CN114773551B - Two-dimensional covalent organic framework compound with high fluorescence quantum yield, and preparation and application thereof - Google Patents
Two-dimensional covalent organic framework compound with high fluorescence quantum yield, and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a two-dimensional covalent organic framework compound with high fluorescence quantum yield and preparation and application thereof, and provides a novel design strategy, wherein the two-dimensional sql topological structure framework compound which is orderly expanded is obtained through [4+4] imine condensation, the covalent organic framework compound has high crystallinity and unique pore structure, and has a rigid and flexible construction module, so that fluorescence non-radiative relaxation caused by intramolecular rotation is effectively inhibited, and the novel covalent organic framework compound has higher fluorescence quantum yield and good application prospect in the photoluminescence and sensing fields.
Description
Technical Field
The invention belongs to the field of Covalent Organic Frameworks (COFs) materials, and particularly relates to a novel two-dimensional covalent organic framework compound with high fluorescence quantum yield, and preparation and application thereof.
Background
The application of light has driven the advancement of modern civilization in humans. With the development of technology, people are increasingly dependent on the related technical results. The traditional inorganic luminescent materials, such as rare earth, metal complex and the like, have the problems of limited resources, high price, difficult synthesis, poor stability and the like, and meanwhile, the problems of incompatibility of environment and ecology limit the wide application of the materials.
Covalent Organic Frameworks (COFs) are a novel class of porous organic crystalline materials with periodic pore structures, which are formed by covalent bonding of organic building blocks. The long-range order of the COFs material endows the frame material with adjustable, predictable and modifiable characteristics, so that the frame material has potential application prospects in the fields of photoelectric equipment and the like. Generally, COFs materials exhibit excellent optical characteristics and are widely used in various fields such as electroluminescent diodes, substance detection, bio/chemical sensing, and the like. The materials are classified according to their luminescence modes, and they can be mainly classified into several types such as photoluminescence, chemiluminescence, electroluminescence, etc. For two-dimensional COFs materials, non-radiative relaxation due to intramolecular bond rotation/vibration and aggregation-induced quenching (ACQ) caused by pi-pi layered stacking results in poor photoluminescence performance of most two-dimensional COFs materials in the solid state, which limits the application of fluorescent COFs materials to some extent. The luminescence performance is hopefully improved by weakening the inter-layer pi-pi interaction, introducing the inter-molecular/internal hydrogen bond to limit the rotation vibration of the molecular bond, and the like.
Based on the crystal engineering principle, the invention introduces the rigid construction unit with optical activity through reasonable selection of the construction unit, assembles the construction unit with non-planar construction unit, effectively inhibits non-radiative relaxation caused by rotation of material molecular bonds, and prepares a two-dimensional covalent organic framework compound with high fluorescence quantum yield.
Disclosure of Invention
The invention provides a two-dimensional covalent organic framework compound with high fluorescence quantum yield, a preparation method and application thereof.
The technical scheme of the invention is as follows:
a two-dimensional covalent organic framework compound with high fluorescence quantum yield is formed by mutually connecting dibenzo [ g, d ] thick dinaphthyl type four-connection nodes (I) and tetraphenyl ethylene type four-connection nodes (II) in a two-dimensional plane; in at least one part of the two-dimensional covalent organic framework compound, each tetraphenyl four-connection node is respectively connected with 4 adjacent dibenzo [ g, d ] thick dinaphthyl four-connection nodes, and each dibenzo [ g, d ] thick dinaphthyl four-connection node is respectively connected with 4 adjacent tetraphenyl four-connection nodes to form a two-dimensional sql topological structure;
in the formulas (I) and (II), the broken line represents the junction.
The ratio of the number of moles of dibenzo [ g, d ] thick dinaphthyl-based tetraconnecting node to the number of moles of tetraphenyl-based tetraconnecting node in at least a portion of the two-dimensional covalent organic framework compound having a high fluorescence quantum yield is (0.8 to 1.2): (0.8 to 1.2), preferably 1:1, a step of;
the linking group of the two-dimensional covalent organic framework compound with high fluorescence quantum yield contains a dynamic covalent bond, and the linking mode is selected from one of-C=N-, -C=N-N=C-, -C=N-NH-, -C=C (CN) -, and is preferably-C=N-;
when the mode of attachment is-c=n-, the two-dimensional covalent organic framework compound with high fluorescence quantum yield comprises a framework unit of formula (III):
the BET specific surface area of the two-dimensional covalent organic framework compound with high fluorescence quantum yield is 40-4000 m 2 And/g, the pore diameter is 0.6-6.0 nm.
A method for preparing a two-dimensional covalent organic framework compound with high fluorescence quantum yield, comprising the steps of:
step one, adding dibenzo [ g, d ] thick dinaphthyl type four-connection node molecules (1), tetraphenyl ethylene type four-connection node molecules (2), a reaction solvent and a catalyst into a reaction container, freezing by liquid nitrogen, vacuumizing and sealing;
the ratio of the amounts of substances of the dibenzo [ g, d ] condensed dinaphthyl type four-connection node molecule (1) and the tetraphenyl ethylene type four-connection node molecule (2) is 1:1, a step of;
the reaction solvent is mesitylene and dioxane with the volume ratio of 1:1;
the catalyst is 6-9 mol/L acetic acid, preferably 6mol/L acetic acid; the volume amount of the catalyst is 1-10 mL/mmol, preferably 5mL/mmol, based on the amount of the substance of the dibenzo [ g, d ] condensed dinaphthyl type tetralin connecting node molecule (1); the catalyst accounts for 10-20% of the volume of the reaction solvent;
step two, placing the sealed reaction container at 80-180 ℃ (preferably 120 ℃) to react for 72-168 hours (preferably 96 hours) to generate solid precipitate;
step three, cooling to room temperature, filtering to obtain a precipitate, soaking, washing and drying the precipitate by using an organic solvent to obtain the two-dimensional covalent organic framework compound;
the method for soaking and washing by using the organic solvent comprises the following steps: sequentially washing with two or three of N, N-dimethylformamide, tetrahydrofuran and acetone, and then respectively Soxhlet extracting with tetrahydrofuran and acetone for 24-48 h;
the drying method comprises the following steps: vacuum-pumping to 20mTorr at 80 ℃ in a vacuum drying oven, and drying for 24 hours;
in the formulas (1) and (2),
R 1 is aldehyde (-CHO) or amino (-NH) 2 )，R 2 Is aldehyde (-CHO) or amino (-NH) 2 )；
Preferably R 1 Is amino (-NH) 2 )，R 2 Is aldehyde (-CHO).
The two-dimensional covalent organic framework compound with high fluorescence quantum yield can be applied to preparation of photoluminescent materials.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a novel design strategy of a two-dimensional covalent organic framework compound with high fluorescence quantum yield, and the two-dimensional sql topological structure framework compound which is orderly expanded is obtained through [4+4] imine condensation. The covalent organic framework compound has high crystallinity and unique pore structure, has rigid and flexible construction modules, and effectively inhibits fluorescence non-radiative relaxation caused by intramolecular rotation, so that the novel covalent organic framework compound has higher fluorescence quantum yield and has good application prospect in the photoluminescence and sensing fields.
Drawings
FIG. 1 is a schematic diagram of the topology of a covalent organic framework compound TPE-DBC-COF with high quantum yield in example 1 of the present invention.
FIG. 2 is a schematic representation of the synthesis of the covalent organic framework compound TPE-DBC-COF with high quantum yield in example 1 of the present invention.
FIG. 3 is a powder X-ray (PXRD) test pattern and a simulated pattern of a covalent organic framework compound TPE-DBC-COF with high quantum yield in example 1 of the present invention.
FIG. 4 is an infrared (FT-IR) spectrum of a covalent organic framework compound TPE-DBC-COF with high quantum yield in example 1 of the invention.
FIG. 5 is a fluorescence emission spectrum of TPE-DBC-COF prepared in example 1 in various organic solutions.
Detailed Description
The objects, technical solutions and advantages of the present invention will be further described in detail with reference to the following examples and the accompanying drawings, and the described specific examples are only for explaining the present invention and are not intended to limit the present invention.
Example 1.
The preparation method of the covalent organic framework compound (called TPE-DBC-COF) with high fluorescence quantum yield effect comprises the following steps:
referring to scheme 2,2,7,10,15-tetra (4-aminobenzene) -dibenzo [ g, d]Condensed dinaphthyl (DBC-PhNH) 2 ) (27.71 mg,0.04 mmol) and 4,4',4", 4' - (ethylene-1, 2-tetrayl) tetrabenzaldehyde (17.8 mg,0.04 mmol) was added to a mixed reaction solvent of mesitylene (0.6 mL) and dioxane (0.6 mL), and uniformly dispersing the mixture in an ampere bottle by ultrasonic to obtain orange turbid solution. 6M acetic acid (0.20 mL) was added to the ampoules as catalyst. Quick freezing at 77K in a liquid nitrogen bath, and circulating three times for degassing by freezing-evacuating-thawing, and then sealing. The ampoules were placed in an oven at 120 ℃ for 4 days at constant temperature, cooled to room temperature after the reaction was completed and the yellow solid was collected by filtration. The collected solids were washed sequentially with N, N-dimethylacetamide (3X 10 mL) and acetone (3X 10 mL). After soxhlet extraction of the solid with tetrahydrofuran and acetone for 48h, it was dried under vacuum at 80℃for 24h, and the TPE-DBC-COF obtained was a yellow powder.
Product characterization and performance testing
Referring to fig. 3, powder X-ray diffraction (PXRD) measurements indicate that TPE-DBC-COF has diffraction peaks at 2theta 3.18,5.92,9.41, 11.67, 19.59 and 24.37, and the structure is simulated by using Materials Studio software, so that the crystal structure of TPE-DBC-COF is analyzed, and the corresponding simulated PXRD pattern generated by two-dimensional sql topology is well matched with the experimental PXRD pattern, thus proving the correctness of the structure.
Referring to FIG. 4, a Fourier transform infrared (FT-IR) spectrum was tested and compared with the IR spectrum of the corresponding product TPE-DBC-COF at 1620cm for the relevant monomers needed for synthesis -1 Characteristic tensile vibration of the c=n bond was generated, demonstrating successful synthesis of TPE-DBC-COF.
Referring to FIG. 5, 2mg of TPE-DBC-COF was ultrasonically dispersed in 3mL of various organic solvents and its fluorescence emission spectra were tested using a fluorescence spectrometer (F-4600) at 298K and 365nm excitation wavelengths, showing that TPE-DBC-COF has strong fluorescence in acetone, DMF and tetrahydrofuran, wherein the fluorescence quantum yield of TPE-DBC-COF in tetrahydrofuran is up to 43.74%.
The foregoing examples have shown only the preferred embodiments of the invention, which are described in more detail and detail, but are not to be construed as limiting the scope of the invention. The technical features of the embodiments may be arbitrarily combined, and for brevity, all of the possible combinations of the technical features of the above embodiments are not described, but all of them should be considered as the scope of the description. It will be apparent to those skilled in the art that modifications and variations can be made without departing from the spirit of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. A two-dimensional covalent organic framework compound with high fluorescence quantum yield is characterized by being formed by mutually connecting dibenzo [ g, d ] thick dinaphthyl type four-connection nodes (I) and tetraphenyl ethylene type four-connection nodes (II) in a two-dimensional plane; in at least one part of the two-dimensional covalent organic framework compound, each tetraphenyl four-connection node is respectively connected with 4 adjacent dibenzo [ g, d ] thick dinaphthyl four-connection nodes, and each dibenzo [ g, d ] thick dinaphthyl four-connection node is respectively connected with 4 adjacent tetraphenyl four-connection nodes to form a two-dimensional sql topological structure;
the linking group of the two-dimensional covalent organic framework compound with high fluorescence quantum yield contains a dynamic covalent bond, and the linking mode is selected from-C=N-;
in the formulas (I) and (II), the dotted line represents the joint;
the two-dimensional covalent organic framework compound with high fluorescence quantum yield comprises a framework unit shown in a formula (III):
2. the two-dimensional covalent organic framework compound with high fluorescence quantum yield according to claim 1, wherein the ratio of the number of moles of dibenzo [ g, d ] fused dinaphthyl-based tetral junction to the number of moles of tetraphenyl-based tetral junction in at least a portion of the two-dimensional covalent organic framework compound with high fluorescence quantum yield is (0.8-1.2): (0.8-1.2).
3. The method of preparing a two-dimensional covalent organic framework compound with high fluorescence quantum yield according to claim 1, comprising the steps of:
step one, adding dibenzo [ g, d ] thick dinaphthyl type four-connection node molecules (1), tetraphenyl ethylene type four-connection node molecules (2), a reaction solvent and a catalyst into a reaction container, freezing by liquid nitrogen, vacuumizing and sealing;
the reaction solvent is mesitylene and dioxane with the volume ratio of 1:1;
the catalyst is acetic acid with the concentration of 6-9 mol/L;
step two, placing the sealed reaction container at 80-180 ℃ for reaction for 72-168 hours to generate solid precipitate;
step three, cooling to room temperature, filtering to obtain a precipitate, soaking, washing and drying the precipitate by using an organic solvent to obtain the two-dimensional covalent organic framework compound;
in the formulas (1) and (2),
R 1 is aldehyde or amino, R 2 Is aldehyde or amino.
4. The method according to claim 3, wherein the ratio of the amounts of the substances in the dibenzo [ g, d ] condensed dinaphthyl-based tetralin-based connecting node molecule (1) and the tetraphenyl-based tetralin-based connecting node molecule (2) in the first step is 1:1.
5. the process according to claim 3, wherein the catalyst is used in the first step in a volume amount of 1 to 10mL/mmol based on the amount of the substance of the dibenzo [ g, d ] condensed dinaphthyl-type tetralin-attaching-node molecule (1).
6. The process according to claim 3, wherein the catalyst in the first step is 10 to 20% by volume of the reaction solvent.
7. The process according to claim 3, wherein R in the formulae (1), (2) 1 Is amino, R 2 Is aldehyde group.
8. Use of a two-dimensional covalent organic framework compound with high fluorescence quantum yield according to claim 1 for the preparation of photoluminescent material.
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| CN107011525A (en) * | 2017-03-08 | 2017-08-04 | 宁波大学 | A kind of zinc metal-organic framework material and its preparation method and application |
| CN111607051A (en) * | 2020-06-08 | 2020-09-01 | 江南大学 | Three-dimensional fluorescent covalent organic framework material and preparation method and application thereof |
| CN112210057A (en) * | 2020-07-02 | 2021-01-12 | 上海师范大学 | Fluorescent three-dimensional covalent organic framework material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107011525A (en) * | 2017-03-08 | 2017-08-04 | 宁波大学 | A kind of zinc metal-organic framework material and its preparation method and application |
| CN111607051A (en) * | 2020-06-08 | 2020-09-01 | 江南大学 | Three-dimensional fluorescent covalent organic framework material and preparation method and application thereof |
| CN112210057A (en) * | 2020-07-02 | 2021-01-12 | 上海师范大学 | Fluorescent three-dimensional covalent organic framework material and preparation method and application thereof |
Non-Patent Citations (1)
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| Wai-Shing Wong等.Enantiopure Aromatic Saddles Bearing the Fenestrindane Core.J. Org. Chem..2019,869-878. * |
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