80mL tetrahydrofurans.After being cooled to 0 DEG C, it is slowly added to TiCl4
(3.8g, 20mmol) is subsequently agitated for 1h, and 12h is then stirred at 85 DEG C, and after being cooled to room temperature, 80mL dilute hydrochloric acid (1mol/ is added
L), it is adjusted to neutrality, DCM is extracted three times, collected organic layer, and anhydrous magnesium sulfate drying is spin-dried for solvent and obtains crude product, with volume
Than being 60:1 petroleum ether and the mixture of ethyl acetate are leacheate, SiO2For stationary phase, column chromatography for separation obtains white solid
0.87g, yield 46%.
(2) the four imido synthesis of chloro- 3,4,9,10- of intermediate N, N- bis- (2- ethylhexyls) -1,6,7,12-.It will
5g (9.5mmol) 1,6,7,12- tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides, 60mL quinoline, 4.9g (38mmol) 2- ethyl hexyls
Amine is added in 250mL three-necked flasks, under nitrogen protection, 150 DEG C of reaction 12h.It is cooled to room temperature, filters after reaction, and
It is washed four times with 5%KOH solution (1mol/L), is then washed to neutrality, after standing for 24 hours, filtering, dry crude product, with body
Product is than being 2：The mixed liquor of 1 dichloromethane and petroleum ether is leacheate, SiO2For stationary phase, column chromatography for separation obtains product 3.8g,
Yield 52%.
(3) the rubescent optical molecule N of aggregation inducing, N- bis- (2- ethylhexyls) -1,6,7,12- four [4- (2- (4- methoxybenzenes
Base) -1,2- diphenylacetylenes) phenoxy group] the imido synthesis of -3,4,9,10-
By 0.23g (0.3mmol) N, N- bis- (2- ethylhexyls) -1,6,7,12- tetra- chloro- 3,4,9,10- acid imides,
0.68g (1.8mmol) 4- (2- (4- methoxyphenyls) -1,2- diphenylacetylenes) phenol, 0.25g (1.8mmol) potassium carbonate,
N-Methyl pyrrolidone 50mL is added in 250mL three-necked flasks, is stirred at 90 DEG C for 24 hours, after reaction stops, being cooled to room temperature,
It pours into beaker, after (1mol/L) hydrochloric acid to acidity is added, stands for 24 hours, filtering, vacuum drying crude product is with volume ratio
2:1 petroleum ether and the mixture of dichloromethane are leacheate, SiO2For stationary phase, column chromatography for separation further uses volume
Than being 30:1 dichloromethane and recrystallizing methanol purification, obtain red powder solid 0.46g, yield 72%.
Embodiment 4
In presently preferred technical solution, R1For isopropyl, R2For-OC2H5。
(1) synthesis of intermediate 4- positive 12-alkoxy benzophenones.By N-dodeeyl bromide (6.2g, 25mmol) and 4-
Dihydroxy benaophenonel (4.95g, 25mmol) be added three-necked flask in, be added 300mL acetone after, add potassium carbonate (3.5g,
25mmol), 60 DEG C are then heated to continue to stir 12h.Wait for that reaction stops postcooling to room temperature, filtrate is collected in filtering, and rotation is steamed
Dry solvent obtains crude product, with volume ratio for 60：1 petroleum ether and the mixed liquor of ethyl acetate are eluant, eluent, SiO2For fixation
Phase obtains 4- positive 12-alkoxy benzophenone 7.4g, yield 81% after column chromatography for separation purification.
(2) synthesis of intermediate 4- (2- (4- n-dodecanes phenyl) -1,2- diphenylacetylenes) phenol.?
Addition 4- dihydroxy benaophenonels (1.9g, 10mmol) in 250mL round-bottomed flasks, 4- positive 12-alkoxy benzophenones (4.4g,
12mmol), Zn powder (3.3g, 50mmol).Vacuum and exchange nitrogen three times after, be added 80mL tetrahydrofurans.After being cooled to 0 DEG C, delay
It is slow that TiCl is added4(4.7g, 25mmol), is subsequently agitated for 0.5h.Then at 70 DEG C, for 24 hours, after being cooled to room temperature, 80mL is added in stirring
Dilute hydrochloric acid (1mol/L), is adjusted to neutrality, and DCM is extracted three times, collected organic layer, and anhydrous magnesium sulfate drying is spin-dried for solvent and obtains
Crude product, with volume ratio for 20:1 petroleum ether and the mixture of ethyl acetate are leacheate, SiO2For stationary phase, column chromatography point
From white solid 1.1g, yield 42%.
2) the four chloro- imido synthesis of 3,4,9,10- of intermediate N, N- diisopropyl -1,6,7,12-.By 5g
(9.5mmol) 1,6,7,12- tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides, water 100mL, 3.4g (57mmol) isopropylamine are added
Into 250mL three-necked flasks, under nitrogen protection, 100 DEG C of reaction 36h.It is cooled to room temperature after reaction, filters, be used in combination 5%
KOH solution (1mol/L) is washed four times, and neutrality is then washed to, and after standing for 24 hours, is filtered, dry crude product is with volume ratio
1：The mixed liquor of 1 dichloromethane and petroleum ether is leacheate, SiO2For stationary phase, column chromatography for separation obtains product 2.8g, yield
48%.
(3) the rubescent optical molecule N of aggregation inducing, N- diisopropyls -1,6,7,12- four [4- (2- (4- n-dodecane oxygroup benzene
Base) -1,2- diphenylacetylenes) phenoxy group] the imido synthesis of -3,4,9,10-
By 0.18g (0.3mmol) N, N- diisopropyl -1,6,7,12- tetra- chloro- 3,4,9,10- acid imides, 0.63g
(1.2mmol) 4- (2- (4- n-dodecanes phenyl) -1,2- diphenylacetylenes) phenol, 0.16g (1.2mmol) carbonic acid
Potassium, N-Methyl pyrrolidone 50mL are added in 250mL three-necked flasks, and 36h is stirred at 85 DEG C and is cooled to room after reaction stops
Temperature is poured into beaker, after (1mol/L) hydrochloric acid to acidity is added, is stood for 24 hours, filtering, vacuum drying crude product, with volume ratio
It is 3:1 petroleum ether and the mixture of dichloromethane are leacheate, SiO2For stationary phase, column chromatography for separation further uses body
Product is than being 20:1 dichloromethane and recrystallizing methanol purification, obtain red powder solid 0.55g, yield 71%.
Embodiment 5
In presently preferred technical solution, R1For cyclohexyl, R2For-OC6H13。
(1) synthesis of intermediate 4- positive hexyloxies benzophenone.By bromo n-hexane (12.4g, 50mmol) and 4- hydroxyls
Benzophenone (4.95g, 25mmol) be added three-necked flask in, be added 300mL acetone after, add potassium carbonate (7.0g,
50mmol), 50 DEG C are then heated to and continues stirring for 24 hours.Wait for that reaction stops postcooling to room temperature, filtrate is collected in filtering, and rotation is steamed
Dry solvent obtains crude product, with volume ratio for 30：1 petroleum ether and the mixed liquor of ethyl acetate are eluant, eluent, SiO2For fixation
Phase obtains 4- positive hexyloxy benzophenone 5.9g, yield 83% after column chromatography for separation purification.
(2) synthesis of intermediate 4- (2- (4- positive hexyloxies phenyl) -1,2- diphenylacetylenes) phenol.Justify in 250mL
4- dihydroxy benaophenonels (1.9g, 10mmol), 4- positive hexyloxies benzophenone (3.4g, 12mmol), Zn powder are added in the flask of bottom
(3.9g,60mmol).Vacuum and exchange nitrogen three times after, be added 80mL tetrahydrofurans.After being cooled to 0 DEG C, it is slowly added to TiCl4
(5.7g, 30mmol), is subsequently agitated for 0.8h.Then 36h is stirred at 70 DEG C, and after being cooled to room temperature, 80mL dilute hydrochloric acid is added
(1mol/L), is adjusted to neutrality, and DCM is extracted three times, collected organic layer, and anhydrous magnesium sulfate drying is spin-dried for solvent and obtains crude product,
With volume ratio for 40:1 petroleum ether and the mixture of ethyl acetate are leacheate, SiO2For stationary phase, column chromatography for separation obtains white
Color solid 0.96g, yield 43%.
(3) the four chloro- imido synthesis of 3,4,9,10- of intermediate N, N- dicyclohexyl -1,6,7,12-.By 5g
(9.5mmol) 1,6,7,12- tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides, 1.9g (19mmol) cyclohexylamine are added to 250mL tri-
In mouth flask, 80mL cyclohexylamine is then added as reaction dissolvent (cyclohexylamine is both reactant and solvent) nitrogen protection
Under, 135 DEG C of reaction 12h.It is cooled to room temperature, filters after reaction, 5%KOH solution (1mol/L) washing four times is used in combination, then
It is washed to neutrality, after standing for 24 hours, filtering, dry crude product, with volume ratio for 3：The mixed liquor of 1 dichloromethane and petroleum ether
For leacheate, SiO2For stationary phase, column chromatography for separation obtains product 5.9g, yield 90%.
(4) the rubescent optical molecule N of aggregation inducing, N- dicyclohexyls -1,6,7,12- four [4- (2- (4- positive hexyloxies phenyl) -
1,2- diphenylacetylenes) phenoxy group] the imido synthesis of -3,4,9,10-
By 0.21g (0.3mmol) N, N- dicyclohexyl -1,6,7,12- tetra- chloro- 3,4,9,10- acid imides, 0.68g
(1.5mmol) 4- (2- (4- positive hexyloxies phenyl) -1,2- diphenylacetylenes) phenol, 0.21g (1.5mmol) potassium carbonate, N-
Methyl pyrrolidone 50mL is added in 250mL three-necked flasks, and 48h is stirred at 80 DEG C and is cooled to room temperature, after reaction stops
Enter in beaker, after (1mol/L) hydrochloric acid to acidity is added, stands for 24 hours, filtering, vacuum drying crude product, with volume ratio for 1:1
Petroleum ether and dichloromethane mixture be leacheate, SiO2For stationary phase, column chromatography for separation, further use volume ratio for
25:1 dichloromethane and recrystallizing methanol purification, obtain red powder solid 0.48g, yield 72%.
Embodiment 6
In presently preferred technical solution, R1For cyclohexyl, R2For-OC2H5。
(1) synthesis of intermediate 4- oxethyl-diphenyl-ketones.By bromic ether (3.2g, 30mmol) and 4- hydroxy benzophenones
Ketone (4.95g, 25mmol) is added in three-necked flask, after 300mL acetone is added, adds potassium carbonate (4.1g, 30mmol), then
55 DEG C are warming up to continue to stir 20h.Wait for that reaction stops postcooling to room temperature, filtrate is collected in filtering, and rotation solvent evaporated obtains slightly
Product, with volume ratio for 50：1 petroleum ether and the mixed liquor of ethyl acetate are eluant, eluent, SiO2For stationary phase, column chromatography for separation
4- positive hexyloxy benzophenone 4.9g, yield 86% are obtained after purification.
(2) synthesis of intermediate 4- (2- (4- ethoxyl phenenyls) -1,2- diphenylacetylenes) phenol.In 250mL round bottoms
4- dihydroxy benaophenonels (1.9g, 10mmol), 4- oxethyl-diphenyl-ketones (2.7g, 12mmol), Zn powder are added in flask
(3.9g,50mmol).Vacuum and exchange nitrogen three times after, be added 80mL tetrahydrofurans.After being cooled to 0 DEG C, it is slowly added to TiCl4
(5.7g, 25mmol), is subsequently agitated for 0.5h.Then 36h is stirred at 70 DEG C, and after being cooled to room temperature, 80mL dilute hydrochloric acid is added
(1mol/L), is adjusted to neutrality, and DCM is extracted three times, collected organic layer, and anhydrous magnesium sulfate drying is spin-dried for solvent and obtains crude product,
With volume ratio for 50:1 petroleum ether and the mixture of ethyl acetate are leacheate, SiO2For stationary phase, column chromatography for separation obtains white
Color solid 0.8g, yield 41%.
(3) the four chloro- imido synthesis of 3,4,9,10- of intermediate N, N- bis- (dodecyl) -1,6,7,12-.It will
5g (9.5mmol) 1,6,7,12- tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides, 60mL quinoline, 7.1g (38mmol) lauryl amine add
Enter into 250mL three-necked flasks, under nitrogen protection, 150 DEG C of reactions are for 24 hours.It is cooled to room temperature after reaction, filters, be used in combination 5%
KOH solution (1mol/L) is washed four times, and neutrality is then washed to, and after standing for 24 hours, is filtered, dry crude product is with volume ratio
2：The mixed liquor of 1 dichloromethane and petroleum ether is leacheate, SiO2For stationary phase, column chromatography for separation obtains product 4.5g, yield
55%.
(4) bis- dodecyl -1,6,7,12- of the rubescent optical molecule N of aggregation inducing, N-, four [4- (2- (4- ethoxybenzenes
Base) -1,2- diphenylacetylenes) phenoxy group] the imido synthesis of -3,4,9,10-
By bis- dodecyls -1,6 of 0.26g (0.3mmol) N, N-, 7,12- tetra- chloro- 3,4,9,10- acid imides,
0.47g (1.2mmol) 4- (2- (4- ethoxyl phenenyls) -1,2- diphenylacetylenes) phenol, 0.16g (1.2mmol) potassium carbonate,
N-Methyl pyrrolidone 50mL is added in 250mL three-necked flasks, and 48h is stirred at 80 DEG C and is cooled to room temperature after reaction stops,
It pours into beaker, after (1mol/L) hydrochloric acid to acidity is added, stands for 24 hours, filtering, vacuum drying crude product is with volume ratio
1:1 petroleum ether and the mixture of dichloromethane are leacheate, SiO2For stationary phase, column chromatography for separation further uses volume
Than being 25:1 dichloromethane and recrystallizing methanol purification, obtain red powder solid 0.49g, yield 71%.
The rubescent optical property of the aggregation inducing of obtained final product exists with embodiment 1, these products in above-described embodiment
It not shining in its good solvent such as tetrahydrofuran, fluorescence enhances rapidly after 50% or more water (volume fraction of water) is added, when
When water content is 90%, fluorescence emission peak is more than 620nm.
The invention is not limited in above-described embodiments, on the basis of technical solution disclosed by the invention, the skill of this field
For art personnel according to disclosed technology contents, one can be made to some of which technical characteristic by not needing performing creative labour
A little to replace and deform, these are replaced and deformation is within the scope of the invention.
Claims (7)
1. a kind of preparation method of aggregation inducing red-luminescing material, which is characterized in that include the following steps：
(1) it is 1~1.5 according to molar ratio with 4- dihydroxy benaophenonels by the benzophenone derivates for carrying substituent group on the positions 4-：1
Ratio be put into three-necked flask, add with 4- dihydroxy benaophenonel molar ratios be 4~6:1 catalyst zinc powder, then takes out
Solvents tetrahydrofurane is added in vacuum nitrogen gas afterwards repeatedly for three times, then under the conditions of ice-water bath, is slowly added to and 4- hydroxyl hexichol
Ketone molar ratio is 2~3:1 catalyst titanium tetrachloride, is subsequently agitated for 0.5~1h, and 12~36h is then stirred at 65~85 DEG C,
The tetraphenylethylene derivative with hydroxyl is obtained after separating-purifying；
(2) under inert gas protection, by organic amine and 1,6,7,12- tetra- chloro- 3,4,9,10- tetracarboxylic acid dianhydrides according to mole
Than being 2~6:1 ratio is put into three-necked flask, is then added solvent A, under nitrogen protection, 100~150 DEG C of 12~36h of reaction,
1,6,7,12- tetrachloro imide derivatives are obtained after separating-purifying；
(3) under inert gas protection, tetraphenylethylene derivative, the step 2) gained 1,6 of hydroxyl will be carried obtained by step 1),
7,12- tetrachloros imide derivative and potassium carbonate are 4~6 according to molar ratio:1:4~6 ratio is added to three-necked flask
In, solvent N-methyl pyrilidone is then added, 24~48h is stirred at 80~90 DEG C, structural formula such as [I] are obtained after separating-purifying
Shown in aggregation inducing red-luminescing material；
The aggregation inducing red-luminescing material has the structural formula as shown in [I]：
The benzophenone derivates with substituent group are 4- methyl benzophenones, 4- methoxy benzophenones, 4- on the positions 4-
Oxethyl-diphenyl-ketone, 4- positive hexyloxies benzophenone, 4- oxy-octyl benzophenones or 4- positive 12-alkoxy benzophenones
In one kind；
The 4- oxethyl-diphenyl-ketones, 4- positive hexyloxies benzophenone, 4- oxy-octyl benzophenones, 4- n-dodecane oxygroups
Benzophenone is obtained by following methods：
It is 1~2 by molar ratio:1 bromoalkane and 4- dihydroxy benaophenonels is added in three-necked flask, after solvent acetone is added, then
It is 1~2 to be added with 4- dihydroxy benaophenonel molar ratios:1 potassium carbonate then heats to 50~60 DEG C and continues stirring 12~for 24 hours,
4- oxethyl-diphenyl-ketones, 4- positive hexyloxies benzophenone, 4- oxy-octyl benzophenones or 4- are respectively obtained after separating-purifying
Positive 12-alkoxy benzophenone；
Separating-purifying includes：
Wait for that reaction stops postcooling to room temperature, filtrate is collected in filtering, and rotation solvent evaporated obtains crude product, with volume ratio for 30
~60：1 petroleum ether and the mixed liquor of ethyl acetate are eluant, eluent, SiO2For stationary phase, column chromatography for separation purifies to obtain the final product.
2. the preparation method of aggregation inducing red-luminescing material according to claim 1, which is characterized in that when the bromoalkane
When being chosen for a kind of in bromic ether, bromo n-hexane, n-octane bromide or N-dodeeyl bromide respectively, 4- carry alcoxyl
The benzophenone derivates of base are respectively 4- oxethyl-diphenyl-ketones, 4- positive hexyloxies benzophenone, 4- n-octyloxy hexichol first
Ketone or 4- positive 12-alkoxy benzophenones.
3. the preparation method of aggregation inducing red-luminescing material according to claim 1, which is characterized in that the organic amine is
One kind in cyclohexylamine, n-butylamine, n-hexylamine, n-octyl amine, n-dodecylamine, isopropylamine or 2 ethyl hexylamine.
4. the preparation method of aggregation inducing red-luminescing material according to claim 1, which is characterized in that the solvent A is
One kind in cyclohexylamine, water, quinoline or imidazoles.
5. the preparation method of aggregation inducing red-luminescing material according to claim 1, which is characterized in that the step (1)
In, the separating-purifying of the tetraphenylethylene derivative with hydroxyl includes：
Wait for that reaction stops postcooling to room temperature, reaction system is adjusted to neutrality by the dilute hydrochloric acid that a concentration of 1mol/L is added, then
Three times with dichloromethane extraction, collected organic layer is dried with anhydrous magnesium sulfate, and rotation solvent evaporated obtains crude product, with volume
Than being 20~60：1 petroleum ether and the mixed liquor of ethyl acetate are eluant, eluent, SiO2For stationary phase, column chromatography for separation purifies
To the tetraphenylethylene derivative with hydroxyl.
6. the preparation method of aggregation inducing red-luminescing material according to claim 1, which is characterized in that the step (2)
In, the separating-purifying of 1,6,7,12- tetrachloro imide derivative includes：
It waits for being cooled to room temperature after reaction, is adjusted to neutrality reaction system with the KOH solution of a concentration of 1mol/L, stand
After for 24 hours, filtering is dried to obtain crude product, and it is 1~3 then to use volume ratio：1 dichloromethane and the mixed liquor of petroleum ether are to wash
De- agent, SiO2For stationary phase, column chromatography for separation obtains 1,6,7,12- tetrachloro imide derivatives.
7. the preparation method of aggregation inducing red-luminescing material according to claim 1, which is characterized in that the step (3)
In, the separating-purifying of aggregation inducing red-luminescing material includes：
It after reaction stops, being cooled to room temperature, pours into beaker, after the hydrochloric acid to acidity of a concentration of 1mol/L is added, stand for 24 hours,
Filtering, vacuum drying obtain crude product, and it is 1~3 then to use volume ratio：1 petroleum ether and the mixed liquor of dichloromethane are elution
Agent, SiO2For stationary phase, column chromatography for separation purification, it is 20~30 further to use volume ratio：1 methanol and recrystallize with dichloromethane
Purification obtains the aggregation inducing red-luminescing material after dry.
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