A polymeric quinoline acridinedione macrocyclic derivative, and a preparation method and application thereof

Abstract

The patent application discloses a kind of polyquinoline acridinedione macrocyclic derivatives and its preparation method and application.The application is by methylene bridging, multiple single-molecule fragments of quinoline acridinedione is gathered into macrocycle, the difference between the electron-withdrawing and electron-donating properties of carbonyl and nitrogen atom is synthesized into a variety of quinoline acridinedione macrocyclic derivatives containing the relative distribution structure of carbonyl and nitrogen atom, the interaction of carbonyl and nitrogen atom heterocycle is conducive to realize high color purity molecular luminescence.Because the free rotation of benzene ring and intramolecular vibration caused by single fragment molecule itself is not fixed, energy is attenuated in the form of non-radiative transition, and the benzene ring after being polymerized into ring can efficiently emit light due to the limited rotation, and improve the color purity of luminescence.

Description

TECHNICAL FIELD

[0001] The present patent application relates to the technical field of organic light-emitting materials, and more particularly to a multi-quinoline acridinedione macrocyclic derivative and a preparation method and application thereof. BACKGROUND

[0002] With the rise of high-tech products such as large-screen smart phones, tablet computers and wearable devices, the traditional liquid crystal display material is increasingly difficult to meet the demand of mobile terminals for display screens that are increasingly thin, low-consumption. Organic light-emitting diode (OLED) has great application potential in the fields of flat panel display, smart phone and solid-state lighting due to its light weight, good flexibility, wide working temperature range, short reaction time, high brightness and contrast, wide viewing angle and other advantages. As of now, although there have been many reports on quinoline acridinedione light-emitting materials based on small-molecule organic electroluminescent devices, the large planar nature of quinoline dione molecules will form π-π stacking in the aggregate state, resulting in fluorescence quenching and thus reducing the efficiency of the device. In addition, the luminescent material modified by quinoline acridinedione lacks inherent large steric space groups, resulting in severe efficiency roll-off and poor performance.

[0003] Therefore, it is an urgent technical problem for those skilled in the art to find an organic electroluminescent material that can simultaneously have high fluorescence quantum yield and low efficiency roll-off in the aggregate state.

[0004] PATENT APPLICATION CONTENT

[0005] In order to overcome the defects of severe quenching and severe efficiency roll-off described in the prior art, a multi-quinoline acridinedione macrocyclic derivative containing a methylene bridge, a carbonyl group and a nitrogen atom is provided, which effectively overcomes the defects of intramolecular vibration and intramolecular rotation of monomolecular segment quinoline acridinedione compounds, effectively improves the fluorescence quantum efficiency in the aggregate state of the solid thin film, and improves the device performance.

[0006] Another purpose of the present patent application is to provide a preparation method of the multi-quinoline acridinedione macrocyclic derivative.

[0007] Another purpose of the present patent application is to provide an application of the multi-quinoline acridinedione macrocyclic derivative.

[0008] The above-mentioned purposes of the present patent application are achieved by the following technical solutions:

[0009] A multi-quinoline acridinedione macrocyclic derivative, the structure general formula of the multi-quinoline acridinedione macrocyclic derivative is any one of formula (I~III):

[0010]

[0011] wherein n is ≥ 1; R 11 -R 12 may be independently any one of S, O, Se, carbonyl and sulfone; R1-R 10 may be independently selected from any one of the following groups:

[0012]

[0013] The present patent application also provides a preparation method of the above-mentioned polyquinoline acridinedione macrocyclic derivative, comprising the following steps:

[0014] S1. 5-(tert-butyl)isophthalic acid is prepared by oxidation using 1-tert-butyl-3,5-xylene and potassium permanganate; the reaction equation is as follows:

[0015]

[0016] S2. 5-(tert-butyl)-2-iodoisophthalic acid is generated by catalytic iodination of 5-(tert-butyl)isophthalic acid prepared in step S1 using iodine; the reaction equation is as follows:

[0017]

[0018] S3. 5-(tert-butyl)-2-iodoisophthalic acid dimethyl ester is prepared by esterification of 5-(tert-butyl)-2-iodoisophthalic acid prepared in step S2 using iodomethane; the reaction equation is as follows:

[0019]

[0020] S4. 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalic acid dimethyl ester is prepared by carbon-nitrogen coupling reaction of 5-(tert-butyl)-2-iodoisophthalic acid dimethyl ester prepared in step S3 under copper catalysis with bis(4-bromophenyl)amine; the reaction equation is as follows:

[0021]

[0022] S5. 3,11-dibromo-7-(tert-butyl)quinoline[3,2,1-de]acridine-5,9-dione is prepared by hydrolysis of 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalic acid dimethyl ester prepared in step S4 using sodium hydroxide, and then acyl chloride using oxalyl chloride; the reaction equation is as follows:

[0023]

[0024] S6. The 3, 11-dibromo-7-(tert-butyl) quinoline [3, 2, 1-de] acridine-5, 9-dione prepared in step S5 is reacted with 2, 4-dimethoxybenzeneboronic acid under catalysis of tetrakis (triphenylphosphine) palladium to prepare 7-(tert-butyl)-3, 11-bis (2, 4-dimethoxyphenyl) quinoline [3, 2, 1-de] acridine-5, 9-dione; the reaction equation is as follows:

[0025]

[0026] S7. The 7-(tert-butyl)-3, 11-bis (2, 4-dimethoxyphenyl) quinoline [3, 2, 1-de] acridine-5, 9-dione prepared in step S6 is polymerized with paraformaldehyde under catalysis of boron trifluoride diethyl ether to prepare the target compound; the reaction equation is as follows:

[0027]

[0028] Preferably, in step S1, the molar ratio of the 1-tert-butyl-3, 5-xylene and potassium permanganate is 1: (2-3), the reaction temperature of the oxidation reaction is 80-100°C, and the reaction time is 20-36h.

[0029] Preferably, in step S2, the molar ratio of the iodine and 5-(tert-butyl) isophthalic acid is 1: (1-2), the reaction temperature of the iodination reaction is 60-80°C, and the reaction time is 3-5h.

[0030] Preferably, in step S3, in the esterification reaction, the molar ratio of the iodomethane and 5-(tert-butyl)-2-iodo isophthalic acid is 1: (2.3-2.5), the reaction temperature of the esterification reaction is 60-80°C, and the reaction time is 4-12h.

[0031] Preferably, in step S4, in the carbon-nitrogen coupling reaction, the molar ratio of the 5-(tert-butyl)-2-iodo isophthalic acid dimethyl ester and bis (4-bromophenyl) amine is 1: (1-2), the reaction temperature of the carbon-nitrogen coupling reaction is 100-120°C, and the reaction time is 24-48h.

[0032] Preferably, in step S5, the 2-(bis (4-bromophenyl) amino)-5-(tert-butyl) isophthalic acid dimethyl ester is first hydrolyzed with sodium hydroxide, and then acylated with oxalyl chloride, the molar ratio of the reactants is 1: (3-5), the reaction temperature of the acyl chloride reaction is 20-40°C, and the reaction time is 0.5-2h.

[0033] Preferably, in step S6, the molar ratio of 3,11-dibromo-7-(tert-butyl) quinoline [3,2,1-de] acridine-5,9-dione and 2,4-dimethoxybenzene boronic acid is 1:(3-4), the reaction temperature of the Suzuki reaction is 80-90℃, and the reaction time is 12-24h.

[0034] Preferably, in step S7, the molar ratio of 7-(tert-butyl)-3,11-bis(2,4-dimethoxyphenyl) quinoline [3,2,1-de] acridine-5,9-dione and paraformaldehyde is 1:(7-9), the reaction temperature of the polymerization reaction is room temperature, and the reaction time is 24-48h.

[0035] The application of the polymeric quinoline acridinedione macrocyclic derivative in the present patent application as a luminescent material, a luminescent device, a fluorescent sensor, a separation material, a supramolecular self-assembly, a nano drug carrier, and a smart response material.

[0036] Compared with the prior art, the present patent application has the following beneficial effects:

[0037] The polymeric quinoline acridinedione macrocyclic derivative with a methylene bridge and containing a carbonyl group and a nitrogen atom in the present patent application effectively overcomes the defects of intramolecular vibration and intramolecular rotation of a single-molecule fragment quinoline acridinedione compound, effectively improves the fluorescence quantum efficiency in a solid-state thin film aggregate state, and improves the device performance.

[0038] In addition, the polymeric quinoline acridinedione macrocyclic derivative formed by a methylene bridge can effectively inhibit quenching caused by the large planar property of a single-molecule fragment quinoline acridinedione compound in an aggregate state due to the intrinsic macrocyclic effect, thereby effectively improving the fluorescence quantum efficiency of the macrocyclic molecule. At the same time, due to the macrocyclic effect, the macrocyclic molecule has the advantages of narrow emission, high color purity, and low efficiency roll-off. The polymeric quinoline acridinedione macrocyclic derivative has significant economic value in the preparation of a luminescent material, a luminescent device, a fluorescent sensor, a separation material, a supramolecular self-assembly, a nano drug carrier, and a smart response material, and has a good application prospect in the field of full-color display and solid-state lighting.

[0039] At the same time, the polymeric quinoline acridinedione macrocyclic derivative in the present patent application has low raw material cost, a simple preparation process, a conventional synthesis method, and high synthesis yield, and can be prepared in large batches, which is conducive to factory production and application popularization. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the compound W1 prepared in Example 1 of the present patent application;

[0041] Figure 2A mass spectrum of compound W1 prepared in Example 1 of the present patent application;

[0042] Figure 3 A UV absorption spectrum of compound W1 prepared in Example 1 of the present patent application in toluene solution;

[0043] Figure 4 A fluorescence emission spectrum of compound W1 prepared in Example 1 of the present patent application in toluene solution;

[0044] Figure 5 A quantum efficiency plot of compound W1 prepared in Example 1 of the present patent application;

[0045] Figure 6 A 1H NMR spectrum of compound W2 prepared in Example 2 of the present patent application;

[0046] Figure 7 A UV absorption spectrum of compound W2 prepared in Example 2 of the present patent application in toluene solution;

[0047] Figure 8 A fluorescence emission spectrum of W2 prepared in Example 2 of the present patent application in 1 x 10 -5 mol / L toluene solution;

[0048] Figure 9 A quantum efficiency plot of compound W2 prepared in Example 1 of the present patent application. DETAILED DESCRIPTION

[0049] The embodiments of the present patent application will be described in detail below with examples, but those skilled in the art will understand that the following examples are only for illustration of the present patent application and should not be regarded as limiting the scope of the present patent application. The specific conditions are not specified in the examples, and the conventional conditions or the conditions recommended by the manufacturer are used. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be purchased on the market.

[0050] It should be noted that:

[0051] In the present patent application, all the embodiments and preferred embodiments mentioned in the present text can be combined with each other to form new technical solutions, if not specifically stated.

[0052] In the present patent application, the percentage (%) or the part refers to the percentage by weight or the weight part of the composition, if not specifically stated.

[0053] In the present patent application, the components or the preferred components involved can be combined with each other to form new technical solutions, if not specifically stated.

[0054] In the present patent application, unless otherwise stated, the numerical range "a~b" represents a shorthand notation for any real combination of numbers between a and b, where a and b are both real numbers. For example, the numerical range "1~5" represents that all real numbers between "1~5" have been listed herein, and "1~5" is just a shorthand notation for these numerical combinations.

[0055] The "range" disclosed in the present patent application in the form of lower limit and upper limit can be one or more lower limits, and one or more upper limits, respectively.

[0056] In the present patent application, unless otherwise stated, each reaction or operation step can be carried out sequentially or according to the sequence. Preferably, the reaction method herein is carried out sequentially.

[0057] Unless otherwise stated, the professional and scientific terms used herein have the same meaning as those familiar to the skilled person. In addition, any method or material similar or equivalent to the described content can also be applied in the present patent application.

[0058] The present patent application provides a kind of polyquinoline acridine diketone macrocyclic derivative, the polyquinoline acridine diketone macrocyclic derivative structural general formula is any one of formula (I~III):

[0059]

[0060] Wherein, n is ≥1;R 11 -R 12 Can be independently S, O, Se, carbonyl and sulfone group in any one of;R1-R 10 Can be independently selected from any one of the following groups:

[0061]

[0062] The polymeric quinoline acridinedione macrocyclic derivative provided by the patent application is based on a polymeric quinoline acridinedione macrocyclic system, and a plurality of single-molecule fragments of quinoline acridinedione are aggregated into a macrocycle by means of a methylene bridge. A plurality of quinoline acridinedione macrocyclic derivatives containing a relative distribution structure of carbonyl and nitrogen atoms are synthesized by utilizing the difference in electron-withdrawing and electron-donating properties of carbonyl and nitrogen atoms. The interaction between the carbonyl and nitrogen atom heterocycles is conducive to realizing high color purity molecular luminescence. The free rotation of benzene rings and intramolecular vibration caused by the fact that the single-fragment molecules are not fixed will attenuate energy in the form of non-radiative transition, while the benzene rings after being aggregated into a ring can efficiently luminesce and improve the color purity of luminescence due to the limited rotation thereof. Meanwhile, the polymeric quinoline acridinedione macrocycle formed by the methylene bridge can effectively avoid fluorescence quenching caused by the large planar property of single-molecule quinoline acridinedione molecules in an aggregated state, and improve the performance of a device. In addition, the macrocycle-induced luminescence enhancement effect brought by the polymer can effectively improve the luminescent efficiency of the molecules.

[0063] The patent application also provides a preparation method of the above-mentioned polymeric quinoline acridinedione macrocyclic derivative, comprising the following steps:

[0064] S1. 5-(tert-butyl)isophthalic acid is prepared by oxidation using 1-tert-butyl-3,5-xylene and potassium permanganate; the reaction equation is as follows:

[0065]

[0066] S2. 5-(tert-butyl)-2-iodoisophthalic acid is generated by catalytic iodination of 5-(tert-butyl)isophthalic acid prepared in step S1 using iodine; the reaction equation is as follows:

[0067]

[0068] S3. 5-(tert-butyl)-2-iodoisophthalic acid dimethyl ester is prepared by esterification of 5-(tert-butyl)-2-iodoisophthalic acid prepared in step S2 using iodomethane; the reaction equation is as follows:

[0069]

[0070] S4. 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalic acid dimethyl ester is prepared by carbon-nitrogen coupling reaction of 5-(tert-butyl)-2-iodoisophthalic acid dimethyl ester prepared in step S3 under copper catalysis; the reaction equation is as follows:

[0071]

[0072] S5. The 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalate dimethyl ester obtained in step S4 is first hydrolyzed with sodium hydroxide, and then acylated with oxalyl chloride to obtain 3,11-dibromo-7-(tert-butyl)quinolino[3,2,1-de]acridin-5,9-dione; the reaction equation is as follows:

[0073]

[0074] S6. The 3,11-dibromo-7-(tert-butyl)quinolino[3,2,1-de]acridin-5,9-dione obtained in step S5 is reacted with 2,4-dimethoxyphenylboronic acid under tetra(triphenylphosphine)palladium catalysis to obtain 7-(tert-butyl)-3,11-bis(2,4-dimethoxyphenyl)quinolino[3,2,1-de]acridin-5,9-dione; the reaction equation is as follows:

[0075]

[0076] S7. The 7-(tert-butyl)-3,11-bis(2,4-dimethoxyphenyl)quinolino[3,2,1-de]acridin-5,9-dione obtained in step S6 is polymerized with paraformaldehyde under the catalysis of boron trifluoride diethyl ether to prepare the target compound; the reaction equation is as follows:

[0077]

[0078] In some preferred embodiments, the molar ratio of 1-tert-butyl-3,5-xylene and potassium permanganate in step S1 is 1:2 to 3; the reaction temperature is 80 to 100°C; and the reaction time is 20 to 36 hours.

[0079] In some preferred embodiments, the molar ratio of 1-tert-butyl-3,5-xylene and potassium permanganate in step S1 is 1:2.5; the reaction temperature is 90°C; and the reaction time is 28 h.

[0080] In some preferred embodiments, in step S2, the molar ratio of iodine to 5-(tert-butyl)isophthalic acid is 1:1 to 2; the reaction temperature is 60 to 80°C; and the reaction time is 3 to 5 hours.

[0081] In some preferred embodiments, the molar ratio of iodine to 5-(tert-butyl)isophthalic acid in step S2 is 1:1.5; the reaction temperature is 70°C; and the reaction time is 4 hours.

[0082] In some preferred embodiments, in step S3, the molar ratio of iodomethane and 5-(tert-butyl)-2-iodophthalic acid is 1:2.3-2.5; the reaction temperature is 60-80°C; and the reaction time is 4-12 h.

[0083] In some more preferred embodiments, the molar ratio of methyl iodide and 5-(tert-butyl)-2-iodoisophthalic acid in step S3 is 1:2.4; the reaction temperature is 70°C; and the reaction time is 8h.

[0084] In some preferred embodiments, the molar ratio of dimethyl 5-(tert-butyl)-2-iodoisophthalate and bis(4-bromophenyl)amine in step S4 is 1:1-2; the reaction temperature is 100-120°C; and the reaction time is 24-48h.

[0085] In some more preferred embodiments, the molar ratio of dimethyl 5-(tert-butyl)-2-iodoisophthalate and bis(4-bromophenyl)amine in step S4 is 1:1.5; the reaction temperature is 110°C; and the reaction time is 36h.

[0086] In some preferred embodiments, the inert gas in step S4 is nitrogen, argon or helium.

[0087] In some more preferred embodiments, the inert gas in step S4 is nitrogen.

[0088] In some preferred embodiments, in step S5, dimethyl 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalate is hydrolyzed with sodium hydroxide, and the molar ratio of dimethyl 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalate to sodium hydroxide is 1:3-3.5; the reaction temperature is 80-110°C; and the reaction time is 8-16h.

[0089] In some more preferred embodiments, in step S5, the hydrolysis reaction is carried out, and the molar ratio of dimethyl 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalate to sodium hydroxide is 1:3; the reaction temperature is 85°C; and the reaction time is 9h.

[0090] In some preferred embodiments, the hydrolysis reaction in step S5 further comprises post-treatment of cooling, acidification, concentration and extraction.

[0091] In some more preferred embodiments, step S5 further comprises, after the solution after the reaction is cooled to room temperature, adding concentrated hydrochloric acid to the resulting mixture, acidifying to ph=1; then concentrating the organic phase under reduced pressure, and then extracting with dichloromethane three times, drying with anhydrous sodium sulfate, and concentrating the organic phase under reduced pressure to obtain the crude product of 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalic acid.

[0092] In some preferred embodiments, in step S5, the acylchlorination of 2-(bis(4- bromophenyl)amino)-5-(tert-butyl)isophthalic acid is carried out using oxalyl chloride, the molar ratio of the reactants is 1:3-5, the reaction temperature is 20-40 °C, and the reaction time is 0.5-2 h.

[0093] In some more preferred embodiments, in step S5, the acylchlorination of 2-(bis(4- bromophenyl)amino)-5-(tert-butyl)isophthalic acid is carried out using oxalyl chloride, the molar ratio of the reactants is 1:4, the reaction temperature is 30 °C, and the reaction time is 1.5 h.

[0094] In some preferred embodiments, in step S5, the inert gas is nitrogen, argon or helium.

[0095] In some more preferred embodiments, in step S5, the inert gas is nitrogen.

[0096] In some preferred embodiments, in step S5, the acylchlorination reaction requires an acid binding agent, and the acid binding agent is anhydrous N,N-dimethylformamide.

[0097] In some preferred embodiments, in step S6, the molar ratio of 3,11-dibromo-7-(tert- butyl)quinoline[3,2,1-de]acridine-5,9-dione and 2,4-dimethoxybenzeneboronic acid is 1:3-4, the reaction temperature is 80-90 °C, and the reaction time is 12-24 h.

[0098] In some more preferred embodiments, in step S6, the molar ratio of 3,11-dibromo-7-(tert- butyl)quinoline[3,2,1-de]acridine-5,9-dione and 2,4-dimethoxybenzeneboronic acid is 1:3.5, the reaction temperature is 85 °C, and the reaction time is 18 h.

[0099] In some preferred embodiments, in step S6, the inert gas is nitrogen, argon or helium.

[0100] In some more preferred embodiments, in step S6, the inert gas is nitrogen.

[0101] In some preferred embodiments, in step S7, the molar ratio of 7-(tert-butyl)-3,11-bis(2,4- dimethoxyphenyl)quinoline[3,2,1-de]acridine-5,9-dione and paraformaldehyde is 1:7-9, the reaction temperature is room temperature, and the reaction time is 24-48 h.

[0102] In some more preferred embodiments, in step S7, the molar ratio of 7-(tert-butyl)-3,11-bis(2,4- dimethoxyphenyl)quinoline[3,2,1-de]acridine-5,9-dione and paraformaldehyde is 1:8, the reaction temperature is room temperature, and the reaction time is 36 h.

[0103] In some preferred embodiments, the polymerization reaction in step S7 is catalyzed by boron trifluoride diethyl ether.

[0104] In some preferred embodiments, the polymerization reaction in step S7 includes concentration, separation, drying, and thermal sublimation post-processing.

[0105] In some more preferred embodiments, step S7 further includes concentrating the organic phase of the solution after the reaction under reduced pressure to obtain a crude product; then using ethyl acetate and petroleum ether as eluent to perform silica gel column chromatography separation, and finally placing the crude product in a vacuum drying oven to dry overnight; and finally using a vacuum thermal sublimation separation machine to separate the target product.

[0106] The present patent application also provides the use of the above-mentioned polyquinoline acridinedione macrocyclic derivatives as luminescent materials, luminescent devices, fluorescent sensors, separation materials, supramolecular self-assembly, nano-drug carriers, and smart response materials.

[0107] The preparation method of the polyquinoline acridinedione macrocyclic derivatives will be described in detail below with compounds W1 and W2 as examples.

[0108] Example 1

[0109] This example provides a polyquinoline acridinedione macrocyclic derivative W1, which has the chemical name of 27,67-di-tert-butyl-14,16,34,36,54,56,74,76-octamethoxy-25,29,65,69-tetrahydro-2,6(3,11)- diquinoline [3,2,1-de] acridine-1,3,5,7(1,3)-tetrabenzo-cyclooctane-25,29-65,69-tetraone, and has a molecular structure shown in the following formula:

[0110]

[0111] The preparation method of the compound W1 includes the following steps:

[0112] S1. Preparation of 5-(tert-butyl) isophthalic acid

[0113] Take 1-tert-butyl-3,5-dimethylbenzene (4.86g, 30mmol) into a 500ml three-necked round-bottom flask, and add 200ml of a t-butanol aqueous solution (volume ratio 1:1), and stir the mixture and heat to 95°C; then take potassium permanganate (14.22g, 90mmol) and slowly add (80mg at a time), after the addition is complete, warm to 90°C, and react for 28h. After the reaction is completed and the mixture is cooled to room temperature, add sodium thiosulfate to the three-necked flask until the purple color fades, and then add concentrated hydrochloric acid until ph = 1. Remove the organic phase by rotary evaporation, and place the mixture in a Buchner funnel with filter paper, and wash with cold water to obtain white solid 5.33g (yield 80%).

[0114] The reaction equation in this step is as follows:

[0115]

[0116] Preparation of 5-(tert-butyl)-2-iodoisophthalic acid

[0117] Take 5-(tert-butyl) isophthalic acid (2.22g, 10mmol), iodine (3.81g, 15mmol), and palladium acetate (0.023g, 0.1mmol) into a 250ml two-necked round-bottom flask, add 10mL of anhydrous toluene, and react at 70°C for 4h. After the reaction is completed, remove the organic phase by rotary evaporation, and finally perform silica gel column chromatography separation using ethyl acetate and petroleum ether as the developing agent to obtain white solid 2.19g (yield 63%), and the product does not need to be further treated.

[0118] The reaction equation in this step is as follows:

[0119]

[0120] Preparation of 5-(tert-butyl)-2-iodoisophthalic acid dimethyl ester

[0121] Take 5-(tert-butyl)-2-iodoisophthalic acid (3.48g, 10mmol), iodomethane (3.41g, 24mmol), and add them into a 100ml two-necked flask, and add 60ml of anhydrous toluene solution. After ultrasonic mixing, stir the mixture at 70°C for 8h, and stir the reaction mixture at room temperature overnight (12h). Extract with ethyl acetate and remove the organic phase by rotary evaporation, and then vacuum dry. Use silica gel powder as the stationary phase, and petroleum ether and dichloromethane as the eluent (petroleum ether:CH2Cl2, 1:2) to purify the product, and obtain white powder 3.23g, yield 86%.

[0122] The reaction equation in this step is as follows:

[0123]

[0124] S4. Preparation of dimethyl 2-(bis(4-bromophenyl)amino)-5-(tert- butyl)isophthalate Dimethyl 5-(tert-butyl)-2-iodoisophthalate (3.76 g, 10 mmol), bis(4- bromophenyl)amine (4.91 g, 15 mmol), potassium carbonate (2.48 g, 18 mmol), cuprous iodide (3.80 g, 20 mmol) and copper powder (0.96 g, 15 mmol), phase transfer catalyst 18-crown-6 (1 mL) were added to a 100 mL two-necked flask containing 60 mL of o-dichlorobenzene solution. After stirring at 110 °C for 36 h under nitrogen atmosphere, the reaction mixture was extracted with saturated brine and dichloromethane. The black solid was obtained by distillation under reduced pressure and column chromatography using silica gel powder as stationary phase and petroleum ether / dichloromethane as eluent to give 3.27 g of yellow solid (yield 57 %).

[0125] The reaction equation in this step is as follows:

[0126]

[0127] S5. Preparation of 3,11-dibromo-7-(tert-butyl)quinoline[3,2,1-de]acridine-5,9- dione

[0128] Dimethyl 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalate (5.73 g, 10 mmol), sodium hydroxide (1.2 g, 30 mmol) were added to a 250 mL single-necked round-bottom flask, followed by 100 mL of aqueous solution (50 mL) and anhydrous ethanol (50 mL), stirred and heated to 85 °C for 9 h. To the reaction mixture, concentrated hydrochloric acid was added until ph = 1, and then the organic phase was concentrated under reduced pressure, followed by extraction with dichloromethane three times, dried with anhydrous sodium sulfate, and the organic phase was concentrated under reduced pressure to obtain 4.85 g of crude product of 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalic acid (yield 89 %).

[0129] 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalic acid (0.27 g, 0.5 mmol) was added to a 100 mL two-necked round-bottom flask, and 12 mL of dry dichloromethane, oxalyl chloride (0.25 g, 2 mmol) and 1 drop of anhydrous N,N-dimethylformamide were added at 0 °C, and then stirred at 30 °C for 1.5 h under nitrogen atmosphere. After the reaction was completed, the organic phase and oxalyl chloride were removed by rotary evaporation. Then 12 mL of dichloromethane and anhydrous tin tetrachloride (0.52 g, 2 mmol) were added under ice bath, and then stirred at 30 °C for 1.5 h under nitrogen atmosphere. The organic phase was removed under reduced pressure, and finally column chromatography was performed using ethyl acetate and petroleum ether as developing agents to obtain 0.089 g of yellow solid (yield 35 %).

[0130] The reaction equation in this step is as follows:

[0131]

[0132] Preparation of 7-(tert-butyl)-3, 11-bis(2, 4-dimethoxyphenyl) quino- [3, 2, 1-de] acridine-5, 9-dione

[0133] Into a 250 ml two necked flask, 3, 11-dibromo-7-(tert-butyl) quino- [3, 2, 1-de] acridine-5, 9-dione (0.25 g, 0.5 mmol), 2, 4-dimethoxybenzene- boronic acid (0.32 g, 1.75 mmol), tetrakis triphenyl phosphine palladium (0.16 g, 0.14 mmol) were added, the flask was evacuated under vacuum and replaced with dry nitrogen three times, then 60 mL THF and 8 mL saturated Na2C03 aqueous solution were added. The reaction was stirred at 85 °C under nitrogen atmosphere for 18 hours. Extraction was done using saturated brine and dichloromethane. The black solid was obtained by distillation under reduced pressure, column chromatography was done using silica gel powder as stationary phase and petroleum ether / dichloromethane as eluent to obtain yellow powder 0.22 g (yield 70 %).

[0134] The reaction equation in this step is as follows:

[0135]

[0136] Preparation of 27, 67-di-tert-butyl-14, 16, 34, 36, 54, 56, 74, 76-octamethoxy- 25, 29, 65, 69-tetrahydro-2, 6(3, 11)-diquinolino[3, 2, 1-de] acridine-1, 3, 5, 7(1, 3)- tetra-benzocyclooctane-25, 29-65, 69-tetraone

[0137] Into a 100 ml two necked flask, 7-(tert-butyl)-3, 11-bis(2, 4-dimethoxy- phenyl) quino[3, 2, 1-de] acridine-5, 9-dione (3.13 g, 5 mmol) and paraformaldehyde (3.6 g, 40 mmol), boron trifluoride diethyl ether (5.68 g, 40 mmol) were added in 30 ml dichloromethane solution. The reaction was stirred at room temperature for 36 hours. Extraction was done using saturated brine and dichloromethane. The black solid was obtained by distillation under reduced pressure, column chromatography was done using silica gel powder as stationary phase and petroleum ether / dichloromethane as eluent to isolate and purify, finally the crude product was dried in vacuum oven overnight to obtain 1.98 g of yellow powder (yield 31 %), finally the target product W1 was isolated using vacuum thermal sublimation isolator.

[0138] The reaction equation in this step is as follows:

[0139]

[0140] Example 2

[0141] This example provides another polymeric quinoline acridinedione macrocyclic derivative W2, which has a chemical name of tris(7-(tert-butyl)-3,11-bis(2,4-dimethoxyphenyl)quinoline[3,2,1-de]acridine-5,9-dione) and has a molecular structure shown in the following formula:

[0142]

[0143] The preparation method of the compound W2 includes the following steps:

[0144] S1. Preparation of 5-(tert-butyl)isophthalic acid

[0145] Weigh 1-tert-butyl-3,5-dimethylbenzene (4.86 g, 30 mmol) into a 500 ml three-necked round-bottom flask, and add 200 ml of a tert-butyl alcohol aqueous solution (volume ratio 1:1), and stir the mixture and heat to 95°C; then weigh potassium permanganate (14.22 g, 90 mmol), and slowly add (80 mg at a time), and after the addition is complete, warm to 90°C, and react for 28 h. After the reaction is completed and the mixture is cooled to room temperature, add sodium thiosulfate to the three-necked flask until the purple color fades, and then add concentrated hydrochloric acid to ph = 1. Remove the organic phase by rotary evaporation, and place the mixture in a Buchner funnel with filter paper, and wash with cold water to obtain white solid 5.33 g (yield 80%).

[0146] The reaction equation in this step is as follows:

[0147]

[0148] S2. Preparation of 5-(tert-butyl)-2-iodo isophthalic acid

[0149] Weigh 5-(tert-butyl)isophthalic acid (2.22 g, 10 mmol), iodine (3.81 g, 15 mmol), and palladium acetate (0.023 g, 0.1 mmol) into a 250 ml two-necked round-bottom flask, and then add 10 mL of anhydrous toluene, and react at 70°C for 4 h. After the reaction is completed, remove the organic phase by rotary evaporation, and finally perform silica gel column chromatography separation using ethyl acetate and petroleum ether as the developing agent to obtain white solid 2.19 g (yield 63%), and the product does not need to be further treated.

[0150] The reaction equation in this step is as follows:

[0151]

[0152] S3. Preparation of 5-(tert-butyl)-2-iodoisophthalic acid dimethyl ester

[0153] To a 100 mL two-necked flask, 5-(tert-butyl)-2-iodoisophthalic acid (3.48 g, 10 mmol), iodomethane (3.41 g, 24 mmol) and 60 mL of anhydrous toluene were added successively. After ultrasonic mixing to homogeneity, the mixture was stirred at 70 °C for 8 h and the reaction mixture was stirred at room temperature overnight (12 h). Extraction with ethyl acetate and rotary evaporation to remove the organic phase was followed by drying under vacuum. The product was purified using silica gel powder as stationary phase and petroleum ether and dichloromethane as eluents (petroleum ether: CH2Cl2, 1:2) to give 3.23 g of white powder in 86% yield.

[0154] The reaction equation in this step is as follows:

[0155]

[0156] S4. Preparation of 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalic acid dimethyl ester To a 100 mL two-necked flask, 5-(tert-butyl)-2-iodoisophthalic acid dimethyl ester (3.76 g, 10 mmol), bis(4-bromophenyl)amine (4.91 g, 15 mmol), potassium carbonate (2.48 g, 18 mmol), cuprous iodide (3.80 g, 20 mmol) and copper powder (0.96 g, 15 mmol), phase transfer catalyst 18-crown-6 (1 mL) were added to 60 mL of o-dichlorobenzene. After stirring at 110 °C for 36 h under nitrogen, extraction with saturated brine and dichloromethane was performed. Distillation under reduced pressure gave a black solid which was purified by column chromatography using silica gel powder as stationary phase and petroleum ether / dichloromethane as eluents to give 3.27 g of yellow solid (57% yield).

[0157] The reaction equation in this step is as follows:

[0158]

[0159] S5. Preparation of 3,11-dibromo-7-(tert-butyl)quinoline[3,2,1-de]acridine-5,9-dione

[0160] To a 250 ml single necked round bottom flask was added 2-(bis(4- bromophenyl)amino)-5-(tert-butyl)isophthalic acid dimethyl ester (5.73 g, 10 mmol), sodium hydroxide (1.2 g, 30 mmol) followed by 100 ml of water (50 ml) and anhydrous ethanol (50 ml), stirred and heated to 85 °C for 9 h. To the reaction mixture was added concentrated hydrochloric acid to ph = 1, the organic phase was then concentrated under reduced pressure followed by extraction three times with dichloromethane, dried over anhydrous sodium sulphate and the organic phase was concentrated under reduced pressure to obtain 4.85 g of crude 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalic acid (yield 89 %).

[0161] To a 100 ml two necked round bottom flask was added 2-(bis(4- bromophenyl)amino)-5-(tert-butyl)isophthalic acid (0.27 g, 0.5 mmol), anhydrous dichloromethane 12 ml, oxalyl chloride (0.25 g, 2 mmol) was added at 0 °C followed by 1 drop of anhydrous N,N-dimethylformamide; stirred at 30 °C under nitrogen for 1.5 h. After completion of the reaction the organic phase and oxalyl chloride was removed by rotary evaporation. Then 12 ml of dichloromethane was added under ice bath and anhydrous tin tetrachloride (0.52 g, 2 mmol) was added, stirred at 30 °C under nitrogen for 1.5 h. The organic phase was removed under reduced pressure and finally column chromatography was performed using ethyl acetate and petroleum ether as eluent to obtain 0.089 g of yellow solid (yield 35 %).

[0162] The reaction equation in this step is as follows:

[0163]

[0164] S6. Preparation of 7-(tert-butyl)-3, 11-bis(2, 4-dimethoxyphenyl) quinoline [3, 2, 1-de] acridine-5, 9-dione

[0165] To a 250 ml two necked round bottom flask was added 3, 11-dibromo-7-(tert- butyl) quinoline [3, 2, 1-de] acridine-5, 9-dione (0.25 g, 0.5 mmol), 2, 4- dimethoxyphenyl boronic acid (0.32 g, 1.75 mmol), tetrakis triphenyl phosphine palladium (0.16 g, 0.14 mmol), the flask was evacuated under vacuum and replaced with dry nitrogen three times, followed by 60 mL THF and 8 mL saturated aqueous Na2CO3 solution was added. The reaction was stirred at 85 °C under reflux for 18 h. The reaction mixture was extracted with saturated brine and dichloromethane. Distilled under reduced pressure to obtain black solid, column chromatography was performed using silica gel powder as stationary phase and petroleum ether / dichloromethane as eluent to obtain 0.22 g of yellow powder (yield 70 %).

[0166] The reaction equation in this step is as follows:

[0167]

[0168] S7. Preparation of Tris(7-(tert-butyl)-3,11-bis(2,4-dimethoxyphenyl)quinoline[3,2,1-de]acridine-5,9-dione)

[0169] 7-(tert-butyl)-3,11-bis(2,4-dimethoxyphenyl)quinoline[3,2,1-de]acridine-5,9-dione (3.13 g, 5 mmol) and paraformaldehyde (7.2 g, 80 mmol), boron trifluoride diethyl ether (11.36 g, 80 mmol) were added into a two-necked flask containing 30 mL dichloromethane solution. The reaction was stirred at room temperature for 36 hours. The product was extracted with saturated brine and dichloromethane. The black solid was obtained by distillation under reduced pressure. The product was purified by column chromatography using silica gel powder as stationary phase and petroleum ether / dichloromethane as eluent. Finally, the crude product was dried in a vacuum drying oven overnight to obtain 2.49 g of yellow powder (yield 26%). Finally, the target product W2 was separated using a vacuum thermal sublimation separator.

[0170] The reaction equation in this step is as follows:

[0171]

[0172] Structural characterization and performance test

[0173] The polyquinoline acridinedione macrocyclic derivatives W1 and W2 prepared in Example 1 and Example 2 were characterized and tested for performance.

[0174] The test method is as follows:

[0175] Compound structure detection: Bruker 400 MHz superconducting nuclear magnetic resonance instrument was used, and deuterated chloroform was used as the solvent;

[0176] Mass spectrometry detection: the compounds W1 and W2 prepared in Example 1 and Example 2 were dissolved in dichloromethane to prepare a solution with a concentration of 1 mg / mL, and mass spectrometry was performed using a liquid chromatograph-mass spectrometer LCMS-2020.

[0177] Ultraviolet absorption spectrum detection: Shimadzu ultraviolet-visible spectrophotometer UV-2700 was used, and the scanning range was 200-450 nm;

[0178] Emission spectrum detection: steady-state / transient fluorescence spectrometer (FLS980) was used, the excitation wavelength was 390 nm, the test temperature was 300 K under nitrogen protection.

[0179] The test results are as follows:

[0180] The 1H NMR spectrum of the polyquinoline acridine dione macrocyclic derivative W1 prepared in Example 1 is as follows: Figure 1 As shown. From Figure 1 It can be seen that its characteristic wavenumbers (ppm) are as follows: ¹H NMR (400MHz, Chloroform-d) δ 8.79 (s, 4H), 8.69 (s, 4H), 8.16 (d, J = 8.8 Hz, 4H), 7.66 (dd, J = 8.8, 2.3 Hz, 4H), 7.05 (s, 4H), 6.62 (s, 4H), 4.01 (s, 4H), 3.90 (d, J = 19.2 Hz, 24H), 1.48 (s, 18H). The chemical shifts in the ¹H NMR molecular spectrum correspond one-to-one with the hydrogen atoms of the target product, and the number is reasonable.

[0181] The mass spectrum of compound W1 prepared in Example 1 of this patent application is shown below. Figure 2 As shown. From Figure 2 As can be seen, Figure 2 The relative molecular mass of the compound is 1275, which is consistent with the relative molecular mass of compound W1 prepared in Example 1. Based on the above results of the proton NMR spectrum and mass spectrum, it can be concluded that the product obtained in Example 1 is W1.

[0182] Figure 3 The UV-Vis absorption spectrum of compound W1 prepared in Example 1 is shown. The instrument used for testing was a Shimadzu UV-2700 UV-Vis spectrophotometer, and the solvent was tetrahydrofuran with a concentration of 1×10⁻⁶. -5 mol / L. From Figure 3 It can be seen that the main absorption peak of compound W1 is located at 465 nm.

[0183] Figure 4 The fluorescence emission spectrum of compound W1 prepared in Example 1 was obtained using an Edinburgh FLS980 fluorometer and tetrahydrofuran as the solvent with a concentration of 1×10⁻⁶. -5 mol / L, excitation wavelength 390 nm. From Figure 4 It can be seen that the main emission peak position of compound W1 prepared in Example 1 is 500 nm, and the FWHM is 48 nm.

[0184] Figure 5 The quantum efficiency diagram of compound W1 prepared in Example 1 is shown. The instrument used for testing was an Edinburgh FLS980 fluorescence spectrometer, and the solvent was anhydrous toluene solution with a concentration of 1×10⁻⁶. -5 mol / L, excitation wavelength 365 nm. From Figure 5 It can be seen that the quantum efficiency of compound W1 prepared in Example 1 is 93.82%, which is high.

[0185] The compound W1 in the patent application has a narrow half-peak width of 48 nm, and has the advantages of narrow emission, high color purity and high efficiency, which is mainly due to the formation of a polyquinoline acridinedione macrocyclic derivative by a methylene bridge. Due to the intrinsic macrocyclic effect, the quenching caused by the large planar property of the monomolecular fragment quinoline acridinedione compound in the aggregate state can be effectively inhibited, thereby effectively improving the fluorescence quantum efficiency of the macrocyclic molecule.

[0186] The nuclear magnetic resonance hydrogen spectrum of the polyquinoline acridinedione macrocyclic derivative W2 prepared in Example 2 is shown in Figure 6 . As can be seen from Figure 6 , 1H NMR (400 MHz, Chloroform-d) δ 8.79 (s, 6H), 8.58 (s, 6H), 8.23 (s, 6H), 8.02 (s, 6H), 7.90 (s, 6H), 6.61 (s, 6H), 4.12 (q, J = 7.1 Hz, 42H), 1.28 (s, 27H). The nuclear magnetic resonance hydrogen spectrum peak can be one-to-one corresponding to the target product, and the number is reasonable. The mass spectrum of the compound W2 prepared in Example 2 is consistent with its relative molecular mass, which is not described here.

[0187] Using Shimadzu UV-visible spectrophotometer UV-2700, the W2 prepared in the example is dissolved in dichloromethane solution to prepare 1×10 -3 mol / L mother liquor, and then diluted to 1×10 -5 mol / L toluene solution for testing.

[0188] Figure 7 The UV-visible absorption spectrum of W2 prepared in Example 2 in 1×10 -5 mol / L toluene. As can be seen from Figure 7 , the main absorption peak position of W2 is 449 nm.

[0189] Using fluorescence emission spectrum: FLS980 fluorescence instrument, the W2 prepared in the example is dissolved in dichloromethane solution to prepare 1×10 -3 mol / L mother liquor, and when testing, it is diluted to 1×10 -5 mol / L solution.

[0190] Figure 8 The fluorescence emission spectrum of W2 prepared in Example 2 in 1×10 -5 mol / L toluene solution. As can be seen from Figure 8It can be seen that the main emission peak position of W2 is 466 nm, which is blue light emission, and the half peak width of W2 is 21 nm, that is, short-wave emission is achieved, that is, the polyquinoline acridinedione macrocyclic derivative system provided in the patent application is diverse, and short-wave emission can be achieved, for example, blue light emission can be achieved.

[0191] The compound W2 in the patent application has a very narrow half peak width of 21 nm, has the advantages of narrow emission, high color purity and high efficiency, which is mainly due to the polyquinoline acridinedione macrocyclic derivative formed by the methylene bridge, and due to the intrinsic macrocyclic effect, the quenching caused by the large planar property of the single molecule fragment quinoline acridinedione compound in the aggregate state can be effectively inhibited, thereby effectively improving the fluorescence quantum efficiency of the macrocyclic molecule.

[0192] Figure 9 The quantum efficiency diagram of the compound W2 prepared in Example 2 is prepared, the test instrument is Edinburgh FLS980 fluorescence instrument, the solvent is anhydrous toluene solution, the concentration is 1×10 -5 mol / L, and the excitation wavelength is 365 nm. From Figure 9 It can be seen that the quantum efficiency of the compound W2 prepared in Example 2 is 95.14%, which has a high quantum efficiency.

[0193] In summary, the polyquinoline acridinedione macrocyclic derivative provided in the patent application has good luminescent performance, and can be used as a new type of OLED luminescent molecule with good performance, low cost and good color purity. In the preparation of luminescent materials, luminescent devices, fluorescent sensing, separation materials, supramolecular self-assembly, nano drug loading and intelligent response materials, it has significant economic value, and has good application prospect in full-color display and solid-state lighting fields.

[0194] At the same time, the patent application realizes controllable preparation of polyquinoline acridinedione macrocyclic derivatives; the preparation cost is low, the raw material source is wide, and large-scale production can be realized, and has broad commercialization prospect.

[0195] The patent application is based on a polyquinoline acridinedione macrocyclic system, with the help of methylene bridge, a plurality of single molecule fragments of quinoline acridinedione is aggregated into a macrocycle, the difference between the electron-withdrawing and electron-donating properties of the carbonyl and nitrogen atom is synthesized into a plurality of quinoline acridinedione macrocyclic derivatives containing the relative distribution structure of carbonyl and nitrogen atom, the interaction of carbonyl and nitrogen atom heterocycle is conducive to realize high color purity of molecular luminescence. Due to the free rotation of benzene ring and intramolecular vibration caused by the fixation of single fragment molecule itself, the energy will be attenuated in the form of non-radiative transition, and the benzene ring after the polymerization into a ring can efficiently luminesce due to the limited rotation and improve the color purity of luminescence. At the same time, the polyquinoline acridinedione macrocycle formed by the methylene bridge can effectively avoid the fluorescence quenching caused by the large planar property of single molecule quinoline acridinedione under the aggregation state, and improve the device performance. In addition, the macrocycle induced luminescence enhancement effect brought by the polymer can effectively improve the luminescent efficiency of the molecule.

[0196] Therefore, the polyquinoline acridinedione macrocyclic derivative provided by the patent application can be used as a luminescent material or a smart material, and has good application prospect in the field of full-color display and solid-state lighting.

[0197] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "exemplary embodiment", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the patent application. In the present specification, the exemplary description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0198] Although several embodiments of the present patent application have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, replacements and variations of the embodiments can be made without departing from the principles and purposes of the present patent application, and the scope of the present patent application is defined by the claims and their equivalents.

Claims

1. A polyquinoline acridine dione macrocyclic derivative, characterized in that, The general structural formula of the polyquinoline acridine dione macrocyclic derivative is: ； Where n is 2-3; R1-R 10 It can be independently selected from any of the following groups: 。 2. The method for preparing the polyquinoline acridine dione macrocyclic derivative according to claim 1, characterized in that, Includes the following steps: S1. 5-(tert-butyl)-isophthalic acid is prepared by oxidation with 1-tert-butyl-3,5-xylene and potassium permanganate; the reaction equation is as follows: ； S2. The 5-(tert-butyl)-isophthalic acid obtained in step S1 is subjected to catalytic iodination with iodine to produce 5-(tert-butyl)-2-iodoisophthalic acid; the reaction equation is as follows: ； S3. The 5-(tert-butyl)-2-iodophthalic acid obtained in step S2 is esterified with iodomethane to obtain dimethyl 5-(tert-butyl)-2-iodophthalate; the reaction equation is as follows: ； S4. The dimethyl 5-(tert-butyl)-2-iodophthalate obtained in step S3 is reacted with bis(4-bromophenyl)amine in a carbon-nitrogen coupling reaction under copper catalysis to obtain 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)phthalate; the reaction equation is as follows: ； S5. The 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalate dimethyl ester obtained in step S4 was first hydrolyzed with sodium hydroxide, and then acylated with oxaloyl chloride to obtain 3,11-dibromo-7-(tert-butyl)quinolino[3,2,1-de]acridin-5,9-dione; the reaction equation is as follows: ； S6. The 3,11-dibromo-7-(tert-butyl)quinolino[3,2,1-de]acridin-5,9-dione obtained in step S5 is reacted with 2,4-dimethoxyphenylboronic acid under tetra(triphenylphosphine)palladium catalysis to obtain 7-(tert-butyl)-3,11-bis(2,4-dimethoxyphenyl)quinolino[3,2,1-de]acridin-5,9-dione; the reaction equation is as follows: ； S7. The 7-(tert-butyl)-3,11-bis(2,4-dimethoxyphenyl)quinolino[3,2,1-de]acridin-5,9-dione obtained in step S6 was polymerized with paraformaldehyde under the catalysis of boron trifluoride diethyl ether to prepare the target compound; the reaction equation is as follows: 。 3. The method for preparing polyquinoline acridine dione macrocyclic derivatives according to claim 2, characterized in that, In step S1, the molar ratio of 1-tert-butyl-3,5-xylene and potassium permanganate is 1:(2~3), the reaction temperature of the oxidation reaction is 80~100 ℃, and the reaction time is 20~36 h.

4. The method for preparing the polyquinoline acridine dione macrocyclic derivative according to claim 2, characterized in that, In step S2, the molar ratio of iodine to 5-(tert-butyl)isophthalic acid is 1:(1~2), the reaction temperature of the iodination reaction is 60~80 °C, and the reaction time is 3~5 h.

5. The method for preparing the polyquinoline acridine dione macrocyclic derivative according to claim 2, characterized in that, In the esterification reaction described in step S3, the molar ratio of iodomethane and 5-(tert-butyl)-2-iodophthalic acid is 1:(2.3~2.5), the reaction temperature of the esterification reaction is 60~80℃, and the reaction time is 4~12 h.

6. The method for preparing the polyquinoline acridine dione macrocyclic derivative according to claim 2, characterized in that, In the carbon-nitrogen coupling reaction described in step S4, the molar ratio of dimethyl 5-(tert-butyl)-2-iodophthalate and bis(4-bromophenyl)amine is 1:(1~2), the reaction temperature of the carbon-nitrogen coupling reaction is 100~120 °C, and the reaction time is 24~48 h.

7. The method for preparing the polyquinoline acridine dione macrocyclic derivative according to claim 2, characterized in that, In step S5, the 2-(bis(4-bromophenyl)amino)-5-(tert-butyl)isophthalate dimethyl ester is first hydrolyzed with sodium hydroxide, and then acylated with oxalyl chloride. The molar ratio of the reactants is 1:(3~5). The reaction temperature of the acylation reaction is 20~40 °C, and the reaction time is 0.5~2 h.

8. The method for preparing the polyquinoline acridine dione macrocyclic derivative according to claim 2, characterized in that, In step S6, the molar ratio of 3,11-dibromo-7-(tert-butyl)quinolino[3,2,1-de]acridin-5,9-dione and 2,4-dimethoxyphenylboronic acid is 1:(3~4), and the Suzuki reaction is carried out at a temperature of 80~90℃ for 12~24h.

9. The method for preparing the polyquinoline acridine dione macrocyclic derivative according to claim 2, characterized in that, In step S7, the molar ratio of 7-(tert-butyl)-3,11-bis(2,4-dimethoxyphenyl)quinolino[3,2,1-de]acridin-5,9-dione and paraformaldehyde is 1:(7~9). The polymerization reaction is carried out at room temperature for 24~48 hours.

10. The application of the polyquinoline acridine dione macrocyclic derivative of claim 1 as a luminescent material, luminescent device, or fluorescence sensor.

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