CN107033144A - A kind of dithienyl ethene terylene acid imide near-infrared fluorescent molecular switch and preparation method thereof - Google Patents
A kind of dithienyl ethene terylene acid imide near-infrared fluorescent molecular switch and preparation method thereof Download PDFInfo
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Abstract
The invention discloses one kind, the invention provides a kind of near-infrared fluorescent molecular switch, its synthetic method and application, its object is to by the way that multiple dithienyl ethene are connected with single terylene acid imide by the way that oxygen bridge key is non-conjugated, the shortcoming that single dithienyl ethene is not enough to fully switch one fluorophor of control can be solved, effectively strengthen fluorescent switch speed and efficiency is quenched, construct efficient butterfly dithienyl ethene terylene acid imide, wherein dithienyl ethene is photochromic unit, for controlling the luminous with being quenched of near-infrared fluorescent group, terylene acid imide is fluorogen, the fluorogen is used to send 650nm~800nm near-infrared fluorescents, thus solve prior art near-infrared diarylethene role in fluorescent molecule switch and there are many obvious shortcomings, as photostability is poor, synthesis is complicated, fluorescence quantum yield is low, the slow technical problem of photoresponse.
Description
Technical field
The invention belongs to fluorescent probe technique field, the near-infrared fluorescent point controlled more particularly, to a kind of dual wavelength
Sub switch butterfly dithienyl ethene-terylene acid imide, its preparation method and application.
Background technology
Photochromic material refers to, by its optical property can be reversibly changed after different-waveband light source activation, occur color
One class material of change.Diarylethene is because being formed with bistable characteristic and good fatigue resistance most has application prospect
One of photochromic compound.The role in fluorescent molecule switch constructed by diarylethene and fluorophor can pass through diaryl second
The photochromic action of alkene regulates and controls the fluorescent emission behavior of fluorophor, so as to realize the light-operated switch of molecular fluorescence, it is in light
Shown strongly in the application in the fields such as storage, photoswitch, all-optical transistor, chemical sensitisation, opto-electronic device, bio-imaging
Growth momentum, the field that any organic fluorescent dye is related to is likely to obtain new connotation by introducing diarylethene
" switch ".
Absorb or emission spectrum is in the study hotspot that visible or near infrared region fluorescent dye is many different fields, it is special
It is not that this is referred to as the near infrared fluorescent dye in the range of " biological window " positioned at 650-1000nm for absorption or launch wavelength,
They have extensively in the association area such as cell marking, bio-imaging, molecular switch and molecular device, laser medium and photoelectric material
Application.Molecular fluorescence has following advantage as a kind of transducing signal：The high sensitivity of Single Molecule Detection is can reach, also may be used
Switch, can realize the communication between people and molecule, also there is visual sub- nano-space to submicron and highly differentiate, and
It is the resolution of sub- millisecond time, the external biosystem molecule of life is not only widely used in highly sensitive fluoroscopic examination
Probe is studied, but also for intravital optical image probe.However, the maximum emission wavelength of conventional fluorescent typically exists
Below 600nm, the biomolecule in UV-visible region, human body also can produce good absorb to the wavelength in this region.
In addition, the light wave in this region is all more dispersed, so that tissue can not be penetrated deeply, in addition, can also be produced in this region
Powerful autofluorescence, so as to result in high ambient noise, these reasons have resulted in traditional dyestuff and have been not suitable for being applied to body
Interior imaging, in contrast, in near-infrared (NIR) area, the i.e. region in 650-900nm, biomolecule has in this region
Seldom absorption, the deep enough organization internal of near-infrared fluorescent energy, can be as deep as several centimeters, while substantially not autologous in this region
Fluorescence, can obtain many high RSTs, low ambient noise.
In order to obtain the role in fluorescent molecule switch of near-infrared diarylethene, people have attempted various methods, wherein, it is the most frequently used
Method be exactly the pi-conjugated length extended on thienyl group, but effect is not notable.Yam seminars are matched somebody with somebody by introducing metal
Compound, makes diarylethene planarization extend its conjugated structure indirectly to realize the red shift of role in fluorescent molecule switch.And field
Standing grain academician seminar employs introduces electron donor-acceptor structure in diarylethene, realizes the red shift of its wavelength, so as to construct
The diarylethene role in fluorescent molecule switch of near-infrared.But above method synthesis is more complicated, its product fluorescence quantum yield is low, light
Low-response.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of naphthalene of dithienyl ethene-three is embedding
Hexichol acid imide molecule and preparation method thereof, and it is applied to near-infrared fluorescent molecule, its object is to by by four two
Thienyl ethene is connected with single terylene acid imide by the way that oxygen bridge key is non-conjugated, constructs efficient butterfly dithienyl
Ethene-terylene acid imide, wherein dithienyl ethene are photochromic unit, for the hair for controlling near-infrared fluorescent to roll into a ball
Light is with being quenched, and terylene acid imide is fluorogen, and the fluorogen is used to send 650nm~800nm near-infrared fluorescents, thus
Solve prior art near-infrared diarylethene role in fluorescent molecule switch and there are many obvious shortcomings, such as photostability is poor, synthesis
Complexity, fluorescence quantum yield is low, the slow technical problem of photoresponse.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of dithienyl ethene-terylene
Acid imide molecule, the molecule passes through oxygen bridge by 2~4 dithienyl vinyl groups and single terylene imide group
Key is non-conjugated to be connected.
Preferably, described dithienyl ethene-terylene acid imide molecule is four (R- dithienyls ethene)-three
The embedding hexichol acid imide of naphthalene, it has the general structure as shown in formula (I)：
Wherein, R is-H ,-C1-C12Alkyl ,-OH,Heterocycle or polymer chain,
The n is 0~12 integer, and X is O, S or N；R1For-H ,-C1-C12Alkyl or
Preferably, the R is
According to another aspect of the present invention, there is provided a kind of four described (R- dithienyls ethene)-terylenes
Imido preparation method, comprises the following steps：
(1) compound A, compound B and sodium carbonate are dispersed in the mixed solution of glycol dimethyl ether and water,
Under nitrogen protection, the Pd (PPh of catalyst dosage are added3)4, 80~100 DEG C of 12~24h of reaction are heated to, are separated after the completion of reaction
Compound C, the A, B and C molecular structure such as formula (A) are obtained after purification, shown in formula (B) and formula (C)；
(2) the compound C, para hydroxybenzene boric acid and sodium carbonate are dispersed in the mixing of glycol dimethyl ether and water
In solution, under nitrogen protection, the Pd (PPh of catalyst dosage are added3)4, it is heated to 80~100 DEG C of 12~48h of reaction, reaction
After the completion of obtain compound D after separating-purifying, shown in its molecular structure such as formula (D)：
(3) compound E, compound F and potassium carbonate are dispersed in the mixed solution of toluene and water, in nitrogen protection
Under, add the Pd (PPh of phase transfer catalyst 4-butyl ammonium hydrogen sulfate and catalyst dosage3)4, it is heated to 70~90 DEG C of reactions 12
Compound G, described E, F and G molecular structure such as formula (E), formula (F) and formula are obtained after the completion of~24h, reaction after separating-purifying
(G)：
(4) the compound G and potassium carbonate are dispersed in monoethanolamine, 100~150 is heated under nitrogen protection
DEG C 6~12h of reaction, obtains compound H, shown in its molecular structure such as formula (H) after separating-purifying after the completion of reaction；
(5) the compound H is dissolved in chloroform, the bromine of 10~50 molar equivalents, heating is then added dropwise into solution
Flow back 8~24h, obtains compound J after the completion of reaction after separating-purifying, shown in its molecular structure such as formula (J)；
(6) the compound D, compound J and potassium carbonate are scattered in 1-METHYLPYRROLIDONE, added under nitrogen protection
Heat is to 60~100 DEG C of 8~24h of reaction, and after reaction terminates, separating-purifying obtains compound K, the as near-infrared shown in formula (I)
Role in fluorescent molecule switch, wherein substituent R areR1For
Preferably, step (4) described reaction temperature is 135 DEG C.
Preferably, step (5) the bromine molar equivalent that is added dropwise is 30.
According to another aspect of the present invention, there is provided a kind of described dithienyl ethene-terylene acid imide
The application of molecule, applied to near-infrared fluorescent molecular switch.
Preferably, the role in fluorescent molecule switch passes through>The ultraviolet photocontrol of 495nm visible ray or 300nm~400nm its
Fluorescence "ON", "Off" behavior.
Preferably, the role in fluorescent molecule switch is applied to near-infrared bio-imaging as near infrared fluorescent probe, passes through light
Regulate and control it and be self-assembly of micro nano structure..
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect.
(1) (terylene acyl is sub- with single fluorogen by multiple photochromic units (dithienyl ethene) by the present invention
Amine) it is connected, it is possible to resolve single dithienyl ethene is not enough to fully switch the shortcoming of one fluorophor of control, effectively adds
Hyperfluorescence switching speed and efficiency is quenched.
(2) the excellent optical property of near-infrared fluorescent molecular switch of the invention determines that it is especially suitable for optical information and deposited
Application in terms of storage, bio-imaging, near infrared light electronic device.It is biological that the role in fluorescent molecule switch of the present invention is applied to near-infrared
During imaging, it is regulated and controled by light and is self-assembly of micro nano structure, is had more than in non-polar solven and polymeric media
3000 fluorescent switch contrast, its open loop state has higher fluorescence quantum yield, fluorescence in the 302nm ultraviolet lighting several seconds
Cycling switch is almost quenched completely 10 times, its fluorescence losses is no more than 5%, with good fatigue resistance.
Brief description of the drawings
Fig. 1 is the knot of four (R- dithienyls ethene)-terylene acid imide near-infrared fluorescent molecular switches of the invention
Structure formula；
Fig. 2 is the four imido fluorescent switch principle schematics of (R- dithienyls ethene)-terylene of the invention；
Fig. 3 is four (R- dithienyls ethene) imido synthetic route charts of-terylene of the invention；
Fig. 4 is the hydrogen nuclear magnetic spectrogram of the compound K of embodiment 1；
Fig. 5 is the spectrogram of the compound K of embodiment 1 photochromic absorption and transmitting in different solvents；
Fig. 6 is that the compound K of embodiment 1 absorbs in tetrahydrofuran solution and fluorescence invertible switch circulates figure；
Fig. 7 is the shape appearance figure of the compound K of embodiment 1 self assembly after 302nm ultraviolet lightings 1min and 5min.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
A kind of dithienyl ethene-terylene acid imide molecule of the present invention, the molecule is by 2~4 dithienyls
Vinyl group is connected with single terylene imide group by the way that oxygen bridge key is non-conjugated.It is preferred that scheme, its be four (R- bis-
Thienyl ethene)-terylene acid imide, it has the general structure as shown in formula (I)：
Wherein, R is-H ,-C1-C12Alkyl ,-OH,Heterocycle or polymer chain,
The n is 0~12 integer, and X is O, S or N；R1For-H ,-C1-C12Alkyl or
As preferred scheme, R is
Four described (R- dithienyls ethene) imido preparation methods of-terylene, comprise the following steps：
(1) by compound A, compound B and sodium carbonate according to mol ratio 1:1:5 are dispersed in glycol dimethyl ether and water
4:In 1 mixed solution, under nitrogen protection, the Pd (PPh of catalyst dosage are added3)4, it is heated to 80~100 DEG C of reactions 12
Compound C, the A, B and C molecular structure such as formula (A), formula (B) and formula are obtained after the completion of~24h, reaction after separating-purifying
(C) shown in；
(2) by the compound C, para hydroxybenzene boric acid and sodium carbonate according to mol ratio 1:1:5 are dispersed in ethylene glycol
The 4 of dimethyl ether and water:In 1 mixed solution, under nitrogen protection, the Pd (PPh of catalyst dosage are added3)4, it is heated to 80~
100 DEG C of 12~48h of reaction, obtain compound D, shown in its molecular structure such as formula (D) after separating-purifying after the completion of reaction：
(3) by compound E, compound F and potassium carbonate according to mol ratio 1:1:5 are dispersed in the 2 of toluene and water:1
In mixed solution, under nitrogen protection, the Pd (PPh of phase transfer catalyst 4-butyl ammonium hydrogen sulfate and catalyst dosage are added3)4,
70~90 DEG C of 12~24h of reaction are heated to, compound G, described E, F and G molecule knot is obtained after the completion of reaction after separating-purifying
Structure such as formula (E), formula (F) and formula (G)：
(4) by the compound G and potassium carbonate according to mol ratio 1:10 are dispersed in monoethanolamine, under nitrogen protection
100~150 DEG C of 6~12h of reaction are heated to, compound H are obtained after the completion of reaction after separating-purifying, its molecular structure such as formula (H)
It is shown；
(5) the compound H is dissolved in chloroform, the bromine of 10~50 molar equivalents, heating is then added dropwise into solution
Flow back 8~24h, obtains compound J after the completion of reaction after separating-purifying, shown in its molecular structure such as formula (J)；
(6) by the compound D, compound J and potassium carbonate according to mol ratio 4:1:10 are scattered in 1-METHYLPYRROLIDONE
In, 60~100 DEG C of 8~24h of reaction are heated under nitrogen protection, and after reaction terminates, separating-purifying obtains compound K, is
Near-infrared fluorescent molecular switch shown in formula (I), wherein substituent R isR1For
Step (4) described reaction temperature is 135 DEG C；It may not be reacted less than this temperature or yield is very low, higher than this
Individual temperature can generate the accessory substances such as oxidation；Step (5) the bromine molar equivalent that is added dropwise both had ensured instead for 30,30 moles of bromine
It should can reduce the volatilization of bromine again completely, amount can generate much many bromine accessory substances influence purifications, measure many bromine volatilizations seriously less, dirty
Contaminate ambient influnence health.
The dithienyl ethene that the present invention is provided-terylene acid imide molecule can apply to near-infrared fluorescent molecule
Switch.The role in fluorescent molecule switch passes through>The ultraviolet photocontrol of 495nm visible ray or 300nm~400nm its fluorescence "ON",
"Off" behavior.It is applied to near-infrared bio-imaging as near infrared fluorescent probe, regulates and controls it by light and is self-assembly of micro-nano
Rice structure.
The present invention is by multiple photochromic units (dithienyl ethene) and single fluorogen (terylene acid imide)
It is connected, photochromic units multiple first improve the speed of role in fluorescent molecule switch fluorescent quenching and efficiency is quenched.Fig. 1 is this hair
The general structure of bright four (R- dithienyls ethene)-terylenes acid imide near-infrared fluorescent molecular switch；Fig. 2 is the present invention
The four imido fluorescent switch principle schematics of (R- dithienyls ethene)-terylene.Photochromic unit (DTE) with
Fluorophor (TDI) is non-conjugated be connected after, not only maintain fluorogen and dithienyl ethene each independent optical property, and also
Realize photochromic unit to the regulation and control of the light of fluorophore fluorescence (by the light irradiation of different wave length, realize the transmitting of fluorescence with
It is quenched), cardinal principle is the FRET of intramolecular：During open loop state, DTE absorption spectrum and TDI fluorescence light
Spectrum is not overlapping, it is impossible to realize the energy transfer of intramolecular, and when when ultraviolet lighting, DTE is changed into closed loop state, it absorbs light
Spectrum and TDI fluorescence spectrum have greater overlap, can occur obvious intramolecular fluorescence energy transfer, so that TDI fluorescent quenchings.
It is embodiment below：
Embodiment 1
Near-infrared fluorescent molecular switch shown in a kind of formula (I), wherein substituent R isR1For
Its synthetic route is as shown in figure 3, preparation method comprises the following steps：
(1) 1- (the bromo- 2- methylthiophenes -3- bases of 5-) -2- [2- methyl -5- (4- octyloxyphenyls) thiene-3-yl] perfluor
The synthesis of cyclopentene (compound C, shown in structural formula such as formula (C)).
Double (the bromo- 2- methylthiophenes -3- bases of the 5-) perfluoro-cyclopentenes of 1,2- are added into 100ml twoport round-bottomed flasks
(1.58g, 3mmol), 4- octyloxies phenyl boric acid (0.75g, 3mmol), natrium carbonicum calcinatum (1.59g, 15mmol), water (6ml) and
Glycol dimethyl ether (DME, 24ml) simultaneously uses magnetic agitation, and into mixed liquor, drum nitrogen 30min fully removes solvent and reactant
Oxygen in system.Then zero valent palladium catalyst Pd (PPh are added under nitrogen flowing3)4(0.17g, 0.15mmol), immediately with double
Pipe carefully vacuumizes denitrogen gas three times, makes the strict deoxygenation of whole system.90 DEG C of heating stirrings are warming up to react to 16h.Treat temperature
Recover to room temperature, product is extracted with ether, wash three times, filtered after anhydrous sodium sulfate drying, be spin-dried for solvent, use silica gel column layer
Analyse separating-purifying product and (use n-hexane/dichloromethane=1:19 mixed liquor elution), obtain violet solid 0.92g, yield 47%
。1H NMR(CDCl3,ppm):δ=0.89 (t, 3H, J=6.9Hz ,-CH3),1.29(m,2H,-CH2-),1.41-1.51(m,
10H,-CH2-),1.79(m,2H,-CH2-),1.88(s,3H,thiophene-CH3),1.94(s,3H,thiophene-CH3),
3.97 (t, 2H, J=6.6Hz, Ph-CH2-), 6.90 (d, 2H, J=8.8Hz, Ph-H), 7.05 (s, 1H, thiophene-H),
7.11 (s, 1H, thiophene-H), 7.44 (d, 2H, J=8.8Hz, Ph-H) .MS (APCI, m/z):651.3([M]+), analysis
Compound C is confirmed that it is, shown in structural formula such as formula (C)：
(2) 1- [5- (4- hydroxy benzenes) -2- methylthiophene -3- bases] -2- [2- methyl -5- (4- octyloxyphenyls) thiophene -3-
Base] perfluoro-cyclopentene (compound D, structural formula such as formula (D) shown in) synthesis.
Compound C (0.30g, 0.46mmol), 4- hydroxyl phenyl boric acid pinacols are added into 25ml twoport round-bottomed flask
Ester (0.10g, 0.46mmol), sodium carbonate (0.24g, 2.26mmol), water (2.5ml) and glycol dimethyl ether (10ml) are simultaneously violent
It is uniformly mixed, vacuumizes denitrogen gas three times to eliminate the oxygen in reaction system.Catalyst Pd is added under nitrogen flowing
(PPh3)4(26.6mg, 0.023mmol), vacuumizes denitrogen gas three times again, is warming up to 90 DEG C and is stirred vigorously reaction 24h.Treat cold
But to room temperature, extracted with ether, wash three times, after anhydrous sodium sulfate drying, filter and be spin-dried for solvent, gained crude product is with two
Chloromethanes：N-hexane=3:2 mixed solution obtains blue solid 0.15g through silica gel column chromatography after purification as eluant, eluent, production
Rate 49%, as compound D, shown in structural formula such as formula (D)：
(3) compound G synthesis.
The addition compound E (2.5g, 4.46mmol) into 500ml twoport round-bottomed flask, compound F (2.16g,
4.46mmol), potassium carbonate (3.08g, 22.3mmol), toluene (160ml) and water (80ml) are simultaneously stirred vigorously well mixed, take out true
Idle discharge nitrogen three times is to eliminate the oxygen in reaction system.Then phase transfer catalyst tetrabutyl hydrogen sulfate is added under nitrogen flowing
Ammonium (0.15g, 0.446mmol), Pd (PPh3)4(0.26g, 0.223mmol), vacuumizes denitrogen gas three times again, is warming up to 80 DEG C
It is stirred vigorously reaction 16h.Room temperature is cooled to, is extracted with dichloromethane, is washed three times, after anhydrous sodium sulfate drying, filtering
And solvent is spin-dried for, gained crude product obtains red solid 3.49g using dichloromethane as eluant, eluent after purification through silica gel column chromatography,
Yield 94%, wherein R1For 2,6- diisopropyl phenyls, as compound G, shown in structural formula such as formula (G)：
(4) synthesis of compound K.
The addition compound J (0.11g, 0.10mmol) into 50ml twoport round-bottomed flask, compound D (0.25g,
0.40mmol), potassium carbonate (0.07g, 0.50mmol) and 1-METHYLPYRROLIDONE (20ml), under nitrogen atmosphere, are stirred vigorously
It is well mixed, it is warming up to 80 DEG C and is stirred vigorously reaction 14h.Room temperature is cooled to, reaction solution watery hydrochloric acid washing, suction filtration gained is solid
Body, is dissolved after drying with dichloromethane, is then washed three times, after anhydrous sodium sulfate drying, is filtered and be spin-dried for solvent, gained is thick
Product is with dichloromethane：N-hexane=2:1 mixed solution obtains blue-green as eluant, eluent and consolidated after purification through silica gel column chromatography
Body 0.11g, i.e. compound K, yield 34%, its nucleus magnetic hydrogen spectrum figure is as shown in figure 4, the structural formula of compound K is as follows：
Wherein, R isR1For
Fig. 4 is the hydrogen nuclear magnetic spectrogram of the present embodiment compound K, and the collection of illustrative plates is confirmed that it is the structure shown in formula (I), and R isR1For
R and R in formula (I) structural formula1(R is-H ,-C to other corresponding substituents1-C12Alkyl ,-OH,Heterocycle or polymer chain, the n be 0~12 integer, X be O, S or
N；R1For-H ,-C1-C12Alkyl or) butterfly molecule can be prepared according to the similar synthesis thinking of embodiment 1.
Fig. 5 is near-infrared fluorescent molecular switch (compound K) photochromic Absorption and emission spectra in different solvents
Figure, its open loop state has higher fluorescence quantum yield, and fluorescence is almost quenched completely in the 302nm ultraviolet lighting several seconds, can be real
The multiple Reversible Cycle of existing fluorescence.As shown in Figure 5, a and b figures be Absorption and emission spectras of the K in toluene with ultraviolet lighting when
Between change, c and d figures are the change of K Absorption and emission spectras in tetrahydrofuran, e and f figures are K in N, N- dimethyl formyls
The change of Absorption and emission spectra in amine.Compound K has identical UV absorption and light in THF, DMF, dilute toluene solution
Discoloration is caused, illustrating the polarity of solvent does not influence photochromic speed.Light is absorbed by the open loop state and photostationary state that contrast K
Spectrum, finding the solution of isoconcentration has almost identical ultraviolet-visible absorption spectroscopy, and showing the polarity of solvent does not influence K suction
Receive, the light conversion ratio approximately equal of photostationary state in different solvents, K weak solution after 2~5s of 302nm ultraviolet lights,
Most of open loop state is changed into closed loop state, and its fluorescence is almost quenched completely.After illumination 20s, its fluorescence intensity is almost empty with solution
White baseline is overlapped.It is contemplated that the near-infrared fluorescent molecular switch has the fluorescent switch ratio and faster fluorescence response speed of superelevation
Rate.The wherein a length of 302nm of ultraviolet light wave, the concentration of K in the solution is 5 × 10-7M, fluorescence exciting wavelength is 600nm.
Fig. 6 absorbs the invertible switch with fluorescence for near-infrared fluorescent molecular switch (compound K) in tetrahydrofuran solution
Circulation figure.As shown in Figure 6, a figures are the change of K absorption spectrum intensity at 608nm in tetrahydrofuran, its concentration is 1 ×
10-6M, circulates illumination condition：302nm ultraviolet lighting 5s, then>495nm visible rays shine 10min；B figures are K in tetrahydrofuran
The change of emission spectrum fluorescence intensity at 697nm, its concentration is 1 × 10-6M, circulates illumination condition：302nm ultraviolet lighting 5s,
Then>495nm visible rays shine 10min.The near-infrared fluorescent molecular switch has good fatigue resistance, and circulation light shines 10 times,
Its fluorescence-intensity decay is no more than 5%.
Fig. 7 be IR fluorescence molecular switch (compound K) in DMF solution, through 302nm ultraviolet lightings 1min (a figures) and
The self assembly shape appearance figure that 5min (b figures) stands three days afterwards, the concentration of wherein K in the solution is 2 × 10-6M。
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (9)
1. a kind of dithienyl ethene-terylene acid imide molecule, it is characterised in that the molecule is by 2~4 Dithiophenes
Base vinyl group is connected with single terylene imide group by the way that oxygen bridge key is non-conjugated.
2. dithienyl ethene as claimed in claim 1-terylene acid imide molecule, it is characterised in that it is four (R-
Dithienyl ethene)-terylene acid imide, it has the general structure as shown in formula (I)：
Wherein, R is-H ,-C1-C12Alkyl ,-OH,Heterocycle or polymer
Chain, the n is 0~12 integer, and X is O, S or N；R1For-H ,-C1-C12Alkyl or。
3. molecule as claimed in claim 2, it is characterised in that the R is。
4. a kind of four (R- dithienyls ethene) imido preparation method of-terylene as claimed in claim 3, it is special
Levy and be, comprise the following steps：
(1) compound A, compound B and sodium carbonate are dispersed in the mixed solution of glycol dimethyl ether and water, in nitrogen
Under protection, catalyst Pd (PPh are added3)4, 80~100 DEG C of 12~24h of reaction are heated to, are obtained after the completion of reaction after separating-purifying
Shown in compound C, the A, B and C molecular structure such as formula (A), formula (B) and formula (C)；
(2) the compound C, para hydroxybenzene boric acid and sodium carbonate are dispersed in the mixed solution of glycol dimethyl ether and water
In, under nitrogen protection, add catalyst Pd (PPh3)4, 80~100 DEG C of 12~48h of reaction are heated to, are separated after the completion of reaction
Compound D is obtained after purification, shown in its molecular structure such as formula (D)：
(3) compound E, compound F and potassium carbonate are dispersed in the mixed solution of toluene and water, under nitrogen protection,
Add phase transfer catalyst 4-butyl ammonium hydrogen sulfate and catalyst Pd (PPh3)4, it is heated to 70~90 DEG C of 12~24h of reaction, reaction
After the completion of compound G, described E, F and G molecular structure such as formula (E), formula (F) and formula (G) are obtained after separating-purifying：
(4) the compound G and potassium carbonate are dispersed in monoethanolamine, 100~150 DEG C is heated under nitrogen protection instead
Answer and obtain compound H after separating-purifying after the completion of 6~12h, reaction, shown in its molecular structure such as formula (H)；
(5) the compound H is dissolved in chloroform, the bromine of 10~50 molar equivalents is then added dropwise into solution, 8 are heated to reflux
Compound J is obtained after the completion of~24h, reaction after separating-purifying, shown in its molecular structure such as formula (J)；
(6) the compound D, compound J and potassium carbonate are scattered in 1-METHYLPYRROLIDONE, are heated under nitrogen protection
60~100 DEG C of 8~24h of reaction, after reaction terminates, separating-purifying obtains compound K, the as near-infrared fluorescent shown in formula (I)
Molecular switch, wherein substituent R areR1For。
5. preparation method as claimed in claim 4, it is characterised in that step (4) described reaction temperature is 135 DEG C.
6. preparation method as claimed in claim 4, it is characterised in that step (5) the bromine molar equivalent that is added dropwise is 30.
7. a kind of dithienyl ethene-terylene acid imide molecule as described in claims 1 to 3 any one should
With, it is characterised in that applied to near-infrared fluorescent molecular switch.
8. application as claimed in claim 7, it is characterised in that the role in fluorescent molecule switch passes through>495nm visible ray or
Its fluorescent switch behavior of 300nm~400nm ultraviolet photocontrol.
9. application as claimed in claim 7, it is characterised in that the role in fluorescent molecule switch is used as near infrared fluorescent probe application
In near-infrared bio-imaging, it is regulated and controled by light and is self-assembly of micro nano structure.
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