CN110698684B - Covalent organic framework material with diarylethene photonic switch and synthetic method and application thereof - Google Patents
Covalent organic framework material with diarylethene photonic switch and synthetic method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of covalent organic framework materials, in particular to a covalent organic framework material with a diarylethene photonic switch, a synthetic method and application thereof. The method comprises the following steps: adding TAPB-BPTA-COF, azido cyclopentene thiophene and a catalyst into a reaction device, adding a solvent, performing degassing treatment, and adding triethylamine; stirring to obtain the product; the azidocyclopentene thiophene is 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-azidomethyl-3-thienyl) cyclopentene. The diaryl alkene post-modified on the covalent organic framework material has two active isomers of open loop and closed loop, can realize reversible conversion under the regulation of light, thereby realizing the light regulation of the size of COF pore diameter, changing COF with large pore diameter into COF with small pore diameter, increasing the contact area and interaction force with small molecule gas, and realizing the absorption and separation of gas small molecules.
Description
Technical Field
The invention relates to the technical field of covalent organic framework materials, in particular to a covalent organic framework material with a diarylethene photonic switch, a synthetic method and application thereof.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Covalent organic framework materials are ordered crystalline porous materials built with light elements (C, N, O, H, B, etc.) covalently linked. The nano-crystalline silicon dioxide has wide application prospect in the aspects of photoelectricity, catalysis, gas storage, energy storage, drug release, treatment and the like due to the high surface area, low density and high thermal stability. For example, patent document 201910464714.0 discloses a method for synthesizing a side chain-modified covalent organic framework compound, in which COFs is synthesized from BPTA, DMA, and TAPB as raw materials, and the COFs is reacted with azide Click to form a side chain-modified covalent organic framework compound. The invention can prepare a novel filling material capable of specifically adsorbing and removing toxic and harmful gases in air by modifying the side chain of the COFs skeleton, and is used for manufacturing military and civil masks with different functions.
Disclosure of Invention
The invention aims to solve and realize the following problems: the preparation method comprises the steps of preparing a crystalline material which can reversibly respond to light, and adjusting the size of the aperture by utilizing reversible change, thereby realizing the adsorption and separation of gas micromolecules. Therefore, the invention provides a covalent organic framework material with a diarylethene photonic switch and a synthetic method thereof.
In order to realize the purpose, the invention discloses the following technical scheme:
firstly, the invention discloses a covalent organic framework material with a diarylene photonic switch, which has a structure shown in a formula (I):
the invention further discloses a preparation method of the covalent organic frame type compound with the diaryl alkene optical molecular switch, which comprises the following steps: adding TAPB-BPTA-COF, azido cyclopentene thiophene and a catalyst into a reaction device, adding a solvent, performing degassing treatment, and adding triethylamine; stirring and reacting to obtain the product; the azidocyclopentene thiophene is 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-azidomethyl-3-thienyl) cyclopentene.
As a further technical scheme, the solvent is anhydrous N, N-dimethylformamide.
As a further technical scheme, the catalyst is cuprous iodide.
As a further technical scheme, the dosage of the catalyst is 0.5 percent of the mass of TAPB-BPTA-COF.
As a further technical scheme, the dosage of the triethylamine is as follows: the volume ratio of the solvent to the triethylamine is 25: 2; the solvent is used in an amount enough to dissolve the azido cyclopentene thiophene.
As a further technical scheme, the mass ratio of the usage amount of the azido cyclopentene thiophene to the TAPB-BPTA-COF is 1: 2.
As a further technical solution, the degassing method comprises: and (3) placing the reaction bottle in liquid nitrogen, freezing the solution, vacuumizing, unfreezing the reaction bottle in an ethanol solution after the solution is frozen, and circulating the steps for 2-4 times.
As a further technical scheme, the reaction time is 48-72 h.
The invention further discloses a covalent organic framework material with the diarylethene photonic switch in a closed ring state, which has a structure shown in a formula (II):
secondly, the invention discloses a preparation method of the covalent organic framework material with the diarylethene photonic switch in the closed ring state, which comprises the following steps: and (2) irradiating the covalent organic framework material (formula (I)) with the diarylethene photonic switch by using an ultraviolet lamp with the wavelength of 365nm to obtain the diarylethene photonic switch-containing covalent organic framework material.
As a further technical scheme, the irradiation time is 10-50 minutes.
Finally, the invention discloses a covalent organic frame type compound with a diarylethene photonic switch and a preparation method thereof, and the covalent organic frame material with the diarylethene photonic switch in a closed ring state and the preparation method thereof are applied to the fields of photoelectricity, catalysis, gas storage, energy storage and the like.
The covalent organic framework material prepared by the invention is characterized in that: the diarylene prepared in the covalent organic framework material has two active isomers of open loop and closed loop, and undergoes photoisomerization, and generates cyclization reaction under the irradiation of an ultraviolet lamp, and the open loop is converted into a closed loop; the ring-opening reaction is carried out under the irradiation of visible light, and the closed ring body is converted into the open ring body, so that the covalent organic framework material has the following characteristics: (1) good thermal stability, (2) excellent fatigue resistance, (3) fast light responsiveness, and (4) high open-closed loop conversion rate.
Compared with the prior art, the invention has the following beneficial effects: the light-responsive diarylethene molecules modified after COF are opened, the aperture is reduced from the original 2.74nm to 1.22nm, the aperture is greatly reduced, the contact area of the gas small molecules and the frame is increased, so that the interaction force between the gas small molecules and the frame is enhanced, the aperture is reduced, the selectivity of the gas small molecules is also increased, reversible open loop and closed loop of diarylethene can be realized through light adjustment, the size and the structure of the diarylethene molecules are changed, the adjustment of the aperture size can be realized, and the selective absorption and separation of the gas small molecules are realized.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a NMR spectrum of azidocyclopentenylthiophene prepared in example 1 of the present invention.
FIG. 2 is a NMR carbon spectrum of azidocyclopentene thiophene prepared in example 1 of the present invention.
Fig. 3 is a diffraction pattern (XRD) of the polycrystalline powders of COF-MQo and COF-MQc prepared in example 3 and example 4, respectively, according to the present invention.
FIG. 4 is a graph of the infrared absorption spectrum of COF-MQo prepared in example 3 of the present invention.
FIG. 5 is a thermogravimetric analysis curve of COF-MQo prepared in example 3 and TAPB-BPTA-COF prepared in example 1 of the present invention.
FIG. 6 is a nitrogen sorption and desorption curve of COF-MQo prepared in example 3 of the present invention.
FIG. 7 shows UV absorption curves of TAPB-BPTA-COF prepared in example 2, COF-MQo prepared in example 3, and COF-MQc prepared in example 4 of the present invention.
FIG. 8 is a graph showing the effect of color change of the conversion of COF-MQo to COF-MQc in example 4 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms also are intended to include the plural forms as well, unless the context clearly indicates otherwise, and it should be further understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
As described above, the conventional covalent organic framework material has the disadvantages of large pore size, inflexibility, small response to external stimuli, weak interaction force with small molecules of gas, mismatched size, and failure to meet the requirements of absorption and separation of small molecules of gas. Therefore, the present invention provides a covalent organic framework material with diarylethene photonic switch and a synthesis method thereof, and the present invention will be further described with reference to the specific embodiments.
Example 1
The synthesis of the azido cyclopentene thiophene comprises the following steps:
(1) synthesis of 5- (5-chloro-2-methylthiophen-3-yl) -5-oxopentanoic acid:
to a solution of 2-chloro-5-methylthiophene (2.0g,15.03mmol) and glutaric anhydride (2.05g,18.03mmol) in dry dichloromethane (40mL) at-5 deg.C was added aluminum (III) chloride (5.0g,37.5mmol) in portions over 30 minutes under a nitrogen atmosphere. The reaction mixture was stirred at 0 ℃ for 2 hours and then at room temperature for 12 hours. Ice was added and the aqueous layer was further extracted with chloroform (3X 25 mL). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, the solvent was removed by distillation under the reduced pressure, and the crude product was purified by silica gel flash column chromatography (ethyl acetate/hexane) to give 5- (5-chloro-2-methylthiophen-3-yl) -5-oxopentanoic acid (3.1g,12.57mmol) in 84% yield in pale green color.
1H NMR(300MHz,CDCl3)：2.02(2H，tt),2.48(2H,t),2.65(3H,s),2.87(2H,t),7.18(1H,s),11.12(1H,s)。
(2) Synthesis of 1- (5-chloro-2-methylthiophen-3-yl) -5- (2, 5-dimethylthien-3-yl) pentane-1, 5-dione:
under a nitrogen atmosphere, oxalyl chloride (15.8g,124.4mmol) and N, N-dimethylformamide (0.12g,1.58mmol) were added to anhydrous dichloroethane (60mL) at 0 deg.C and stirred for five minutes, followed by addition of 5- (5-chloro-2-methylthiophen-3-yl) -5-oxopentanoic acid (3.9g,15.8 mmol). The mixture was slowly warmed to room temperature and stirred for 12 hours, and rotary evaporated to give a black solid residue. The black solid residue and 2, 5-dimethylthiophene (3.5mg,31.6mmol) were added to anhydrous dichloromethane (60mL) under a nitrogen atmosphere and stirred for five minutes. Tin tetrachloride (12.5g,48mmol) was added dropwise at-20 ℃. Slowly warm to room temperature and stir at room temperature for 16 hours. The reaction was quenched with ice, extracted with dichloromethane, washed with salt and dried over anhydrous sodium sulfate. The solvent was removed by distillation under the reduced pressure, and the residue was purified by column chromatography (petroleum ether: ethyl acetate 9:1) to give 1- (5-chloro-2-methylthiophen-3-yl) -5- (2, 5-dimethylthiophen-3-yl) pentane-1, 5-dione (2.6g,7.64mmol) as an off-white needle-like solid intermediate in 48.4% yield.
1H NMR(400MHz,CDCl3,):7.19(1H,s),7.00(1H,s),2.87(4H,dd),2.67(3H,s),2.66(3H,s),2.40(3H,s),2.10–2.03(2H,m)。
(3) Synthesis of 5-chloro-3- (2- (2, 5-dimethylpyridin-3-yl) cyclopent-1-enyl) -2-methylthiophene:
to tetrahydrofuran (15mL) was added zinc powder (510mg,7.85mmol) under a nitrogen atmosphere, stirred for 5 minutes, then titanium tetrachloride (490mg,2.6mmol) was added dropwise, and stirred at room temperature for 1 hour. 1- (5-chloro-2-methylthiophen-3-yl) -5- (2, 5-dimethylthien-3-yl) pentane-1, 5-dione (450mg.1.32mmol) and pyridine (200mg,2.6mmol) were added and refluxed for 9 hours. After the reaction, a few drops of water were added and filtered. The solvent was removed by distillation under the reduced pressure, and the product, 5-chloro-3- (2- (2, 5-dimethylpyridin-3-yl) cyclopent-1-enyl) -2-methylthiophene (356mg,1.16mmol), was purified by column chromatography as a white solid in 88% yield.
1H NMR(400MHz,CDCl3):6.58(1H,s),6.40(1H,s),2.72(4H,dd),2.35(3H,s),2.02–1.99(2H,m),1.89(3H,s),1.85(3H,s)。
(4) Synthesis of 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-aldehydyl-3-thienyl) cyclopentene:
5-chloro-3- (2- (2, 5-dimethylpyridin-3-yl) cyclopent-1-enyl) -2-methylthiophene (1.8g,5.8mmol) was dissolved in anhydrous tetrahydrofuran (50mL) under a nitrogen atmosphere, and n-butyllithium (1.6mol/L in hexane, 7.2mL) was added. After stirring at room temperature for 1 hour, N.N-dimethylformamide (0.9mL) was added, and stirring at room temperature was continued for 1 hour. The reaction was terminated and quenched by addition of 2mol/L hydrochloric acid solution (48 mL). Extraction was performed with diethyl ether, washed with an aqueous solution of sodium bicarbonate, washed with water, and dried over anhydrous sodium sulfate. The solvent was removed by distillation under the reduced pressure, and purification was performed by column chromatography (petroleum ether: ethyl acetate 9:1) to give 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-aldehydimethyl-3-thienyl) cyclopentene (1.5g,4.96mmol) as an orange solid in a yield of 85%.
1HNMR(CDCl3):9.73(1H,s),7.44(1H,s),6.39(1H,s),2.35(3H,s),2.80-2.76(4H,t),2.09-2.02(5H,m),1.85(3H,s)。
(5) Synthesis of 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-hydroxymethyl-3-thienyl) cyclopentene:
1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-aldehydyl-3-thienyl) cyclopentene (0.91mg,3.00mmol) was dissolved in tetrahydrofuran (20mL), and NaBH was added4(0.17g,3.60mmol), the reaction was heated to reflux for 2h, cooled to room temperature and quenched with water (40 mL). Extraction with ethyl acetate, drying of the organic phase over magnesium sulfate, filtration, removal of the solvent by distillation under reduced pressure, and purification by column chromatography (petroleum ether: ethyl acetate 9:1) gave 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-hydroxymethyl-3-thienyl) cyclopentene (0.75mg,2.46mmol) as a pale yellow powder in 82% yield.
2-1HNMR(CDCl3):6.55(1H,s),6.42(1H,s),4.55(2H,s),2.76-2.73(4H,t),2.33(3H,s),2.05-2.00(2H,m),1.98(3H,s),1.85(3H,s)。
(6) Synthesis of 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-azidomethyl-3-thienyl) cyclopentene:
1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-hydroxymethyl-3-thienyl) cyclopentene (0.84g,2.76mmol) was dissolved in anhydrous tetrahydrofuran (90mL) under nitrogen, cooled to 0 deg.C, and 1, 8-diazabicycloundecen-7-ene (0.44g,2.88mmol) was added dropwise. After stirring for 15 minutes, a solution of diphenyl azide phosphate (0.91g,3.29mmol) in tetrahydrofuran (10mL) was added. After stirring at 0 ℃ for 30 minutes, the reaction mixture was warmed to room temperature and reacted for 12 hours. After the reaction, water quenching was added, extraction was performed with ethyl acetate, and the organic phase was washed with sodium bicarbonate, then with water, and dried over magnesium sulfate. The solvent was removed by distillation under the reduced pressure, and purification by column chromatography (petroleum ether) was carried out to give 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-azidomethyl-3-thienyl) cyclopentene (0.73g,2.22mmol) as a pale yellow oil in 81% yield.
As shown in FIG. 1, the hydrogen nuclear magnetic resonance spectrum of the 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-azidomethyl-3-thienyl) cyclopentene is:1HNMRCDCl3):6.70(1H,s),6.40(1H,s),4.32(2H,s),2.77-2.749(4H,t),2.35(3H,s),2.06-1.99(2H,m),1.96(3H,m),1.85(3H,s)。
as shown in FIG. 2, the NMR spectrum of 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-azidomethyl-3-thienyl) cyclopentene is shown as follows:13CNMR(CDCl3):134.90,134.85,134.27,134.02,132.42,131.27,131.23,127.89,48.24,37.27,21.91,14.13,13.31,12.99。
HRMS(ESI,m/z)calculated for C17H19N3S2[M+Na+]352.0918,found:352.0893。
the synthesis process of the azido cyclopentene thiophene comprises the following steps:
example 2
The synthesis of TAPB-BPTA-COF comprises the following steps:
(1) to a 10mL Pyrex tube was added 1,3, 5-tris- (4-aminophenyl) benzene (TAPB) (28.1mg, 0.081mmol), 2, 5-bis (2-propynyloxy) terephthalaldehyde (BPTA) (29mg, 0.12mmol), 1mL of o-dichlorobenzene and 1mL of n-butanol.
(2) The resulting suspension was sonicated for 30 seconds at room temperature, then 100 μ L of 6M acetic acid was added. The tubes were freeze-thawed for 3 cycles and sealed and heated at 120 ℃ for 3 days. The resulting yellow powder was collected by filtration and washed with tetrahydrofuran (3X 20mL), then dried under vacuum at 120 ℃ for 24 hours to give TAPB-BPTA-COF (36mg, yellow-green powder) in 73% yield.
The reaction process is as follows:
example 3
Synthesis of a covalent organic framework material with diarylenephotolytic molecular switch (COF-MQo) comprising the following steps:
to a 10mL Pyrex tube were added TAPB-BPTA-COF (50mg, 0.195) synthesized in example 2 and 1mL of N, N-dimethylformamide, and then 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-azidomethyl-3-thienyl) cyclopentene (148mg,0.44mmol) and cuprous iodide (3mg) synthesized in example 2, the tube was degassed by three freeze-thaw cycles, and finally 77. mu.L of triethylamine was added and the tube was sealed, and the mixture was reacted at room temperature for 72 hours. The precipitate was collected by centrifugation, washed five times with THF and acetone, and dried under vacuum at room temperature to give COF-MQo in 80% isolated yield (80mg, yellow-green powder).
The reaction process is as follows:
example 4
The synthesis of covalent organic framework material (COF-MQc) with diarylene photonic switch in closed loop state, i.e. the conversion of COF-MQo to COF-MQc, includes the following steps:
5mg of the COF-MQo prepared in example 3 was irradiated with a portable UV lamp at 365nm for 30 minutes to obtain COF-MQc.
The structure transformation process is as follows:
performance testing
Fig. 3 is a diffraction pattern (XRD) of the polycrystalline powder of COF-MQo and COF-MQc prepared in example 3 and example 4, respectively, wherein a is COF-MQo, and b is COF-MQo which is closed-loop COF-MQc irradiated under 365nm ultraviolet lamp for 30 minutes, and it can be seen that the PXRD structure of the material remains intact and unchanged before and after irradiation with the ultraviolet lamp.
FIG. 4 is an IR absorption spectrum of COF-MQo prepared in example 3, wherein a is an IR absorption curve of TAPB-BPTA-COF, b is an IR absorption curve of 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-azidomethyl-3-thienyl) cyclopentene, and c is an IR absorption curve of COF-MQo. It can be seen that: the position of the characteristic peak of C.ident.C in TAPB-BPTA-COF is 2100cm-1And a characteristic peak of C ≡ C-H at 3290cm-1The COF-MQo of the azido cyclopentene thiophene after the post-modification obviously disappears, and the azido cyclopentene thiophene is successfully modified on TAPB-BPTA-COF.
FIG. 5 is a thermogravimetric analysis curve of COF-MQo prepared in example 3 and TAPB-BPTA-COF prepared in example 1. In the graph, a is a thermogravimetric analysis curve of TAPB-BPTA-COF, b is a thermogravimetric analysis curve of COF-MQo, and COF-MQo has obvious weight loss at 258 ℃.
FIG. 6 is a nitrogen draw line for COF-MQo prepared in example 3. In the figure, a is an adsorption-desorption curve of TAPB-BPTA-COFD, and the BET surface area is 1320.4656m2g-1In the figure, b is the adsorption-desorption curve of COF-MQo, and the BET surface area is 35.1543m2g-1Because the azido cyclopentene thiophene molecule is modified in the pore channel of the TAPB-BPTA-COF material, the pore diameter is reduced, and the BET surface area is greatly reduced.
FIG. 7 shows UV absorption curves of TAPB-BPTA-COF prepared in example 2, COF-MQo prepared in example 3, and COF-MQc prepared in example 4 of the present invention. In the figure, a is the ultraviolet absorption curve of TAPB-BPTA-COF, b is the ultraviolet absorption curve of COF-MQo, and c is the ultraviolet absorption curve of COF-MQc. It can be seen that: the invention obtains COF-MQo, and obtains COF-MQc by using 365nm ultraviolet lamp for irradiation.
FIG. 8 is a graph showing the effect of color change of the conversion of COF-MQo to COF-MQc in example 4 of the present invention. It can be seen that COF-MQo undergoes a ring-closure reaction accompanied by a color change under uv lamp illumination.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A covalent organic framework material with a diarylene photonic switch, which has a structure shown in formula (I):
2. a method for preparing a covalent organic framework material with a diarylethene photonic switch is characterized in that: adding TAPB-BPTA-COF, azido cyclopentene thiophene and a catalyst into a reaction device, adding a solvent, performing degassing treatment, and adding triethylamine; stirring to obtain the product; the azidocyclopentene thiophene is 1- (2, 5-dimethyl-3-thienyl) -2- (2-methyl-5-azidomethyl-3-thienyl) cyclopentene;
the BPTA is 2, 5-bis (2-propinyloxy) terephthalaldehyde;
the reaction process of the TAPB-BPTA-COF is as follows:
the reaction process of reacting TAPB-BPTA-COF and azido cyclopentene thiophene is as follows:
3. the method of claim 2, wherein: the solvent is anhydrous N, N-dimethylformamide.
4. The method of claim 2, wherein: the catalyst is cuprous iodide.
5. The method of claim 2, wherein: the dosage of the catalyst is 0.5 percent of the mass of TAPB-BPTA-COF.
6. The method of claim 2, wherein: the volume ratio of the solvent to the triethylamine is 25: 2.
7. The method of claim 2, wherein: the mass ratio of the usage amount of the azido cyclopentene thiophene to the TAPB-BPTA-COF is 1: 2.
8. The method of claim 2, wherein: the degassing treatment method comprises the following steps: and (3) placing the reaction bottle in liquid nitrogen, freezing the solution, vacuumizing, unfreezing the reaction bottle in an ethanol solution after the solution is frozen, and circulating the steps for 2-4 times.
9. A covalent organic framework material with a diarylene photonic switch in a closed-loop state, having the structure of formula (II):
10. a method for preparing a covalent organic framework material with a diarylethene photonic switch in a closed ring state comprises the following steps: the method is characterized in that: irradiating the covalent organic framework material with the diarylenephotolytic molecular switch according to claim 1 and/or the covalent organic framework material with the diarylenephotolytic molecular switch prepared by the method according to any one of claims 2 to 8 with ultraviolet rays.
11. The method of claim 10, wherein the covalent organic framework material with the diarylethene photonic switch in a closed-loop state comprises: the method is characterized in that: the wavelength of the ultraviolet ray is 365nm, and the irradiation time is 10-50 minutes.
12. Use of the covalent organic framework material with a diarylene photonic switch of claim 1 and/or the covalent organic framework material with a diarylene photonic switch prepared by the method of any one of claims 2 to 8 and/or the covalent organic framework material with a diarylene photonic switch in a closed-loop state of claim 9 and/or the covalent organic framework material with a diarylene photonic switch in a closed-loop state prepared by the method of claim 10 or 11 in the fields of photoelectricity, catalysis, gas storage and energy storage.
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