CN115433070A - Room-temperature phosphorescent molecule based on column [5] arene and preparation method and application thereof - Google Patents

Abstract

The invention discloses a column [5]]Aromatic room temperature phosphorescent molecules and a preparation method and application thereof. The room temperature phosphorescent molecule is a column [5] which is shown as the following formula (1) and conjugated with a pair of m-benzaldehyde groups]Aromatic hydrocarbons or columns conjugated with a pair of pyridylphenyl groups [5]]Aromatic hydrocarbons:

wherein Ar is selected from one of the substituents represented by the following formulae (2) and (3):

r is selected from one of the substituents represented by the following formulae (4) and (5):

the room temperature phosphorescent molecule has trans-space charge transfer in molecules, effectively reduces energy level difference between a singlet state and a triplet state to promote transition between laser systems, and can regulate quantum yield and phosphorescence lifetime 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 photophysical science, and particularly relates to a room temperature phosphorescent molecule based on column [5] arene, a preparation method thereof and application thereof in a light-emitting layer of an organic electroluminescent device.

Background

The room temperature phosphorescent molecules have wide application in the fields of chemistry, biology, materials and the like, and play an important role in aspects such as phosphorescence sensing and detection, biological imaging, display materials, optical devices and the like. Most of the traditional room temperature phosphorescent molecules are complexes containing transition metals such as ruthenium, platinum and the like, and the high price and the poor stability of the complexes make the complexes difficult to apply on a large scale. In comparison, the pure organic room temperature phosphorescent molecules do not contain noble metals, are suitable for large-scale preparation, and have wide application prospects. However, intersystem crossing of pure organic molecules is insufficient, excitons hardly achieve transition from singlet state to triplet state, compared to complexes, and thus phosphorescent properties are poor. To solve this problem, introduction of carbonyl groups or heavy atoms and reduction of the difference in energy levels of singlet and triplet states using charge transfer have become common approaches.

For example, in the document j.phys.chem.b 2021,125,4520-4526, the authors constructed phosphorescent molecules containing carbazole donors and pyromellitic diimide acceptors, and achieved room temperature phosphorescent emission by intramolecular charge transfer between donors and acceptors. In the document Angew. Chem. Int. Ed.2020,59,8210-8217, the authors have constructed coordination compounds containing intramolecular charge transfer by the coordination of monovalent copper to a carbazole donor and an azacyclo-carbene acceptor, which compounds also exhibit room temperature phosphorescent properties.

In these examples, the construction of molecules typically uses charge transfer based on chemical bonds, while charge transfer across space is rarely mentioned, which greatly limits the structural diversity and stimulus responsiveness of phosphorescent chromophores.

The phenomenon of trans-space charge transfer induced room temperature phosphorescence is very common in nature, and the room temperature phosphorescence property of solid powder such as bovine serum albumin is realized by trans-space charge transfer. Single crystal diffraction results of bovine serum albumin prove that various intermolecular interactions exist in the molecule, and the interaction of the heteroatom and the carbonyl group forms a trans-space charge transfer channel, so that room-temperature phosphorescence is generated.

The column aromatic hydrocarbon is a macrocyclic compound, has the characteristics of easy derivatization, structural rigidity, excellent host-guest properties and the like, and is widely used for constructing various functional materials. The column aromatic hydrocarbon has an annular cavity with fixed size and stable configuration, and is very suitable for researching cross-space charge transfer. Therefore, the macrocyclic skeleton of the pillared arene is used as a construction element of the room temperature phosphorescent molecule, so that not only can a mechanism of trans-space charge transfer be disclosed, but also a novel phosphorescent chromophore can be developed.

Disclosure of Invention

Aiming at the bottleneck problem existing in the field at present, the invention provides a room temperature phosphorescent molecule based on column [5] arene, which has novel structure, reliable property and convenient synthesis, a preparation method thereof and application thereof in a light-emitting layer of an organic electroluminescent device.

The column [5]]The room temperature phosphorescent molecules of the aromatic hydrocarbon have trans-space charge transfer in molecules, thereby effectively reducing the energy level difference between a singlet state and a triplet state, promoting intersystem crossing of excitons, and realizing that the cyan phosphorescence can be emitted under excitation of exciting light of 350-380 nm at room temperature. While the column [5]]The room temperature phosphorescent molecule of the aromatic hydrocarbon has guest-regulated room temperature phosphorescent emission, and the diameter of the molecule is smaller than that of the molecule through adsorption or desorption

And can be volatilized into gas at room temperature and can be packed in column [5]]The arene complex organic halide 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 conjugated with a pair of m-benzaldehyde groups or a pillar [5] arene conjugated with a pair of pyridylphenyl groups, having the following formula (1):

in formula (1), ar is selected from one of the substituents shown in the following formulas (2) and (3):

in the formula (1), R is selected from one of the substituents shown in the following formulas (4) and (5):

at room temperature, the room temperature phosphorescent molecule solid powder based on the column [5] arene can emit cyan phosphorescence under the excitation of exciting light of 350-380 nm, and has obvious phosphorescence emission, convenient detection and stable property.

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 pyridine phenyl groups provided by the invention are almost the same in phosphorescence property, and the phosphorescence mechanism is trans-space charge transfer from a 1, 4-dialkyl benzene donor to a m-benzaldehyde acceptor or a pyridine acceptor. This charge transfer reduces the difference in energy levels between singlet and triplet states, providing the possibility for intersystem crossing of excitons. In addition, the aldehyde group on the m-benzaldehyde or the nitrogen heteroatom on the pyridine promotes spin-orbit coupling, so that intersystem crossing is facilitated, and therefore, the two kinds of pillared [5] arene derivatives show room-temperature phosphorescence.

The invention also provides a preparation method of the room temperature phosphorescent molecule based on the column [5] arene, and the method is simple to operate, reliable in route and low in cost.

A preparation method of room temperature phosphorescent molecules based on column [5] arene comprises the following steps:

(a) Utilizing a strategy that ceric ammonium nitrate can oxidize one repeating unit of the pillared aromatic hydrocarbon into p-benzoquinone, dispersing full alkyl pillared [5] aromatic hydrocarbon and ceric ammonium nitrate into a mixed solution of dichloromethane and water, stirring the full alkyl pillared [5] aromatic hydrocarbon into full methyl pillared [5] aromatic hydrocarbon or full ethyl pillared [5] aromatic hydrocarbon under the protection of inert gas at room temperature for reaction, evaporating a solvent to dryness after the reaction is finished, dissolving the obtained solid into dichloromethane, washing, drying, filtering, separating and concentrating to obtain pillared [4] arene [1] quinone;

(b) Dispersing the column [4] arene [1] quinone and sodium hydrosulfite obtained in the step (a) into 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 macrocycle into hydroquinone by the sodium hydrosulfite. After the reaction is finished, separating liquid, drying the obtained organic phase, filtering, evaporating the solvent to dryness, and obtaining the column [5] arene containing a pair of phenolic hydroxyl groups;

(c) Dissolving the column [5] arene containing the 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, stirring at room temperature for reaction, and changing the phenolic hydroxyl groups into trifluoromethanesulfonic acid esters. After the reaction is finished, washing, separating liquid, drying the obtained organic phase, filtering, separating and concentrating to obtain column [5] arene containing the pair of triflate;

(d) Dissolving the column [5] arene containing a pair of triflates and arylboronic acid obtained in the step (c) in tetrahydrofuran, adding potassium carbonate as an alkali, adding a catalyst of tetrakis (triphenylphosphine) palladium, stirring and reacting at 80-90 ℃ under the protection of inert gas, carrying out Suzuki coupling on the column [5] arene containing a pair of triflates 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 the 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 containing a pair of conjugated structures is the column [5] arene conjugated with a pair of m-benzaldehyde groups; when the aryl boric acid is 4- (4-pyridyl) phenylboronic acid, the column [5] arene containing a pair of conjugated structures is the column [5] arene conjugated with a pair of pyridine phenyl groups.

Preferably, in the step (a), the molar ratio of the per-alkyl-column [5] arene to the cerium ammonium nitrate is 1 (1.8-2.2). The addition of too much ammonium cerium nitrate leads to excessive oxidation, resulting in a pillared arene derivative containing more p-benzoquinone motifs.

Preferably, in step (a), the separation is specifically performed by using a silica gel column chromatography, and an 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.

Preferably, in step (b), the sodium dithionite is in excess so that the p-benzoquinone moiety in the pillared [4] aren [1] quinone is completely reduced. If the amount of sodium dithionite added is insufficient, part of the pillared [4] aren [1] quinone will be unreduced.

Preferably, in step (c), the separation is performed by silica gel column chromatography, and 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.

Preferably, in step (d), the molar ratio of the column [5] arene containing the para-triflate to the arylboronic acid is 1: (2.5-4). If the amount of the arylboronic acid added is small, a pillar aromatic derivative which is not completely reacted is generated;

preferably, in the step (d), the separation is performed by using a silica gel column chromatography, an 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.

The invention also provides a column [5]]Host-guest complexes of room temperature phosphorescent molecules of aromatic hydrocarbons, obtained by adsorption of guest molecules by host molecules, said host molecules being column [5] based according to claim 1]The room temperature phosphorescent molecule of aromatic hydrocarbon, wherein the guest molecule is a molecule with a diameter smaller than that of the room temperature phosphorescent molecule

And can volatilize into gas state at room temperature and can be filled into a column [5]]Aromatic hydrocarbon complexed organic halides.

The invention also provides a column [5]]A method for regulating and controlling the guest response of room temperature phosphorescent molecules of aromatic hydrocarbons by gas induced phosphorescence, wherein the method is based on a column [5]]The room temperature phosphorescent molecule adsorption or desorption molecule diameter of the aromatic hydrocarbon is less than

And can be volatilized into gas at room temperature and can be packed in column [5]]The arene complex organic halide realizes the enhancement or weakening of quantum yield and shortens or prolongs the phosphorescence life.

The principle of the gas-induced phosphorescence light control method based on object response provided by the invention is that after an object molecule containing halogen enters a cavity of column [5] arene, the intensity of cross-space charge transfer is changed, and meanwhile, the intersystem crossing of a host molecule is enhanced by the heavy atom effect of the halogen on the object, 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 column [5] arene in a luminescent layer of an organic electroluminescent device.

Compared with the prior art, the invention at least has the following beneficial effects:

1. the phosphorescence molecule based on the column [5] arene provided by the invention has stable property, can be used for a long time, and has simple and convenient synthesis and low cost.

2. The phosphorescence molecule based on the pillar [5] arene provided by the invention has a novel light-emitting mechanism, and is different from a room-temperature phosphorescence mechanism induced by charge transfer through chemical bonds in principle.

3. The phosphorescence molecule based on the column [5] arene has gas induced phosphorescence regulation of guest response, and can conveniently realize regulation of quantum yield and phosphorescence life through introduction and removal of guest molecules.

4. The invention provides a new idea and a new choice for the design and preparation of pure organic room temperature phosphorescent molecules, and simultaneously provides a new construction element for the research of cross-space charge transfer.

Drawings

FIGS. 1 (a) and (b) are graphs of steady-state spectra and time-resolved spectra of two kinds of pillared [5] arene derivatives prepared in example 2 and example 3, and FIGS. 1 (c) and (d) are graphs of experimental data results of phosphorescent emission lifetimes of two kinds of pillared [5] arene derivatives prepared in example 2 and example 3;

FIG. 2 is a graph showing the results of experimental data on phosphorescence control in the presence of bromoethane vapor for column [5] arene conjugated with a pair of m-benzaldehyde groups, measured in example 5.

Detailed Description

The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.

Example 1

The synthesis method of the column [5] arene P5-4 containing a pair of triflate comprises the following steps:

weighing 5-12.0-12.5 g of all-methyl column [5] arene P in a 500mL round-bottom flask, sequentially adding 10.5-11.0 g of ceric ammonium nitrate, 250mL of dichloromethane, 20mL of water and argon for protection, and stirring at room temperature for reaction for 1h. After the reaction is finished, the solvent is dried by spinning, the obtained solid is dissolved in 100-120 mL of dichloromethane, washed three times by 100-120 mL of water, dried for 30-35 min by anhydrous sodium sulfate, filtered, separated by silica gel column chromatography, and used as eluent: 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%).

Column [4] arene [1] quinone P5-2.0-3.5 g is weighed into a 250mL round-bottom flask, and 100mL dichloromethane, 100mL water and 5.0-5.5 g sodium hydrosulfite 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 min by using anhydrous sodium sulfate, filtering and solvent spin-drying are carried out, and light yellow solid is obtained, namely the column [5] arene P5-3 containing the phenolic hydroxyl group (2.5-2.6 g, the yield is 83.3-86.7%).

Weighing column [5] arene P5-3.0-2.5 g containing a pair of phenolic hydroxyl groups, and adding 100mL of dichloromethane and 20mL of pyridine in sequence. Under the protection of argon, 5.0-5.5 mL of trifluoromethanesulfonic anhydride is added dropwise into an ice bath, and the system reacts at room temperature for 24h. After the reaction is finished, washing the mixture for three times by using 100-120 mL of water, separating liquid, drying an organic phase for 30-35 min by using anhydrous sodium sulfate, filtering, carrying out chromatographic separation by using a silica gel column, and using an eluent: petroleum ether: ethyl acetate =20, and concentration gave a white solid, i.e., column [5] arene P5-4 containing a pair of triflates (1.9-2.1 g, yield 69.5-76.9%).

The product prepared in this example has the following characterization data:

column [5] arene P5-4 containing a pair of triflates:

¹ H NMR(500MHz,CDCl₃ ,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 synthetic method of the column [5] arene P5-5 conjugated with the para-m-benzaldehyde comprises the following steps:

column [5] arene P5-40.30-0.35 g containing the pair of triflates prepared in example 1 is taken and put into a Schlenk tube of 15mL, 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 are added, and the mixture is stirred and reacted for 24 hours at 90 ℃. After the reaction is finished, the solvent is dried by spinning, and is separated by silica gel column chromatography, and the eluent is prepared from the following components: petroleum ether: ethyl acetate =3, and the concentration is performed to obtain a white solid, namely column [5] arene P5-5 conjugated with the m-benzaldehyde (0.15-0.17 g, yield 55.6-63.0%).

The characterization data for column [5] arene P5-5, conjugated with a pair of m-benzaldehyde, of the product prepared in this example are as follows:

¹ H NMR(400MHz,CDCl₃ ,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,CDCl₃ ,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]⁺ C₅₇ H₅₄ O₁₀ Na⁺ 921.3609,found 921.3597,error–1.3ppm.

example 3

The synthesis method of column [5] arene P5-6 conjugated with a pair of pyridine phenyl groups comprises the following steps:

column [5] arene P5-40.30-0.35 g containing the pair of triflates prepared in example 1 is taken and put into a Schlenk tube of 15mL, 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 are added, and the mixture is stirred and reacted for 24 hours at 90 ℃. After the reaction is finished, the solvent is dried by spinning, and is separated by silica gel column chromatography, and the eluent is prepared by the following steps: petroleum ether: ethyl acetate =3, and the mixture was concentrated to obtain a white solid, i.e., column [5] arene P5-6 conjugated with a pair of pyridylphenyl groups (0.18 to 0.20g, yield 59.4 to 66.0%).

The characterization data for column [5] arene P5-6 conjugated with a pair of pyridylphenyl groups of the product prepared in this example are as follows:

¹ H NMR(500MHz,acetone-d₆ ,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,CDCl₃ ,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 column [5] arene P5-5 conjugated with a pair of m-benzaldehyde group prepared in example 2 and the column [5] arene P5-6 conjugated with a pair of pyridylphenyl group prepared in example 3 were subjected to a phosphorescent property test. The prompt is a steady state spectrum, and the emission spectrum is scanned immediately with the excitation light unchanged. Delay is a time resolved spectrum and the emission spectrum is measured with a Delay of 0.1 ms after excitation. Ex is the excitation light. The different excitation wavelengths were used for the two compounds because of the slight difference in the absorption maxima, which was determined by the position of the absorption maxima.

(1) Recrystallizing the prepared compound P5-5 or P5-6 with chloroform, methanol system or ethyl acetate, hexane system to obtain crystalline solid powder.

(2) And (2) putting 100-120 mg of the crystalline solid powder obtained in the step (1) into a vacuum drying oven, heating to 120 ℃, and vacuum-drying 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 a service life.

The experimental results are shown in fig. 1, and it can be seen from the analysis of the experimental results that:

the plot shows the plateau spectrum curve measured by scanning immediately with the excitation light constant. Delay is a time resolved spectral plot, measured as 0.1 milliseconds Delay after excitation. Because of the slight difference of the maximum absorption peak, the excitation light of 375nm is used for compound P5-5, and the excitation light of 365nm is used for compound P5-6 to determine the corresponding excitation wavelength 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 pyridine phenyl groups both have room temperature phosphorescence properties, wherein the phosphorescence emission peak of the compound P5-5 is positioned at 420-550 nm, while the phosphorescence emission peak of the compound P5-6 is wider and positioned at 400-580 nm. Both quantum yields were around 8% and the phosphorescence lifetimes (where compound P5-5 tested for emission lifetime at 475nm and compound P5-6 tested for emission lifetime at 450 nm) were on the order of milliseconds. It is feasible to implement room temperature phosphorescence of pillararene using a cross-space charge transfer strategy.

Example 5

Gas induced phosphorescence control experiment of guest response:

(1) Recrystallizing the prepared compound P5-5 or P5-6 with chloroform, methanol system or ethyl acetate, hexane system to obtain crystalline solid powder.

(2) And (2) putting 100-120 mg of the crystalline solid powder obtained in the step (1) into a vacuum drying oven, heating to 120 ℃, and vacuum-drying for 24 hours to remove residual solvent molecules.

(3) And (3) putting the crystalline solid powder obtained in the step (2) into an open strain bottle of 1.5mL, putting the strain bottle into a closed strain bottle of 20mL 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), placing the crystalline solid powder in a quartz plate, and measuring 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 it can be seen from the analysis of the experimental results that:

the bromoethane steam is utilized to regulate and control the room temperature phosphorescence properties of the column [5] arene P5-5 conjugated with a pair of m-benzaldehyde groups or the column [5] arene P5-6 conjugated with a pair of pyridine phenyl groups. Crystalline solid powder of column [5] arene P5-5 conjugated with a pair of m-benzaldehyde groups showed enhanced quantum yield of 77.2% with a factor of enhancement of about 8 after fumigation with bromoethane vapor. Meanwhile, the phosphorescence life of the crystalline solid powder is reduced from millisecond level to microsecond level, and the change of phosphorescence property caused by heavy atom effect is met.

Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (10)

1. A room temperature phosphorescent molecule based on a column [5] arene, characterized in that the room temperature phosphorescent molecule based on the column [5] arene is a column [5] arene conjugated with a pair of m-benzaldehyde groups or a column [5] arene conjugated with a pair of pyridylphenyl groups, which has the following formula (1):

in formula (1), ar is selected from one of the substituents shown in the following formulas (2) and (3):

in the formula (1), R is selected from one of the substituents shown in the following formulas (4) and (5):

2. the room temperature phosphorescent molecule based on the pillared [5] arene of claim 1, wherein the room temperature phosphorescent molecule solid powder based on the pillared [5] arene can emit cyan phosphorescence under the excitation of excitation light of 350-380 nm at room temperature.

3. The method for preparing a room temperature phosphorescent molecule based on a pillared [5] arene according to claim 1, which comprises the following steps:

(a) Dispersing full alkyl pillar [5] arene and ammonium ceric nitrate in a mixed solution of dichloromethane and water, wherein the full alkyl pillar [5] arene is full methyl pillar [5] arene or full ethyl pillar [5] arene, stirring and reacting at room temperature under the protection of inert gas, evaporating a solvent to dryness after the reaction is finished, dissolving the obtained solid in dichloromethane, washing, drying, filtering, separating and concentrating to obtain pillar [4] arene [1] quinone;

(b) Dispersing the column [4] arene [1] quinone obtained in the step (a) and sodium hydrosulfite in a mixed solution of dichloromethane and water, stirring and reacting at room temperature under the protection of inert gas, separating liquid after the reaction is finished, drying the obtained organic phase, filtering, and evaporating the solvent to obtain column [5] arene containing a pair of phenolic hydroxyl groups;

(c) Dissolving the column [5] arene containing the pair of phenolic hydroxyl groups obtained in the step (b) in dichloromethane, adding pyridine, dropwise adding trifluoromethanesulfonic anhydride at 0-5 ℃ under the protection of inert gas, stirring at room temperature for reaction, washing and separating after the reaction is finished, drying the obtained organic phase, filtering, separating and concentrating to obtain the column [5] arene containing the pair of trifluoromethanesulfonic acid esters;

(d) Dissolving the column [5] arene containing a pair of triflate obtained in the step (c) and arylboronic acid in tetrahydrofuran, adding potassium carbonate and tetrakis (triphenylphosphine) palladium, stirring and reacting at 80-90 ℃ under the protection of inert gas, evaporating a solvent after the reaction is finished, separating and concentrating the obtained solid to obtain the 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 containing a pair of conjugated structures is the column [5] arene conjugated with a pair of m-benzaldehyde groups; when the aryl boric acid is 4- (4-pyridyl) phenylboronic acid, the column [5] arene containing a pair of conjugated structures is the column [5] arene conjugated with a pair of pyridine phenyl groups.

4. The method for preparing a room temperature phosphorescent molecule based on pillar [5] arene, according to the claim 3, wherein, in the step (a), the molar ratio of the full alkyl pillar [5] arene to the cerium ammonium nitrate is 1 (1.8-2.2); the separation is carried out by using a silica gel column chromatography, wherein an 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.

5. The method for preparing a pillar [5] arene-based room temperature phosphorescent molecule according to claim 3, wherein in the step (b), sodium dithionite is in excess so that the p-benzoquinone moiety in pillar [4] arene [1] quinone is completely reduced.

6. The method for preparing a room temperature phosphorescent molecule based on column [5] arene, according to the claim 3, wherein in the step (c), the separation is performed by 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.

7. The method for preparing a pillar [5] arene-based room temperature phosphorescent molecule according to claim 3, wherein in the step (d), the molar ratio of the pillar [5] arene containing the one-to-one triflate to the arylboronic acid is 1: (2.5-4); the separation is specifically carried out by using a silica gel column chromatography, wherein an 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.

8. Based on post [5]A host-guest complex of a phosphorescent molecule at room temperature of an aromatic hydrocarbon, wherein the host-guest complex is obtained by adsorbing a guest molecule to a host molecule according to claim 1Based on column [5]]The room temperature phosphorescent molecule of aromatic hydrocarbon, wherein the guest molecule is a molecule with a diameter smaller than that of the room temperature phosphorescent molecule

And can be volatilized into gas at room temperature and can be packed in column [5]]Aromatic hydrocarbon complexed organic halides.

9. Column [5] based according to claim 1]A method for controlling a guest-response gas-induced phosphorescence of a room temperature phosphorescent molecule of an aromatic hydrocarbon, characterized in that the method for controlling a gas-induced phosphorescence is such that the method is based on a column [5]]The room temperature phosphorescent molecule adsorption or desorption molecule diameter of the aromatic hydrocarbon is less than

And can be volatilized into gas at room temperature and can be packed in column [5]]The arene complex organic halide realizes the enhancement or weakening of quantum yield and shortens or prolongs the phosphorescence life.

10. Use of the pillared [5] arene-based room temperature phosphorescent molecule of claim 1 in the light emitting layer of an organic electroluminescent device.

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