CN101671343A - Double plug-and-socket supermolecular device with function of molecular keyboard lock and preparation thereof - Google Patents
Double plug-and-socket supermolecular device with function of molecular keyboard lock and preparation thereof Download PDFInfo
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Abstract
The invention provides a method for preparing a double plug-and-socket supermolecular device with function of a molecular keyboard lock. A donor anthryl bridge double crownether 1 and an acceptor naphthyl diimide bridged two-site object 2-2H.2PF6 can form stable pseudorotaxane through a mode of polyvalent bonding, and the formation and disassociation of a pseudorotaxane system can be realized through acid-alkali regulation and control; the reversible process is accompanied by solution color change and fluorescence change, and the plug-and-socket molecular device is controllable. The pseudorotaxane system not only can prevent anthryl groups in the double crownether from being influenced by photooxidation reaction, but also can be used as a logic functional device, i.e. a molecular keyboardlock; and the double plug-and-socket supermolecular device has wide application prospect in the technical fields of nanometer robots and nanometer information treatment.
Description
[technical field]
The invention belongs to molecular device and molecular switch technical field.Particularly a kind of dibit point object 2-2H2PF by electron rich (D) anthracene bridging double comb ether 1 and electron deficiency (A) benzene-naphthalene diimide bridging
6Double plug-socket supramolecule preparation of devices method of forming.
[background technology]
In recent years, the research of molecular device and molecule machine has attracted chemists' extensive attention.To the simulation of biological machine molecule basic function in various physical mechanical devices of macroscopic and the life system, allow people that the intellectuality life in future has been full of yearning on the molecule rank, the chemist that more lets on wherein is extremely excited.On basis to nature and the study of macroscopical machine works mechanism, chemists have successfully constructed functional devices such as molecular switch, molecule tweezers, molecule shuttle, molecular motor, molecule elevator, molecule valve, molecule automobile, molecule muscle, and molecule arithmetic processor now.Wherein other information processing device of molecular level is particularly noticeable.
Molecule assembling can couple together each functional module, realizes assembly with specific function, and can also control the relative orientation of each functional molecular, realizes electronics or the optical property optimized.Yet overstable host-guest interaction also is not easy to obtain.The multivalence that extensively exists in the life system interacts, and can strengthen the bonding stability of Subjective and Objective, has caused supermolecular scholar's extensive attention.Multivalence interaction phenomenon is that the biochemist finds in the process of research carbohydrate-protein interaction, and the back is incorporated among the design of supramolecule Subjective and Objective by the supermolecular scholar.Multivalence interacts more weak supramolecule to be interacted and amplifies, the bonding of multivalence pattern has less dissociation constant, it can make assembly have the stability of similar mechanical internal lock molecule, and has a characteristic of dynamic exchange, can also take place under particular stimulation that reversible dissociates and bonding, be the defect mode that is used to make up molecular device.In recent years, multivalence interacts and constantly is applied to the structure of supramolecule assembling, molecular device and molecule machine, the aspects such as modification of unit molecule nano thin-film.Loosely connected different with each binding site in the biological multivalence system, in supramolecule multivalence system, the connection between each binding site can be regulated by artificial.In order to obtain more stable super-molecule assembling body, except the valence state by the effect of increase multivalence, the pre-organized property in complementarity between the Subjective and Objective and space also is very important, has stronger affinity between the well-designed rigidity multivalence Subjective and Objective.Yet the complementarity between this rigidity Subjective and Objective may need to be accurate to below the atomic level, is difficult to artificial arbitrarily control.But by the optimization to the Subjective and Objective structure, we still can improve the bond strength between the Subjective and Objective, and this is that living things system institute is unallowed.
Since finding that dibenzo 24 hats 8 (DB24C8) can form assembly with secondary ammonium salt positively charged ion, DB24C8 is obtaining extensive studies because of its symmetry and modifiability aspect the supramolecule self-assembly, and DB24C8 and the cationic Subjective and Objective of secondary ammonium salt are to also becoming the important building block that makes up various molecular devices.On the basis of unit point DB24C8 research, chemists also tend to rigid backbone a plurality of DB24C8 be coupled together, the spatial orientation of the big ring of control crown ether perhaps forms rigid cage shape molecule to adapt to the guest molecule of special shape to obtain special topological framework.The combination in a plurality of crown ethers site has strengthened binding ability undoubtedly, has expanded the structural performance of DB24C8.The intramolecular multivalence of main generation interacts between the object of multidigit point DB24C8 and multidigit point, and Gibson etc. then interact by the length inhibition multivalence that increases flexible chain between the site and make its formation supermolecule polymer.In contrast, between three crown ethers of the rigidity bridging that Stoddart etc. make up and the multidigit point object of rigidity bridging, then formed overstable mixture, they have also made up a molecule elevator that soda acid is controlled on this basis.This shows that the multivalence that can regulate between the Subjective and Objective by the hard and soft property of chain between the regulation and control multivalence Subjective and Objective site interacts, thereby can be used for the regulation and control of molecular device based on this.
[summary of the invention]
The present invention aims to provide a kind of double plug-socket supramolecule device with molecule keyboard lock function and preparation method thereof.We design the benzene-naphthalene diimide bridging dibit point object 2-2H2PF that has synthesized an electron rich (D) anthracene bridging double comb ether 1 and electron deficiency (A)
6, find to form between them stable multivalence mixture standard [3] rotaxane.This assembly not only can protect anthryl group not to be subjected to the influence of photooxidation reaction, but also has the logic function of molecule keypad lock.
For realizing purpose of the present invention, the invention discloses the synthetic method of the double comb ether 1 of anthracene bridging, its chemical formula is C
55H
74O
16, it is characterized in that its synthetic route is as follows:
Synthesis step is as follows:
(1) 1,2-dimethoxy benzene and 1: 2 in molar ratio chloroformic solution of butyraldehyde are added drop-wise in the sulphuric acid soln of 300mL 84%; Under vigorous stirring, continue reaction 3-5 hour; After reaction finishes, reaction solution is poured in the mixture of ice and water, cooling with the strong aqua neutralization, is used CH then
2Cl
2Aqueous phase extracted merges organic phase, uses anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure obtains brown solid; Use the amount of ethyl acetate recrystallization, with a small amount of glacial acetic acid ethyl ester washing leaching cake, getting faint yellow solid after the drying is compound 6;
(2) compound 6 and Bu4NBr were added in the HBr solution of 150-200mL 40% N in 20: 1 in molar ratio
2Back flow reaction is 2 days under the protection; Reaction solution is poured in the mixture of ice and water, suction filtration, washing joins CH behind the filtration cakes torrefaction
2Cl
2In, suction filtration is used the Glacial acetic acid recrystallization, and obtaining the brown-green solid is compound 7;
(3) tetrahydrofuran solution (80mL) and the 1.1 normal NaOH aqueous solution (80mL) with Triethylene glycol mix, under the ice bath mechanical stirring, tetrahydrofuran (THF) (160mL) solution of 1 normal Tosyl chloride is dropwise added above-mentioned reaction solution in 3 hours, under condition of ice bath, continue reaction 5 hours; Revolve to steam and remove tetrahydrofuran (THF), to the water that wherein adds about 50mL, use the ethyl acetate extraction water layer again, merge organic phase, use anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure; The thick product that obtains is joined 500mL methyl alcohol, be heated to backflow, be cooled to 0 ℃ then, suction filtration, filter cake obtain compound 10 after with recrystallizing methanol;
(4) with pyrocatechol, 10 and K
2CO
3Added in the exsiccant acetonitrile, in 1: 2.1: 4.2 in molar ratio at N
2Under the protection vigorous stirring, reflux 3 days; After reaction finishes, be cooled to room temperature, suction filtration is used CH
2Cl
2Washing leaching cake, merging filtrate is spin-dried for, with thick product at CH
2Cl
2/ H
2Distribute among the O, water is used CH again
2Cl
2Washed twice merges organic phase, uses anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure; Cross silicagel column (SiO
2, ethyl acetate: methyl alcohol=20: 1), collect the 3rd point, obtaining opaque thickness oily matter is compound 9;
(5) compound 9 is dissolved in the 45mL tetrahydrofuran (THF), the aqueous solution (45mL) that adds 4 normal NaOH, under abundant ice bath intense agitation, in 3 hours, dropwise add tetrahydrofuran (THF) (160mL) solution of 2 normal Tosyl chlorides in the above-mentioned reaction solution; Continue reaction 8-10 hour, revolve to steam and remove tetrahydrofuran (THF), use CH
2Cl
2Aqueous layer extracted merges organic phase, uses anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure; Cross silicagel column (SiO
2, ethyl acetate: sherwood oil=2: 1), obtaining faint yellow opaque thickness oily matter is compound 8;
(6) with 10 equivalent Cs
2CO
3Join in the round-bottomed flask with anhydrous acetonitrile, the 200mL anhydrous acetonitrile of 1 equivalent 7 and 2 equivalents 8 places dropping funnel, under intense agitation anhydrous acetonitrile is heated to backflow then; Solution in the dropping funnel was dropwise splashed into round-bottomed flask in 48 hours; N
2Protection continues reaction 3 days down; Be cooled to room temperature, suction filtration; Cross silicagel column (SiO
2, CH2Cl
2/ CH
3OH), collect the point that fluorescence is arranged; CHCl then
3/ Virahol recrystallization, with the small amount of methanol washing, obtaining the faint yellow solid powder after the drying is double comb ether 1 again.
The invention discloses the dibit point object 2-2H2PF of the benzene-naphthalene diimide bridging of electron deficiency (A)
6Synthetic method, its chemical formula is C
32H
30F
12N
4O
6P
2, it is characterized in that its synthetic route is as follows:
Synthesis step is as follows:
(1) under the ice bath intense agitation, with the two carbonic anhydrides ((Boc) of di-t-butyl
2O) chloroformic solution dropwise added in the chloroformic solution of 10 normal propylene diamine in 3 hours; Reaction solution at room temperature continued to stir 16 hours, washed the organic phase anhydrous Na then with water
2SO
4Drying, removal of solvent under reduced pressure, obtaining colorless oil is compound 3;
(2) with Et
3N, MgSO
4, newly steamed phenyl aldehyde and 31: 3.75: 2.75 in molar ratio: 2.5 join in the methyl alcohol, and stirring at room 4 hours is chilled to-5 ℃, divide four times and added 15 equivalent NaBH in 30 minutes
4, continue reaction 1 hour at-5 ℃, be warming up to 0 ℃ and reacted again 1-3 hour; Add the entry termination reaction, coming together with ethyl acetate product, merges organic phase, washes with water; With 0.5N HCl product is come together into water with the form of hydrochloride, and then neutralize with strong aqua, coming together once more with chloroform product, merges organic phase, through anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure, obtaining colorless oil is compound 4;
(3) trifluoroacetic acid of 15mL is slowly splashed into the CH of 6.4mmol 4
2Cl
2Solution at room temperature continues to stir 12 hours, is spin-dried for, and obtaining oily matter is compound 5;
(4) with 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2 and Et
3N added in the Virahol in 1: 2.25: 3.2 in molar ratio, and reaction is 3 days under the stirring and refluxing, and suction filtration is used washed with isopropyl alcohol, obtains faint yellow solid after the drying; This solid is dissolved in methyl alcohol, and to wherein dripping dense HCl, regulating the pH value is 2, continues to stir 2-4 hour, is spin-dried for solvent then, and the gained solid is added in the acetone, drips saturated NH in this solution
4PF
6The aqueous solution up to the solution clarification, continues to stir 2-4 hour, is spin-dried for, and adds 50mL water again and stirs 5 hours, and suction filtration is used the 50mL water washing again, and obtaining pressed powder after the drying is object 2-2H2PF
6
The dibit point object 2-2H2PF of described anthracene bridging double comb ether 1 and described benzene-naphthalene diimide bridging
6Form double plug-socket supramolecule device with molecule keyboard lock function.
Described double plug-socket supramolecule preparation of devices method under the room temperature, will wait mole an anthracene bridging double comb ether 1 and a 2-2H2PF
6Solution mix and just can obtain stable standard [3] rotaxane assembly, can realize the formation of pseudorotaxane system and dissociate by the soda acid regulation and control.
Described double plug-socket supramolecule device application is in two figure places and three figure place molecule keypad lock.
The invention discloses the preparation method of double plug-socket system that the dibit point object 2-2H2PF6 by the double comb ether 1 of anthracene bridging and benzene-naphthalene diimide bridging forms, with and molecular linkage dish lock function.
The present invention specifically describes as follows:
According to the synthetic route of double comb ether 1, can obtain anthracene double comb ether 1 through the reaction of 6 steps, compound is by the sign of fusing point, nuclear-magnetism and high resolution mass spectrum.
According to benzene-naphthalene diimide bridging dibit point object 2-2H2PF
6Synthetic route, can obtain object 2-2H2PF through 4 step reactions
6, compound is by the sign of fusing point, nuclear-magnetism and high resolution mass spectrum.
Under the room temperature, will wait mole 1 and 2-2H2PF
6Solution mix and just can obtain stable standard [3] rotaxane assembly.Demonstrated the characteristic displacement that tangible assembly forms on the nuclear magnetic spectrogram, then provided the molecular ion peak of assembly on the mass spectrum, occurred on the uv-absorbing spectrogram owing to main body anthryl group (D) and the close mutually charge transfer absorption peak that produces of object benzene-naphthalene diimide group (A), the color of solution is by faint yellow the blackish green of adducts that become of Subjective and Objective self, and significantly quencher takes place fluorescence.This assembly can carry out deprotonation to guest molecule by the adding Tributylamine and dissociate, and trifluoroacetic acid is protonated again later can to form assembly and add.So this standard [3] rotaxane assembly is a controlled double plug-socket device.
The photoxidation addition reaction of anthracene can take place in anthracene bridging double comb ether 1 through the irradiation of daylight in the presence of oxygen in solution state, generate one 9,10 anthracene oxygen adduct, the destruction of causing the anthracene aroma system, the complete quencher of the characteristic fluorescence of anthracene.And 1 and 2-2H2PF
6Standard [3] the rotaxane assembly of forming can protect anthracene that photooxidation reaction does not take place.
This double plug-socket device also has the logic function of molecule keypad lock.Respectively with Tributylamine (B) and visible light (L) as two inputs, this double plug-socket device can be realized the molecule keypad lock of one two figure place.In the input of two different order (BL, LB), BL can quencher [12-2H] 2PF
6Fluorescence, be a correct password input.Ironically, when the password order LB of input error, the fluorescence intensity at 415nm place has increased near one times, this variation can be regarded as a guard signal, be that correct password input causes quenching of fluorescence, wrong password input then can causing fluorescence rises one times, gives the alarm.
On the basis of the molecule keypad lock of above-mentioned two figure places, O
2(O) also can be used as an other input, and trifluoroacetic acid (A) can be used as the interference input of an increase, like this, four input systems (A, B, L and O) just can be constructed three figure place molecule keypad lock of a more complicated safety.Under OBL and BOL input, [12-2H] 2PF
6The pseudorotaxane system is dissociated earlier and is issued third contact of a total solar or lunar eclipse oxidizing reaction in the participation of oxygen, quenching of fluorescence and less than threshold value, and output valve is 0; BLO and LBO input down, the input of oxygen all dissociate and illumination after, so photooxidation reaction can not take place, fluorescence rises and greater than threshold value, output valve is 1; Under LOB and the OLB input, all inputs before pseudorotaxane dissociates of oxygen and illumination, so photooxidation reaction can not take place, fluorescence rises and greater than threshold value, output valve is 1.So having only this two kind of three figure place combination of OBL and BOL is correct input password of this improvement molecule keypad lock, these two independently password can be so that two different people have password separately.And wrong input order, BLO, LBO, LOB, OLB then can cause the fluorescence of system to rise, and trigger the warning function of molecule keypad lock.Above-mentioned molecule keypad lock can also and add acid by heating and realize the function that makes zero, because heating can be so that anthracene oxidation adduct be taken off the structure that oxygen molecule recovers anthracene again, adding acid then can be so that the structure of pseudorotaxane forms again, and therefore, this molecule keypad lock can be reused.
Designed controlled double plug-socket device among the present invention, the mentality of designing novelty, the preparation method is simple, and two figure places of its realization and three-figure molecule keyboard lock function have increased its application aspect the nanometer message handler especially.
[description of drawings]
Fig. 1 double comb ether 1 and benzene-naphthalene diimide dibit point object 2-2H2PF
6Molecular structural formula.
Fig. 2 pseudorotaxane [12-2H] [2PF
6] nuclear magnetic spectrogram.
2 (a) [2-2H] [2PF
6], 2 (b) pseudorotaxane [12-2H] [2PF
6] and nuclear magnetic spectrogram (400MHz, the CDCl of 2 (c) 1
3/ CD
3CN=1: 1,5mM, 298K)
Fig. 3 pseudorotaxane [12-2H] [2PF
6] ESI-MS figure.
Fig. 4 pseudorotaxane [12-2H] [2PF
6] the uv-absorbing spectrogram.
4 (a) 1,4 (b) 2-2H2PF
6, 4 (c) [12-2H] 2PF
6Ultra-violet absorption spectrum (1.5mM)
Fig. 5 pseudorotaxane [12-2H] [2PF
6] nuclear-magnetism of soda acid regulation and control changes spectrogram.
5 (a) [12-2H] 2PF
6, 5 (b) [12-2H] 2PF
6Add 4 equivalents (Bu)
3N, 5 (c) [12-2H] 2PF
6Add 4 equivalents (Bu)
3N and 4 equivalent CF
3The nuclear magnetic spectrogram of COOH (400MHz, CDCl
3/ CD
3CN=1: 1,5mM, 298K)
The synoptic diagram of Fig. 6 double plug-socket device.
Fig. 7 double comb ether 1 and pseudorotaxane [12-2H] [2PF
6] nuclear-magnetism before and after the illumination changes spectrogram.
Before 7 (a), 1 illumination, after 7 (b), 1 illumination, 7 (c) [12-2H] 2PF
6Former and 7 (d) [12-2H] 2PF of illumination
6Nuclear-magnetism before the illumination changes spectrogram (400MHz, CDCl
3/ CD
3CN=1: 1,5mM, 298K)
Fig. 8 double comb ether 1 changes spectrogram with the uv-absorbing of light application time.
The ESI-FTICR mass spectrum of Fig. 9 double comb ether 1 behind radiation of visible light.
Figure 10 pseudorotaxane [12-2H] [2PF
6] add before and after the soda acid and the fluorescent emission spectrogram before and after the illumination
10 (a) 1; 10 (b) [12-2H] 2PF6 visible light is according to front and back, 10 (c) [12-2H] 2PF6 adds 5 equivalents (Bu) 3N, 10 (d) [12-2H] 2PF6 adds 5 equivalents (Bu) 3N and 5 equivalent CF3COOH, 10 (e) [12-2H] 2PF6 adds 5 equivalents (Bu) the 3N fluorescence spectrum figure (CDCl3/CD3CN=1: 1 behind radiation of visible light again, 0.01mM excitation wavelength is 375nm).
Figure 11 two figure places and three figure place molecule keypad lock synoptic diagram.
The molecule keypad lock truth table of 11 (a), two figure places; The molecule keypad lock synoptic diagram of 11 (b), two figure places, three figure place molecule keypad lock synoptic diagram of 11 (c) improvement.
[embodiment]
The present invention is described further below by example:
The anthracene bridging double comb ether 1 that the present invention relates to is synthetic as follows:
(1) compound 6
Under ice bath mechanical stirring condition, (13mL, 100mmol) (20mL, 50mL chloroformic solution 200mmol) is added drop-wise in the sulphuric acid soln of 300mL 84% with butyraldehyde with 1,2-dimethoxy benzene.Under vigorous stirring, continue reaction 5 hours.After reaction finishes, reaction solution is poured in the 500mL mixture of ice and water, cooling with the strong aqua neutralization, is used CH then
2Cl
2(300mL * 3) aqueous phase extracted merges organic phase, uses anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure obtains brown solid.With amount of ethyl acetate (150mL) recrystallization, refrigerator freezes to put and spends the night, suction filtration, with a small amount of glacial acetic acid ethyl ester washing leaching cake, after the drying faint yellow solid (12g, 63%).M.p.238-239℃；
1H?NMR(400MHz，CDCl
3)：δ1.15(t，J＝7.4Hz，6H)，1.81-1.91(m，4H)，3.41(t，J＝7.6Hz，4H)，4.06(s，12H)，7.40(s，4H).
(2) compound 7
With compound 6 (5g, 13mmol) and Bu4NBr (200mg 0.6mmol) adds in the HBr solution of 180mL 40% N
2Back flow reaction is 2 days under the protection.Reaction solution is poured in the 200mL mixture of ice and water, suction filtration, washing joins 100mL CH behind the filtration cakes torrefaction
2Cl
2In, stirring 3 hours, suction filtration is used the Glacial acetic acid recrystallization, obtains brown-green solid (2g, 47%).M.p.＞300℃；
1H?NMR(400MHz，DMSO-d
6)：δ1.10(t，J＝7.3Hz，6H)，1.60-1.72(m，4H)，3.16(t，J＝10Hz，4H)，7.33(s，4H)，9.32(s，-OH，4H).
(3) compound 10
With Triethylene glycol (70mL, 0.52mol) tetrahydrofuran (THF) (80mL) solution and NaOH (22g, 0.55mol) water (80mL) solution join in the round-bottomed flask of 2L, under the ice bath mechanical stirring, with Tosyl chloride (88g, 0.48mol) tetrahydrofuran (THF) (160mL) solution dropwise added above-mentioned reaction solution at 3 hours, under condition of ice bath, continue reaction 5 hours.Revolve to steam and remove tetrahydrofuran (THF),,, merge organic phase, use anhydrous Na with ethyl acetate (250mL * 3) aqueous layer extracted again to the water that wherein adds about 50mL
2SO
4Drying, removal of solvent under reduced pressure.The thick product that obtains is joined 500mL methyl alcohol, be heated to backflow, be cooled to 0 ℃ then, suction filtration, filter cake obtain 10 after with recrystallizing methanol.Filtrate was spin-dried for silicagel column (SiO
2, ethyl acetate: sherwood oil=2: 1), collect second point, product is a faint yellow opaque thickness oily matter (40g, 27%).
(4) compound 9
With pyrocatechol (3.1g, 28mmol), 10 (18.2g, 60mmol), K
2CO
3(16.6g 120mmol) adds in the 200mL exsiccant acetonitrile, at N
2Under the protection vigorous stirring, reflux 3 days.After reaction finishes, be cooled to room temperature, suction filtration is used 100mL CH
2Cl
2Washing leaching cake, merging filtrate is spin-dried for, with thick product at 150mL CH
2Cl
2/ 150mL H
2Distribute among the O, water is used 150mL CH again
2Cl
2Washed twice merges organic phase, uses anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure.Cross silicagel column (SiO
2, ethyl acetate: methyl alcohol=20: 1), collect the 3rd point, obtain opaque thickness oily matter (7.7g, 74%).
(5) compound 8
With 9 (4.87g, 13mmol) be dissolved in the 45mL tetrahydrofuran (THF), add NaOH (2.08g, water 52mmol) (45mL) solution, under abundant ice bath intense agitation, (5.0g, tetrahydrofuran (THF) 26mmol) (160mL) solution dropwise added in the above-mentioned reaction solution at 3 hours with Tosyl chloride.Continue reaction 8-10 hour, revolve to steam and remove tetrahydrofuran (THF), use CH
2Cl
2(150mL * 3) aqueous layer extracted merges organic phase, uses anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure.Cross silicagel column (SiO
2, ethyl acetate: sherwood oil=2: 1), obtain faint yellow opaque thickness oily matter (6.3g, 71%).
(6) double comb ether 1
With Cs
2CO
3(6.6g, 20mmol) and the 150mL anhydrous acetonitrile join in the 500mL round-bottomed flask, (0.65g, 2mmol) (2.7g, 200mL anhydrous acetonitrile 4mmol) places dropping funnel to and 8, purges N in reaction flask with 7
2, under intense agitation, anhydrous acetonitrile is heated to backflow then.Solution in the dropping funnel was dropwise splashed into round-bottomed flask in 48 hours.N
2Protection continues reaction 3 days down.Be cooled to room temperature, suction filtration is used 150mL CH
2Cl
2Washing leaching cake, merging filtrate is spin-dried for.Cross silicagel column (SiO
2, CH2Cl
2/ CH
3OH=100: 1-60: 1), collect the point that fluorescence is arranged.And then at CHCl
3/ Virahol (2: 1) recrystallization with the small amount of methanol washing, obtains faint yellow solid powder (400mg, 20%) again after the drying.M.p，182-184℃；
1H?NMR(400MHz，CDCl
3)：δ1.10(t，J＝7.2Hz，6H)，1.74-1.83(m，4H)，3.33(t，J＝7.2Hz，4H)，3.84-3.95(m，24H)，4.03-4.05(m，8H)，4.14-4.16(m，8H)，4.30-4.32(m，8H)，6.85-6.86(m，8H)，7.36(s，4H).
13C?NMR(400MHz，CDCl
3)：δ15.1，23.9，30.9，69.3，69.6，70.0，70.2，71.5，71.6，104.7，114.2，121.6，125.8，129.6，148.5，149.1；HRMS(ESI)calcd?for?C55H74O16Na：1025.4869；found：1025.4862.
The dibit point object 2-2H2PF of the benzene-naphthalene diimide bridging of the electron deficiency that the present invention relates to (A)
6Synthetic as follows:
(1) compound 3
Under the ice bath intense agitation, with the two carbonic anhydrides ((Boc) of 0.05mol di-t-butyl
2O) chloroform (250mL) solution dropwise added the chloroform (500mL) of 0.5mol propylene diamine in 3 hours.Reaction solution at room temperature continued to stir 16 hours, water (250mL * 8) washing then, organic phase anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure obtains colorless oil.
(2) compound 4
With Et
3N (2.8mL, 20mmol), MgSO
4(9g, 75mmol), (5.8mL 55mmol) joins in the 60mL methyl alcohol with 50mmol 3, and stirring at room 4 hours is chilled to-5 ℃, divides four times at 30min adding NaBH newly to steam phenyl aldehyde
4(11.34g 300mmol), continues reaction 1 hour at-5 ℃, is warming up to 0 ℃ and reacts 1 hour again.Add 200mL water termination reaction, coming together with ethyl acetate (200mL * 3) product, merges organic phase, water (100mL * 4) washing.Use 0.5N HCl (100mL * 4) that product is come together into water with the form of hydrochloride again, and then neutralize with strong aqua, coming together once more with chloroform (100mL * 3) product, merges organic phase, through anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure obtains colorless oil.
(3) compound 5
The trifluoroacetic acid of 15mL is slowly splashed into the CH of 6.4mmol 4
2Cl
2(15mL) solution at room temperature continues to stir 12 hours, is spin-dried for, and obtains oily matter.
(4) object 2-2H2PF
6
With 1,4,5, and 8-naphthalene tetracarboxylic dianhydride (536mg, 2mmol), 2 (4.5mmol) and Et
3(18mL 7mmol) adds the 40mL Virahol to N, and reaction is 3 days under the stirring and refluxing, and suction filtration with Virahol (15mL) washing, obtains faint yellow solid after the drying.This solid is dissolved in 40mL methyl alcohol, and to wherein dripping dense HCl, regulating the pH value is 2, continues to stir 4 hours, is spin-dried for solvent then, and the gained solid is added in the 30mL acetone, drips saturated NH in this solution
4PF
6The aqueous solution up to the solution clarification, continues to stir 3 hours, is spin-dried for, and adds 50mL water again and stirs 5 hours, and suction filtration is used the 50mL water washing again, obtains pressed powder after the drying.2-2H2PF
6: faint yellow solid (800mg, 47%).M.p.＞236℃(decomposition)；
1H?NMR(400MHz，CDCl
3)：δ2.10-2.20(m，4H)，3.13(t，J＝6.4Hz，4H)，4.20(s，4H)，4.22(t，J＝6.4Hz，4H)，7.44-7.54(m，10H)，8.73(s，4H).
13C?NMR(400MHz，CD
3CN)：δ25.2，38.0，46.2，52.7，127.6，127.7，130.1，130.8，131.0，131.4，131.8，164.7.HRMS(ESI)calcd?for?C34H34F6N4O6P：707.2216；found：707.2210.
Double plug-socket supramolecule preparation of devices
Under the room temperature, will wait mole 1 and 2-2H2PF
6Solution mix and just can obtain stable standard [3] rotaxane assembly.First evidence that forms overstable adducts comes from 1 and 2-2H2PF
6ESI-MS data (see figure 3) Deng the mole mixing solutions.For 1+2-2H2PF
6Solution, we observe a very strong molecular ion peak 782.6, corresponding to [1+2-2H]
2+, the peak of other ionic species is relatively all more weak by force.This explanation 1 and 2-2H2PF
6Between formed overstable adducts, and the stability of this adducts is enough to withstand the test of electro-spray ionization.
Further the result of ESI-MS has been supported in nuclear-magnetism research.1+2-2H2PF
6The one dimension nuclear magnetic spectrogram of (1: 1) is all very simple, and more clear (see figure 2) between the spectrum peak.With the contrast of Subjective and Objective self nuclear magnetic spectrogram, do not find free Subjective and Objective species, formed 1: 1 very strong adducts between this explanation Subjective and Objective.According to accordingly
1H-
1H COSY nuclear magnetic spectrum, we are to adducts [12-2H] 2PF
6The one dimension nuclear magnetic spectrogram carried out detailed ownership.At first, in two adductss, the H on the benzene-naphthalene diimide
jWith the H on the anthracene
fTo High-Field tangible displacement has taken place all, and H on the propyl group
gAlso to low field displacement having taken place, had pi-pi accumulation between this explanation naphthalene and the anthracene, makes the other side's proton be in the shadow zone of self.In addition, with NH
2 +The methene proton H that links to each other
mAnd H
wAnd the methene proton H that links to each other with imide N
kTo High-Field bigger displacement has taken place all; Obvious variation has also all taken place in the methene proton on the crown ether cycle.All these results show 1 and 2-2H2PF
6Between formed overstable pseudorotaxane.Further evidence also comprises, the color of solution is by faint yellow the blackish green of adducts that become of Subjective and Objective self, a tangible charge transfer (CT) absorption peak has appearred in (Fig. 4) adducts on the UV spectrum at the 640nm place, has proved the existence of charge transfer effect between mutual close anthracene and benzene-naphthalene diimide (D-A) group.So, 1 and 2-2H2PF
6Form the motivating force stablize pseudorotaxane and be mainly pi-pi accumulation and charge transfer interaction between hydrogen bond action, anthracene and the benzene-naphthalene diimide between secondary ammonium salt and the crown ether cycle.
Acid-base reaction can be used for controlling the assembly of DB24C8 and secondary ammonium salt, and can also be used to control various molecular devices and make the motion of its reversible.In system of the present invention, can control the formation of assembling and dissociate with soda acid equally.As shown in Figure 5, to equal proportion adducts [12-2H] 2PF
6Solution in, add 4 times (Bu)
3N can make assembly dissociate fully, presents free double comb ether and free and takes off the characteristic peak of the object of proton.The CF that in this solution, adds 4 times again
3COOH, the characteristic peak of assembly has been resumed again.Thereby CF
3COOH and (Bu)
3The acid base pair that N forms can be controlled dissociating of assembly by reversible, and can realize the reversible adjusting of corresponding function.
In sum, we can think [12-2H] 2PF
6The pseudorotaxane system is a good double plug-socket device (Fig. 6), the object 2-2H2PF of dibit point
6As plug, double comb ether 1 can be realized reversible plug function by the soda acid regulation and control between the two, and also be accompanied by electronic transfer process under the excited state as socket.
The photooxidation reaction of anthracene double comb ether 1
Under illumination condition, photooxidation reaction can take place in the anthracene in the anthracene double comb ether 1.ESI-FTICR mass spectrum (Fig. 9) has provided the direct evidence of oxidation adduct, solution state 1 after rayed, mass spectrum has provided a series of quasi-molecular ions m/z1036,1052,1057 and 1073, corresponds respectively to species [1O
2+ H]
+, [1O
2+ NH
4]
+, [1O
2+ Na]
+[1O
2+ K]
+(see figure 8) on the ultra-violet absorption spectrum, along with the continuous increase of light application time, the characteristic absorbance of anthracene also fades away, and absorption peak is to the displacement of short wavelength's direction, and takes up more partially absorbing of long wavelength, shows as solution colour and deepens.These aromatic structures that all show anthracene under solar light irradiation are destroyed.But as double comb ether 1 and 2-2H2PF
6Formed after the overstable pseudorotaxane, the anthracene in 1 is just no longer responsive to light.With overstable assembly [12-2H] 2PF
6Shine under identical ultraviolet light conditions with independent 1, adopt nuclear-magnetism as monitoring means (as shown in Figure 7), we find that independent 1 is all oxidized, the H of anthracene characteristic peak
fAnd H
gAll disappear from spectrogram, solution colour is also deepened gradually.And for assembly [12-2H] 2PF
6, nuclear-magnetism and solution colour are all without any variation.Thereby the structure of benzene-naphthalene diimide can protect the anthracene unit on the double comb ether not influenced by photooxidation reaction well.So, 2-2H2PF
6Can be used as the shielding device of anthracene double comb ether 1 photooxidation reaction.
The realization of molecule keyboard lock function
For above-mentioned [12-2H] 2PF
6The pseudorotaxane system, the adding Tributylamine takes off object after the proton, and free 1 anthracene characteristic fluorescence strengthens, and illumination subsequently issues third contact of a total solar or lunar eclipse oxidizing reaction, causes the quenching of fluorescence (Figure 10) of anthracene.We are the logical gate that specific function can be realized in the basis with this change in fluorescence process.With alkali [(Bu)
3N] and visible light as input, as output, fluorescence intensity 100 is made as threshold value to anthracene double comb ether 1, just can realize a NAND logical gate by different inputs in the fluorescent emission at 415nm place.This NAND logic function is by different input styles and input order decision.When without any when input, pseudorotaxane does not dissociate photooxidation reaction does not take place yet, and fluorescence intensity is greater than threshold value, output valve is 1 (Figure 10-b); When independent input alkali, pseudorotaxane dissociates, and the fluorescence intensity of anthracene strengthens and greater than threshold value, output valve is 1 (Figure 10-c); When independent input visible light, pseudorotaxane does not dissociate photooxidation reaction does not take place yet, and fluorescence intensity is constant and greater than threshold value, output valve is 1 (Figure 10-b); When importing visible light in the ban and importing alkali again, but pseudorotaxane dissociates photooxidation reaction does not take place, and the fluorescence intensity of anthracene strengthens and greater than threshold value, output valve is 1 (Figure 10-c); When importing alkali in the ban and importing visible light again, pseudorotaxane dissociates earlier the photooxidation reaction of anthracene takes place subsequently, the quenching of fluorescence of anthracene and less than threshold value, output valve are 0 (Figure 10-e).The NAND logical gate of this specific input order can further be regarded the molecule keypad lock of one two figure place as, and two inputs are respectively alkali (B) and light (L).In the input of two different order (BL, LB), BL can quencher [12-2H] 2PF
6Fluorescence, be a correct password input.Ironically, when the password order LB of input error, the fluorescence intensity at 415nm place has increased near one times, this variation can be regarded as a guard signal, be that correct password input causes quenching of fluorescence, wrong password input then can causing fluorescence rises one times, gives the alarm.The truth table of this two figure places molecule keypad lock and synoptic diagram are as shown in figure 11.
O
2Be indispensable in a photo-oxidation process condition, and can whether control photoxidation x reaction by the degasification of solution system.So, O
2(O) also can see an other input as.And trifluoroacetic acid (A) can be used as the interference input of an increase, and like this, four input systems (A, B, L and O) just can be constructed three figure place molecule keypad lock of a more complicated safety.Under OBL and BOL input, [12-2H] 2PF
6The pseudorotaxane system is dissociated earlier and is issued third contact of a total solar or lunar eclipse oxidizing reaction in the participation of oxygen, quenching of fluorescence and less than threshold value, and output valve is 0; BLO and LBO input down, the input of oxygen all dissociate and illumination after, so photooxidation reaction can not take place, fluorescence rises and greater than threshold value, output valve is 1; Under LOB and the OLB input, all inputs before pseudorotaxane dissociates of oxygen and illumination, so photooxidation reaction can not take place, fluorescence rises and greater than threshold value, output valve is 1.So having only this two kind of three figure place combination of OBL and BOL is correct input password of this improvement molecule keypad lock, these two independently password can be so that two different people have password separately.And wrong input order, BLO, LBO, LOB, OLB then can cause the fluorescence of system to rise, and trigger the warning function of molecule keypad lock.Above-mentioned molecule keypad lock can also and add acid by heating and realize the function that makes zero, because heating can be so that anthracene oxidation adduct be taken off the structure that oxygen molecule recovers anthracene again, adding acid then can be so that the structure of pseudorotaxane forms again, and therefore, this molecule keypad lock can be reused.
Claims (5)
1, a kind of preparation method of anthracene bridging double comb ether is characterized in that its synthetic route is as follows:
Synthesis step is as follows:
(1) 1,2-dimethoxy benzene and 1: 2 in molar ratio chloroformic solution of butyraldehyde are added drop-wise in the sulphuric acid soln of 300mL 84%; Under vigorous stirring, continue reaction 3-5 hour; After reaction finishes, reaction solution is poured in the mixture of ice and water, cooling with the strong aqua neutralization, is used CH then
2Cl
2Aqueous phase extracted merges organic phase, uses anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure obtains brown solid; Use the amount of ethyl acetate recrystallization, with a small amount of glacial acetic acid ethyl ester washing leaching cake, getting faint yellow solid after the drying is compound 6;
(2) compound 6 and Bu4NBr were added in the HBr solution of 150-200mL 40% N in 20: 1 in molar ratio
2Back flow reaction is 2 days under the protection; Reaction solution is poured in the mixture of ice and water, suction filtration, washing joins CH behind the filtration cakes torrefaction
2Cl
2In, suction filtration is used the Glacial acetic acid recrystallization, and obtaining the brown-green solid is compound 7;
(3) tetrahydrofuran solution 80mL and the 1.1 normal NaOH aqueous solution 80mL with Triethylene glycol mix, under the ice bath mechanical stirring, the tetrahydrofuran solution 160mL of 1 normal Tosyl chloride is dropwise added above-mentioned reaction solution in 3 hours, under condition of ice bath, continue reaction 5 hours; Revolve to steam and remove tetrahydrofuran (THF), to the water that wherein adds about 50mL, use the ethyl acetate extraction water layer again, merge organic phase, use anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure; The thick product that obtains is joined 500mL methyl alcohol, be heated to backflow, be cooled to 0 ℃ then, suction filtration, filter cake obtain compound 10 after with recrystallizing methanol;
(4) with pyrocatechol, 10 and K
2CO
3Added in the exsiccant acetonitrile, in 1: 2.1: 4.2 in molar ratio at N
2Under the protection vigorous stirring, reflux 3 days; After reaction finishes, be cooled to room temperature, suction filtration is used CH
2Cl
2Washing leaching cake, merging filtrate is spin-dried for, with thick product at CH
2Cl
2/ H
2Distribute among the O, water is used CH again
2Cl
2Washed twice merges organic phase, uses anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure; Cross silicagel column (SiO
2, ethyl acetate: methyl alcohol=20: 1), collect the 3rd point, obtaining opaque thickness oily matter is compound 9;
(5) compound 9 is dissolved in the 45mL tetrahydrofuran (THF), adds the aqueous solution 45mL of 4 normal NaOH, under abundant ice bath intense agitation, in 3 hours, dropwise add the tetrahydrofuran (THF) 160mL solution of 2 normal Tosyl chlorides in the above-mentioned reaction solution; Continue reaction 8-10 hour, revolve to steam and remove tetrahydrofuran (THF), use CH
2Cl
2Aqueous layer extracted merges organic phase, uses anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure; Cross silicagel column (SiO
2, ethyl acetate: sherwood oil=2: 1), obtaining faint yellow opaque thickness oily matter is compound 8;
(6) with 10 equivalent Cs
2CO
3Join in the round-bottomed flask with anhydrous acetonitrile, the 200mL anhydrous acetonitrile of 1 equivalent compound 7 and 2 equivalent compounds 8 places dropping funnel, under intense agitation anhydrous acetonitrile is heated to backflow then; Solution in the dropping funnel was dropwise splashed into round-bottomed flask in 48 hours; N
2Protection continues reaction 3 days down; Be cooled to room temperature, suction filtration; Cross silicagel column (SiO
2, CH2Cl
2/ CH
3OH), collect the point that fluorescence is arranged; CHCl then
3/ Virahol recrystallization, with the small amount of methanol washing, obtaining the faint yellow solid powder after the drying is double comb ether 1 again.
2, a kind of dibit point object 2-2H2PF of benzene-naphthalene diimide bridging
6The preparation method, it is characterized in that its synthetic route is as follows:
Synthesis step is as follows:
(1) under the ice bath intense agitation, with the two carbonic anhydrides (Boc) of di-t-butyl
2The chloroformic solution of O dropwise added in the chloroformic solution of 10 normal propylene diamine in 3 hours; Reaction solution at room temperature continued to stir 16 hours, washed the organic phase anhydrous Na then with water
2SO
4Drying, removal of solvent under reduced pressure, obtaining colorless oil is compound 3;
(2) with Et
3N, MgSO
4, newly steamed phenyl aldehyde and 31: 3.75: 2.75 in molar ratio: 2.5 join in the methyl alcohol, and stirring at room 4 hours is chilled to-5 ℃, divide four times and added 15 equivalent NaBH in 30 minutes
4, continue reaction 1 hour at-5 ℃, be warming up to 0 ℃ and reacted again 1-3 hour; Add the entry termination reaction, coming together with ethyl acetate product, merges organic phase, washes with water; With 0.5N HCl product is come together into water with the form of hydrochloride, and then neutralize with strong aqua, coming together once more with chloroform product, merges organic phase, through anhydrous Na
2SO
4Drying, removal of solvent under reduced pressure, obtaining colorless oil is compound 4;
(3) trifluoroacetic acid of 15mL is slowly splashed into the CH of 6.4mmol 4
2Cl
2Solution at room temperature continues to stir 12 hours, is spin-dried for, and obtaining oily matter is compound 5;
(4) with 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2 and Et
3N added in the Virahol in 1: 2.25: 3.2 in molar ratio, and reaction is 3 days under the stirring and refluxing, and suction filtration is used washed with isopropyl alcohol, obtains faint yellow solid after the drying; This solid is dissolved in methyl alcohol, and to wherein dripping dense HCl, regulating the pH value is 2, continues to stir 2-4 hour, is spin-dried for solvent then, and the gained solid is added in the acetone, drips saturated NH in this solution
4PF
6The aqueous solution up to the solution clarification, continues to stir 2-4 hour, is spin-dried for, and adds 50mL water again and stirs 5 hours, and suction filtration is used the 50mL water washing again, and obtaining pressed powder after the drying is object 2-2H2PF6.
3, a kind of dibit point object 2-2H2PF by the described anthracene bridging of claim 1 double comb ether 1 and the described benzene-naphthalene diimide bridging of claim 2
6The double plug with molecule keyboard lock function-socket supramolecule device of forming.
4, the described double plug of a kind of claim 3-socket supramolecule preparation of devices method under the room temperature, will wait mole an anthracene bridging double comb ether 1 and a 2-2H2PF
6Solution mix and just can obtain stable standard [3] rotaxane assembly, can realize the formation of pseudorotaxane system and dissociate by the soda acid regulation and control.
5, the described double plug of a kind of claim 3-socket supramolecule device application is in two figure places and three figure place molecule keypad lock.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153733A (en) * | 2011-01-28 | 2011-08-17 | 华南理工大学 | Supermolecular polymer photoelectric material and application thereof |
| WO2013099224A1 (en) * | 2011-12-27 | 2013-07-04 | 国立大学法人山口大学 | Network polymer and polymer gel electrolyte |
| CN113444079A (en) * | 2021-05-25 | 2021-09-28 | 浙江工业大学 | Rotaxane molecular machine based on crown ether and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102153733A (en) * | 2011-01-28 | 2011-08-17 | 华南理工大学 | Supermolecular polymer photoelectric material and application thereof |
| CN102153733B (en) * | 2011-01-28 | 2012-09-26 | 华南理工大学 | Supermolecular polymer photoelectric material and application thereof |
| WO2013099224A1 (en) * | 2011-12-27 | 2013-07-04 | 国立大学法人山口大学 | Network polymer and polymer gel electrolyte |
| CN113444079A (en) * | 2021-05-25 | 2021-09-28 | 浙江工业大学 | Rotaxane molecular machine based on crown ether and preparation method |
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