Synthesis and application of spirofluorene embedded macrocyclic aromatic hydrocarbon and conjugated nanoring

Abstract

The invention discloses synthesis and application of spirofluorene embedded macrocyclic aromatic hydrocarbon and a conjugated nanoring. The core of the invention is to design spirofluorene and oxa-spirofluorene embedded macrocyclic aromatic hydrocarbon, and a series of spirofluorene and oxa-spirofluorene embedded conjugated nanoring are constructed with high yield through efficient, simple and convenient derivatization reaction. The functional macrocyclic aromatic hydrocarbons and conjugated nanoring have excellent photophysical properties, so that the functional macrocyclic aromatic hydrocarbons and conjugated nanoring are used for constructing chiral luminescent materials. Researches show that the newly found racemic conjugated nanoring can be split by a high performance liquid chromatography chiral column, so that a pure enantiomer is obtained. A circular dichroism spectrometer and a circular polarization luminescence spectrometer are used for researching the chiral characteristics of the enantiomer.

Description

Technical Field

[0001] The present invention belongs to the exploration of the synthesis method and application of macrocyclic compounds in the field of supramolecular chemistry research, and in particular to a synthesis method of macrocyclic aromatic hydrocarbons and conjugated nanorings containing spirofluorene moieties and the research on chiral luminescence properties. Background Art

[0002] Spirofluorene, as a kind of rigid spirocyclic aromatic compound formed by two orthogonally arranged fluorene units bridged by a central sp³ hybridized carbon atom, its unique steric hindrance effect and molecular orbital delocalization characteristics endow it with significant two-way electron transport ability and tunable photoluminescence characteristics. This structure shows multi-dimensional application value in the field of organic semiconductor materials: as the core component of the electron transport layer to improve the efficiency of perovskite solar cells; as a blue light emitter to optimize the performance of OLED devices; its derivatives can also construct an interface charge rapid transport channel by combining with graphene quantum dots. In the field of supramolecular chemistry, due to its three-dimensional rigid skeleton and the diversity of modifiable sites, spirofluorene has become a strategic molecular building block for constructing covalent organic frameworks (COFs) and mechanically interlocked molecular devices. However, there are still significant technical bottlenecks in the development of existing spirofluorene-based supramolecular systems: (1) Lack of stereochemical control. The current construction strategy based on 2,7-position functionalized spirofluorene moieties fails to effectively utilize its inherent axial chirality characteristics, resulting in the lack of stereoselective control of the obtained macrocyclic compounds and restricting their applications in chiral recognition and asymmetric catalysis; (2) The paradox of conjugate extension and solubility. Although the traditional linear fused ring amplification strategy can improve the degree of π-conjugation, it leads to the deterioration of solubility caused by molecular planar stacking, and the complex synthesis route and harsh post-modification conditions further cause the contradiction between precise control of molecular structure and large-scale preparation. In this context, there is an urgent need to develop a new synthesis strategy with both efficient cyclization and controllable conjugate extension functions. By designing a dynamic reversible ring-forming reaction system and combining site-selective post-modification technology, the conformational regulation and electronic structure optimization of macrocyclic aromatic hydrocarbons can be achieved. This technical path can not only break through the solubility limit and maintain solution processability, but also enhance the photophysical properties through the construction of non-planar conjugate topologies, providing theoretical support and industrialization breakthroughs for the development of a new generation of optoelectronic functional materials. Summary of the Invention

[0003] The present invention addresses some problems faced by the chemistry of macrocyclic aromatic hydrocarbons containing spirofluorene motifs: (1) the spirofluorene motifs introduced are based on 2,7-position connection, and the chirality of the spirocyclic compound is not fully utilized; (2) generally, the more connected benzene rings, the better the photophysical properties, but the worse the monomer solubility, and the simplicity of the synthesis method and the excellence of the macrocyclic molecule are sometimes not achieved at the same time. The present invention provides a simple, efficient and universal method for synthesizing spirofluorene-embedded macrocyclic aromatic hydrocarbons and conjugated nanorings. By using the strategy of pre-reserving modifying groups and taking 2,2`-disubstituted-9,9`-spirobifluorene-embedded macrocyclic aromatic hydrocarbons as precursors, a series of novel 2,2`-disubstituted-9,9`-spirobifluorene-embedded conjugated nanorings are developed, laying a solid foundation for further exploring new materials and new applications. The core of the present invention is to design macrocyclic aromatic hydrocarbons embedded in spirofluorene and oxyspirofluorene, and to construct a series of spirofluorene and oxyspirofluorene embedded conjugated nanorings with high yield through efficient and simple derivatization reactions. These functional macrocyclic aromatic hydrocarbons and conjugated nanorings have excellent photophysical properties and are therefore used to construct chiral luminescent materials. Studies have shown that a newly discovered class of racemic conjugated nanorings can be separated by a high-performance liquid chromatography chiral column to obtain pure enantiomers. The chiral properties of the enantiomers were studied using a circular dichroism spectrometer.

[0004] To achieve the above purpose, the present invention discloses the following technical contents: The synthesis method of spirofluorene-embedded macrocyclic aromatic hydrocarbons and conjugated nanorings is characterized by having the following structure: (1) Synthesis of 2,2`-disubstituted-9,9`-spirobifluorene endonucleated macrocyclic aromatic building blocks; (2) Synthesis of 2,2`-disubstituted-9,9`-spirobifluorene-embedded macrocyclic aromatics; (3) Synthesis of 2,2`-disubstituted-9,9`-spirobifluorene endogenous conjugated nanorings; in: (1) Structure of 2,2`-disubstituted-9,9`-spirobifluorene embedded macrocyclic aromatic building blocks

[0005] (2) Structure of 2,2`-disubstituted-9,9`-spirobifluorene endonucleated macrocyclic aromatic hydrocarbons

[0006]

[0007]

[0008] (3) Structure of 2,2`-disubstituted-9,9`-spirobifluorene endogenous conjugated nanorings

[0009] Among them: Compounds with (P, P) and (M, M) configurations are a pair of enantiomers; the compound with (P, M)-configuration is a meso form; the -OAc functional group in Compounds 1-2 can be replaced by -H (hydrogen), -OR (alkoxy), -OBn (benzyloxy); the methoxy group in Compounds 1-5 can be replaced by a solubilizing group -OR (alkoxy), a water-soluble group (carboxylate, sulfonate, ammonium salt, phosphite); the embedded fragment 2,2'-disubstituted-9,9'-spirobifluorene in Compounds 1-5 is replaced by the following functional fragments:

[0010] The present invention further discloses a method for synthesizing a spirobifluorene-embedded macrocyclic aromatic hydrocarbon building block, a spirobifluorene-embedded macrocyclic aromatic hydrocarbon, and a spirobifluorene-embedded conjugated nanoring thereof, which is characterized in that: a 2,2'-disubstituted-9,9'-spirobifluorene-embedded macrocyclic aromatic hydrocarbon building block is designed; further, it reacts with paraformaldehyde under the catalysis of a Lewis acid, and then, through alkaline hydrolysis and trifluoromethanesulfonylation reaction, a series of 2,2'-disubstituted-9,9'-spirobifluorene-embedded macrocyclic aromatic hydrocarbons are obtained in high yield. Finally, a series of 2,2'-disubstituted-9,9'-spirobifluorene-embedded conjugated nanorings are obtained from the 2,2'-disubstituted-9,9'-spirobifluorene-embedded macrocyclic aromatic hydrocarbon.

[0011] Its characteristics include the following aspects: (1) Synthesis of the 2,2'-disubstituted-9,9'-spirobifluorene-embedded macrocyclic aromatic hydrocarbon building block; (2) Synthesis of the 2,2'-disubstituted-9,9'-spirobifluorene-embedded macrocyclic aromatic hydrocarbon; (3) Synthesis of the 2,2'-disubstituted-9,9'-spirobifluorene-embedded conjugated nanoring.

[0012] Among them: Taking the synthesis of the 2,2'-disubstituted-9,9'-spirobifluorene-embedded macrocyclic aromatic hydrocarbon and the conjugated nanoring as examples: (1) The synthesis method of the 2,2'-disubstituted-9,9'-spirobifluorene-embedded macrocyclic aromatic hydrocarbon building block is as follows: Add 5.68 g of bis(pinacolato) 2,2'-disubstituted-9,9'-spirobifluorene-7,7'-diboronate, 5.12 g of 2-bromo-5-acetoxyanisole, 1.00 g of [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium, 5.25 g of potassium carbonate, 80 mL of 1,4-dioxane, and 20 mL of H2O into a 250 mL round-bottom flask. Under argon protection, reflux at 105 °C for 48 h. Remove the solvent under reduced pressure. Add 50 mL of N,N-dimethylformamide, 6.0 mL of pyridine, and 4.8 mL of acetyl chloride to the reaction system and react for 2 h. Quench with water, extract with dichloromethane, dry the organic phase with anhydrous sodium sulfate, concentrate under reduced pressure, mix with silica gel, and purify by silica gel column chromatography to obtain Compound 1 as a white solid.

[0013] (2)The synthesis method of 2,2'-disubstituted-9,9'-spirobifluorene-embedded macrocyclic aromatic hydrocarbons is as follows: Add 320 mg of Compound 1, 60 mg of paraformaldehyde, 100 mL of 1,2-dichloroethane, and 0.8 mL of boron trifluoride diethyl ether complex into a 250 mL round-bottom flask and react for 1 h. Quench with saturated sodium bicarbonate solution, extract with dichloromethane, dry the organic phase with anhydrous sodium sulfate, concentrate under reduced pressure, and separate by silica gel column chromatography to obtain Compound 2 as a white solid.

[0014] Add 150 mg of Compound 2 with acetoxy substitution, 120 mg of sodium hydroxide, 0.3 mL of pure water, and 8 mL of tetrahydrofuran into a 25 mL round-bottom flask and perform ultrasonic heating treatment for 40 minutes. Concentrate under reduced pressure and separate by silica gel column chromatography to obtain white solid Compound 3.

[0015] Add Compound 3, 10 mL of dichloromethane, 2.0 mL of pyridine, and 1.6 mL of trifluoromethanesulfonic anhydride into a 50 mL round-bottom flask and react for 1 h. Slowly quench with water, extract with dichloromethane, dry the organic phase with anhydrous sodium sulfate, and separate by silica gel column chromatography to obtain white solid Compound 4.

[0016] (3)The synthesis method of 2,2'-disubstituted-9,9'-spirobifluorene-embedded conjugated nanorings is as follows: Add a nickel catalyst, 2,2'-bipyridine, and N-methylpyrrolidone into a 25 mL reaction tube. Heat at 85 °C, add Compound 4, and react for 4 - 12 hours. Cool the reaction to room temperature, extract with dichloromethane and distilled water, dry the organic phase with anhydrous sodium sulfate, concentrate under reduced pressure, and separate by silica gel column chromatography to obtain Compound 5. The present invention further discloses the application of 2,2`-disubstituted-9,9`-spirobifluorene-incorporated macrocyclic aromatic hydrocarbons in constructing novel chiral conjugated nanorings. Research shows that a newly discovered class of racemic conjugated nanorings can be resolved by a chiral column of high performance liquid chromatography, thereby obtaining pure enantiomers. The chiral properties of the enantiomers were studied using a circular dichroism spectrometer and a circularly polarized luminescence spectrometer. The results indicate that, different from traditional macrocyclic aromatic hydrocarbons, this new class of spirofluorene-incorporated macrocyclic aromatic hydrocarbons and conjugated nanorings have excellent chiral luminescence properties. The synthetic innovation of these functional conjugated nanorings will provide infinite vitality and vigor for the research in the fields of chiral luminescence, chiral catalysis, etc.

[0017] The positive effects of the synthesis and application of the series of spirofluorene-incorporated macrocyclic aromatic hydrocarbons and conjugated nanorings disclosed by the present invention are as follows: (1) The introduced spirofluorene moiety has inherent chirality, opening up a new idea for creating novel chiral macrocyclic host compounds.

[0018] (2) The synthetic method for synthesizing spirofluorene-incorporated macrocyclic aromatic hydrocarbons from spirofluorene moieties is very simple and has a high yield.

[0019] (3) The derivatization of the incorporated macrocyclic aromatic hydrocarbons is simple and easy to operate, and is expected to achieve industrial-scale production.

[0020] (4) Compared with traditional macrocyclic aromatic hydrocarbons, the spirofluorene-incorporated macrocyclic aromatic hydrocarbons and conjugated nanorings disclosed by the present invention have excellent chiral luminescence properties and have broad application prospects in the fields of chiral luminescence, chiral catalysis, etc. Description of the Drawings

[0021] Figure 1 . High performance liquid chromatography chiral column separation of 2,2`-disubstituted-9,9`-spirobifluorene-incorporated conjugated nanorings; Figure 2 . Circular dichroism spectrum of 2,2`-disubstituted-9,9`-spirobifluorene-incorporated conjugated nanorings; Figure 3 . Fluorescence spectrum of 2,2`-disubstituted-9,9`-spirobifluorene-incorporated conjugated nanorings; Figure 4 . Circularly polarized luminescence spectrum of the film of 2,2`-disubstituted-9,9`-spirobifluorene-incorporated conjugated nanorings. Detailed Description of the Invention Unless otherwise specified, the technical means used in the present invention are all methods well-known to those skilled in the art. In addition, the embodiments should be understood as illustrative and not limiting the scope of the present invention. The essence and scope of the present invention are only defined by the claims. For those skilled in the art, various changes or modifications to the material components and dosages in these embodiments also fall within the protection scope of the present invention without departing from the essence and scope of the present invention. The raw materials and reagents used in the present invention are all commercially available (purchased from Bidepharm). (1) The synthesis method of the 2,2`-disubstituted-9,9`-spirobifluorene-embedded macrocyclic aromatic hydrocarbon building block is as follows:

[0022] Add 5.68 g of 2,2`-disubstituted-9,9`-spirobifluorene diboronic acid bis(pinacol ester), 5.12 g of 2-bromo-5-methoxyphenol, 1.00 g of [1,1-bis(diphenylphosphino)ferrocene] dichloropalladium, 5.25 g of potassium carbonate, 80 mL of 1,4-dioxane, and 20 mL of H2O into a 250 mL round-bottom flask. Reflux at 105 °C for 48 h under argon protection. Remove the solvent under reduced pressure. Add 50 mL of N,N-dimethylformamide, 6.0 mL of pyridine, and 4.8 mL of acetyl chloride to the reaction system and react for 2 h. Quench with water, extract with dichloromethane, dry the organic phase with anhydrous sodium sulfate, concentrate under reduced pressure, mix with silica gel, and purify by silica gel column chromatography to obtain the white solid compound 1. Characterization data of compound 1: 1 H NMR (400 MHz, CDCl3) δ 7.84(dd, J = 7.4, 3.0 Hz, 4H), 7.55 (d, J = 7.8 Hz, 2H), 7.35 (t, J = 7.4 Hz,2H), 7.11 (dd, J = 16.6, 7.9 Hz, 4H), 6.86 (s, 2H), 6.80 (d, J = 7.5 Hz, 2H),6.65 – 6.57 (m, 4H), 3.61 (s, 6H), 2.26 (s, 6H). 1313C NMR (101 MHz, CDCl3) δ169.56, 157.05, 150.83, 149.14, 148.85, 141.78, 140.70, 137.40, 131.08, 129.19, 128.35, 127.78, 125.35, 124.30, 120.08, 119.48, 113.57, 105.26, 66.14, 55.63, 21.27. (2) The synthetic method of 2,2`-disubstituted-9,9`-spirobifluorene-embedded macrocyclic aromatic hydrocarbons is as follows:

[0023] Add 320 mg of compound 1, 60 mg of paraformaldehyde, 100 mL of 1,2-dichloroethane, and 0.8 mL of boron trifluoride diethyl etherate into a 250 mL round-bottom flask, and react for 1 h. After quenching with saturated sodium bicarbonate solution, extract with dichloromethane. The organic phase is dried over anhydrous sodium sulfate, concentrated under reduced pressure, and separated by silica gel column chromatography to obtain white solid compound 2.

[0024] Characterization data of compound 2:( P, P ) / ( M, M )-2: 1 1H NMR (400 MHz, CDCl3, 298K) δ7.90 (d, J = 7.6 Hz, 4H), 7.77 (d, J = 7.9 Hz, 4H), 7.40 (t, J = 7.5 Hz, 4H), 7.24 (d, J = 7.9 Hz, 4H), 7.13 (t, J = 7.5 Hz, 4H), 6.84 (d, J = 7.5 Hz, 4H), 6.76 (s, 8H), 6.44 (s, 4H), 3.50 (s, 4H), 3.41 (s, 12H), 2.17 (s, 12H). 13CNMR (101 MHz, CDCl3, 298K) δ 169.31, 155.52, 149.17, 148.53, 148.49, 141.96,140.36, 137.14, 131.83, 129.01, 128.66, 127.77, 127.69, 125.46, 124.42,123.44, 119.95, 119.67, 105.82, 66.06, 55.68, 28.85, 20.91. HRMS (MALDI-TOF): m / z calcd for [( P, P ) / ( M, M )-2] •+ , C 88 H 64 O 12 •+ , 1312.4398, found 1312.4392. ( P, M )-2: 1 H NMR (400 MHz, CDCl3, 298K) δ 7.80 (s, 4H), 7.78 (s,4H), 7.47 (d, J J = 7.9 Hz, 4H), 7.32 (t, J J = 7.5 Hz, 4H), 7.07 (t, J J = 7.5 Hz,4H), 6.85 (s, 4H), 6.80 (s, 4H), 6.76 (d, J J = 7.5 Hz, 4H), 6.49 (s, 4H), 3.60(d, J J = 15.8 Hz, 2H), 3.51 (s, 12H), 3.39 (d, J J = 16.0 Hz, 2H), 2.13 (s,12H). 13 C NMR (101 MHz, CDCl 3, 298K) δ 169.18, 155.41, 149.30, 148.42, 141.70, 140.68, 137.10, 131.93, 129.08, 128.22, 127.62, 125.33, 124.21, 123.34, 119.99, 119.51, 106.10, 66.10, 55.75, 28.84, 20.89. HRMS (MALDI-TOF): m / z calcd for [( P, M )-2] •+ , C 88 H 64 O 12 •+ , 1312.4398, found 1312.4392.

[0025] In a 25 mL round-bottom flask, add 150 mg of the acetoxy-substituted compound 2, 120 mg of sodium hydroxide, 0.3 mL of pure water, and 8 mL of tetrahydrofuran. Sonicate and heat for 40 minutes. Concentrate under reduced pressure and separate by silica gel column chromatography to obtain the white solid compound 3.

[0026] Characterization data of compound 3: ( P, P ) / ( M, M )-3: 1 H NMR (400 MHz, Acetone-d6, 298K) δ 8.41 (s, 4H), 8.09 (d, J = 7.6 Hz, 4H), 7.95 (d, J = 8.0 Hz, 4H), 7.44 (t, J = 7.5 Hz, 4H), 7.35 (dd, J = 8.0, 1.2 Hz, 4H), 7.15 (t, J = 7.5 Hz, 4H), 6.77 (s, 4H), 6.75 – 6.63 (m, 8H), 6.41 (s, 4H), 3.70 (s, 4H), 3.45 (s, 12H). 1313C NMR (101 MHz, Acetone, 298K) δ 156.60, 155.46, 150.04, 149.41, 142.82, 140.32, 139.32, 132.42, 129.89, 128.67, 128.24, 125.25, 124.61, 122.93, 120.90, 120.43, 120.18, 100.60, 66.94, 55.84, 19.84. HRMS (MALDI-TOF): m / z calcd for [( P, P ) / ( M, M )-3] •+ , C 80 H 56 O8 •+ , 1144.3975, found 1144.3970. ( P, M )-3: 1 1H NMR (400 MHz, Acetone-d6, 298K) 1H NMR (400 MHz, Acetone-d6, 298 K) δ 8.41(s, 4H), 7.91 (d, J = 7.6 Hz, 4H), 7.84 (d, J = 8.0 Hz, 4H), 7.40 (d, J = 7.9Hz, 4H), 7.37 (d, J = 7.6 Hz, 4H), 7.12 (t, J = 7.4 Hz, 4H), 6.89 (s, 4H),6.75 (s, 4H), 6.67 (d, J = 7.5 Hz, 4H), 6.44 (s, 4H), 3.80 (d, J = 15.6 Hz,2H), 3.59 (d, J = 15.7 Hz, 2H), 3.45 (s, 12H). HRMS (MALDI-TOF): m / z calcdfor [( P, M )-3]•+, C80H56O8•+, 1144.3975, found 1144.3970.

[0027] Add 150 mg of the acetoxy-substituted compound 2, 120 mg of sodium hydroxide, 0.3 mL of pure water, and 8 mL of tetrahydrofuran to a 25 mL round-bottom flask, and perform ultrasonic heating treatment for 40 minutes. Concentrate under reduced pressure and separate by silica gel column chromatography to obtain the white solid compound 3. Subsequently, transfer compound 3 to a 50 mL round-bottom flask, add 10 mL of dichloromethane, 2.0 mL of pyridine, and 1.6 mL of trifluoromethanesulfonic anhydride, and react for 1 h. Slowly add water to quench the reaction, extract with dichloromethane, dry the organic phase with anhydrous sodium sulfate, and separate by silica gel column chromatography to obtain the white solid compound 4.

[0028] Characterization data of compound 4: ( P, P ) / ( M, M )-4: 1 1H NMR (400 MHz, CDCl3, 298K) δ 7.90 (d, J = 7.6 Hz, 1H), 7.75 (d, J = 7.9 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.18 (d, J = 8.0 Hz, 1H), 7.15 (t, J = 7.6 Hz, 1H), 6.80 (d, J = 7.6 Hz, 1H), 6.78 (s, 1H), 6.77 (s, 1H), 6.66 (s, 1H), 3.92 (s, 1H), 3.45 (s, 3H). 19 19F NMR (376 MHz, CDCl3, 298K) δ -73.65. 13 13C NMR (101 MHz, CDCl3, 298K) δ 156.10, 149.07, 148.49, 146.92, 141.51, 141.12, 135.94, 132.39, 131.09, 128.97, 128.11, 127.95, 125.08, 124.39, 122.92, 120.21, 120.14, 119.94, 117.02, 104.88, 66.05, 55.85, 27.96. HRMS (MALDI-TOF): m / z calcd for [( P, P ) / ( M, M )-4] •+ , C 84 H 52 F 12 O 16 S4 •+, 1672.1947, found 1672.1941. ( P, M )-4: 1 1H NMR (400 MHz, CDCl3, 298K) δ 7.80 (d, J = 2.8 Hz, 4H), 7.79 (d, J = 2.2 Hz, 4H), 7.38 (d, J = 8.0 Hz, 4H), 7.34 (t, J = 7.6 Hz, 4H), 7.10 (t, J = 7.5 Hz, 4H), 6.85 (s, 4H), 6.75 (d, J = 4.0 Hz, 8H), 6.69 (s, 4H), 4.01 (d, J = 16.1 Hz, 2H), 3.68 (d, J = 15.9 Hz, 2H), 3.56 (s, 12H). 19 19F NMR (376 MHz, CDCl3, 298K) δ -73.71. 13 13C NMR (101 MHz, CDCl3, 298K) δ 155.97, 149.02, 148.56, 146.38, 141.51, 141.30, 135.90, 132.76, 130.92, 129.11, 128.03, 127.85, 125.21, 124.21, 123.13, 120.17, 119.76, 116.99, 105.02, 65.99, 55.95, 27.75. HRMS (MALDI-TOF): m / z calcd for [( P, M )-4] •+ , C 84 H 52 F 12 O 16 S4 •+ , 1672.1947, found 1672.1941.

[0029]

[0030] Add nickel catalyst, 2, 2`-bipyridine and N-methylpyrrolidone to a 25 mL reaction tube. Heat at 85 °C, add Compound 4, and react for 4 - 12 hours. Cool the reaction to room temperature, extract with dichloromethane and distilled water, dry the organic phase with anhydrous sodium sulfate, concentrate under reduced pressure, and separate by silica gel column chromatography to obtain Compound 5.

[0031] Characterization data of Compound 5: (P, P ) / ( M, M )-5: 1 1H NMR (400 MHz, CDCl3, 298K) δ7.85 (d, J = 8.0 Hz, 4H), 7.82 (d, J = 7.6 Hz, 4H), 7.72 (dd, J = 7.9, 1.1Hz, 4H), 7.32 (t, J = 7.5 Hz, 4H), 7.24 (s, 4H), 7.09 (t, J = 7.5 Hz, 4H),6.93 (s, 8H), 6.84 (d, J = 7.6 Hz, 4H), 3.92 (s, 12H), 3.46 (s, 4H). 13 13C NMR(101 MHz, CDCl3, 298K) δ 156.16, 149.52, 149.44, 141.79, 141.62, 141.25,139.57, 136.48, 129.48, 129.31, 128.61, 127.65, 125.33, 124.13, 120.15,119.81, 103.17, 66.94, 56.09, 36.04. HRMS (MALDI-TOF): m / z calcd for [( P, P ) / ( M, M )-5] •+ , C 80 H 52 O4 •+ , 1076.3866, found 1076.3860. ( P, M )-5: 1 1H NMR (400 MHz,CDCl3, 298K) δ 7.87 (d, J = 8.0 Hz, 4H), 7.80 (d, J = 7.6 Hz, 4H), 7.63 (dd,J = 8.0, 1.5 Hz, 4H), 7.29 (t, J = 7.5 Hz, 4H), 7.24 (s, 4H), 7.13 (d, J =1.2 Hz, 4H), 7.04 (t, J = 7.5 Hz, 4H), 6.92 (s, 4H), 6.78 (d, J = 7.6 Hz,4H), 3.89 (s, 12H), 3.50 – 3.36 (dd, 4H). 13C NMR (101 MHz, CDCl3, 298K) δ155.99, 150.10, 148.71, 142.05, 141.75, 140.71, 139.63, 136.88, 129.77,129.69, 129.50, 127.58, 127.47, 125.24, 123.78, 120.12, 120.07, 103.27,67.18, 56.14, 35.80. HRMS (MALDI-TOF): m / z calcd for [( P, M )-5] •+ , C 80 H 52 O4 •+ ,1076.3866, found 1076.3860. Example

[0032]

[0033] HPLC chiral column separation experimental method: (1) Fluidity selection: Use dichloromethane as the mobile phase and use acetonitrile to adjust the polarity; (2) Filtration: Use a 0.22 μm organic phase filter to remove particulate matter and protect the chromatographic column; (3) Chromatographic column selection: Use dichloromethane as the fluidity, record the peak time, then use acetonitrile to adjust the polarity, and re-pre-experiment to screen the optimal solvent ratio; (4) Column temperature: set to 25°C; (5) Instrument parameter settings: flow rate 1.0 mL / min; detection wavelength: external absorption (commonly used UV detector); (6) Detection and data analysis: resolution (Rs), Rs ≥ 1.5, expansion and splitting; (7) Fraction collection and verification: Fractions were collected by preparative HPLC and retested by HPLC to confirm enantiomeric purity ( Figure 1 ).

[0034] The research results show that: Circular dichroism spectroscopy research results found that ( M, M )-5 and ( P, P )-5 This pair of enantiomers has excellent chirality (attached Figure 2 ); At the same time, the fluorescence spectrum research results show that the pair of enantiomers has strong fluorescence emission ( Figure 3 ). Therefore, this type of new chiral luminescent compound can be used to construct chiral luminescent thin films. Example

[0035] With the (M, M ) - 5 and P, P ) - 5 as raw materials, their transparent solutions were evenly coated on a glass plate, and after natural drying, they were directly tested by a circularly polarized luminescence instrument. The research results show that the films obtained from M, M ) - 5 and P, P ) - 5 all have strong chiral luminescence properties ( Figure 4 ).

Claims

1. Spirofluorene is embedded with macrocyclic aromatic hydrocarbons and conjugated nanorings, characterized in that It has the following structure: (1) Structure of 2,2`-disubstituted-9,9`-spirobifluorene embedded macrocyclic aromatic building blocks ; (2) Structure of 2,2`-disubstituted-9,9`-spirobifluorene-embedded macrocyclic aromatic hydrocarbons ； ； ； (3) Structure of 2,2`-disubstituted-9,9`-spirobifluorene endogenous conjugated nanorings ； Among them: the compounds of (P, P) and (M, M) configurations are a pair of enantiomers; the compound of (P, M)-configuration is a racemate; the -OAc functional group in compounds 1~2 can be replaced by -H (hydrogen), -OR (alkoxy), -OBn (benzyloxy); the methoxy group in compounds 1~5 can be replaced by the solubilizing group -OR (alkoxy), water-soluble groups (carboxylates, sulfonates, ammonium salts, phosphites); the embedded fragment 2,2`-disubstituted-9,9`-spirobifluorene in compounds 1~5 is replaced by the following functional fragments: .

2. The method for synthesizing spirofluorene-embedded macrocyclic aromatic hydrocarbons and conjugated nanorings according to claim 1, characterized in that as follows: Take the synthesis of 2,2`-disubstituted-9,9`-spirobifluorene endonucleated macrocyclic aromatics and conjugated nanorings as an example: ； Among them, the compounds of (P, P) and (M, M) configurations are a pair of enantiomers; the compound of (P, M)-configuration is a mesomorph; OTf is the abbreviation of trifluoromethanesulfonyloxy; the embedded fragment 2,2`-disubstituted-9,9`-spirobifluorene in compound 1 is replaced with the following functional fragments, and the same series of analogs of compounds 2, 3, 4 and 5 can be obtained by the same synthetic route and method; 。 3. The method for synthesizing spirofluorene-embedded macrocyclic aromatic hydrocarbons and conjugated nanorings according to claim 1, characterized in that Take the synthesis of 2,2`-disubstituted-9,9`-spirobifluorene endonucleated macrocyclic aromatics and conjugated nanorings as an example: (1) The synthesis method of 2,2'-disubstituted-9,9'-spirobifluorene endonucleated macrocyclic aromatic hydrocarbon building blocks is as follows: In a round-bottom flask, 5.68 g of 2,2`-disubstituted-9,9`-spirobifluorene diboronic acid di(pinacol ester), 5.12 g of 2-bromo-5-acetoxyanisole, 1.00 g of [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium, 5.25 g of potassium carbonate, 80 mL of 1, 4-dioxane, 20 mL of H2O were added, and the mixture was refluxed at 105 °C for 48 h under argon protection; the solvent was removed under reduced pressure and concentrated, 50 mL of N,N-dimethylformamide, 6.0 mL of pyridine and 4.8 mL of acetyl chloride were added to the reaction system, the mixture was reacted at room temperature for 2 h, water was added to quench the mixture, the mixture was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, mixed with silica gel, and purified by silica gel column chromatography to obtain compound 1 as a white solid; (2) The synthesis method of 2,2'-disubstituted-9,9'-spirobifluorene endonucleated macrocyclic aromatic hydrocarbons is as follows: 320 mg of compound 1, 60 mg of paraformaldehyde, 100 mL of 1,2-dichloroethane were added to a round-bottom flask, and 0.8 mL of boron trifluoride ether was added under stirring. The mixture was reacted at room temperature for 1 h, quenched with saturated sodium bicarbonate solution, extracted with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and separated by silica gel column chromatography to obtain compound 2 as a white solid; In a round-bottom flask, 150 mg of acetoxy-substituted compound 2, 120 mg of sodium hydroxide, 0.3 mL of purified water, and 8 mL of tetrahydrofuran were added, and ultrasonic heating was performed for 2.5 h; the mixture was concentrated under reduced pressure, and separated by silica gel column chromatography to obtain a white solid compound 3; In a round-bottom flask, add 10 mL of compound 3, dichloromethane, 2.0 mL of pyridine and 1.6 mL of trifluoromethanesulfonic anhydride, move to room temperature and react for 1 h; slowly add water to quench, extract with dichloromethane, dry the organic phase with anhydrous sodium sulfate, and separate with silica gel column chromatography to obtain a trifluoromethylsulfonyl ester functionalized biphenyl aromatic macrocycle containing spirofluorene units connected at the 2,2' position, as a white solid compound 4; (3) The synthesis method of 2,2`-disubstituted-9,9`-spirobifluorene endogenous conjugated nanoring is as follows: Add nickel catalyst, 2, 2`-bipyridine and 12 mL N-methylpyrrolidone to the reaction tube, heat to 85°C, add compound 4, and react for 4 to 12 hours; cool the reaction to room temperature, add dichloromethane and distilled water to extract, dry the organic phase with anhydrous sodium sulfate, concentrate under reduced pressure, and separate by silica gel column chromatography to obtain compound 5.

4. Application of the 2,2'-disubstituted-9,9'-spirobifluorene-embedded macrocyclic aromatic hydrocarbons described in claim 1 in constructing novel chiral conjugated nanorings.

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