CN1724534A - Metal aza porphyrin compound containing fluorene diaryl ethylene and its preparation method and application - Google Patents
Metal aza porphyrin compound containing fluorene diaryl ethylene and its preparation method and application Download PDFInfo
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- CN1724534A CN1724534A CN 200510027783 CN200510027783A CN1724534A CN 1724534 A CN1724534 A CN 1724534A CN 200510027783 CN200510027783 CN 200510027783 CN 200510027783 A CN200510027783 A CN 200510027783A CN 1724534 A CN1724534 A CN 1724534A
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Abstract
The invention discloses a fluorine-containing diarylethylene metal aza porphyrin compound, its synthesizing method and application, wherein the compound has a rather large molar absorption coefficient and strong near-infrared fluorescence-emission, the charge of alkyl fluorine can increase the solubility of the material in organic solvent and its light-emitting performance. By employing the opening/closing ring reaction of the dithiofuran ethylene, the fluorescent change of the compound can be adjusted, and the non-destructive reading out can be achieved.
Description
Technical field
The invention belongs to the photochromic material technical field, be specifically related to a kind of diarylethene metal aza porphyrin compound and its production and application.Specifically, relate to a kind of di-thiofuran ethylene substituted metal aza porphyrin compounds that contains polynary alkyl fluorenes and preparation method thereof and application luminous, the variable color field.
Background technology
Photochromic compound since its in luminous energy memory, information storage, coating, pigment and related industries potential using value and more and more come into one's own.Fast development along with sophisticated technologies such as modern biology, space flight needs information storage material quick more, vast capacity.On time of response even wish to reach nanosecond, picosecond, final objective is a canned data on molecule even atomic level.High performance photon storage medium be can satisfy requirement like this have one of storage medium of potentiality.At present, the focus of organic photochromic research mainly concentrates on: on the compounds such as diarylethene, fulgide, spiro-pyrans.In these several compounds, be representative main and that widely attract attention with the dithiazole ethylene photochromic material especially.
Because di-thiofuran ethylene has a series of useful characteristics.People are pouring into many enthusiasm and energy aspect synthetic this compounds.On the one hand be that expectation makes up the novel molecular material that may have advanced or new characteristic, be in order to satisfy the needs of practical application on the other hand, and compound is modified.In the compound of the di-thiofuran ethylene open loop bodily form formula of being reported at present, under UV-irradiation, become colored closed loop body after, the maximum absorption wavelength of its closed loop body seldom reaches 700nm above (near-infrared region) mostly less than 700nm.Even the photochromic compound of minority closed loop body more than 700nm arranged, its solubleness is also not so good.We know that in the practical application, photochromic compound needs to exist with solid-state form, and di-thiofuran ethylene can be entrained in the polymer or be grafted on the polymer side chain, then coating or evaporation film-forming.If solubleness is bad, just influenced the effect of filming.And then be unfavorable for practical application.
In addition, aspect the suitableization research of diarylethene, can reach or near the practicability requirement such as performances such as thermostability and time of response, and reading method is also very not fully up to expectations.In order successfully to carry out wiping the storage of rewriting formula optical information, the dichromatism attitude of photochromic material also must detect with non-failure mode, and promptly nondestructive is read.Traditional information read method is to utilize specific refractory power or transmission change and read.Obviously, in these the two kinds methods of difference of utilizing uv-visible absorption spectra as playback mode, can write information or wipe equally as the light of reading, may cause fading photochromic reactions generation and destroy canned data, just reveal the authenticity and integrity that has encircled the prime information record.
Therefore, design, the di-thiofuran ethylene molecule of the better performance that exploitation makes new advances continues to explore ideal nondestructive reading method, is necessary and field that have broad application prospects.
The present invention synthesizes the dithiazole ethylene metal aza porphyrin compounds that a class contains polynary alkyl fluorenes with innovating, this compounds has structure innovation, bigger molar absorptivity and the emission of strong near-infrared fluorescent, solvability is good, characteristics such as photochromic quantum efficient height.Therefore, on reading method, can be complementary, help practical application with existing GaAlAs/GaAs semi-conductor near infrared laser wavelength; Simultaneously, bigger molar absorptivity and the emission of strong near-infrared fluorescent, it helps the storage of optical information and the sensitivity of reading.Deliquescent increase helps the film forming of compound.Such material can be applicable to fields such as high density information storage, molecular light switch, multicolour demonstration and three-dimensional storage, has good application prospects.
Summary of the invention
The objective of the invention is to propose a kind of photochromic material of maximum absorption wavelength in the scope of near-infrared region that closes ring body, can be complementary with existing GaAlAs/GaAs semi-conductor near infrared laser wavelength when the information of its storage is read.
The present invention also aims to propose synthetic photochromic material, improve the storage of optical information and the sensitivity of reading with bigger molar absorptivity and strong near-infrared fluorescent emission.
The present invention proposes to embed the alkyl fluorenes with good luminous and solubility property, improves its luminous efficiency and solubleness, utilizes the ON/OFF ring of di-thiofuran ethylene to react the change in fluorescence of regulating material, and realizes that by this nondestructive of information reads.
The target compound that the present invention proposes is a kind of metal aza porphyrin compound containing fluorene diaryl ethylene, has following chemical structure of general formula:
Wherein, M is metal or non-metallic atoms such as Mg, Fe, Zn, Cu, Ca, Ni, Co, Si, Sn, Rh, Ge, Ru, Pt, Pd, Ir, Os or Eu.X is a kind of among N, O, the S.Each R
1-R
8Can be identical, also can be different, they can be any in hydrogen, alkane, alkoxyl group, aromatic hydrocarbons, halogen rope, hydroxyl, the sulfonic group.
Preferred L is a kind of among Mg, Fe, Zn, Ni, Co, Ru, Pt, Ir, Os, the Eu; R
1, R
2Be H or C
1-C
18Alkyl, alkoxyl group; R
3, R
4Be alkyl, R
5-R
8A kind of in H, alkyl, halogen, the aryl.
More preferably M is a kind of among Mg, Fe, Zn, Ni, Ru, Pt, Ir, the Eu; R
1, R
2Be C
1-C
12Alkyl, alkoxyl group; R
3, R
4Be alkyl, R
5-R
8A kind of in H, alkyl, halogen or the benzene
More preferably M is a kind of among Mg, Zn, Ni, Ru, Pt, Ir, the Eu; R
1, R
2Be C
4-C
12Alkyl, alkoxyl group; R
3, R
4Be C
1-C
2, R
5-R
6A kind of in H, the halogen, R
7-R
8A kind of in H, alkyl or the benzene.
Most preferred M is a kind of among Mg, Zn, Ru, the Eu; R
1, R
2Be C
8-C
12Straight chained alkyl; R
3, R
4Be CH
3R
5, R
6Be H; R
7, R
8Be H or methyl or benzene.
The feature of preferred compound has as follows:
When M is Mg, R
1, R
2Be the octane base; R
3, R
4Be CH
3R
5, R
6Be H; R
7, R
8Be methyl; X is S.Promptly eight-[2-(9,9-two octyls-6-)-and fluorenyl-3,5-dimethyl-4-] thiophene substituted nitrogen heterocyclic porphyrin magnesium compound, as structural formula (A).
When M is Zn, R
1, R
2Be the normal hexane base; R
3, R
4Be ethyl; R
5, R
6Be H; R
7, R
8Be methyl, X is S.Promptly eight-[2-(9,9-two hexyls-6-)-and fluorenyl-5-ethyl-4-] thiophene substituted nitrogen heterocyclic porphyrin zn cpds, as structural formula (B).
When M is Ru, R
1, R
2Be C
12Alkyl; R
3, R
4Be CH
3R
5, R
6Be H; R
7, R
8Be (also) phenyl; X is S.Be eight-[6-(9,9-two C
12Alkyl-6-)-fluorenyl-2-methyl-3-phenyl-4-] thiophene substituted nitrogen heterocyclic porphyrin ruthenium compound, as structural formula (C).
When M is Eu, R
1, R
2Equal octane base; R
3, R
4Be CH
3R
5, R
6Be H; R
7, R
8Be methyl; X is O.Be eight-[2-(9,9-two octyls-6-)-and fluorenyl-3,5-dimethyl-4-] furyl substituted nitrogen heterocyclic porphyrin europium compound, as structural formula (D).
This
The preparation process of the compound that invention proposes is as follows:
Method 1: under the certain temperature condition, under the effect of catalyzer, Malaysia dintrile and the haloalkyl fluorenes that halogenated thiophene is replaced reacts in the A solvent earlier, gets alkyl fluorenes substituted thiophene base Malaysia dintrile intermediate.
Then with the back resultant in the B solvent with organometallics lucifuge reaction, after question response is finished, concentrate, separate, purify pure product target compound.
Temperature of reaction is 25-200 ℃, and catalyzer is Ni (dppp) Cl
2, a kind of among triphenyl phosphorus palladium, tetran-butylphosphonium bromide amine or the DBU, the reaction times is 1-80 hour, reaction solvent A, B are polar solvent.Reaction equation is as follows:
Method 2: under the certain temperature condition, a certain amount of halogenated thiophene replacement Malaysia dintrile and organometallics are reacted in the C solvent, generate eight halo di-thiofuran ethylene Base Metal aza porphyrin compounds.Then with this product under the effect of catalyzer, react in the D solvent with the haloalkyl fluorenes.
Temperature of reaction is 0-200 ℃, and the reaction times is 1-72 hour, and reaction solvent is a polar solvent, and catalyzer is Ni (dPPP) Cl
2, a kind of among triphenyl phosphorus palladium, tetran-butylphosphonium bromide amine or the DBU.
In above-mentioned preparation method one and the method two, X is Cl, Br, halogen atoms such as I; Most preferred catalyzer is Ni (dPPP) Cl
2Or DBU; Solvent is DMF, THF, n-Octanol, propyl carbinol or Virahol.Reaction equation is as follows:
The experimental technique that contains assorted aza porphyrin compound variable color of fluorene diaryl ethylene metal and change in fluorescence:
Photochromic
Earlier target compound being dissolved in a kind of organic solvent, being made into certain concentration, is λ with wavelength
1This solution certain hour of rayed h
1, this solution becomes green by blueness gradually as can be seen; Be λ with wavelength again
2Rayed h
2Hour, solution changes to blueness from green again.
In the described chromophoric method, preferred strength of solution is 5 * 10
-7-5 * 10
-5Mol, organic solvent are a kind of in tetrahydrofuran (THF), methyl alcohol, ethanol, methylene dichloride or the trichloromethane, λ
1Be 300-500nm, λ
2Be 500-800nm, h
1And h
2Be respectively 0.5-5 hour.
More preferably strength of solution is 5 * 10
-6-5 * 10
-5Mol, organic solvent are a kind of in tetrahydrofuran (THF), methylene dichloride, the trichloromethane, λ
1Be 300-450nm, λ
2Be 600-800nm, h
1And h
2Be respectively 0.5-2 hour.
Most preferred strength of solution is 5 * 10
-6-1 * 10
-5Mol, organic solvent are methylene dichloride or trichloromethane, λ
1Be 300-350nm, λ
2Be 600-750nm, h
1And h
2For being respectively 0.5-1 hour.
The mensuration of change in fluorescence
Fluorometric assay before photochromic: at first target compound is dissolved in a kind of organic solvent, concentration is 1 * 10
-7-1 * 10
-5Mol; Survey its fluorescence data with fluorescence analyser then.During mensuration, its excitation wavelength is λ
1, wavelength scanning range is 200-800nm.
In the above-mentioned measuring method, preferred organic is a kind of in THF, methylene dichloride, trichloromethane or the benzene; Excitation wavelength lambda
1Be 300-500nm.
Preferred organic solvent is a kind of in THF, trichloromethane or the benzene; Excitation wavelength lambda
1Be 400-500nm.
Fluorometric assay after photochromic: with wavelength is the target illuminated compound solution regular hour h of λ 2
1, this solution becomes green by blueness gradually as can be seen simultaneously, treats that it reaches photostationary state (ultraviolet does not change); Fluorescence after photochromic takes place measuring it on the fluorescence analyser again, the excitation wavelength of this moment is λ
3, as can be seen, very big variation has taken place in the fluorescence of photochromic front and back.
At this measuring method, preferred organic is a kind of in THF, methylene dichloride, trichloromethane or the benzene, illumination wavelength lambda
2Be 200-500nm, time h
1Be 3-60 minute, excitation wavelength lambda
3Be 300-500nm.
Preferred organic solvent is a kind of in THF, methylene dichloride, trichloromethane or the benzene; , illumination wavelength lambda
2Be 300-500nm, time h
1Be 3-30 minute, excitation wavelength lambda
3Be 350-500nm.。
Most preferred organic solvent is THF, trichloromethane or benzene, illumination wavelength lambda
2Be 350-450nm, time h
1Be 10-20 minute, excitation wavelength lambda
3Be 400-500nm.
As seen from the above technical solution, the dithiazole ethylene metal aza porphyrin photochromic compound that the present invention is designed, synthetic convenient, the structure uniqueness.This compounds has the characteristics of unique polynary fluorenes, and the maximal ultraviolet of its closed loop body-visible absorption wavelength near existing GaAlAs/GaAs semi-conductor near infrared laser wavelength, helps practical application near infrared region.And designed synthetic target compound has bigger molar absorptivity and strong near-infrared fluorescent emission, and it helps the storage of optical information and the sensitivity of reading.Owing to the adding of alkyl fluorenes, increased the solvability of this material, improved its luminescent properties.Utilize the ON/OFF ring of di-thiofuran ethylene to react the change in fluorescence of regulating compound, and realize that by this nondestructive reads, have good application prospects and realistic meaning.Such material can be widely used in extensive fields such as high density information storage, molecular light switch, multicolour demonstration and three-dimensional storage.
Description of drawings
Fig. 1 is compound M
1The variation diagram of uv-visible absorption spectroscopy.
Fig. 2 is compound M
1The change in fluorescence figure of photochromic front and back takes place.
Embodiment
Further set forth the present invention below in conjunction with example, but example does not limit protection scope of the present invention.
Embodiment 1 utilizes method 1 synthesising target compound M
1
Synthesizing of intermediate: add 2-halo-9 successively in the 100mL single port flask, 9 '-dioctyl fluorene 3mmol, 1,2-dinitrile-1,2-two (2-methyl-5-halo-3-thiophene)-ethene 1.3mmol, MAGNESIUM METAL or sodium are some; With tetrahydrofuran (THF) or ether is solvent, and adds a certain catalyzer.Argon gas vacuum displacement system three times, lucifuge refluxes and spends the night in argon atmospher.Pour in the water, separatory, the inorganic phase of extracted with diethyl ether merges organic layer, concentrates.With sherwood oil and methylene dichloride is eluent, crosses silicagel column.Obtain light yellow solid and be intermediate, productive rate is 64%.MS(m/e)：1047.8。
1H-NMR(400MHz，CDCl
3，ppm)：0.86(t，12H，-CH
3)，2.23(s，6H，-CH
3)，6.62(s，2H，-CH-)，1.02-1.23(m，48H，-CH
2-)，1.95(m，8H，-CH
2-)，7.25-7.36(m，4H，Ar)7.43-7.48(m，6H，Ar)7.79-7.84(m，4H，Ar)。
Synthesizing of target compound:
The magnesium powder 10mmol that removes oxide film joins in the 50mL exsiccant Virahol, and under the argon shield, heated and stirred backflow 24h, generates linen Mg (i-PrO) therebetween gradually
2, be cooled to room temperature, add the above-mentioned midbody compound M ' of 1.5mmol, lucifuge, the 36h that under argon shield, refluxes still, cooling, removal of solvent under reduced pressure, the methylene dichloride dissolving, water, saturated NaCl solution washing are used anhydrous MgSO successively
4Drying is filtered, concentrates, and be eluent with chloroform or methylene dichloride, cross silicagel column, get blackish green solid, productive rate about 48%.Mass spectrum: MS (m/e): 4342.Ultimate analysis: calculated value (%): C:81.86; H:9.10; N:2.58.Measured value (%): C:81.39; H:8.76; N:2.19.
Embodiment 2 utilizes method 2 synthesising target compound M
1
Under argon shield, the 20mmol MAGNESIUM METAL joined in the 100mL exsiccant Virahol refluxed 24 hours; Be cooled to room temperature, add 1 of 2mmol again, 2-dinitrile-1; 2-two (2-methyl-5-halo-3-thiophene)-vinyl compound continues to reflux 36 hours, is reflected in lucifuge and the argon shield and carries out; after question response is finished, cooling, removal of solvent under reduced pressure; washing; drying is filtered, and concentrates; cross silicagel column, get pure product eight halo di-thiofuran ethylene Base Metal aza porphyrin compounds.Productive rate about 55%.
Then with this aza porphyrin under the effect of catalyzer, with 2-halo-9,9 '-dioctyl fluorene is reacted in polar solvent, lucifuge refluxes and to spend the night in the argon atmospher.Be cooled to room temperature, filter, concentrate, make eluent with the sherwood oil proportioning, cross silicagel column with chloroform or methylene dichloride, blackish green solid, purify product, productive rate about 46%.
Embodiment 3 photochromic chromophoric methods
With before the UV-irradiation, target compound among the embodiment 1 or 2--aza porphyrin compound has three strong absorption peaks, lays respectively at the broad absorption band a little less than 653nm, 340nm and 315nm and, between 400-450nm.When with wavelength being its dichloromethane solution of UV-irradiation of 300-365nm or trichloromethane, obvious variation has taken place in its absorption spectrum.The dynamic change collection of illustrative plates that figure below obtains for the interval different time.We can see clearly that the strong absorption peak at the 653nm place weakens gradually, and locates to have occurred new absorption peak about 720nm, and strengthen gradually.After having shone about 30min, this system has reached photostationary state, and respectively 320,396,471,570, one group of isobestic point has appearred in the 683nm place.The color of solution has also become deep green by blue-greenish colour.The generation of new absorption peak 720nm is because the generation of closed loop compound.The aza porphyrin core of opened loop compound and peripheral thiophene are systems independently separately, do not interact between them.After photochromic reactions took place, the aza porphyrin conjugated system had extended to whole thiphene ring, so the conjugated pi system is increased, made its uv-visible absorption spectroscopy red shift to the 720nm place.This process is a reversible, and when using the dichloromethane solution of its photostationary state of rayed about 750-800nm, it can return to the absorption spectrum and the color of initial state again gradually.The variation of the uv-visible absorption spectroscopy of compound as shown in Figure 2.
The mensuration of embodiment 4 change in fluorescence
At first target compound in embodiment 1 or the example 2 is dissolved in organic solvent THF or the trichloromethane, being made into concentration is 1 * 10
-7-1 * 10
-5The solution of mol; Survey its fluorescence data with fluorescence analyser then.During mensuration, its excitation wavelength is 300-500nm, and the scanning wavelength scope is 300-800nm.
After recording the fluorescence data before the above-mentioned illumination, be this solution of rayed 10-20 minute of 350-450nm again with wavelength, the while as can be seen this solution become green by blueness gradually, treat that it reaches photostationary state (uv-vis spectra no longer changes); Fluorescence after photochromic takes place measuring it on the fluorescence analyser again, the excitation wavelength of this moment is 400-500nm, and as can be seen, fluorescent emission intensity is that the variation with the irradiation time of ambient light changes.That is to say, when compound was in open loop respectively and closes ring status, its fluorescence had obvious difference, and the relative quantum productive rate is also different, very big variation has taken place in the fluorescence of photochromic front and back, take this can this change in fluorescence as to storing the nondestructive reading method of information.As Fig. 2:
The first step: with 2-halo-9,9 '-2 18 alkyl fluorenes 6mmol and 1,2-dinitrile-1,2-two (2-methyl-5-halo-3-furans)-ethene 2.5mmol, number of metal magnesium or sodium add in the 200mL single port flask according to this; Adding a certain catalyzer, is solvent with tetrahydrofuran (THF) or ether.Lucifuge back flow reaction under argon shield.After question response is finished, mother liquor is poured in the water, separatory repeatedly extracts inorganic phase, merges organic layer, concentrates.Sherwood oil and methylene dichloride with certain proportioning are eluent, cross silicagel column.Obtain solid and be pure product intermediate M '.
Second step: in 100mL exsiccant Virahol or propyl carbinol; add and remove under the magnesium powder or magnesium chips 20mmol argon shield of oxide film; heated and stirred refluxes and finishes until reaction, is cooled to room temperature, adds the above-mentioned the first step midbody compound of 2mmol M '; lucifuge, still under argon shield, be back to the reaction finish; cooling, removal of solvent under reduced pressure, methylene dichloride dissolving; water, saturated NaCl solution washing are used anhydrous MgSO successively
4Drying is filtered, and concentrates, and joining a certain proportion of sherwood oil with chloroform or methylene dichloride is eluent, crosses silicagel column, gets blackish green solid, is pure target product.
Embodiment 6 target compound M
3Synthetic (method 2)
Under protection of inert gas, 30mmolHCl solution is carried out surface-treated MAGNESIUM METAL put in the 150mL exsiccant Virahol and to reflux 2 days; Be cooled to room temperature, add 1 of 3mmol again, 2-dinitrile-1; 2-two (6-halo-3-thionaphthene)-vinyl compound continues to reflux 72 hours, is reflected in lucifuge and the argon shield and carries out; after question response is finished, cool to room temperature, underpressure distillation removes and desolvates; washing; drying is filtered, and concentrates; cross silicagel column, get pure product eight halogenated diphenyl thiophthene vinyl metal aza porphyrin compounds.
Under the effect of catalyzer, with 2-halo-9,9 '-two-(dodecyl)-fluorenes reacts in polar solvent with above-mentioned this aza porphyrin intermediate, lucifuge in argon atmospher, and back flow reaction is spent the night.After question response is finished, be cooled to room temperature, filter, concentrated mother liquor is made eluent with chloroform and sherwood oil with certain proportioning, column chromatography, purify product, productive rate is 41%.
By embodiment 5 and 6 synthetic target compound M
2And M
3With enforcement 1 or 2 synthetic compound M
1Has similarly photochromic and change in fluorescence characteristic.Thereby has a same using value.
Claims (9)
1, a kind of metal aza porphyrin compound containing fluorene diaryl ethylene is characterized in that having following chemical structure of general formula:
Wherein, M is metal or non-metallic atoms such as Mg, Fe, Zn, Cu, Ca, Ni, Co, Si, Sn, Rh, Ge, Ru, Pt, Pd, Ir, Os or Eu; X is a kind of among N, O, the S; Each R
1-R
8For identical or different, be a kind of in hydrogen, alkane, alkoxyl group, aromatic hydrocarbons, halogen, hydroxyl or the sulfonic group.2, compound according to claim 1 is characterized in that, M is a kind of among Mg, Zn, Ru, the Eu; R
1, R
2Be C
4-C
12Alkyl; R
3, R
4Be CH
3Or C
2H
5R
5, R
6Be H or alkyl; R
7, R
8Be H, methyl, benzene or acene, X is a kind of among N, O, the S.
3, as compound as described in the claim 2, when it is characterized in that M is Mg, R
1, R
2Be the octane base; R
3, R
4Be CH
3R
5, R
6Be H; R
7, R
8Be methyl; X is S, said compound is eight-[2-(9,9-two octane bases-6-)-and fluorenyl-3,5-dimethyl-4-] thiophene substituted nitrogen heterocyclic porphyrin magnesium compound.
4, as compound as described in the claim 2, when it is characterized in that M is Zn, R
1, R
2Be the normal hexane base; R
3, R
4Be ethyl; R
5, R
6Be H; R
7, R
8Be methyl, X is S, said compound is eight-[2-(9,9-two normal hexane bases-6-)-and fluorenyl-5-ethyl-4-] thiophene substituted nitrogen heterocyclic porphyrin zn cpds.
5, as compound as described in the claim 2, when it is characterized in that M is Ru, R
1, R
2Be C
12Alkyl; R
3, R
4Be CH
3R
5, R
6Be H; R
7, R
8Be (also) phenyl; X is S, said compound is eight-[6-(9,9-two C
12Alkyl-6-)-fluorenyl-2-methyl-3-phenyl-4-] thiophene substituted nitrogen heterocyclic porphyrin ruthenium compound.
6, as compound as described in the claim 2, it is characterized in that, when M is Eu, R
1, R
2Equal octane base; R
3, R
4Be CH
3R
5, R
6Be H; R
7, R
8Be methyl; X is O, said compound is eight-[2-(9,9-two octane bases-6-)-and fluorenyl-3,5-dimethyl-4-] furyl substituted nitrogen heterocyclic porphyrin europium compound.
7, as the preparation method of compound as described in arbitrary among the claim 1-6, it is characterized in that comprising the steps:
Method 1: under the effect of catalyzer, under 25-200 ℃ temperature condition, earlier with 1,2-dinitrile-1,2-two (5-halo-3-thiophene)-ethylene compounds and haloalkyl fluorenes react in the A solvent; Then the back resultant is reacted with organometallics in the B solvent; Catalyzer is Ni (dppp) Cl
2A kind of among triphenyl phosphorus palladium, tetran-butylphosphonium bromide amine or the DBU, the reaction times is 1-80 hour, reaction solvent A, B are polar solvent; Perhaps
Method 2: under 0-200 ℃ temperature condition, earlier with 1,2-dinitrile-1,2-two (5-halo-3-thiophene)-ethylene compounds and organometallics react in the C solvent and generate eight halo di-thiofuran ethylene Base Metal aza porphyrin compounds; Then with this product under the effect of catalyzer, react in the D solvent with the haloalkyl fluorenes; Reaction times is 1-72 hour, and reaction solvent C, D are polar solvent, and catalyzer is Ni (dppp) Cl
2, a kind of among triphenyl phosphorus palladium, tetran-butylphosphonium bromide amine or the DBU.
8, a kind of chromophoric method as compound photochromic as described in one of claim 1-6 is characterized in that concrete steps are as follows:
Target compound is dissolved in the organic solvent, is λ with wavelength
1This solution of rayed, time h
1, its solution colour gradually changes, at last from light blue change to blackish green deeply; After treating that it reaches photostationary state, be λ with wavelength again
2Rayed h
2Hour, solution changes to blueness from green again; Wherein: organic solvent is tetrahydrofuran (THF), methyl alcohol, ethanol, methylene dichloride or trichloromethane, λ
1Be 300-500nm, λ
2Be 500-800nm, h
1And h
2Be respectively 0.5-5 hour.
9, a kind of fluorescent emission method as compound as described in one of claim 1-6 is characterized in that concrete steps are as follows:
(1) at first target compound is dissolved in the organic solvent, concentration is 1 * 10
-7-1 * 10
-5Mol; Survey its fluorescence data with fluorescence analyser then, during mensuration, its excitation wavelength is λ
1, the scanning wavelength scope is 200-800nm;
(2) record fluorescence data before the illumination described in the step (1) after, be λ with wavelength again
2This solution of rayed, time h
1, this solution is become blackish green gradually by blueness, treat that it reaches photostationary state, fluorescence after photochromic takes place measuring it on the fluorescence analyser again, and the excitation wavelength of this moment is λ
3, very big variation has taken place in the fluorescence intensity of photochromic front and back;
Wherein, organic solvent is a kind of in THF, methylene dichloride, trichloromethane or the benzene; Excitation wavelength lambda
1Be 300-500nm, illumination wavelength lambda
2Be 200-500nm, time h
1Be 3-60 minute, excitation wavelength lambda
3Be 300-500nm.
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Cited By (6)
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| CN102268128A (en) * | 2010-06-07 | 2011-12-07 | 海洋王照明科技股份有限公司 | Porphyrin copolymer containing thienophenazine unit as well as preparation method and application thereof |
| CN102276800A (en) * | 2010-06-09 | 2011-12-14 | 海洋王照明科技股份有限公司 | Triphenylamine unit porphyrin copolymer as well as preparation method and application thereof |
| CN102295747A (en) * | 2010-06-23 | 2011-12-28 | 海洋王照明科技股份有限公司 | Pyrrole-pyrrole-dione unit-containing porphyrin copolymer and preparation method as well as application thereof |
| CN101386783B (en) * | 2008-10-22 | 2012-03-21 | 重庆大学 | Sulfotetraphenyl porphyrin nano luminescent material and preparation method thereof |
| CN103145749A (en) * | 2010-11-11 | 2013-06-12 | 华东理工大学 | Multi-thiophene group containing photochromic compound |
| CN113896904A (en) * | 2021-11-16 | 2022-01-07 | 曲阜师范大学 | Quaternary supermolecule anti-counterfeiting system of cucurbituril [8] -diarylethene derivative-terpyridyl imidazole-europium and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101386783B (en) * | 2008-10-22 | 2012-03-21 | 重庆大学 | Sulfotetraphenyl porphyrin nano luminescent material and preparation method thereof |
| CN102268128A (en) * | 2010-06-07 | 2011-12-07 | 海洋王照明科技股份有限公司 | Porphyrin copolymer containing thienophenazine unit as well as preparation method and application thereof |
| CN102268128B (en) * | 2010-06-07 | 2013-03-20 | 海洋王照明科技股份有限公司 | Porphyrin copolymer containing thienophenazine unit as well as preparation method and application thereof |
| CN102276800A (en) * | 2010-06-09 | 2011-12-14 | 海洋王照明科技股份有限公司 | Triphenylamine unit porphyrin copolymer as well as preparation method and application thereof |
| CN102276800B (en) * | 2010-06-09 | 2013-03-20 | 海洋王照明科技股份有限公司 | Triphenylamine unit porphyrin copolymer as well as preparation method and application thereof |
| CN102295747A (en) * | 2010-06-23 | 2011-12-28 | 海洋王照明科技股份有限公司 | Pyrrole-pyrrole-dione unit-containing porphyrin copolymer and preparation method as well as application thereof |
| CN102295747B (en) * | 2010-06-23 | 2013-03-20 | 海洋王照明科技股份有限公司 | Pyrrole-pyrrole-dione unit-containing porphyrin copolymer and preparation method as well as application thereof |
| CN103145749A (en) * | 2010-11-11 | 2013-06-12 | 华东理工大学 | Multi-thiophene group containing photochromic compound |
| CN103145749B (en) * | 2010-11-11 | 2015-07-15 | 华东理工大学 | Multi-thiophene group containing photochromic compound |
| CN113896904A (en) * | 2021-11-16 | 2022-01-07 | 曲阜师范大学 | Quaternary supermolecule anti-counterfeiting system of cucurbituril [8] -diarylethene derivative-terpyridyl imidazole-europium and preparation method thereof |
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| CN100494201C (en) | 2009-06-03 |
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