CN112341452A - Compound, preparation method thereof and triplet-triplet annihilation up-conversion system - Google Patents
Compound, preparation method thereof and triplet-triplet annihilation up-conversion system Download PDFInfo
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Abstract
The invention relates to the technical field of up-conversion materials, in particular to a compound, a preparation method thereof and a triplet-triplet annihilation up-conversion system. The invention discloses a compound with a structure shown in a formula (I), which has a thermal activation delayed fluorescence characteristic and a heavy atom effect, can be used as a thermal activation delayed fluorescence material and a triplet-triplet annihilation up-conversion photosensitizer, and the heavy atom effect can obviously increase the lowest triplet exciton concentration of the photosensitizer and improve the up-conversion quantum efficiency. The up-conversion photosensitizer with the structure shown in the formula (I) has visible light absorption and red light or near infrared light emission performances, and forms a triplet-triplet annihilation up-conversion system with 9, 10-diphenylanthracene, so that up-conversion luminescence under the condition of high excitation light power density is realized in an organic solvent, green light can be effectively converted into blue light, and the up-conversion quantum yield can reach 24.4%.
Description
Technical Field
The invention relates to the technical field of up-conversion materials, in particular to a compound, a preparation method thereof and a triplet-triplet annihilation up-conversion system.
Background
Upconversion is the process of converting low-energy, long-wavelength light into short-wavelength, high-energy light, i.e. anti-stokes luminescence. At present, the methods for realizing up-conversion generally include two-photon absorption up-conversion, rare earth ion energy transfer up-conversion and triplet-triplet annihilation up-conversion. Compared with two-photon absorption and rare earth ion energy transfer up-conversion, the triplet-triplet annihilation up-conversion system can realize up-conversion luminescence with higher quantum yield under lower excitation power density, and can work under incoherent light, even sunlight, so that the system has important application prospects in the fields of photocatalysis, solar power generation, biological imaging and the like.
Triplet-triplet annihilation (TTA) up-conversion is the transfer of excited-state energy by a photosensitizer to an annihilator, causing two molecules of excited triplet annihilator (T)1) Generating an excited singlet state (S) of high energy1) And radiates high energy photons. The photosensitizer is an important component of a triplet-triplet annihilation up-conversion system, and the up-conversion quantum efficiency is greatly influenced by the photophysical properties of the photosensitizer. In recent years, researchers have developed a variety of materials to build triplet-triplet annihilation up-conversion systems. Many complexes of transition metals (Pt, Pd, Ir, etc.) are widely used as up-conversion photosensitizers due to their high intersystem crossing rate, with some systems having up-conversion quantum yields in excess of 30%. Recently, researchers report a plurality of non-transition metal photosensitizers, such as organic compounds with heavy atom effect, thermally activated delayed fluorescence molecules and the like, and the photosensitizers can realize up-conversion luminescence without transition metals, so that a new way is provided for constructing an up-conversion system. However, upconversion systems based on these non-transition metal photosensitizers mostly show low upconversion quantum yields. Therefore, developThe high-efficiency non-transition metal photosensitizer has important application value.
Disclosure of Invention
The invention provides a compound, a preparation method thereof and a triplet-triplet annihilation upconversion system, which solves the problems that most upconversion systems of non-transition metal photosensitizers show low upconversion quantum yield and high excitation threshold.
The specific technical scheme is as follows:
the invention provides a compound, which has a structure shown in a formula (I);
wherein A is an electron withdrawing group and R is hydrogen or
x is a halogen atom.
In the invention, A is benzothiazole, benzothiadiazole or benzodithiadiazole.
The structure shown in formula (I) provided by the invention takes A as an electron-withdrawing unit and takes halogen-substituted 9, 9-dimethylacridine as an electron-donating unit. The compound has the characteristics of heat activation delayed fluorescence and heavy atom effect.
The compound provided by the invention is specifically as follows:
the invention also provides a preparation method of the compound, which comprises the following steps:
step 1: mixing A-x or x-A-x, a ligand, 9-dimethylacridine, alkali and a solvent, and carrying out Buchwald-Hartwing reaction under the condition of a catalyst to obtain a compound with a structure shown in a formula (II);
step 2: carrying out electrophilic substitution reaction on a compound with a structure shown in a formula (II) and a halogenating agent to obtain a compound shown in a formula (I);
wherein the content of the first and second substances,
a is an electron withdrawing group and R is hydrogen or
x is a halogen atom, and x is a halogen atom,
r' is hydrogen or
In step 1 of the present invention, the Buchwald-Hartwig reaction is preferably carried out in an atmosphere of nitrogen or inert gas;
the reaction starting materials A to x are preferably:
the starting materials x-A-x are preferably:
the ligand is tri-tert-butylphosphine tetrafluoroborate;
the base is sodium tert-butoxide;
the catalyst is palladium catalyst which is palladium acetate;
the solvent is toluene; and adding the toluene into the reaction system after water removal and oxygen removal treatment.
The molar ratio of the A-x to the 9, 9-dimethylacridine is 1: 1.5;
the molar ratio of the x-A-x to the 9, 9-dimethylacridine is 1: 2.2;
the Buchwald-Hartwig reaction is carried out at the temperature of 120 ℃ for 48 hours, and after the Buchwald-Hartwig reaction is finished, a product is required to be purified, wherein the purification specifically comprises the following steps: pouring the reaction into ice water, extracting by using dichloromethane, concentrating an organic phase, and performing concentration by using a solvent with a volume ratio of 2:1, carrying out column chromatography separation on the mixed solution of normal hexane and dichloromethane to obtain the compound with the structure shown in the formula (II).
Intermediate: the compound of formula (ii) is preferably:
in step 2 of the invention, the halogenating agent is N-halogenated succinimide;
when R' in the compound with the structure shown in the formula (II) is hydrogen, the molar ratio of the compound to the halogenating agent is preferably 1: 4; when R' in the compound with the structure shown as the formula (II) is
When the molar ratio of the halogenating agent to the halogenating agent is 1: 8;
the temperature of the electrophilic substitution reaction is 0 ℃, and the time is 6-12 h;
after the electrophilic substitution reaction is finished, purifying a product, wherein the purification specifically comprises the following steps: pouring the reaction solution into ice water, extracting by using dichloromethane, concentrating an organic phase, and performing concentration by using a solvent with a volume ratio of 3:1, performing column chromatography separation on n-hexane and dichloromethane to obtain the compound with the structure shown in the formula (I).
The compound provided by the invention has the characteristics of heat activation and delayed fluorescence. Therefore, the invention also provides the application of the compound with the structure shown in the formula (I) or the compound with the structure shown in the formula (I) prepared by the preparation method in the thermal activation delayed fluorescent material. The thermal activation delayed fluorescence material is also used as a photosensitizer to construct a triplet-triplet annihilation up-conversion system, and by selecting a proper annihilation agent, after the thermal activation delayed fluorescence photosensitizer absorbs energy, the lowest excited singlet exciton reaches the lowest excited triplet state through intersystem crossing, at the moment, the exciton of the lowest excited triplet state reaches the excited triplet state of the annihilation agent through a triplet-triplet energy transfer process, and finally up-conversion luminescence is realized through a triplet-triplet annihilation process. The heavy atom effect can enhance the spin-orbit coupling effect of molecules, so that the intersystem crossing rate of excitons from the lowest excited singlet state to the lowest excited triplet state is increased, the concentration of the lowest excited triplet state excitons of the photosensitizer is enhanced, and the up-conversion quantum yield is improved.
The compound provided by the invention has the characteristics of thermal activation delayed fluorescence and heavy atom effect, so the invention also provides the application of the compound with the structure shown in the formula (I) or the compound with the structure shown in the formula (I) prepared by the preparation method in a triplet-triplet annihilation up-conversion photosensitizer. The compound with the structure shown in the formula (I) is a novel up-conversion photosensitizer.
The present invention also provides a triplet-triplet annihilation upconversion system comprising 1: 5 or 1: 5 compound, annihilator and solvent.
In the present invention, the annihilator is preferably 9, 10-diphenylanthracene;
the solvent is toluene.
The up-conversion photosensitizer has visible light absorption and red light or near infrared light emission performances, and forms a triplet-triplet annihilation up-conversion system with the annihilation agent 9, 10-diphenylanthracene, so that green light can be effectively converted into blue light, and the up-conversion photosensitizer has high up-conversion quantum yield.
In the triplet-triplet annihilation up-conversion system of the present invention, the ratio of 1: 5 the molar concentration of the compound is 1mM, and the molar concentration of the annihilation agent is 5 mM;
the molar ratio of the structural compound shown in the formula (I) to the annihilator is 1: 5.
according to the technical scheme, the invention has the following advantages:
the compound with the structure shown in the formula (I) has a thermal activation delayed fluorescence characteristic and a heavy atom effect, can be used as a thermal activation delayed fluorescence material and a triplet-triplet annihilation up-conversion photosensitizer, and the heavy atom effect can remarkably increase the minimum triplet exciton concentration of the photosensitizer and improve the up-conversion quantum efficiency. The up-conversion photosensitizer with the structure shown in the formula (I) has visible light absorption and red light or near infrared light emission performances, and forms a triplet-triplet annihilation up-conversion system with 9, 10-diphenylanthracene, so that up-conversion luminescence under the condition of high excitation light power density is realized in an organic solvent, green light can be effectively converted into blue light, and the up-conversion quantum yield can reach 24.4%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 shows the UV-visible absorption spectrum and fluorescence emission spectrum (excitation wavelength 520nm) obtained by dissolving BTDZ-2DMAc-4Br in toluene solution in example 7 of the present invention;
FIG. 2 is a diagram of the upconversion emission spectrum of BTDZ-2DMAc-4Br as an upconversion photosensitizer and 9, 10-diphenylanthracene as an annihilation agent in a toluene solution in example 7 of the present invention;
FIG. 3 is a transient state spectrum of BTDZ-2DMAc-4Br in toluene solution with 377nm as excitation wavelength in example 8 of the present invention;
FIG. 4 is a transient state spectrum of BTDZ-2DMAc-4Br as an up-conversion photosensitizer and 9, 10-diphenylanthracene as an annihilator in a toluene solution in example 8 of the present invention.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: preparation of compound BTZ-DMAc-2Cl with structure shown in formula (I).
(1) Intermediate: synthesis of Compound BTZ-DMAc having the Structure represented by the formula (II)
To a 100mL three-necked flask were added BTZ-Br (500mg, 2.34mmol), 9, 9-dimethylacridine (DMAc, 735mg, 3.51mmol), palladium acetate (78mg, 0.35mmol) and tri-tert-butylphosphine tetrafluoroborate (305mg, 1.05mmol), sodium tert-butoxide (808mg, 8.42mmol), 30mL of toluene which had been subjected to oxygen removal by water removal under an argon atmosphere was added, and the reaction was carried out at 120 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was poured into 50mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 3:1) to obtain 601mg of red powder with a yield of 75%. MS (EI) m/z 342.12.
(2) Synthesis of BTZ-DMAc-2Cl having structure shown in formula (I)
In a 100mL round-bottom flask, BTZ-DMAc (300mg, 0.88mmol) was dissolved in chloroform (7 mL). A solution of N-chlorosuccinimide (NCS, 470mg, 3.52mmol) in chloroform (28mL) was slowly added dropwise at 0 ℃ and stirred for 8 hours. After the reaction was completed, the reaction solution was poured into 100mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 3:1) to obtain 145mg of red powder with a yield of 40%. MS (EI) m/z 410.04.
Example 2: preparation of compound BTZ-2DMAc-4Cl with structure shown in formula (I).
(1) Intermediate: synthesis of Compound BTZ-2DMAc having the Structure represented by the formula (II)
To a 100mL three-necked flask were added BTZ-Br (500mg, 1.71mmol), 9, 9-dimethylacridine (DMAc, 787mg, 3.76mmol), palladium acetate (57mg, 0.26mmol) and tri-tert-butylphosphine tetrafluoroborate (223mg, 0.77mmol), sodium tert-butoxide (591mg, 6.16mmol), 22mL of toluene which had been treated with water and oxygen removal were added under an argon atmosphere, and the mixture was reacted at 120 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was poured into 50mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 2:1) to obtain 658mg of red powder with a yield of 70%. MS (EI) m/z 549.22.
(2) Synthesis of compound BTZ-2DMAc-2Cl having structure shown in formula (I)
In a 100mL round-bottom flask, BTZ-2DMAc (300mg, 0.55mmol) was dissolved in chloroform (5 mL). A solution of N-chlorosuccinimide (NCS, 588mg, 4.4mmol) in chloroform (35mL) was slowly added dropwise at 0 ℃ and stirred for 8 hours. After the reaction was completed, the reaction solution was poured into 100mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 2:1) to obtain 144mg of red powder, the yield of which was 38%. MS (EI) m/z 685.07.
Example 3: preparation of compound BTZ-DMAc-2Br with structure shown in formula (I).
(1) Intermediate: synthesis of Compound BTDZ-DMAc having the Structure represented by the formula (II)
To a 100mL three-necked flask were added BTDZ-Br (500mg, 2.32mmol), 9, 9-dimethylacridine (DMAc, 728mg, 3.48mmol), palladium acetate (78mg, 0.34mmol) and tri-tert-butylphosphine tetrafluoroborate (303mg, 1.04mmol), sodium tert-butoxide (802mg, 8.35mmol), 30mL of toluene which had been subjected to water removal and oxygen removal under an argon atmosphere was added, and the reaction was carried out at 120 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was poured into 50mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 3:1) to obtain 574mg of red powder with a yield of 72%. MS (EI) m/z 343.11.
(2) Synthesis of compound BTDZ-DMAc-2Br with structure shown as formula (I)
In a 100mL round-bottom flask, BTDZ-DMAc (300mg, 0.87mmol) was dissolved in chloroform (4 mL). A solution of N-bromosuccinimide (NBS, 619mg, 3.48mmol) in chloroform (7mL) was slowly added dropwise at 0 deg.C and stirred for 6 hours. After the reaction was completed, the reaction solution was poured into 50mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 3:1) to obtain 218mg of red powder, yield 50%. MS (EI) m/z 498.94.
Example 4: preparation of compound BTDZ-2DMAc-4Br with structure shown in formula (I).
(1) Intermediate: synthesis of Compound BTDZ-2DMAc having the Structure represented by the formula (II)
To a 100mL three-necked flask were added BTDZ-2Br (500mg, 1.70mmol), 9, 9-dimethylacridine (DMAc, 783mg, 3.76mmol), palladium acetate (57mg, 0.26mmol) and tri-tert-butylphosphine tetrafluoroborate (223mg, 0.77mmol), sodium tert-butoxide (588mg, 6.12mmol), 22mL of toluene which had been subjected to water and oxygen removal treatment was added under an argon atmosphere, and the mixture was reacted at 120 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was poured into 50mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 2:1) to obtain 609mg of red powder with a yield of 65%. MS (EI) m/z 550.22.
(2) Synthesis of compound BTDZ-2DMAc-4Br with structure shown as formula (I)
In a 100mL round-bottom flask, BTDZ-2DMAc (300mg, 0.54mmol) was dissolved in chloroform (3 mL). A solution of N-bromosuccinimide (NBS, 769mg, 4.32mmol) in chloroform (9mL) was slowly added dropwise at 0 deg.C, and stirred for 6 hours. After the reaction was completed, the reaction solution was poured into 50mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 2:1) to obtain 239mg of red powder, yield 51%. MS (EI) m/z 861.86.
Example 5: preparation of compound BDTDZ-DMAc-2I with structure shown in formula (I).
(1) Intermediate: synthesis of compound BDTDZ-DMAc with structure shown as formula (II)
BDTDZ-Br (500mg, 1.83mmol), 9, 9-dimethylacridine (DMAc, 575mg, 2.75mmol), palladium acetate (61mg, 0.27mmol) and tri-tert-butylphosphine tetrafluoroborate (239mg, 0.82mmol), sodium tert-butoxide (632mg, 6.59mmol) were added to a 100mL three-necked flask, 24mL of toluene which had been treated to remove water and oxygen were added under an argon atmosphere, and the mixture was reacted at 120 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was poured into 50mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 3:1) to obtain 514mg of red powder with a yield of 70%. MS (EI) m/z 401.08.
(2) Synthesis of compound BDTDZ-DMAc-2I with structure shown as formula (I)
In a 100mL round-bottom flask, BDTDZ-DMAc (300mg, 0.75mmol) was dissolved in chloroform (8 mL). A solution of N-iodosuccinimide (NIS, 675mg, 3mmol) in chloroform (15mL) was slowly added dropwise at 0 deg.C and stirred for 12 hours. After the reaction was completed, the reaction solution was poured into 100mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 3:1) to obtain 269mg of red powder with a yield of 55%. MS (EI) m/z 652.87.
Example 6: preparation of compound BDTDZ-2DMAc-4I with structure shown in formula (I).
(1) Intermediate: synthesis of compound BDTDZ-2DMAc with structure shown as formula (II)
BDTDZ-2Br (500mg, 1.42mmol), 9, 9-dimethylacridine (DMAc, 658mg, 3.14mmol), palladium acetate (48mg, 0.21mmol) and tri-tert-butylphosphine tetrafluoroborate (186mg, 0.64mmol), sodium tert-butoxide (494mg, 5.14mmol) were added to a 100mL three-necked flask, 18mL of toluene which had been treated with water and oxygen removal were added under an argon atmosphere, and reacted at 120 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was poured into 50mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 2:1) to obtain 536mg of red powder in 62% yield. MS (EI) m/z 608.18.
(2) Synthesis of compound BDTDZ-2DMAc-4I with structure shown as formula (I)
In a 100mL round-bottom flask, BDTDZ-2DMAc (300mg, 0.49mmol) was dissolved in chloroform (5 mL). A solution of N-iodosuccinimide (NIS, 882mg, 3.92mmol) in chloroform (20mL) was slowly added dropwise at 0 deg.C and stirred for 12 hours. After the reaction was completed, the reaction solution was poured into 100mL of ice water, extracted with dichloromethane three times, the organic phase was concentrated, and separated by column chromatography (n-hexane: dichloromethane, v: v, 2:1) to obtain 294mg of red powder, the yield being 54%. MS (EI) m/z 1111.77.
Example 7: triplet-triplet annihilation up-conversion luminescent system using compound BTDZ-2DMAc-4Br of example 4 as photosensitizer
Preparing a 1mM BTDZ-2DMAc-4Br toluene solution, and respectively obtaining an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of BTDZ-2DMAc-4Br in the toluene solution by using an ultraviolet-visible spectrophotometer and a fluorometer with 520nm as an excitation wavelength, wherein as shown in figure 1, the absorption peak of BTDZ-2DMAc-4Br in the toluene solution is 490 nm, the emission peak is 650 nm, and the BTDZ-2DMAc-4Br has visible light absorption and red light or near infrared light emission performances.
In a molar ratio of 1: and 5, preparing a double-component toluene solution of BTDZ-2DMAc-4Br and 9, 10-diphenylanthracene, wherein the concentration of the BTDZ-2DMAc-4Br is 1mM, the concentration of the 9, 10-diphenylanthracene is 5mM, adsorbing the uniformly mixed double-component toluene solution by a capillary, and exciting the double-component solution by a 520-nanometer wavelength light source with different laser power densities. FIG. 2 is a spectrum of upconversion luminescence spectra of the mixed solution of this example, as shown in FIG. 2, the upconversion luminescent system of this example obtained upconversion luminescence with different intensities, the luminescence range is 410-490 nm, and the upconversion quantum yield corresponding to blue light is 24.4%.
Example 8: triplet-triplet annihilation up-conversion luminescent system using compound BTDZ-2DMAc-4Br of example 4 as photosensitizer
A1 mM BTDZ-2DMAc-4Br toluene solution is prepared, a 377nm excitation wavelength is used for exciting the solution, and a transient spectrum of BTDZ-2DMAc-4Br in the toluene solution is shown in a figure 3.
In a molar ratio of 1: and 5, preparing a double-component toluene solution of BTDZ-2DMAc-4Br and 9, 10-diphenylanthracene, wherein the concentration of the BTDZ-2DMAc-4Br is 1mM, the concentration of the 9, 10-diphenylanthracene is 5mM, adsorbing the uniformly mixed double-component toluene solution by a capillary tube, and exciting the component solution by taking 377 nanometers as an excitation wavelength. FIG. 4 is a transient spectrum of the mixed solution of this example, showing that the lifetime of the mixed solution is shortened relative to that of BTDZ-2DMAc-4Br solution, indicating that there is triplet-triplet energy conversion between the photosensitizer and the annihilator.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A compound having the structure of formula (i);
wherein A is an electron withdrawing group and R is hydrogen or
x is a halogen atom.
2. A compound according to claim 1, wherein a is benzothiazole, benzothiadiazole, or benzodithiadiazole.
3. A method for preparing a compound, comprising the steps of:
step 1: mixing A-x or x-A-x, a ligand, 9-dimethylacridine, alkali and a solvent, and carrying out Buchwald-Hartwing reaction under the condition of a catalyst to obtain a compound with a structure shown in a formula (II);
step 2: carrying out electrophilic substitution reaction on a compound with a structure shown in a formula (II) and a halogenating agent to obtain a compound shown in a formula (I);
wherein the content of the first and second substances,
a is an electron withdrawing group and R is hydrogen or
x is a halogen atom, and x is a halogen atom,
r' is hydrogen or
4. The production method according to claim 3, wherein the ligand is tri-tert-butylphosphine tetrafluoroborate;
the base is sodium tert-butoxide;
the catalyst is a palladium catalyst;
the solvent is toluene;
the halogenating agent is N-halogenated succinimide.
5. The method according to claim 3, wherein the molar ratio of the A-x to the 9, 9-dimethylacridine is 1: 1.5;
the molar ratio of the x-A-x to the 9, 9-dimethylacridine is 1: 2.2;
the molar ratio of the compound with the structure shown in the formula (II) to the halogenating agent is 1: 8.
6. Use of a compound of formula (i) according to claim 1 or 2 or a compound of formula (i) obtained by the process according to any one of claims 3 to 5 in a thermally activated delayed fluorescence material.
7. Use of the compound of formula (i) according to claim 1 or 2 or the compound of formula (i) prepared by the preparation method according to any one of claims 3 to 5 in triplet-triplet annihilation up-conversion photosensitizers.
8. A triplet-triplet annihilation up-conversion system comprising the compound of formula (i) according to claim 1 or 2 or the compound of formula (i) prepared by the preparation method according to any one of claims 3 to 5, an annihilating agent, and an organic solvent.
9. The triplet-triplet annihilation up-conversion system of claim 8 wherein the molar ratio of the structural compound of formula (i) to the annihilator is 1: 5.
10. the triplet-triplet annihilation up-conversion system of claim 8 wherein the annihilator is 9, 10-diphenylanthracene;
the organic solvent is toluene.
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