Crystalline organic light-emitting material and preparation method and application thereof
By using a donor-acceptor co-crystal structure formed by a cyclic trinaphthalene diimide derivative and perylene molecules, the problem of insufficient performance of existing two-photon absorption materials is solved, achieving a combination of high-efficiency two-photon absorption and photothermal conversion performance, and exhibiting excellent near-infrared fluorescence emission and rapid photothermal conversion performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-10
- Publication Date
- 2026-04-10
AI Technical Summary
Existing technologies make it difficult to construct high-performance two-photon absorbing materials using purely organic structural units, and existing materials have limited optical and photothermal conversion properties.
A crystalline organic light-emitting material with a donor-acceptor (DA) eutectic structure is formed by stacking cyclic trinaphthalimide derivatives and perylene molecules through non-covalent π···π interactions and intermolecular CH···π and CH···O interactions, thereby achieving a combination of two-photon absorption and photothermal conversion performance.
It achieves high efficiency in two-photon absorption and near-infrared fluorescence emission, with a two-photon absorption cross-section of 541 GM. It can be rapidly heated to 120 degrees Celsius under high-energy laser excitation, exhibiting good photothermal conversion performance and stability. The synthesis method is simple and low-cost.
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Figure CN121824541A_ABST
Abstract
Description
Technical Field
[0001] This application relates to a crystalline organic light-emitting material, its preparation method and application, belonging to the field of organic solid-state light-emitting material technology. Background Technology
[0002] Two-photon absorption upconversion fluorescence refers to the nonlinear optical process in which a material simultaneously absorbs two low-energy photons, transitions to a high-energy state, and subsequently emits a higher-energy, shorter-wavelength photon. Compared to traditional single-photon fluorescence, it offers better spatial resolution, better penetration into deep tissues, and lower background fluorescence interference. Research on two-photon absorption has made rapid progress in recent years, with researchers developing many nanomaterials with excellent two-photon absorption cross-sections through rare-earth element doping. However, constructing high-performance two-photon absorption materials using purely organic structural units remains challenging.
[0003] Macrocyclic compounds have profoundly influenced the establishment of supramolecular chemistry due to their rich molecular recognition and self-assembly properties. Compared with flexible macrocycles, rigid macrocycles with π-conjugated aromatic units, in addition to their stable shape, tend to have large internal / external π-surfaces. These characteristics not only endow these macrocycles with a wide range of host-guest properties but also make them ideal building blocks for constructing various supramolecular structures. Constructing diverse chiral organic macrocyclic materials through host-guest molecular recognition has proven to be an effective way to regulate the photoelectrochemical properties between host and guest molecules. Summary of the Invention
[0004] In view of the above, the purpose of this application is to provide a pure organic eutectic luminescent material constructed from a cyclic trinaphthalene diimide derivative and an organic small molecule perylene, which can effectively achieve near-infrared upconversion two-photon excited fluorescence.
[0005] According to a first aspect of this application, a crystalline organic light-emitting material is provided, the crystalline organic light-emitting material comprising a cyclic trinaphthalene diimide derivative and perylene, the cyclic trinaphthalene diimide derivative having the structure shown in Formula I:
[0006] Formula I The cyclic trinaphthalene diimide derivative and the perylene molecule are connected by non-covalent π···π interaction, and the cyclic trinaphthalene diimide derivative molecules are stacked together by CH···π and CH···O interaction to form the crystalline organic light-emitting material.
[0007] The crystalline organic light-emitting material of this application uses a cyclic trinaphthalene diimide derivative as an electron acceptor and perylene as an electron donor, and constructs a high-performance organic light-emitting material through a donor-acceptor (DA) eutectic bonding.
[0008] The crystalline organic light-emitting material of this application is rich in stable π···π interactions. Through intramolecular non-covalent π···π interactions and intermolecular CH···π and CH···O interactions, it is easy to undergo effective electron delocalization and polarization, thereby obtaining near-infrared fluorescence emission.
[0009] In some embodiments of the first aspect of this application, the chemical structural formula of the crystalline organic light-emitting material is C 345 H 243 N 21 O 54 .
[0010] In some embodiments of the first aspect of this application, each cyclic triazonaphthalimide derivative molecule in the crystalline organic light-emitting material is surrounded by three perylene molecules.
[0011] In some embodiments of the first aspect of this application, the structural unit cells of the crystalline organic light-emitting material belong to the orthorhombic crystal system. P1 Space group.
[0012] In some embodiments of the first aspect of this application, when the cyclic triazonaphthalimide derivative is in the R configuration (Formula 1), the unit cell parameters of the crystalline organic light-emitting material are a = 16.01 Å, b = 24.31 Å, c = 24.48 Å, α = 61°, β = 76°, γ = 83°, and the unit cell volume is 8117.62 Å. 3 Z=1, Dc=1.135g / cm 3 ; Formula 1 In some other embodiments of the first aspect of this application, when the cyclic triazonaphthalimide derivative is in the S configuration (Formula 2), the cell parameters of the crystalline organic light-emitting material are a = 16.05 Å, b = 24.54 Å, c = 24.69 Å, α = 60°, β = 77°, γ = 84°, and the cell volume is 8207.32 Å. 3 Z=1, Dc=1.122g / cm 3 ; Equation 2.
[0013] The inventors discovered in their research that the crystalline organic light-emitting material of this application forms a donor-acceptor (DA) eutectic structure through covalent π··π interactions between cyclic triazophthalimide derivatives and perylene molecules, thereby achieving both two-photon absorption performance and excellent photothermal conversion performance. The cyclic triazophthalimide derivatives in this application have two configurations, R / S, both of which can form a donor-acceptor (DA) eutectic structure with perylene molecules, thus obtaining the crystalline organic light-emitting material of this application.
[0014] The second aspect of this application provides a method for preparing the crystalline organic light-emitting material provided in the first aspect of this application, including: A mixed solution containing cyclotrimeric naphthalene and perylene is reacted at 80-120°C for 60-80 hours to obtain the crystalline organic light-emitting material.
[0015] In some embodiments of the second aspect of this application, the mass ratio of the cyclic trinaphthalene diimide derivative to perylene in the mixed solution is 1:1 to 1:3.
[0016] In some embodiments of the second aspect of this application, the concentration of the cyclic triadimenide derivative in the mixed solution is 0.5-1 mg / ml; In some embodiments of the second aspect of this application, the concentration of perylene in the mixed solution is 1-2 mg / ml.
[0017] In this application, the solvent of the mixed solution needs to meet the requirement that the cyclotrimeric naphthalene and perylene can reach the required concentration. Those skilled in the art are capable of obtaining the solvent. In some embodiments, the solvent of the mixed solution is selected from a mixed solvent of N,N-dimethylformamide solution and acetonitrile. Preferably, in the mixed solvent, the volume ratio of N,N-dimethylformamide solution to acetonitrile is (2-3):1.
[0018] In some embodiments of the second aspect of this application, the reaction is followed by a solvent removal step. In some embodiments, the reaction can be carried out in a constant temperature oven to achieve solvent evaporation while maintaining the reaction temperature.
[0019] The third aspect of this application provides the application of the crystalline organic light-emitting material provided in the first aspect of this application as a multifunctional crystalline optical material.
[0020] The beneficial effects that this application can produce include: 1) The near-infrared fluorescence emission band of the organic eutectic luminescent material provided in this application is located around 790nm, and it has good two-photon absorption performance. The two-photon absorption cross section of the eutectic can reach 541GM at 1040nm. Compared with the relatively simple fluorescence excitation mode in existing materials, the organic eutectic luminescent material of this application achieves a high efficiency two-photon absorption cross section.
[0021] 2) The crystalline organic light-emitting material provided in this application has good photothermal conversion performance. Under high-energy laser excitation, it can rapidly heat up to 120 degrees Celsius within 150 seconds, and its cycling performance remains stable after five cycles. Addressing the limitation of existing optical materials having only one specific performance characteristic, the crystalline organic light-emitting material of this application achieves both upconversion fluorescence with two-photon absorption and highly efficient photothermal conversion performance.
[0022] 3) The synthesis method of the crystalline organic light-emitting material provided in this application has the advantages of simple synthesis method, low production cost, mild reaction conditions, and suitability for large-scale production. Furthermore, the synthesized crystalline organic light-emitting material has the advantages of simple preparation method, good crystallinity, and high purity. Attached Figure Description
[0023] Figure 1 A schematic diagram (a) and an NMR spectrum (b) of the synthesis of the cyclic triadimenide derivative of Example 1.
[0024] Figure 2 This is a schematic diagram of the structure of the crystalline organic light-emitting material of this application.
[0025] Figure 3 Crystalline organic light-emitting material prepared for Example 2 of this application R Fluorescence spectrum (a), solid-state UV spectrum (b), and circular dichroism spectrum (c) of -3NDI-PE.
[0026] Figure 4 Crystalline organic light-emitting material prepared for Example 2 of this application R Two-photon fluorescence spectra (a), fitting curve (b), and two-photon absorption cross-section diagram (c) of -3NDI-PE excited by variable power.
[0027] Figure 5 Crystalline organic light-emitting material prepared for Example 2 of this application R Photothermal conversion curve (a) and photothermal conversion curve cycle diagram (b) of -3NDI-PE. Detailed Implementation
[0028] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0029] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.
[0030] In the embodiments of this application, the yield is calculated as follows: the yield calculation formula is (actual yield / theoretical yield) × 100%.
[0031] Preparation Example 1: Preparation of Cyclic Trimeric Naphthalene Diimide Derivatives 1,4,5,8-Naphthalenetetracarboxylic anhydride (CAS: 81-30-1, 3.98 g) and (RR)-trans-1,2-cyclohexanediamine (CAS No. 1121-22-8, 1.71 g) were dissolved in 200 ml of anhydrous N,N-dimethylformamide solution in a 500 ml round-bottom flask. The mixture was refluxed at 150 °C for 5 hours, followed by distillation under vacuum. The dark red residue was dissolved in dichloromethane and separated by silica gel column chromatography (dichloromethane / acetone, 0-10% acetone) to obtain the R-configuration cyclotrimeric diimide derivative. R -3NDI), with a yield of approximately 12%. The synthetic route and NMR spectra are shown below. Figure 1 As shown.
[0032] Using the same method, 1,4,5,8-naphthalenetetracarboxylic anhydride and (SS)-trans-1,2-cyclohexanediamine (adamas CAS No. 21436-03-3) were reacted to obtain an S-configured cyclic trimeric naphthalenediimide derivative. S -3NDI).
[0033] Preparation Example 2: Preparation of the crystalline organic light-emitting material 3NDI-PE of this application The preparation example obtained in Example 1 R -3NDI (11.0 mg, 0.01 mmol) and perylene (22.0 mg, 0.087 mmol) were dissolved in 10 ml DMF and 4.5 ml acetonitrile in a 20 ml glass bottle, and then heated in a constant temperature oven at 100 °C for 72 h. After cooling to room temperature, blocky dark green crystals were observed, which are the crystalline organic light-emitting material of this application (named...). R- 3NDI-PE), with a yield of approximately 70%. Its structure was determined using a single-crystal diffractometer. Data were measured using a Synergy R single-crystal diffractometer manufactured by Rigaku, employing Cu Ka radiation (λ = 1.54178 Å) at 100 K. The test results show that: R- The structural formula of 3NDI-PE is C 345 H 243 N 21 O 54 It belongs to the orthorhombic crystal system, space group 1. P1. The unit cell parameters are a = 16.01 Å, b = 24.31 Å, c = 24.48 Å, α = 61°, β = 76°, γ = 83°, and the unit cell volume is 8117.62 Å. 3 Z=1, Dc=1.135g / cm 3 Its structural diagram is as follows: Figure 2 As shown, R- In 3NDI-PE, each cyclic triazophthalimide derivative molecule is tightly surrounded by three perylene molecules, forming a DADAD-type closely packed pizza-like two-dimensional layered structure. These two-dimensional layered structures are stacked to form the crystalline organic light-emitting material of this application. The centroid distance between the benzene rings of the electron donor and acceptor (d...) π...π The interlayer CH···O interaction distance is 3.35-3.39 Å; the interlayer CH···O interaction distance is 2.35-2.76 Å. S-type crystalline organic light-emitting materials. S- 3NDI-PE was synthesized in the same manner as described above. Single-crystal diffraction results showed that: S- The structural formula of 3NDI-PE is C 345 H 243 N 21 O 54 It belongs to the orthorhombic crystal system, space group 1. P 1. The unit cell parameters are a = 16.05 Å, b = 24.54 Å, c = 24.69 Å, α = 60°, β = 77°, γ = 84°, and the unit cell volume is 8207.32 Å. 3 Z=1, Dc=1.122g / cm 3 .
[0034] The crystalline organic light-emitting material of this application exhibits a significantly deeper crystal color compared to the precursor due to the strong non-covalent π-π interaction between the cyclic trinaphthalene diimide derivative and perylene molecules. The crystal is dark green, which is mainly attributed to the significant reduction in band gap after self-assembly between the donor and acceptor.
[0035] Example 1 R- Photoluminescence (PL) spectra of 3NDI-PE were obtained using a UV / V / NIR fluorescence spectrometer at Edinburgh (FLS1000) with an excitation wavelength of 400 nm. The fluorescence emission spectra are shown below. Figure 3 As shown in Figure (a), it can be seen that R- The optimal emission wavelength for 3NDI-PE fluorescence is 790 nm, which falls within the near-infrared emission region. UV-visible absorption data were also recorded using a PerkinElmer Lamda-950 UV spectrophotometer. The UV absorption spectrum is shown below. Figure 3 As shown in Figure (b), it can be seen that R-3NDI-PE exhibits full-spectrum absorption in the 200-800 nm wavelength range. Furthermore, R- 3NDI-PE and S- The circular dichroism (CD) spectrum of solid-state NDI-PE was measured using the KBr pellet method on a JASCO-J1500 polarization spectrometer. The results are as follows: Figure 3 As shown in Figure (c), it can be seen from Figure c that the chirality of cyclohexanediamine is well preserved in the cocrystal, and the CD spectrum shows a good Cotton effect.
[0036] Example 2 The two-photon excited near-infrared fluorescence and two-photon absorption cross section of the crystalline organic light-emitting material of this application were detected by the following method, specifically including the following steps: Two-photon excited fluorescence spectra were obtained using an Astrella / OperA femtosecond laser as the excitation source and collected using a marine optical spectrophotometer (QE65 Pro). R- Emission spectrum of 3NDI-PE. Upconversion fluorescence emission spectra were measured with varying power under a fixed excitation of 1064 nm. Furthermore, while maintaining consistent testing conditions, the emission spectra were measured in the 960–1080 nm range. R- The solid-state two-photon fluorescence (TPEF) intensity of 3NDI-PE was compared with that of Rhodamine B (RhB) for quantitative calculation. R- TPEF section of 3NDI-PE. Results are as follows. Figure 4 As shown in the figure, figure a is the two-photon fluorescence spectrum excited by variable power, figure b is the power-dependent linear fitting curve, and figure c is the two-photon absorption cross-section. Figure a shows that under 1064 nm laser excitation, as the excitation power increases, R- The fluorescence emission intensity of 3NDI-PE was significantly improved. As shown in Figure b, the square of the excitation power exhibits a good linear relationship with the fluorescence intensity, indicating that the upconversion fluorescence originates from a two-photon absorption mechanism. As shown in Figure c, R- The maximum two-photon absorption cross section of 3NDI-PE at 1040nm can reach 541GM.
[0037] Example 3 The photothermal conversion performance of the crystalline organic light-emitting material in this application was tested through the following steps: Under 808nm laser irradiation (DL-S-808-3000mW, China) R- Photothermal testing was conducted using 3NDI-PE. Real-time temperature changes were recorded using an infrared thermal imager (HM-TPK 20-3AQF / W, China). Monitoring... R-The photothermal effect was measured by the temperature of the 3NDI-PE crystal powder. To evaluate the single-wavelength photothermal conversion efficiency, R- 3NDI-PE was irradiated with an NIR laser for 235 seconds, the laser was turned off, and the temperature was measured again for 215 seconds. This cycle was repeated five times. The results are as follows: Figure 5 As shown in the figure, Figure a is the heating and cooling curves with varying power, and Figure b is a cyclic graph of the heating and cooling curves. Figure a shows that as the laser power increases, R- The heating rate of 3NDI-PE crystal powder was significantly improved at 808 nm and 0.8 W / cm² power. R -3NDI-PE crystals can be rapidly heated to 120 degrees Celsius within 150 seconds. As can be seen from Figure b, R- 3NDI-PE eutectic powder exhibits good cycling stability.
[0038] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A crystalline organic light emitting material, characterized by, The crystalline organic light-emitting material contains a cyclic triazonaphthalene diimide derivative and perylene, wherein the cyclic triazonaphthalene diimide derivative has the structure shown in Formula I: Formula I The cyclic trinaphthalene diimide derivative and the perylene molecule are connected by non-covalent π···π interaction, and the cyclic trinaphthalene diimide derivative molecules are stacked together by CH···π and CH···O interaction to form the crystalline organic light-emitting material.
2. The crystalline organic light emitting material according to claim 1, characterized in that, The chemical structural formula of the crystalline organic light-emitting material is C 345 H 243 N 21 O 54 .
3. The crystalline organic light emitting material according to claim 1, characterized in that, In the crystalline organic light-emitting material, each cyclic trinaphthalene diimide derivative molecule is surrounded by three perylene molecules.
4. The crystalline organic light-emitting material according to claim 1, characterized in that, The structural unit of the crystalline organic light-emitting material belongs to an orthorhombic system, P1 space group.
5. The crystalline organic light emitting material according to claim 1, wherein The crystal cell parameter of the crystalline organic light-emitting material is a = 16.01 A, b = 24.31 A, c = 24.48 A, a = 61°, b = 76°, g = 83°, and the crystal cell volume is 8117.62 A 3 ; Z = 1, Dc = 1.135 g / cm 3 ; Alternatively, the crystal cell parameters of the crystalline organic light emitting material are a = 16.05 A, b = 24.54 A, c = 24.69 A, a = 60°, β = 77°, γ = 84°, and the crystal cell volume is 8207.32 A 3 . Z = 1, Dc = 1.122 g / cm 3 .
6. The method for preparing the crystalline organic light-emitting material according to any one of claims 1-5, characterized in that, include: A mixed solution containing cyclotrimeric naphthalene and perylene is reacted at 80-120°C for 60-80 hours to obtain the crystalline organic light-emitting material.
7. The method of claim 6, wherein, In the mixed solution, the mass ratio of the cyclic trinaphthalene diimide derivative to perylene is 1:1 to 1:
3.
8. The method according to claim 6, characterized in that, In the mixed solution, the concentration of the cyclic triadimenyl diimide derivative is 0.5-1 mg / ml; Preferably, the concentration of perylene in the mixed solution is 1-2 mg / ml.
9. The method according to claim 6, characterized in that, The solvent of the mixed solution is selected from a mixed solvent of N,N-dimethylformamide solution and acetonitrile; preferably, the volume ratio of N,N-dimethylformamide solution to acetonitrile in the mixed solvent is (2-3):
1.
10. The application of the crystalline organic light-emitting material according to any one of claims 1-5 as a multifunctional crystalline optical material.