Indolo[3,2,1-jk]carbazole derivatives, methods for their preparation and use, and organic room-temperature phosphorescent doped polymer materials

Abstract

The application provides an indol[3,2,1-jk]carbazole derivative and a preparation method and application thereof and an organic room-temperature phosphorescence doped polymer material, and belongs to the technical field of organic chemistry. The application provides an indol[3,2,1-jk]carbazole derivative, which is indol[3,2,1-jk]carbazole-11-nitrile (ICz-pCN), indol[3,2,1-jk]carbazole-10-nitrile (ICz-oCN) and indol[3,2,1-jk]carbazole-9-nitrile (ICz-mCN) respectively, and exhibits excellent optical properties when being doped into a rigid polymer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic chemistry, and particularly relates to an indol[3,2,1-jk]carbazole derivative, a preparation method and application thereof, and an organic room-temperature phosphorescence doped polymer material. BACKGROUND

[0002] Organic room-temperature phosphorescence (RTP) materials can slowly release the stored excitation energy in the form of light at room temperature, have long-lasting afterglow, small background interference, large Stokes shift, small biological toxicity, easy modification and preparation, and low cost. However, the preparation of organic small-molecule materials requires harsh conditions and involves the introduction of heavy atoms harmful to the human body. In addition, the poor processing performance and flexibility of these materials cannot be ignored. In contrast, polymer materials have attracted more and more attention due to their excellent mechanical properties and processing performance, easy chemical modification, and simple preparation process. Traditionally, organic molecules cannot emit phosphorescence at room temperature due to their inherent weak spin-orbital coupling, which means that excitons cannot effectively cross the singlet and triplet states. Therefore, it is usually necessary to establish strong intermolecular interactions to build a rigid network structure to generate and enhance at room temperature, so more and more people begin to study the doping of organic molecules into rigid polymers to suppress non-radiative decay and improve the utilization rate of triplet excitons by using the rigid network structure of the polymer itself. However, super-long RTP afterglow polymers with bright and long-lasting afterglow longer than two seconds are almost constructed by grafting copolymerization of rigid polymer matrices polyvinyl alcohol (PVA) and polyacrylamide (PAM). Since polyvinyl alcohol (PVA) and polyacrylamide (PAM) contain strong hydrogen bonds in their structures, their performance may be greatly reduced after water absorption, and even they may lose the RTP property. SUMMARY

[0003] In view of this, the present application aims to provide an indol[3,2,1-jk]carbazole derivative, a preparation method and application thereof, and an organic room-temperature phosphorescence doped polymer material. The indol[3,2,1-jk]carbazole derivative provided by the present application has excellent organic room-temperature phosphorescence properties, which is conducive to the inhibition of thermal vibration inactivation of doped molecules and the arousal of super-long RTP of organic room-temperature phosphorescence materials.

[0004] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0005] The present application provides an indol[3,2,1-jk]carbazole derivative, which has a structure as shown in any one of formulae I-III:

[0006]

[0007] The application further provides a preparation method of the indolo[3,2,1-jk]carbazole derivative.

[0008] The 9H carbazole, the compound M, NaH and an organic solvent are mixed to perform an electrophilic substitution reaction, so that an electrophilic substitution product is obtained, and the compound M has a structure shown in any one of formulae M1-M3.

[0009]

[0010] The electrophilic substitution product, K2CO3, BnEt3NCl, Pd(OAc)2, PPh3 and an organic solvent are mixed to perform a cyclization reaction, so that the indolo[3,2,1-jk]carbazole derivative is obtained.

[0011] Preferably, the temperature of the electrophilic substitution reaction is 150-180 DEG C, and the time is 18-24 h.

[0012] Preferably, the temperature of the cyclization reaction is 160-180 DEG C, and the time is 6-12 h.

[0013] The application further provides an application of the indolo[3,2,1-jk]carbazole derivative in preparing an organic room-temperature phosphorescent material.

[0014] The application further provides an organic room-temperature phosphorescent doped polymer material, which comprises the indolo[3,2,1-jk]carbazole derivative and a rigid polymer matrix.

[0015] Preferably, the mass ratio of the indolo[3,2,1-jk]carbazole derivative to the rigid polymer matrix is 1:10-1000.

[0016] Preferably, the mass of the indolo[3,2,1-jk]carbazole derivative is 0.1-0.5% of the mass of the rigid polymer matrix.

[0017] Preferably, the rigid polymer matrix comprises one or more of polyvinyl alcohol, polymethyl methacrylate, polylactic acid, polyacrylonitrile, polypropylene, polystyrene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, methyl methacrylate, butadiene, styrene terpolymer, polyacrylamide and polycarbonate.

[0018] The application further provides a preparation method of the organic room-temperature phosphorescent doped polymer material, comprising the following steps.

[0019] The indolo[3,2,1-jk]carbazole derivative and the rigid polymer matrix are mixed and dried into a film, so that a thin film is obtained.

[0020] The thin film is mechanically thermoplasticized to obtain the organic room-temperature phosphorescence doped polymer material.

[0021] The present application provides a kind of indol [3,2,1-jk] carbazole derivatives, respectively indol [3,2,1-jk] carbazole-11-nitrile (ICz-pCN), indol [3,2,1-jk] carbazole-10-nitrile (ICz-oCN) and indol [3,2,1-jk] carbazole-9-nitrile (ICz-mCN), doped into rigid polymer matrix shows excellent optical properties.Data of example show that in normal air environment and inert atmosphere, bright and super long afterglow RTP life is 2.10s, 2.15s, 2.50s.

[0022] The present application also provides a kind of preparation method of indol [3,2,1-jk] carbazole derivatives, the preparation method of the present application is simple to operate, easy to realize industrial production.

[0023] The present application also provides a kind of organic room-temperature phosphorescence doped polymer material, indol [3,2,1-jk] carbazole derivatives are doped into rigid polymer matrix and show excellent optical properties.

[0024] The present application also provides the preparation method of the above technical solution described machine room-temperature phosphorescence doped polymer material, at room temperature, indol [3,2,1-jk] carbazole derivatives (doped phosphor molecules) and rigid polymer matrix are mixed and dried into film, again the thin film prepared by mechanical thermoplasticization, polymer chain will occur chain disentangling and partial chain orientation, form more closely stacked, thereby strengthen polymer cohesion and reduce free volume, it is favorable for organic room-temperature phosphorescence material to inhibit doped molecule thermal vibration inactivation and arouse super long RTP. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 NMR spectrum of ICz-pCN is for the hydrogen spectrum;

[0026] Figure 2 NMR spectrum of ICz-pCN is for the carbon spectrum;

[0027] Figure 3 NMR spectrum of ICz-mCN is for the hydrogen spectrum;

[0028] Figure 4 NMR spectrum of ICz-mCN is for the carbon spectrum;

[0029] Figure 5 NMR spectrum of ICz-oCN is for the hydrogen spectrum;

[0030] Figure 6 NMR spectrum of ICz-oCN is for the carbon spectrum;

[0031] Figure 7The PL photographs of the ICZ-pCN / PMMA, ICZ-mCN / PMMA and ICz-oCN / PMMA films doped with 0.1% and 0.5% respectively are taken at room temperature before and after the removal of 365 nm light irradiation;

[0032] Figure 8 The transient and delayed spectra of 0.1% ICz-pCN, 0.5% ICz-pCN, 0.1% ICz-mCN, 0.5% ICz-mCN, 0.1% ICz-oCN and 0.5% ICz-oCN films, wherein (a) is the transient spectrum and (b) is the delayed spectrum;

[0033] Figure 9 The delayed PL lifetime curves of ICZ-pCN / PMMA, ICZ-mCN / PMMA and ICz-oCN / PMMA films with different doping mass fractions. DETAILED DESCRIPTION

[0034] The present application provides an indol[3,2,1-jk]carbazole derivative, which has a structure shown in any one of formula I-III:

[0035]

[0036] The present application also provides a preparation method of the indol[3,2,1-jk]carbazole derivative, which comprises the following steps:

[0037] The 9H carbazole, compound M, NaH and organic solvent are mixed to perform an electrophilic substitution reaction, so as to obtain an electrophilic substitution product, and the compound M has a structure shown in any one of formula M1-3.

[0038]

[0039] The electrophilic substitution product, K2CO3, BnEt3NCl, Pd(OAc)2, PPh3 and organic solvent are mixed to perform a cyclization reaction, so as to obtain the indol[3,2,1-jk]carbazole derivative.

[0040] In the present application, the raw materials used are commercially available in the art, unless otherwise specified.

[0041] The 9H carbazole, compound M, NaH and organic solvent are mixed to perform an electrophilic substitution reaction, so as to obtain an electrophilic substitution product, and the compound M has a structure shown in any one of formula M1-3.

[0042] In the present application, the 9H carbazole has a structure shown in formula IV:

[0043]

[0044] In the specific embodiment of the present application, the 9H-carbazole is preferably prepared by a method comprising the following steps:

[0045] In a 100 mL two-necked flask, NMP (50 mL) was added, 2-aminobiphenyl (2.50 g, 14.77 mmol), [Cp*IrCl2]2(0.25 g, 0.31 mmol), Cu(OAc)2(0.54 g, 2.97 mmol) and PivOH (3.05 g, 29.86 mmol) were added, and the mixture was stirred at 120°C in air for 3 h. After cooling, the reaction mixture was extracted with ethyl acetate, the combined organic layers were dried over anhydrous MgSO4, filtered and concentrated in vacuo. The crude product was purified by column chromatography on silica gel using petroleum ether / dichloromethane (5:1, v / v) to obtain a white solid (1.31 g, yield 53%), which was the 9H-carbazole, denoted as LCZ.

[0046] In the present application, the principle of the electrophilic substitution reaction is shown in the following formula:

[0047]

[0048] In the present application, the temperature of the electrophilic substitution reaction is preferably 150-180°C, and the time is preferably 18-24 h.

[0049] In the present application, the molar ratio of the 9H-carbazole to the compound M is preferably 8.97:9.87.

[0050] In the present application, the organic solvent is preferably DMF.

[0051] The present application does not have special limitations on the amount of NaH and organic solvent, and the amount well known to those skilled in the art can be used.

[0052] In the specific embodiment of the present application, LCZ, NaH and DMF are preferably stirred at 0°C for 1 h, and then the compound M is added to the mixture to perform the electrophilic substitution reaction.

[0053] After the completion of the electrophilic substitution reaction, the present application preferably cools the obtained system, extracts the reaction mixture with ethyl acetate, dries the combined organic layers over anhydrous MgSO4, filters and concentrates in vacuo. The crude product is purified by column chromatography on silica gel using petroleum ether / dichloromethane (v / v=3:1) to obtain the electrophilic substitution product.

[0054] After obtaining the electrophilic substitution product, the present application mixes the electrophilic substitution product, K2CO3, BnEt3NCl, Pd(OAc)2, PPh3 and an organic solvent to perform a cyclization reaction, thereby obtaining the indolo[3,2,1-jk]carbazole derivative.

[0055] In the present application, the principle of the cyclization reaction is shown in the following formula:

[0056]

[0057] In the present application, the temperature of the cyclization reaction is preferably 160-180℃, and the time is preferably 6-12h.

[0058] In the present application, the equivalent ratio of the electrophilic substitution product to K2CO3 is preferably 1:5.

[0059] In the present application, the equivalent ratio of the electrophilic substitution product to BnEt3NCl is preferably 1:1.

[0060] In the present application, the organic solvent is preferably N,N-dimethylacetamide.

[0061] In the present application, the electrophilic substitution product, K2CO3 and BnEt3NCl are dissolved in the organic solvent, the reaction mixture is degassed by N2 bubbling for 15 minutes, Pd(OAc)2 and PPh3 are added, and the resulting mixture is heated to perform the cyclization reaction.

[0062] After the cyclization reaction is completed, the resulting system is preferably cooled, the reaction mixture is extracted with dichloromethane, the combined organic layers are dried with anhydrous MgSO4, filtered and concentrated under vacuum, and the crude product is purified by silica gel column chromatography using petroleum ether / dichloromethane (v / v=1:1) to obtain a gray solid, which is the indol[3,2,1-jk]carbazole derivative.

[0063] The present application also provides the use of the indol[3,2,1-jk]carbazole derivative described in the above technical solution in the preparation of an organic room-temperature phosphorescent material.

[0064] The present application also provides an organic room-temperature phosphorescent doped polymer material comprising the indol[3,2,1-jk]carbazole derivative described in the above technical solution and a rigid polymer matrix.

[0065] In the present application, the mass ratio of the indol[3,2,1-jk]carbazole derivative to the rigid polymer matrix is preferably 1:10-1000.

[0066] In the present application, the mass of the indol[3,2,1-jk]carbazole derivative is preferably 0.1-0.5% of the mass of the rigid polymer matrix.

[0067] In the present application, the rigid polymer matrix preferably comprises one or more of polyvinyl alcohol (PVA), polymethyl methacrylate (PMMA), polylactic acid (PLA), polyacrylonitrile (PAN), polypropylene (PP), polystyrene (PS), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), methyl methacrylate, butadiene, styrene terpolymer (MBS), polyacrylamide (PAM), and polycarbonate (PC).

[0068] In the present application, the polystyrene (PS) preferably comprises high-impact polystyrene (HIPS).

[0069] The present application also provides a preparation method of the organic room-temperature phosphorescent doped polymer material as described in the technical solutions above, comprising the following steps:

[0070] After mixing the indolizine[3,2,1-jk]carbazole derivative and the rigid polymer matrix, a film is obtained by drying.

[0071] The film is subjected to mechanical thermal plasticization to obtain the organic room-temperature phosphorescent doped polymer material.

[0072] The present application mixes the indolizine[3,2,1-jk]carbazole derivative and the rigid polymer matrix, and then dries to obtain a film.

[0073] In the present application, the indolizine[3,2,1-jk]carbazole derivative and the rigid polymer matrix are preferably used in the form of a solution, and the solvent of the solution is preferably dichloromethane. The present application does not have special limitations on the concentration of the solution, and a concentration known to those skilled in the art can be used.

[0074] In the present application, the drying to form a film preferably comprises natural evaporation and drying in sequence, and the drying is preferably performed in an oven, and the temperature of the drying is preferably 60℃, and the time is preferably 12h.

[0075] In the present application, the temperature of the mechanical thermal plasticization is preferably 140℃, and the time is preferably 2-3min, and the mechanical thermal plasticization is preferably performed on an open two-roller mill.

[0076] After the mechanical thermal plasticization is completed, the present application preferably further comprises shearing and molding in sequence, and the shearing is preferably cutting into a square of 2.5cm×2.5cm.

[0077] In the present application, the molding preferably comprises the following steps: preheating, hot pressing and cold pressing in a flat plate vulcanizing machine in sequence, the preheating time is preferably 3 min, and the temperature is preferably 190℃; the hot pressing pressure is preferably 5 MPa, the time is preferably 5 min, and the temperature is preferably 190℃; the cold pressing time is preferably 3 min, and the temperature is preferably 20℃, preferably finally obtaining a square sheet with a shape of 3 cm x 3 cm and a thickness of 1 mm.

[0078] In order to further illustrate the present application, the indol[3,2,1-jk]carbazole derivatives provided by the present application and the preparation method and application thereof, and the organic room-temperature phosphorescent doped polymer material are described in detail below in conjunction with examples, but they cannot be understood as limiting the protection scope of the present application.

[0079] Example 1

[0080] (1) Synthesis of 9H-carbazole (LCZ)

[0081] In a 100 mL two-necked flask, NMP (50 mL) was added, 2-aminobiphenyl (2.50 g, 14.77 mmol), [Cp*IrCl2]2(0.25 g, 0.31 mmol), Cu(OAc)2(0.54 g, 2.97 mmol) and PivOH (3.05 g, 29.86 mmol) were added, and stirred in air at 120℃ for 3 h. After cooling, the reaction mixture was extracted with ethyl acetate, the combined organic layer was dried over anhydrous MgSO4, filtered and concentrated in vacuum. The crude product was purified by silica gel column chromatography using petroleum ether / dichloromethane (5:1, v / v) to obtain a white solid (1.31 g, yield 53%).1H NMR (500 MHz, DMSO-d6) δ 11.27 (s, 1H), 8.13 (d, J = 7.7 Hz, 2H), 7.51 (d, J = 8.1 Hz, 2H), 7.41 (t, J = 7.6 Hz, 2H), 7.18 (t, J = 7.4 Hz, 2H).13C NMR (126 MHz, DMSO-d6) δ 139.66, 125.44, 122.34, 120.08, 118.42, 110.87. Anal. calcd. For C 18 H 13 N:C 88.17, H 6.55, N 8.28; found: C 88.18, H 6.53, N 8.29.

[0082] (2) Synthesis of indol[3,2,1-jk]carbazole-11-carbonitrile (ICz-pCN):

[0083] In a 100 mL flask, a solution of LCZ (1.50 g, 8.97 mmol) and NaH (0.43 g, 17.94 mmol) in DMF (50 mL) was stirred at 0 °C for 1 h. Compound M1 (1.97 g, 9.87 mol) was added to the mixture and stirred at 150 °C for 18 h. After cooling, the reaction mixture was extracted with ethyl acetate, the combined organic layers were dried over anhydrous MgS04, filtered and concentrated in vacuo. The crude product was purified by column chromatography on silica gel using petroleum ether / dichloromethane (3:1, v / v) to give a white solid (2.67 g, yield 78%).

[0084] A solution of 2X4Q (4.29 g, 12.4 mmol, 1 eq), K2C03(8.57 g, 62.1 mmol, 5 eq) and BnEt3NCl (2.82 g, 12.4 mmol, 1 eq) was dissolved in N,N-dimethylacetamide (100 mL) and the reaction mixture was degassed by bubbling N2for 15 min. Pd(OAc)2(0.42 g, 1.9 mmol, 0.15 eq) and PPh3(1.14 g, 4.3 mmol, 0.35 eq) were added and the resulting mixture was heated to 160 °C for 6 h. After cooling, the reaction mixture was extracted with dichloromethane, the combined organic layers were dried over anhydrous MgS04, filtered and concentrated in vacuo. The crude product was purified by column chromatography on silica gel using petroleum ether / dichloromethane (1 :1, v / v) to give a grey solid (2.366 g, yield 72%).

[0085] 1 HNMR (500 MHz, Chloroform-d) δ 8.41 (d, J = 1.7 Hz, 1H), 8.17 (d, J = 7.8 Hz, 1H), 8.11 (dd, J = 8.0, 2.8 Hz, 1H), 8.07 (d, J = 7.5 Hz, 1H), 7.93 - 7.86 (m, 2H), 7.82 (dd, J = 8.4, 1.6 Hz, 1H), 7.68 - 7.60 (m, 2H), 7.46 (dd, J = 8.9, 6.1 Hz, 1H). 13 C NMR (126 MHz, CDC13) δ 144.01, 139.75, 138.07, 130.30, 130.07, 129.95, 127.17, 127.01, 123.85, 123.37, 123.00, 120.56, 119.78, 119.72, 118.87, 116.74, 112.49, 112.23, 104.50, 77.28, 77.03, 76.77. Anal. Calcd. For C 19 H 10N2: C 85.70, H 3.79, N 10.52. Found: C 85.71, H 3.78, N 10.51.

[0086] (3) Synthesis of indolo[3,2,1-jk]carbazole-10-carbonitrile (ICz-mCN):

[0087] Using the same synthetic procedure as ICz-pCN, only replacing compound M1 with M2, 2.24 g of white solid was obtained with a yield of 68%. 1 H NMR (500 MHz, DMSO-d6) δ 8.86 (d, J = 1.6 Hz, 1H), 8.43 (dd, J = 8.1, 2.2 Hz, 2H), 8.30 - 8.23 (m, 3H), 7.79 (dt, J = 8.0, 1.5 Hz, 1H), 7.70 - 7.61 (m, 2H), 7.46 (t, J = 7.6 Hz, 1H). 13 C NMR (126 MHz, CDC13) δ 144.36, 138.10, 137.13, 133.27, 129.86, 127.21, 124.93, 123.64, 123.32, 123.27, 122.65, 121.08, 120.12, 119.45, 118.90, 116.73, 115.30, 112.24, 109.01. Anal. calcd. For C 19 H 10 N2: C 85.70, H 3.79, N 10.52. Found: C 85.71, H 3.78, N 10.51.

[0088] (4) Synthesis of indolo[3,2,1-jk]carbazole-9-carbonitrile (ICz-oCN):

[0089] Using the same synthetic procedure as ICz-pCN, only replacing compound M1 with M3, 2.40 g of white solid was obtained with a yield of 73%. 1 H NMR (500 MHz, DMSO-d6) δ 8.65 (d, J = 8.3 Hz, 1H), 8.56 - 8.50 (m, 1H), 8.24 (dd, J = 7.7, 1.3 Hz, 1H), 8.17 (d, J = 7.4 Hz, 2H), 8.00 - 7.92 (m, 1H), 7.68 - 7.58 (m, 2H), 7.50 (t, J = 7.8 Hz, 1H), 7.45 (t, J = 7.5 Hz, 1H). 13C NMR (126 MHz, CDC13) δ 143.81, 139.54, 138.98, 131.52, 131.13, 130.19, 127.56, 127.23, 123.60, 123.11, 122.69, 121.40, 120.82, 120.57, 119.90, 119.79, 119.04, 118.91, 116.58, 115.59, 96.00. Anal. calcd. for C 19 H 10 N2: C 85.70, H 3.79, N 10.52. Found: C 85.72, H 3.75, N 10.55.

[0090] Figure 1 NMR of ICz-pCN; Figure 2 NMR of ICz-pCN; Figure 3 NMR of ICz-mCN; Figure 4 NMR of ICz-mCN; Figure 5 NMR of ICz-oCN; Figure 6 NMR of ICz-oCN.

[0091] Preparation of organic molecule doped PMMA material

[0092] 5 g of PMMA was dissolved in 200 mL of dichloromethane at room temperature, and 0.1% (5 mg), 0.5% (25 mg) of indolo[3,2,1-jk]carbazole (FHCs) derivatives were dissolved in 10 mL of dichloromethane, and the resulting solution was mixed and stirred for 30 min. Then it was placed in a petri dish and naturally evaporated and dried, and the dried flexible film was baked in an oven at 60°C for 12 h. Then, the film was subjected to thermoplastic treatment on an open two-roller mill at 140°C for 2 min. The film was cut into 2.5 cm x 2.5 cm 2 squares, weighing 1.3 g, and placed in a mold, preheated in a flat plate curing machine for 3 min (190°C), and then hot-pressed at a pressure of 5 MPa for 5 min (190°C), and finally cold-pressed for 3 min to obtain a square sheet with a shape of 3 cm x 3 cm and a thickness of 1 mm.

[0093] The thermoplastic processing was carried out on the dry films of PMMA solution doped with 0.1% and 0.5% of ICz-pCN, ICz-mCN and ICz-oCN, respectively, to obtain 0.1% ICz-pCN, 0.5% ICz-pCN, 0.1% ICz-mCN, 0.5% ICz-mCN, 0.1% ICz-oCN and 0.5% ICz-oCN flakes, respectively. Then the flakes were excited by 365 nm UV light for 10 s. The remaining afterglow phenomenon was shown in Fig. 2, which was significantly improved in both the crystal and the solution dry film state, indicating that the thermoplastic processing indeed effectively promoted the room-temperature phosphorescence emission of the polymer. At the same time, this also confirmed the effectiveness of the rigid polymer matrix PMMA in inhibiting the vibrational thermal deactivation of ICz-pCN, ICz-mCN and ICz-oCN. Figure 7

[0094] Although the organic phosphorescent molecules before chemical locking contain both cyanide and bromine atoms which are beneficial to the enhancement of spin-orbit coupling and intersystem crossing, the room-temperature phosphorescence emission is still weak in the presence of a large population of triplet exciton species, which indicates that internal rotation will cause severe deactivation of the triplet exciton at room temperature. After the flakes were activated by 365 nm light for 5 s, bright and super-long blue room-temperature phosphorescence afterglow phenomenon was emitted. The afterglow duration was observed by naked eye in a dark environment for more than 30 s. Figure 8 The transient and delayed spectra of 0.1% ICz-pCN, 0.5% ICz-pCN, 0.1% ICz-mCN, 0.5% ICz-mCN, 0.1% ICz-oCN and 0.5% ICz-oCN flakes were shown in Fig. 3, where (a) is the transient spectrum and (b) is the delayed spectrum. It can be seen that the transient fluorescence emission peaks of 0.1% ICz-pCN, 0.5% ICz-pCN, 0.1% ICz-mCN, 0.5% ICz-mCN, 0.1% ICz-oCN and 0.5% ICz-oCN are at 378 nm, 373 nm and 389 nm, 392 nm and 370 nm, 373 nm, respectively, which are near-ultraviolet fluorescence emission. The doping mass fraction has little effect on the fluorescence emission. The delayed phosphorescence spectra of 0.1% ICz-pCN, 0.5% ICz-pCN, 0.1% ICz-mCN, 0.5% ICz-mCN, 0.1% ICz-oCN and 0.5% ICz-oCN flakes show that the main emission peaks are at 451 nm and 472 nm, 444 nm and 473 nm, 457 nm and 491 nm, 458 nm and 491 nm, 447 nm and 478 nm, respectively, which are sky blue in color according to the position of the emission peak and the corresponding photos. The phosphorescence spectra show that ICz-pCN and ICz-mCN are accompanied by insignificant delayed fluorescence.

[0095] ​Time-resolved RTP decay curves are as follows Figure 9 As shown in Table 1, the RTP afterglow lifetimes fitted for different dopant mass fractions of ICz-pCN, ICz-mCN, and ICz-oCN are 2.33 s and 2.14 s, 2.15 s and 1.97 s, and 2.50 s and 2.33 s, respectively. PMMA films doped with Cz-pCN, Cz-mCN, and Cz-oCN can exhibit RTP, but the longest phosphorescence lifetime is only 0.53 s. When chemical locking is introduced to control the internal rotation of the dopant, the phosphorescence lifetime increases significantly, by up to five times. This indicates that the room-temperature phosphorescence properties are mainly related to the internal rotation and vibration of the overall doped chromophore molecular framework. The RTP efficiencies calculated for PMMA films doped with ICz-pCN, ICz-mCN, and ICz-oCN are 6.9% and 6.5%, 5.1% and 7.9%, and 3.8% and 11.7%, respectively. Room temperature phosphorescence has low quantum efficiency, meaning that the three-state excitons mainly emit bright and extremely long afterglow. On the other hand, taking the ICz-mCN / PMMA film with relatively strong delayed fluorescence as an example, the measured delayed fluorescence lifetime can reach 1.88 s, which indicates that the ICz-mCN / PMMA film undergoes a continuous reverse intersystem crossing after the ultraviolet excitation stops.

[0096] Table 1 shows the lifetimes and ratios of each component in the fit.

[0097]

[0098] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An organic room-temperature phosphorescent doped polymer material, characterized in that, It includes an indole[3,2,1-jk]carbazole derivative and a rigid polymer matrix; the indole[3,2,1-jk]carbazole derivative has the structure shown in Formula II:

2. The organic room-temperature phosphorescent doped polymer material according to claim 1, characterized in that, The preparation method of the indole[3,2,1-jk]carbazole derivative includes the following steps: An electrophilic substitution reaction was carried out by mixing 9H carbazole, compound M, NaH and an organic solvent to obtain the electrophilic substitution product, wherein compound M has the structure shown in formula M2: The electrophilic substitution product, K2CO3, BnEt3NCl, Pd(OAc)2, PPh3 and an organic solvent were mixed and subjected to a cyclization reaction to obtain the indole[3,2,1-jk]carbazole derivative.

3. The organic room-temperature phosphorescent doped polymer material according to claim 2, characterized in that, The electrophilic substitution reaction is carried out at a temperature of 50–180 °C for a time of 18–24 h.

4. The organic room-temperature phosphorescent doped polymer material according to claim 2, characterized in that, The cyclization reaction is carried out at a temperature of 160–180°C for 6–12 hours.

5. The organic room-temperature phosphorescent doped polymer material according to claim 1, characterized in that, The mass ratio of the indole[3,2,1-jk]carbazole derivative to the rigid polymer matrix is ​​1:10 to 1000.

6. The organic room-temperature phosphorescent doped polymer material according to claim 5, characterized in that, The mass of the indole[3,2,1-jk]carbazole derivative is 0.1 to 0.5% of the mass of the rigid polymer matrix.

7. The organic room-temperature phosphorescent doped polymer material according to claim 1, characterized in that, The rigid polymer matrix includes one or more of the following: polyvinyl alcohol, polymethyl methacrylate, polylactic acid, polyacrylonitrile, polypropylene, polystyrene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, methyl methacrylate, butadiene, styrene terpolymer, polyacrylamide, and polycarbonate.

8. The method for preparing the organic room-temperature phosphorescent doped polymer material according to claim 1, characterized in that, Includes the following steps: The indole[3,2,1-jk]carbazole derivative was mixed with a rigid polymer matrix and then dried to form a film. The film was subjected to mechanical thermoplasticization to obtain the organic room temperature phosphorescent doped polymer material.

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