CN102851025B - Intelligent rare-earth luminescent supramolecular device with photocontrollability and preparation thereof - Google Patents
Intelligent rare-earth luminescent supramolecular device with photocontrollability and preparation thereof Download PDFInfo
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- CN102851025B CN102851025B CN201210381334.9A CN201210381334A CN102851025B CN 102851025 B CN102851025 B CN 102851025B CN 201210381334 A CN201210381334 A CN 201210381334A CN 102851025 B CN102851025 B CN 102851025B
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Abstract
The invention relates to an intelligent rare-earth luminescent supramolecular device with photocontrollability, which is a pseudorotaxane assembly [1.2] [PF6] mixed by a 24C8 subject macrocycle 1 with rare-earth metal europium complex and a diheteroaryl ethylene object 2.PF6. The chemical formula is C92H80EuF21N5O15PS4. The intelligent rare-earth luminescent supramolecular device can be used for controlling reading and erasing of characteristic fluorescence of the rare-earth metal europium complex. The supramolecular device has the obvious advantages of high efficiency, high sensitivity, remote controllability, high cleanness, high fatigue resistance and the like; under the circulating irradiation of ultraviolet light 365nm and near-infrared light 614nm, the reading and erasing of the characteristic fluorescence of the rare-earth metal europium complex of the assembly can be controlled; under the condition of room temperature, the rare-earth metal fluorescence color changes can be easily observed by naked eyes; and thus, the supramolecular device has wide application prospects in the fields of nano information processing technology and nano memory materials.
Description
Technical field
The invention belongs to molecular device and molecular switch technical field, particularly a kind of rare earth luminous supramolecule device of intelligence and preparation thereof with light controllability.
Background technology
Device and machine play irreplaceable effect in the mankind's life.The machine that the electronic computer technology of mainly take is now representative and the microminiaturization of device are close to a limit.Simulation to functional biological molecule basic function in the various physical mechanical devices of macroscopic view and complicated natural system in molecule rank, allows people be full of yearning to following intellectuality life.The scientist that develops into of supramolecular chemistry provides a kind of new long-pending little of the method for (bottom-up) manufactures and designs molecular level greatly machine is to meet people's needs.What by many discontinuous molecular elements, assembled is considered to the device of a molecular level to realize the assembly of specific function.
In Energy spectrum device, rare earth luminescence has the narrow emission peak of long wavelength's wire, long fluorescence lifetime, large unique spectral qualities such as Stokes shift, device based on rare earth luminous has good development prospect, and rare earth luminous device is all being widely used aspect fluorescence imaging, luminescent material and senser element so far.With macroscopical machine type seemingly, the machine of molecular level and device running also need both luminous energy of energy input, the input of electric energy or chemical energy, shows as again arranging of electronic cloud in molecule.Wherein luminous energy there is easy acquisition, be swift in response, remote controlled, clean significant advantage, therefore utilize luminous energy as the power of regulatory molecule device, for the preparation of explanation, store, process, the device aspect of the molecular level of the artificial intelligence of transitional information has very wide application potential.
Summary of the invention
The object of the invention is for above-mentioned technical Analysis, a kind of rare earth luminous supramolecule device of intelligence and preparation thereof with light controllability is provided, and this supramolecule device is for the 24 hat large rings 1 of 8 main body with rare earth metal europium complex and have light isomery function Bisheteroarylethene object 2PF
6assembly, it has the significant advantages such as efficient, sensitive, remote controlled, green clean, high resistance to fatigue, in the nanometer information processing technology and nanometer material with memory field, has broad application prospects.
Technical scheme of the present invention:
The rare earth luminous supramolecule device of intelligence of light controllability, serves as reasons with the large rings 1 of 24 hat 8 main body and the Bisheteroarylethene object 2PF with light isomery function of rare earth metal europium complex
6mix pseudorotaxane assembly [the 12] [PF forming
6], its chemical formula is C
92h
80euF
21n
5o
15pS
4, its structural formula is:
Have a preparation for the rare earth luminous supramolecule device of intelligence of light controllability, step is as follows:
1) by chloroform and acetonitrile by volume for 1:1 mixes, obtain mixed organic solvents;
2) under normal temperature, 24 hats 8 of preparation are encircled greatly to Rare Earth Europium Complex 1 and Bisheteroarylethene object 2PF
6be dissolved in respectively in above-mentioned mixed organic solvents, with the large ring Rare Earth Europium Complex 1 of 24 hat 8 and Bisheteroarylethene object 2PF
6be 1 mmole/50-80mL with the amount ratio of mixed organic solvents;
3) under normal temperature, above-mentioned two kinds of solution are mixed, with the large ring Rare Earth Europium Complex 1 of 24 hat 8 and Bisheteroarylethene object 2PF
6mol ratio be 1:1, can make stable pseudorotaxane assembly [12] [PF
6].
The chemical formula of the large ring 1 of described 24 hat 8 main body is C
63h
53euF
9n
3o
14s
3, structural formula is:
Its synthetic method, step is as follows:
1) ammoniacal liquor that is 29.3% by 2-acetopyridine, 4-formyl radical benzo 24 hats 8, KOH and mass concentration in molar ratio 2:0.7:4:4 adds in dry ethanol, at N
2under protection vigorous stirring, remain at 35 ℃ of temperature and react 72 hours, after completion of the reaction, cool to room temperature, suction filtration, uses washing with alcohol filter cake, the CH that is 2:1 in volume ratio by thick product
2cl
2in-water mixed liquid, distribute, water is used CH again
2cl
2washed twice, merges organic phase, and with ethyl alcohol recrystallization, obtaining white solid is terpyridyl benzo 24 hats 8;
2) by [Eu (tta)
3] .3H
2o and terpyridyl benzo 24 hats 8 in molar ratio 1:1 join in dry tetrahydrofuran (THF), [Eu (tta)
3] .3H
2o and terpyridyl benzo 24 hats 8 are 0.2mmol/30-60mL with the amount ratio of tetrahydrofuran (THF), at N
2under protection vigorous stirring, react 4 hours, after completion of the reaction, revolve desolventizing, with ether and normal hexane, carry out recrystallization, obtain yellow solid and be the large ring 1 of 24 hat 8 main body.
Described Bisheteroarylethene object 2PF
6chemical formula be C
29h
27f
12n
2oPS, structural formula is:
Its synthetic method, step is as follows:
1) the bromo-2-thiotolene of 3-acetal is dissolved in anhydrous tetrahydro furan, the amount ratio of 3-bromo-2-thiotolene acetal and anhydrous tetrahydro furan is 12mmol/40-60ml, magnetic stirs,-78 ℃, the nitrogen protection emitter of making a bet adds n-Butyl Lithium, react after half an hour, after reaction solution being cooled to-95 ℃, add 1-(1, 2-dimethyl-5-anisole indyl) tetrahydrofuran solution of seven fluorine cyclopentenes, amount ratio is 12mmol/20-60ml, the bromo-2-thiotolene of 3-acetal, n-Butyl Lithium and 1-(1, 2-dimethyl-5-anisole indyl) mol ratio of seven fluorine cyclopentenes is 12:15.6:12, reaction remained at-78 ℃ after 2 hours, be warming up to room temperature standing 8 hours, then add saturated NH
4cl solution, be extracted with ethyl acetate, be spin-dried for, add methylene dichloride to dissolve, splash into mass concentration and be 10% rare HCl and tosic acid, under induction stirring, heat 40 ℃ of backflows, therebetween with the carrying out of TLC detection reaction, question response object point stops after disappearing refluxing, be cooled to 20 ℃, with saturated aqueous common salt and washing until water layer is colourless, collect organic phase, with anhydrous magnesium sulfate drying, filter, revolve to steam and remove methylene dichloride, obtain light green solid, with methylene dichloride, dissolve this solid, the column chromatography for separation that is 12:1 by the volume ratio of sherwood oil and ethyl acetate, collect green portion, revolve and steam except desolventizing, add methylene dichloride to dissolve, under stirring, add sherwood oil until no longer include precipitation generation, suction filtration is to dry, obtaining white crystal is Bisheteroarylethene aldehyde,
2) by Et
3n, MgSO
4, benzylamine and Bisheteroarylethene aldehyde in molar ratio 4:1:1.2:1 join in methyl alcohol, Et
3the amount ratio of N and methyl alcohol is 4mmol/50-70mL, at N
2under 70 ℃ of backflows of the lower heating of protection, react 6 hours, be cooled to 0 ℃, divide and in 30 minutes, add NaBH four times
4, Bisheteroarylethene aldehyde and NaBH
4mol ratio be 1:16, continue reaction 2-4 hour, add water termination reaction, with acetic acid ethyl ester, extract and product, merge organic phase, wash with water, then the HCl that is 0.5N by concentration by product, the form with hydrochloride extracts into water, with chloroform, again extract and product, merge organic phase, through anhydrous MgSO
4dry, removal of solvent under reduced pressure, obtaining colorless oil is Bisheteroarylethene amine;
3) Bisheteroarylethene amine is dissolved in methyl alcohol, the amount ratio of Bisheteroarylethene amine and methyl alcohol is 0.8mmol/40-60mL, and then dripping mass concentration is 10% rare HCl, regulating pH value is 2, continues to stir 4-6h, is spin-dried for solvent, gained solid is added in acetone, drip saturated NH
4pF
6the aqueous solution, until solution clarification continues to stir 3h, is spin-dried for, then adds water to stir 5h, and suction filtration, then washes with water, obtains white solid after dry and is and has light isomery function Bisheteroarylethene object 2PF
6.
A kind of application of the prepared rare earth luminous supramolecule device of the intelligence with light controllability, for controlling reading and wiping of rare earth metal europium complex characteristic fluorescence, method is: utilize UV-light 365nm and near infrared light 614nm to irradiate this supramolecule device circulation, can realize cancellation and the recovery of Rare Earth Europium characteristic fluorescence.
Advantage of the present invention is: this supramolecule device has the significant advantages such as efficient, sensitive, remote controlled, green clean, high resistance to fatigue, with UV-light 365nm and near infrared light 614nm circulation, irradiate assembly and can control reading and wiping of rare earth metal europium complex characteristic fluorescence, can be easy to see that rare earth metal fluorescence color changes by naked eyes at ambient temperature, this supramolecule device has broad application prospects in the nanometer information processing technology and nanometer material with memory field.
Accompanying drawing explanation
Fig. 1 is for irradiating Bisheteroarylethene object 2PF with UV-light (365nm) 10s, 20s, 40s, 80s, 300s and visible ray (614nm) 300s
6nuclear magnetic spectrogram.
Fig. 2 is for irradiating different time front and back Bisheteroarylethene object 2PF by UV-light (365nm)
6uV, visible light Change of absorption spectrogram.
Fig. 3 is pseudorotaxane [12] [PF
6] nuclear magnetic spectrogram.
Fig. 4 is that 24 hats 8 of rare earth metal europium complex encircle greatly 1 fluorescent emission spectrogram and irradiate Bisheteroarylethene object 2PF by UV-light (365nm)
6uV, visible light Change of absorption spectrogram.
Fig. 5 is for irradiating pseudorotaxane [12] [PF by UV-light (365nm)
6] the fluorescent emission variation diagram of rare-earth europium before and after different time.
Fig. 6 is pseudorotaxane [12] [PF
6] test of light regulation and control resistance to fatigue.
Fig. 7 is pseudorotaxane [12] [PF
6] by change in fluorescence figure after K ionic dissociation.
Embodiment
Below by example, the present invention is described further:
Embodiment:
A preparation for the rare earth luminous supramolecule device of intelligence of light controllability, step is as follows:
Synthesizing of the large ring 1 of (1) 24 hat 8 main body, step is as follows:
1) by 0.24g(2mmol) 2-acetopyridine, 0.48g (0.7mmol) 4-formyl radical benzo 24 hats 8,0.30g(4mmol) KOH and 10mL(4mmol) mass concentration is 29.3% ammoniacal liquor adds in the ethanol that 50mL is dry, at N
2under protection vigorous stirring, remain at 35 ℃ of temperature and react 72 hours, after completion of the reaction, cool to room temperature, suction filtration, uses washing with alcohol filter cake, the CH that is 2:1 in 200mL volume ratio by thick product
2cl
2in-water mixed liquid, distribute, water is used 150mL CH again
2cl
2washed twice, merges organic phase, and with ethyl alcohol recrystallization, obtaining white solid is terpyridyl benzo 24 hat 8, yield:41%.
1h NMR (400MHz, CDCl
3) δ 8.76 (d, J=4.6Hz, 2H), 8.69 (t, J=3.8Hz, 4H); 7.91 (dd, J=10.9,4.5Hz, 2H), 7.51 (dd, J=8.3; 1.6Hz, 1H), 7.44 (s, 1H), 7.38 (dd, J=6.8; 5.4Hz, 2H), 7.00 (d, J=8.3Hz, 1H), 6.91 (s; 4H), 4.35 – 4.24 (m, 4H), 4.19 (d, J=3.8Hz, 4H); 3.98 (dd, J=11.7,3.1Hz, 8H), 3.90 (s, 8H);
13c NMR (100MHz, CDCl
3) δ 156.3,155.8,149.9,149.0,136.9,131.6,123.8,121.4,120.7,118.5,114.1,113.7,113.1,71.3,69.9,69.4; HRMS (FTMALDI) m/z[M+H]
+calcd for C
39h
42n
3o
8 +680.2966 found 680.2973; [M+Na]
+calcd for C
39h
41n
3naO
8 +702.2786, found702.2789; [M+K]
+calcd forC
39h
41kN
3o
8 +718.2525, found 718.2524.Anal.Calcdfor C
39h
41n
3o
8: C, 68.91; H, 6.08; N, 6.18.Found:C, 68.91; H, 6.06; N, 6.15;
2) by 0.17g (0.2mmol) [Eu (tta)
3] .3H
2o and 0.14g (0.2mmol) terpyridyl benzo 24 hats 8 join in the tetrahydrofuran (THF) that 45mL is dry, at N
2under protection vigorous stirring, react 4 hours, after completion of the reaction, revolve desolventizing, with ether and normal hexane, carry out recrystallization, obtain yellow solid and be the large ring 1 of 24 hat 8 main body, yield:83%.
1h NMR (400MHz, CDCl
3) δ 35.72 (s, 3H), 12.90 (d, J=6.5Hz, 2H), 10.75 (s, 2H); 8.35 (s, 2H), 7.00 – 6.72 (m, 12H), 6.24 (s, 3H); 5.61 (s, 3H), 4.13 (dd, J=61.9,41.3Hz, 24H);
19f NMR (400MHz, CDCl
3) δ 79.99 (s, 3H);
13c NMR (101MHz, CDCl
3) δ 159.33,157.21,151.28,150.48,148.97,132.93,126.65,124.55,123.85,121.50,118.98,114.14,114.00,113.77,112.96,100.01,99.04,94.60,71.98,70.33,69.98,69.49; HRMS (FTMALDI) m/z[M – TTA]
+calcd forC
55h
49euF
6n
3o
12s
2+ 1274.1869, found 1274.1868.Anal.Calcd forC
63h
53euF
9n
3o
14s
3: C, 50.61; H, 3.57; N, 6.21.Found:C, 50.77; H, 3.58; N, 6.17.
(2) Bisheteroarylethene object 2PF
6synthetic, step is as follows:
1) the bromo-2-thiotolene of 3.35g (12mmol) 3-acetal is dissolved in 40ml anhydrous tetrahydro furan, magnetic stirs ,-78 ℃, nitrogen protection are made a bet, and emitter adds 6.5mL(15.6mmol) n-Butyl Lithium, react after half an hour, reaction solution is cooled to after-95 ℃, add the 1-(1 of 0.84g (12mmol), 2-dimethyl-5-anisole indyl) seven fluorine cyclopentenes and tetrahydrofuran (THF) 20mL, reaction remained at-78 ℃ after 2 hours, be warming up to room temperature standing 8 hours, then add the saturated NH of 100mL
4cl solution, by 200ml ethyl acetate, extract, be spin-dried for, add 60mL methylene dichloride to dissolve, splash into 0.3mL mass concentration and be 10% rare HCl and 40mg tosic acid, under induction stirring, heat 40 ℃ of backflows, therebetween with the carrying out of TLC detection reaction, question response object point stops after disappearing refluxing, be cooled to 20 ℃, with saturated aqueous common salt and washing until water layer is colourless, collect organic phase, with anhydrous magnesium sulfate drying, filter, revolve to steam and remove methylene dichloride, obtain light green solid, with 5ml methylene dichloride, dissolve this solid, the column chromatography for separation that is 12:1 by the volume ratio of sherwood oil and ethyl acetate, collect green portion, revolve and steam except desolventizing, add 5ml methylene dichloride to dissolve, under stirring, add sherwood oil until no longer include precipitation generation, suction filtration is to dry, obtaining white crystal is Bisheteroarylethene aldehyde, yield:50%.Mp:158-159 ° of C,
1h NMR (400MHz CDCl
3) δ 9.77 (s, 1H) 7.77 (s, 1H) 7.11-7.09 (d, J=8.9Hz, 1H) 6.90 (s, 1H) 6.82-6.80 (d, J=9.8Hz, 1H), 3.73 (s, 3H) 3.54 (s, 3H) 1.91 (s, 3H) 1.80 (s, 3H),
13c NMR (100MHz CDCl
3) δ 181.2,154.2,150.7,140.2,137.2,135.8,131.2,126.6,124.7,111.0,109.0,100.6,100.5,99.4,54.7,29.2,28.7,14.7,10.6, HRMS (ESI) m/z[M+H]
+calcd for C
22h
17f
6nO
2s
+474.0948 found 474.0957,
2) by 0.23g (4mmol) Et
3n, 0.12g(1mmol) MgSO
4, 0.13g (1.2mmol) benzylamine and 0.47g (1mmol) Bisheteroarylethene aldehyde joins in 50ml methyl alcohol, at N
2under 70 ℃ of backflows of the lower heating of protection, react 6 hours, be cooled to 0 ℃, divide the NaBH that added altogether 0.61g (16mmol) for four times in 30 minutes
4continue reaction 4 hours, add 10ml water termination reaction, with 200mL acetic acid ethyl ester, extract and product, merge organic phase, use 100mL water washing, by product, the form with hydrochloride extracts into water the HCl that is 0.5N by 100mL concentration again, with 100mL chloroform, again extract and product, merge organic phase, through anhydrous MgSO
4dry, removal of solvent under reduced pressure, obtaining colorless oil is Bisheteroarylethene amine, yield:80%.
1hNMR (400MHz, CD
3cN) δ 7.28-7.10 (m, 6H), 6.93 (s, 1H); 6.73 (d, J=2.4Hz, 1H), 6.71 (s; 1H), 3.75 (s, 2H), 3.61 (s; 5H), 3.53 (s, 3H), 2.08 (s; 8H), 2.02 (s, 3H), 1.88-1.84 (m; 3H), 1.66 (s, 3H);
13c NMR (101MHz, CD
3cN) δ 154.58,142.91, and 140.19,139.09,131.89,127.95,127.80,126.48,125.50,124.54,124.11,110.96,110.15,100.60,99.56,54.87,51.76,46.62,29.41,13.54,10.70; HRMS (FTMALDI) m/z[M+Na]
+calcd for C
29h
26f
6n
2naOS
+587.1568 found 587.1564;
3) 0.45g (0.8mmol) Bisheteroarylethene amine is dissolved in 40mL methyl alcohol, then dripping mass concentration is 10% rare HCl, and regulating pH value is 2, continues to stir 5h, is spin-dried for solvent, and gained solid is added in 40mL acetone, drips saturated NH
4pF
6the aqueous solution, until solution clarification continues to stir 3h, is spin-dried for, then adds 40mL water to stir 5h, and suction filtration, then uses 50mL water washing, obtains white solid after dry and is and has light isomery function Bisheteroarylethene object 2PF
6, yield:90%.
1h NMR (400MHz, CD
3cN) δ 7.34-7.23 (m, 6H), 7.04 (s, 1H), 6.82-6.77 (m, 2H); 3.88 (s, 2H), 3.73 (s, 2H), 3.69 (s, 3H); 3.61 (s, 3H), 2.10 (s, 3H), 1.75 (s, 3H);
13c NMR (100MHz, CD
3cN) δ 154.61,141.62, and 139.21,138.06,136.65,131.92,128.53,128.25,127.52,126.59,125.44,124.92,110.93,110.20,100.66,99.42,54.89,51.33,45.91,29.45,13.54,10.72; HRMS (FTMALDI) m/z[M-PF
6]
+calcd for C
29h
26f
6n
2oS
+565.1743 found 565.1750.
Bisheteroarylethene object 2PF
6the research of photoresponse character:
By to Bisheteroarylethene object 2PF
6feature nuclear-magnetism peak carry out its photoresponse performance of marker detection, Fig. 1 is for irradiating Bisheteroarylethene object 2PF with UV-light (365nm) 10s, 20s, 40s, 80s, 300s and visible ray (614nm) 300s
6nuclear magnetic spectrogram, shows in figure: along with the continuous growth of irradiation time under UV-irradiation, and object Bisheteroarylethene 2PF
6feature nuclear-magnetism peak there is obvious displacement; With visible ray 614nm, irradiate object 300s subsequently, its feature nuclear-magnetism peak returns to again original position completely, and this shows that object has extraordinary optical Response.Fig. 2 is for irradiating different time front and back Bisheteroarylethene object 2PF by UV-light (365nm)
6uV, visible light Change of absorption spectrogram, in figure, show: along with the continuous growth of irradiation time under UV-irradiation, having there is obvious variation at ultraviolet-visible absorption spectroscopy in object, has occurred new absorption peak in 500-750nm region, and this has also shown that object has extraordinary optical Response.
(3) have the preparation of the rare earth luminous supramolecule device of intelligence of light controllability, step is as follows:
1) by chloroform and acetonitrile by volume for 1:1 mixes, obtain mixed organic solvents;
2) under normal temperature, the 0.15g (0.1mmol) of preparation 24 is preced with to the large ring 1 of 8 main body and 0.07g (0.1mmol) Bisheteroarylethene object 2PF
6be dissolved in respectively in above-mentioned 6mL mixed organic solvents;
3) under normal temperature, above-mentioned two kinds of solution are mixed, can make stable pseudorotaxane assembly [12] [PF
6].
This has the rare earth luminous supramolecule device of intelligence of light controllability, for controlling reading and wiping of rare earth metal europium complex characteristic fluorescence, method is: utilize UV-light 365nm and near infrared light 614nm to irradiate this supramolecule device circulation, can realize cancellation and the recovery of Rare Earth Europium characteristic fluorescence.
The detection analysis of the spectra overlapping that Subjective and Objective generation fluorescence resonance energy transmits:
Fig. 3 is pseudorotaxane [12] [PF
6] nuclear magnetic spectrogram, in figure, show: Subjective and Objective is with 1:1 mixed in molar ratio together time, the methylene radical charateristic avsorption band on object to low mobile, show that the large ring of guest molecule and main body has formed pseudorotaxane [12] [PF
6], thereby make to occur that fluorescence resonance energy transmittance process can occur between Subjective and Objective in distance, provide condition.Fluorescence resonance energy transmittance process also need the fluorescent emission spectrogram of donor and the ultra-violet absorption spectrum of acceptor overlapping.
Fig. 4 is that 24 hats 8 of rare earth metal europium complex encircle greatly 1 fluorescent emission spectrogram and irradiate Bisheteroarylethene object 2PF by UV-light (365nm)
6uV, visible light Change of absorption spectrogram, shows in figure: the ultraviolet-visible absorption spectroscopy after object photoresponse and the fluorescence emission spectrum of main body have extraordinary overlapping.
The light-operated property research of this supramolecule device:
With UV-light 365nm and near infrared light 614nm circulation, irradiate assembly and can control reading and wiping of rare earth metal europium complex characteristic fluorescence.Fig. 5 is for irradiating pseudorotaxane [12] [PF by UV-light (365nm)
6] the fluorescent emission variation diagram of rare-earth europium before and after different time, in figure, show: when constantly irradiate pseudorotaxane [12] [PF with UV-light 365nm
6], europium complex characteristic fluorescence peak intensity constantly declines, and this is that variation has occurred guest molecule structure due under light stimulus, thereby there is fluorescence resonance energy transmission with host molecule, has caused fluorescence decline.
Fig. 6 is pseudorotaxane [12] [PF
6] test of light regulation and control resistance to fatigue, in figure, show: with near infrared light 614nm, constantly irradiate pseudorotaxane [12] [PF
6], europium complex characteristic fluorescence peak intensity constantly recovers.With UV-light 365nm, constantly irradiate pseudorotaxane [12] [PF
6], europium complex characteristic fluorescence peak intensity is constantly quencher again, and this process has extraordinary fatigue performance.
Fig. 7 is pseudorotaxane [12] [PF
6] by change in fluorescence figure after K ionic dissociation, in figure, show: after adding potassium ion, pseudorotaxane [12] [PF
6] be dissociated, it is large that the distance between Subjective and Objective becomes, and between Subjective and Objective, fluorescence resonance energy transmission can not occur, and therefore can lock this molecular device with potassium ion.
The significant advantages such as that the rare earth luminous supramolecule devices of this intelligence has is efficient, sensitive, remote controlled, green clean, high resistance to fatigue, have broad application prospects in the nanometer information processing technology and nanometer material with memory field.
Claims (5)
1. the rare earth luminous supramolecule device of intelligence with light controllability, is characterized in that: serve as reasons with the large rings 1 of 24 hat 8 main body and the Bisheteroarylethene object 2PF with light isomery function of rare earth metal europium complex
6mix pseudorotaxane assembly [the 12] [PF forming
6], its chemical formula is C
92h
80euF
21n
5o
15pS
4, its structural formula is:
2. there is as claimed in claim 1 a preparation for the rare earth luminous supramolecule device of intelligence of light controllability, it is characterized in that step is as follows:
1) by chloroform and acetonitrile by volume for 1:1 mixes, obtain mixed organic solvents;
2) under normal temperature, 24 hats 8 of preparation are encircled greatly to Rare Earth Europium Complex 1 and Bisheteroarylethene object 2PF
6be dissolved in respectively in above-mentioned mixed organic solvents, with the large ring Rare Earth Europium Complex 1 of 24 hat 8 and Bisheteroarylethene object 2PF
6be 1 mmole/50-80mL with the amount ratio of mixed organic solvents;
3) under normal temperature, above-mentioned two kinds of solution are mixed, with the large ring Rare Earth Europium Complex 1 of 24 hat 8 and Bisheteroarylethene object 2PF
6mol ratio be 1:1, can make stable pseudorotaxane assembly [12] [PF
6].
3. there is according to claim 2 the preparation of the rare earth luminous supramolecule device of intelligence of light controllability, it is characterized in that: the synthetic method of the large ring 1 of described 24 hat 8 main body, step is as follows:
1) ammoniacal liquor that is 29.3% by 2-acetopyridine, 4-formyl radical benzo 24 hats 8, KOH and mass concentration in molar ratio 2:0.7:4:4 adds in dry ethanol, at N
2under protection vigorous stirring, remain at 35 ℃ of temperature and react 72 hours, after completion of the reaction, cool to room temperature, suction filtration, uses washing with alcohol filter cake, the CH that is 2:1 in volume ratio by thick product
2cl
2in-water mixed liquid, distribute, water is used CH again
2cl
2washed twice, merges organic phase, and with ethyl alcohol recrystallization, obtaining white solid is terpyridyl benzo 24 hats 8;
2) by [Eu (tta)
3] .3H
2o and terpyridyl benzo 24 hats 8 in molar ratio 1:1 join in dry tetrahydrofuran (THF), [Eu (tta)
3] .3H
2o and terpyridyl benzo 24 hats 8 are 0.2mmol/30-60mL with the amount ratio of tetrahydrofuran (THF), at N
2under protection vigorous stirring, react 4 hours, after completion of the reaction, revolve desolventizing, with ether and normal hexane, carry out recrystallization, obtain yellow solid and be the large ring 1 of 24 hat 8 main body.
4. there is according to claim 2 the preparation of the rare earth luminous supramolecule device of intelligence of light controllability, it is characterized in that: described Bisheteroarylethene object 2PF
6synthetic method, step is as follows:
1) the bromo-2-thiotolene of 3-acetal is dissolved in anhydrous tetrahydro furan, the amount ratio of 3-bromo-2-thiotolene acetal and anhydrous tetrahydro furan is 12mmol/40-60ml, magnetic stirs,-78 ℃, the nitrogen protection emitter of making a bet adds n-Butyl Lithium, react after half an hour, after reaction solution being cooled to-95 ℃, add 1-(1, 2-dimethyl-5-anisole indyl) tetrahydrofuran solution of seven fluorine cyclopentenes, amount ratio is 12mmol/20-60ml, the bromo-2-thiotolene of 3-acetal, n-Butyl Lithium and 1-(1, 2-dimethyl-5-anisole indyl) mol ratio of seven fluorine cyclopentenes is 12:15.6:12, reaction remained at-78 ℃ after 2 hours, be warming up to room temperature standing 8 hours, then add saturated NH
4cl solution, be extracted with ethyl acetate, be spin-dried for, add methylene dichloride to dissolve, splash into mass concentration and be 10% rare HCl and tosic acid, under induction stirring, heat 40 ℃ of backflows, therebetween with the carrying out of TLC detection reaction, question response object point stops after disappearing refluxing, be cooled to 20 ℃, with saturated aqueous common salt and washing until water layer is colourless, collect organic phase, with anhydrous magnesium sulfate drying, filter, revolve to steam and remove methylene dichloride, obtain light green solid, with methylene dichloride, dissolve this solid, the column chromatography for separation that is 12:1 by the volume ratio of sherwood oil and ethyl acetate, collect green portion, revolve and steam except desolventizing, add methylene dichloride to dissolve, under stirring, add sherwood oil until no longer include precipitation generation, suction filtration is to dry, obtaining white crystal is Bisheteroarylethene aldehyde,
2) by Et
3n, MgSO
4, benzylamine and Bisheteroarylethene aldehyde in molar ratio 4:1:1.2:1 join in methyl alcohol, Et
3the amount ratio of N and methyl alcohol is 4mmol/50-70mL, at N
2under 70 ℃ of backflows of the lower heating of protection, react 6 hours, be cooled to 0 ℃, divide and in 30 minutes, add NaBH four times
4, Bisheteroarylethene aldehyde and NaBH
4mol ratio be 1:16, continue reaction 2-4 hour, add water termination reaction, with acetic acid ethyl ester, extract and product, merge organic phase, wash with water, then the HCl that is 0.5N by concentration by product, the form with hydrochloride extracts into water, with chloroform, again extract and product, merge organic phase, through anhydrous MgSO
4dry, removal of solvent under reduced pressure, obtaining colorless oil is Bisheteroarylethene amine;
3) Bisheteroarylethene amine is dissolved in methyl alcohol, the amount ratio of Bisheteroarylethene amine and methyl alcohol is 0.8mmol/40-60mL, and then dripping mass concentration is 10% rare HCl, regulating pH value is 2, continues to stir 4-6h, is spin-dried for solvent, gained solid is added in acetone, drip saturated NH
4pF
6the aqueous solution, until solution clarification continues to stir 3h, is spin-dried for, then adds water to stir 5h, and suction filtration, then washes with water, obtains white solid after dry and is and has light isomery function Bisheteroarylethene object 2PF
6.
5. an application as claimed in claim 1 with the rare earth luminous supramolecule device of intelligence of light controllability, it is characterized in that: for controlling reading and wiping of rare earth metal europium complex characteristic fluorescence, method is: utilize UV-light 365nm and near infrared light 614nm to irradiate this supramolecule device circulation, can realize cancellation and the recovery of Rare Earth Europium characteristic fluorescence.
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