CN107337670A - The regulation and control method of azophenlyene metalloid fullerene derivate, preparation method and lifetime of excited state - Google Patents
The regulation and control method of azophenlyene metalloid fullerene derivate, preparation method and lifetime of excited state Download PDFInfo
- Publication number
- CN107337670A CN107337670A CN201710513282.9A CN201710513282A CN107337670A CN 107337670 A CN107337670 A CN 107337670A CN 201710513282 A CN201710513282 A CN 201710513282A CN 107337670 A CN107337670 A CN 107337670A
- Authority
- CN
- China
- Prior art keywords
- azophenlyene
- fullerene
- formula
- metalloid
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Abstract
The invention discloses the regulation and control method of azophenlyene metalloid fullerene derivate, preparation method and lifetime of excited state.Metal fullerene derivative in the present invention is by addition reaction, has what the azophenlyene class compound of electron characteristic obtained in metal fullerene surface modification, the lifetime of excited state of metal fullerene can be regulated and controled by the method.The excitation state kinetic property of azophenlyene metalloid fullerene derivate is characterized using femtosecond transient absorption spectra, the change of lifetime of excited state is then compared by data digital simulation.The azophenlyene metalloid fullerene derivate structure of offer is novel, with long-life excitation state, can easy, efficient, sensitive regulation and control metal fullerene excite step response, such azophenlyene metalloid fullerene derivate can be used in optical physics and photochemistry, solve the problems, such as that existing metal fullerene lifetime of excited state is short, control methods are indefinite, control measures are complicated, poor sensitivity.
Description
Technical field
The present invention relates to metal fullerene Material Field, more particularly to a kind of azophenlyene metalloid with long lifetime of excited state
The regulation and control method and method of testing of fullerene derivate and preparation method thereof, lifetime of excited state.
Background technology
Molecule with long-life excitation state can ensure efficiently to carry out energy transmission, can participate in various optical physics and
Photochemical reaction, have in luminescence generated by light, phosphorescent biological imaging or molecule sensing, optical dynamic therapy, photocatalysis organic reaction
Important application.
Traditional triplet sensitising agent is mainly some transient metal complexes, shortcoming be visible region absorptance compared with
Weak, the short life of triplet excited state, cost is high, and species is few.Organic triplet sensitising agent compensate for the upper of transient metal complex
Some shortcomings are stated, it is a kind of molecule with strong visible absorption ability and longer life triplet, but its stability
Difference, the controllable ability of lifetime of excited state are weak.
The physicochemical properties of metal fullerene are extremely abundant, have good optical characteristics and Quantum Properties.Metal is rich
Strangle alkene embedded metal include from lanthanum to most of rare earth metal, embed cluster include monometallic, bimetallic, metal nitride,
The types such as metal carbides, metal oxide, metal sulfide, carbonitride, the number of embedded atom are enumerated from list
Atom is also numerous and disorderly changeable to seven atoms, the point group symmetry of carbon cage.And modify some functions on the carbon cage of metal fullerene
Molecule, it is possible to obtain having concurrently the novel substance of metal fullerene and functional molecular characteristic, so as to which regulatory molecule is in different solvents
Solvability, photoelectric properties and biochemical function.Metal fullerene Stability Analysis of Structures, there are light absorbs near infrared region from ultraviolet,
Photochemical properties are excellent, can be by changing the embedded cluster species of metal fullerene, and carbon cage symmetry and derivatization mode are gone
Regulate and control excitation state kinetic property, be a kind of ideal material for studying long-life excitation state.Therefore, we intend selecting excellent
Metal fullerene molecule develop the new material with long-life excitation state.
Some are reported at present using metal fullerene as the derivative of electron donor/acceptor or outside metal fullerene
The conjugates or heterozygote of a photaesthesia are modified, study its photo-excited electron kinetics Quality Research.These researchs master
Pay close attention to metal fullerene and excite ultrafast separation of charge and recombination mechanism, metastable state radical ion pair to the light of electron acceptor system
Formation, solvent effect etc., charge-separated state short life is largely the time scale in psec or nanosecond, and excitation state is stable
Property is poor, decay is fast.Meanwhile factor and the mechanism of action for influenceing metal fullerene lifetime of excited state are not yet clear and definite.
In a word, the research ability first meeting clue of metal fullerene lifetime of excited state is regulated and controled using suitable mode, simultaneously as
The excellent properties that metal fullerene has in itself, and long-life excitation state system is in optical physics and photochemistry, solar energy
It is worth using the major application in the fields such as, luminescence generated by light, artificial photosynthesis, therefore studies the life-span of metal fullerene excitation state
Regulation and control and the mechanism of action have important scientific meaning and practical value.
The content of the invention
In order to solve the problems, such as that existing metal fullerene lifetime of excited state is short, stability is poor, current metal fullerene is overcome
The technical problems such as control methods indefinite, control measures are complicated, the poor sensitivity of lifetime of excited state, the invention provides azophenlyene class
Metal fullerene derivative, its structure is novel, has long-life excitation state, while provide the azophenlyene metalloid fullerene and spread out
Preparation method, the regulation and control method of lifetime of excited state and the method for testing of biology.
Azophenlyene metalloid fullerene derivate provided by the present invention, shown in its structural formula such as formula (I)：
In formula, EMF refers to metal fullerene；
R1C including straight or branched1~C6Any one in alkyl；
R2、R3Each include H, the C of straight or branched independently of one another1~C6Any one in alkyl；Optionally, institute
State C1~C6Alkyl is any one in methyl, ethyl, isopropyl；
R4Including any one in H or aromatic radical；Optionally, the aromatic radical is phenyl；
L1Including being not present or selected from C1~C6Any one in straight chained alkyl, aromatic radical；Optionally, the aromatic radical
For phenyl.
In another embodiment, the metal fullerene is A to above-mentioned azophenlyene metalloid fullerene derivate2C2@C2n,
Wherein A=Sc, La, Y, n=39~44；Or metal fullerene is B3N@C2m, wherein B=Sc, La, Y, Ho, Lu, Dy, Er, m=
39~44；Optionally, the metal fullerene is Sc2C2@C82, the further alternative isomer for metal fullerene
Sc2C2@C82-C2v。
In another embodiment, the azophenlyene metalloid fullerene derives above-mentioned azophenlyene metalloid fullerene derivate
Thing includes any one in following structure：
It is further alternative, including any one in following structure：
Wherein,It is Sc2C2@C82-C2v。
The preparation method of the azophenlyene metalloid fullerene derivate of formula (I) provided by the invention, comprises the steps：In ammonia
In the presence of base acid, the aldehyde radical azophenlyene class compound of metal fullerene and formula (II) is subjected to addition reaction, obtains formula (I) azophenlyene
Metalloid fullerene derivate, wherein, the aldehyde radical azophenlyene class structural formula of compound of formula (II) is as follows：
In formula (II), R2、R3C including H, straight or branched1~C6Any one in alkyl；Optionally, the C1~
C6Alkyl is any one in methyl, ethyl, isopropyl；
R4Including any one in H or aromatic radical；Optionally, the aromatic radical is phenyl；
L1Including being not present, C1~C6Any one in straight chained alkyl or aromatic radical；Optionally, the aromatic radical is benzene
Base.
In another embodiment, the metal fullerene is A to above-mentioned preparation method2C2@C2n, wherein A=Sc, La,
Y, n=39~44；Or metal fullerene is B3N@C2m, wherein B=Sc, La, Y, Ho, Lu, Dy, Er, m=39~44；Optionally,
The metal fullerene is Sc2C2@C82, further alternative metal fullerene is the isomer 5c of metal fullerene2C2@
C82-C2v。
In another embodiment, the aldehyde radical azophenlyene class compound structure of the formula (II) is included such as above-mentioned preparation method
Any one in lower structure：
Above-mentioned preparation method in another embodiment, the aldehyde radical azophenlyene class chemical combination of the metal fullerene and formula (II)
The mol ratio of thing is 1: 1~1.8.
In another embodiment, the addition reaction includes 1,3- Dipolar Cycloadditions, guest to above-mentioned preparation method
Any one in lattice reaction, [2+2] cycloaddition reaction, [2+4] cycloaddition reaction, Cabbeen addition；Optionally, the addition
Reaction is 1,3- Dipolar Cycloadditions.
In another embodiment, the amino acid is included in ethyl glycine, methylglycine above-mentioned preparation method
Any one.
In another embodiment, the azophenlyene metalloid fullerene derivate includes following structure to above-mentioned preparation method
In any one：
It is further alternative, including any one in following structure：
Wherein,It is Sc2C2@C82-C2v。
Above-mentioned preparation method in another embodiment, obtained addition compound product is further separated, step includes：It is logical
High performance liquid chromatography is crossed to be separated the azophenlyene metalloid fullerene derivate of final obtained formula (I).
Above-mentioned preparation method in another embodiment, wherein the preparation of the aldehyde radical azophenlyene class compound of the formula (II)
Method includes：
Azophenlyene class compound is added in oxidant and dimethylformamide (DMF), Isosorbide-5-Nitrae-dioxane is added, obtains
To the aldehyde radical azophenlyene class compound of formula (II).
In the preparation method of the aldehyde radical azophenlyene class compound of above-mentioned formula (II), the azophenlyene class compound includes
In any one.
In the preparation method of the aldehyde radical azophenlyene class compound of above-mentioned formula (II), the oxidant is anhydrous POCl3.
In the preparation method of the aldehyde radical azophenlyene class compound of above-mentioned formula (II), the azophenlyene class compound and dimethyl formyl
The mol ratio of amine is 1: 1~1: 1.8.
The regulation and control method of metal fullerene lifetime of excited state provided by the invention, including：In the presence of amino acid, by metal
Fullerene and the aldehyde radical azophenlyene class compound of formula (II) carry out addition reaction.
The method of testing of the long-life excitation state of the azophenlyene metalloid fullerene derivate of formula (I) provided by the invention, bag
Include：
(1) the azophenlyene metalloid fullerene derivate of formula (I) is excited using visible ray；
(2) femtosecond transient absorption spectra, analyzing molecules excitation state kinetic property are obtained using femtosecond transient absorption instrument；
(3) compare the size of the time constant of lifetime of excited state by data digital simulation, and then compare lifetime of excited state
Change.
In another embodiment, the excited by visible light light source is exciting for 530nm~650nm to above-mentioned method of testing
Light, laser energy are 15~35mw.
The azophenlyene metalloid fullerene derivate of formula (I) provided by the invention can be adjusted with respect to its unmodified electron donating group
Lifetime of excited state is controlled, in optical physics and photochemistry, optionally, being passed for luminescence generated by light, phosphorescent biological imaging, molecule
It is further alternative in sense, optical dynamic therapy, photocatalysis organic reaction, as triplet sensitising agent.
Compared with prior art, the present invention has the advantages that：
(1) azophenlyene metalloid fullerene derivate structure produced by the present invention is novel, and the metal fullerene is through formula (II)
The compound-modified electron donating group of aldehyde radical azophenlyene class after, lifetime of excited state can be extended to longer nanosecond order by nanosecond order
Or musec order, lifetime of excited state length, stability are good.
(2) by dexterously in metal fullerene outside finish electron donating group, further extending metal fullerene
Lifetime of excited state, a kind of universal method of regulation and control metal fullerene lifetime of excited state is realized, can easy, efficient, sensitive regulation and control gold
Belong to the step response that excites of fullerene, it is workable, established well to expand its application in optical physics, photochemistry
Basis.
(3) the excitation state electron dynamics of azophenlyene metalloid fullerene derivate can be analyzed by femtosecond transient absorption spectra
Characteristic, being capable of regulatory molecule Excited State Properties more directly perceived, easy, accurate.
(4) the metal fullerene species that can be selected in the preparation method of azophenlyene metalloid fullerene derivate is various, system
Standby, separation and the method comparative maturity of purified metal fullerene.
(5) species of the external modification group of metal fullerene and the derivatization mode of metal fullerene are a lot, synthesis
Simplicity, cost are cheap.
Brief description of the drawings
Fig. 1 is metal fullerene Sc2C2@C82-C2vFemtosecond transient absorption spectra figure.
Fig. 2 is metal fullerene Sc2C2@C82-C2vThe singlet state and triplet electron energy level figure of the molecule of excitation state.
Fig. 3 is the femtosecond transient absorption spectra figure of the azophenlyene metalloid fullerene derivate of the Chinese style of embodiment 3 (1).
Fig. 4 is the singlet state and triplet of the azophenlyene metalloid fullerene compound excited state molecule of the Chinese style of embodiment 3 (1)
Electron energy level figure.
Embodiment
Below in conjunction with the accompanying drawings, the embodiment of the present invention is described in detail, it is to be understood that the guarantor of the present invention
Shield scope is not limited by embodiment.
ScNi used in following embodiments 22Alloy is purchased from Beijing Non-Fervoous Metal Inst..
Embodiment 1
The preparation method of amino benzenes compounds with electron donating group
1. the preparation method of the azophenlyene class compound of formula (1a), reaction scheme are：
Specific steps include：
(1) by the nothing of formula (1c) 8g (38mmol) 5,10- dihydros -5,10- dimethylphenazine and 5.8g (37mmol)
Water POCl3 is added in 13ml dry DMFs, is then added 115ml Isosorbide-5-Nitrae-dioxane, is stirred at room temperature, solution reddens
Solidification, 100ml 20% acetic anhydride sodium solution is then added, is stirred overnight, is then evaporated, obtain solid；
(2) obtained solid water and dichloromethane are extracted, product is dissolved in dichloromethane, pure again with silicagel column
Change, obtain formula (1a) product.
The proton nmr spectra of formula (1a) product is：1H NMR (400MHz, CDCl3- d, 293K)=3.03 (s, 3H, N-
CH3), 3.08 (s, 3H, N-CH3), 6.38 (d, 1H), 6.41 (dd, 1H), 6.45 (dd, 1H), 6.78 (d, 1H), 6.79 (dt,
3H), 9.66 (s, 1H).
2. the preparation method of the azophenlyene class compound of formula (2a), reaction scheme are：
Specific steps include：
(1) by 9.0g (51.1mmol) azophenlyene of formula (2c) and 6.5g metallic potassium and metallic potassium mixture (metallic potassium:
Metallic sodium=10: 1) it is dissolved in 150ml 1,2- dimethyl ethanes, 24h is stirred under the conditions of 40 DEG C；Then 14.1ml is added
Bromo propane, stir 2h, filtering is evaporated obtained product 2e, crosses silica gel post separation；
(2) 1g (3.5mmol) 2e products are added to the nothing of 0.58g (3.7mmol) anhydrous POCl3 and 1.3ml
In water DMF, 12ml Isosorbide-5-Nitrae-dioxane is then added, is stirred at room temperature, solution reddens solidification；Then the 20% of 10ml is added
Acetic anhydride sodium solution, be stirred overnight, be evaporated, obtained solid water and dichloromethane extraction, product are dissolved in dichloromethane
In alkane, with silicagel column repurity, formula (2a) product is obtained.
The proton nmr spectra of formula (2a) product is：1HNMR (400MHz, CDCl3- d, 293K)=1.22 (m, 6H), 3.03
(s, 1H), 3.08 (s, 1H), 6.38 (d, 1H), 6.41 (dd, 1H), 6.45 (dd, 1H), 6.78 (d, 1H), 6.79 (dt, 3H),
9.76 (s, 1H).
3. the preparation method of the azophenlyene class compound of formula (3a), reaction scheme are：
Specific steps include：
(1) 2, the 7- diphenyl azophenlyene of 660mg (2.0mmol) formula (3c) is stirred at reflux in 10ml acetonitriles, is added
0.2ml water, 1ml iodomethane, 3.5g (33.6mmol) sodium hydrogensulfite, 0.21g (2.0mmol) sodium carbonate and 60mg
The ammonium salt of the chlorion of (0.25mmol), enter 20ml water after stirring 40h, carry out that reaction is quenched, obtain product 3e, yield 45% is left
It is right；
(2) 1.35g (4mmol) 3e products are added to the nothing of 0.58g (3.7mmol) anhydrous POCl3 and 1.3ml
In water DMF, 12ml Isosorbide-5-Nitrae-dioxane is then added, is stirred at room temperature, solution reddens solidification；Then the 20% of 10ml is added
Acetic anhydride sodium solution, be stirred overnight, be then evaporated, obtained solid water and dichloromethane extraction, product are dissolved in two
In chloromethanes, then with silicagel column repurity, formula (3a) product is obtained.
The proton nmr spectra of formula (3a) product is：1HNMR (400MHz, CDCl3- d, 293K)=3.20 (s, 6H), 6.44
(d, 2H), 6.64 (dd, 2H), 6.89 (dd, 2H), 7.29 (s, 2H), 7.33 (dt, 2H), 7.41 (dt, 1H), 7.52 (d, 4H),
9.81 (s, 1H).
Embodiment 2
Metal fullerene Sc2C2@C82-C2vPreparation method
In the species of metal fullerene, metal fullerene Sc2C2@C82Yield is of a relatively high, excellent, and species is rich
Richness, the comparative maturity of research.Meanwhile metal fullerene Sc2C2@C82There are three kinds of isomers, be C respectivelys、C2vAnd C3vStructure
Type, different isomers Excited State Properties are different.For Sc2C2@C82-C2vBody, it is seen that under the conditions of light activated, electronics
By ground state transition to excitation state, effective intersystem crossing occurs, obtains the relaxation process of the triplet of a long-life, but receive
Further application of second (ns) order of magnitude for excitation state nevertheless suffers from limitation.Therefore, the application selects metal fullerene Sc2C2@
C82-C2vAs initiation material, it is contemplated that by the regulation and control of external modification group, so as to obtain the body that a triplet lifetime extends
It is to be used for photochemistry and photophysical process, is further applied with being advantageous to metal fullerene.
Metal fullerene Sc2C2@C82-C2vPreparation method, be to pass through arc discharge method in DC arc discharge stove
(Kratschmer-Huffman methods) synthesis, detailed process includes：
(1) the solid graphite rod that external diameter is 8mm is first drilled to the hollow plumbago pipe that internal diameter is 6mm or so, then by ScNi2Close
Gold and graphite powder are well mixed according to the ratio that mass ratio is 3: 1, are subsequently filled in graphite-pipe, are tamped；
(2) populated metal/graphite rod is arranged on to anode and the fixation of electric arc furnaces, bell is closed, opens vavuum pump；
The valve between furnace chamber and vavuum pump is opened, to electric arc stove evacuation, when being evacuated to air pressure and be less than 10Pa, opening cooling circulating water,
Electric welding machine is opened, regulation electric current to 100A, stepper motor movement metal/graphite rod is opened and is allowed to contact with negative electrode graphite plate, it is right
Metal/graphite rod is preheated, and is excluded the air and moisture wherein adsorbed, is preheated 30 minutes or so, close electric welding machine, closes
Valve between closed furnace chamber and vavuum pump, stops vavuum pump；Breather valve is slowly opened, 200Torr He gas is filled with to electric arc furnaces, is beaten
Electric welding machine is driven, regulation electric current to 130A, stepper motor movement metal/graphite rod is opened and is allowed to disengage with negative electrode graphite plate,
Now highfield being formed between negative electrode and anode and being discharged, continuing regulation stepper motor makes two pole tensions keep 40V or so, now
Electric discharge is the most stable；Dazzling yellow-green light is sent during electric discharge, between the two poles of the earth, now temperature can be up to 4000K between the two poles of the earth
More than, while the metal/graphite rod of anode is put by the electronic impact of cathode emission into the particle to disperse, particle in the electric arc of high temperature
Electric region atomization, the atom of gasification cool down during arc zone is flown away from and then reassemble into cluster, generate containing richness
Strangle the product of alkene and metal fullerene；
(3) with the consumption of anode metal/graphite rod, must adjust stepper motor at any time makes the two poles of the earth stable discharging, metal/stone
After inker is exhausted, electric arc furnaces cooling is waited, the grey soot that electric arc furnaces collects gained is opened, is put into paper bag, in soxhlet type
Extracted 12 hours or so with toluene in device, produce the extract solution containing various empty fullerenes and metal fullerene；
(4) toluene containing fullerene and metal fullerene is extracted into solution through qualitative filter paper multiple times of filtration, then with height
Effect liquid phase chromatogram separates and purification, separation and purification step are：First entered using Buckyprep posts (20 × 250mm, Cosmosil)
The row first step separates, and is separated essentially according to the size of Fullerene Carbon cage, and appearance time on a column is 48~
56min；Then, obtained crude product is subjected to second step separation, with Buckyprep-M posts (20 × 250mm, Cosmosil),
Mainly the fullerene of hollow carbon cage is separated with the metal fullerene for having the embedded cluster of metal, the appearance on chromatogram pillar
Time is probably 28~34min；Finally, then with Buckyprep posts (20 × 250mm, Cosmosil) purified, tripe systems
The metal fullerene of type separates, and the time of chromatographic peak appearance position correspondence is 49~53 minutes；Wherein, the step of the above three separation and
In purification experiment, using toluene as mobile phase, the flow velocity of toluene is 12ml/min, and sample introduction concentration is 1mg/ml, fixes sample introduction every time
12ml, wavelength, while binding matrix Assisted Laser Desorption ionization time of flight mass spectrometry in separation process are monitored using 310nm UV
Each chromatographic peak is analyzed, obtains the Sc of more than 99% purity2C2@C82-C2v。
Embodiment 3
The preparation method of azophenlyene metalloid fullerene derivate
1. the preparation method of the azophenlyene metalloid fullerene of formula (1), step include：
(1) 0.91 × 10 is taken3Nmol (i.e. 1mg) Sc2C2@C82-C2vSolid sample be dissolved in toluene, add 0.97 ×
103Nmol (i.e. 0.1mg) Ethylglycocoll and 1.35 × 103Nmol (i.e. 0.6mg) compound 1a, is filled with argon gas and goes bail for
Gas is protected, cycloaddition reaction is carried out, reacts 20min under 120 DEG C of stirring conditions；
(2) after reactant cooling half an hour, solution is evaporated, product is dissolved in toluene, is then carried out with high performance liquid chromatography
Separation and purification, separation and purification step are：Separated, tested using Buckyprep posts (20 × 250mm, Cosmosil)
In using toluene as mobile phase, the flow velocity of toluene is 12ml/min, and sample concentration is 1mg/ml, and fixed sample introduction 12ml, is used every time
310nm UV monitoring wavelength, appearance time is 28min on Buckyprep pillars, and detection production is carried out with MALDI-TOF mass spectrums
The molecular weight of thing, obtained main component are the azophenlyene metalloid fullerene of formula (1).
The proton nmr spectra of the azophenlyene metalloid fullerene of formula (1) is：1HNMR (400MHz, CDCl3- d, 293K)=
7.91 (m, 2H), 7.79 (d, 2H), 7.60 (dd, 2H), 7.51 (dd, 2H), 6.87 (d, 2H), 7.74 (dt, 2H), 7.20 (m,
4H), 6.75 (m, 2H), 6.63 (d, 6H), 4.25 (bs, 2H), 3.71 (m, 1H), 3.9 (m, 2H).
2. the preparation method of the azophenlyene metalloid fullerene of formula (2), step include：
(1) 0.91 × 10 is taken3Nmol (i.e. 1mg) Sc2C2@C82-C2vSolid sample be dissolved in toluene, add 0.97 ×
103Nmol (i.e. 0.1mg) Ethylglycocoll and 1.2 × 103Nmol (i.e. 0.76mg) compound 2a, is filled with argon gas and goes bail for
Gas is protected, cycloaddition reaction is carried out, reacts 20min under 120 DEG C of stirring conditions；
(2) after reactant cooling half an hour, solution is evaporated, product is dissolved in toluene, is then carried out with high performance liquid chromatography
Separation and purification, separation and purification step are：Separated, tested using Buckyprep posts (20 × 250mm, Cosmosil)
In using toluene as mobile phase, the flow velocity of toluene is 12ml/min, and sample concentration is 1mg/ml, and fixed sample introduction 12ml, is used every time
310nm UV monitoring wavelength, appearance time is 27min on Buckyprep pillars, and detection production is carried out with MALDI-TOF mass spectrums
The molecular weight of thing, obtained main component are the phenyl amines metal fullerene of formula (2).
The proton nmr spectra of the azophenlyene metalloid fullerene of formula (2)：1HNMR：(CDCl3- d, 600MHz, 293K), δ=
6.89 (dt, 3H), 6.83 (d, 1H), 6.55 (dd, 1H), 6.47 (dd, 1H), 6.41 (d, 1H), 4.20 (bs, 2H), 3.73 (m,
1H), 3.15 (s, 3H), 3.05 (s, 1H), 3.03 (m, 2H), 3.00 (s, 1H), 1.20 (m, 6H).
3. the preparation method of the azophenlyene metalloid fullerene of formula (3), step include：
(1) 0.91 × 10 is taken3Nmol (i.e. 1mg) Sc2C2@C82-C2vSolid sample be dissolved in toluene, add 0.97 ×
103Nmol (i.e. 0.1mg) Ethylglycocoll and 1.2 × 103Nmol (i.e. 0.8mg) compound 3a, is filled with argon gas and protects
Gas, cycloaddition reaction is carried out, reacts 20min under 120 DEG C of stirring conditions；
(2) after reactant cooling half an hour, solution is evaporated, product is dissolved in toluene, is then carried out with high performance liquid chromatography
Separation and purification, separation and purification step are：Separated, tested using Buckyprep posts (20 × 250mm, Cosmosil)
In using toluene as mobile phase, the flow velocity of toluene is 12ml/min, and sample concentration is 1mg/ml, and fixed sample introduction 12ml, is used every time
310nm UV monitoring wavelength, appearance time is 28min on Buckyprep pillars, and detection production is carried out with MALDI-TOF mass spectrums
The molecular weight of thing, obtained main component are the azophenlyene metalloid fullerene of formula (3).
The proton nmr spectra of the azophenlyene metalloid fullerene of formula (3)：1HNMR (400MHz, CDCl3- d, 293K)=7.52
(d, 4H), 7.41 (dt, 1H), 7.33 (dt, 2H), 7.29 (s, 2H), 6.89 (dd, 2H), 6.64 (dd, 2H), 6.44 (d, 2H),
4.17 (bs, 2H), 3.8 (m, 2H), 3.64 (m, 1H), 3.20 (s, 6H), 2.07 (s, 3H).
Embodiment 4
Metal fullerene Sc2C2@C82-C2vWith the excitation state kinetics quality detection of the azophenlyene metalloid fullerene of formula (1)
And durability analysis
Test the device used：The pump probe spectroscope and ultrafast laser amplification system of repacking.
The centre wavelength 530nm of pump light, pulse energy are about 10 micro- Jiao, pass through an optical parametric amplifier
(TOPAS-800-fs) (a Ti is passed through：Sapphire regenerative amplifiers excite, and centre wavelength is 800nm, the pulse duration
Probably it is 25fs, pulse energy is 3 MJs) send laser.Seed light is the Ti of a locked mode：Sapphire laser system
(Micra 5, Coherent), pump light 1KHz Nd：YLF Lasers (Evolution 30, Coherent).Weaker spy
The white light (WLC) that light-metering pulse (each sample pulse is less than 0.5 micro- Jiao) passes through a continuous-stable (is the light beam with 800nm
It is rotated in the thick CaF of 4.55mm2Focus on and produce on crystal) caused by 400-700nm.Pump light and detection light are all linear polarizations
Light.The response of pump probe spectroscope is probably 80fs, is realized by the pumping and direct impulse of crosscorrelation.Pump light and
Detection light has accurate space overlap, and diameter is 800 μm and 300 μm respectively, and center is the thick sample cells of a 1.2mm, is passed through
One laser analysis device (BG-USB-SP620, Ophir-Spiricon) obtains optimal transient absorption signal.
The change of pump light and detecting optical pulses delay is that (minimum 1.56fs, maximum are prolonged by changing optical delay line
Slow 3.2ns) come what is realized.Being modulated at 500Hz for machinery is utilized manipulation pumping pulse, such as the spectrum of transient absorption has
There is no pulse alternately to be recorded.Detection light splits first is divided into two very small parts, while occurs in copped wave
Above device and monitor, the stability for detecting light is to go to manipulate by two independent photodiode detectors, is then separated into
Two parts, 70% concentrates on sample cell one detectable signal of generation overlapping with pump light, and 30% light shines sample from another way
Product pond ensures good signal to noise ratio up.
The pumping spectral absorption figure of transient state can be imaged by 1024-pixel intuitively to be seen, then passes through ExiPro
2.6 softwares are further handled.
1. metal fullerene Sc2C2@C82-C2vExcitation state kinetics quality detection and durability analysis
Detecting step：
(1) concentration for choosing 1~2ml is 10-4Mol/L~10-2Mol/L metal fullerene Sc2C2@C82-C2vToluene
Solution, the toluene solution sample of metal fullerene is installed on the turntable that rotating speed is 5000rpm, to ensure the mistake in measurement
The sample that light is got in journey is fresh forever；
(2) excited from 530nm visible ray, detected from 570nm detection light；
(3) scope of scanning is 400nm~800nm；
(4) in the curve changed over time from different wavelength, select what the data creating of Single wavelength changed over time
Dynamics varying curves, obtain data (referring to Fig. 1)；
(5) relative permeability for detecting light is fitted with the variation relation of time delay using computer programming, obtained
To the dynamic (dynamical) time relaxation situation of molecule photo-excited electron.
Lifetime of excited state is analyzed：
As shown in Figure 1, when molecule excites in 530nm light, electronics is by ground state transition to SnExcitation state, then by one
It is individual than to relax towards up to S faster2(the second excited singlet state) state, relaxation time τ is 1.5ps.For Sc2C2@C82-C2v, choose
In the excitation state kinetic curve of 530nm exciting light and 570nm detection light detection compound, by theoretical fitting data,
It was found that with the extension of time, signal is gradually decayed under 0, then there is a slow reply again, if signal returns
It is exactly that electron transition has been returned to S again to 00Ground state, have now found that and do not replied in the time scale that can be tested, so
It is the excited state relaxation processes of a comparison long-life.
Specific theoretical calculation data are referring to Fig. 2.Due to S2State and T5The energy level difference of (the 5th excited triplet state) state compares
It is small, and track transition the form matches, so can occur from S2To T5Intersystem crossing, relaxation time τ is 73.5ps, then T5
The life-span of excitation state is long, produces one from T5The reply relatively slow to T1 (the first excited triplet state), relaxation time
Probably it is 2.2ns.
2. the excitation state kinetics quality detection and durability analysis of the azophenlyene metalloid fullerene of formula (1)
Detecting step：
(1) concentration for choosing 1~2ml is 10-4Mol/L~10-2The first of the azophenlyene metalloid fullerene of mol/L formula (1)
Benzole soln, solution example is installed to the turntable that rotating speed is 5000rpm, to ensure light is got to during measurement sample
It is fresh forever；
(2) 530nm excited by visible light is selected, 570nm detection light is detected；
(3) scope of scanning is 400nm~800nm；
(4) in the curve changed over time from different wavelength, select the data of Single wavelength do change over time it is dynamic
Mechanical change curve, obtain datagram 1；
(5) relative permeability for detecting light is fitted with the variation relation of time delay using computer programming, obtained
To the dynamic (dynamical) time relaxation situation of molecule photo-excited electron
Lifetime of excited state is analyzed：
Choose the metal fullerene Sc in embodiment 32C2@C82-C2vObtained outside by 1,3 Dipolar Cycloaddition
Research object of the azophenlyene metalloid fullerene of formula (1) as photo-excited electron kinetic property, same selection 530nm's is visible
Light is excited, and 570nm light is detected, as shown in Figure 3 after the excitation state kinetic curve fittings of obtained compound.
The electronics of the azophenlyene metalloid fullerene of formula (1) transits to S after being excitednState, by a quick relaxation
To S2(the second excited singlet state) state, then S2State and T4Energy difference between (the 4th excited triplet state) state is close, orbital fashion
Matching, so intersystem crossing occurs to T4State, then undergo one it is relatively long from T4To T1The relaxation of state, relaxation time are more than
1.6ns.Specific theoretical calculation data are referring to Fig. 4.It can be seen in figure 3 that the azophenlyene metalloid fullerene of formula (1) is in light
Excite down, the signal value of kinetic curve becomes negative from positive, is then gradually deviated from 0 point.
The metal fullerene Sc of electron donor is not modified2C2@C82-C2vIn the time scale that can be detected (3ns)
It can be seen that the trend for having signal to reply, illustrates life-span of excitation state still in ns time scale.But in metal fowler
Alkene Sc2C2@C82-C2vAfter outside finish electron donor, (3ns) does not have signal in the time scale that this instrument can detect
The trend of reply.Thus illustrate, external connected electronic donor azophenlyene class compound can further extend metal fullerene Sc2C2@C82-C2v
In the life-span of excitation state, the excitation state of a more long-life is obtained, for the metal fullerene further application in terms of photochemistry
With important directive significance.
Note：τ is the time constant obtained when being fitted with double exponential curve, is arrived corresponding to the electrons decay of molecular-excited state
The time (being lifetime of excited state) of different energy levels.
The description of the foregoing specific illustrative embodiment to the present invention is to illustrate and the purpose of illustration.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed
And change.The purpose of selecting and describing the exemplary embodiment is that explain that the certain principles of the present invention and its reality should
With so that those skilled in the art can realize and utilize the present invention a variety of exemplaries and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (10)
1. azophenlyene metalloid fullerene derivate, shown in its structural formula such as formula (I)：
In formula, EMF refers to metal fullerene；
R1C including straight or branched1~C6Any one in alkyl；
R2、R3Each include H, the C of straight or branched independently of one another1~C6Any one in alkyl；Optionally, the C1~
C6Alkyl is any one in methyl, ethyl, isopropyl；
R4Including any one in H or aromatic radical；Optionally, the aromatic radical is phenyl；
L1Including being not present or selected from C1~C6Any one in straight chained alkyl, aromatic radical；Optionally, the aromatic radical is benzene
Base.
2. the preparation method of the azophenlyene metalloid fullerene derivate of formula (I), comprises the steps：, will in the presence of amino acid
Metal fullerene and the aldehyde radical azophenlyene class compound of formula (II) carry out addition reaction, obtain the azophenlyene metalloid fullerene of formula (I)
Derivative, wherein, the aldehyde radical azophenlyene class structural formula of compound of formula (II) is as follows：
In formula (II), R2、R3C including H, straight or branched1~C6Any one in alkyl, optionally, the C1~C6Alkane
Base is any one in methyl, ethyl, isopropyl；
R4Including any one in H or aromatic radical；Optionally, the aromatic radical is phenyl；
L1Including being not present, C1~C6Any one in straight chained alkyl or aromatic radical；Optionally, the aromatic radical is phenyl.
3. the preparation method described in azophenlyene metalloid fullerene derivate according to claim 1 or claim 2, it is special
Sign is：The metal fullerene is A2C2@C2n, wherein A=Sc, La, Y, n=39~44；Or metal fullerene is B3N@C2m,
Wherein B=Sc, La, Y, Ho, Lu, Dy, Er, m=39~44；Optionally, the metal fullerene is Sc2C2@C82, further may be used
The metal fullerene of choosing is the isomer Sc of metal fullerene2C2@C82-C2v。
4. azophenlyene metalloid fullerene derivate according to claim 1, it is characterised in that：The azophenlyene class of the formula (I)
Metal fullerene derivative includes any one in following structure：
It is further alternative, including any one in following structure：
Wherein,It is Sc2C2@C82-C2v。
5. preparation method according to claim 2, it is characterised in that：The aldehyde radical azophenlyene class compound of the formula (II) includes
Any one in structure as follows：
Optionally, the amino acid includes any one in ethyl glycine, methylglycine.
6. preparation method according to claim 2, it is characterised in that：It is anti-that the addition reaction includes 1,3- dipole-diople interactions
Should, objective case reaction, [2+2] cycloaddition reaction, [2+4] cycloaddition reaction, any one in Cabbeen addition；Optionally, institute
It is 1,3- Dipolar Cycloadditions to state addition reaction.
7. preparation method according to claim 2, it is characterised in that：The metal fullerene and the aldehyde radical azophenlyene of formula (II)
The mol ratio of class compound is 1: 1~1.8.
8. the regulation and control method of metal fullerene lifetime of excited state, including：In the presence of amino acid, by metal fullerene and formula (II)
Aldehyde radical azophenlyene class compound carry out addition reaction.
9. the method for testing of the long-life excitation state of the azophenlyene metalloid fullerene derivate of formula (I), including：
(1) the azophenlyene metalloid fullerene derivate of formula (I) is excited using visible ray；
(2) femtosecond transient absorption spectra, analyzing molecules excitation state kinetic property are obtained using femtosecond transient absorption instrument；
(3) compare the size of the time constant of lifetime of excited state by data digital simulation, and then compare the change of lifetime of excited state
Change.
10. purposes of the azophenlyene metalloid fullerene derivate of formula (I) in optical physics and photochemistry, optionally, in light
Purposes in photoluminescence, phosphorescent biological imaging, molecule sensing, optical dynamic therapy, photocatalysis organic reaction, it is further alternative,
As triplet sensitising agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710513282.9A CN107337670A (en) | 2017-06-28 | 2017-06-28 | The regulation and control method of azophenlyene metalloid fullerene derivate, preparation method and lifetime of excited state |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710513282.9A CN107337670A (en) | 2017-06-28 | 2017-06-28 | The regulation and control method of azophenlyene metalloid fullerene derivate, preparation method and lifetime of excited state |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107337670A true CN107337670A (en) | 2017-11-10 |
Family
ID=60218715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710513282.9A Pending CN107337670A (en) | 2017-06-28 | 2017-06-28 | The regulation and control method of azophenlyene metalloid fullerene derivate, preparation method and lifetime of excited state |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107337670A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108114754A (en) * | 2017-12-04 | 2018-06-05 | 中国科学院化学研究所 | Composite material, preparation method and the application of carboxylated metal fullerene modified titanic oxide |
| CN111732950A (en) * | 2020-07-28 | 2020-10-02 | 苏州科技大学 | Azaanthracene derivative TTA-UC weak light up-conversion system and preparation method and application thereof |
| CN113828356A (en) * | 2021-07-13 | 2021-12-24 | 中国科学院化学研究所 | Application of fullerene donor-acceptor composite material in photocatalysis |
-
2017
- 2017-06-28 CN CN201710513282.9A patent/CN107337670A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| BO WU等: "Visible-Light Photoexcited Electron Dynamics of Scandium Endohedral Metallofullerenes: The Cage Symmetry and Substituent Effects", 《J. AM. CHEM. SOC.》 * |
| RAJEEV K. DUBEY等: "Close Proximity Dibenzo[a,c]phenazine–Fullerene Dyad: Synthesis and Photoinduced Singlet Energy Transfer", 《EUR. J. ORG. CHEM.》 * |
| YUTA TAKANO等: "An Endohedral Metallofullerene as a Pure Electron Donor:Intramolecular Electron Transfer in Donor−Acceptor Conjugates of La2@C80 and 11,11,12,12-Tetracyano-9,10-anthra‑p‑quinodimethane(TCAQ)", 《J. AM. CHEM. SOC.》 * |
| YUTA TAKANO等: "Stabilizing Ion and Radical Ion Pair States in a Paramagnetic Endohedral Metallofullerene/π‑Extended Tetrathiafulvalene Conjugate", 《J. AM. CHEM. SOC.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108114754A (en) * | 2017-12-04 | 2018-06-05 | 中国科学院化学研究所 | Composite material, preparation method and the application of carboxylated metal fullerene modified titanic oxide |
| CN108114754B (en) * | 2017-12-04 | 2019-08-16 | 中国科学院化学研究所 | Composite material, preparation method and the application of carboxylated metal fullerene modified titanic oxide |
| CN111732950A (en) * | 2020-07-28 | 2020-10-02 | 苏州科技大学 | Azaanthracene derivative TTA-UC weak light up-conversion system and preparation method and application thereof |
| CN111732950B (en) * | 2020-07-28 | 2020-11-10 | 苏州科技大学 | Azaanthracene derivative TTA-UC weak light up-conversion system and preparation method and application thereof |
| CN113828356A (en) * | 2021-07-13 | 2021-12-24 | 中国科学院化学研究所 | Application of fullerene donor-acceptor composite material in photocatalysis |
| CN113828356B (en) * | 2021-07-13 | 2023-01-24 | 中国科学院化学研究所 | Application of fullerene donor-acceptor composite material in photocatalysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bozdemir et al. | Synthesis of symmetrical multichromophoric BODIPY dyes and their facile transformation into energy transfer cassettes | |
| Zhang et al. | Altering intercomponent interactions in a photochromic multi-state [2] rotaxane | |
| Rio et al. | Fullerodendrimers with peripheral triethyleneglycol chains: synthesis, mass spectrometric characterization, and photophysical properties | |
| CN111875602B (en) | Cyano-modified pyridino-imidazole derivative and preparation method and application thereof | |
| Lungerich et al. | Three short stories about hexaarylbenzene–porphyrin scaffolds | |
| Xue et al. | A highly sensitive fluorescent sensor based on small molecules doped in electrospun nanofibers: detection of explosives as well as color modulation | |
| Jiang et al. | Tetraphenylethene end-capped [1, 2, 5] thiadiazolo [3, 4-c] pyridine with aggregation-induced emission and large two-photon absorption cross-sections | |
| CN107337670A (en) | The regulation and control method of azophenlyene metalloid fullerene derivate, preparation method and lifetime of excited state | |
| Li et al. | Tetrahydro [5] helicene thioimide-based fluorescent and chromogenic chemodosimeter for highly selective and sensitive detection of Hg2+ | |
| Munch et al. | Ethynyl‐Tolyl Extended 2‐(2′‐Hydroxyphenyl) benzoxazole Dyes: Solution and Solid‐state Excited‐State Intramolecular Proton Transfer (ESIPT) Emitters | |
| Bell et al. | Melt-induced fluorescent signature in a simple naphthalenediimide | |
| Ziessel et al. | Electronic Energy Transfer in Molecular Dyads Built Around Boron–Ethyne‐Substituted Subphthalocyanines | |
| Yang et al. | A luminescence molecular switch via modulation of PET and ICT processes in DCM system | |
| Zhang et al. | Design of Stimuli‐Responsive Phenothiazine Derivatives with Triplet‐Related Dual Emission and High‐Contrast Mechanochromism Guided by Polymorph Prediction | |
| Qu et al. | The Aggregation Regularity Effect of Multiarylpyrroles on Their Near‐Infrared Aggregation‐Enhanced Emission Property | |
| Yamada et al. | Synthesis and photochemical properties of α-diketoporphyrins as precursors for π-expanded porphyrins | |
| Kawabata et al. | Singlet energy transfer in bis (phenylethynyl) phenylene-bridged zinc–free base hybrid diporphyrins | |
| Ma et al. | Dihydropyridine-based fluorescence probe for nitric oxide | |
| CN107337629B (en) | The regulation method of phenyl amines metal fullerene derivative, preparation method and lifetime of excited state | |
| CN108314636A (en) | A kind of polyaryl sulphur oscillation luminescent material and its preparation method and application | |
| CN107344717A (en) | Metal fullerene derivative and its preparation method, the regulation and control methods and applications of paramagnetic properties | |
| Ochiai et al. | Copper (II) Complexes of 10, 20-Diaryl-5, 15-diazaporphyrin: Alternative Synthesis, Excited State Dynamics, and Substituent Effect on the 1O2-Generation Efficiency | |
| CN114853656B (en) | Carbazole derivative with AEE characteristic, preparation method and application | |
| CN110330532A (en) | A kind of novel phosphorescent iridium complex and the preparation method and application thereof | |
| Chevalier et al. | Rapid Synthesis of Unsymmetrical Sulforhodamines Through Nucleophilic Amination of a Monobrominated Sulfoxanthene Dye |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180424 Address after: 100064 room, room 5, No. 5, Haidian District Road, Beijing, China Applicant after: BEIJING FUNAKANG BIOTECHNOLOGY CO., LTD. Address before: 100064 Beijing Haidian District Haidian District development road 5, 5 floor 523 room. Applicant before: BEIJING FUNAKANG BIOTECHNOLOGY CO., LTD. Applicant before: Institute of Chemistry, Chinese Academy of Sciences |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171110 |
|
| RJ01 | Rejection of invention patent application after publication |