Synthesis and application of derivative containing dibenzothiophene unit
By introducing dibenzothien groups at different positions on the dibenzyme core, designing a herringbone stacking structure and regulating the molecular distortion angle, the problem of insufficient molecular structure and photoelectric properties in the prior art is solved, and an organic semiconductor material with high mobility and strong luminescence is achieved.
Patent Information
- Application Number
- CN202510402875.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-01
- Publication Date
- 2025-08-12
AI Technical Summary
In the prior art, the single linking site of dibenzothiophene and dibenzylithionyl compounds is caused by insufficient research on molecular structure and photoelectric properties, lack of regulatory means, and it is difficult to achieve high mobility and strong emission organic semiconductor materials.
By introducing dibenzothien groups at different positions on the dibenzyme core, three isomer herringbone stacking structures are designed, and the molecular twist angle and intermolecular interaction are used to regulate the molecular twist angle and intermolecular interaction between the dibenzymes.
Compounds with different photophysical and photochemical properties are realized, which show high mobility and strong luminescence properties, providing new ideas for high mobility and strong luminescence organic semiconductors, and the synthesis steps are simple, the raw materials are easy to obtain, and the yield is high.
Smart Images
Figure CN120463679A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of molecular structure and organic photoelectricity. Specifically, we design and synthesize a derivative containing a dibenzothiophene unit and its application. Summary of the Invention
[0002] The present invention relates to the field of molecular structure and organic photoelectricity. Specifically, we design and synthesize a class of derivatives containing dibenzothiophene units and their applications.
[0003] The purpose of the present invention is to develop new molecular structures and new materials for optoelectronic applications. According to literature reports, dibenzothiophene has high electrical conductivity, and the biphenyl skeleton connection can rotate, providing space for molecular conformation adjustment. The rod-shaped molecular geometry formed by the combination of the two tends to adopt an HB stacking arrangement. By introducing dibenzothiophene groups at different positions on the diphenylethylene core, three isomeric herringbone stacking structures were designed, which are considered to be ideal structures for achieving both high mobility and strong emission in organic semiconductors. Not only does it utilize the luminescent properties and multiple modification sites of dibenzothiophene, but it also cleverly regulates the molecular twist angle and intermolecular interaction through the SH bond between the sulfur atom and the hydrogen atoms of the adjacent molecules. By changing the molecular torsion angle, the intermolecular interaction and π-π staking can be effectively reduced, thereby exhibiting different photophysical and photochemical properties. This design strategy provides a new approach for achieving organic semiconductors with high mobility and strong luminescence.
[0004] The present invention relates to the fields of molecular structure and organic optoelectronics. Specifically, we designed and synthesized a class of derivatives containing dibenzothiophene units and their applications. First, we purchased 4,4'-bis(diethoxyphosphonomethyl)biphenyl powder and dry NaH powder. Then, using ultra-dry tetrahydrofuran as the solvent, the mixture was stirred in an ice-water bath for 1 hour. Next, dibenzothiophene-2-carboxaldehyde, dibenzothiophene-3-carboxaldehyde, and dibenzothiophene-4-carboxaldehyde solid powders were dissolved in ultra-dry tetrahydrofuran and added to the respective reactions using a syringe. The mixture was stirred overnight at room temperature, and deionized water was added to quench the reaction. The resulting suspension was filtered under negative pressure, and the solid product was repeatedly washed with ethanol and dichloromethane. After drying, the final products, 2-DBTVB, 3-DBTVB, and 4-DBTVB powders, were obtained. The correctness of our compound synthesis was confirmed by mass spectrometry, single crystal analysis, and other means, and the correctness of our dibenzothiophene unit-containing isomers was also confirmed.
[0005] Through testing, we can see that by introducing dibenzothiophene groups at different positions on the diphenylethylene core, this type of compound exhibits different properties, including the shift of absorption and emission peaks. For example, the absorption and emission spectra show that the absorption peak wavelengths of 3-DBTVB and 4-DBTVB tetrahydrofuran dilute solutions are located at 373nm and 360nm, respectively, and the emission peak wavelengths are located at 424nm, 450nm and 421nm, 442nm; the absorption peaks of solid-state single crystals are located at 381nm and 378nm, and the emission peaks are located at 478nm and 513nm. Therefore, it is particularly important to study its internal mechanism, and it is also a topic for our future research. Furthermore, the laser threshold changes at different access sites, from 4.77μJ / cm3 for 3-DBTVB to 4.77μJ / cm4 for 4-DBTVB. 2 to 7.29 μJ / cm for 4-DBTVB 2 . At the same time, this type of compound has a very high fluorescence quantum yield and shows strong luminescence in both solution and solid state, indicating that the three molecules are densely packed and do not cause fluorescence quenching. This type of compound has a simple synthesis step and can be quickly synthesized in large quantities, providing conditions for subsequent research. At the same time, this type of compound has the property of laser gain and can be used as an excellent laser medium. At the same time, through single crystal analysis tests, it can be seen that this type of compound is all herringbone stacked. By analyzing and calculating the CH-π and π-π spacing and the SH interaction between S atoms and H atoms between adjacent molecules, the effects of herringbone stacking and changes in the connection sites of dibenzothiophene groups on mobility and fluorescence quantum yield are more effectively analyzed, proving that this type of molecule is a very good class of optoelectronic organic semiconductor materials.
[0006] It should be understood that the advantages of the present invention will be described in the following description, and the following detailed description is exemplary and explanatory. The objectives and other advantages of the present invention can be achieved and obtained through the structures specifically pointed out in the description, claims and drawings. BRIEF DESCRIPTION OF THE DRAWINGS
[0007] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments:
[0008] Figure 1This is the reaction formula for the synthesis of dibenzothiophene derivatives in Example 1 of the present invention. 400 mg, 0.88 mmol of 4,4'-bis(diethoxyphosphonomethyl)biphenyl and a small amount of NaH were weighed on an analytical balance and placed in a reaction flask. 20 mL of tetrahydrofuran (THF) solvent was added and dissolved and activated in an ice-water bath under N2 protection for 1 hour. Then, 374 mg, 1.76 mmol of dibenzothiophene-2-carboxaldehyde, dibenzothiophene-3-carboxaldehyde, and dibenzothiophene-4-carboxaldehyde in THF were quickly injected into each reaction mixture, and the entire reaction process was carried out at room temperature. After stirring overnight, water was added to quench the reaction. The product has low solubility in most organic solvents. After multiple washings, purification by suction filtration, and purification twice by sublimation in a tubular furnace, 2-DBTVB, 3-DBTVB, and 4-DBTVB powders were obtained, respectively, and the product was synthesized cumulatively.
[0009] Figure 2 The second embodiment of the present invention is Figure 1 Three different dibenzothiophene group derivatives were obtained by changing different connection sites, and their molecular formulas are listed in the figure.
[0010] Figure 3 The single crystal images of 2-DBTVB, 3-DBTVB, and 4-DBTVB of Example 3 of the present invention are shown in Figure 1. It can be seen that these compounds all have herringbone stacking.
[0011] Figure 4 The absorption and emission spectra of 2-DBTVB, 3-DBTVB, and 4-DBTVB in tetrahydrofuran solution and solid state, respectively, are shown in Figure 4. As can be seen, the absorption and emission spectra shift with changes in the attachment sites of dibenzothiophene and the bisphenylethylene group, exhibiting significant differences, reflecting the influence of molecular arrangement and π-π stacking.
[0012] Figure 5 The laser spectra of the 2-DBTVB, 3-DBTVB, and 4-DBTVB micro-nanocrystals of Example 5 of the present invention are shown. Under excitation by a 400nm femtosecond laser, laser emission can be achieved at the crystal edge. The laser wavelengths are 471nm, 481nm, and 485nm, and the laser thresholds are 5.21, 4.77, and 7.29μJ / cm², respectively. This demonstrates excellent gain properties.
[0013] Figure 6 These are 2-DBTVB, 3-DBTVB, and 4-DBTVB according to Example 6 of the present invention. From the fluorescence field crystal photos, it can be seen that the micro-nanocrystals prepared by the PVT method of this type of compound have regular geometric morphology.
[0014] Figure 7The electron cloud distributions of HOMO and LUMO of 2-DBTVB, 3-DBTVB, and 4-DBTVB according to the seventh embodiment of the present invention are obtained by theoretical calculation and experimental testing. DETAILED DESCRIPTION
[0015] The following will describe the embodiments of the present invention in detail with reference to the accompanying drawings and examples, so that the invention can fully understand how to apply technical means to solve technical problems in previous years and achieve the technical effects, and implement them accordingly. It should be noted that as long as there is no conflict, the various features in the various embodiments of the present invention can be combined with each other, and the resulting technical solutions are all within the scope of protection of the present invention.
[0016] The invention discloses the synthesis and application of a class of derivatives containing dibenzothiophene units.
[0017] Through design and modification, a series of derivatives containing dibenzothiophene units were synthesized.
[0018] Derivatives containing dibenzothiophene units have the advantages of simple synthesis steps, cheap and readily available raw materials, simple purification methods, high yields, and high fluorescence quantum yields.
[0019] The derivatives containing dibenzothiophene units have higher solid fluorescence quantum yield.
[0020] Derivatives containing dibenzothiophene units have obvious herringbone stacking and show coordinated mobility and luminescence.
[0021] Derivatives containing dibenzothiophene units are a class of compounds with laser gain properties.
[0022] The micro-nanocrystals of derivatives containing dibenzothiophene units have regular geometric morphology, which is conducive to the production of devices such as OLET and is an interesting class of organic semiconductor optoelectronic materials.
[0023] Theoretical calculations and experimental measurements of the HOMO and LUMO electron cloud distributions of derivatives containing dibenzothiophene units demonstrated the influence of intermolecular interactions on electrical properties, laying the foundation for the subsequent preparation of OLET devices. This design strategy provides new ideas for achieving organic semiconductors with high mobility and strong luminescence.
[0024] Example 1:
[0025] Figure 1400 mg (0.88 mmol) of 4,4'-bis(diethoxyphosphonomethyl)biphenyl and a small amount of NaH were weighed on an analytical balance and placed in a reaction flask. 20 mL of tetrahydrofuran (THF) was added and the mixture was dissolved and activated in an ice-water bath under N2 protection for 1 hour. Then, 374 mg (1.76 mmol) of dibenzothiophene-2-carboxaldehyde, dibenzothiophene-3-carboxaldehyde, and dibenzothiophene-4-carboxaldehyde dissolved in THF were rapidly injected into the reaction mixture. The entire reaction was carried out at room temperature. After stirring overnight, the reaction was quenched with water. The product has low solubility in most organic solvents. It was purified by multiple washings, filtration, and two purifications by sublimation in a tube furnace. Finally, 2-DBTVB, 3-DBTVB, and 4-DBTVB powders were obtained, respectively, to form a cumulative synthesis product.
[0026] Example 2:
[0027] Figure 2 Three different dibenzothiophene group derivatives were obtained by changing the different connection sites. It is worth noting that dibenzothiophene aldehydes at positions 2, 3, and 4 can all be connected.
[0028] Example 3:
[0029] Figure 3 We analyzed the single crystals of the prepared compounds 2-DBTVB, 3-DBTVB, and 4-DBTVB, confirming that this type of compound has a herringbone stacking structure, which affirmed the rationality and feasibility of the design.
[0030] Example 4:
[0031] Figure 4 Figure 2 shows the absorption and emission spectra of 2-DBTVB, 3-DBTVB, and 4-DBTVB in tetrahydrofuran solutions and solid states. It can be seen that as the attachment sites of dibenzothiophene and the distyryl group change, both the absorption and emission spectra shift, exhibiting significant differences. The absorption peak wavelengths for dilute tetrahydrofuran solutions of 2-DBTVB, 3-DBTVB, and 4-DBTVB are located at 367nm, 373nm, and 360nm, respectively, while the emission peak wavelengths are located at 422 and 442nm, 424 and 450nm, and 421 and 442nm, respectively. The absorption peaks for solid-state single crystals are located at 370nm, 381nm, and 378nm, while the emission peaks are located at 470nm, 478nm, and 513nm, reflecting the influence of molecular arrangement and π-π stacking.
[0032] Embodiment 5:
[0033] Figure 5The laser gain properties of 2-DBTVB, 3-DBTVB, and 4-DBTVB were tested. Micro-nanocrystals with three molecules of regular morphology were prepared by PVT. Under the excitation of a 400nm femtosecond laser, laser emission was achieved at the crystal edge. The laser wavelengths were 471nm, 481nm, and 485nm, and the laser thresholds were 5.21, 4.77, and 7.29μJ / cm 2 . , showing a very good gain property.
[0034] Example 6:
[0035] Figure 6 In order to utilize the PVT method, crystals were grown at sublimation temperatures of 320, 320, and 360°C and deposition temperatures of 260, 270, and 260°C, respectively, laying the foundation for the subsequent preparation of optoelectronic devices.
[0036] Embodiment seven:
[0037] Figure 7 The electron cloud distribution of HOMO and LUMO of 2-DBTVB, 3-DBTVB and 4-DBTVB is theoretically calculated and experimentally tested. The HOMO and LUMO energy levels of the three molecules range from -5.15 to -5.22 and -1.78 to -1.94, respectively. Their π electron density is mainly distributed on the main chain of diphenylethylene, so the electron density of the HOMO energy level has a higher concentration on diphenylethylene.
Claims
1. Synthesis and application of derivatives containing dibenzothiophene units.
2. The derivative containing dibenzothiophene units according to claim 1, characterized in that A series of compounds with dibenzothiophene units were designed and synthesized. These compounds have the characteristics of low raw materials, simple synthesis, and easy purification.
3. The derivative containing dibenzothiophene units according to claim 2, characterized in that Its structure is:
4. The derivative containing dibenzothiophene units according to claim 3, characterized in that It is an isomer with obvious differences in stacking arrangements, and there are strong π-π stacking and CH-π stacking.
5. The derivative containing dibenzothiophene units according to claim 4, characterized in that Its molecular stacking is herringbone stacking, which is a new type of compound that combines high mobility and strong luminescence.
6. The derivative containing dibenzothiophene units according to claim 5, characterized in that Micro-nanocrystals grown using the PVT method have strong laser gain properties.
7. The derivative of dibenzothiophene unit according to claim 6, characterized in that It has transfer properties and can be used in organic field-effect transistor applications.
8. The derivative containing dibenzothiophene units according to claim 7, characterized in that It is a very good type of optoelectronic material with high external quantum efficiency and is expected to be used in the OLED field.