CN110408383B - Pure organic room temperature phosphorescent material with twisted donor-acceptor structure and preparation method and application thereof - Google Patents
Pure organic room temperature phosphorescent material with twisted donor-acceptor structure and preparation method and application thereof Download PDFInfo
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- C07D—HETEROCYCLIC COMPOUNDS
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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Abstract
The invention relates to a pure organic room temperature phosphorescent material with a twisted donor-acceptor structure, and a preparation method and application thereof. According to the invention, a pure organic room temperature phosphorescent material with long luminescence life and higher luminescence efficiency is obtained by simply constructing a pi-conjugated structure with a twisted donor-acceptor structure; the preparation method is simple, the raw materials are cheap and easy to obtain, the reaction steps are few, the reaction conditions are mild, the yield is high, and the industrialization is easy to realize; the preparation method is beneficial to introducing different functional groups at the tail end of the alkyl side chain, and promotes the application of the pure organic room temperature phosphorescent material in the aspects of organic electroluminescent devices, chemical sensing, biological imaging, data encryption, anti-counterfeiting marks and the like.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a pure organic room temperature phosphorescent material with a twisted donor-acceptor structure, and a preparation method and application thereof.
Background
Phosphorescence is a slowly emitting, optically cooled luminescence phenomenon, i.e., luminescence that continues for a period of time after excitation ceases (as shown in fig. 1). Compared with the traditional fluorescent material, the phosphorescent material has the advantages of long luminescence life, and the long luminescence life can eliminate the interference of organism autofluorescence (nanosecond level) and reduce background noise, thereby realizing biological imaging with high resolution and high signal-to-noise ratio. On the other hand, in the electroluminescent process, the phosphorescent material can utilize singlet excitons and triplet excitons to emit light simultaneously to break through the upper limit value of 25% internal quantum efficiency of the traditional fluorescent material, and theoretically, a high-efficiency organic electroluminescent diode device with the internal quantum efficiency as high as 100% is realized. Therefore, the development of efficient and long-life phosphorescent materials and the exploration of their application value in the field of advanced technology have attracted great attention in the scientific and industrial fields.
Although phosphorescent materials have wide application prospects in many high and new technology fields such as photoelectric devices, information storage, chemical sensing, photoresponse switching, molecular probes, biological imaging and the like (adv.mater.2016, 28,655-660 j.am.chem.soc.2014,136,6395-6400 nat.mater.2009, 8,747-751, adv.mater 2017, 10.1002/adma.201701244. However, most of the phosphorescent materials reported so far are based on inorganic compounds and organometallic complexes. The inorganic compound has limited variety and poor processability and depends on the doping of expensive rare earth metal; in contrast, organometallic complexes are diverse and have good processability, but also rely on expensive rare earth metals, and these drawbacks limit the practical application of inorganic and organometallic complex-based phosphorescent materials to some extent. Aiming at the above disadvantages, the pure organic phosphorescent material without precious metal shows its unique advantages: (1) The pure organic compound has wide sources, is easy to modify, can be processed by solution and prepared in a large area, and can reduce the production cost to a certain extent; (2) The pure organic compound has small cytotoxicity and good biocompatibility, so that the pure organic compound has great development potential in the field of life science; (3) The pure organic compound has the characteristics of good flexibility, lightness and thinness, so that the pure organic compound has attractive application prospects in the fields of flexible display, wearable electronic equipment and the like. However, room Temperature Phosphorescence (RTP) is rarely found in pure organic compounds, mainly due to: (1) Triplet oxygen and water vapor, etc. in air trap triplet excitons to quench phosphorescence (j. Phys. Chem. 1977,81, 1932-1939); (2) Intramolecular vibration, rotation, etc. motion causes non-radiative relaxation of excitons to quench phosphorescence. Thus, phosphorescent emission of pure organic compounds is usually achieved under ultra-low temperature and anhydrous and oxygen-free conditions (J.Am. Chem. Soc.2013,135, 2160-2163), and this extremely demanding requirement largely limits their practical applications. In view of this, the development of a pure organic RTP material with long light-emitting lifetime and high light-emitting efficiency is a key scientific problem to be solved urgently in the development of the current organic light-emitting material, and is a great challenge!
Crystals of benzophenone and its derivatives were found to have RTP luminescence characteristics in 2010, and the theory of "Crystallization Induced Phosphorescence (CIP)" was first proposed (j.phys.chem.c., 2010,114, 6090-6099). Under the guidance of CIP theory, a series of diphenylethanedione derivatives, benzophenone derivatives, and even some natural products such as starch, cellulose and bovine serum albumin were also found in succession to have RTP luminescent properties (sci. China. Chem.2013,56, 1183-1186, sci. China. Chem.2013,56,1178-1182, adv. Optical mater.2015, 3,1184-1190, adv. Mater.2015,27, 6195-6201. Furthermore, the RTP luminescence phenomenon of different pure organic molecular systems was also observed successively, and various design strategies for pure organic RTP materials were developed, such as eutectic induction, matrix assistance, singlet fission, H-aggregation induction, intermolecular electron coupling, and the like.
Although the luminescence property of the pure organic room temperature phosphorescent material is greatly improved in nearly five years, the pure organic room temperature phosphorescent material with long luminescence life and higher luminescence efficiency is still extremely lacked, the material structure is single, the luminescence property is poorer, and the molecular design principle with broad spectrum property is lacked.
Disclosure of Invention
The invention aims to provide a pure organic room temperature phosphorescent material with a twisted donor-acceptor structure, and a preparation method and application thereof, and solves the problems of extreme shortage of the quantity of the pure organic room temperature phosphorescent material, single molecular structure, poor luminous performance and the like in the prior art.
The technical scheme adopted by the invention for solving the technical problem is as follows: a pure organic room temperature phosphorescent material with a twisted donor-acceptor structure, wherein the pure organic room temperature phosphorescent material has a structural formula of any one of the following I and II:
wherein X is H, F, cl, br or I; r is H, alkyl chain with 1-10 carbons, glycerol chain with 1-10 carbons, phenyl, bromophenyl, iodophenyl, allyl, 2-hydroxyethyl, 2-aminoethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl or 2-morpholinoethyl; r' is alkyl chain of 1-10 carbons or glycol chain of 1-10 carbons.
The invention also provides a preparation method of the pure organic room temperature phosphorescent material, which comprises the following steps:
mixing the compound shown in the formula III with a reaction raw material, an alkaline reagent and a dehydrating agent, and carrying out esterification reaction in a polar organic solvent to obtain a pure organic room temperature phosphorescent material with a twisted donor-acceptor structure;
when the pure organic room temperature phosphorescent material shown in the formula I is prepared, the reaction raw material is ROH; when the pure organic room temperature phosphorescent material shown in the formula II is prepared, the reaction raw material is OH-R' -OH; wherein X is H, F, cl, br or I; r is H, alkyl chain with 1-10 carbons, glycol chain with 1-10 carbons, phenyl, bromophenyl, iodophenyl, allyl, 2-hydroxyethyl, 2-aminoethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-morpholinoethyl, or alkyl or glycol chain with 1-10 carbons; r' is an alkyl chain of 1-10 carbons or a glycol chain of 1-10 carbons.
In the preparation method of the invention, the reaction raw material is ROH, and the molar ratio of the ROH to the compound shown in the formula III is 1.
In the preparation method, the reaction raw material is OH-R '-OH, and the molar ratio of the OH-R' -OH to the compound shown in the formula III is 1.
In the preparation method of the present invention, the alkaline agent is Dimethylaminopyridine (DMAP).
In the production method of the present invention, the dehydrating agent is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) or Dicyclohexylcarbodiimide (DCC).
In the production method of the present invention, the molar ratio of the basic agent, the dehydrating agent and the compound represented by the formula iii is 2.
In the preparation method of the present invention, the polar organic solvent is dichloromethane.
In the preparation method of the invention, the reaction temperature of the esterification reaction is room temperature; the reaction time of the esterification reaction is 6 to 24 hours.
The pure organic room temperature phosphorescent material is applied to advanced data confidentiality and anti-counterfeiting marks based on the difference of room temperature phosphorescent light-emitting life.
The pure organic room temperature phosphorescent material with the twisted donor-acceptor structure, the preparation method and the application thereof have the following beneficial effects: according to the invention, a pure organic room temperature phosphorescent material with long luminescence life and high luminescence efficiency is obtained by simply constructing a pi-conjugated structure with a twisted donor-acceptor structure, and the design principle has the advantages of simplicity and universality; the pure organic room temperature phosphorescent material has long luminescent life and high luminescent efficiency, has better luminescent performance than most of the existing pure organic room temperature phosphorescent materials, and is applied to organic electroluminescent devices, chemical sensing, biological imaging, data encryption, anti-counterfeiting marks and other aspects; the preparation method is simple, the raw materials are cheap and easy to obtain, the reaction steps are few, the reaction conditions are mild, the yield is high, and the industrialization is easy to realize; the preparation method is beneficial to introducing different functional groups at the tail end of the alkyl side chain, and promotes the application of the pure organic room temperature phosphorescent material in the aspects of organic electroluminescent devices, chemical sensing, biological imaging, data encryption, anti-counterfeiting marks and the like.
Drawings
FIG. 1 is a schematic diagram of the difference between fluorescence and phosphorescence emission lifetimes;
FIG. 2 is a photograph of the luminescence of the crystals of Compound A2 under UV lamp irradiation and after the UV lamp was turned off;
FIG. 3 is a superposition of the steady-state emission spectrum of Compound A1 in the crystalline state and the steady-state emission spectrum after a delay of 10 ms;
FIG. 4 is a time-resolved phosphorescence emission decay curve of Compound A1 in the crystalline state;
FIG. 5 is a superposition of the steady state emission spectrum of Compound A2 in the crystalline state and the steady state emission spectrum after a delay of 10 ms;
FIG. 6 is a time-resolved phosphorescence emission decay curve of Compound A2 in the crystalline state;
FIG. 7 is a superposition of the steady state emission spectrum of Compound A3 in the crystalline state and the steady state emission spectrum after a delay of 10 ms;
FIG. 8 is a time-resolved phosphorescence emission decay curve of Compound A3 in the crystalline state;
FIG. 9 is a superposition of the steady state emission spectrum of Compound A4 in the crystalline state and the steady state emission spectrum after a delay of 5 milliseconds;
FIG. 10 is a time-resolved phosphorescence emission decay curve of Compound A4 in the crystalline state;
FIG. 11 is a graph showing the superposition of the steady-state emission spectrum of Compound A5 in the crystalline state and the steady-state emission spectrum after a delay of 10 ms;
FIG. 12 is a time-resolved phosphorescence emission decay curve of Compound A5 in the crystalline state;
FIG. 13 is a superposition of the steady state emission spectrum of Compound A6 in the crystalline state and the steady state emission spectrum after a delay of 1 ms;
FIG. 14 is a time-resolved phosphorescence emission decay curve of Compound A6 in the crystalline state;
FIG. 15 is a schematic diagram of the application of pure organic room temperature phosphorescent material in advanced data protection and anti-counterfeit labels involved in the present invention;
FIG. 16 is of Compound A1 1 H NMR spectrum;
FIG. 17 is a drawing of Compound A2 1 H NMR spectrum;
FIG. 18 is of Compound A3 1 H NMR spectrum;
FIG. 19 is of Compound A4 1 H NMR spectrum;
FIG. 20 is of Compound A5 1 H NMR spectrum;
FIG. 21 is of Compound A6 1 H NMR spectrum.
Detailed Description
The pure organic room temperature phosphorescent material with a twisted donor-acceptor structure, the preparation method and the application thereof are further described in the following by combining the drawings and the examples:
the invention obtains a pure organic room temperature phosphorescent material with long luminescent life and higher luminescent efficiency by constructing a pi-conjugated structure with a twisted donor-acceptor structure, and the design principle has better universality. The invention provides a simple and universal design principle, and promotes the application of pure organic room temperature phosphorescent materials in organic electroluminescent devices, chemical sensing, biological imaging, data encryption, anti-counterfeiting marks and other aspects.
The present invention can reduce the energy level difference between a singlet excited state and a triplet excited state by simply constructing a pi-conjugated structure having a twisted donor-acceptor structure, thereby increasing the intersystem crossing rate between the singlet excited state and the triplet excited state and improving the luminous efficiency of phosphorescence. Meanwhile, the radiation rate of a triplet excited state is favorably reduced and the luminescent life of phosphorescence is prolonged based on a larger pi-conjugated structure, and the application of the pure organic room-temperature phosphorescent material in organic electroluminescent devices, chemical sensing, biological imaging, data encryption, anti-counterfeiting marks and other aspects can be promoted by further introducing different functional groups at the tail end of an alkyl side chain.
The invention relates to a pure organic room temperature phosphorescent material with a twisted donor-acceptor structure, which has a structural formula of any one of the following I and II:
wherein X is H, F, cl, br or I; r is H, alkyl chain with 1-10 carbons, glycol chain with 1-10 carbons, phenyl, bromophenyl, iodophenyl, allyl, 2-hydroxyethyl, 2-aminoethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl or 2-morpholinoethyl; r' is alkyl chain of 1-10 carbons or glycol chain of 1-10 carbons.
The invention also provides a preparation method of the pure organic room temperature phosphorescent material, which comprises the following steps:
mixing the compound shown in the formula III with a reaction raw material, an alkaline reagent and a dehydrating agent, and carrying out esterification reaction in a polar organic solvent to obtain the pure organic room temperature phosphorescent material with a twisted donor-acceptor structure. The reaction temperature of the esterification reaction is room temperature; the reaction time of the esterification reaction is 6 to 24 hours.
When the pure organic room temperature phosphorescent material shown in the formula I is prepared, the reaction raw material is ROH; when the pure organic room temperature phosphorescent material shown in the formula II is prepared, the reaction raw material is OH-R' -OH; wherein X is H, F, cl, br or I; r is H, an alkyl chain of 1-10 carbons, a glycol chain of 1-10 carbons, phenyl, bromophenyl, iodophenyl, allyl, 2-hydroxyethyl, 2-aminoethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-morpholinoethyl, or an alkyl or glycol chain of 1-10 carbons; r' is alkyl chain of 1-10 carbons or glycol chain of 1-10 carbons.
Wherein, when the reaction raw material is ROH, the molar ratio of the ROH to the compound shown in the formula III is 1. When the reaction raw material is OH-R '-OH, the molar ratio of the OH-R' -OH to the compound shown in the formula III is 1. The alkaline agent is Dimethylaminopyridine (DMAP). The dehydrating agent is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) or Dicyclohexylcarbodiimide (DCC). The molar ratio of the basic agent, the dehydrating agent and the compound represented by the formula III is 2. The polar organic solvent is dichloromethane.
The following is a detailed description of specific examples.
Example 1: synthesis of Compound A1
2- (9H-carbazol-9-yl) benzoic acid (402.0mg, 1.4 mmol), DMAP (324.1 mg, 2.8mmol), EDCl (0.55g, 2.8mmol) and n-butanol (103.8mg, 1.4 mmol) were each weighed and dissolved in dichloromethane (10 mL), and the reaction was stirred at room temperature for 24 hours under nitrogen protection. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted 3 times with dichloromethane, the organic phases were combined and dried over anhydrous magnesium sulfate, concentrated under reduced pressure, separated by silica gel column chromatography (eluent petroleum ether: dichloromethane = 2. FIG. 16 shows 1 H NMR(400MHz,CDCl 3 )δ:8.11-8.15(m,3H), 7.75(dt,J 1 ＝7.6Hz,J 2 ＝1.2Hz,1H),7.55-7.62(m,2H),7.34-7.38(m,2H), 7.24-7.27(m,2H),7.13(s,1H),7.10(s,1H),3.60(t,J＝6.4Hz,2H), 0.68-0.73(m,2H),0.59-0.64(m,2H),0.52(t,J＝6.8Hz,3H).HR-MS (MALDI-TOF,m/z):calcd for C23H21NO2,343.1572.Found,343.1589.
FIG. 3 is a superposition of the steady-state emission spectrum of Compound A1 in the crystalline state and the steady-state emission spectrum after a delay of 10 ms. The graph shows that the position of the emission peak in the steady state emission spectrum after a delay of 10 msec is coincident with the position of the emission peak at a long wavelength band in the steady state emission spectrum, indicating that the emission peak at the short wavelength band in the steady state emission spectrum is a fluorescent emission of short lifetime and the emission peak at the long wavelength band is a phosphorescent emission of long lifetime.
FIG. 4 is a time-resolved phosphorescence emission decay curve of Compound A1 in the crystalline state, from which the phosphorescence emission lifetime was calculated to 659.94 milliseconds using a one-time exponential fit.
Example 2: synthesis of Compound A2
The synthesis method of the compound A2 was the same as that of A1, and the reaction substrates were 2- (9H-carbazol-9-yl) benzoic acid (574.6 mg,2.0 mmol) and n-hexanol (204.3 mg,2.0 mmol), and purification gave a white crystalline compound A2 (0.6 g, yield: 80.8%). FIG. 17 shows 1 H NMR(400 MHz,CDCl 3 )δ:8.11-8.15(m,3H),7.74(dt,J 1 ＝8.0Hz,J 2 ＝1.2Hz,1H), 7.55-7.62(m,2H),7.34-7.38(m,2H),7.23-7.27(m,2H),7.13(s,1H),7.11(s, 1H),3.58(t,J＝6.4Hz,2H),0.87-1.03(m,2H),0.57-0.86(m,9H). MALDI-TOF,m/z:371.3.
Fig. 5 is a superposition of the steady-state emission spectrum of compound A2 in the crystalline state and the steady-state emission spectrum after a delay of 10 ms. The graph shows that the position of the emission peak in the steady state emission spectrum after a delay of 10 msec is coincident with the position of the emission peak at a long wavelength band in the steady state emission spectrum, indicating that the emission peak at the short wavelength band in the steady state emission spectrum is fluorescent emission with a short lifetime and the emission peak at the long wavelength band is phosphorescent emission with a long lifetime.
FIG. 6 is a time-resolved phosphorescence emission decay curve of Compound A2 in the crystalline state, from which the phosphorescence emission lifetime can be calculated as 1.02 seconds using a one-time exponential fit.
Example 3: synthesis of Compound A3
The synthesis method of the compound A3 was the same as that of A1, and reaction substrates were 2- (9H-carbazol-9-yl) benzoic acid (574.6 mg,2.0 mmol) and 2-morpholine ethanol (262.3 mg,2.0 mmol), and the compound A3 was purified as a white crystalline compound (0.17 g, yield: 42.5%). FIG. 18 shows 1 H NMR (400MHz,CDCl 3 )δ:8.11-8.14(m,3H),7.75(dt,J 1 ＝8.0Hz,J 2 ＝1.6Hz, 1H),7.56-7.62(m,2H),7.34-7.36(m,2H),7.24-7.28(m,2H),7.14(s,1H),7.12 (s,1H),3.68(t,J＝6.0Hz,2H),3.40(t,J＝4.4Hz,4H),1.90(t,J＝4.4 Hz,4H),1.65(t,J＝6.0Hz,3H).HR-MS(MALDI-TOF,m/z):calcd for C25H24N2O3,400.1787.Found,400.1681.
Fig. 7 is a superposition of the steady state emission spectrum of compound A3 in the crystalline state and the steady state emission spectrum after a delay of 10 ms. The graph shows that the position of the emission peak in the steady state emission spectrum after a delay of 10 msec is coincident with the position of the emission peak at a long wavelength band in the steady state emission spectrum, indicating that the emission peak at the short wavelength band in the steady state emission spectrum is fluorescent emission with a short lifetime and the emission peak at the long wavelength band is phosphorescent emission with a long lifetime.
Fig. 8 is a time-resolved phosphorescence emission decay curve of compound A3 in the crystalline state, and the emission lifetime of phosphorescence can be calculated to be 835.93 milliseconds using one-time exponential fitting.
Example 4: one-pot synthesis of compounds A4 and A5
The compounds A4 and A5 are synthesized by a one-pot method, and the synthesis method is the same as that of the compound A1.The reaction substrates were 2- (9H-carbazol-9-yl) benzoic acid (2.87g, 10.0 mmol) and ethylene glycol (651.7 mg,10.5 mmol), and purification gave white crystalline compounds A4 (1.8 g, yield: 54.3%) and A5 (1.0 g, yield: 33.3%), respectively. Figure 19 shows compound A4: 1 H NMR(400MHz, CDCl 3 )δ:8.17-8.25(m,3H),7.80(dt,J 1 ＝7.6Hz,J 2 ＝1.6Hz,1H),7.66(dt, J 1 ＝7.6Hz,J 2 ＝1.2Hz,1H),58(dd,J 1 ＝7.6Hz,J 2 =0.04hz, 1h), 7.38-7.42 (m, 2H), 7.28-7.32 (m, 2H), 7.12 (s, 1H), 7.10 (s, 1H), 3.69 (t, J =4.4hz, 2h), 2.80 (t, J =4.4hz, 2h), HR-MS (MALDI-TOF, m/z): calcd for c21h17nr23, 331.1208.Found,331.1228 fig. 20 shows compound A5: 1 H NMR (400MHz,CDCl 3 )δ:7.95-8.01(m,3H),7.75(dt,J 1 ＝7.6Hz,J 2 ＝1.6Hz, 1H),7.61(t,J＝7.6Hz,1H),7.48(d,J＝7.6Hz,1H),7.11-7.21(m,4H), 6.91(s,1H),6.89(s,1H),2.91(s,2H).HR-MS(MALDI-TOF,m/z):calcd for C40H28N2O4,600.2049.Found,600.2051.
fig. 9 is a superposition of the steady state emission spectrum of compound A4 in the crystalline state and the steady state emission spectrum after a delay of 5 milliseconds. The graph shows that the position of the emission peak in the steady state emission spectrum after a delay of 5 msec is coincident with the position of the emission peak at a long wavelength band in the steady state emission spectrum, indicating that the emission peak at the short wavelength band in the steady state emission spectrum is a fluorescent emission of short lifetime and the emission peak at the long wavelength band is a phosphorescent emission of long lifetime.
Fig. 10 is a time-resolved phosphorescence emission decay curve of compound A4 in the crystalline state, and the emission lifetime of phosphorescence can be calculated to be 240.64 ms by one-time exponential fitting.
Fig. 11 is a graph showing a superposition of the steady-state emission spectrum of compound A5 in the crystalline state and the steady-state emission spectrum after a delay of 10 msec. The graph shows that the position of the emission peak in the steady state emission spectrum after a delay of 10 msec is coincident with the position of the emission peak at a long wavelength band in the steady state emission spectrum, indicating that the emission peak at the short wavelength band in the steady state emission spectrum is a fluorescent emission of short lifetime and the emission peak at the long wavelength band is a phosphorescent emission of long lifetime.
Fig. 12 is a time-resolved phosphorescence emission decay curve of compound A5 in the crystalline state, and the emission lifetime of phosphorescence can be calculated to be 871.84 msec by using a first order exponential fit.
Example 5: synthesis of Compound A6
Synthetic route for compound A6:
synthesis of Compound 1: carbazole (1.67g, 10.0 mmol), methyl o-iodobenzoate (3.93g, 15.0 mmol), copper powder (127.1mg, 2.0 mmol), cuprous iodide (95.2 mg, 0.5 mmol) and potassium carbonate (1.8g, 13.0 mmol) were each weighed and dissolved in n-butyl ether (10 mL), heated under reflux under nitrogen, and stirred for reaction for 48 hours. After completion of the reaction, the reaction mixture was filtered through celite, washed with dichloromethane several times, the filtrate was concentrated under reduced pressure, separated by silica gel column chromatography (eluent: petroleum ether: dichloromethane =2: 1), and recrystallized from a mixed solvent of n-hexane/dichloromethane to obtain white crystalline compound 1 (2.12 g, yield: 70.8%). 1 H NMR(400MHz,CDCl3)δ:8.10-8.14(m,3H),7.73-7.78 (dt,J 1 ＝8.0Hz,J 2 ＝1.2Hz,1H),7.58-7.61(m,2H),7.35-7.39(m,2H), 7.24-7.28(m,2H),7.14(s,1H),7.11(s,1H),3.19(s,3H).HR-MS (MALDI-TOF,m/z):calcd for C20H15NO2,301.1103.Found,301.1132.
Synthesis of compound A6: compound 1 (602.7mg, 2.0mmol) was weighed, dissolved in N, N-Dimethylformamide (DMF) (10 mL), stirred under nitrogen, N-bromosuccinimide (NBS) (373.8mg, 2.1mmol) was added in portions, and the reaction was stirred at room temperature overnight. After completion of the reaction, water was added to the reaction mixture, extracted 3 times with dichloromethane, the organic phases were combined and dried over anhydrous magnesium sulfate, concentrated under reduced pressure, separated by silica gel column chromatography (eluent petroleum ether: dichloromethane = 2. FIG. 21 shows 1 H NMR(400MHz,CDCl 3 )δ:8.12-8.19(m,3H),7.77(t, J＝7.6Hz,1H),7.63(t,J＝7.6Hz,1H),7.51(d,J＝7.6Hz,1H), 7.45-7.48(m,2H),6.97(s,1H),6.95(s,1H),3.28(s,3H).HR-MS (MALDI-TOF,m/z):calcd for C20H13Br2NO2,459.1307.Found,458.9215.
Fig. 13 is a graph showing a superposition of the steady-state emission spectrum of compound A6 in the crystalline state and the steady-state emission spectrum after a delay of 1 msec. The graph shows that the position of the emission peak in the steady state emission spectrum after a delay of 1 msec is coincident with the position of the emission peak at a long wavelength band in the steady state emission spectrum, indicating that the emission peak at the short wavelength band in the steady state emission spectrum is a fluorescent emission of short lifetime and the emission peak at the long wavelength band is a phosphorescent emission of long lifetime.
Fig. 14 is a time-resolved phosphorescence emission decay curve of compound A6 in the crystalline state, and the emission lifetime of phosphorescence can be calculated to be 4.48 msec using a first order exponential fit.
Example 6: room temperature phosphorescent light emitting properties of compounds A1 to A6
The compound A1-A6 can be precipitated into crystals in a mixed solvent of n-hexane/dichloromethane, and the precipitated crystals have room-temperature phosphorescence. Taking compound A2 prepared in example 2 as an example, as shown in fig. 2, the crystals of compound A2 fluoresce blue under uv light, and after the uv light is turned off, the crystals still emit yellow light visible to the naked eye, i.e., phosphorescence.
TABLE 1 luminescence properties of the crystals of the compounds A1 to A6 at room temperature
Note that: lambda [ alpha ] em : a fluorescence emission peak; lambda [ alpha ] p : a phosphorescence emission peak; tau is f : fluorescence lifetime; phi ( f : fluorescence quantum yield; tau. p : phosphorescent lifetime; phi ( p : the phosphorescence quantum yield.
As can be seen from Table 1, the compounds A1 to A6 all have room temperature phosphorescence emission properties in the crystalline state, and the emission lifetimes of the compounds A1 to A6 are all on the order of milliseconds, especially the emission lifetime of the compound A2 is as long as 1.02 seconds, which is one of the pure organic room temperature phosphorescence materials with the longest emission lifetime reported at present. The compound A6 has a short emission lifetime due to the heavy atom effect of bromine atoms, but has an increased emission efficiency.
Example 7: application of pure organic room temperature phosphorescent material in advanced data protection and anti-counterfeiting label
The structural formulas of a typical solid-state fluorescent luminescent material tetraphenylethylene and pure organic room temperature phosphorescent materials A7 and A8 related to the invention are shown as follows:
the pure organic room temperature phosphorescent material has different luminescence life, and can realize high-grade data protection and anti-counterfeit label application by utilizing a time resolution luminescence technology according to the difference of the luminescence life. As shown in fig. 15, the letter "R" is a common solid-state fluorescent material, tetraphenylethylene, with a luminescence lifetime on the nanosecond scale; the letter "T" is a short-lived room temperature phosphorescent material A7, which has a luminescence lifetime of 129.2 milliseconds; the letter "P" is another long-lived room temperature phosphorescent material, A8, which has a luminescence lifetime of 795.0 milliseconds. Under 365nm ultraviolet radiation and other radiation, letters R, T and P can be seen, and the luminous form is short-life fluorescence; when the ultraviolet lamp is turned off, the letter "R" disappears, the letters "T" and "P" are visible, and the light emission form is phosphorescence with longer service life; after 500 milliseconds of turning off the uv lamp, the letter "T" also disappears, leaving only the letter "P" visible, which is a form of long-lived phosphorescence.
The present invention describes the synthesis method and luminescent property of pure organic room temperature phosphorescent material with twisted donor-acceptor structure in detail through the above examples, but the present invention is not limited to the above method, i.e. the present invention can be implemented without depending on the above reaction conditions. It will be understood by those skilled in the art that equivalent substitutions of reaction solvent and dehydrating agent, and changes in the reaction conditions, etc., are within the scope and disclosure of the present invention.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings, and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (1)
1. The application of a pure organic room temperature phosphorescent material in data encryption and anti-counterfeiting marks based on the difference of room temperature phosphorescent light-emitting life time is characterized in that the structural formula of the pure organic room temperature phosphorescent material is any one of the following I and II:
wherein X is H, F, cl, br or I; r is H, alkyl chain with 1-10 carbons, phenyl, bromophenyl, iodophenyl, allyl, 2-hydroxyethyl, 2-aminoethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl or 2-morpholinoethyl; r' is an alkyl chain of 1-10 carbons.
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