Asymmetric synthesis method of [4] helicene and optical application of [4] helicene

Abstract

The invention relates to the field of luminescent materials, in particular to a preparation method and application of a helical alkene molecule with unique optical properties. The invention mainly relates to helical alkene molecular compounds as shown in a formula I, a formula II and a formula III. The invention relates to a racemate, a stereoisomer or a tautomer thereof, and a preparation method and application thereof. According to the invention, asymmetric addition reaction catalyzed by chiral phosphoric acid is utilized, raw materials which are simple, cheap and easy to synthesize are used for synthesizing a formula I, a formula II and a formula III under mild conditions, and a preparation method of chiral molecules with unique optical properties is provided. The compound provided by the invention has an expected application prospect in the fields of asymmetric catalysis, luminescent materials and the like. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the fields of organic chemistry and optical materials, and more specifically to a method for the asymmetric synthesis of a [4] helicene molecule and its application value as an optical material. Background Art

[0002] Helicene compounds are a class of non-planar aromatic compounds with spiral chirality and ortho-fusion. They have excellent optical and electrical properties and show good performance in nonlinear optical materials, chiral optical materials, liquid crystal materials, etc. Therefore, the study of the synthesis and properties of helicene compounds has become one of the research hotspots in organic chemistry.

[0003] Luminescent chiral molecules may exhibit circularly polarized luminescence (CPL). CPL refers to the phenomenon in which chiral polarized materials emit left-handed or right-handed circularly polarized light. This fascinating property was first discovered in 1948 in a chiral crystal of sodium uranyl acetate. Samoilov observed circularly polarized luminescence signals from electronic energy level transitions in sodium uranyl acetate crystals in liquid helium, and Oosterhoff first applied circularly polarized luminescence to probe the excited state structure of molecules. Since then, the study of circularly polarized luminescent materials has garnered widespread attention from scientists worldwide. This growing interest is primarily due to three advances: first, the development of CPL spectroscopy between the 1960s and 1980s, the subsequent commercialization of CPL devices from the ultraviolet to the infrared (IR) region, and the opportunities for using chiral molecules in optoelectronics, spintronics, and biology. CP light can be used in organic light-emitting diodes (OLEDs), spintronic lighting, and 3D displays. It can also be used to encode light in anti-counterfeiting systems and provide high sensitivity in CP bioimaging and detection. Circularly polarized light has broad application prospects in quantum optical computing, optical spin electronics, biomedicine, and high-efficiency display.

[0004] Helicenes' remarkable properties offer numerous applications in CPLs, including chiral ligands, chiral dyes, optical switches, and chiral sensors, promising applications. However, the chiral optical response of most helicene molecules is concentrated in the ultraviolet region, limiting their widespread application in these chiral optoelectronic devices. This poses new challenges for helicene design strategies. Through strategies such as π-conjugation extension, construction of multiple helicenes, and heteroatom doping, helicenes with diverse structural characteristics have emerged in recent years, successfully extending their chiral optical response into the visible light region. While boron and nitrogen-doped helicenes have been reported, oxygen-doped examples are relatively rare, with limited applications in optical applications. The patent demonstrates that helicene molecules can effectively hybridize with oxygen atoms, filling a significant gap in current research. Summary of the Invention

[0005] In view of the current research status, the present invention fills the gap in the study of the photoelectric properties of oxygen-hetero and other heteroatom helicene molecules and explores the unknown application potential of their photoelectric effect. This invention provides an asymmetric synthesis method for the preparation of [4] helicene molecules with unique optical properties. The method utilizes an asymmetric addition reaction catalyzed by chiral phosphoric acid. The operation is simple and easy. Starting from simple, cheap and easy-to-synthesize raw materials, the target compound can be synthesized under mild conditions. This provides new opportunities for the research field of heteroatom helicene and the development of luminescent materials.

[0006] The present invention provides compounds of helicene molecules represented by the following formulas I, II, and III, and their racemates, stereoisomers, or tautomers:

[0007]

[0008]

[0009] X1 and X2 can be oxygen atoms, sulfur atoms, amino groups, -OP(O)(OH)2, =CH or -(CH2) n , n is an integer from 0 to 2;

[0010] R1, R2, R3, R4, R5, R6, R7, R8 are the same or different and are independently selected from H, -OH, halogen, -CN, unsubstituted or optionally substituted by one, two or more R a Substituted with the following groups: C 1-40 Alkyl, C 1-40 Alkoxy, -NH2, -OC(O)C 1-40 Alkyl, -OC(O)C 3-20 Cycloalkyl, -OC(O)3-20 membered heterocyclic group, -OC(O)C 6-20 Aryl, -OC(O)5-20 membered heteroaryl, -OP(O)(OH)2;

[0011] Every R a the same or different, independently selected from oxo (=O), -OH, halogen, -CN, -NO2, -NH2, C 1-40 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 aryl or 5-20 membered heteroaryl.

[0012] According to an embodiment of the present invention, the compound of formula I has a structure shown in the following formula I':

[0013]

[0014] The compound of formula II has the structure shown in formula II:

[0015]

[0016] The compound of formula III has the structure shown in the following formula III':

[0017]

[0018] X1 and X2 can be oxygen atoms, sulfur atoms, amino groups, -OP(O)(OH)2, =CH or -(CH2) n , n is an integer from 0 to 2;

[0019] R1, R2, R3, R4, R5, R6, R7, R8 are the same or different and are independently selected from H, -OH, halogen, -CN, the following groups which are unsubstituted or optionally substituted by one, two or more Ra: C 1-40 Alkyl, C 1-40 Alkoxy, -NH2, -OC(O)C 1-40 Alkyl, -OC(O)C 3-20 Cycloalkyl, -OC(O)3-20 membered heterocyclic group, -OC(O)C 6-20 Aryl, -OC(O)5-20 membered heteroaryl, -OP(O)(OH)2;

[0020] Each Ra is the same or different and is independently selected from oxo (=O), -OH, halogen, -CN, -NO2, -NH2, C 1-40 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 aryl or 5-20 membered heteroaryl.

[0021] As an example, the compound of formula I is selected from the following compound M1:

[0022]

[0023] The compound of formula II is selected from the following compound M2:

[0024]

[0025] The compound of formula III is selected from the following compound M3:

[0026]

[0027] The present invention also provides a method for preparing the compounds represented by formula I, II, and III, comprising the following steps:

[0028]

[0029] Preparation of I

[0030]

[0031] Preparation of II

[0032]

[0033] Preparation of III

[0034] Wherein, R1, R2, R3, R4, R5, R6, R7, R8, X1, and X2 have the same definitions as above.

[0035] According to an embodiment of the present invention, the catalyst of the reaction is composed of chiral phosphoric acid, and the amount of the catalyst is 1-100 mol%.

[0036] According to an embodiment of the present invention, the solvent of the reaction can be dichloromethane, chloroform, tetrahydrofuran, methanol, 1,2-dichloroethane, acetonitrile, 1,4-dioxane, ether, ethyl acetate, anisole, toluene, xylene compounds, trifluorotoluene or mesitylene:

[0037] According to an embodiment of the present invention, the reaction temperature for preparation of I is room temperature, the reaction temperature for preparation of II is 0° C., and the reaction temperature for preparation of III is room temperature. The reaction time may be 12 to 72 hours.

[0038] Definitions and Explanations of Terms

[0039] Unless otherwise indicated, the definitions of groups and terms in this specification and claims, including definitions used as examples, exemplary definitions, preferred definitions, definitions in tables, and definitions of specific compounds in the Examples, may be arbitrarily combined and coupled with one another. The resulting group definitions and compound structures shall fall within the scope of the description of this specification.

[0040] "More" means more than three.

[0041] The term "halogen" refers to fluorine, chlorine, bromine and iodine.

[0042] The term "C 1-40 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 40 carbon atoms. For example, "C 1-6The term "alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, or the like or isomers thereof.

[0043] The term "C 3-20 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having 3 to 20 carbon atoms, preferably "C 3-10 Cycloalkyl". The term "C 3-10 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. 3-10 The cycloalkyl group may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring.

[0044] The term "3-20 membered heterocyclyl" refers to a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cyclic alkane, which contains 1-5 heteroatoms independently selected from N, O and S, and a non-aromatic cyclic group with a total ring number of 3-20 (such as 3, 4, 5, 6, 7, 8, 9, 10, etc.), preferably a "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" refers to a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cyclic alkane, which contains 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclyl group can be attached to the rest of the molecule through any of the carbon atoms or the nitrogen atom (if present). In particular, the heterocyclic group may include, but is not limited to, a 4-membered ring such as azetidinyl, oxetanyl; a 5-membered ring such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, such as, but not limited to, a 5,5-membered ring such as hexahydrocyclopenta [c] pyrrole-2 (1H) -yl ring, or a 5,6-membered bicyclic ring such as hexahydropyrrolo [1,2-a] pyrazine-2 (1H) -yl ring. The nitrogen-containing ring may be partially unsaturated, i.e., it may contain one or more double bonds, such as, but not limited to, 2,5-dihydro-1H-pyrrolyl, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolinyl. According to the present invention, the heterocyclic group is non-aromatic. When the 3-20-membered heterocyclic group is linked to other groups to form the compounds of the present invention, the linking may be to a carbon atom of the 3-20-membered heterocyclic group or to a heteroatom on the 3-20-membered heterocyclic group ring. For example, when the 3-20-membered heterocyclic group is selected from piperazinyl, the linking may be to a nitrogen atom on the piperazinyl ring and to a carbon atom in the para position thereof. Alternatively, when the 3-20-membered heterocyclic group is selected from piperidinyl, the linking may be to a nitrogen atom on the piperidinyl ring and to a carbon atom in the para position thereof.

[0045] The term "C 6-20 "Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-14 Aryl". The term "C 6-14 "Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl) such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl”), such as anthracenyl. When the C 6-20 When the aryl group is substituted, it may be monosubstituted or polysubstituted. Furthermore, there is no limitation on the position of substitution, and for example, substitution may be at the ortho, para or meta position.

[0046] The term "5-20 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, for example "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms each independently selected from N, O and S and, in addition, in each case may be benzo-fused. In particular, the heteroaryl group is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and benzo derivatives thereof, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or acininyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like. When the 5-20 membered heteroaryl group is linked to other groups to form the compound of the present invention, the linking may be to a carbon atom on the 5-20 membered heteroaryl ring or to a heteroatom on the 5-20 membered heteroaryl ring. When the 5-20 membered heteroaryl group is substituted, it may be monosubstituted or polysubstituted. Furthermore, there is no limitation on the substitution site; for example, a hydrogen atom linked to a carbon atom on the heteroaryl ring may be substituted, or a hydrogen atom linked to a heteroatom on the heteroaryl ring may be substituted.

[0047] Unless otherwise specified, a heterocyclic group, heteroaryl group, or heteroarylene group includes all possible isomeric forms thereof, such as positional isomers thereof. Thus, for some illustrative non-limiting examples, the following may be substituted or bonded to other groups at one, two, or more positions of the 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-position, etc. (if present): pyridin-2-yl, pyridin-2-ylene, pyridin-3-yl, pyridin-3-ylene, pyridin-4-ylene, and pyridin-4-ylene; thienyl or thienylene group includes thien-2-yl, thien-2-ylene, thien-3-ylene, and thien-3-ylene; pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, and pyrazol-5-yl.

[0048] Unless otherwise stated, the definitions of terms herein also apply to groups containing the term, e.g. 1-40 The definition of alkyl also applies to C 1-40 Alkoxy, etc.

[0049] Beneficial effects

[0050] Compared with the prior art, the advantages and positive effects of the present invention are:

[0051] The present invention successfully prepares [4] helicene molecules with circularly polarized luminescence effect. The preparation process is simple and has the following advantages:

[0052] First, the method disclosed in the present invention for preparing oxahelicene molecules with circularly polarized luminescence properties has cheap raw materials, is very easy to master the synthesis method, has mild reaction conditions, most processes only require room temperature, and the product yield is high.

[0053] Second, the helicene molecules provided by the present invention have the characteristics of high racemization energy barrier and good stability, and have good application prospects in the field of chiral optoelectronic materials.

[0054] Third, the molecules prepared by the present invention are easy to derivatize and can be expanded to different substrates. They all have good CPL activity, which is conducive to subsequent research in the field of [4] helicene molecules and heteroatom helicene molecules. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] The present invention will be further described below with reference to the accompanying drawings and embodiments, in which:

[0056] Figure 1 This is the ultraviolet spectrum of the dichloromethane solution of the product of specific embodiment 4 of the present invention;

[0057] Figure 2 This is the fluorescence spectrum of the product of specific example 4 of the present invention in dichloromethane solution;

[0058] Figure 3This is the circular dichroism spectrum of the product of specific example 4 of the present invention in dichloromethane solution;

[0059] Figure 4 is the asymmetric absorption factor of the product of specific embodiment 4 of the present invention in dichloromethane solution. DETAILED DESCRIPTION

[0060] To make the objectives, technical solutions, and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the examples described herein are only some embodiments of the present invention, rather than all embodiments. All other embodiments obtained by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0061] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0062] Example 1: Preparation of chiral compound M1

[0063]

[0064] The asymmetric addition reaction of 1,3-dimethyl-6H-naphtho[2,1-c]chromen-11-ol and (E)N-(2,5-dichloro-4-oxocyclohexa-2,5-dien-1-ylidene)-4-methylbenzenesulfonamide was catalyzed by CPA at room temperature, according to the reaction equation above. The substrate and chiral phosphoric acid were added to a reaction flask, followed by toluene. The mixture was stirred at room temperature for 12 hours and monitored by thin-layer chromatography. After completion of the reaction, column chromatography was performed directly using petroleum ether and ethyl acetate as the mobile phases, yielding the product in 78% yield and 98% enantioselectivity.

[0065] Compound characterization:

[0066] 1H-NMR (400MHz, CDCl3) δ7.69 (d, J=8.8Hz, 1H), 7.53 (d, J=7.9Hz, 1H), 7.28 (s, 1H), 7.25 (d, J=8.2Hz, 2H), 7.10-6.99 (m, 2H), 6.87 (d, J=8.0Hz, 2 H), 6.39 (s, 1H), 6.24 (s, 1H), 6.17 (s, 1H), 5.90 (s, 2H), 4.79 (d, J=13.2 Hz, 1H), 4.47 (d, J=13.2Hz, 1H), 2.06 (s, 3H), 1.98 (s, 3H), 1.52 (s, 3H). 13 C-NMR (101MHz, CDCl3) δ156.45, 152.76, 146.36, 144.18, 138.72, 138.33, 135.81, 135.26, 132.52, 130.65, 129.82, 129.58, 127.94, 127.65, 1 27.50, 127.16, 127.09, 123.68, 123.61, 122.61, 122.25, 120.30, 119.82, 118.17, 113.57, 112.60, 71.11, 21.51, 21.17, 20.55.HRMS(El)calcd for C 32 H 25 Cl2NO5SNa + [M+Na + ]: 628.0723, found: 628.0722.

[0067] Example 2: Preparation of chiral compound M2

[0068]

[0069] The asymmetric addition reaction of 1,3-dimethyl-6H-naphtho[2,1-c]chromen-11-ol and methyl3,6-dioxocyclohexa-1,4-diene-1-carboxylate was catalyzed by CPA at room temperature, according to the reaction equation above. The substrate and chiral phosphoric acid were added to a reaction flask, followed by dichloromethane as the solvent. The mixture was stirred at 0°C for 12 hours and monitored by thin-layer chromatography. After completion of the reaction, column chromatography was performed directly using petroleum ether and ethyl acetate as the mobile phases, yielding the product in 80% yield and 94% enantioselectivity.

[0070] Compound characterization:

[0071] 1H NMR (400MHz, DMSO-d6) δ9.89 (s, 1H), 7.89 (d, J = 9.0Hz, 1H), 7.71 (d, J = 8.0Hz, 1H), 7.2 5 (d, J=8.0Hz, 1H), 7.16 (d, J=8.9Hz, 1H), 6.94 (d, J=10.1Hzz1H), 6.66 (s, 1H), 6.62 (d , J=10.2Hz, 1H), 6.40 (s, 1H), 5.12 (d, J=13.6Hz, 1H), 4.61 (d, J=13.6Hz, 1H), 4.11 (p, J=6.2Hz, 1H), 2.16 (s, 3H), 1.58 (s, 3H), 0.51 (d, J=6.3Hz, 3H), 0.43 (d, J=6.3Hz, 3H). 13 C NMR (101MHz, DMSO-d6) δ184.04, 183.36, 161.73, 157.85, 155.63, 143.90, 138.69, 138.02, 136.31, 133.87, 133.49, 131.94, 130.89, 129.53,127.41,126.72,125.61,125.40,119.65,118.07,115.21,110.43,70.29,68.64,21.73,21.24,21.00,20.96.HRMS(EI)calcd for C 29 H 25 O6Na + [M+Na + ]: 491.1465, found: 491.1460.

[0072] Example 3: Preparation of Chiral Compound M3

[0073]

[0074] The reductive hydrogenation reaction of M2 was catalyzed by Pd / C at room temperature, according to the reaction equation above. M2 was dissolved in tetrahydrofuran and then added to Pd / C. The reaction was allowed to proceed under a H2 atmosphere at room temperature for 12 hours, monitored by thin-layer chromatography. After completion of the reaction, column chromatography was performed directly using petroleum ether and ethyl acetate as the mobile phases, yielding the product in 95% yield and 98% enantioselectivity.

[0075] NMR characterization

[0076] 1H NMR (400MHz, DMSO-d6) δ9.65 (s, 1H), 9.38 (s, 1H), 8.77 (s, 1H), 7.86 (d, J=8.9Hz, 1H), 7.73 ( d, J=8.0Hz, 1H), 7.24 (d, J=8.9Hz, 1H), 7.20 (d, J=7.9Hz, 1H), 6.87 (d, J=8.9Hz, 1H), 6.52 (d , J=8.8Hz, 1H), 6.45 (s, 1H), 5.85 (s, 1H), 4.93 (d, J=13.4Hz, 1H), 4.48 (d, J=13.4Hz, 1H), 4. 10 (p, J=6.3Hz, 1H), 2.11 (s, 3H), 1.69 (s, 3H), 0.41 (d, J=6.3Hz, 3H), -0.01 (d, J=6.1Hz, 3H).

[0077] 13 C NMR (151MHz, DMSO-d6) δ168.83, 156.27, 153.73, 153.71, 148.10, 139.36, 136.19, 133.86, 132.51, 130.44, 130.25, 127.82, 125.91, 124.77,124.25,123.10,119.21,118.16,117.61,116.76,114.87,112.36,70.66,67.84,21.41,21.34,21.18,19.98.HRMS(EI)calcd for C 29 H 27 O6 + [M+H + ]: 471.1802, found: 471.1805.

[0078] Example 4: Testing of Luminescent Properties of Chiral Compounds

[0079] The luminescence properties of compounds M1a, M2a, and M3a are now tested.

[0080] The structure of M1a is:

[0081]

[0082] The structure of M2a is:

[0083]

[0084] The structure of M3a is:

[0085]

[0086] The target product was prepared to a concentration of 2x10 -5 M in dichloromethane solution, and then measured the changes in UV spectrum, fluorescence spectrum and circular dichroism spectrum over time. The UV spectrum of the sample shows that the intensity of UV absorption first increases and then decreases with the illumination. M1a has absorption signals near 245nm and 352nm, M2a has absorption signals near 249nm and 351nm, and M3a has absorption signals near 246nm and 346nm. The relative positions of the signals are not much different, and their signal intensities decrease one by one ( Figure 1 The fluorescence spectra of the samples show that the intensity of fluorescence emission first increases and then decreases with illumination. In pure dichloromethane solution, the maximum emission wavelengths of M1a are around 410nm and 433nm, the maximum emission wavelength of M2a is around 412nm, and the maximum emission wavelength of M3a is around 469nm. The absorption peaks are blue-shifted ( Figure 2 The circular dichroism spectra of the samples showed that the asymmetric absorption signals of the samples gradually weakened with illumination. M1a showed negative signals at 256nm and 291nm, with asymmetry factors of 0.0035 and 0.0043, respectively. M2a showed negative signals at 271nm, with asymmetry factors of 0.0063. M3a showed negative signals at 246nm and 268nm, with asymmetry factors of 0.0021 and 0.0050, respectively. There were significant differences in their signal intensities ( Figure 3 Finally, the asymmetry factor diagram of the circular dichroism spectrum is attached ( Figure 4 ).

[0087] The above is an exemplary description of the embodiments of the present invention. However, the scope of protection of the present invention is not limited to the above specific embodiments. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A compound represented by Formula I, Formula II or Formula III, or a racemate, stereoisomer or tautomer thereof: in, X1 and X2 can be oxygen atoms, sulfur atoms, amino groups, -OP(O)(OH)2, =CH or -(CH2) n , n is an integer from 0 to 2; R1, R2, R3, R4, R5, R6, R7, R8 are the same or different and are independently selected from H, -OH, halogen, -CN, unsubstituted or optionally substituted by one, two or more R a Substituted with the following groups: C 1-40 Alkyl, C 1-40 Alkoxy, -NH2, -OC(O)C 1-40 Alkyl, -OC(O)C 3-20 Cycloalkyl, -OC(O)3-20 membered heterocyclic group, -OC(O)C 6-20 Aryl, -OC(O)5-20 membered heteroaryl, -OP(O)(OH)2; Every R a The same or different, independently selected from oxo (=O), imino (=NR), -OH, halogen, -CN, -NO2, -NH2, C 1-40 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 aryl or 5-20 membered heteroaryl.

2. The compound according to claim 1, characterized in that The compound of formula I has the structure shown in formula I' The compound of formula II has the structure shown in formula II' The compound of formula III has the structure shown in the following formula III' Wherein, X1 and X2 can be oxygen atoms, sulfur atoms, amino groups, -OP(O)(OH)2, =CH or -(CH2) n , n is an integer from 0 to 2; R1, R2, R3, R4, R5, R6, R7, R8, R9 are the same or different and are independently selected from H, -OH, halogen, -CN, unsubstituted or optionally substituted by one, two or more R a Substituted with the following groups: C 1-40 Alkyl, C 1-40 Alkoxy, -NH2, -OC(O)C 1-40 Alkyl, -OC(O)C 3-20 Cycloalkyl, -OC(O)3-20 membered heterocyclic group, -OC(O)C 6-20 Aryl, -OC(O)5-20 membered heteroaryl, -OP(O)(OH)2; Every R a the same or different, independently selected from oxo (=O), -OH, halogen, -CN, -NO2, -NH2, C 1-40 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic group, C 6-20 aryl or 5-20 membered heteroaryl.

3. The compound according to claim 1 or 2, characterized in that The compound of formula I is selected from the following compound M1: The compound of formula II is selected from the following compound M2: The compound of formula III is selected from the following compound M3:

4. The method for preparing the compound according to any one of claims 1 to 3, characterized in that: The steps include: Wherein, R1, R2, R3, R4, R5, R6, R7, R8, X1 and X2 have the definitions as described in any one of claims 1 to 3.

5. The method according to claim 4, characterized in that The reaction is to catalyze the asymmetric addition reaction of condensed ring phenol and quinone compound; the catalyst of the reaction is chiral phosphoric acid, and the amount of the catalyst is 1-100 mol%.

6. The method of claim 4, wherein the catalytic asymmetric addition reaction of condensed ring phenol and quinone compound is characterized in that: To prepare compound I or II, add the fused phenol, quinone, and chiral phosphoric acid to a reaction flask, followed by solvent. Stir at room temperature or 0°C, and monitor the reaction by thin-layer chromatography. To prepare compound III, dissolve compound II in tetrahydrofuran and add palladium / carbon. React at room temperature under a H2 atmosphere for 12 hours, and monitor the reaction by thin-layer chromatography.

7. A compound having asymmetric circularly polarized luminescence, characterized in that The invention comprises at least one of the compound according to any one of claims 1 to 3, or its racemate, stereoisomer or tautomer.

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