CN115433070B - Room temperature phosphorescent molecule based on column [5] arene, and preparation method and application thereof - Google Patents

Room temperature phosphorescent molecule based on column [5] arene, and preparation method and application thereof Download PDF

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CN115433070B
CN115433070B CN202210951966.8A CN202210951966A CN115433070B CN 115433070 B CN115433070 B CN 115433070B CN 202210951966 A CN202210951966 A CN 202210951966A CN 115433070 B CN115433070 B CN 115433070B
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arene
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temperature phosphorescent
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黄飞鹤
朱黄天之
邢浩
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ZJU Hangzhou Global Scientific and Technological Innovation Center
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Abstract

The invention discloses a column-based [5]]Room temperature phosphorescent molecules of aromatic hydrocarbon, and a preparation method and application thereof. The room temperature phosphorescent molecule is a column [5] having a pair of m-benzaldehyde groups conjugated as shown in the following formula (1)]Aromatic hydrocarbons or columns conjugated with a pair of pyridyl groups [5]]Aromatic hydrocarbons:wherein Ar is selected from one of substituents represented by the following formulas (2) and (3):r is selected from one of substituents shown in the following formulas (4) and (5):the room temperature phosphorescent molecule has trans-space charge transfer in the molecule, effectively reduces the energy level difference between the singlet state and the triplet state and promotes the exciton systemAnd the room temperature phosphorescent molecules can also regulate quantum yield and phosphorescent life through adsorption or desorption of guest molecules.

Description

Room temperature phosphorescent molecule based on column [5] arene, and preparation method and application thereof
Technical Field
The invention belongs to the field of photophysics science, and particularly relates to a room-temperature phosphorescent molecule based on pillar [5] arene, a preparation method thereof and application thereof in a luminescent layer of an organic electroluminescent device.
Background
The room temperature phosphorescent molecules are widely applied in the fields of chemistry, biology, materials and the like, and play an important role in the aspects of phosphorescence sensing and detection, biological imaging, display materials, optical devices and the like. Most of the conventional room temperature phosphorescent molecules are complexes containing transition metals such as ruthenium and platinum, which are expensive and have poor stability, making them difficult to apply on a large scale. In contrast, the pure organic room temperature phosphorescent molecule does not contain noble metal, is suitable for large-scale preparation, and has wide application prospect. However, the intersystem crossing of pure organic molecules is insufficient, and excitons are difficult to realize transition from a singlet state to a triplet state, compared to the complex, and thus phosphorescent properties are poor. To solve this problem, the introduction of carbonyl groups or heavy atoms and the reduction of the level difference between the singlet state and the triplet state by charge transfer have become common approaches.
For example, in the document j.Phys.chem.b 2021,125,4520-4526, the authors construct phosphorescent molecules containing carbazole donors and phthalimide acceptors, and achieve room temperature phosphorescent emission by charge transfer between donor and acceptor molecules within the molecule. In the document angel.chem.int.ed.2020, 59,8210-8217, authors construct complex compounds containing intramolecular charge transfer by coordination of monovalent copper to carbazole donors and to azacyclic carbene acceptors, which also exhibit phosphorescent properties at room temperature.
In these examples, the construction of molecules typically uses chemical bond-based charge transfer, whereas trans-space charge transfer is rarely mentioned, which greatly limits the structural diversity and stimulus responsiveness of phosphorescent chromophores.
Room temperature phosphorescence induced by trans-space charge transfer is quite common in nature, and the room temperature phosphorescence properties of solid powders such as bovine serum albumin are achieved by trans-space charge transfer. Single crystal diffraction results of bovine serum albumin confirm that there are multiple intermolecular interactions inside the molecule, and that the interactions of heteroatoms and carbonyl groups form a trans-space charge transfer channel, resulting in room temperature phosphorescence.
The column arene is one kind of macrocyclic compound, and has the features of easy derivatization, high structural rigidity, excellent main and guest body properties, etc. and may be used widely in constructing various functional materials. The column arene has a ring cavity with fixed size and stable configuration, and is very suitable for researching trans-space charge transfer. Therefore, the macrocyclic skeleton of the pillar aromatic hydrocarbon is used as a building element of the room-temperature phosphorescent molecule, so that not only can the mechanism of trans-space charge transfer be revealed, but also a novel phosphorescent chromophore can be expanded.
Disclosure of Invention
Aiming at the bottleneck problems in the prior art, the invention provides a room-temperature phosphorescent molecule based on pillar [5] arene, which has novel structure, reliable property and convenient synthesis, a preparation method thereof and application thereof in a luminescent layer of an organic electroluminescent device.
The column-based [5]]The room temperature phosphorescence molecules of aromatic hydrocarbon have trans-space charge transfer in molecules, effectively reduce the energy level difference between singlet state and triplet state, promote intersystem leap of excitons, and realize that the blue phosphorescence can be emitted under the excitation of 350-380 nm excitation light at room temperature. While the column-based [5]]The room temperature phosphorescence molecules of aromatic hydrocarbon have guest-controlled room temperature phosphorescence emission, and the diameter of the molecules is smaller than that of the molecules through adsorption or desorptionAnd can volatilize into gas state at room temperature, can be used as a column [5]]The organic halide of arene complexation realizes the enhancement or weakening of quantum yield and shortens or prolongs the phosphorescence life.
A room temperature phosphorescent molecule based on a pillar [5] arene, which is a pillar [5] arene having a pair of m-benzaldehyde groups conjugated or a pillar [5] arene having a pair of pyridyl groups conjugated, represented by the following formula (1):
in the formula (1), ar is selected from one of substituents represented by the following formulas (2) and (3):
in the formula (1), R is selected from one of substituents represented by the following formulas (4) and (5):
at room temperature, the room temperature phosphorescence molecular solid powder based on column [5] arene can emit cyan phosphorescence under the excitation of 350-380 nm excitation light, and the phosphorescence emission is obvious, the detection is convenient, and the property is stable.
The column [5] arene conjugated with a pair of m-benzaldehyde groups provided by the invention and the column [5] arene conjugated with a pair of pyridyl groups provided by the invention are almost identical in phosphorescence property, and the phosphorescence mechanism is trans-space charge transfer from a 1, 4-dialkylbenzene donor to an m-benzaldehyde receptor or a pyridine receptor. The charge transfer reduces the energy level difference between the singlet state and the triplet state, and provides possibility for intersystem crossing of excitons. In addition, the aldehyde group on m-benzaldehyde or the nitrogen heteroatom on pyridine promotes spin-orbit coupling, which is favorable for intersystem crossing, so that both column [5] arene derivatives exhibit room temperature phosphorescence.
The invention also provides a preparation method of the room-temperature phosphorescent molecule based on the column [5] arene, which has the advantages of simple operation, reliable route and low cost.
A preparation method of room-temperature phosphorescent molecules based on column [5] arene comprises the following steps:
(a) The method comprises the steps of (1) utilizing a strategy that ammonium cerium nitrate can oxidize one repeating unit of column aromatic hydrocarbon into p-benzoquinone, dispersing full alkyl column [5] aromatic hydrocarbon and ammonium cerium nitrate in a mixed solution of dichloromethane and water, wherein the full alkyl column [5] aromatic hydrocarbon is full methyl column [5] aromatic hydrocarbon or full ethyl column [5] aromatic hydrocarbon, stirring and reacting at room temperature under the protection of inert gas, evaporating a solvent after the reaction is finished, dissolving the obtained solid in dichloromethane, washing, drying, filtering, separating and concentrating to obtain column [4] aromatic hydrocarbon [1] quinone;
(b) Dispersing the column [4] arene [1] quinone and sodium dithionite obtained in the step (a) in a mixed solution of dichloromethane and water, stirring and reacting at room temperature under the protection of inert gas, and reducing the p-benzoquinone unit in the macrocyclic ring into hydroquinone by the sodium dithionite. After the reaction is finished, separating the liquid, drying the obtained organic phase, filtering, evaporating the solvent to obtain column [5] arene containing a pair of phenolic hydroxyl groups;
(c) Dissolving the column [5] arene containing a pair of phenolic hydroxyl groups obtained in the step (b) in dichloromethane, adding pyridine as an acid binding agent, dropwise adding trifluoromethanesulfonic anhydride at 0-5 ℃ under the protection of inert gas, and stirring at room temperature for reaction to change the phenolic hydroxyl groups into trifluoromethanesulfonic acid ester. After the reaction is finished, washing, separating liquid, drying, filtering, separating and concentrating the obtained organic phase to obtain column [5] arene containing a pair of trifluoro methane sulfonate;
(d) Dissolving a pair of column [5] arene containing trifluoro methane sulfonate and arylboronic acid obtained in the step (c) in tetrahydrofuran, adding potassium carbonate as alkali, adding catalyst tetra (triphenylphosphine) palladium, stirring and reacting at 80-90 ℃ under the protection of inert gas, carrying out Suzuki coupling on the pair of column [5] arene containing trifluoro methane sulfonate and arylboronic acid under the catalysis of palladium, evaporating the solvent to dryness after the reaction is finished, separating the obtained solid, and concentrating to obtain column [5] arene containing a pair of conjugated structures;
in the step (d), when the arylboronic acid is 3-formylphenylboronic acid, the column [5] arene having a pair of conjugated structures is a column [5] arene conjugated with a pair of m-benzaldehyde groups; when the arylboronic acid is 4- (4-pyridyl) phenylboronic acid, the column [5] arene containing a pair of conjugated structures is a column [5] arene conjugated with a pair of pyridyl groups.
Preferably, in the step (a), the molar ratio of the full alkyl column [5] arene to the ceric ammonium nitrate is 1 (1.8-2.2). Too much addition of ceric ammonium nitrate can result in excessive oxidation, resulting in a column arene derivative containing more p-benzoquinone moieties.
Preferably, in the step (a), the separation is specifically performed by using a silica gel column chromatography, the eluent of the silica gel column chromatography is a mixed solution of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 10:1.
Preferably, in step (b), sodium dithionite is in excess such that the p-benzoquinone moiety in the column [4] arene [1] quinone is completely reduced. If the amount of sodium dithionite added is insufficient, this results in a portion of the column [4] arene [1] quinone not being reduced.
Preferably, in the step (c), the separation is specifically performed by using a silica gel column chromatography, the eluent of the silica gel column chromatography is a mixed solution of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 20:1.
Preferably, in step (d), the molar ratio of the aromatic hydrocarbon to the arylboronic acid of the pair of triflate containing columns [5] is 1: (2.5-4). If the amount of arylboronic acid added is small, then an incompletely reacted column aromatic hydrocarbon derivative will be produced;
preferably, in the step (d), the separation is specifically performed by using a silica gel column chromatography, the eluent of the silica gel column chromatography is a mixed solution of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 3:1.
The invention also provides a column-based [5]]A host-guest complex of room temperature phosphorescent molecules of aromatic hydrocarbon, which is obtained by adsorbing a guest molecule by a host molecule which is the column [5] based on the above-mentioned claim 1]Room temperature phosphorescent molecules of aromatic hydrocarbon, wherein the guest molecules are molecules with the molecular diameter smaller thanAnd can volatilize into gas state at room temperature, can be used as a column [5]]Aromatic hydrocarbon complex organic halides.
The invention also provides a column-based [5]]Method for modulating the guest response of room temperature phosphorescent molecules of aromatic hydrocarbons by gas-induced phosphorescence modulationThe method is to base column [5]]The room temperature phosphorescent molecule adsorption or desorption molecular diameter of aromatic hydrocarbon is smaller thanAnd can volatilize into gas state at room temperature, can be used as a column [5]]The organic halide of arene complexation realizes the enhancement or weakening of quantum yield and shortens or prolongs the phosphorescence life.
The principle of the gas-induced phosphorus light control method of the guest response provided by the invention is that after the guest molecule containing halogen enters the cavity of the column [5] arene, the intensity of trans-space charge transfer is changed, and meanwhile, the intersystem leap of the host molecule is enhanced by the heavy atomic effect of the halogen on the guest, so that the quantum yield is improved, and the phosphorescence service life is shortened.
Preferably, the organic halide is bromoethane.
The invention also provides application of the room temperature phosphorescent molecule based on the pillar [5] arene in a luminescent layer of an organic electroluminescent device.
Compared with the prior art, the invention has at least the following beneficial effects:
1. the phosphorescent molecule based on the column [5] arene has stable property, can be used for a long time, and is simple and convenient to synthesize and low in cost.
2. The phosphorescent molecule light-emitting mechanism based on the pillar [5] arene is novel and is different from a room-temperature phosphorescent mechanism induced by charge transfer of a chemical bond in principle.
3. The phosphorescent molecule based on the pillar [5] arene has the gas-induced phosphorescence regulation and control of guest response, and can conveniently realize the regulation and control of quantum yield and phosphorescence service life through the introduction and removal of the guest molecule.
4. The invention provides a new thought and a new choice for the design and preparation of the pure organic room temperature phosphorescent molecules, and simultaneously provides a new construction element for researching trans-space charge transfer.
Drawings
FIGS. 1 (a) and (b) are steady-state spectra and time-resolved spectra of two kinds of column [5] arene derivatives prepared in example 2 and example 3, and FIGS. 1 (c) and (d) are graphs of experimental data of phosphorescent emission lifetimes of two kinds of column [5] arene derivatives prepared in example 2 and example 3;
FIG. 2 is a graph showing experimental data for phosphorescent modulation of a p-m-benzaldehyde conjugated column [5] arene in the presence of bromoethane vapor as measured in example 5.
Detailed Description
The invention will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1
A method for synthesizing a pair of trifluoromethanesulfonic acid ester-containing column [5] arene P5-4:
weighing all-methyl column [5] arene P5-1.0-12.5 g into a 500mL round bottom flask, sequentially adding 10.5-11.0 g of ceric ammonium nitrate, 250mL of dichloromethane, 20mL of water and argon protection, and stirring at room temperature for reaction for 1h. After the reaction is finished, spin-drying the solvent, dissolving the obtained solid in 100-120 mL of dichloromethane, washing with 100-120 mL of water three times, drying with anhydrous sodium sulfate for 30-35 min, filtering, separating by silica gel column chromatography, and eluting with the following components: petroleum ether: ethyl acetate = 10:1, concentrating to obtain red solid, namely column [4] arene [1] quinone P5-2 (8.2-8.5 g, yield 71.2-73.8%).
The column [4] arene [1] quinone P5-2.0-3.5 g is weighed into a 250mL round bottom flask, and 100mL of dichloromethane, 100mL of water and 5.0-5.5 g of sodium dithionite are sequentially added. The system reacts for 24 hours at room temperature, liquid separation is carried out, an organic phase is dried for 30-35 minutes by anhydrous sodium sulfate, filtering and spin-drying are carried out on the solvent, and light yellow solid is obtained, namely, the column [5] arene P5-3 (2.5-2.6 g, yield is 83.3-86.7%) containing a pair of phenolic hydroxyl groups.
The column [5] arene P5-3.0-2.5 g containing a pair of phenolic hydroxyl groups in sequence is weighed, and 100mL of dichloromethane and 20mL of pyridine are sequentially added. 5.0-5.5 mL of trifluoromethanesulfonic anhydride is added dropwise into an ice bath under the protection of argon, and the system is reacted for 24 hours at room temperature. After the reaction is finished, washing with 100-120 mL of water for three times, separating liquid, drying an organic phase with anhydrous sodium sulfate for 30-35 min, filtering, separating by using a silica gel column chromatography, and eluting with the following components: petroleum ether: ethyl acetate=20:1, and the mixture was concentrated to give a white solid, namely column [5] arene P5-4 (1.9 to 2.1g, yield 69.5 to 76.9%) containing a pair of triflates.
The product characterization data prepared in this example are as follows:
column [5] arene P5-4 containing a pair of triflates:
1 H NMR(500MHz,CDCl 3 ,298K)δ(ppm):7.33(s,2H),6.80(s,2H),6.78(s,2H),6.76(s,2H),6.69(s,2H),3.85(s,4H),3.79(m,6H),3.72(s,6H),3.68(s,6H),3.66(s,6H),3.61(s,6H).
example 2
The synthesis method of the column [5] arene P5-5 conjugated with a pair of m-benzaldehyde comprises the following steps:
a pair of trifluoromethane sulfonate-containing column [5] arene P5-40.30-0.35 g prepared in example 1 was taken in a 15mL Schlenk tube, 0.15-0.18 g of 3-formylphenylboronic acid, 20-23 mg of tetrakis (triphenylphosphine) palladium, 0.20-0.22 g of potassium carbonate and 5.0-6.0 mL of tetrahydrofuran were added thereto, and the mixture was stirred at 90℃for 24 hours. After the reaction, spin-drying the solvent, separating by silica gel column chromatography, and eluting with the following eluent: petroleum ether: ethyl acetate=3:1, and concentrating to obtain white solid, i.e. column [5] arene P5-5 (0.15-0.17 g, yield 55.6-63.0%) conjugated with a pair of m-benzaldehyde.
The characterization data for the P5-5 column [5] aromatic hydrocarbon conjugated with a pair of meta-benzaldehyde prepared in this example are as follows:
1 H NMR(400MHz,CDCl 3 ,298K)δ(ppm):9.94(s,2H),7.83(d,J＝7.7Hz,2H),7.62(s,2H),7.34(t,J＝7.6Hz,2H),7.17(d,J＝7.6Hz,2H),7.02(s,2H),6.82(s,2H),6.71(s,2H),6.48(s,2H),5.88(s,2H),3.88(t,J＝7.1Hz,4H),3.76(d,J＝14.0Hz,4H),3.72–3.67(m,8H),3.63(s,6H),3.38(s,6H),3.30(s,6H). 13 C NMR(100MHz,CDCl 3 ,298K)δ(ppm):192.35,150.99,150.73,150.53,143.02,139.48,136.81,136.18,135.29,132.14,130.82,129.00,128.80,128.65,128.22,127.56,127.27,114.25,113.99,113.77,113.73,56.05,56.00,55.74,55.33,34.14,33.44,29.79.FTICR MS:m/z calcd for[M+Na] + C 57 H 54 O 10 Na + 921.3609,found 921.3597,error–1.3ppm.
example 3
The synthesis method of the column [5] arene P5-6 conjugated with a pair of pyridyl groups comprises the following steps:
a pair of trifluoromethane sulfonate-containing column [5] arene P5-40.30-0.35 g prepared in example 1 was taken in a 15mL Schlenk tube, 0.2-0.24 g of 4- (4-pyridyl) phenylboronic acid, 20-23 mg of tetrakis (triphenylphosphine) palladium, 0.20-0.22 g of potassium carbonate and 5.0-6.0 mL of tetrahydrofuran were added thereto, and the mixture was stirred at 90℃for 24 hours. After the reaction, spin-drying the solvent, separating by silica gel column chromatography, and eluting with the following eluent: petroleum ether: ethyl acetate=3:1, and concentrating to obtain white solid, namely, column [5] arene P5-6 (0.18-0.20 g, 59.4-66.0% yield) conjugated with a pair of pyridyl groups.
The characterization data for column [5] arene P5-6 conjugated with a pair of pyridyl groups for the product prepared in this example is as follows:
1 H NMR(500MHz,acetone-d 6 ,298K)δ(ppm):8.70(d,J＝5.4Hz,4H),7.80(d,J＝7.8Hz,4H),7.75(d,J＝5.3Hz,4H),7.36(d,J＝7.8Hz,4H),7.21(s,2H),6.85(s,2H),6.82(s,2H),6.69(s,2H),5.94(s,2H),3.91(d,J＝18.4Hz,4H),3.82(s,2H),3.70(m,16H),3.52(s,6H),3.39(s,6H). 31 C NMR(125MHz,CDCl 3 ,298K)δ(ppm):151.22,151.07,151.00,150.78,150.41,147.94,143.22,139.88,136.66,135.98,131.96,129.93,128.83,128.71,128.61,127.94,127.79,127.56,126.49,121.42,114.60,114.33,113.90,56.22,55.97,55.77,55.57,34.22,30.18,29.21.HRMS:m/z calcd[M+H] + 997.4428,found 997.4422,error–0.6ppm.
example 4
The phosphorescent properties of the column [5] arene P5-5 having a pair of m-benzaldehyde groups conjugated thereto prepared in example 2 and the column [5] arene P5-6 having a pair of pyridyl groups conjugated thereto prepared in example 3 were tested. The campt is a steady state spectrum, and the emission spectrum is scanned immediately with excitation light maintained. Delay is the time resolved spectrum, and the emission spectrum is measured with a Delay of 0.1 ms after excitation. Ex is excitation light. The two compounds used different excitation wavelengths because there is a slight difference in the maximum absorption peak between them, and the excitation wavelength is determined according to the position of the maximum absorption peak.
(1) Recrystallizing the prepared compound P5-5 or P5-6 with chloroform, methanol system or ethyl acetate system or hexane system to obtain crystalline solid powder.
(2) And (3) placing 100-120 mg of the crystalline solid powder obtained in the step (1) in a vacuum drying oven, heating to 120 ℃ and drying in vacuum for 24 hours to remove residual solvent molecules.
(3) And (3) placing the crystalline solid powder obtained in the step (2) into a quartz plate, and measuring a steady-state emission spectrum, an excitation spectrum, a time-resolved emission spectrum and service life.
The experimental results are shown in fig. 1, and from analysis of the experimental results, it can be seen that:
in the figure, the campt is a steady-state spectrum curve, and is measured by immediately scanning while maintaining the excitation light unchanged. Delay is a time resolved spectroscopic curve measured with a Delay of 0.1 ms after excitation. Because of the slight difference in the maximum absorption peaks, compounds P5-5 used excitation light at 375nm and compounds P5-6 used excitation light at 365nm to determine the corresponding excitation wavelengths of the two compounds.
The column [5] arene P5-5 conjugated with a pair of m-benzaldehyde groups and the column [5] arene P5-6 conjugated with a pair of pyridyl groups both have room temperature phosphorescent properties, wherein the phosphorescent emission peak of the compound P5-5 is located at 420-550 nm, and the phosphorescent emission peak of the compound P5-6 is wider and located at 400-580 nm. Both quantum yields were around 8%, phosphorescent lifetime (where compounds P5-5 tested for emission lifetime at 475nm and compounds P5-6 tested for emission lifetime at 450 nm) on the order of milliseconds. It is feasible to implement room temperature phosphorescence of pillar arenes using a trans-space charge transfer strategy.
Example 5
Experiment of the aero-phosphorescent modulation of guest response:
(1) Recrystallizing the prepared compound P5-5 or P5-6 with chloroform, methanol system or ethyl acetate system or hexane system to obtain crystalline solid powder.
(2) And (3) placing 100-120 mg of the crystalline solid powder obtained in the step (1) in a vacuum drying oven, heating to 120 ℃ and drying in vacuum for 24 hours to remove residual solvent molecules.
(3) Placing the crystalline solid powder obtained in the step (2) into an open 1.5mL strain bottle, placing the strain bottle into a closed 20mL strain bottle containing 5.0-5.5 mL of bromoethane, and standing for 24h.
(4) Pouring out the crystalline solid powder in the 1.5mL strain bottle in the step (3), and placing the crystalline solid powder in a quartz plate to measure the steady-state emission spectrum, the excitation spectrum, the time-resolved emission spectrum and the service life.
The experimental results are shown in fig. 2, and from analysis of the experimental results, it can be seen that:
it is feasible to control the room temperature phosphorescent properties of the pillar [5] arene P5-5 conjugated with a pair of m-benzaldehyde groups or the pillar [5] arene P5-6 conjugated with a pair of pyridyl groups by utilizing bromoethane vapor. After fumigation with bromoethane vapor, the crystalline solid powder of column [5] arene P5-5 conjugated with a pair of meta-benzaldehyde groups showed an enhanced quantum yield of 77.2% by a factor of about 8. At the same time, the phosphorescence lifetime of the crystalline solid powder is reduced from millisecond level to microsecond level, and the phosphorescence property change caused by heavy atom effect is met.
Further, it will be understood that various changes and modifications may be made by those skilled in the art after reading the foregoing description of the invention, and such equivalents are intended to fall within the scope of the claims appended hereto.

Claims (10)

1. A room temperature phosphorescent molecule based on a pillar [5] arene, which is characterized in that the room temperature phosphorescent molecule based on the pillar [5] arene is a pillar [5] arene with a pair of m-benzaldehyde groups conjugated as shown in the following formula (1):
，
in formula (1), ar is a substituent represented by the following formula (2):
，
in the formula (1), R is selected from one of substituents represented by the following formulas (4) and (5):
。
2. the room temperature phosphorescent molecule based on pillar [5] arene according to claim 1, wherein the solid powder of the room temperature phosphorescent molecule based on pillar [5] arene can emit cyan phosphorescence under excitation of 350-380 nm excitation light at room temperature.
3. The method for preparing room temperature phosphorescent molecules based on column [5] arene according to claim 1, comprising the steps of:
(a) Dispersing full alkyl column [5] arene and ceric ammonium nitrate into mixed liquid of dichloromethane and water, wherein the full alkyl column [5] arene is full methyl column [5] arene or full ethyl column [5] arene, stirring and reacting at room temperature under the protection of inert gas, evaporating solvent after the reaction is finished, dissolving the obtained solid into dichloromethane, washing, drying, filtering, separating and concentrating to obtain column [4] arene [1] quinone;
(b) Dispersing the column [4] arene [1] quinone obtained in the step (a) and sodium dithionite in a mixed solution of dichloromethane and water, stirring and reacting at room temperature under the protection of inert gas, separating the solution after the reaction is finished, drying the obtained organic phase, filtering, and evaporating the solvent to obtain the column [5] arene containing a pair of phenolic hydroxyl groups;
(c) Dissolving the column [5] arene containing a pair of phenolic hydroxyl groups obtained in the step (b) in dichloromethane, adding pyridine, dropwise adding trifluoromethanesulfonic anhydride under the protection of inert gas at 0-5 ℃, stirring at room temperature for reaction, washing, separating liquid after the reaction is finished, drying the obtained organic phase, filtering, separating and concentrating to obtain the column [5] arene containing a pair of trifluoromethanesulfonic esters;
(d) Dissolving the column [5] arene containing a pair of trifluoro methane sulfonate and 3-formylphenyl boric acid obtained in the step (c) in tetrahydrofuran, adding potassium carbonate and tetra (triphenylphosphine) palladium, stirring for reaction at 80-90 ℃ under the protection of inert gas, evaporating the solvent after the reaction is finished, separating the obtained solid, and concentrating to obtain the column [5] arene conjugated with a pair of m-benzaldehyde groups.
4. The method for preparing room temperature phosphorescent molecules based on column [5] arene according to claim 3, wherein in step (a), the molar ratio of the full alkyl column [5] arene to cerium ammonium nitrate is 1 (1.8-2.2); the separation is specifically carried out by using a silica gel column chromatography, the eluent of the silica gel column chromatography is petroleum ether and ethyl acetate mixed solution, and the volume ratio of petroleum ether to ethyl acetate is 10:1.
5. A method of preparing room temperature phosphorescent column [5] arene-based molecules according to claim 3, characterised in that in step (b) sodium dithionite is in excess such that the p-benzoquinone moiety in the column [4] arene [1] quinone is fully reduced.
6. The method for preparing room temperature phosphorescent molecules based on column [5] arene according to claim 3, wherein in step (c), the separation is specifically performed by using silica gel column chromatography, the eluent of the silica gel column chromatography is petroleum ether and ethyl acetate mixed solution, and the volume ratio of petroleum ether to ethyl acetate is 20:1.
7. The method for preparing a room temperature phosphorescent molecule based on a column [5] arene according to claim 3, wherein in the step (d), the molar ratio of the column [5] arene containing a pair of triflates to 3-formylphenylboronic acid is 1: (2.5-4); the separation is specifically carried out by using a silica gel column chromatography, the eluent of the silica gel column chromatography is petroleum ether and ethyl acetate mixed solution, and the volume ratio of petroleum ether to ethyl acetate is 3:1.
8. The host-guest complex of the room temperature phosphorescent molecule based on the column [5] arene is characterized in that the host-guest complex is obtained by adsorbing a guest molecule by a host molecule, wherein the host molecule is the room temperature phosphorescent molecule based on the column [5] arene according to claim 1, and the guest molecule is an organic halide which has a molecular diameter of less than 4.7A, can volatilize into a gaseous state at room temperature and can be complexed by the column [5] arene.
9. The method for controlling the gas-induced phosphorescence of guest response of room temperature phosphorescent molecules based on the pillar [5] arene according to claim 1, wherein the method for controlling the gas-induced phosphorescence is an organic halide which enables the room temperature phosphorescent molecules based on the pillar [5] arene to be adsorbed or desorbed to have a molecular diameter smaller than 4.7 a and to volatilize into a gas state at room temperature and to be complexed by the pillar [5] arene, thereby realizing the enhancement of quantum yield and shortening the phosphorescence lifetime.
10. Use of the room temperature phosphorescent pillar [5] arene-based molecules according to claim 1 in the light emitting layer of an organic electroluminescent device.
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CN109400501A (en) * 2018-11-28 2019-03-01 中国科学院上海高等研究院 Functionalization column arene derivatives and preparation method thereof
CN114573749A (en) * 2022-03-10 2022-06-03 浙江大学杭州国际科创中心 Room temperature phosphorescent copolymer and preparation method and application thereof

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CN109400501A (en) * 2018-11-28 2019-03-01 中国科学院上海高等研究院 Functionalization column arene derivatives and preparation method thereof
CN114573749A (en) * 2022-03-10 2022-06-03 浙江大学杭州国际科创中心 Room temperature phosphorescent copolymer and preparation method and application thereof

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