Preparation and application of chiral organic photoelectric material

Abstract

The invention discloses a chiral organic photoelectric material and a preparation method and application thereof, the material has a long phosphorescence lifetime and a large luminescence asymmetric factor, can be fully used as a chiral room temperature phosphorescence material, and can be used for preparing an organic luminescent device. The organic photoelectric material is simple in synthesis method, easy to purify and ideal in yield.

Description

Technical Field

[0001] The present invention relates to the field of optoelectronic materials, and in particular to a chiral organic optoelectronic material and a preparation method and application thereof. Background Art

[0002] Currently, long-lasting room-temperature phosphorescence (RTP) is a striking optical phenomenon that can last for several seconds after the excitation source stops. The long-lasting afterglow phenomenon expands the dimension of the luminescent signal and brings potential application value in the fields of optical multiplexing, anti-counterfeiting and information protection.

[0003] Organic small molecule RTP materials have attracted extensive research due to their ease of preparation, low cost, abundance, good flexibility, high stability, biocompatibility, and ease of processing. In recent years, with the deepening of research, chiral RTP materials have become a hot topic. This is primarily because these materials not only possess the advantages of RTP but also offer numerous advantages, such as improved imaging contrast, reduced glare, and greater energy efficiency. They also hold great potential for applications such as bioresponsive imaging, spintronic optical communications, and 3D displays. However, due to the limited availability of chiral structures, chiral RTP materials are currently relatively scarce, and the development of more chiral RTP materials remains urgent. Summary of the Invention

[0004] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, one of the objects of the present invention is to provide a chiral organic optoelectronic material having a long phosphorescence lifetime and a large asymmetry factor, which can be fully used as a chiral RTP material and can be used to prepare organic light-emitting devices.

[0005] The second object of the present invention is to provide a method for preparing the above-mentioned organic photoelectric material, which is relatively simple to synthesize, easy to purify, and has an ideal yield.

[0006] A third object of the present invention is to provide applications of the above-mentioned organic photoelectric material.

[0007] The purpose of the present invention is achieved through the following technical solutions.

[0008] A chiral organic photoelectric material, the general formula of which is as follows: , wherein R1 is an atom of Group IVA, VA, or VIA; R2 and R3 are absent or are atoms of Group VIA; and R4 is a hydrogen atom; Said Ar1 is selected from the following structures: , wherein R5, R6, R7, and R8 are hydrogen, halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, amino, hydroxy, aryl, or heteroaryl; Said Ar2 is selected from the following structures: , among which R9, R 10 、R 11 、R 12 、R 13 、R 14 is hydrogen, halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, amino, hydroxy, aryl, or heteroaryl; Preferably, R1 is S, N or C; Preferably, R2 and R3 are O; Preferably, said R4 is H; Preferably, Ar1 is , wherein R5, R6, R7, and R8 are hydrogen; Preferably, Ar2 is , among which R9, R 10 、R 11 、R 12 、R 13 、R 14 is hydrogen; Preferably, the organic photoelectric material is any one of the following: .

[0009] The above-mentioned method of preparing a chiral organic optoelectronic material comprises the following steps: Under an inert atmosphere, tris(dibenzylideneacetone)dipalladium and tri(tert-butyl)phosphine are dissolved in toluene, and then o-dibromodiphenyl sulfide, o-diaminonaphthalene, and sodium tert-butoxide are added. After passing an inert gas, the reaction is carried out at 80-110° C. for 12-48 hours to obtain a chiral organic optoelectronic material. The molar amount of tris(dibenzylideneacetone)dipalladium is 3%-6% of o-dibromodiphenyl sulfide; the molar amount of tri(tert-butyl)phosphine is 15%-40% of o-dibromodiphenyl sulfide; the molar amount of sodium tert-butoxide is more than twice that of o-dibromodiphenyl sulfide; and the molar amount of o-diaminonaphthalene is 0.9-1.1 times that of o-dibromodiphenyl sulfide. Preferably, m-chloroperbenzoic acid is added dropwise to the dichloromethane solution of the chiral organic optoelectronic material, and the reaction is carried out at -10-0° C. for 5-60 minutes to obtain the chiral organic optoelectronic material.

[0010] The application of the above-mentioned organic photoelectric materials in organic electronic devices includes organic solar cells, organic light-emitting diodes, organic field-effect transistors and organic sensors.

[0011] Compared with the prior art, the present invention has the following advantages and beneficial effects: (1) The organic photoelectric material of the present invention has a chiral structure, has greater rigidity, has a longer phosphorescence lifetime, and has a larger asymmetry factor, and can be fully used as a chiral room temperature phosphorescent material and can be used to prepare organic light-emitting devices; (2) The synthesis method of the present invention is relatively simple and practical, easy to purify, and has an ideal yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 1 is the mass spectrum of the product obtained in Example 1 of the present invention.

[0013] Figure 2 This is a graph showing the luminescence changes of the product obtained in Example 1 of the present invention after excitation and de-excitation.

[0014] Figure 3 The HPLC spectrum of a chiral structure of the product obtained in Example 1 of the present invention is shown.

[0015] Figure 4 This is the HPLC spectrum of another chiral structure of the product obtained in Example 1 of the present invention. DETAILED DESCRIPTION

[0016] The present invention will be further described in detail below with reference to the examples, but the embodiments of the present invention are not limited thereto.

[0017] Example 1: Synthesis of NS (1) Synthesis of o-dibromodiphenyl sulfide To a two-necked flask, 1-bromo-2-iodobenzene (141.45 g, 500.0 mmol), thiosemicarbazide (31.899 g, 350 mmol), copper acetate (9.98 g, 50 mmol), potassium carbonate (82.9 g, 600 mmol), and DMSO (500 mL) were added. The reaction solution was stirred at 120°C for 12 h. After the reaction was completed, the solution was cooled to room temperature and poured into 100 mL of water. The product was extracted with dichloromethane and washed with water. The organic layer was concentrated and passed through a silica gel column to obtain the pure product o-dibromodiphenyl sulfide with a yield of 75%. 1 HNMR (400 MHz, CDCl3): δ 7.64 (dd, J = 7.7, 0.9 Hz, 2H), 7.24 (td, J = 7.5, 1.3Hz, 2H), 7.18–7.08 (m, 4H); 13C NMR (101 MHz, CDCl3): δ 135.70, 133.53, 132.45, 128.80, 128.18, 125.84. The H-NMR and C-NMR spectra showed a total of 8 hydrogen atoms and 6 carbon atoms, which matched well with the NMR spectra, indicating that the product, o-dibromodiphenyl sulfide, was obtained. The synthesis route is shown in the following formula (1): ; Formula (1).

[0018] (2) Synthesis of NS A catalyst consisting of tri(tert-butyl)phosphine (0.9 mL, 0.885 mmol) and tris(dibenzylideneacetone)dipalladium (0.135 g, 0.147 mmol) was dissolved in 10 mL of toluene and stirred at room temperature for 15 min. o-Dibromodiphenyl sulfide (0.495 g, 0.144 mmol), o-diaminonaphthalene (0.45 g, 1.58 mmol), and sodium tert-butoxide (0.4149 g, 4.32 mmol) were dissolved in 40 mL of toluene and stirred at 90°C for 24 hours. The mixture was then cooled to room temperature and filtered to remove salts and other insoluble matter. The filtrate was then removed from the solvent and subjected to column chromatography to obtain the pure product NS in a 55% yield. 1 H NMR (400 MHz, DMSO- d 6 ): δ 8.38 (d, J = 8.7 Hz, 1H), 8.20 (d, J = 8.2 Hz, 1H), 7.85 (d, J =8.7 Hz, 1H), 7.68–7.52 (m, 3H), 7.38 (t, J = 7.6 Hz, 1H), 7.17 (d, J = 8.4 Hz,1H), 6.96 (d, J = 8.8 Hz, 1H), 6.86 (t, J = 7.5 Hz, 3H), 6.78 (d, J = 7.0 Hz, 2H),6.71 (t, J = 7.3 Hz, 2H), 6.63–6.53 (m, 3H), 6.48 (d, J = 8.4 Hz, 1H), 4.27 (s,2H). 13 C NMR (101 MHz, DMSO- d 6): δ 144.45, 144.18, 138.22, 135.93, 134.78,134.00, 133.77, 131.28, 130.22, 128.94, 128.91, 127.87, 127.39, 127.27,127.15, 127.04, 127.00, 126.76, 124.99, 124.29, 122.64, 120.94, 120.14,118.64, 116.81, 110.93. ESI-MS (m / z): [M] + calculated for C 32 H 22 N2S, 466.60; found, 466.8; the synthetic route is shown in the following formula (2): ; Formula (2).

[0019] Example 2: Synthesis of NSO To a dichloromethane solution of NS (100 mg) was added meta-chloroperbenzoic acid (41 mg) dropwise. After reacting at 0°C for half an hour, the mixture was poured into water, extracted with dichloromethane, washed with water, dried by rotary evaporation, and passed through a silica gel column to obtain pure product NSO with a yield of 85%. 1 HNMR (500 MHz, DMSO- d 6): δ 8.80 (dd, J = 7.4, 1.3 Hz, 2H), 7.89 (d, J = 7.9 Hz,2H), 7.81 (dt, J = 8.3, 1.0 Hz, 2H), 7.68-7.59 (m, 2H), 7.45 (td, J = 7.0, 1.4Hz, 2H), 7.36 (ddd, J = 6.6, 5.4, 1.4 Hz, 4H), 7.20 (ddtd, J = 22.3, 15.0, 7.4,1.4 Hz, 6H), 6.28 (d, J = 6.8 Hz, 1H), 5.40 (d, J = 6.8 Hz, 1H). 13 C NMR (125 MHz, DMSO- d6): δ 143.40, 142.99, 135.93, 133.74, 133.08, 131.77, 130.68, 128.75,128.55, 128.19, 128.15, 127.59, 126.69, 126.59, 125.40, 125.30, 123.99,123.89, 122.83, 122.48, 121.63, 121.11, 120.34, 118.41, 117.25. ESI-MS (m / z):[M] + calculated for C 32 H 22 N2OS, 482.60; found, 482.8; the synthesis route is shown in the following formula (3): ; Formula (3).

[0020] Example 3: Synthesis of NSO2 To a dichloromethane solution of NS (100 mg) was added meta-chloroperbenzoic acid (82 mg) dropwise. After reacting at 0°C for half an hour, the mixture was poured into water, extracted with dichloromethane, washed with water, dried by rotary evaporation, and passed through a silica gel column to obtain pure product NSO2 with a yield of 95%. 1 HNMR (500 MHz, DMSO- d 6): δ 8.87-8.74 (m, 2H), 7.94-7.87 (m, 2H), 7.85-7.77 (m,2H), 7.70-7.59 (m, 4H), 7.37-7.06 (m, 10H), 6.28 (d, J = 6.8 Hz, 1H), 5.40 (d, J = 6.8 Hz, 1H). 13 C NMR (125 MHz, DMSO- d 6): δ 142.99, 138.19, 135.93, 133.74,133.08, 130.68, 129.68, 128.76, 128.55, 128.15, 127.59, 127.16, 126.69,126.59, 125.40, 125.33, 125.30, 123.99, 123.89, 123.26, 122.48, 121.63,121.11, 119.83, 118.41, 117.25. ESI-MS (m / z): [M]+ calculated for C 32 H 22 N2O2S, 498.60; found, 498.8; the synthesis route is shown in the following formula (4): ; Formula (4).

[0021] The test results of the organic photoelectric materials of Examples 1 to 3 are as follows: Figure 1 The mass spectrum of the final product obtained in Example 1 of the present invention is Figure 1 As can be seen, the mass spectrum is consistent with the corresponding compound, which means that the target compound is obtained; Figure 2 The final product obtained in Example 1 of the present invention is a graph showing changes in luminescence after excitation and excitation; Figure 3 and Figure 4 This is the chiral HPLC spectrum of the final product obtained in Example 1 of the present invention.

[0022] To better demonstrate that the method of the present invention can be used to successfully synthesize organic optoelectronic materials, and that the organic optoelectronic materials exhibit chiral room temperature phosphorescence, the final products prepared in Examples 1-3 were subjected to performance testing, primarily examining their NMR, mass spectra, HOMO, LUMO, thermal properties, and optical properties. The test results are shown in Table 1. The NMR spectra were measured using an NMR spectrometer; the mass spectra were measured using an ESI-MS mass spectrometer; the HOMO and LUMO were determined electrochemically using cyclic voltammetry, using ferrocene as a calibrant, a saturated calomel electrode as a reference electrode, and a platinum electrode as a working electrode; and the thermal decomposition temperature (T) was used. d ) is measured by measuring the change of sample weight with temperature in an inert environment, and the temperature corresponding to 5% weight loss is used as the thermal decomposition temperature; the luminescence asymmetry factor (g em ) is the sample in doped film (1% doped with β-estradiol), measured by JASCOCPL-300 spectrometer; phosphorescence lifetime (τ RTP ) is the sample in the doped film (1% doped with β-estradiol), measured by transient fluorescence spectrometry; Table 1 .

[0023] As shown in Table 1, the T d All of them reached above 303°C, indicating that the products obtained in Examples 1-3 all had good thermal stability.

[0024] As shown in Table 1, Examples 1-3 all exhibit chiral room-temperature phosphorescence properties, have long phosphorescence lifetimes, and possess large asymmetry factors, making them suitable for use as chiral room-temperature phosphorescent materials. Examples 1-3 are highly suitable for use in organic electronic devices, particularly as light-emitting layer materials and host materials in organic light-emitting diode (OLED) devices, and can be used to prepare organic light-emitting devices. They can also be used in other light-emitting fields.

[0025] The synthesis method of the invention is relatively simple, easy to purify and has an ideal yield.

[0026] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A chiral organic optoelectronic material, characterized in that: The general formula of the organic photoelectric material is as follows: ， wherein R1 is an atom of Group IVA, VA, or VIA; R2 and R3 are absent or are atoms of Group VIA; and R4 is a hydrogen atom; Said Ar1 is selected from the following structures: , wherein R5, R6, R7, and R8 are hydrogen, halogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, amino, hydroxy, aryl, or heteroaryl; Said Ar2 is selected from the following structures: , among which R9, R 10 、R 11 、R 12 、R 13 、R 14 It is hydrogen, halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, amino, hydroxy, aryl, or heteroaryl.

2. The chiral organic optoelectronic material according to claim 1, characterized in that: The R1 is S, N or C.

3. The chiral organic optoelectronic material according to claim 1, characterized in that: Said R2 and R3 are O.

4. The chiral organic optoelectronic material according to claim 1, characterized in that: The R4 is H.

5. The chiral organic optoelectronic material according to claim 1, characterized in that: Said Ar1 is , wherein R5, R6, R7, and R8 are hydrogen.

6. The chiral organic optoelectronic material according to claim 1, characterized in that: Said Ar2 is , among which R9, R 10 、R 11 、R 12 、R 13 、R 14 For hydrogen.

7. The chiral organic optoelectronic material according to claim 1, characterized in that: The organic photoelectric material is any one of the following: 。 8. A method for preparing a chiral organic optoelectronic material according to any one of claims 1 to 7, characterized in that: The following steps are involved: Under an inert atmosphere, tris(dibenzylideneacetone)dipalladium and tri(tert-butyl)phosphine are dissolved in toluene, and then o-dibromodiphenyl sulfide, o-diaminonaphthalene, and sodium tert-butoxide are added. After passing an inert gas, the reaction is carried out at 80-110°C for 12-48 hours to obtain a chiral organic optoelectronic material. The molar amount of tris(dibenzylideneacetone)dipalladium is 3%-6% of o-dibromodiphenyl sulfide; the molar amount of tri(tert-butyl)phosphine is 15%-40% of o-dibromodiphenyl sulfide; the molar amount of sodium tert-butoxide is more than twice that of o-dibromodiphenyl sulfide; and the molar amount of o-diaminonaphthalene is 0.9-1.1 times that of o-dibromodiphenyl sulfide.

9. The method for preparing a chiral organic optoelectronic material according to claim 8, characterized in that: m-Chloroperbenzoic acid is added dropwise to the dichloromethane solution of the chiral organic photoelectric material, and the mixture is reacted at -10-0° C. for 5-60 minutes to obtain the chiral organic photoelectric material.

10. Use of the chiral organic optoelectronic material according to any one of claims 1 to 7 in an organic electronic device, characterized in that: The organic electronic devices are organic solar cells, organic light emitting diodes, organic field effect transistors and organic sensors.

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