A tetrathiafulvalene tetrakisbenzaldehyde schiff base cage compound and application thereof
By synthesizing tetrathiofulvalene tetrabenzaldehyde Schiff base cage-like compounds, the problems of narrow light absorption range and instability of TTF-type compounds were solved, achieving wide light absorption and efficient photothermal conversion, thus expanding their application in photothermal materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHENZHEN UNIV GENERAL HOSPITAL
- Filing Date
- 2025-10-31
- Publication Date
- 2026-05-29
Smart Images
Figure CN121021536B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the fields of crystallography and materials science, specifically to a tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound and its applications. Background Technology
[0002] Tetrathiofulvalene (TTF) is currently a hot research topic. Its cyclic system can be sequentially oxidized to generate monovalent and divalent cations, and this oxidation process is highly reversible. Its oxidation potential can be effectively controlled by introducing electron-donating or electron-withdrawing substituents. Furthermore, TTF compounds possess a significantly rigid planar structure, a characteristic that makes its derivatives more prone to close-packing within the molecule. The sulfur atoms can interact with each other at different positions in various ways, constructing a network of intermolecular interactions, thereby enhancing intermolecular forces and improving system stability. These interactions enable TTF to act as excellent electron donors, achieving efficient redox reactions in complex environments.
[0003] TTF-based compounds, due to their unique charge transfer capabilities and tunable electronic structures, show great promise for applications in photothermal materials, but they also face several key challenges. First, TTFs have a narrow light absorption range, typically limited to the ultraviolet to visible light (200-400 nm) region, failing to effectively utilize the near-infrared region of the solar spectrum, which has a higher energy content, resulting in low photothermal conversion efficiency. Second, the fulvalene framework in TTF molecules possesses strong electron-donating properties, making TTF molecules prone to degradation in oxidative environments, further narrowing their light absorption range and limiting the possibility of long-term, high-efficiency operation. Finally, the traditional synthesis steps for TTF-based compounds are cumbersome, and structural regulation is complex, requiring precise control of intermolecular interactions to optimize their photothermal performance.
[0004] Therefore, constructing TTF-type compound materials that combine functionality and stability not only transforms their inherent properties into application performance, but also provides an effective path for technological breakthroughs in fields such as solar energy utilization, photothermal therapy, and photothermal catalysis. Summary of the Invention
[0005] The purpose of this invention is to overcome at least one of the shortcomings of the prior art, such as narrow light absorption range, narrow light absorption range, and complex synthesis, and to provide a tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound and its application.
[0006] The technical solution adopted in this invention is:
[0007] In a first aspect, the present invention provides a tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound, wherein the molecular formula of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound is C2. 126 H 108 N16 S 12 The molecular weight is 2231.08, and the unit cell parameters are: a = 17.0810(12) Å, b = 19.3138(13) Å, c = 22.0054(4) Å; α = 104.811(2)°, β = 101.466(2)°, γ = 101.348(2)°, V = 6639.3(8) Å. 3 Z = 2, and the space group is P-1.
[0008] Specifically, the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound belongs to the triclinic crystal system.
[0009] In some embodiments, the method for synthesizing the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound includes the following steps:
[0010] 1) Dissolve tetrathione-fulvalene tetrabenzaldehyde and tris(2-aminoethyl)amine separately in organic solvent A;
[0011] 2) Then, organic solvent B is added to the tetrathiofulvalene tetrabenzaldehyde-dichloromethane solution to form a layer;
[0012] 3) Finally, add the tris(2-aminoethyl)amine-dichloromethane solution to the upper layer of the layered solution formed in step 2), and allow the reaction to stand to obtain the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound.
[0013] In some embodiments, the molar ratio of the tetrathiofulvalene tetrabenzaldehyde and tris(2-aminoethyl)amine is 3:(3.5-4.5).
[0014] In some embodiments, the settling reaction time is 100-125 h.
[0015] In some embodiments, the organic solvent A is selected from at least one of dichloromethane, chloroform, chlorobenzene, dichloroethane, or tetrachloroethane.
[0016] In some embodiments, the organic solvent B is selected from at least one of methanol, ethanol, and tetrahydrofuran.
[0017] In some embodiments, the molar ratio of the tetrathiofulvalene tetrabenzaldehyde and tris(2-aminoethyl)amine is 3:4.
[0018] In some embodiments, when the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound is used as a photothermal conversion material, the excitation wavelength of the photothermal conversion material is 800-1100 nm.
[0019] Secondly, the present invention provides a photothermal conversion material prepared from the aforementioned tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound.
[0020] The beneficial effects of this invention are:
[0021] The tetrathiofulvalene radical, which acts as an electron donor, forms a tetrathiofulvalene tetrabenzaldehyde Schiff base cage-like compound crystal, which significantly improves the light absorption efficiency and photothermal conversion efficiency, making it promising for applications in tumor photothermal therapy, photothermal power generation, and solar-driven seawater desalination.
[0022] The compounds in this invention, such as tetrathiofulvalene tetrabenzaldehyde and tris(2-aminoethyl)amine, can be obtained using commercially available reagents and raw materials, and the crystals grow very easily. It has advantages such as simple operation, fast growth rate, short growth cycle, low cost, and easy acquisition of large-size crystals. Attached Figure Description
[0023] Figure 1 The diagram shows the three-dimensional structure of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage-like compound synthesized in the embodiments of the present invention. Figure a is a schematic diagram of the ball-and-stick model, and Figure b is a schematic diagram of the structural formula.
[0024] Figure 2 This is the mass spectrum of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound synthesized in an embodiment of the present invention.
[0025] Figure 3 The 1H NMR spectrum of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound synthesized in this embodiment of the invention.
[0026] Figure 4 The absorbance curve of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound synthesized in the embodiments of the present invention is shown in dichloromethane as a solvent.
[0027] Figure 5 The curve shows the temperature change over time of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound synthesized in this embodiment of the invention under 808 nm laser irradiation.
[0028] Figure 6 The temperature curves of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound synthesized in this embodiment of the invention during 10 light-cooling cycles under 808 nm laser irradiation.
[0029] Figure 7 The temperature curves of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound synthesized in this embodiment of the invention during 10 light-cooling cycles under 1064 nm laser irradiation. Detailed Implementation
[0030] The present invention will be further described below with reference to specific embodiments, but the present invention is not limited thereto. Unless otherwise specified, the test methods and experimental reagents used in the specific embodiments are all conventional products in the art.
[0031] Example
[0032] The synthesis steps of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage-like compound crystal in this embodiment are as follows:
[0033] Step 1:
[0034] Weigh 12.4 mg of tetrathiofulvalene tetrabenzaldehyde into a 3 mL glass sample bottle, add 1 mL of dichloromethane to dissolve it, and then slowly add 0.5 mL of methanol along the bottle wall to allow the methanol and dichloromethane to form separate layers with the methanol on the upper layer.
[0035] Step 2:
[0036] Weigh 7.8 mg of tris(2-aminoethyl)amine into a 1.5 mL glass sample vial and add 1 mL of dichloromethane to dissolve it completely.
[0037] Step 3:
[0038] Take 0.5 mL of the solution obtained in step 2 and slowly add it dropwise along the bottle wall to the liquid obtained in step 1, so that the solution obtained in step 2 is above the methanol, causing it to separate into layers with the methanol.
[0039] Step 4:
[0040] Allow it to stand for 5 days to allow it to diffuse freely and undergo a Schiff base reaction, thus obtaining tetrathiofulvalene tetrabenzaldehyde Schiff base cage-like compound crystals.
[0041] The specific characteristics are as follows:
[0042] The sample of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage-like compound obtained in the above steps was subjected to crystal form analysis and NMR analysis. For example... Figure 1 As shown, the chemical formula of the sample crystal is C. 126 H 108 N 16 S 12 The unit cell parameters are: a = 17.0810(12) Å, b = 19.3138(13) Å, c = 22.0054(4) Å; α = 104.811(2)°, β = 101.466(2)°, γ = 101.348(2)°, V = 6639.3(8) Å. 3 Z = 2; space group is P-1.
[0043] The mass spectrum and NMR spectrum of the sample crystal are as follows: Figure 2 and Figure 3 As shown. The peak positions of the sample's NMR are... 1 H NMR (500 MHz, CDCl3, 298 K) δ (ppm), 8.21 (s, 4H), 7.96 (s, 8H), 7.21-7.20 (t, 8H), 7.04-7.02 (t, 16H), 6.90-6.89 (t, 16H), 7.76- 7.75 (t, 8H), 3.83-3.79 (t, 16H), 3.61-3.56 (q, 8H), 3.01-2.97 (q, 8H), 2.88 (s, 8H), 2.65-2.63 (t, 8H).
[0044] like Figure 4 As shown, in dichloromethane solvent, the sample exhibits high transmittance in the ultraviolet region, with an ultraviolet absorption cutoff edge above 400 nm, indicating that the material possesses excellent optical transparency in the visible light range, providing a foundation for its application in optical window materials and transparent functional films.
[0045] Furthermore, the near-infrared photothermal conversion performance of the synthesized tetrathiofulvalene tetrabenzaldehyde Schiff base cage-like compound crystalline sample powder (approximately 20 mg in mass) was systematically tested.
[0046] like Figure 5 As shown, under irradiation with an 808 nm near-infrared laser, the sample temperature rises rapidly, reaching a maximum temperature of 168.3 °C from room temperature in just 32 seconds, exhibiting significant photothermal response characteristics.
[0047] like Figure 6 As shown, in 10 consecutive light-cooling cycles of 808 nm laser, the sample exhibited good stability and repeatability. Each cycle could rapidly heat up to above 160 °C within 40 seconds, and no obvious performance degradation was observed, indicating that the cage-like compound has a stable structure and the potential for long-term use.
[0048] like Figure 7 As shown, under the same cyclic conditions of 1064 nm laser, the sample also exhibits excellent photothermal performance, and can be repeatedly heated to above 90 °C in just 30 seconds, further confirming that it has efficient and stable photothermal conversion capabilities in the multi-band near-infrared region, expanding its application prospects in photothermal therapy, photo-driven devices and infrared sensing.
[0049] The above is a further detailed description of the present invention and should not be considered as a limitation on the specific implementation of the present invention. For those skilled in the art, simple deductions or substitutions without departing from the concept of the present invention are all within the protection scope of the present invention.
Claims
1. A tetrathiofulvalene tetrabenzaldehyde Schiff base cage-like compound, characterized in that, The molecular formula of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound is C 126 H 108 N 16 S 12 The molecular weight is 2231.08, and the unit cell parameters are: a =17.0810(12) Å, b = 19.3138(13) Å, c = 22.0054(4) Å; α = 104.811(2)°, β = 101.466(2)°, γ = 101.348(2)°, V = 6639.3(8)Å 3 , Z = 2, space group is P -1; The structural formula of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound is as follows: 。 2. The tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound according to claim 1, characterized in that, The tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound belongs to the triclinic crystal system.
3. The method for synthesizing the tetrathiofulvalene tetrabenzaldehyde Schiff base cage-like compound according to claim 1, characterized in that, The synthesis method includes the following steps: 1) Tetrathiofulvalene tetrabenzaldehyde and tri(2-aminoethyl)amine are dissolved in dichloromethane, wherein the molar ratio of the amounts of tetrathiofulvalene tetrabenzaldehyde and tri(2-aminoethyl)amine is 3:(3.5-4.5). 2) Then methanol is added to the tetrathiofulvalene tetrabenzaldehyde-dichloromethane solution to form a layer; 3) Finally, add the tris(2-aminoethyl)amine-dichloromethane solution to the upper layer of the layered solution formed in step 2), and allow the reaction to stand to obtain the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound.
4. The synthesis method according to claim 3, characterized in that, The static reaction time is 100-125 h.
5. The synthesis method according to claim 3, characterized in that, The molar ratio of tetrathiofulvalene tetrabenzaldehyde and tris(2-aminoethyl)amine is 3:
4.
6. The application of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound according to claim 1 in the preparation of photothermal conversion materials. The excitation wavelength of the tetrathiofulvalene tetrabenzaldehyde Schiff base cage compound is 800-1100 nm.