Dibenzoselenazine compounds, their preparation methods and applications

Abstract

The present invention discloses a dibenzophenoselenazine compound with a structural formula shown in Formula I, and its preparation method and application: wherein, R is selected from 4-nitrophenyl, 4-cyanophenyl, phenyl, 4-methoxyphenyl, 4-methylphenyl, 2-naphthyl, 1-naphthyl, 2-anthryl, 3,5-dimethylphenyl, 3,5-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,5-dimethoxyphenyl, 4-(1,1'-biphenyl)-4-yl, 4-trifluoromethylphenyl, styryl, 4-N,N-dimethylphenyl, 4-(10-phenylanthracen-9-yl)phenyl, 10-([1,1'-biphenyl]-4-yl)anthracenyl. This compound has good red solid fluorescence function and is expected to have good applications in the fields of organic optoelectronic devices, chemical sensors and biological probes.

Description

Technical Field:

[0001] The present invention relates to the technical field of organic molecular luminescence, and particularly relates to dibenzophenoselenazine compounds, their preparation methods and applications. Background Art:

[0002] Red light solid luminescent molecules have extensive applications in traditional research fields such as fluorescence, thermally activated delayed fluorescence, hybrid local and charge transfer compounds, and bioimaging, making red solid luminescent materials have good application prospects. (SmartMat 2021, 2(3), 326 - 346; Dyes and Pigments 2022, 203, 110332)

[0003] Currently, there are few reported organic luminescent small molecules with red solid luminescence performance in the literature, mainly including: DTPA - FO and TPA - FOCN with a 2,7 - disubstituted fluorenone molecular skeleton (Chinese Chemical Letters 2019, 30(1947–1950)); tDBBPZ - DPXZ and DBPZ - DPXZ with a dibenzophenazine molecular skeleton (ACS Appl. Mater. Interfaces 2019, 11, 29086 - 29093), and 3 - DMAC - BP (ACS Appl. Mater. Interfaces 2019, 11, 26144 - 26151); compounds containing a phenothiazine molecular skeleton (Frontiers in Chemistry 2020, 8, 483); compounds with a benzothiadiazole molecular skeleton (SmartMat 2021, 2(3), 326 - 346); compounds with a perylene molecular skeleton (Chemical Society Reviews 2023, 52(19), 6715 - 6753); compounds with a quinoline - malononitrile molecular skeleton (Angewandte Chemie International Edition 2020, 59(25), 9812 - 9825); and thiazolo[4,5 - e]thieno[2,3 - b]pyridine - type compounds reported by this research group (Journal of Materials Chemistry C 2017, 5, 3456 - 3460). There is an urgent need to study new organic luminescent small molecules with red solid luminescence performance. Summary of the Invention:

[0004] The purpose of the present invention is to provide a dibenzophenoselenazine compound, its preparation method and application.

[0005] The present invention is achieved through the following technical solutions:

[0006] The dibenzophenaselanine compound has a structural formula as shown in Formula I:

[0007]

[0008] Wherein, R is selected from 4-nitrophenyl, 4-cyanophenyl, phenyl, 4-methoxyphenyl, 4-methylphenyl, 2-naphthyl, 1-naphthyl, 2-anthryl, 3,5-dimethylphenyl, 3,5-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,5-dimethoxyphenyl, 4-(1,1'-biphenyl)-4-yl, 4-trifluoromethylphenyl, styryl, 4-N,N-dimethylphenyl, 4-(10-phenylanthracen-9-yl)phenyl, 10-([1,1'-biphenyl]-4-yl)anthracenyl.

[0009] The method for preparing the dibenzophenaselenazine compound comprises the following steps:

[0010] (1) Using dinaphthylamine as a raw material, under the action of Se, SeO2, and I2, a reaction is performed at 100-180°C to obtain compound A1:

[0011] The molar ratio of dinaphthylamine, Se, SeO2 and I2 is 1:0.2~1:0.2~1:0.1~0.5; the reaction formula is:

[0012]

[0013] (2) Compound A1 and a fluorinated compound are used as raw materials, and DMF is used as a solvent under alkaline conditions at 100-150° C. to obtain the target compound I; the molar ratio of compound A1, fluorinated compound, and base is 1:1-2:1-5; the base is KOH, NaH or CaH; the reaction formula is:

[0014]

[0015] or,

[0016] Compound A1 and bromide are used as raw materials, palladium acetate and tri-tert-butylphosphine are used as catalysts (20 mol%), xylene is used as solvent, and the target compound I is obtained by reaction at 100-150° C. under alkaline conditions; the molar ratio of compound A1, bromide and base is 1:1-4:1-5; the base is NaOH, KOH, t-BuOK, NaH or CaH; the reaction formula is:

[0017]

[0018] Preferably, in step (1), the solvent is sulfolane or N-methylpyrrolidone, and the concentration of dinaphthylamine is 0.2-2.0 mol / L.

[0019] Preferably, the concentration of compound A1 in step (2) is 0.1-2.0 mol / L.

[0020] The present invention also protects the application of the dibenzophenaselanizine compounds as red solid fluorescent functional materials in the preparation of fluorescent materials for use in the fields of organic optoelectronic devices, chemical sensors and biological probes.

[0021] The effective effects of the present invention are as follows:

[0022] 1. The present invention provides a novel dibenzophenaselanine compound, which has not been reported in the literature and has a novel structure.

[0023] 2. The preparation method of the present invention has the advantages of being rapid, convenient and low-cost. The obtained dibenzophenaselanizine compounds have good red solid fluorescence function and are expected to have good applications in the fields of organic optoelectronic devices, chemical sensors and biological probes, and have good application prospects for red fluorescent materials. Specific implementation method:

[0024] The following is a further description of the present invention, rather than a limitation of the present invention.

[0025] Instruments and drugs: The nuclear magnetic spectrum (NMR) of the present invention is measured by AVANCE 400 or AVANCE 600 instruments produced by Bruker, Germany, with the solvent peak as the internal standard; the mass spectrum of the present invention is measured by ThermoUltiMate3000 ISQ EC (ESI source) produced by Thermo Fisher Scientific, USA; chemical reagents are purchased from Shanghai Bid Pharmaceutical Technology Co., Ltd., J&K Company, Alfar-Aser Company, Aladdin Chemical Reagent Company, etc.; silica gel for column chromatography is purchased from Qingdao Ocean Chemical Plant.

[0026] Example 1: Synthesis of Compound A1

[0027]

[0028] Under room temperature, dinaphthylamine (538 mg, 2 mmol), Se (32 mg, 0.4 mmol), SeO2 (44 mg, 0.4 mmol), I2 (51 mg, 0.2 mmol) were weighed in a reaction bottle, 10 mL of sulfolane was added, and the mixture was heated at 100°C for 4 hours. After the reaction was completed, the mixture was extracted, dried, and purified by column chromatography to obtain a green solid (560 mg, 81%).

[0029] MS (ESI + ):m / z:347([M+H] + ); 11H NMR (400 MHz, DMSO-d6) δ 9.10 (brs, 1H), 8.07–7.69 (m, 6H), 7.56 (t, J = 7.6 Hz, 2H), 7.37 (s, 2H), 7.16 (d, J = 8.7 Hz, 2H).

[0030] Example 2: Synthesis of Compound A1

[0031]

[0032] At room temperature, 2,2'-diaminobiphenyl (2690 mg, 10 mmol), Se (790 mg, 10 mmol), SeO2 (1110 mg, 10 mmol), and I2 (1270 mg, 5 mmol) were successively weighed into a reaction flask, 5 mL of N-methylpyrrolidone was added, and the mixture was heated at 180 °C for 1 hour. After the reaction was completed, extraction, drying, and purification by column chromatography were carried out to obtain a green solid (2700 mg, 78%).

[0033] Example 3: Synthesis of Compound I-1

[0034]

[0035] Compound A1 (173 mg, 0.5 mmol), 4-nitrofluorobenzene (71 mg, 0.5 mmol), KOH (28 mg, 0.5 mmol), and DMF (5 mL) were reacted at 100 °C; after the reaction was completed, the mixture was cooled to room temperature, ethyl acetate was added, and the organic phase was washed with water and saturated sodium chloride solution respectively, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by flash column chromatography to obtain 183 mg of a yellow solid with a yield of 78%.

[0036] MS (ESI + ): m / z: 469 ([M+H] + ); 1 1H NMR (600 MHz, CDCl3) δ 8.23 (d, J = 8.3 Hz, 2H), 8.05–7.98 (m, 2H), 7.93 (dd, J = 15.3, 8.3 Hz, 4H), 7.74–7.71 (m, 2H), 7.63 (t, J = 7.7 Hz, 2H), 7.57 (t, J = 7.5 Hz, 2H), 7.00–6.91 (m, 2H)

[0037] Example 4: Synthesis of Compound I-2

[0038]

[0039] The synthesis method refers to Example 3. Compound A1 (173 mg, 0.5 mmol), 4-nitrofluorobenzene (121 mg, 1 mmol), NaH (60 mg, 2.5 mmol), DMF (0.25 mL) were reacted at 150 °C to obtain 190 mg of a yellow solid with a yield of 85%.

[0040] MS(ESI + ): m / z: 449 ([M+H] + ); 1 H NMR (500 MHz, DMSO-d6) δ 8.17 (d, J = 8.3 Hz, 2H), 8.10 (d, J = 8.7 Hz, 2H), 8.06 (d, J = 8.1 Hz, 2H), 7.84 (d, J = 8.5 Hz, 2H), 7.72–7.67 (m, 2H), 7.66–7.59 (m, 2H), 7.60–7.54 (m, 2H), 6.99–6.82 (m, 2H).

[0041] Example 5: Synthesis of Compound I-3

[0042]

[0043] The synthesis method refers to Example 3. Compound A1 (173 mg, 0.5 mmol), 4-trifluoromethylfluorobenzene (164 mg, 1 mmol), CaH (84 mg, 2 mmol), DMF (2 mL) were reacted at 130 °C to obtain 184 mg of a yellow solid with a yield of 75%.

[0044] MS(ESI + ): m / z: 492 ([M+H] + ); 1 H NMR (600 MHz, CDCl3) δ 8.23 (d, J = 8.4 Hz, 2H), 7.90 (d, J = 8.1 Hz, 4H), 7.71 (dd, J = 8.6, 1.4 Hz, 2H), 7.64–7.57 (m, 2H), 7.54 (t, J = 7.5 Hz, 2H), 7.37 (d, J = 8.7 Hz, 2H), 7.02 (d, J = 8.6 Hz, 2H).

[0045] Example 6: Synthesis of Compound I-4

[0046]

[0047] Compound A1 (173 mg, 0.5 mmol), bromobenzene (314 mg, 2 mmol), NaOH (20 mg, 0.5 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (5 mL) were reacted at 100°C; after the reaction was completed, the mixture was cooled to room temperature, ethyl acetate was added, and the organic phase was washed with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate, filtered, concentrated, and separated and purified by rapid column chromatography to obtain 169 mg of a yellow solid with a yield of 80%. MS (ESI + ):m / z:424([M+H] + ); 1 H NMR(600MHz, CDCl3)δ8.26–8.05(m,2H),7.81(d,J=8.1Hz,2H),7.74–7.64(m,2H) ,7.58(t,J=7.6Hz,2H),7.47–7.31(m,6H),7.26–7.20(m,2H),7.17–6.99(m,1H).

[0048] Example 7: Synthesis of Compound I-5

[0049]

[0050] The synthetic method refers to Example 6, compound A1 (173 mg, 0.5 mmol), 4-methoxybromobenzene (94 mg, 0.5 mmol), KOH (140 mg, 2.5 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (0.25 mL) were reacted at 150°C to obtain 172 mg of a yellow solid with a yield of 78%.

[0051] MS (ESI + ):m / z:454([M+H] + ); 1 H NMR(600MHz, CDCl3)δ8.20–8.11(m,2H),7.71(dd,J=8.1,1.2Hz,2H),7.56–7.48(m,4H),7.45( d,J=8.8Hz,2H),7.39–7.33(m,2H),7.08(d,J=8.7Hz,2H),7.00(d,J=8.9Hz,2H),3.88(s,3H).

[0052] Example 8: Synthesis of Compound I-6

[0053]

[0054] The synthesis method refers to Example 6, compound A1 (173 mg, 0.5 mmol), 4-methylbromobenzene (256 mg, 1.5 mmol), t-BuOK (112 mg, 1 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (0.25 mL) were reacted at 130°C to obtain 175 mg of a yellow solid with a yield of 80%.

[0055] MS (ESI + ):m / z:438([M+H] + ); 1 H NMR (600MHz, CDCl3) δ8.18(d,J=8.1Hz,2H),7.75(d,J=8.1Hz,2H),7.60(d,J=8.9Hz,2H),7 .58–7.52(m,2H),7.45–7.33(m,2H),7.33–7.26(m,4H),7.19(d,J=8.9Hz,2H),2.40(s,3H).

[0056] Example 9: Synthesis of Compound I-7

[0057]

[0058] Synthesis method: Refer to Example 6, compound A1 (173 mg, 0.5 mmol), 2-bromonaphthalene (207 mg, 1 mmol), NaH (24 mg, 1 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (3 mL) were reacted at 120°C to obtain 182 mg of a yellow solid with a yield of 77%. MS (ESI + ):m / z:474([M+H] + ) 1 H NMR (400MHz, CDCl3) δ8.35-8.11(m,6H),8.02–7.86(m,4H),7.72–7.55(m,6H),7.32–8.25(m,2H),7.11(s,1H).

[0059] Example 10: Synthesis of Compound I-8

[0060]

[0061] Synthesis method: Refer to Example 6, compound A1 (173 mg, 0.5 mmol), 1-bromonaphthalene (207 mg, 0.5 mmol), CaH (105 mg, 2.5 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (1 mL) were reacted at 110°C to obtain 178 mg of a yellow solid with a yield of 75%. MS (ESI + ):m / z:474([M+H] + ); 1 H NMR (600MHz, CDCl3) δ8.35(d,J=8.5Hz,1H),8.17(d,J=8.6Hz,2H),7.90(dd,J=25.5,8.3Hz,2H),7.76(d,J=7.1Hz,1H),7.59(t,J=7.7Hz, 1H),7.56(d,J=8.0Hz,2H),7.49(t,J=7.7Hz,2H),7.43(t,J=7.5Hz,1H),7.37(t,J=7.6Hz,1H),7.30–7.21(m,4H),6.69(d,J=9.1Hz,2H).

[0062] Example 11: Synthesis of Compound I-9

[0063]

[0064] The synthesis method refers to Example 6, compound A1 (173 mg, 0.5 mmol), 2-bromoanthracene (129 mg, 0.5 mmol), KOH (140 mg, 2.5 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (0.25 mL) were reacted at 150°C to obtain 214 mg of a yellow solid with a yield of 82%.

[0065] MS (ESI + ):m / z:524([M+H] + ); 1 H NMR(600MHz, CDCl3)δ8.35(s,1H),8.23(d,J=8.4Hz,2H),8.19(s,1H),7.99–7.92(m,2H),7.88(d,J=8.2Hz,1H),7 .85(d,J=8.2Hz,2H),7.79(d,J=8.8Hz,2H),7.64(s,1H),7.62–7.56(m,4H),7.54–7.45(m,3H),7.42–7.37(m,2H).

[0066] Example 12: Synthesis of Compound I-10

[0067]

[0068] The synthesis method refers to Example 6, compound A1 (173 mg, 0.5 mmol), 3,5-dimethylbromobenzene (278 mg, 1.5 mmol), t-BuOK (112 mg, 1 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (0.25 mL) were reacted at 130°C to obtain 175 mg of a yellow solid with a yield of 78%.

[0069] MS (ESI + ):m / z:452([M+H] + ); 1 H NMR (600MHz, CDCl3) δ8.18(s,2H),7.79(d,J=8.0Hz,2H),7.65(s,2H),7.56(t,J=7. 7Hz,2H),7.42(s,2H),7.33(d,J=8.8Hz,2H),6.93(s,2H),6.84(s,1H),2.30(s,6H).

[0070] Example 13: Synthesis of Compound I-11

[0071]

[0072] Synthesis method: Refer to Example 6, compound A1 (173 mg, 0.5 mmol), 3,5-dimethoxybromobenzene (217 mg, 1 mmol), NaH (24 mg, 1 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (3 mL), react at 120°C to obtain 190 mg of a yellow solid with a yield of 79%. MS (ESI + ):m / z:484([M+H] + ); 1 HNMR (600MHz, CDCl3) δ8.15 (s, 2H), 7.81 (d, J = 8.0Hz, 2H), 7.56 (s, 2H), 7.44 (t, J = 7. 7Hz,2H),7.36(s,2H),7.30(d,J=8.8Hz,2H),6.82(s,2H),6.52(s,1H),3.81(s,6H).

[0073] Example 14: Synthesis of Compound I-12

[0074]

[0075] Synthesis method: Refer to Example 6, compound A1 (173 mg, 0.5 mmol), 4-bromobiphenyl (117 mg, 0.5 mmol), CaH (105 mg, 2.5 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (1 mL) were reacted at 110°C to obtain 188 mg of a yellow solid with a yield of 75%. MS (ESI + ):m / z:500([M+H] + ); 1 H NMR (600MHz, CDCl3) δ8.23(d,J=8.4Hz,2H),7.84(d,J=8.1Hz,2H),7.79(d,J=8.8Hz,2H),7.62–7. 51(m,8H),7.48(t,J=7.5Hz,2H),7.41(t,J=7.7Hz,2H),7.30(t,J=7.4Hz,1H),7.28–7.22(m,2H).

[0076] Example 15: Synthesis of Compound I-13

[0077]

[0078] Synthesis method: Refer to Example 6, compound A1 (173 mg, 0.5 mmol), bromostyrene (275 mg, 1.5 mmol), t-BuOK (112 mg, 1 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (0.25 mL) were reacted at 130°C to obtain 180 mg of a yellow solid with a yield of 80%. MS (ESI + ):m / z:450([M+H] + ); 1 H NMR (600MHz, CDCl3) δ8.25–8.06(m,2H),7.85(d,J=8.1Hz,2H),7.76–7.62(m,2H),7.57(t,J=7.6Hz, 2H),7.46–7.35(m,6H),7.29–7.24(m,2H),7.17–6.99(m,1H), 6.68-6.56(m,1H), 6.05-5.98(m,1H).

[0079] Example 16: Synthesis of Compound I-14

[0080]

[0081] Synthesis method: Refer to Example 6, compound A1 (173 mg, 0.5 mmol), 4-bromo-N,N-dimethylaniline (200 mg, 1 mmol), NaH (24 mg, 1 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (3 mL), react at 120°C to obtain 182 mg of a yellow solid with a yield of 78%. MS (ESI + ):m / z:467([M+H] + ); 1 H NMR (600MHz, CDCl3) δ8.16(d,J=8.5Hz,2H),7.68(d,J=8.0Hz,2H),7.59–7.28(m,8H),7.04–6.80(m,4H),3.05(s,6H).

[0082] Example 17: Synthesis of Compound I-15

[0083]

[0084] Synthesis method: Refer to Example 6, compound A1 (173 mg, 0.5 mmol), 2,6-dimethoxybromobenzene (109 mg, 0.5 mmol), CaH (105 mg, 2.5 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (1 mL), react at 110 ° C to obtain 178 mg of yellow solid, with a yield of 74%. MS (ESI + ):m / z:484([M+H] + ); 1 H NMR (600MHz, CDCl3) δ8.25 (s, 2H), 7.85 (d, J = 8.0Hz, 2H), 7.60 (s, 2H), 7.45 (t, J = 7. 7Hz,2H),7.32(s,2H),7.28(d,J=8.8Hz,2H),6.98(s,1H),6.82(s,2H),3.85(s,6H).

[0085] Example 18: Synthesis of Compound I-16

[0086]

[0087] Synthesis method: Refer to Example 6, compound A1 (173 mg, 0.5 mmol), 2,5-dimethoxybromobenzene (217 mg, 1 mmol), CaH (105 mg, 2.5 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (1 mL) were reacted at 140°C to obtain 184 mg of a yellow solid with a yield of 76%. MS (ESI + ):m / z:484([M+H] + ); 1 HNMR(600MHz, CDCl3)δ8.30(s,2H),7.89(d,J=8.0Hz,2H),7.63(s,2H),7.55(t,J=7.7Hz,2H),7.40(s,2 H),7.32(d,J=8.8Hz,2H),7.01-6.98(m,1H),6.82(s,1H),6.68-6.58(m,1H),3.85(s,3H),3.75(s,3H).

[0088] Example 19: Synthesis of Compound I-17

[0089]

[0090] Synthesis method: Reference Example 6, compound A1 (173 mg, 0.5 mmol), 9-phenyl-10-(4-bromophenyl) anthracene (205 mg, 0.5 mmol), KOH (140 mg, 2.5 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (0.25 mL) were reacted at 150°C to obtain 285 mg of a yellow solid with a yield of 84%. MS (ESI + ):m / z:676([M+H] + ); 1 H NMR (600MHz, CDCl3) δ8.57(d,J=8.6Hz,2H),8.22(s,2H),7.99–7.83(m,4H),7.85–7.77(m,2H),7.65–7.60(m,4H),7.59(t,J=7. 6Hz,2H),7.57–7.52(m,2H),7.52–7.47(m,2H),7.47–7.40(m,3H),7.38–7.29(m,2H),7.24–7.18(m,2H),6.49(d,J=9.1Hz,2H).

[0091] Example 20: Synthesis of Compound I-18

[0092]

[0093] Synthesis method: Reference Example 6, compound A1 (173 mg, 0.5 mmol), 10-bromo-9-(4-biphenyl)anthracene (409 mg, 1 mmol), KOH (140 mg, 2.5 mmol), palladium acetate (23 mg, 0.5 mmol), tri-tert-butylphosphine (20 mg, 0.1 mmol) and xylene (2 mL) were reacted at 120°C to obtain 260 mg of a yellow solid with a yield of 76%. MS (ESI + ):m / z:676([M+H] + ); 1 H NMR(600MHz, CDCl3)δ8.60(d,J=8.6Hz,2H),8.21(m,2H),7.95–7.75(m,6H),7.67–7.61(m ,4H),7.60(t,J=7.6Hz,2H),7.57–7.41(m,7H),7.38–7.19(m,4H),6.49(d,J=9.1Hz,2H).

[0094] The spectral properties of the dibenzophenaselanine compounds obtained in Examples 3-20 in the solid state (excitation wavelength is 400 nm) were tested, and the results are shown in the following table:

[0095] Compound I-1 I-2 I-3 I-4 I-5 I-6 I-8 I-10 I-12 I-14 <![CDATA[λ em / nm]]> 510 620 435 625 650 625 610 600 625 620

[0096] It can be seen from the above results that in the examples, 8 compounds have emission wavelengths greater than 600nm, which are in the red light emission wavelength region, have strong red solid luminescence function, and are expected to have certain applications in organic optoelectronic devices, chemical sensors, and biological probes.

Claims

1. A dibenzophenaselanine compound having a structural formula as shown in Formula I: Among them, R is selected from 4-nitrophenyl, 4-cyanophenyl, phenyl, 4-methoxyphenyl, 4-methylphenyl, 2-naphthyl, 1-naphthyl, 2-anthryl, 3,5-dimethylphenyl, 3,5-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,5-dimethoxyphenyl, 4-(1,1'-biphenyl)-4-yl, 4-trifluoromethylphenyl, styryl, 4-N,N-dimethylphenyl, 4-(10-phenylanthracen-9-yl)phenyl, 10-([1,1'-biphenyl]-4-yl)anthryl.

2. The preparation method of the dibenzophenoselenazine compound according to claim 1, characterized in that, The method comprises the following steps: (1) Using dinaphthylamine as a raw material, under the action of Se, SeO2 and I2, a reaction is performed at 100-180°C to obtain compound A1: the molar ratio of dinaphthylamine, Se, SeO2 and I2 is 1:0.2-1:0.2-1:0.1-0.5; the reaction formula is: (2) Compound A1 and a fluorinated compound are used as raw materials, and DMF is used as a solvent under alkaline conditions at 100-150° C. to obtain the target compound; the molar ratio of compound A1, fluorinated compound, and base is 1:1-2:1-5; the base is KOH, NaH or CaH; the reaction formula is: or, Compound A1 and bromide are used as raw materials, palladium acetate and tri-tert-butylphosphine are used as catalysts, xylene is used as solvent, and the target compound I is obtained by reaction at 100-150° C.; the molar ratio of compound A1, bromide and base is 1:1-4:1-5; the base is NaOH, KOH, t-BuOK, NaH or CaH; the reaction formula is:

3. The preparation method according to claim 2, wherein In step (1), the solvent is sulfolane or N-methylpyrrolidone, and the concentration of dinaphthylamine is 0.2-2.0 mol / L.

4. The preparation method according to claim 2, characterized in that, The concentration of compound A1 in step (2) is 0.1-2.0 mol / L.

5. The preparation method according to claim 2, wherein, In step (2), the molar fraction of tri-tert-butyl phosphine in the catalyst composed of palladium acetate and tri-tert-butyl phosphine is 20%.

6. Use of the dibenzophenoselenazine compound according to claim 1, characterized in that, The application of red solid fluorescent functional materials in the preparation of fluorescent materials.

7. The application according to claim 6, characterized in that Used in the fields of organic optoelectronic devices, chemical sensors and biological probes.

Images