Narrow-band emission ortho-substituted diaryl benzene as well as preparation method and application thereof
By designing and synthesizing ortho-substituted diarylbenzene molecules and utilizing the spatial conjugation effect, a narrowband emission material with a half-width of less than 35 nm was successfully prepared. In particular, 91-Phen-Pyre-Ben achieved an ultra-narrowband emission of 6 nm, which solved the problem of the difficulty in shrinking narrowband emission materials in the existing technology and improved the color purity and application potential of organic light-emitting materials.
Patent Information
- Application Number
- CN202411592749.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-08
- Publication Date
- 2026-02-27
AI Technical Summary
Existing technologies make it difficult to synthesize ultranarrow band organic light-emitting materials with a half-width of less than 10 nm, and design strategies based on boron-nitrogen structures are difficult to further reduce the emission peak. Research on spatial conjugation effects is also insufficient.
Three ortho-substituted diarylbenzene molecules were designed and synthesized by altering the size of the aryl moiety to form a large dihedral angle, thereby breaking valence conjugation and forming stable spatial conjugation. The synthesis was carried out using the classic Suzuki coupling reaction, which involved reacting arylboronic acid and 9-(2-bromophenyl)phenanthrene in an anaerobic environment. After extraction, drying, and column chromatography separation, 19-Naph-Phen-Ben, 99-Phen-Ben, and 91-Phen-Pyre-Ben were prepared.
Narrowband emission with a half-width of less than 35 nm in solution was achieved, with 91-Phen-Pyre-Ben emission being tunable to an ultra-narrowband emission of 6 nm, significantly improving the purity of the emitted color and showing potential for application in optoelectronic devices.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of weakly interacting organic light-emitting materials, in particular to a class of ortho-substituted diarylbenzenes with narrow-band emission and a preparation method and application thereof. BACKGROUND
[0002] In the past few decades, the theory of electronic structure regulation through-bond conjugation (TBC) has been widely applied in traditional planar conjugated molecular systems, which has enabled many synthetic organic functional materials to exhibit excellent performance.
[0003] However, the influence of through-space conjugation (TSC) on electronic structure and its further influence mechanism on material performance have not been fully studied. People call the material whose luminescence is based on the weak interaction of space conjugation as "weakly interacting organic light-emitting material".
[0004] Color purity is one of the important performance parameters of display devices, and improving color purity requires materials to have a small full width at half maximum (FWHM). Compared with inorganic compounds, it is more difficult to improve the color purity of organic compounds, because there is vibration coupling and structural relaxation between the ground state and the excited state of organic compounds, which usually leads to a FWHM of more than 40 nm. This wide emission peak is not conducive to the practical application of organic compounds. Therefore, how to design and synthesize organic materials with narrow-band emission has been the goal of researchers.
[0005] In recent years, Takuji Hatakeyama of Kyoto University found that v-DABNA with boron-nitrogen structure has a FWHM of only 14 nm, and proposed a multiple resonance effect to explain this phenomenon (Nat. Photon. 2019, 13, 678-682). Subsequently, narrow-band emission materials based on this design strategy have been continuously developed. Takuma Yasuda of Kyushu University synthesized BBCz-R, which emits red light at 615 nm and has a FWHM of only 21 nm (J. Am. Chem. Soc. 2020, 142, 19468-19472); Liang Duan and Dongdong Zhang of Tsinghua University designed ββCNICZ, which emits green light and has a FWHM of only 13 nm (Adv. Mater. 2023, 35, 2211316).
[0006] Currently, many organic narrow-band light-emitting molecules have been developed based on the design strategy of boron-nitrogen structure, but their half-peak width is generally more than 10 nm, which is difficult to reduce to the level comparable to quantum dots. Therefore, it is still a great challenge to synthesize and develop ultra-narrow-band organic light-emitting materials with a half-peak width of less than 10 nm. In addition, researchers have begun to seek other design strategies for constructing narrow-band emission, such as spatial conjugation effect. Can weakly interacting organic light-emitting bodies with ultra-narrow-band emission be realized by inhibiting the emission peak of material vibration level through spatial conjugation? This brings people a new way of thinking. SUMMARY
[0007] In view of the above technical problems and the deficiencies in the field, the present application provides three specific structures of ortho-substituted diarylbenzene weak interaction base light-emitting body molecules.
[0008] The ortho-substituted diarylbenzene with narrow-band emission is a compound 19-Naph-Phen-Ben, 99-Phen-Ben or 91-Phen-Pyre-Ben with the following structure:
[0009]
[0010] The three ortho-substituted diarylbenzene molecules of the present application have naphthalene ring, phenanthrene ring and pyrene ring as aryl groups, and the diaryl groups are substituted at the ortho position of the benzene ring, so that a large dihedral angle is formed between the aryl group and the benzene ring, thereby destroying the conjugation of the valence bond and forming stable spatial conjugation.
[0011] The present application finds that the three ortho-substituted diarylbenzene molecules all exhibit a half-peak width of less than 35 nm in solution.
[0012] The present application finds that changing the size of the aryl group in the ortho-substituted diarylbenzene molecule, such as changing the aryl group from naphthalene ring to phenanthrene ring and then to pyrene ring, while the aryl group two is fixed as phenanthrene ring, can significantly inhibit the emission peak of the material vibration level, thereby reducing the emission half-peak width of the material. Specifically, 19-Naph-Phen-Ben has a FWHM of 32 nm, 99-Phen-Ben exhibits a FWHM of 30 nm, and 91-Phen-Pyre-Ben has a FWHM of 27 nm.
[0013] Further research finds that optimizing the test conditions of 91-Phen-Pyre-Ben solution (such as reducing the temperature) can induce an ultra-narrow-band emission with a FWHM of 6 nm.
[0014] The present application also provides a preparation method of the ortho-substituted diarylbenzene with narrow-band emission, based on the following synthesis route:
[0015]
[0016] The preparation method comprises:
[0017] In an oxygen-free environment, the reactant I (9-(2-bromophenyl)phenanthrene), the reactant II (aryl boronic acid, wherein Ar represents aryl), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) and potassium carbonate (K2CO3) are reacted in a mixed solvent containing toluene and deionized water, after the reaction, organic solvent and deionized water are added for extraction and separation, the organic phase is dried, the solvent is removed, and column chromatography is used for separation to obtain the product III, i.e. the narrow-band emission ortho-substituted diarylbenzene.
[0018] In the reactant II, Ar is a naphthalene ring, a phenanthrene ring or a pyrene ring, i.e. the reactant II can be 1-naphthalene boronic acid, 9-phenanthrene boronic acid or 1-pyrene boronic acid.
[0019] In the product III, Ar is a naphthalene ring, a phenanthrene ring or a pyrene ring introduced by the reactant II.
[0020] In the preparation method, the molar ratio of the reactant I to the reactant II can be 1:1-1.1.
[0021] In the preparation method, the molar ratio of the reactant I, tetrakis(triphenylphosphine)palladium and potassium carbonate can be 1:0.02-0.2:3-6.
[0022] In the preparation method, the volume ratio of deionized water to toluene in the mixed solvent can be 1:4-8.
[0023] In the preparation method, the dosage ratio of the reactant I to the mixed solvent can be 2-4 mmol:35 mL.
[0024] In the preparation method, the reaction temperature can be 80-120℃, for example, 115℃, and the reaction time can be 8-16 hours, for example, 12 hours.
[0025] In the preparation method, the organic solvent can comprise ethyl acetate and / or dichloromethane.
[0026] In the preparation method, the organic phase can be dried by using anhydrous sodium sulfate.
[0027] In the preparation method, the solvent can be removed by heating under reduced pressure.
[0028] In the preparation method, the eluent used for column chromatography separation can be dichloromethane and petroleum ether in a volume ratio of 1:1-10.
[0029] The application further provides the narrow-band emission ortho-substituted diarylbenzene in the application of a light-emitting material.
[0030] The application further provides application of the narrow-band emission ortho-substituted diarylbenzene as a light-emitting material in an optoelectronic device.
[0031] The light-emitting temperature of the narrow-band emission ortho-substituted diarylbenzene can be 80-320 K.
[0032] The light-emitting mode of the narrow-band emission ortho-substituted diarylbenzene can be photoluminescence. The corresponding excitation wavelength of 19-Naph-Phen-Ben and 99-Phen-Ben can be 300 nm, and the corresponding excitation wavelength of 91-Phen-Pyre-Ben can be 345 nm.
[0033] The narrow-band emission ortho-substituted diarylbenzene can emit light in a solution. The solvent in the solution can be 2-methyltetrahydrofuran (2-MeTHF) or the like.
[0034] Compared with the prior art, the application has the following beneficial effects:
[0035] The three kinds of ortho-substituted diarylbenzene weakly interacting organic light-emitting materials provided by the application have a significant narrow-band emission effect in a solution, and the half-peak width is less than 35 nm, wherein 91-Phen-Pyre-Ben can be controlled to have an ultra-narrow-band emission (FWHM less than 10 nm) of 6 nm, which greatly improves the color purity of the weakly interacting light-emitting body, and has the potential to be applied to a light-emitting layer of an optoelectronic device (such as an organic light-emitting diode).
[0036] The ortho-substituted diarylbenzene molecule synthesized by the application is prepared from 9-(2-bromophenyl)phenanthrene, and a classic suzuki coupling reaction is performed with aryl boronic acid to obtain a weakly interacting organic light-emitting body with unique narrow-band emission. The preparation method provided by the application is simple in operation, reliable in route, and low in cost. By changing the size of the aryl group, the intramolecular spatial conjugation can be controlled, and the half-peak width of the weakly interacting organic light-emitting body can be significantly reduced.
[0037] The application not only further perfects the spatial conjugation mechanism of the weakly interacting organic light-emitting body, but also provides a new idea for designing an organic material with narrow-band emission, and expands the application scenarios of the weakly interacting organic light-emitting body, such as application in an OLED device to realize high color purity and high saturation of the device. BRIEF DESCRIPTION OF DRAWINGS
[0038] Figure 1 The nuclear magnetic hydrogen spectrum of 19-Naph-Phen-Ben prepared in Example 1 is shown in the following figure;
[0039] Figure 2 The nuclear magnetic carbon spectrum of 19-Naph-Phen-Ben prepared in Example 1 is shown in the following figure;
[0040] Figure 3 NMR spectrum of 99-Phen-Ben prepared in Example 2;
[0041] Figure 4 NMR spectrum of 99-Phen-Ben prepared in Example 2;
[0042] Figure 5 NMR spectrum of 99-Phen-Ben prepared in Example 2;
[0043] Figure 6 NMR spectrum of 99-Phen-Ben prepared in Example 2;
[0044] Figure 7 Photoluminescence spectra of 2-MeTHF solutions of 19-Naph-Phen-Ben, 99-Phen-Ben and 91-Phen-Pyre-Ben at different temperatures. DETAILED DESCRIPTION
[0045] The application will be further described with reference to the drawings and specific examples. It should be understood that these examples are intended to illustrate the application and are not intended to limit the scope of the application.
[0046] Example 1
[0047] Synthesis of 19-Naph-Phen-Ben:
[0048]
[0049] To a mixture of 9-(2-bromophenyl)phenanthrene (1.00 g, 3.01 mmol), 1-naphthaleneboronic acid (518 mg, 3.01 mmol), tetrakis(triphenylphosphine)palladium (346.8 mg, 0.30 mmol) and potassium carbonate (2.49 g, 18.06 mmol) under nitrogen protection, 30 mL of toluene and 5 mL of deionized water were added, then the temperature was raised to 115°C, and the reaction was carried out for 12 hours, then dichloromethane and deionized water were added to separate the liquid, the aqueous phase was discarded, the organic phase was dried with anhydrous sodium sulfate, then filtered, the organic phase was rotary evaporated, and column chromatography was performed with petroleum ether:dichloromethane = 10:1 (v / v) as the eluent to obtain 858 mg of 19-Naph-Phen-Ben white powder (yield 75%).
[0050] Figure 1 NMR spectrum of 19-Naph-Phen-Ben, Figure 2 NMR spectrum of 19-Naph-Phen-Ben.
[0051] The product prepared in this example has the following characterization data:
[0052] 19-Naph-Phen-Ben
[0053] 1 H NMR (500 MHz, CD2CI2) δ 8.67 - 8.46 (m, 2H), 7.94 - 7.10 (m, 17H), 7.08 - 6.97 (m, 1H). 13 C NMR (126 MHz, CD2CI2) δ 141.07, 140.85, 140.74, 140.73, 139.75, 139.26, 138.23, 138.18, 133.93, 133.83, 133.03, 132.51, 132.35, 132.34, 132.24, 132.06, 131.98, 131.69, 131.54, 131.44, 130.59, 130.46, 130.10, 130.09, 129.63, 128.98, 128.94, 128.79, 128.50, 128.45, 128.02, 127.93, 127.90, 127.85, 127.83, 127.74, 127.66, 127.59, 127.17, 127.06, 127.04, 127.02, 126.99, 126.96, 126.86, 126.78, 126.75, 126.55, 126.35, 126.26, 126.03, 126.01, 125.86, 125.13, 125.02, 123.17, 122.95, 122.88, 122.79, 54.43, 54.22, 54.00, 53.78, 53.57.
[0054] Example 2
[0055] Method for synthesis of 99-Phen-Ben:
[0056]
[0057] To a mixture of 9-(2-bromophenyl)phenanthrene (1.00 g, 3.01 mmol), 9-phenanthreneboronic acid (668 mg, 3.01 mmol), tetrakis(triphenylphosphine)palladium (346.8 g, 0.30 mmol) and potassium carbonate (2.49 g, 18.06 mmol) under nitrogen protection, 30 mL of toluene and 5 mL of deionized water were added, then heated to 115 °C, and reacted for 12 hours, then dichloromethane and deionized water were added to separate the solution, the water phase was discarded, the organic phase was dried with anhydrous sodium sulfate, then filtered, the organic phase was rotary evaporated, and column chromatography was used for separation, with petroleum ether:dichloromethane = 10:1 (v / v) as the eluent, to obtain 932 mg of 99-Phen-Ben white powder (yield 72%).
[0058] Figure 3 The nuclear magnetic hydrogen spectrum of 99-Phen-Ben is shown in Figure 1. Figure 4 The nuclear magnetic carbon spectrum of 99-Phen-Ben is shown in Figure 2.
[0059] The product prepared in this example has the following characterization data:
[0060] 99-Phen-Ben
[0061] 1 H NMR (500 MHz, CD2Cl2) δ 8.61-8.42 (m, 4H), 7.93-7.85 (m, 2H), 7.74-7.24 (m, 16H). 13 C NMR (126 MHz, CD2Cl2) δ 140.44, 140.16, 137.66, 137.29, 131.91, 131.84, 131.37, 131.01, 130.94, 130.92, 130.03, 129.96, 129.54, 129.46, 129.14, 128.30, 128.18, 127.46, 127.43, 127.40, 127.11, 127.09, 126.54, 126.43, 126.36, 126.25, 126.23, 126.17, 126.00, 125.90, 122.54, 122.47, 122.24, 122.19, 53.85, 53.63, 53.42, 53.20, 52.98.
[0062] Example 3
[0063] Synthesis method of 91-Phen-Pyre-Ben:
[0064]
[0065] To a mixture of 9-(2-bromophenyl)phenanthrene (1.00 g, 3.01 mmol), 1-pyreneboronic acid (740 mg, 3.01 mmol), tetrakis(triphenylphosphine)palladium (346.8 g, 0.30 mmol) and potassium carbonate (2.49 g, 18.06 mmol) under nitrogen, 30 mL of toluene and 5 mL of deionized water were added, followed by heating to 115 °C for 12 h, then dichloromethane and deionized water were added to extract the solution, the aqueous phase was discarded, the organic phase was dried over anhydrous sodium sulfate and filtered, the organic phase was rotary evaporated, and the product was separated by column chromatography using petroleum ether:dichloromethane = 10:1 (v / v) as eluent to obtain 957 mg of 91-Phen-Pyre-Ben light yellow powder (yield 70%).
[0066] Figure 5 The 1H NMR spectrum of 91-Phen-Pyre-Ben is shown in Figure 1. Figure 6 The 13C NMR spectrum of 91-Phen-Pyre-Ben is shown in Figure 2.
[0067] The product characterization data prepared in this example are as follows:
[0068] 91-Phen-Pyre-Ben
[0069] 1 H NMR (500 MHz, CD2Cl2) δ 8.61 (dd, J = 6.6, 2.9 Hz, 1H), 8.47 (t, J = 8.6 Hz, 2H), 8.39 (d, J = 8.3 Hz, 1H), 8.22 (d, J = 9.2 Hz, 1H), 8.19 - 8.05 (m, 6H), 8.01 - 7.76 (m, 13H), 7.73 - 7.58 (m, 12H), 7.56 - 7.51 (m, 2H), 7.39 (d, J = 19.7 Hz, 2H), 7.32 (d, J = 7.1 Hz, 1H), 7.26 (q, J = 7.2 Hz, 2H), 7.14 (t, J = 7.6 Hz, 1H). 13C NMR (126 MHz, CD2Cl2) δ 141.45, 141.11, 141.04, 138.34, 138.19, 137.59, 137.16, 132.90, 132.66, 132.49, 132.43, 132.16, 131.84, 131.76, 131.69, 131.49, 131.46, 131.39, 131.31, 130.68, 130.64, 130.54, 130.37, 130.15, 130.01, 129.77, 129.66, 129.28, 129.25, 128.99, 128.79, 128.35, 128.23, 128.02, 127.96, 127.92, 127.86, 127.77, 127.71, 127.68, 127.62, 127.55, 127.48, 127.16, 127.03, 126.99, 126.82, 126.53, 126.46, 126.38, 126.35, 126.32, 126.12, 125.54, 125.48, 125.35, 125.24, 125.12, 125.09, 125.05, 124.98, 124.31, 124.11, 123.22, 122.88, 122.86, 122.70, 54.43, 54.22, 54.00, 53.78, 53.57.
[0070] Example 4
[0071] The photophysical properties of 19-Naph-Phen-Ben, 99-Phen-Ben and 91-Phen-Pyre-Ben prepared in Examples 1-3 were tested.
[0072] Specifically comprising the following steps:
[0073] 19-Naph-Phen-Ben, 99-Phen-Ben and 91-Phen-Pyre-Ben were dissolved in 2-MeTHF solvent respectively, and were prepared into 10 μM concentration. The prepared solution was excited with a suitable excitation wavelength, and the photophysical properties were tested. The excitation wavelength of 19-Naph-Phen-Ben solution and 99-Phen-Ben solution was 300 nm, and the excitation wavelength of 91-Phen-Pyre-Ben solution was 345 nm. The results showed that Figure 7), 19-Naph-Phen-Ben exhibited a narrow band emission of 32 nm at 320 K with a FWHM of 27 nm at 80 K; while 99-Phen-Ben had a FWHM of 32 nm at 320 K and 26 nm at 80 K; the FWHM of 91-Phen-Pyre-Ben was further reduced with a FWHM of 27 nm at 320 K and even a super-narrow band emission of 6 nm at 80 K. Therefore, all the ortho-substituted diarylbenzenes have the property of narrow band emission and show a great application prospect of weakly interacting organic light-emitting materials in optoelectronic devices.
[0074] Furthermore, it is to be understood that various alterations and modifications can be made to the application herein disclosed in the above description without departing from the scope of the application as defined by the appended claims.
Claims
1. A narrow-band emission ortho-substituted diarylbenzene, characterized in that, Compounds 19-Naph-Phen-Ben, 99-Phen-Ben, or 91-Phen-Pyre-Ben with the following structures are examples:
2. The method for preparing narrowband-emitting ortho-substituted diarylbenzenes according to claim 1, characterized in that, Based on the following synthetic route: The preparation method includes: In an anaerobic environment, reactants I and II were reacted with tetrakis(triphenylphosphine)palladium and potassium carbonate in a mixed solvent containing toluene and deionized water. After the reaction was completed, organic solvent and deionized water were added for extraction and separation. The organic phase was dried, the solvent was removed, and the product III, namely the narrow-band emission ortho-substituted diarylbenzene, was obtained by column chromatography. In reactant II, Ar is a naphthalene ring, a phenanthrene ring, or a pyrene ring; In product III, Ar is a naphthalene ring, phenanthrene ring, or pyrene ring introduced from reactant II.
3. The preparation method according to claim 2, characterized in that, The molar ratio of reactant I to reactant II is 1:1 to 1.
1.
4. The preparation method according to claim 2, characterized in that, The molar ratio of reactant I, tetra(triphenylphosphine)palladium, and potassium carbonate is 1:0.02-0.2:3-6.
5. The preparation method according to claim 2, characterized in that, The volume ratio of deionized water to toluene in the mixed solvent is 1:4 to 8.
6. The preparation method according to claim 2, characterized in that, The ratio of reactant I to mixed solvent is 2–4 mmol: 35 mL.
7. The preparation method according to claim 2, characterized in that, The reaction temperature is 80–120℃, and the reaction time is 8–16 hours.
8. The preparation method according to claim 2, characterized in that, The organic solvent includes ethyl acetate and / or dichloromethane; The organic phase was dried using anhydrous sodium sulfate. Solvent removal is achieved by heating under reduced pressure. The eluent used in column chromatography is dichloromethane and petroleum ether in a volume ratio of 1:1 to 10.
9. The application of the narrow-band emission ortho-substituted diarylbenzene according to claim 1 in luminescent materials.
10. The application of the narrowband emitting ortho-substituted diarylbenzene according to claim 1 as a luminescent material in optoelectronic devices.