CN107344717B - The regulation methods and applications of metal fullerene derivative and its preparation method, paramagnetic properties - Google Patents
The regulation methods and applications of metal fullerene derivative and its preparation method, paramagnetic properties Download PDFInfo
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Abstract
The invention discloses metal fullerene derivative and its regulation methods and applications of preparation method, paramagnetic properties.Metal fullerene derivative in the present invention is through addition reaction, in a kind of metal fullerene derivative that paramagnetic metal fullerene surface modification azobenzene NO free radical small molecule obtains.By different illumination radioglold category fullerene derivates, pass through the paramagnetic properties of the variation regulation metal fullerene of relative position between metal fullerene and the double spin centers of NO free radical molecule.The metal fullerene derivant structure of offer is novel, with photoswitch property and can it is easy, efficient, sensitive regulate and control metal fullerene paramagnetic properties, solve it is existing by cooling or chemical modification mode regulate and control the technical issues of sensitivity existing for the paramagnetic properties of metal fullerene is low, complicated for operation, control methods signal unidirectionally changes, it can be used as molecule light functional switch, in all-optical network, light exchange.
Description
Technical field
The present invention relates to a kind of molecule light functional switch technical field, in particular to metal fullerene derivative and its preparations
The regulation method and metal fullerene derivative of method and metal fullerene derivative paramagnetic properties are used as molecule light function and open
The application of pass.
Background technique
Metal fullerene is broadly divided into paramagnetism and two kinds diamagnetic, is whether to have spin single electron with itself
It distinguishes.Metal or cluster are put into metal fullerene and constitute embedded metal fullerene, such internal group and outside
Environment separation is opened, even the group of high reaction activity can be also stabilized in inside.This makes embedded metal fullerene in room
It can be stabilized under temperature, there is very long spin to be concerned with the consistency time, be all widely used in quantum calculation and the communications field.
Since embedded metal fullerene internal group is protected by carbon cage, so be difficult to manipulate its structure and magnetism, it is usually suitable with electronics
Magnetic Resonance Spectrum is come the case where reflecting the variation of the property of magnetic core, spin and intercouple.
Paramagnetic metal fullerene has broad application prospects, more using electron spin freedom degree design and operation speed
The next-generation microelectronic component high, energy consumption is lower, function is more, highly integrated.For embedded metal fullerene, metallic atom or
The unique structure of diversity and fullerene of metal cluster assigns its distinguished spin properties, makes molecular scale
On spin probe.The metal fullerene Gd@C of more representational one kind paramagnetic properties82And its derivative is in biomedicine
Field has to be widely applied very much, is important mri contrast agent.In addition, paramagnetic metal fullerene is also used as an amount
Sub- bit cell is widely applied in quantum calculation and quantum chemistry.
The paramagnetic properties of influence metal fullerene, existing regulation gold can be removed by the dynamic (dynamical) property of cluster in regulation cage
The research for belonging to the paramagnetic properties of fullerene, which mainly has to change, carries out special chemical modification outside temperature or carbon cage, can be in certain journey
Distribution or the limitation spin relaxation for changing spin on degree, can also go to influence spin signals by spin-spin interaction.
Such as: Y2@C79N molecule, at room temperature, the Y in carbon cage2A quick random motion, therefore the electricity of molecule is presented in cluster
Sub- paramagnetic spectroscopic signal (ESR) shows three lines of 1: 2: 1 feature, and when the temperature is lowered, anisotropy occurs in ESR signal,
Illustrate Y2@C79Rotational alignment is uneven under N molecular resonance state, limits the rotation of cluster in cage.In short, alternating temperature is by limitation cage
The movement of cluster influences paramagnetic signal, and regulation sensitivity is low.Using being chemically modified outside carbon cage to metal fullerene, can change
The symmetry for becoming metal fullerene, also will affect cluster kinetic property, equally will limit cluster movement, such as outside carbon cage
Pyrroles's cyclic group is modified, not only results in the anisotropy of molecular paramagnetism, and cause unpaired electron in internal magnetization
Divergent distribution on core.Similarly, in Sc3C2@C80Outside is chemically modified, and three Sc are become by originally equivalent chemical environment
Difference, embedded cluster movement are restricted, and anisotropy occurs in ESR signal.Therefore, existing that paramagnetic can be changed using chemical modification
Signal, but signal intensity is unidirectionally, cannot flexibly to regulate and control to signal.
Summary of the invention
In order to solve it is existing by cooling or chemical modification mode regulate and control spirit existing for the paramagnetic properties of metal fullerene
The technical issues of sensitivity is low, complicated for operation, control methods signal unidirectionally changes, the present invention provide a kind of structure novel and can letters
Just, efficiently, the metal fullerene derivative and preparation method thereof of sensitive regulation metal fullerene paramagnetic properties, utilize azobenzene light
The characteristics of isomerization, changes the distance at double spin centers, regulates and controls the paramagnetic properties of metal fullerene.A kind of metal is provided simultaneously
The regulation method and metal fullerene derivative of fullerene derivate paramagnetic properties are used as the application of molecule light functional switch.
Metal fullerene derivative provided by the present invention, shown in structural formula such as formula (I):
In formula (I) compound, n=1,2,3；
Refer to paramagnetic metal fullerene.
I.e. the compound of formula (I) structure is to modify small point of azobenzene NO free radical in paramagnetic metal fullerene surface
Son.
The paramagnetic metal fullerene can be Sc3C2@C80、La@C82、Y@C82、Sc@C82、Y2@C79N、Gd@C82, preferably
Sc3C2@C80。
The metal fullerene derivative of formula (I) is the compound of following structural formula:
It is preferred that Sc3C2@C80。
The preparation method of the metal fullerene derivative of formula (I) provided by the invention, includes the following steps: anti-through addition
It answers, in the azobenzene NO free radical small molecule of the metal fullerene surface modification formula (II) with paramagnetic properties, obtains formula (I)
Metal fullerene derivative, wherein the azobenzene NO free radical small molecule structure formula of formula (II) is as follows:
In formula, n=1,2,3.
The compound of i.e. above-mentioned formula (II) structure is 2 containing azo group, the derivative of 2,6,6- tetramethyl piperidines-nitrogen oxides
One of object.
The addition reaction can be 1,3- Dipolar Cycloaddition, objective case reaction, [2+2] cycloaddition reaction, [2+4] ring
One of addition reaction, Cabbeen addition.
The paramagnetic metal fullerene can be La@C82、Y@C82、Sc@C82、Y2@C79N、Sc3C2@C80、Gd@C82, preferably
Sc3C2@C80。
The azobenzene NO free radical small molecule is concretely:
The preparation method further include: separate metal fullerene derivative obtained by high performance liquid chromatography.
The preparation method, which may further comprise:, passes through ground substance assistant laser for metal fullerene derivative after separation
Desorption ionization time of-flight mass spectrometer (MALDI-TOF) is analyzed.
The regulation method of the metal fullerene derivative paramagnetic properties of formula (I) provided by the invention, includes the following steps: to adopt
With the metal fullerene derivative of ultraviolet light formula (I)；Ultraviolet light is closed, the metal fowler of radiation of visible light formula (I) is opened
Ene derivative.
Using the metal fullerene derivative of ultraviolet light formula (I) so that azobenzene compound from it is trans- be changed into it is suitable
The ESR signal of formula configuration, metal fullerene weakens；Ultraviolet light is closed, the metal fullerene for opening radiation of visible light formula (I) is derivative
Object, so that azobenzene derivatives become anti-configuration, the ESR signal enhancing of metal fullerene by cis-.
It is come the essence for regulating and controlling the paramagnetic properties of metal fullerene by regulating and controlling the light of different-waveband in above-mentioned regulation method
Regulate and control the suitable of metal fullerene by the variation of relative position between metal fullerene and the double spin centers of NO free radical molecule
Magnetic characteristic.Specific principle of adjustment and control is: using ultraviolet light metal fullerene derivative, ultraviolet lighting make azobenzene compound from
It is trans- to be changed into cis-configuration, reduce the distance at double spin centers, spin-spin interaction enhancing, so that metal fowler
The ESR signal of alkene weakens；Close ultraviolet light and open visible light, azobenzene derivatives become anti-configuration by cis- so that it is double from
The distance at rotation center increases, and spin-spin interaction weakens, the ESR signal enhancing of metal fullerene.
Preferably, the selectable wave band of the ultraviolet light is 260nm~470nm.
Preferably, the selectable wave band of the visible light is 470nm~700nm.
Preferably, it can be 5~25mw that the illumination, which is mapped to the energy of sample,.
Preferably, the time of light irradiation can be 1min~for 24 hours.
The variation of detection electron paramagnetic signal in the regulation method can use the electronics of any one wave band (X, W-, Q-)
EPR spectrometer is detected.
When using metal fullerene derivative described in ultraviolet light, with the extension of ultraviolet lighting time, metal is rich
The ESR signal for strangling alkene weakens, and after irradiating a period of time, then the ESR signal " closing " of metal fullerene uses radiation of visible light one
The section time, the ESR signal " unlatching " of metal fullerene, thus, the metal fullerene derivative of formula (I) provided by the invention has
Photoswitch property.Switching of the light beam on time, space, wavelength may be implemented in photoswitch, is optical communication, optical computer, light letter
One of Primary Components of optical information systems such as breath processing are the key that construction all-optical networks, the following all-optical network can be made more clever
Activity, intelligence, survivability play increasingly important role in fields such as communication, automatic controls, therefore, are used as light function
During the metal fullerene derivative for the formula (I) that can be switched can be applied to all-optical network, light exchanges, fiber optic communication device is applied also for
In the difference that part test macro and Metropolitan Area Network (MAN), access are netted/point multiplexing and switching equipment.
Compared with prior art, the invention has the following beneficial effects:
(1) the above metal fullerene derivative has photoswitch property, it can be achieved that metal fullerene is electric under the action of light
" unlatching " or " closing " of sub- paramagnetic signal.
(2) the photoisomerization feature for utilizing azobenzene can sensitively regulate and control double spin centers under different illumination conditions
Relative position, the paramagnetic properties of regulation metal fullerene that can be reversible, realizes and accurately and efficiently regulates and controls metal fullerene paramagnetic
Characteristic, regulation method high sensitivity, can regulate and control easy to operate, strong operability repeatedly.
(3) condition of preparation, separation and the purified metal fullerene that can select comparative maturity.
(4) the azobenzene NO free radical molecular properties selected are stable, synthesis is simple, low in cost.
(5) selectable using azobenzene NO free radical as the method type of spin probe modified metal fullerene
More, method of modifying is simple, efficient, strong operability.
Detailed description of the invention
Fig. 1 is the structural formula of the metal fullerene derivative of formula according to the present invention (I).
Fig. 2 is metal fullerene Sc according to the present invention3N@C80Paramagnetic signal becomes under the conditions of derivative ultraviolet-visible illumination
Change figure.
Fig. 3 is metal fullerene Sc according to the present invention3C2@C80Paramagnetic signal under the conditions of derivative ultraviolet-visible illumination
Variation diagram.
Fig. 4 A is metal fullerene Sc3C2The electron paramagnetic resonance spectrum (EPR) signal of@C80 ontology.
Fig. 4 B is metal fullerene Sc3C2The electron paramagnetic resonance spectrum (EPR) signal of@C80 derivative.
Fig. 4 C is metal fullerene Sc3C2@C80 derivative adds the electron paramagnetic resonance spectrum (EPR) signal after H.
Specific embodiment
With reference to the accompanying drawing, specific embodiments of the present invention will be described in detail, it is to be understood that guarantor of the invention
Shield range is not limited by the specific implementation.The ScNi that following embodiments use2Alloy is studied purchased from Beijing non-ferrous metal
Institute.
Embodiment 1
Metal fullerene Sc3N@C80The preparation method of derivative, process include:
(1) metal fullerene Sc3N@C80Preparation method, Sc3N@C80Molecule is to pass through electricity in DC arc discharge furnace
Arc discharge method (- Huffman method) synthesis, detailed process includes: the solid graphite stick for being first 8mm outer diameter
It is drilled to the hollow plumbago pipe that internal diameter is 6mm or so, then by ScNi2Alloy and graphite powder are mixed according to the ratio that mass ratio is 3: 1
Uniformly, it is subsequently filled in graphite-pipe, tamps；Filled metal/graphite stick is mounted on to anode and the fixation of electric arc furnaces, is closed
Closed furnace lid opens vacuum pump；The valve between furnace chamber and vacuum pump is opened, to electric arc stove evacuation, is evacuated to air pressure lower than 10Pa
When, open cooling circulating water, open electric welding machine, adjust electric current to 100A, open the mobile metal/graphite stick of stepper motor be allowed to
The contact of cathode graphite plate, preheats metal/graphite stick, excludes the air and moisture wherein adsorbed, preheats 30 minutes or so
, electric welding machine is closed, the valve between furnace chamber and vacuum pump is closed, stops vacuum pump；Breather valve is slowly opened, is filled to electric arc furnaces
Enter the N of 6Torr2With the He gas of 194Torr, electric welding machine is opened, electric current is adjusted to 130A, opens the mobile metal/stone of stepper motor
Inker is allowed to disengage with cathode graphite plate, forms strong electrical field between cathode and anode at this time and discharges, and continues to adjust stepping
Motor makes two pole tensions keep 40V or so, discharges at this time the most stable；Dazzling yellow-green light is issued when electric discharge, between the two poles of the earth,
Temperature can be up to 4000K or more between the two poles of the earth at this time, at the same the metal/graphite stick of anode by the electronic impact of cathode emission at
The particle to disperse, for particle in the arc discharge area atomization of high temperature, the atom of gasification is cold during flying away from arc zone
But and then cluster is reassembled into, in this way, various fullerenes and metal fullerene just generate；As anode metal/graphite rod disappears
Consumption, must adjust stepper motor at any time makes the two poles of the earth stable discharging；After metal/graphite stick is exhausted, waits electric arc furnaces cooling, open
Electric arc furnaces collects resulting grey soot, is put into paper bag, extracts 12 hours or so with toluene in Soxhlet extractor to get containing each
The extracting solution of kind empty fullerene and metal fullerene；Toluene containing various fullerenes and metal fullerene is extracted into solution warp
Qualitative filter paper be filtered for multiple times after with high performance liquid chromatography separation and purification: first using Buckyprep column (20 × 250mm,
Cosmosil first step separation) is carried out, is separated essentially according to the size of Fullerene Carbon cage, the crude product then obtained carries out
Second step separation mainly the fullerene of hollow carbon cage and has gold with Buckyprep-M column (20 × 250mm, Cosmosil)
The metal fullerene for belonging to embedded cluster separates, and is finally purified again with Buckyprep column (20 × 250mm, Cosmosil),
The metal fullerene of various configuration is separated, wherein using toluene as mobile phase in experiment, the flow velocity of toluene is 12ml/min,
Sample introduction concentration is 1mg/ml, every time fixed sample introduction 12ml, monitors wavelength using the UV of 310nm, while base is combined in separation process
Matter Assisted Laser Desorption ionization time of flight mass spectrometry analyzes each chromatographic peak, and chromatographic peak goes out the peak position corresponding time
It is 45-55 minutes, obtains the Sc of 99% or more purity3N@C80。
(2) 2 containing azo group, the preparation method of 2,6,6- tetramethyl piperidine -1- oxygen -4- formyl adducts (1a), step
Suddenly include: to take being dissolved in the methanol of 2.6ml to formylphenylboronic acid for 8.93mmol, obtain suspension；Under nitrogen protection,
KHF is added at one time when zero degrees celsius2(2.09g, 26.8ml) is added dropwise in suspension under conditions of zero degrees celsius
Water (5.95ml), then removes ice water domain, is stirred at room temperature to fully reacting；Obtained crude product is concentrated, mistake
Night, vacuum drying；Crude product continues to purify, then that obtained solution is molten again with acetone soln Soxhlet extraction 4 hours of 60ml
Into the acetone of 5ml, the anhydrous ether that 30ml is added is precipitated solution, then obtained precipitating is filtered concentration and drying,
Obtain boric acid sylvite.
The boric acid sylvite of 1mmol is added in the acetonitrile solution of 3ml (0.33M), NOBF is added4(120mg,
1.03mmol), it is stirred at room temperature until reaction becomes homogeneous, solution becomes green by slimy suspension in reaction process
Then become black, obtained crude product is added the water of 20ml and the methylene chloride of 10ml, and water layer is with methylene chloride (3 × 10ml)
It is extracted, organic layer is dried with anhydrous sodium sulfate, is then collected solution and is dried under reduced pressure, and is crossed silicagel column and is obtained nitrous
Benzaldehyde.
The nitrosobenzene formaldehyde of 1mmol is dissolved in the acetic acid solution of heat, the p-aminobenzoic acid of 1mmol is also dissolved
In acetic acid, heating is poured into nitrosobenzene formaldehyde the p-aminobenzoic acid solution of heat, is then heated to 118 DEG C, stirring
A few minutes, then slowly cool down, it is seen that there is the solid of light brown to be precipitated, be centrifuged, washing obtains solid crude product；Consolidate what is obtained
Body is dissolved into the aqueous solution of sodium carbonate, then is slowly stirred dropwise addition hydrochloric acid solution, and observation pH value is neutral or neutral meta-alkalescence
?；Product is precipitated again after dropwise addition, and washing, centrifugation obtain solid, are then recrystallized with the acetic acid solution of heat, is precipitated
Product obtains the carboxylic acid compound containing azo group.Carboxylic acid compound and NO free radical small molecule 2 by gained containing azo group,
2,6,6- tetramethyl -4- hydroxy-piperdines-nitrogen oxides carries out esterification, obtains 2 containing azo group, 2,6,6- tetramethyl piperazines
Pyridine -1- oxygen -4- formyl adduct (1a).
(3)Sc3N@C80The preparation method of cycloaddition derivative, comprising: take the Sc of 1mg3N@C80The molten toluene of solid sample,
Add 2,2,6, the 6- tetramethyl piperidine -1- oxygen -4- formoxyl chemical combination of the Ethylglycocoll and 1.2mg of 1mg containing azo group
Object (1a) carries out cycloaddition reaction, is filled with argon gas and makees protection gas, reacts 45min under 120 DEG C of stirring conditions；After cooling half an hour,
Solution is evaporated, reaction product is separated and purified with high performance liquid chromatography (HPLC) after being dissolved in toluene, step are as follows: use
Buckyprep column (20 × 250mm, Cosmosil) is separated, and using toluene as mobile phase in experiment, the flow velocity of toluene is
12ml/min, sample concentration are 1mg/ml, every time fixed sample introduction 12ml, monitor wavelength using the UV of 310nm.
Due to obtained Sc3N@C80The formation of the electrons interference nuclear-magnetism spectrum of free radical in cycloaddition derivative, therefore use H
Neutralize Sc3N@C80The electronics of free radical in cycloaddition derivative, obtains nuclear magnetic resonance spectroscopy: 1H NMR:(CDCl3-d,
600MHz, 293K), δ=7.42,7.34 (bs, 4H), 4.17 (bs, 2H), 3.58 (m, 1H), 3.14 (m, 2H).
Specific synthetic route is as follows:
Embodiment 2
Metal fullerene Sc3C2@C80The preparation method of derivative, steps are as follows:
(1) metal fullerene Sc3C2@C80Preparation method, Sc3C2@C80Molecule is to pass through electricity in DC arc discharge furnace
Arc discharge method (- Huffman method) synthesis, detailed process includes: the solid graphite stick for being first 8mm outer diameter
It is drilled to the hollow plumbago pipe that internal diameter is 6mm or so, then by ScNi2Alloy and graphite powder are mixed according to the ratio that mass ratio is 3: 1
Uniformly, it is subsequently filled in graphite-pipe, tamps；Filled metal/graphite stick is mounted on to anode and the fixation of electric arc furnaces, is closed
Closed furnace lid opens vacuum pump；The valve between furnace chamber and vacuum pump is opened, to electric arc stove evacuation, is evacuated to air pressure lower than 10Pa
When, open cooling circulating water, open electric welding machine, adjust electric current to 100A, open the mobile metal/graphite stick of stepper motor be allowed to
The contact of cathode graphite plate, preheats metal/graphite stick, excludes the air and moisture wherein adsorbed, preheats 30 minutes or so
, electric welding machine is closed, the valve between furnace chamber and vacuum pump is closed, stops vacuum pump；Breather valve is slowly opened, is filled to electric arc furnaces
Enter the He gas of 200Torr, open electric welding machine, adjusts electric current to 130A, open the mobile metal/graphite stick of stepper motor and be allowed to and yin
Pole graphite plate disengages, and forms strong electrical field between cathode and anode at this time and discharges, and continuing adjusting stepper motor keeps the two poles of the earth electric
Pressure keeps 40V or so, discharges at this time the most stable；Dazzling yellow-green light is issued when electric discharge, between the two poles of the earth, at this time between the two poles of the earth
Temperature can be up to 4000K or more, at the same the metal/graphite stick of anode by the electronic impact of cathode emission at the particle to disperse,
For particle in the arc discharge area atomization of high temperature, the atom of gasification is cooling during flying away from arc zone and then reassembles into
Cluster, in this way, various fullerenes and metal fullerene just generate；With the consumption of anode metal/graphite rod, must adjust at any time
Stepper motor makes the two poles of the earth stable discharging；It after metal/graphite stick is exhausted, waits electric arc furnaces cooling, opens electric arc furnaces and collect institute
The grey soot obtained, is put into paper bag, extracts 12 hours or so with toluene in Soxhlet extractor to get various empty fullerenes are contained
With the extracting solution of metal fullerene；It is multiple through qualitative filter paper that toluene containing various fullerenes and metal fullerene is extracted into solution
High performance liquid chromatography separation and purification are used after filtering: first carrying out first using Buckyprep column (20 × 250mm, Cosmosil)
Step separation, is separated essentially according to the size of Fullerene Carbon cage, and the crude product then obtained carries out second step separation, is used
Buckyprep-M column (20 × 250mm, Cosmosil) mainly the fullerene of hollow carbon cage and has metal to embed cluster
Metal fullerene separates, and is finally purified again with Buckyprep column (20 × 250mm, Cosmosil), various configuration
Metal fullerene separates, wherein using toluene as mobile phase in experiment, toluene flow velocity is 12ml/min, and sample introduction concentration is 1mg/
Ml, fixed sample introduction 12ml, monitors wavelength, while binding matrix Assisted Laser Desorption in separation process using the UV of 310nm every time
Ionization time of flight mass spectrometry analyzes each chromatographic peak, chromatographic peak go out the peak position corresponding time be 53-63 minutes, obtain
To the Sc of 99% or more purity3C2@C80；
(2) by metal fullerene Sc made from step 13C2@C80With made from embodiment 1 containing azo group 2,2,6,6- tetra-
Methyl piperidine -1- oxygen -4- formyl adduct carries out cycloaddition reaction, and metal fullerene Sc is made3C2@C80Derivative.
Due to metal fullerene Sc obtained3C2@Cs0Itself there is paramagnetism, i.e., using in H and metal fullerene Sc3C2@
C80The electronics of free radical in derivative, still can interfere the formation of nuclear magnetic resoance spectrum, therefore with metal fullerene Sc3C2@C80It is derivative
The paramagnetic resonance spectrum of object characterizes metal fullerene Sc3C2@C80The physical property of derivative.Wherein, metal fullerene Sc3C2@
C80The electron paramagnetic resonance spectrum (EPR) signal of ontology is referring to attached drawing 4A, metal fullerene Sc3C2The electron paramagnetic of@C80 derivative is total
Vibration wave spectrum signal is referring to attached drawing 4B, metal fullerene Sc3C2@C80 derivative add the electron paramagnetic resonance spectrum (EPR) signal after H referring to
Attached drawing 4C.
Specific synthetic route is as follows:
Embodiment 3
The detection process of photo-excited electron transfer paramagnetic signal
(1) metal fullerene Sc3N@C80The detection method of derivative electron paramagnetic resonance spectrum (EPR) property, comprising: take 0.5mg
The sample of left and right is dissolved in 1mL toluene solution, in the quartz ampoule that solution is filled in as band, the then electron paramagnetic of test sample
Signal (ESR) property.For a period of time with ultraviolet lighting first, metal fullerene Sc is detected every four minutes3N@C80The ESR of derivative
Then signal is shone with visible light again, detect the variation of ESR signal.
As shown in Figure 2, metal fullerene Sc3N@C80Itself there is no paramagnetic signal, goes out after external NO free radical small molecule
Three lines of existing feature.Under conditions of ultraviolet lighting, the electronics transfer that intramolecular occurs leads to the decline (illumination of ESR signal
After 4min, ESR signal just has decline)；Close ultraviolet light, it is seen that light irradiates 8min or so, due to the collision between molecule,
ESR signal is replied.Wherein, I refers to metal fullerene Sc in Fig. 23N@C80Derivative.
(2) metal fullerene Sc3C2@C80The detection method of derivative electron paramagnetic resonance spectrum (EPR) property, comprising: take
The sample of 0.5mg or so is dissolved in 1mL toluene solution, by solution as in the quartz ampoule with plug, the then electricity of test sample
Sub- paramagnetic signal property.For a period of time with ultraviolet lighting first, metal fullerene Sc is detected every four minutes3C2@C80Derivative
ESR signal, is then shone with visible light again, detects the variation of ESR signal.
From the figure 3, it may be seen that metal fullerene Sc3C2@C80Itself has paramagnetism, and 22 of ideal symmetrical are presented at room temperature
Spectral line (3160~3320 Gauss) exists simultaneously NO free radical after modifying azobenzene NO free radical small molecule at room temperature
22 lines of three lines and metal fullerene；After opening ultraviolet light, azobenzene molecule is transformed into cis-configuration by trans-, so that golden
The relative distance belonged between fullerene molecule and NO free radical molecule (double spin centers) becomes smaller, and spin-spin interaction increases
By force, metal fullerene Sc3C2@C80Paramagnetic signal intensity decline, illumination 20 minutes or so, signal " closing "；Opening later can
Light-exposed, with the irradiation of visible light, azobenzene small molecule becomes anti-configuration by cis-, metal fullerene and NO free radical
Relative position becomes remote, and spin-spin interaction weakens, so that Sc3C2@C80ESR signal " opened in visible light according to 6min or so
It opens ".Wherein, II refers to metal fullerene Sc in Fig. 33C2@C80Derivative.
Embodiment 4
Sc3C2@C80The process of ESR signal " unlatching " and " closed " state of metal fullerene derivative
The light of 260nm~470nm is selected to irradiate Sc3C2@C80Metal fullerene derivative, with prolonging for ultraviolet lighting time
Long, the ESR signal of metal fullerene weakens, and irradiates 20 minutes or so, the ESR signal " closing " of metal fullerene；Then it uses
When the radiation of visible light of 470nm~700nm, irradiate 6 minutes or so, the ESR signal " unlatching " of metal fullerene.
Claims (7)
1. metal fullerene derivative, structural formula are as shown in the formula (I):
In formula (I) compound, n=1,2,3；
Refer to paramagnetic metal fullerene, is Sc3C2@C80、Sc3N@C80。
2. metal fullerene derivative according to claim 1, structural formula are as follows:
,For Sc3C2@C80。
3. the preparation method of the metal fullerene derivative of formula (I) includes the following steps: through addition reaction, with paramagnetic spy
The azobenzene NO free radical small molecule of the metal fullerene surface modification formula (II) of property, the metal fullerene for obtaining formula (I) spread out
Biology, wherein the azobenzene NO free radical small molecule structure formula of formula (II) is as follows:
,
In formula, n=1,2,3；
The metal fullerene derivant structure formula of formula (I) are as follows:
, in formula, n=1,2,3；Refer to paramagnetic metal richness
Alkene is strangled, is Sc3C2@C80、Sc3N@C80。
4. preparation method according to claim 3, it is characterised in that: the addition reaction is that 1,3- dipole-diople interaction is anti-
It answers, objective case reaction, [2+2] cycloaddition reaction, [2+4] cycloaddition reaction, one of Cabbeen addition.
5. the regulation method of the metal fullerene derivative paramagnetic properties of formula (I) includes the following steps: using ultraviolet light formula
(I) metal fullerene derivative；Ultraviolet light is closed, the metal fullerene derivative of radiation of visible light formula (I) is opened；Wherein,
The metal fullerene derivant structure formula of formula (I) are as follows:
, in formula, n=1,2,3；Refer to paramagnetic metal richness
Alkene is strangled, is Sc3C2@C80、Sc3N@C80。
6. the regulation method of metal fullerene derivative paramagnetic properties according to claim 5, it is characterised in that: the purple
The wave band that outer light selects is 260nm ~ 470nm, and the wave band that the visible light selects is 470nm ~ 700nm, and the illumination is mapped to sample
The energy of product is 5 ~ 25mw, and the time of light irradiation is 1min ~ for 24 hours.
7. the metal fullerene derivative of formula (I) be used as molecule light functional switch, for all-optical network, light exchange in purposes,
Wherein, the metal fullerene derivant structure formula of formula (I) are as follows:
, in formula, n=1,2,3；Refer to paramagnetic metal richness
Alkene is strangled, is Sc3C2@C80、Sc3N@C80。
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