Process for the preparation of phosphorescent 7h-indolo[2,3-c]quinoline derivatives with photoresponse

Abstract

The preparation method of a phosphorescent group 7H-indole [2,3-c] quinoline series derivative with light response belongs to the field of organic intelligent materials. Several organic phosphorescent materials with NBCz as the core provided in the application can realize a color change from green or yellow-green afterglow to orange-yellow afterglow under the influence of different light activation times of a 365nm ultraviolet lamp, so as to achieve light-induced phosphorescent color change-stimulative response, and therefore can be widely applied to anti-counterfeiting, data encryption and sensing applications. The organic phosphorescent material with NBCz as the core has the following advantages: (1) simple and easy-to-follow synthesis route; (2) simple light activation condition; (3) large stokes shift, and remarkable effect.

Description

Technical Field

[0001] This invention belongs to the field of organic smart materials. The invention relates to a phosphorescent material in PMMA film that exhibits afterglow activation and afterglow color change synergistically induced by light and oxygen, as well as its preparation method and application. Background Technology

[0002] Ultralong organic room-temperature phosphorescence (UORTP) has seen rapid development in recent years due to its wide application in bioimaging, sensors, displays, and data encryption. Since trace impurities significantly affect UORTP performance, host-guest doping has become a popular strategy for constructing UORTP systems and improving their performance. Generally, both small molecules and polymers can serve as hosts, and the host library continues to grow. Important small molecule hosts include carbazole derivatives and triphenylamine (TPA) derivatives, as they can form charge-separated and charge-bound states with guests. PMMA and PVA are often used as polymer hosts because they can provide a rigid environment that significantly suppresses non-radiative relaxation of triplet excitons. Compared to the host library, the expansion of the guest library is more cautious. To date, excellent guests have been reported for derivatives such as 1h-benzo[f]indole (Bd), 7h-benzo[c]carbazole (BCz), 5h-benzo[c]carbazole (BCz-1), n-phenyl-1-naphthylamine (N-1), n-phenyl-2-naphthylamine (N-2), and phenylboronic acid. It is worth mentioning that some guests (such as Bd, BCz and BCz-1) can function well in both small molecule hosts and polymer hosts.

[0003] Dynamic control of UORTP properties is an attractive research topic. Host-guest doping strategies offer a great opportunity for the development of stimulus-responsive smart UORTP materials. Theoretically, to achieve dynamic control of UORTP, four approaches can be proposed based on the host-guest system: (1) directly applying external stimuli to the host alone; (2) external stimuli can be directly applied to the guest alone; (3) both the host and guest can be stimulated by external stimuli; (4) external stimuli can change the intermolecular interactions between the host and guest. Approaches (1) and (4) have been successfully implemented in tuning UORTP properties. A typical example of Pathway (1) is that PMMA films containing Bd derivatives exhibit photoactivated UORTP properties due to photoinduced oxygen consumption in the PMMA matrix. A typical example of Pathway (4) is that PVA films doped with phenylboronic acid derivatives exhibit unique water-induced UORTP changes because water breaks the hydrogen bonds between PVA and the guest. However, there are few reports on the dynamic control of UORT properties using Approaches (2) and (3), due to the unclear structure-property relationship of the guest. Therefore, the structural changes in UORTP color triggered by stimuli are challenging to investigate and have not yet been reported.

[0004] Photoresponsive UORTP is a fascinating research topic due to the excellent spatiotemporal resolution of light. Generally, the photoresponse of UORTP includes two typical response modes: photoactivation and photoinduced color change. To date, photoactivated UORTP has been widely reported, due to the photoinduced consumption of oxygen in the doped polymer film. However, photoinduced color change in UORTP has been rarely reported. Data encryption is an important application scenario for photoresponsive UORTP. For example, by utilizing the photoactivated UORTP properties of Bd derivatives, information can be photoprinted in doped PMMA films. However, encrypted data is easily lost because oxygen returns to the PMMA film and quenches the ORTP. Compared to photoactivated UORTP, photoinduced color change in UORTP allows for long-term preservation of encrypted data, offering significant convenience. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing and applying phosphorescent materials with afterglow activation and afterglow color change synergistically induced by light and oxygen.

[0006] This invention provides a room-temperature organic phosphorescent material with adjustable afterglow, wherein the structural formula is shown below:

[0007]

[0008] Molecular structures of NBCz, FSO2NBCz, PCBNBCz, N2BCzFSO2NBCz.

[0009] Advantages and application prospects of this invention:

[0010] The organic phosphorescent materials based on NBCz provided in this invention can achieve a color change from green or yellow-green afterglow to orange-yellow afterglow under the influence of different photoactivation times of a 365nm ultraviolet lamp, thereby achieving photoinduced phosphorescent color change-stimulation response. Therefore, they can be widely used in anti-counterfeiting, data encryption and sensing applications.

[0011] This organic phosphorescent material with NBCz as its core has the following advantages: (1) the synthesis route is simple and easy to implement; (2) the photoactivation conditions are simple; and (3) the Stokes shift is large and the effect is significant. Attached Figure Description

[0012] Figure 1 The graph shows the fluorescence spectrum and 1 ms delayed phosphorescence spectrum of the NBCz@PMMA film under different irradiation times. The horizontal axis represents wavelength in nanometers; the vertical axis represents emission intensity.

[0013] Figure 2 Optical photographs of the NBCz@PMMA film under UV light (365nm) for different irradiation times and after the UV light is turned off.

[0014] Figure 3 The lifetime decay curves of the NBCz@PMMA membrane are shown.

[0015] Figure 4 The graph shows the fluorescence spectrum and 1 ms delayed phosphorescence spectrum of the compound FSO2NBCz@PMMA film at different irradiation times. The horizontal axis represents wavelength in nanometers; the vertical axis represents emission intensity.

[0016] Figure 5 Optical photographs of the compound FSO2NBCz@PMMA film under UV light (365nm) for different irradiation times and after the UV light is turned off.

[0017] Figure 6 The lifetime decay curves of the compound FSO2NBCz@PMMA membrane are shown.

[0018] Figure 7 The graph shows the fluorescence spectrum and 1 ms delayed phosphorescence spectrum of the compound PCBNBCz@PMMA film at different irradiation times. The horizontal axis represents wavelength in nanometers; the vertical axis represents emission intensity.

[0019] Figure 8 Optical photographs of the compound PCBNBCz@PMMA film under UV light (365nm) for different irradiation times and after the UV light is turned off.

[0020] Figure 9 The lifetime decay curves of the compound PCBNBCz@PMMA film are shown.

[0021] Figure 10 The fluorescence spectrum and 1 ms delayed phosphorescence spectrum of the N2BCzFSO2NBCz@PMMA film at different irradiation times are shown. The horizontal axis represents wavelength in nanometers; the vertical axis represents emission intensity.

[0022] Figure 11 Optical photographs of the N2BCzFSO2NBCz@PMMA film under UV light (365nm) for different irradiation times and after the UV light is turned off.

[0023] Figure 12 The lifetime decay curves of the N2BCzFSO2NBCz@PMMA membrane are shown. Detailed Implementation

[0024] 1. Synthetic route and specific synthetic steps

[0025] 1.1 Synthesis of NBCz

[0026]

[0027] Sodium tert-butoxide (2.883 g, 30 mmol), palladium acetate (0.101 g, 0.45 mmol), and bis(2-diphenylphosphine) ether (0.242 g, 0.45 mmol) were added to a 100 mL Shrek flask. 3-Aminoquinoline (2.884 g, 20 mmol) and o-bromoiodobenzene (4.244 g, 15 mmol) were dissolved in toluene (10 mL, AR grade). The mixture was refluxed at 110 °C for 48 h under a nitrogen atmosphere. After the reaction was complete, the synthesized mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography using petroleum ether and ethyl acetate (v / v, 5:1) as eluents to obtain a pure, colorless, transparent liquid. Yield: 85%.

[0028] Potassium carbonate (2.264 g, 20 mmol), palladium acetate (0.067 g, 0.30 mmol), and trihexylphosphine tetrafluoroborate (0.221 g, 0.60 mmol) were added to a 100 mL Shrek flask. Then, N-(2-bromophenyl)quinoline-3-amine (2.9992 g, 10 mmol) dissolved in N,N-dimethylacetamide (10 mL, AR grade) was added. The mixture was refluxed at 130 °C for 16 h under a nitrogen atmosphere. After the reaction was complete, the resulting mixture was cooled to room temperature, and the solvent was washed twice with saturated brine and dichloromethane. The resulting solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography using petroleum ether and ethyl acetate (v / v, 1:1) as eluents to obtain a pure product as a white powder. Yield: 30%.

[0029] 1H NMR spectrum of NBCz 1 H NMR (400MHz, CDCl3) δ (ppm): 9.30 (s, 1H), 9.19–9.08 (m, 1H), 8.73 (d, J = 8.0Hz, 1H), 8 .59(d,J=8.2Hz,1H),8.31(d,J=7.7Hz,1H),7.79–7.57(m,4H),7.45(t,J=7.5Hz,1H).

[0030] NBCz carbon NMR spectrum 13 C NMR(101MHz,DMSO-d6)δ(ppm)142.66,139.90,139.27,133.18,130.44,127.5 4,127.16,125.73,124.73,123.75,123.45,121.74,120.80,119.86,113.20.

[0031] High-resolution mass spectrometry (HR-ESI-MS) for NBCz Calcd. For NBCz C 15 H 10 N2[M+H] + :219.0922.Found:219.0929.

[0032] 1.2 Synthesis of PCBNBCz

[0033]

[0034] Potassium tert-butoxide (0.062 g, 0.55 mmol), NBCz (0.100 g, 0.46 mmol), and 5-bromo-3-fluorocyanopyridine (0.092 g, 0.46 mmol) were added to a 10 mL Shrek flask. The flask was then sealed and purged with nitrogen. NN dimethylformamide (2 mL, AR grade) was added to the flask, and the mixture was refluxed at room temperature for 12 h under a nitrogen atmosphere. After the reaction was complete, the synthesized mixture was cooled to room temperature, and the solvent was washed with deionized water and ethyl acetate. Yield: 56%.

[0035] 1H NMR spectrum of PCBNBCz 1H NMR (400MHz, CDCl3) δ (ppm): 9.04–8.96 (m, 2H), 8.81–8.76 (m, 1H), 8.69 (dt, J = 8.0, 1.0Hz, 1H), 8.36 (dd, J = 8.1, 1.5Hz, 1H), 8.25 (d, J = 2.0Hz, 1 H), 7.80 (dddd, J=22.3, 8.4, 6.9, 1.5Hz, 2H), 7.68 (dddd, J=8.3, 7.2, 1.2Hz, 1H), 7.59 (dddd, J=8.1, 7.2, 1.0Hz, 1H), 7.39 (dt, J=8.3, 0.9Hz, 1H).

[0036] Carbon NMR spectrum of PCBNBCz 13 C NMR(101MHz,DMSO-d6)δ(ppm):153.07,143.81,141.89,140.60,137.88,137.75,133.55,131.44,130. 59,128.53,128.34,127.19,126.29,124.17,124.08,123.90,123.15,122.48,122.01,115.49,111.99.

[0037] High-resolution mass spectrometry (HR-ESI-MS) of PCBNBCz Calcd. For C 21 H 11 BrN4[M+H] + :401.021.Found:400.895.

[0038] Synthesis of 1.3FSO2NBCz

[0039]

[0040] Potassium tert-butoxide (0.062 g, 0.55 mmol), NBCz (0.100 g, 0.46 mmol), and 4,4-sulfonylbis(fluorobenzene) (0.117 g, 0.46 mmol) were added to a 10 mL Shrek flask. The flask was then sealed and purged with nitrogen. NN dimethylformamide (2 mL, AR grade) was added to the flask, and the mixture was refluxed at 110 °C for 24 h under a nitrogen atmosphere. After the reaction was complete, the synthesized mixture was cooled to room temperature, and the solvent was washed with deionized water and ethyl acetate. Yield: 45%.

[0041] FSO2NBCz 1H NMR spectrum 1H NMR (400MHz, CDCl3) δ (ppm): 9.14 (s, 1H), 8.77 (dd, J=8.1, 1.5Hz, 1H), 8.66 (dt, J=8.0, 1.0Hz, 1H), 8.31 (dd, J=8.4, 1.4Hz, 1H), 8.26–8.22 (m, 2H), 8.1 2–8.07(m,2H),7.85–7.76(m,3H),7.72(ddd,J=8.3,6.9,1.5Hz,1H),7.60( dd,J=3.6,1.0Hz,2H),7.53(ddd,J=8.1,4.7,3.5Hz,1H),7.34–7.27(m,2H).

[0042] FSO2NBCz C NMR spectrum 13 C NMR(101MHz,DMSO-d6)δ(ppm):143.53,140.91,140.44,139.81,137.62,137.49,132.80,131.50,131.40,130. 47,130.16,128.57,128.32,128.21,126.87,124.03,123.98,122.75,122.38,121.66,117.80,117.57,111.67.

[0043] High-resolution mass spectrometry (HR-ESI-MS) of FSO2NBCz (Calcd.For C) 27 H 17 FN2O2S[M+H] + :453.107.Found:452.927.

[0044] Synthesis of 1,4N2BCzFSO2NBCz

[0045]

[0046] Potassium tert-butoxide (0.028 g, 0.25 mmol), FSO₂NBCz (0.093 g, 0.21 mmol), and N₂BCz (0.046 g, 0.21 mmol) were added to separate 10 mL Shrek flasks. The flasks were then sealed and purged with nitrogen. NN dimethylformamide (2 mL, AR grade) was added to the flasks, and the mixture was refluxed at 110 °C for 24 h under a nitrogen atmosphere. After the reaction was complete, the synthesized mixture was cooled to room temperature, and the solvent was washed with deionized water and ethyl acetate. Yield: 30%.

[0047] The 1H NMR spectrum of N2BCzFSO2NBCz 1H NMR(400MHz, DMSO-d6)δ(ppm):9.27(s,1H),8.93(d,J=8.0Hz,1H),8.85(d,J=8.0Hz,1H),8.51–8.43(m,5H),8.31(dd,J=7.8,1.9Hz,1H),8.20( ddd,J=15.6,11.2,8.0Hz,5H),8.06(dd,J=7.9,1.9Hz,1H),7.86–7.80(m,3H),7.79–7.72(m,4H),7.66(t,J=7.7Hz,1H),7.55(q,J=7.3Hz,2H).

[0048] N2BCzFSO2NBCz C NMR spectrum 13 C NMR(101MHz,DMSO-d6)δ(ppm):143.89,140.35,140.10,139.83,137.57,132.82,132.21,130.44,129.87,1 29.54,128.67,128.45,128.24,127.55,126.91,124.03,123.18,122.94,122.80,122.41,120.08,111.49.

[0049] High-resolution mass spectrometry (HR-ESI-MS) of N2BCzFSO2NBCz (Calcd. For C) 41 H 25 N5O2S[M+H] + :652.180.Found:651.797.

[0050] 2. Photoresponse performance: Photoactivated phosphorescence and photoinduced phosphorescence color changes

[0051] In this invention, the target molecule NBCz, when doped into the polymer PMMA, exhibits cyan fluorescence under 365nm ultraviolet light irradiation. After the ultraviolet light is turned off, a green afterglow can be observed. After irradiation with ultraviolet light for 3 minutes, a distinct orange-red afterglow can be seen.

[0052] In this invention, the target molecule FSO2NBCz, when doped into the polymer PMMA, exhibits a white-blue fluorescence under 365nm ultraviolet light. After the ultraviolet light is turned off, a green afterglow can be observed, and after 3 minutes of ultraviolet light irradiation, a distinct orange-yellow afterglow can be seen.

[0053] In this invention, the target molecule PCBNBCz, when doped into the polymer PMMA, exhibits a bluish-green fluorescence under 365nm ultraviolet light. After the ultraviolet light is turned off, a green afterglow can be observed, and after 3 minutes of ultraviolet light irradiation, a distinct yellow afterglow can be seen.

[0054] In this invention, the target molecule N2BCzFSO2NBCz, when doped into the polymer PMMA, exhibits white fluorescence under 365nm ultraviolet light irradiation. After the ultraviolet light is turned off, a yellow afterglow can be observed. After irradiation with ultraviolet light for 3 minutes, a distinct orange-yellow afterglow can be seen.

Claims

1. A photoresponsive 7H-indole[2,3-c]quinoline derivative, characterized in that, The molecular structure of FSO2NBCz, PCBNBCz, or N2BCzFSO2NBCz is one of the following structural formulas: ， 2. The method for preparing photoresponsive 7H-indole[2,3-c]quinoline derivatives as described in claim 1, characterized in that: (1) Synthesis of PCBNBCz ； 0.55 mmol of potassium tert-butoxide, 0.46 mmol of NBCz and 0.46 mmol of 5-bromo-3-fluorocyanopyridine were added to a 10 mL Shrek flask; the flask was then sealed and purged with nitrogen; 2 mL of N,N dimethylformamide was added to the flask and the mixture was refluxed at room temperature for 12 h under a nitrogen atmosphere; after the reaction was completed, the synthesized mixture was cooled to room temperature and the solvent was washed with deionized water and ethyl acetate. (2) Synthesis of FSO2NBCz ； 0.55 mmol of potassium tert-butoxide, 0.46 mmol of NBCz, and 0.46 mmol of 4,4-sulfonylbis(fluorobenzene) were added to a 10 mL Shrek flask; the flask was then sealed and purged with nitrogen; 2 mL of N,N dimethylformamide was added to the flask, and the mixture was refluxed at 110 °C for 24 h under a nitrogen atmosphere; after the reaction was completed, the synthesized mixture was cooled to room temperature and the solvent was washed with deionized water and ethyl acetate; (3) Synthesis of N2BCzFSO2NBCz ； 0.25 mmol of potassium tert-butoxide, 0.21 mmol of FSO2NBCz and 0.21 mmol of N2BCz were added to 10 mL Shrek flasks respectively; the flasks were then sealed and purged with nitrogen; 2 mL of N-N dimethylformamide was added to the flasks and the mixture was refluxed at 110 °C for 24 h under a nitrogen atmosphere; after the reaction was completed, the synthesized mixture was cooled to room temperature and the solvent was washed with deionized water and ethyl acetate.

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