CN117624175B - Macrocyclic-micromolecular host-guest eutectic material and preparation method and application thereof - Google Patents
Macrocyclic-micromolecular host-guest eutectic material and preparation method and application thereof Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
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Abstract
The invention belongs to the technical field of organic eutectic materials, and particularly relates to a macrocyclic-micromolecular host-guest eutectic material, a preparation method and application thereof, wherein the macrocyclic-micromolecular host-guest eutectic material is a host-guest complex eutectic formed by assembling a macrocyclic donor and a micromolecular acceptor through charge transfer interaction, wherein the macrocyclic donor is a macrocyclic molecule with a chiral electron-rich cavity structure, and the acceptor is electron-deficient 7, 8-tetracyano-terephthalquinone dimethane, the structures of which are shown in a formula I and a formula II respectively, and the formula I respectively comprises meso and racemic structures. The macrocyclic-micromolecular host-guest eutectic material has a wide absorption band at 300-1200nm, has excellent photo-thermal conversion performance, particularly has near infrared photo-thermal conversion efficiency up to 92%, is generally higher than the traditional micromolecular organic photo-thermal eutectic material, and has wide application prospects in the aspects of photo-thermal treatment, photo-thermal imaging, sea water desalination and the like.
Description
Technical Field
The invention belongs to the technical field of organic eutectic materials, and particularly relates to a macrocyclic-micromolecular host-guest eutectic material, and a preparation method and application thereof.
Background
Organic photothermal conversion materials have great potential for application in various fields such as photothermal therapy, photothermal/photoacoustic imaging, photo-thermal electronic devices, shape memory devices and the like, and have attracted attention from many researchers. The main research objects of the organic photothermal materials are porphyrin compounds, indocyanine compounds, organic free radicals, polyamines, polypyrroles and the like. The properties of organic photothermal conversion materials depend not only on the structure of the organic molecule but also on the nature and strength of the intermolecular interactions. To prepare more high performance organic photothermal materials, researchers have generally improved in two ways: one aspect is by extending the conjugated length of the molecule or covalently linking the electron donor and electron acceptor fragments; another aspect is to inhibit the radiation transition process by enhancing quenching or increasing the concentration of free radicals. However, the relatively complex design and cumbersome synthesis steps limit the development of the organic photothermal conversion field. Therefore, there is a need to develop new photo-thermal materials to meet the increasing application demands of photo-thermal materials.
In recent years, organic eutectic engineering has received a great deal of attention as a new strategy for developing novel organic functional materials. The organic eutectic is a molecular crystal with an ordered structure, which is assembled by two or more than two different organic molecules through intermolecular non-covalent interaction, and has the advantages of simple preparation, low cost and the like. The synergistic effect between the different components allows the organic co-crystal to exhibit more novel properties such as optoelectronic properties, stimulus responsiveness, etc. Therefore, in order to solve the problems of difficult preparation and low conversion efficiency of the current near infrared photothermal materials, researchers apply an organic eutectic strategy to near infrared photothermal conversion, and particularly to research on charge transfer donor-acceptor photothermal conversion co-crystals (adv. Sci. 2023, 10, 2206830).
At present, the organic eutectic materials for photo-thermal conversion are all assembled by planar small molecule donors and acceptors, and the photo-thermal conversion efficiency in the near infrared region is generally not high, and is extremely rare with the photo-thermal conversion efficiency exceeding 85%, for example, the photo-thermal conversion efficiency of TMPD-PMDA eutectic under 808 nm irradiation is about 87.2% (J. Phys. Chem. Lett. 2021, 12, 5796), and the photo-thermal conversion efficiency of ACAT-CD eutectic under 750 nm irradiation is about 92.2% (CCS CHEMISTRY 2020, 3, 2520). Therefore, there is a need to explore new donor and acceptor motifs, develop new high performance photothermal conversion eutectic materials to meet the increasing photothermal application demands.
Disclosure of Invention
The invention aims to provide a macrocyclic-micromolecular host-guest eutectic material, a preparation method and application thereof, wherein the material is a cavity inclusion compound crystal with a 1:2 complexation ratio, which is formed by assembling a macrocyclic donor with a chiral electron-rich rigid structure and a 7, 8-tetracyano-terephthalquinone dimethane (TCNQ) acceptor with electron deficiency through charge transfer. Meanwhile, the material has excellent photo-thermal conversion performance, and the photo-thermal conversion efficiency is as high as 92%.
The invention aims at realizing the following technical scheme:
The invention provides a macrocyclic-micromolecular host-guest eutectic material, which is a host-guest compound eutectic formed by assembling a macrocyclic donor and a micromolecular acceptor through charge transfer interaction, wherein the macrocyclic donor is a macrocyclic molecule with a chiral electron-rich cavity structure, the acceptor is electron-deficient 7, 8-tetracyano-terephthalquinone dimethane, the structures of the macrocyclic-micromolecular host-guest eutectic material are shown as a formula I and a formula II respectively, and the formula I respectively comprises meso and raceme structures:
further, the macrocyclic donor is in a racemate structure.
Further, the synthesis steps of the macrocyclic donor are as follows: (1) 6-bromo-2-aminonaphthalene and paraformaldehyde are used as raw materials, and react in trifluoroacetic acid solvent at normal temperature to obtain a synthetic compound 1, wherein the specific reaction formula is shown in the following formula III;
Formula III
(2) The method comprises the steps of (1) carrying out reflux reaction on a compound 1 and 2, 4-dimethoxy phenylboric acid serving as raw materials, dichloro [1,1' -bis (diphenylphosphine) ferrocene ] palladium serving as a catalyst and potassium carbonate serving as alkali in a mixed solution of dioxane and water for 12 hours, and separating by column chromatography to obtain a monomer compound 2, wherein the specific reaction formula is shown in the following formula IV;
IV (IV)
(3) Mixing monomer compound 2 and paraformaldehyde according to equimolar amount, dissolving in dichloromethane, adding catalyst amount of trifluoroacetic acid, performing ring closure reaction at normal temperature for 30 minutes, then quenching reaction with saturated sodium bicarbonate solution, extracting, and separating by column chromatography to obtain meso-and racemic-body macrocyclic compounds shown in formula I, wherein the specific reaction formula is shown in formula V;
V (V)
Wherein, in the above step (CH 2O)n is paraformaldehyde.
Further, the macrocyclic-small molecule host-guest eutectic material is assembled from the racemate of the macrocyclic donor and the acceptor by intermolecular charge transfer to form a 1:2 host-guest cavity inclusion complex eutectic.
The invention also provides a preparation method of the macrocyclic-micromolecular host-guest eutectic material, which is prepared by a solvent diffusion method or a solvent-assisted solid-phase grinding method.
Further, the solvent diffusion method includes the steps of:
(1) Weighing the racemate of the macrocyclic donor and TCNQ according to the ratio of 1:2, adding the racemate and TCNQ into benign solvent chloroform, fully dissolving and filtering;
(2) Transferring the filtered solution into a glass bottle, placing the glass bottle into a large glass bottle containing isopropyl ether serving as a poor solvent, sealing the large glass bottle, and performing solvent diffusion at normal temperature to obtain the black macrocyclic-micromolecular host-guest eutectic material.
Further, the solvent-assisted solid phase milling method comprises the steps of: and weighing the raceme and TCNQ of the macrocyclic donor according to the ratio of 1:2, mixing the two solids, dropwise adding 1-2 drops of chloroform solution, and fully grinding to obtain the host-guest eutectic material. During the milling process, the contact between the two components is more sufficient to promote ordered self-assembly of the intermolecular charge transfer complexes in the form of the lowest energy to form a eutectic.
The invention also provides application of the macrocyclic-micromolecular host-guest eutectic material in photothermal therapy, photothermal imaging and sea water desalination.
The invention discloses a macrocyclic-micromolecular host-guest eutectic material which comprises an electron donor and an electron acceptor, wherein the electron donor is a chiral macrocyclic compound containing Tr foster's Base as a framework, the macrocyclic compound is provided with a Ʌ -type rigid framework rich in electrons, and the macrocyclic-micromolecular host-guest eutectic material is assembled with the electron acceptor TCNQ through charge transfer. The macrocyclic compound with chiral Tr-ringer's Base as a framework is taken as a donor, the macrocyclic compound is provided with four electron-rich naphthyl outer walls, a large cavity size and a rigid box-shaped space structure, and two TCNQ molecules can be wrapped by intermolecular charge transfer to form a 1:2 cavity inclusion complex, so that the system has a wide absorption band in a range of 300-1200 nm, and the charge transfer host-guest eutectic can release absorbed light energy in a non-radiative transition form such as conversion or vibration relaxation, so that photo-thermal conversion is effectively carried out, and the photo-thermal conversion efficiency is improved.
The invention has the beneficial effects that:
(1) The host-guest photothermal conversion eutectic material is constructed through non-covalent action, does not need complex chemical synthesis, and has the advantages of simple preparation method, low cost, large-scale production and the like.
(2) The photo-thermal conversion eutectic material develops a novel eutectic pair element, selects a macrocyclic molecule with an electron-rich three-dimensional cavity structure as a donor, and can form a very stable host-guest cavity inclusion complex with an electron-deficient receptor by utilizing a charge transfer effect, which is rarely reported in the prior organic photo-thermal conversion eutectic, and widens the variety of the organic photo-thermal eutectic donor-acceptor.
(3) The macrocyclic-micromolecular host-guest eutectic material has a wide absorption band between 300 and 1200 nm, has excellent photo-thermal conversion performance, especially has near infrared photo-thermal conversion efficiency up to 92 percent, and is generally higher than the traditional micromolecular organic photo-thermal eutectic material.
(4) The photo-thermal conversion eutectic material has wide application prospect in photo-thermal treatment, photo-thermal imaging, sea water desalination and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of compound 1 prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 2 prepared in example 1;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the meso form of the compound of formula I prepared in example 1;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the racemate of the compound of formula I prepared in example 1;
FIG. 5 is a graph showing the morphology of the macrocyclic-small host-guest eutectic prepared in example 2;
FIG. 6 is a single crystal structure of the macrocyclic-small molecule host guest eutectic prepared in example 2;
FIG. 7 is a PXRD pattern of a host guest eutectic material prepared by solvent diffusion and milling according to example 2;
FIG. 8 is an ultraviolet-visible absorption spectrum of the host-guest eutectic material and single components thereof in example 2;
FIG. 9 is a graph showing the results of the photo-thermal conversion experiment of the host-guest eutectic material in example 3.
Detailed Description
The invention is described below by means of specific embodiments. The technical means used in the present invention are methods well known to those skilled in the art unless specifically stated. Further, the embodiments should be construed as illustrative, and not limiting the scope of the invention, which is defined solely by the claims. Various changes or modifications to the materials ingredients and amounts used in these embodiments will be apparent to those skilled in the art without departing from the spirit and scope of the invention.
The 6-bromo-2-aminonaphthalene, 7, 8-tetracyanoquinodimethane, paraformaldehyde, 2, 4-dimethoxy phenylboronic acid, dichloro [1,1' -bis (diphenylphosphine) ferrocene ] palladium and trifluoroacetic acid used in the invention are all commercial raw materials.
Example 1 preparation of macrocyclic compound:
(1) 6-bromo-2-aminonaphthalene (5.0 g) and paraformaldehyde (1.7 g) were weighed into 250 mL reaction bottles, respectively, and 50 mL trifluoroacetic acid was added thereto and stirred at room temperature for 24 hours. After the reaction, the mixture was quenched with a saturated solution of sodium hydrogencarbonate until no bubbles were formed. Dichloromethane and water are extracted, an organic phase is stirred with silica gel, petroleum ether and ethyl acetate (petroleum ether: ethyl acetate=15:1) are used for carrying out column chromatography separation to obtain a precursor compound 1, a nuclear magnetic resonance hydrogen spectrum is shown in figure 1, and a specific reaction formula is shown in a formula III.
Formula III
2) Compound 1 (1.0 g), 2, 4-dimethoxyphenylboronic acid (1.0 g), dichloro [1,1' -bis (diphenylphosphino) ferrocene ] palladium (0.08 g) and potassium carbonate (1.16 g) were weighed into 250 mL reaction bottles, respectively, and dioxane and water (v: v=5: 1) 100 mL, and stirring 12: 12 h under reflux under nitrogen. After the reaction is finished, silica gel is stirred, and a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate=1:1) is used for column chromatography separation to obtain a monomer compound 2, wherein a nuclear magnetic resonance hydrogen spectrum is shown in fig. 2, and a specific reaction formula is shown in a formula IV.
IV (IV)
(3) Monomer compound 2 (0.1 g) and paraformaldehyde (0.015 g) are respectively weighed and fully stirred in a 20 mL dichloromethane solvent for dissolution, then 1.8 mL trifluoroacetic acid catalyst is added, and stirring is carried out at normal temperature for 20 min. And after the reaction is finished, extracting the mixed solution, mixing the sample with silica gel, and carrying out column chromatography separation by using a mixed solution of dichloromethane and methanol (dichloromethane: methanol=150:1) to obtain meso-and racemic-macrocyclic compounds shown in the formula I, wherein nuclear magnetic resonance hydrogen spectrograms of the meso-and racemic-macrocyclic compounds are shown in the figures 3 and 4 respectively, and the specific reaction formula is shown in the formula V.
V (V)
EXAMPLE 2 preparation of macrocyclic-Small molecule host-guest eutectic materials
Solvent diffusion method: the racemate macrocyclic compound of formula i (25 mg) and TCNQ (10 mg) were fully dissolved in 5mL benign solvent chloroform and filtered;
Transferring the filtered solution into a glass bottle, placing the glass bottle into a large glass bottle containing isopropyl ether serving as a poor solvent, sealing the large glass bottle, and performing solvent diffusion for 4 days at normal temperature to obtain a black macrocyclic-micromolecular host-guest eutectic material, wherein as shown in fig. 5, a photograph under an electron microscope shows that the eutectic is in a black sheet shape. In addition, as can be seen from the single crystal diffraction analysis of fig. 6, the macrocyclic compound has a rigid steric cavity structure capable of inclusion of two TCNB molecules by intermolecular charge transfer to form a stable host-guest complex.
(3) Solid milling method: and (3) weighing and mixing the raceme macrocyclic compound (100 mg) and TCNQ (35 mg) solid, and then adding 1-2 drops of chloroform solution to assist in fully grinding until the mixed solid turns black, so that the donor molecule and the receptor molecule are fully combined. Grinding to obtain black solid host-guest eutectic material.
In fig. 7, powder X-ray diffraction (PXRD) patterns of the host-guest eutectic material prepared by solvent diffusion and solid grinding respectively show that the eutectic material prepared by the two methods has sharp and clear X-ray diffraction peaks, which indicates that the material is a long-range ordered and anisotropic crystal and has good crystallization degree. And their diffraction peaks have consistency, indicating identical structures.
EXAMPLE 3 photo-thermal conversion Property of macrocyclic-Small molecule host-guest eutectic materials
Fig. 8 shows ultraviolet-visible absorption spectra of a macrocyclic-small molecule host-guest eutectic, a single-component macrocyclic and TCNQ, and it can be seen that, compared with the single-component, the macrocyclic and small molecules form a host-guest eutectic through charge transfer, and then undergo significant red shift, and the spectral absorption range is 300-1200 nm, which indicates that the eutectic charge transfer degree is greater and the excited state electron transition energy level becomes narrower and denser, that is, the eutectic material can effectively use light in a wide band.
The results of 5 heating-cooling cycle tests on the host-guest eutectic material prepared in example 2 are shown in fig. 9, where fig. 9 (a) is a heating-cooling process diagram, (b) is a cyclic heating-cooling experimental result diagram, and (c) is a temperature change (Δt) -incident light Power (Power) linear fitting diagram; in the figure, the abscissa Time represents Time, and the ordinate Temperature represents Temperature. As can be seen from fig. 9, good photo-thermal conversion stability is maintained in 5 heating-cooling cycles, and the heating and the power of the incident laser have good linear relationship, i.e. the temperature of the photo-thermal conversion eutectic material heating can be accurately controlled by controlling the power of the incident light. As can be seen from fig. 9a, the eutectic material can be rapidly heated to about 130 o C in 120 seconds of illumination, and exhibits excellent photo-thermal conversion performance.
Example 4 photo-thermal conversion efficiency
100 Mg of host-guest eutectic materials are weighed, dispersed on a square quartz plate with a side length of 1 cm, and fixed by using double faced adhesive tape. The system can be heated to about 130 o C in 200 seconds under the irradiation of near infrared laser with the power density of 0.7W cm -2 and the wavelength of 808 and nm. The photo-thermal conversion efficiency of the photo-thermal conversion eutectic material is calculated to be 92% through a cooling curve, and is generally higher than that of the organic micromolecular photo-thermal eutectic material.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (6)
1. The macrocyclic-small molecule host-guest eutectic material is characterized in that the macrocyclic-small molecule host-guest eutectic material is a host-guest complex eutectic formed by assembling a macrocyclic donor and a small molecule acceptor through charge transfer interaction, wherein the macrocyclic donor is a macrocyclic molecule with a chiral electron-rich cavity structure, the acceptor is electron-deficient 7, 8-tetracyano-terephthalquinone dimethane, the structures of the macrocyclic-small molecule host-guest eutectic material are shown as a formula I and a formula II respectively, and the formula I is a raceme structure:
The macrocyclic-small molecule host-guest eutectic material is assembled from a racemate of the macrocyclic donor and the acceptor through intermolecular charge transfer to form a 1:2 host-guest cavity inclusion complex eutectic.
2. The macrocyclic-small molecule host guest eutectic material of claim 1, wherein the macrocyclic donor synthesis step is: (1) 6-bromo-2-aminonaphthalene and paraformaldehyde are used as raw materials, and react in trifluoroacetic acid solvent at normal temperature to obtain a synthetic compound 1, wherein the specific reaction formula is shown in the following formula III;
(2) The method comprises the steps of (1) carrying out reflux reaction on a compound 1 and 2, 4-dimethoxy phenylboric acid serving as raw materials, dichloro [1,1' -bis (diphenylphosphine) ferrocene ] palladium serving as a catalyst and potassium carbonate serving as alkali in a mixed solution of dioxane and water for 12 hours, and separating by column chromatography to obtain a monomer compound 2, wherein the specific reaction formula is shown in the following formula IV;
(3) Mixing the monomer compound 2 and paraformaldehyde according to an equimolar amount, dissolving in dichloromethane, adding a catalyst amount of trifluoroacetic acid, performing ring closure reaction for 30 minutes at normal temperature, then quenching reaction by using a saturated sodium bicarbonate solution, extracting, and separating by column chromatography to obtain a raceme macrocyclic compound shown in a formula I, wherein the specific reaction formula is shown in a formula V;
3. A method of preparing a macrocyclic-small molecule host-guest eutectic material according to any one of claims 1 to 2, wherein the macrocyclic-small molecule host-guest eutectic material is prepared by solvent diffusion or solvent assisted solid phase milling.
4. The method of preparing a macrocyclic-small molecule host guest eutectic material of claim 3, wherein the solvent diffusion process comprises the steps of:
(1) The raceme of the macrocyclic donor and 7, 8-tetracyano-terephthalquinone dimethane are weighed according to the proportion of 1:2, added into benign solvent chloroform, fully dissolved and filtered;
(2) Transferring the filtered solution into a glass bottle, placing the glass bottle into a large glass bottle containing isopropyl ether serving as a poor solvent, sealing the large glass bottle, and performing solvent diffusion at normal temperature to obtain the black macrocyclic-micromolecular host-guest eutectic material.
5. A method of preparing a macrocyclic-small molecule host guest eutectic material according to claim 3, wherein the solvent assisted solid phase milling method comprises the steps of: and weighing the raceme of the macrocyclic donor and 7, 8-tetracyano-terephthalquinone dimethane according to the ratio of 1:2, mixing the two solids, dripping 1-2 drops of chloroform solution, and fully grinding to obtain the host-guest eutectic material.
6. Use of a macrocyclic-small molecule host guest eutectic material according to any of claims 1-2 in desalination of sea water.
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