Patent Grant
11976087
This application is the National Stage Application of PCT/CN2022/076363, filed on Feb. 15, 2022, which claims priority to Chinese Patent Application No. 202111638710.3, filed on Dec. 30, 2021, which is incorporated by reference for all purposes as if fully set forth herein.
The present invention relates to the technical field of light-stimuli responsive materials, and specifically to a light-stimuli responsive coordination polymer, and preparation method and use thereof.
Stimuli-responsive materials are a class of smart materials where their physical/chemical properties are reconfigured with changes in the external environment. They have attracted the attention of researchers due to the great potential applications in intelligent robots, biomedical science, biomimicry and molecular machines. At present, various types of environmental stimuli-responsive materials have been reported. By means of rational design, these materials can respond to a variety of external physical/chemical stimuli, such as heat, electric field, magnetic field, humidity, and light etc.
As a branch of stimuli-responsive materials, light-responsive materials, due to their non-damage and non-contact external means of triggering, have unique attractiveness in energy conversion. These ideal intrinsic properties also endow them with great advantages in practical applications, such as in photoactuator. In recent years, light-driven materials have achieved rapid development, mainly in the external deformations of the materials caused by photochemical reactions or photothermal effects, including bending, coiling, shrink/stretch, swimming, and other behaviors (see: Guo J, Fan J, Liu X, Zhao Z, Tang B, Angew. Chem. Int. Ed, 2020, 59, 8828-8832). These light-responsive molecules mainly include diarylethene, anthracene, schiff bases and azobenzene derivatives, which undergo reversible deformation under light/thermal stimulation. Therefore, the strategy for designing and synthesizing most of the photoactuators are to insert light-responsive molecular moieties into the networks, gels and molecular crystals of liquid crystal polymers, where the light-responsive molecular moieties act as an optical switch unit to achieve fast and reversible light-driven deformation behaviors (see: Wang H, Chen P, Wu Z, Zhao J, Sun J, Lu R, Angew. Chem. Int. Ed, 2017, 56, 9463-9467). However, due to the anisotropic optical-mechanical behavior and crystallinity of the photoactuator, the free volume is closely related to the molecular orientation. Therefore, the “bottom-up” design and synthesis of a class of materials having a hierarchical structure and capable of optical-mechanical energy conversion encounter great challenges.
It is well known that coordination polymers (CPs) are a new class of crystalline materials formed by the self-assembly of inorganic metal ions/metal clusters and organic bridging ligands through coordination bonds. The adjustability and periodicity of the CP structure provide a good solution to the “bottom-up” design and synthesis of CP-based light-driven materials. Namely, a light-responsive molecular moiety can be inserted into a highly ordered and specially arranged CP backbone, such that the photosensitive molecule undergoes a chemical reaction under light irradiation, to generate photoinduced stress, and thus drive the mechanical deformation of the material (see: Shi Y X, Zhang W H, Abrahams B F, Braunstein P, Lang J P, Angew. Chem. Int. Ed, 2019, 58, 9453-9458). Moreover, the photoinduced stress generated by the chemical reaction of the photosensitive molecule in the CP backbone is generally at the molecular level, and cannot cause the CP material to deform significantly macroscopically. It is also a very challenging task to choose an appropriate method to amplify this photoinduced stress to the macroscopic optical-mechanical behavior.
Therefore, the design and synthesis of a new, high-sensitivity solid-state light-stimuli responsive material is of great significance in photo-actuated electronic micro-devices and biomimetic materials.
To solve the above problems, a light-stimuli responsive coordination polymer, and preparation and use thereof are provided. The preparation method of the coordination polymer is simple, and has mild reaction conditions, and fast light conversion rate. The photoactuators prepared therewith can accomplish various behaviors quickly.
According to the technical solution of the present invention, the light-stimuli responsive coordination polymer is a bright yellow bulk crystal and has a chemical formula of [Zn(tkpvb)(Fb)2]n1, crystallographic parameters of:
Specifically, the crystallographic parameters of the light-stimuli responsive coordination polymer further include Dc=1.445/g·cm−3, μ=0.704 (Mo-Kα)/mm−1, total number of diffraction point of 19493, and number of independent diffraction points of 4392.
In a second aspect, the present invention provides a method for preparing the light-stimuli responsive coordination polymer. The method includes the following steps:
Preferably, the molar ratio of zinc nitrate hexahydrate, p-fluorobenzoic acid or a water-soluble salt thereof and 1,2,4,5-tetrakis((E)-2-(4-pyridyl)vinyl)benzene is 1-2.5:1-2.5:1-2.5, and preferably 1:1:1.
Preferably, the reaction temperature is 120 to 125° C., and the time is 5-12 h. More preferably, the reaction temperature is 120° C., and the reaction time is 6 h.
Preferably, the volume ratio of N,N′-dimethylformamide and water in the mixed solvent is 1:1-4, and more preferably, 2:3.
Preferably, the pH is adjusted to 5-6 with hydrochloric acid having a concentration of 0.1 M. More preferably, the pH is adjusted to 5.
The light-stimuli responsive coordination polymer (CP1) of the present invention undergoes a chemical reaction under the irradiation of a light source having a wavelength of 365 nm, where the aromatic ring inside the crystal rotates, and a new and different coordination polymer [Zn (poly-bpbpvpcb) (Fb)2]n2(CP2) is obtained by the single crystal-single crystal method, in which poly-bpbpvpcb represents poly-1,3-bis(4-pyridyl)-(2,5-bis(2-(4-pyridyl)-vinyl)phenyl)cyclobutane, and n3=3000-60000.
In a third aspect, the present invention provides a composite film. the composite film includes a light-stimuli responsive coordination polymer according to claim 1.
Preferably, the composite film has a thickness of 70-90 m.
A method for preparing the composite film includes the following steps:
Preferably, the solvent is selected from the group consisting of ethanol, acetonitrile, diethyl ether, water and any combination thereof, and more preferably ethanol.
Preferably, in Steps S1 and S3, the drying temperature is 60-80° C.
Preferably, the substrate is selected from the group consisting of polyvinyl alcohol (PVA), chitosan, polyvinylidene difluoride, polypropylene and any combination thereof.
Preferably, the substrate is a 10 wt % PVA aqueous solution, and the weight ratio of the light-stimuli responsive coordination polymer to the PVA aqueous solution is 0.1-0.9:11. In Step S3, the drying is performed to remove water in the PVA aqueous solution.
Preferably, in Step S3, the drying is performed at 60-80° C. to remove the solvent.
In a fourth aspect, the present invention provides a photoactuator. The photoactuator is prepared with a composite film according to claim 5.
Specifically, the composite film is prepared into the photoactuator by cutting, folding, and fixing and connecting of multiple composite films, where the photoactuator is two-dimensional or three-dimensional.
In a fifth aspect, the present invention provides use of the light-stimuli responsive coordination polymer or the composite film in photoactuation.
Preferably, the photoactuation is enabled by irradiation with light of 365 nm.
Compared with the prior art, the technical solution of the present invention has the following advantages:
The present invention will be further described below with reference to the accompanying drawings and specific examples, so that those skilled in the art can better understand and implement the present invention; however, the present invention is not limited thereto.
A mixture of zinc nitrate hexahydrate (297 mg, 0.1 mmol), 1,2,4,5-tetrakis((E)-2-(4-pyridyl)vinyl)benzene (490 mg, 0.1 mmol) and p-fluorobenzoic acid (280 mg, 0.1 mmol) was added to a 25 mL of thick-walled pressure flask. Then 10 mL of a mixed solution of N,N′-dimethyl formamide and deionized water at a volume ratio of 2:3 was added, and the system was adjusted to about pH 5 with 0.1 M hydrochloric acid. The flask was sealed, ultrasonically dispersed for 10 min, heated for 8 h in an oven at a temperature programmed to 120° C., and then naturally cooled to room temperature, to obtain a bright yellow lump crystal [Zn (tkpvb) (Fb)2]n1(CP1). The crystal was washed with ethanol, collected, and dried in an oven at 60° C. Yield: 472.8 mg (65%, calculated based on 1,2,4,5-tetrakis((E)-2-(4-pyridyl)vinyl)benzene).
Elemental analysis (%): C48H34F2N4O4Zn; Calculated: C 69.11, H 4.11, N 6.72; Found: C 69.88, H 4.20, N 6.75.
Infrared spectrum (potassium bromide disc method): 3045 (w), 1610 (w), 1504 (w), 1409 (w), 1362 (s), 1219 (m), 1151 (s), 1025 (w), 857 (m), 780 (m), 629 (m), 620 (s), 536 (s) cm−1.
The structure of the compound was characterized by single crystal X-ray diffraction, powder X-ray diffraction and thermogravimetric analysis. The crystallographic parameters are listed in Table 1. The X-ray powder diffraction pattern and thermogravimetric analysis profile are shown in
The compound is monoclinic, and the space group is C2/c.
At room temperature, a small amount of CP1 crystal was placed on a clean glass slide, and irradiated with an LED light having a wavelength of 500 nm for 30 min while a distance of 2 cm was maintained between the light source and the crystal to obtain a [2+2] cycloaddition product [Zn (poly-bpbpvpcb) (Fb)2]n2(CP2) with a conversion rate of 100%.
Elemental analysis (%): C48H34F2N4O4Zn; Calculated: C 69.11, H 4.11, N 6.72; Found: C 69.10, H 4.15, N 6.73.
Infrared spectrum (potassium bromide disc method): 2934 (w), 1735 (w), 1431 (w), 1375 (w), 1245 (w), 1143 (w), 1095 (s), 919 (w), 881 (m), 821 (s), 745 (s), 688 (m), 546 (s) cm−1
The product was tested by single crystal X-ray diffraction. The crystallographic parameters are listed in Table 2. The single-crystal morphology, two-dimensional structure, X-ray diffraction pattern and thermogravimetric analysis profile of the powder are shown in
CP1 was ground into a uniform powder in a mortar (about 30 minutes), and then 200 mg of the powder was dispersed in 4 mL of ethanol, ultrasonicated for 5 h, and dried at 60° C. 2.25 g of 10% PVA aqueous solution was mixed with the powder and stirred for 12 h to obtain a uniform viscous liquid. Subsequently, the mixed solution was added dropwise to a polytetrafluoroethylene mold having a clean surface dried with nitrogen, and allowed to stand overnight at 80° C. in an oven to remove the remaining solvent. After the solvent was completely evaporated, a free-standing composite film 0-PVA was obtained by peeling from the mold.
The composite film was analyzed by scanning electron microscopy (SEM), EDS mapping, and X-ray powder diffraction. The SEM image, EDS mapping image, and X-ray powder diffraction pattern are shown in
0-PVA was cut into a strip of 0.5 cm×2 cm, to prepare a photoactuator 1 (1-PVA). One end of the photoactuator 1 was fixed with a clip, and the other end was tied with a heavy object. The film was irradiated with an LED light having a wavelength of 365 nm (at a distance of about 2 cm) and the process was recorded with a high-speed camera (1200 frames/s). When exposed to irradiation with light of 365 nm, the photoactuator 1 undergoes backlight bending quickly, with a bending angle up to 45°, to lift the heavy object (see
0-PVA was cut into a strip of 0.5 cm×3 cm, and the strip-shaped composite film was fold at an edge (0.5 cm×0.5 cm) by an angle of 900 to form a “knuckle” of a “finger” for grabbing a heavy object. The film material is a photoactuator 2 (2-PVA). 2-PVA was laid flatly, and illuminated with light having a wavelength of 365 nm at a distance of 5 cm from the above, and the process was recorded with a high-speed camera (1200 frames/s). The “finger” began to bend, to grab the heavy object underneath (see
0-PVA was cut into a strip of 0.5 cm×2 cm. Two cut composite films were crisscrossed and fixed together, at an angle of 90°. The film material is a photoactuator 3 (3-PVA). 3-PVA was laid flatly on a flat surface, and a heavy object was placed at a central position. 4-PVA was irradiated with an LED light having a wavelength of 365 nm at a distance of 5 cm from the above (at a distance of about 5 cm) and the process was recorded with a high-speed camera (1200 frames/sec). As shown in FIG. X, when exposed to irradiation with light of 365 nm, four sides of 3-PVA are bent, so the center was arched, similar to the situation where a jack props a heavy object in the center. In this way, 3-PVA can props an object that is 20 times higher than its own weight (see
The present invention discloses a method for preparing a coordination polymer and a method for preparing three photoactuators using the coordination polymer as a raw material. Specifically, in the present invention, a photosensitive coordination polymer [Zn(tkpvb)(Fb)2]n1 (CP1) is hydrothermally synthesized at a low temperature (120° C.), which undergoes an [2+2] cycloaddition reaction under irradiation with light having a wavelength of 365 nm. In this process, a photoinduced stress is generated. The photoinduced stress is amplified by preparing a composite film, and then a series of photoactuators 1-PVA, 2-PVA, and 3-PVA are prepared with CP1 as a raw material. The preparation method of the present invention is simple, and has mild reaction conditions, and fast light conversion rate. By introducing non-contact and non-damage light as a driving source, the mechanical behavior of the photoactuator is accurately controlled. The photoactuator is rapidly responsive, and can complete a variety of mechanical behaviors. The control process is simple and easy to operate, and requires no chemical reagents. conforming the concept of green chemistry.
Obviously, the above-described embodiments are merely examples provided for clarity of description, and are not intended to limit the implementations of the present invention. Other variations or changes can be made by those skilled in the art based on the above description. The embodiments are not exhaustive herein. Obvious variations or changes derived therefrom also fall within the protection scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202111638710.3 | Dec 2021 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/076363 | 2/15/2022 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2023/123626 | 7/6/2023 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20100174047 | Jung et al. | Jul 2010 | A1 |
| 20140088312 | Li et al. | Mar 2014 | A1 |
| Number | Date | Country |
|---|---|---|
| 109096507 | Dec 2018 | CN |
| 109232431 | Jan 2019 | CN |
| 113999402 | Feb 2022 | CN |
| Entry |
|---|
| Dai, et al., “Zinc(II) coordination polymers of tetrakis(4-pyridyl)cyclobutane and various dicarboxylates: Synthesis, structures and luminescent properties,” CrystEngComm, 2012, 14, 6230-6240. (Year: 2012). |
| Gong Wei-Jie et al., “Luminescent cadmium(II) coordination polymers of 1,2,4,5-tetrakis(4-pyridylvinyl)benzene used as efficient multi-responsive sensors for toxic metal ions in water” Dalton Transactions, vol. 46, Nr.:48, pp. 16861-16871 (Dec. 31, 2017). |
| Number | Date | Country | |
|---|---|---|---|
| 20240051973 A1 | Feb 2024 | US |
