Chiral carbon nanoring molecule as well as preparation method and application thereof

Abstract

The invention provides a chiral carbon nano ring molecule as well as a preparation method and application thereof. The chiral carbon nano ring molecule comprises a Dn-NR1 compound and a Dn-NR2 compound. The chiral carbon nanoring molecule provided by the invention has a radial annular conjugated system, has good circular polarization luminescence performance, has circular polarization luminescence asymmetric factors exceeding 10 <-2 >, is suitable for the field of luminescent devices or 3D display, and has excellent comprehensive performance; the preparation method of the chiral carbon nanoring molecule provided by the invention is simple and convenient, and has the characteristics of high optical purity, single configuration and no need of chiral high performance liquid chromatography resolution.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and in particular relates to a chiral carbon nanoring molecule and a preparation method and application thereof. Background Art

[0002] Carbon nanorings refer to cyclic conjugated molecules formed by multiple independent benzene rings or aromatic compounds with a higher degree of conjugation as monomers, with the monomers connected by C-C single bonds. Since the ring structure can be opened by opening only one C-C single bond, carbon nanorings are also considered to be fragments of carbon nanotubes.

[0003] As an aromatic hydrocarbon with unique cyclic conjugation and tunable optoelectronic properties, carbon nanorings exhibit excellent optical and electronic behaviors due to the lack of chain end effects, high symmetry and strain, which gives them great application potential in the field of organic electronics. The adjustable size and topology give nanorings nano-quantum size effects, showing properties different from conventional materials in the fields of optics and electricity. Some carbon nanorings also exhibit chiral optical properties, and their chirality comes from sp 2 The different helical arrangements of hybrid carbon atoms give them excellent photophysical properties or functions, such as circular dichroism (CD) and circularly polarized luminescence (CPL). The unique cylindrical helical conjugation system makes carbon nanorings exhibit a high luminescence asymmetry factor, making them excellent optical functional materials with CPL activity, with great application value in fields such as organic optoelectronic materials.

[0004] In the existing technology, multiple isomers coexist during the synthesis of chiral carbon nanorings, and a single chirality cannot be controlled. Subsequent chiral HPLC separation is required to obtain optically pure chiral macrocycles. This causes chiral carbon nanorings to face problems such as difficult separation, complex operation, and high cost.

[0005] Therefore, developing a method for preparing chiral carbon nanorings with a single chiral configuration, high optical purity, and no need for chiral high-performance liquid chromatography separation is a technical problem that needs to be urgently solved in this field. Summary of the Invention

[0006] In view of the shortcomings of the existing technology, the present invention provides a chiral carbon nanoring molecule and its preparation method and application. The carbon nanoring molecule has a radial cyclic conjugated system and has good circularly polarized luminescence performance. The circularly polarized luminescence asymmetry factor is greater than 10. -2 , suitable for light-emitting devices or 3D display fields, with excellent comprehensive performance.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a chiral carbon nanoring molecule, which includes Dn-NR1 compounds and Dn-NR2 compounds;

[0009] The Dn-NR1 compounds include the following compounds:

[0010]

[0011] The Dn-NR2 compounds include the following compounds:

[0012]

[0013] Wherein, m are each independently an integer between 8 and 12, for example, can be 8, 9, 10, 11 or 12.

[0014] n are each independently an integer between 2 and 5, for example, can be 2, 3, 4 or 5.

[0015] The arc represents a single bond.

[0016] It should be noted that in the numbering of the chiral carbon nanoring molecules provided by the present invention, D n represents the symmetry of the cyclic molecule, and "n" in D n represents the number of repeating units of the cyclic molecule. P and M are helical chiral configurations. NR1 represents that the chiral carbon nanoring molecule has a lactam structure, and NR2 represents that the chiral carbon nanoring molecule has a carbazole structure. For example, the compound D3-(P)-NR2 indicates that the chiral carbon nanoring molecule has cyclic molecule symmetry, there are 3 repeating units in the molecular structure, and it has a P-type helical chiral configuration, and at the same time, the molecule contains a carbazole structure.

[0017] The chiral carbon nanoring molecules in the present invention have a definite chiral configuration, are not easily flipped to cause racemization, and have a radial cyclic conjugated system. The high symmetry makes the chiral carbon nanoring molecules in the present invention have a high circularly polarized luminescence asymmetry factor, and thus have good circularly polarized luminescence performance. The comprehensive performance is excellent. As a good circularly polarized luminescence material, it shows broad application prospects in the fields of circularly polarized detection, encrypted transmission, etc. Moreover, the preparation method of the chiral carbon nanoring molecules provided by the present invention is simple and convenient, and has the characteristics of high optical purity, single configuration, and no need for chiral high performance liquid chromatography separation.

[0018] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved.

[0019] Preferably, the chiral carbon nanoring molecule includes the following compounds:

[0020]

[0021]

[0022] Among them, the arc represents a single bond (the same below).

[0023] Second, the present invention provides a method for preparing a chiral carbon nanoring molecule as described in the first aspect. The method for preparing the Dn-NR1 compound includes the following steps:

[0024] S1. Starting material 1 reacts with 2-bromo-5-phenoxybenzoyl chloride to obtain intermediate I;

[0025] S2. Intermediate I reacts with bis(1,5-cyclooctadiene)nickel to obtain intermediate II;

[0026] S3. Intermediate II reacts with ammonium formate to obtain intermediate III;

[0027] S4. Intermediate III reacts with trifluoromethanesulfonic anhydride to obtain intermediate IV;

[0028] S5. Intermediate IV reacts with bis(pinacolato)diboron to obtain intermediate V;

[0029] S6. Intermediate V reacts with platinum(Ⅱ) dichloride(1,5-cyclooctadiene) to obtain intermediate VI;

[0030] S7. Intermediate VI reacts with triphenylphosphine to obtain the Dn-NR1 compound;

[0031] Among them, starting material 1 is

[0032] m are each independently any integer between 8 and 12, for example, it can be 8, 9, 10, 11 or 12.

[0033] It should be noted that due to the different specific structural configurations, when reacting with the same compound, the structures of the obtained intermediates and the final products will also be different.

[0034] Specifically, when starting material 1 is the obtained intermediate I is intermediate II is intermediate III is intermediate IV is intermediate V is intermediate VI is the finally obtained Dn-NR1 compound is Its specific reaction process is as follows:

[0035]

[0036] Each m is independently an integer between 8 and 12 (m can be 8, 9, 10, 11, or 12); each n is independently an integer between 2 and 5 (n can be 2, 3, 4, or 5).

[0037] -OTf represents a trifluoromethanesulfonate group, -Bpin represents a pinacol borate group, and -COD represents a 1,5-cyclooctadiene group.

[0038] When the starting material 1 is the obtained intermediate I is Intermediate II is Intermediate III is Intermediate IV is Intermediate V is Intermediate VI is The finally obtained Dn-NR1 compound is The specific reaction process is as follows:

[0039]

[0040] Each m is independently an integer between 8 and 12 (m can be 8, 9, 10, 11, or 12); each n is independently an integer between 2 and 5 (n can be 2, 3, 4, or 5).

[0041] -OTf represents a trifluoromethanesulfonate group, -Bpin represents a pinacol borate group, and -COD represents a 1,5-cyclooctadiene group.

[0042] The preparation method of the Dn-NR2 compound includes the following steps:

[0043] (1) The starting material 2 reacts with 3-chloro-2-fluorophenylboronic acid to obtain intermediate A;

[0044] (2) Intermediate A reacts with potassium tert-butoxide to obtain intermediate B;

[0045] (3) Intermediate B reacts with bis(pinacolato)diboron to obtain intermediate C;

[0046] (4) Intermediate C reacts with dichlorobis(1,5-cyclooctadiene)platinum(II) to obtain intermediate D;

[0047] (5) Intermediate D reacts with triphenylphosphine to obtain the Dn-NR2 compound;

[0048] Wherein, the starting material 2 is selected from

[0049] Each m is independently any integer between 8 and 12, for example, it can be 8, 9, 10, 11, or 12.

[0050] It should be noted that due to The specific structural configuration of the product is different, and when reacting with the same compound, the structures of the intermediates and final products obtained will also be different.

[0051] When the starting material 2 is When the intermediate A is obtained Intermediate B is Intermediate C is Intermediate D is The final Dn-NR2 compound obtained is The specific reaction process is as follows:

[0052]

[0053] m is each independently an integer between 8 and 12 (m may be 8, 9, 10, 11 or 12); n is each independently an integer between 2 and 5 (n may be 2, 3, 4 or 5).

[0054] -OTf represents a trifluoromethanesulfonic acid group, -Bpin represents a pinacol borate group, and -COD represents a 1,5-cyclooctadiene group.

[0055] When the starting material 2 is When the intermediate A is obtained Intermediate B is Intermediate C is Intermediate D is The final Dn-NR2 compound obtained is The specific reaction process is as follows:

[0056]

[0057] m is each independently an integer between 8 and 12 (m may be 8, 9, 10, 11 or 12); n is each independently an integer between 2 and 5 (n may be 2, 3, 4 or 5).

[0058] -OTf represents a trifluoromethanesulfonic acid group, -Bpin represents a pinacol borate group, and -COD represents a 1,5-cyclooctadiene group.

[0059] The present invention introduces starting materials 1 and 2 with determined chiral configurations, first synthesizes linear molecules with determined chiral configurations as macrocyclic precursors, and then obtains optically pure chiral carbon nanoring molecules through a Pt-mediated macrocyclization reaction. The preparation method of the chiral carbon nanoring molecules provided by the present invention is simple and convenient, has high optical purity, a single configuration, and does not require chiral high-performance liquid chromatography separation.

[0060] Preferably, step S1 is carried out in solvent A.

[0061] Preferably, the solvent A includes tetrahydrofuran and / or dichloromethane.

[0062] Preferably, in step S1, the molar ratio of the starting material 1 to 2-bromo-5-phenoxybenzoyl chloride is 1:(2.5 - 4), for example, it can be 1:2.5, 1:3 or 1:4, etc.

[0063] Preferably, in step S1, the reaction is carried out in the presence of basic substance A.

[0064] Preferably, the basic substance A includes triethylamine.

[0065] Preferably, the molar ratio of the basic substance A to the starting material 1 is 1:(8 - 15), for example, it can be 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14 or 1:15, etc.

[0066] Preferably, in step S1, the reaction is carried out under a protective gas.

[0067] Preferably, the protective gas includes nitrogen and / or argon.

[0068] Preferably, in step S1, the reaction temperature is 60 - 80 °C (for example, it can be 60 °C, 65 °C, 70 °C, 75 °C or 80 °C, etc.), and the time is 1-2 h (for example, it can be 1 h, 1.5 h or 2 h, etc.).

[0069] Preferably, step S2 is carried out in solvent B.

[0070] Preferably, the solvent B includes tetrahydrofuran.

[0071] Preferably, in step S2, the molar ratio of the intermediate I to bis(1,5-cyclooctadiene)nickel is 1:(6 - 10), for example, it can be 1:6, 1:7, 1:8, 1:9 or 1:10, etc.

[0072] Preferably, in step S2, the reaction is carried out in the presence of a pyridine compound.

[0073] Preferably, the pyridine compound includes 2,2'-bipyridine and / or 4,4’,6,6’-tetramethyl-2,2’-bipyridine.

[0074] Preferably, in step S2, the molar ratio of the intermediate I to the pyridine compound is 1:(6 - 10), for example, it can be 1:6, 1:7, 1:8, 1:9 or 1:10, etc.

[0075] Preferably, in step S2, the reaction is carried out under a protective gas.

[0076] Preferably, the protective gas includes nitrogen and / or argon.

[0077] Preferably, in step S2, the temperature of the reaction is 60 - 80 °C (for example, it can be 60 °C, 65 °C, 70 °C, 75 °C or 80 °C, etc.), and the time is 1 - 2 h (for example, it can be 1 h, 1.5 h or 2 h, etc.).

[0078] Preferably, step S3 is carried out in solvent C.

[0079] Preferably, the solvent C includes ethyl acetate and alcohols.

[0080] Preferably, the alcohols include methanol or ethanol.

[0081] Preferably, in step S3, the molar ratio of intermediate II to ammonium formate is 1:(5 - 10), for example, it can be 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc.

[0082] Preferably, in step S3, the reaction is carried out in the presence of catalyst A.

[0083] Preferably, the catalyst A includes palladium.

[0084] Preferably, the molar ratio of catalyst A to intermediate II is (1 - 5):1, for example, it can be 1:1, 2:1, 3:1, 4:1 or 5:1, etc.

[0085] Preferably, in step S3, the temperature of the reaction is 65 - 85 °C (for example, it can be 65 °C, 70 °C, 75 °C, 80 °C or 85 °C, etc.), and the time is 1.5 - 2.5 h (for example, it can be 1.5 h, 2 h or 2.5 h, etc.).

[0086] Preferably, step S4 is carried out in solvent D.

[0087] Preferably, the solvent D includes dichloromethane and / or chloroform.

[0088] Preferably, in step S4, the molar ratio of intermediate III to trifluoromethanesulfonic anhydride is 1:(5 - 10), for example, it can be 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc.

[0089] Preferably, in step S4, the reaction is carried out in the presence of basic substance B.

[0090] Preferably, the basic substance B includes pyridine.

[0091] Preferably, the molar ratio of the basic substance B to intermediate III is (4 - 10):1, and can be, for example, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc.

[0092] Preferably, in step S4, the reaction is carried out under a protective gas.

[0093] Preferably, the protective gas includes nitrogen and / or argon.

[0094] Preferably, in step S4, the reaction temperature is 20 - 30 °C (which can be, for example, 20 °C, 22 °C, 24 °C, 26 °C, 28 °C or 30 °C, etc.), and the time is 1 - 2 h (which can be, for example, 1 h, 1.5 h or 2 h, etc.).

[0095] Preferably, step S5 is carried out in solvent E.

[0096] Preferably, the solvent E includes 1,4 - dioxane.

[0097] Preferably, in step S5, the molar ratio of intermediate IV to bis(pinacolato)diboron is 1:(4 - 6), and can be, for example, 1:4, 1:5 or 1:6, etc.

[0098] Preferably, in step S5, the reaction is carried out in the presence of catalyst B.

[0099] Preferably, the catalyst B includes palladium acetate and 2 - dicyclohexylphosphino - 2',6' - dimethoxy - 1,1' - biphenyl.

[0100] Preferably, the molar ratio of palladium acetate to 2 - dicyclohexylphosphino - 2',6' - dimethoxy - 1,1' - biphenyl is 1:(1 - 3), and can be, for example, 1:1, 1:2 or 1:3, etc.

[0101] Preferably, the molar ratio of catalyst B to intermediate IV is 1:(0.05 - 0.1), and can be, for example, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09 or 1:0.10, etc.

[0102] Preferably, in step S5, the reaction is carried out in the presence of basic substance C.

[0103] Preferably, the basic substance C includes any one or a combination of at least two of potassium acetate, potassium carbonate or cesium carbonate.

[0104] Preferably, the mass ratio of the basic substance C to intermediate IV is (5 - 10):1, and can be, for example, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc.

[0105] Preferably, in step S5, the reaction is carried out under a protective gas.

[0106] Preferably, the protective gas includes nitrogen and / or argon.

[0107] Preferably, in step S5, the temperature of the reaction is 80 - 90 °C (for example, it can be 80 °C, 82 °C, 84 °C, 86 °C, 88 °C or 90 °C, etc.), and the time is 1.5 - 2.5 h (for example, it can be 1.5 h, 2 h or 2.5 h, etc.).

[0108] Preferably, step S6 is carried out in solvent F.

[0109] Preferably, the solvent F includes 1,2 - dichloroethane.

[0110] Preferably, in step S6, the molar ratio of intermediate V to platinum(IV) chloride cyclooctadiene is 1:(1 - 1.05), for example, it can be 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04 or 1:1.05, etc.

[0111] Preferably, in step S6, the reaction is carried out in the presence of a fluoride.

[0112] Preferably, the fluoride includes cesium fluoride.

[0113] Preferably, the molar ratio of the fluoride to intermediate V is (4 - 8):1, for example, it can be 4:1, 5:1, 6:1, 7:1 or 8:1, etc.

[0114] Preferably, in step S6, the reaction is carried out under a protective gas.

[0115] Preferably, the protective gas includes nitrogen and / or argon.

[0116] Preferably, in step S6, the temperature of the reaction is 70 - 85 °C (for example, it can be 70 °C, 75 °C, 80 °C or 85 °C, etc.), and the time is 24 - 36 h (for example, it can be 24 h, 26 h, 28 h, 30 h, 32 h, 34 h or 36 h, etc.).

[0117] Preferably, step S7 is carried out in solvent G.

[0118] Preferably, the solvent G includes toluene and / or 1,2 - dichlorobenzene.

[0119] Preferably, in step S7, the molar ratio of intermediate VI to triphenylphosphine is 1:(10 - 20), for example, it can be 1:10, 1:12, 1:14, 1:16, 1:18 or 1:20, etc.

[0120] Preferably, in step S7, the reaction is carried out under a protective gas.

[0121] Preferably, the protective gas includes nitrogen and / or argon.

[0122] Preferably, in step S7, the temperature of the reaction is 100 - 115 °C (for example, it can be 100 °C, 103 °C, 106 °C, 109 °C, 112 °C or 115 °C, etc.), and the time is 1.5 - 2.5 h (for example, it can be 1.5 h, 2 h or 2.5 h, etc.).

[0123] Preferably, step (1) is carried out in solvent H.

[0124] Preferably, the solvent H includes water and an organic solvent.

[0125] Preferably, the organic solvent includes tetrahydrofuran or toluene.

[0126] Preferably, in step (1), the molar ratio of starting material 2 to 3-chloro-2-fluorophenylboronic acid is 1:(3 - 5), for example, it can be 1:3, 1:4 or 1:5, etc.

[0127] Preferably, in step (1), the reaction is carried out in the presence of catalyst C.

[0128] Preferably, the catalyst C includes tetrakis(triphenylphosphine)palladium and / or palladium acetate.

[0129] Preferably, the molar ratio of catalyst C to starting material 2 is (0.01 - 0.1):1, for example, it can be 0.01:1, 0.02:1, 0.04:1, 0.06:1, 0.08:1 or 0.1:1, etc.

[0130] Preferably, in step (1), the reaction is carried out in the presence of basic substance D.

[0131] Preferably, the basic substance D includes potassium carbonate and / or potassium acetate.

[0132] Preferably, the molar ratio of basic substance D to starting material 2 is (5 - 10):1, for example, it can be 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc.

[0133] Preferably, in step (1), the reaction is carried out under a protective gas.

[0134] Preferably, the protective gas includes nitrogen and / or argon.

[0135] Preferably, in step (1), the temperature of the reaction is 60-80 °C (for example, it can be 60 °C, 65 °C, 70 °C, 75 °C or 80 °C, etc.), and the time is 20-28 h (for example, it can be 20 h, 22 h, 24 h, 26 h or 28 h, etc.).

[0136] Preferably, step (2) is carried out in solvent I.

[0137] Preferably, the solvent I includes N,N-dimethylformamide.

[0138] Preferably, in step (2), the molar ratio of the intermediate A to potassium tert-butoxide is 1:(3-5), for example, it can be 1:3, 1:4 or 1:5, etc.

[0139] Preferably, in step (2), the reaction is carried out under a protective gas.

[0140] Preferably, the protective gas includes nitrogen and / or argon.

[0141] Preferably, in step (2), the temperature of the reaction is 75-85 °C (for example, it can be 75 °C, 77 °C, 79 °C, 81 °C, 83 °C or 85 °C, etc.), and the time is 10-30 min (for example, it can be 10 min, 15 min, 20 min, 25 min or 30 min, etc.).

[0142] Preferably, step (3) is carried out in solvent J.

[0143] Preferably, the solvent J includes 1,4-dioxane.

[0144] Preferably, in step (3), the molar ratio of the intermediate B to bis(pinacolato)diboron is 1:(4-6), for example, it can be 1:4, 1:5 or 1:6, etc.

[0145] Preferably, in step (3), the reaction is carried out in the presence of catalyst D.

[0146] Preferably, the catalyst D includes palladium acetate and 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl.

[0147] Preferably, the molar ratio of palladium acetate to 2-dicyclohexylphosphino-2',6'-dimethoxy-1,1'-biphenyl is 1:(1-3), for example, it can be 1:1, 1:2 or 1:3, etc.

[0148] Preferably, the molar ratio of the catalyst D to the intermediate B is (0.1-0.5):1, for example, it can be 0.1:1, 0.2:1, 0.3:1, 0.4:1 or 0.5:1, etc.

[0149] Preferably, in step (3), the reaction is carried out in the presence of a basic substance E.

[0150] Preferably, the basic substance E includes any one or a combination of at least two of potassium acetate, potassium carbonate or cesium carbonate.

[0151] Preferably, the molar ratio of the basic substance E to intermediate B is (5-10):1, for example, it can be 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc.

[0152] Preferably, in step (3), the reaction is carried out under a protective gas.

[0153] Preferably, the protective gas includes nitrogen and / or argon.

[0154] Preferably, in step (3), the temperature of the reaction is 80-90 °C (for example, it can be 80 °C, 82 °C, 84 °C, 86 °C, 88 °C or 90 °C, etc.), and the time is 1.5-2.5 h (for example, it can be 1.5 h, 2 h or 2.5 h, etc.).

[0155] Preferably, step (4) is carried out in solvent K.

[0156] Preferably, the solvent K includes 1,2-dichloroethane.

[0157] Preferably, in step (4), the molar ratio of intermediate C to platinum(IV) chloride cyclooctadiene is 1:(1-1.05), for example, it can be 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04 or 1:1.05, etc.

[0158] Preferably, in step (4), the reaction is carried out in the presence of a fluoride.

[0159] Preferably, the fluoride includes cesium fluoride.

[0160] Preferably, the molar ratio of the fluoride to intermediate C is (6-10):1, for example, it can be 6:1, 7:1, 8:1, 9:1 or 10:1, etc.

[0161] Preferably, in step (4), the reaction is carried out under a protective gas.

[0162] Preferably, the protective gas includes nitrogen and / or argon.

[0163] Preferably, in step (4), the temperature of the reaction is 70-85 °C (for example, it can be 70 °C, 75 °C, 80 °C or 85 °C, etc.), and the time is 24-36 h (for example, it can be 24 h, 26 h, 28 h, 30 h, 32 h, 34 h or 36 h, etc.).

[0164] Preferably, step (5) is carried out in solvent L.

[0165] Preferably, the solvent L includes 1,2-dichlorobenzene and / or toluene.

[0166] Preferably, in step (5), the molar ratio of the intermediate D to triphenylphosphine is 1:(10 - 20), for example, it can be 1:10, 1:12, 1:14, 1:16, 1:18 or 1:20, etc.

[0167] Preferably, in step (5), the reaction is carried out under a protective gas.

[0168] Preferably, the protective gas includes nitrogen and / or argon.

[0169] Preferably, in step (5), the reaction temperature is 140 - 150 °C (for example, it can be 140 °C, 142 °C, 146 °C, 148 °C or 150 °C, etc.), and the time is 1.5 - 2.5 h (for example, it can be 1.5 h, 2 h or 2.5 h, etc.).

[0170] In a third aspect, the present invention provides a chiral organic optoelectronic material, which includes the chiral carbon nanoring molecule as described in the first aspect.

[0171] Compared with the prior art, the present invention has at least the following beneficial effects:

[0172] The carbon nanoring molecule described in the present invention has a radial cyclic conjugated system and has good circularly polarized luminescence performance. The circularly polarized luminescence asymmetry factors all exceed 10 -2 , and it is applicable to the field of light-emitting devices or 3D displays, with excellent comprehensive performance; the preparation method of the chiral carbon nanoring molecule provided by the present invention is simple and convenient, with high optical purity, single configuration, and no need for chiral high-performance liquid chromatography separation. Description of the Drawings

[0173] Figure 1 It is the single crystal structure of D3-(P)-NR1 provided in Example 1;

[0174] Figure 2 It is the single crystal structure of D3-(M)-NR2 provided in Example 2;

[0175] Figure 3 It is the absorption spectrum of D3-(P)-NR1 provided in Example 1 in toluene solution;

[0176] Figure 4 It is the fluorescence spectrum of D3-(P)-NR1 provided in Example 1 in toluene solution;

[0177] Figure 5 Circular dichroism spectra of D3-(P)-NR1 provided in Example 1 and D3-(M)-NR1 provided in Example 3 in toluene solution;

[0178] Figure 6 Circularly polarized luminescence spectra of D3-(P)-NR1 provided in Example 1 and D3-(M)-NR1 provided in Example 3 in toluene solution;

[0179] Figure 7 Absorption spectrum of D4-(P)-NR1 provided in Example 1 in toluene solution;

[0180] Figure 8 Fluorescence spectrum of D4-(P)-NR1 provided in Example 1 in toluene solution;

[0181] Figure 9 Circular dichroism spectra of D4-(P)-NR1 provided in Example 1 and D4-(M)-NR1 provided in Example 3 in toluene solution;

[0182] Figure 10 Circularly polarized luminescence spectra of D4-(P)-NR1 provided in Example 1 and D4-(M)-NR1 provided in Example 3 in toluene solution;

[0183] Figure 11 Absorption spectrum of D3-(M)-NR2 provided in Example 2 in toluene solution;

[0184] Figure 12 Fluorescence spectrum of D3-(M)-NR2 provided in Example 2 in toluene solution;

[0185] Figure 13 Circular dichroism spectra of D3-(M)-NR2 provided in Example 2 and D3-(P)-NR2 provided in Example 4 in toluene solution;

[0186] Figure 14 Circularly polarized luminescence spectra of D3-(M)-NR2 provided in Example 2 and D3-(P)-NR2 provided in Example 4 in toluene solution;

[0187] Figure 15 Absorption spectrum of D4-(M)-NR2 provided in Example 2 in toluene solution;

[0188] Figure 16 Fluorescence spectrum of D4-(M)-NR2 provided in Example 2 in toluene solution;

[0189] Figure 17 Circular dichroism spectra of D4-(M)-NR2 provided in Example 2 and D4-(P)-NR2 provided in Example 4 in toluene solution;

[0190] Figure 18 Circularly polarized luminescence spectra of D4-(M)-NR2 provided for Example 2 and D4-(P)-NR2 provided for Example 4 in toluene solution. Detailed implementation manners

[0191] The technical solutions of the present invention will be further described below with reference to the accompanying drawings and through specific implementation manners. However, the following examples are merely simple examples of the present invention and do not represent or limit the scope of the claimed protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0192] Preparation Example 1

[0193] This preparation example provides 2-bromo-5-phenoxybenzoyl chloride and its synthesis method, and the synthesis method is as follows:

[0194] In a Schlenck tube, 2-bromo-5-phenoxybenzoic acid (1.75 g) was added to dichloromethane (30 mL), and a dichloromethane solution of oxalyl chloride (2 M, 8.6 mL) was added under argon protection, and then a drop of dry DMF was added as a catalyst; the reaction mixture was stirred at room temperature for 2 hours, and after removing the solvent under reduced pressure, white solid 2-bromo-5-phenoxybenzoyl chloride was obtained.

[0195] Example 1

[0196] This example provides chiral carbon nanoring molecules D3-(P)-NR1 and D4-(P)-NR1 and their synthesis methods, and their synthesis routes and specific synthesis methods are as follows:

[0197]

[0198] S1: Tetrahydrofuran (16 mL) was added to a dichloromethane solution of 2-bromo-5-phenoxybenzoyl chloride (2 M, 8.6 mL), triethylamine (3 mL) and starting material 1 (800 mg) were added under argon protection, and after stirring at 70 °C for 1.5 hours, the solvent was removed by concentration under reduced pressure, and the crude product was purified by column chromatography (silica gel) using dichloromethane:ethyl acetate (volume ratio 50:1) as the eluent to obtain intermediate I as a white solid (1.53 g, yield: 76%).

[0199] NMR data of intermediate I: 1 H NMR(CDCl3,400MHz,δ / ppm):7.34 - 7.65(m,13H),6.49 - 7.08(m,5H),2.85 - 5.09(m,8H),0.61 - 1.32(m,12H). 1313C NMR (CDCl3, 100 MHz, δ / ppm): 167.53, 157.54, 140.39, 138.37, 136.11, 135.99, 133.23, 128.77, 128.66, 128.26, 127.62, 127.45, 126.80, 123.03, 119.18, 69.93, 44.69, 26.33, 25.91, 25.57.

[0200] Mass spectrometry data of Intermediate I: MALDI-TOF HRMS (m / z): C 42 H 39 Br4N2O2 [M + calc. 950.9638, found 950.9639.

[0201] S2: Intermediate I (900 mg), 2,2'-bipyridine (886 mg), bis(1,5-cyclooctadiene)nickel (1.56 g) and tetrahydrofuran (120 mL) were added to a Schlenck tube. Under argon protection, it was stirred at 70 °C for 1 hour. The solvent was removed by concentration under reduced pressure. The crude product was purified by column chromatography (silica gel) using dichloromethane:ethyl acetate (volume ratio 50:1) as the eluent to obtain Intermediate II as a light yellow solid (250 mg, yield: 42%).

[0202] 1H NMR data of Intermediate II: 1 1H NMR (CDCl3, 400 MHz, δ / ppm): 8.10 - 8.07 (m, 6H), 7.51 (d, J = 6.8 Hz, 4H), 7.47 - 7.41 (m, 6H), 7.38 - 7.35 (m, 2H), 5.25 (d, J = 28.7 Hz, 4H), 5.19 - 5.15 (m, 2H), 4.20 (td, J = 10.5, 9.1, 5.3 Hz, 2H), 1.74 (br, 2H), 1.48 (br, 2H), 0.96 (br, 4H), 0.55 (br, 2H), -0.27 (br, 2H). 13 13C NMR (CDCl3, 100 MHz, δ / ppm): 159.87, 136.89, 133.72, 130.68, 128.70, 128.26, 127.76, 125.72, 123.73, 122.79, 121.36, 112.85, 110.72, 44.68, 29.03, 27.14, 26.55.

[0203] S3: Add intermediate II (380 mg), ammonium formate (190 mg), palladium (32 mg), ethanol (6 mL) and ethyl acetate (6 mL) into a round-bottom flask, stir at 80 °C for 2 hours, filter the reaction mixture to remove palladium, concentrate under reduced pressure and then pour it into methanol / water (volume ratio 1:1) for filtration to obtain intermediate III as a light green solid (270 mg, yield: 99%). Due to the low solubility of intermediate III, its NMR data was not obtained.

[0204] S4: Add intermediate III (330 mg), pyridine (0.30 mL), trifluoromethanesulfonic anhydride (0.62 mL) and dichloromethane (33 mL) into a Schlenck tube, stir at room temperature for 1 hour, then concentrate under reduced pressure to remove the solvent, and purify the crude product by column chromatography (silica gel) using dichloromethane:ethyl acetate (volume ratio 20:1) as the eluent to obtain intermediate IV as a yellow solid (380 mg, yield: 73%).

[0205] NMR data of intermediate IV: 1 H NMR(CDCl3,400MHz,δ / ppm):8.42(d,J=2.7Hz,2H),8.25(d,J=8.9Hz,2H),8.18(s,2H),5.13 - 5.19(m,2H),4.16 - 4.23(m,2H),1.78(br,2H),1.47(br,2H),0.82 - 0.9(m,4H),0.64(br,2H), - 0.31(br,2H). 13 C NMR(CDCl3,100MHz,δ / ppm):160.17,149.51,134.33,132.11,128.50,126.14,124.77,123.52,121.89,121.37,119.97,117.14,114.73,111.91,45.36,29.03,26.96,26.49.

[0206] S5: Add intermediate IV (165 mg), bis(pinacolato)diboron (241 mg), potassium acetate (232 mg), palladium acetate (6.4 mg), 2 - dicyclohexylphosphino - 2',6' - dimethoxy - 1,1' - biphenyl (S - Phos) (23.3 mg) and 1,4 - dioxane (4 mL) into a Schlenck tube, stir at 80 °C for 2 hours under argon protection, and then purify by ultrasonic washing with n - hexane to obtain intermediate V as a yellow solid (140 mg, yield: 98%).

[0207] NMR data of intermediate V: 11H NMR (CDCl3, 400 MHz, δ / ppm): 9.00 (s, 2H), 8.18 (d, J = 10.3 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 5.19 - 5.15 (m, 2H), 4.21 - 4.16 (m, 2H), 1.73 (br, 2H), 1.37 (s, 24H), 1.25 (br, 2H), 0.81 (br, 4H), 0.54 (br, 2H), -0.30 (br, 2H). 13 13C NMR (CDCl3, 100 MHz, δ / ppm): 161.82, 138.29, 136.37, 134.49, 125.81, 122.33, 121.07, 111.68, 84.20, 45.01, 31.55, 28.95, 26.96, 26.43, 24.99, 24.96, 24.80, 22.62, 14.09.

[0208] S6: Add intermediate V (130 mg), platinum(II) 1,5-cyclooctadiene dichloride (79 mg), cesium fluoride (192 mg) and 1,2-dichloroethane (20 mL) to a Schlenck tube. Stir at 70 °C for 24 hours under argon protection, then remove the solvent under reduced pressure to obtain a crude product mainly composed of intermediate VI.

[0209] S7: Add the crude product mainly composed of intermediate VI, triphenylphosphine (827 mg) and toluene (20 mL) to a Schlenck tube. Heat at 110 °C for 2 hours under argon protection, then remove the solvent under reduced pressure. Purify the crude product by column chromatography (silica gel) using dichloromethane:tetrahydrofuran (volume ratio 2:1) as the eluent to obtain D3-(P)-NR1 as a yellow solid (36 mg, yield: 40%) and D4-(P)-NR1 as a yellow solid (4 mg, yield: 3%).

[0210] NMR data of D3-(P)-NR1: 1 1H NMR (CDCl3, 400 MHz, δ / ppm): 8.59 (s, 6H), 7.88 (s, 6H), 7.76 (d, J = 8.7 Hz, 6H), 7.67 (d, J = 8.9 Hz, 6H), 4.99 - 5.04 (m, 6H), 3.98 - 4.04 (m, 6H), 1.70 - 1.79 (m, 12H), 1.15 (br, 6H), 0.82 (br, 6H), 0.69 (br, 12H). 1313C NMR (CDCl3, 100 MHz, δ / ppm): 189.19, 163.35, 139.73, 135.98, 133.44, 131.50, 128.37, 125.83, 123.44, 122.38, 111.50, 44.98, 30.24, 28.04, 26.56.

[0211] Mass spectrometry data of D3-(P)-NR1: MALDI-TOF HRMS (m / z): C 84 H 72 N6O6[M + calc. 1260.5508, found 1260.5511.

[0212] 1H NMR data of D4-(P)-NR1: 1 1H NMR (CDCl3, 400 MHz, δ / ppm): 8.76 (s, 8H), 7.93 (s, 8H), 7.85 (d, J = 1.2 Hz, 16H), 5.05 - 5.09 (m, 8H), 4.04 - 4.08 (m, 8H), 1.75 (br, 16H), 1.11 (br, 8H), 0.83 (br, 8H), 0.70 (br, 8H), 0.57 (br, 8H). 13 13C NMR (CDCl3, 100 MHz, δ / ppm): 162.25, 138.93, 135.49, 132.61, 131.08, 127.75, 124.62, 122.86, 121.98, 110.87, 45.01, 29.70, 29.29, 27.40, 26.06.

[0213] Mass spectrometry data of D4-(P)-NR1: MALDI-TOF HRMS (m / z): C 112 H 96 N8O8[M + calc. 1680.7346, found 1680.7347.

[0214] Example 2

[0215] This example provides chiral carbon nanoring molecules D3-(M)-NR2 and D4-(M)-NR2 and their synthesis methods. The synthesis route and specific synthesis methods are as follows:

[0216]

[0217] (1) The starting material 2 (1.4 g), 3-chloro-2-fluorophenylboronic acid (2.6 g), tetrakis(triphenylphosphine)palladium (430 mg), potassium carbonate (5.14 g), tetrahydrofuran (20 mL) and water (6 mL) were added to a Schlenck tube. After stirring at 70 °C for 24 hours under argon protection, the solvent was removed by concentration under reduced pressure. The crude product was purified by column chromatography (silica gel) using dichloromethane:ethyl acetate (volume ratio 50:1) as the eluent to obtain intermediate A as a white solid (1.3 g, yield: 74%).

[0218] 1H NMR data of intermediate A: 1 H NMR (CDCl3, 400 MHz, δ / ppm): 7.37 (t, J = 7.9 Hz, 2H), 7.26 (s, 2H), 7.24 (s, 2H), 6.94 (s, 2H), 3.34 (br, 2H), 3.20 - 3.24 (m, 2H), 2.93 - 2.98 (m, 2H), 1.69 (br, 2H), 1.08 (br, 4H), 0.91 (br, 2H), 0.65 (br, 2H), 0.54 (br, 2H). 13 C NMR (CDCl3, 100 MHz, δ / ppm): 160.92, 158.85, 139.91, 134.62, 134.52, 132.79, 132.75, 126.95, 125.09, 125.05, 124.67, 124.52, 122.78, 117.32, 117.06, 48.29, 28.20, 26.50, 24.34.

[0219] (2) Intermediate A (1.2 g), potassium tert-butoxide (850 mg) and DMF (80 mL) were added to a Schlenck tube. After stirring at 80 °C for 10 minutes under argon protection, the reaction mixture was quenched with water and extracted three times with petroleum ether. The organic layers were combined and the solvent was removed by concentration under reduced pressure. The crude product was purified by column chromatography (silica gel) using dichloromethane:petroleum ether (volume ratio 1:1) as the eluent to obtain intermediate B as a pale yellow solid (600 mg, yield: 55%).

[0220] 1H NMR data of intermediate B: 11H NMR (CDCl3, 400 MHz, δ / ppm): 8.08 (s, 2H), 8.03 (d, J = 8.2 Hz, 2H), 7.38 (d, J = 1.8 Hz, 2H), 7.22 (dd, J = 8.3, 1.8 Hz, 2H), 4.45 - 4.52 (m, 2H), 4.35 - 4.39 (m, 2H), 1.47 - 1.50 (m, 2H), 1.05 - 1.08 (m, 2H), 0.92 - 1.01 (m, 2H), 0.42 - 0.50 (m, 2H), 0.07 - 0.13 (m, 2H), -1.99 - -1.86 (m, 2H). 13 13C NMR (CDCl3, 100 MHz, δ / ppm): 144.83, 141.00, 131.76, 126.67, 124.48, 121.28, 120.13, 111.53, 104.43, 47.80, 28.90, 27.57, 27.42.

[0221] (3) Intermediate B (600 mg), bis(pinacolato)diboron (1.4 g), potassium acetate (1.36 g), palladium(II) acetate (37.2 mg), S-Phos (136 mg) and 1,4-dioxane (15 mL) were added to a Schlenck tube. After stirring at 80 °C for 2 h under argon protection, the solvent was removed by concentration under reduced pressure and the residue was purified by ultrasonic washing with n-hexane to obtain Intermediate C as a yellow solid (730 mg, 85%).

[0222] NMR data of Intermediate C: 1 1H NMR (CDCl3, 400 MHz, δ / ppm): 8.15 (d, J = 7.9 Hz, 4H), 7.88 (s, 2H), 7.74 (s, 2H), 4.45 - 4.55 (m, 4H), 1.46 - 1.50 (m, 2H), 1.41 (s, 24H), 1.04 (br, 2H), 0.81 (br, 2H), 0.47 (br, 2H), 0.07 (br, 2H), -1.91 (br, 2H). 13 13C NMR (CDCl3, 100 MHz, δ / ppm): 142.82, 137.65, 129.62, 126.01, 120.84, 83.75, 28.92, 27.51, 25.04, 24.84.

[0223] (4) Intermediate C (200 mg), dichlorobis(1,5-cyclooctadiene)platinum(II) (124 mg), cesium fluoride (302 mg) and 1,2-dichloroethane (30 mL) were added to a Schlenck tube. After stirring at 70 °C for 24 h under argon protection, the solvent was removed under reduced pressure to obtain a crude product mainly composed of intermediate D.

[0224] (5) The crude product mainly composed of intermediate D, triphenylphosphine (1.3 g) and 1,2-dichlorobenzene (30 mL) were added to a Schlenck tube. It was heated at 150 °C for 2 h under argon protection, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica gel) using dichloromethane:tetrahydrofuran (volume ratio 2:1) as the eluent to obtain compound D3-(M)-NR2 as a yellow solid (12 mg, yield: 10%) and compound D4-(M)-NR2 as a yellow solid (33 mg, yield: 27%).

[0225] 1H NMR data of D3-(M)-NR2: 1 H NMR (DMSO-d6, 400 MHz, δ / ppm): 8.06 (s, 6H), 8.02 (d, J = 8.6 Hz, 6H), 7.71 (d, J = 8.6 Hz, 6H), 7.21 (s, 6H), 4.37 - 4.44 (m, 6H), 4.20 - 4.24 (m, 6H), 0.90 (br, 6H), 0.79 (br, 6H), -0.46 (br, 12H), -1.77 (br, 6H), -3.92 (br, 6H). 13 C NMR (DMSO-d6, 100 MHz, δ / ppm): 146.28, 143.04, 138.04, 129.04, 124.39, 121.89, 116.21, 115.74, 107.43, 44.32, 25.04, 24.38, 23.17.

[0226] MS data of D3-(M)-NR2: MALDI-TOF HRMS (m / z): C 78 H 72 N6[M + calc. 1092.5813, found 1092.5807.

[0227] 1H NMR data of D4-(M)-NR2: 11H NMR (DMSO-d6, 400 MHz, δ / ppm): 8.17 (s, 8H), 8.13 (d, J = 8.4 Hz, 8H), 7.82 (d, J = 8.5 Hz, 8H), 7.41 (s, 8H), 4.32 - 4.44 (m, 16H), 0.97 (br, 8H), 0.65 (br, 8H), -0.22 (br, 16H), -1.33 (br, 8H), -3.11 (br, 8H). 13 13C NMR (DMSO-d6, 100 MHz, δ / ppm): 145.17, 141.85, 138.30, 128.21, 124.41, 121.66, 116.42, 113.17, 106.17, 45.04, 30.87, 25.98, 25.88, 23.90, 21.96, 13.82.

[0228] The mass spectrometry data of D4-(M)-NR2 MALDI-TOF HRMS (m / z): C 104 H 96 N8[M + calc. 1456.7752, found 1456.7735.

[0229] Example 3

[0230] This example provides chiral carbon nanoring molecules D3-(M)-NR1 and D4-(M)-NR1 and their synthesis methods. The synthesis route and specific synthesis methods are as follows:

[0231]

[0232] S1: Add tetrahydrofuran (9 mL) to a dichloromethane solution (2 M, 4.9 mL) of 2-bromo-5-phenoxybenzoyl chloride. Under argon protection, add triethylamine (1.66 mL) and starting material 1 (450 mg). After stirring at 70 °C for 1.5 hours, concentrate the solvent under reduced pressure. The crude product is purified by column chromatography (silica gel) with dichloromethane:ethyl acetate (volume ratio 50:1) as the eluent to obtain intermediate I, which is a white solid (910 mg, yield: 80%).

[0233] The NMR data of intermediate I: 1 1H NMR (CDCl3, 400 MHz, δ / ppm): 7.31 - 7.86 (m, 13H), 6.50 - 7.11 (m, 5H), 2.80 - 5.17 (m, 8H), 0.61 - 1.53 (m, 12H). 1313C NMR (CDCl3, 100 MHz, δ / ppm): 167.50, 157.96, 157.52, 140.37, 138.44, 136.09, 135.97, 133.81, 133.20, 128.74, 128.64, 128.31, 128.24, 128.11, 127.60, 127.42, 126.78, 123.01, 119.15, 118.35, 117.67, 109.95, 70.59, 69.90, 44.67, 26.31, 25.89, 25.55.

[0234] Mass spectrometry data of Intermediate I: MALDI-TOF HRMS (m / z): C 42 H 39 Br4N2O2 [M + calc. 950.9638, found 950.9639.

[0235] S2: Intermediate I (800 mg), 2,2'-bipyridine (792 mg), bis(1,5-cyclooctadiene)nickel (1.4 g) and tetrahydrofuran (120 mL) were added to a Schlenck tube. Under argon protection, the mixture was stirred at 70 °C for 1 hour. The solvent was removed by concentration under reduced pressure. The crude product was purified by column chromatography (silica gel) using dichloromethane:ethyl acetate (volume ratio 50:1) as the eluent to obtain Intermediate II as a light yellow solid (240 mg, yield: 45%).

[0236] 1H NMR data of Intermediate II: 1 1H NMR (CDCl3, 400 MHz, δ / ppm): 8.09 (d, J = 2.4 Hz, 3H), 8.07 (d, J = 3.0 Hz, 3H), 7.50 - 7.52 (m, 4H), 7.41 - 7.46 (m, 6H), 7.35 - 7.39 (m, 2H), 5.20 - 5.28 (m, 4H), 5.14 - 5.19 (m, 2H), 4.17 - 4.23 (m, 2H), 1.74 (br, 2H), 1.44 (br, 2H), 0.84 (br, 4H), 0.57 (br, 2H), -0.32 (br, 2H). 13 13C NMR (CDCl3, 100 MHz, δ / ppm): 161.65, 159.24, 136.30, 133.52, 128.69, 128.25, 127.74, 126.17, 124.19, 122.77, 121.33, 111.10, 110.70, 70.44, 45.09, 29.56, 27.77, 26.53.

[0237] S3: Add intermediate II (220 mg), ammonium formate (109 mg), palladium (18 mg), ethanol (5 mL) and ethyl acetate (5 mL) into a round-bottom flask, stir at 80 °C for 2 hours, filter the reaction mixture to remove palladium, concentrate under reduced pressure and then pour it into methanol / water (volume ratio 1:1) for filtration to obtain intermediate III as a light green solid (125 mg, yield: 83%). Due to the low solubility of intermediate III, its NMR data was not obtained.

[0238] S4: Add intermediate III (120 mg), pyridine (0.23 mL), trifluoromethanesulfonic anhydride (0.11 mL) and dichloromethane (12 mL) into a Schlenck tube, stir at room temperature for 1 hour, concentrate under reduced pressure to remove the solvent, and purify the crude product by column chromatography (silica gel) using dichloromethane:ethyl acetate (volume ratio 20:1) as the eluent to obtain intermediate IV as a yellow solid (140 mg, yield: 70%).

[0239] NMR data of intermediate IV: 1 H NMR(CDCl3, 400 MHz, δ / ppm): 8.43 (d, J = 2.7 Hz, 2H), 8.25 (d, J = 8.9 Hz, 2H), 8.18 (s, 2H), 7.71 (dd, J = 8.8, 2.7 Hz, 2H), 5.14 - 5.18 (m, 2H), 4.16 - 4.23 (m, 2H), 1.78 (br, 2H), 1.47 (br, 2H), 0.81 - 0.91 (m, 4H), 0.65 (br, 2H), -0.31 (br, 2H). 13 C NMR(CDCl3, 100 MHz, δ / ppm): 160.17, 149.51, 134.33, 132.11, 128.50, 126.14, 124.76, 121.90, 121.37, 120.33, 117.14, 111.91, 45.36, 29.03, 26.96, 26.49.

[0240] S5: Add intermediate IV (120 mg), bis(pinacolato)diboron (170 mg), potassium acetate (160 mg), palladium acetate (4.5 mg), S-Phos (16.5 mg) and 1,4-dioxane (4 mL) into a Schlenck tube, stir at 80 °C for 2 hours under argon protection, and purify by ultrasonic washing with n-hexane to obtain intermediate V as a yellow solid (95 mg, yield: 92%).

[0241] NMR data of intermediate V: 11H NMR (CDCl3, 400 MHz, δ / ppm): 9.01 (s, 2H), 8.22 - 8.16 (m, 4H), 8.13 (d, J = 8.1 Hz, 2H), 5.15 - 5.21 (m, 2H), 4.16 - 4.23 (m, 2H), 1.74 (br, 4H), 1.39 (br, 24H), 0.82 (br, 2H), 0.54 (br, 2H), -0.28 (br, 2H). 13 13C NMR (CDCl3, 100 MHz, δ / ppm): 161.84, 138.31, 136.40, 134.52, 125.84, 122.36, 121.07, 111.69, 84.22, 45.03, 28.96, 26.98, 26.45, 24.98, 24.82.

[0242] S6: Add intermediate V (90 mg), dichloroplatinum(II) 1,5 - cyclooctadiene (55 mg), cesium fluoride (133 mg) and 1,2 - dichloroethane (15 mL) into a Schlenck tube. After stirring at 70 °C for 24 hours under argon protection, remove the solvent under reduced pressure to obtain a crude product mainly composed of intermediate VI.

[0243] S7: Add the crude product mainly composed of intermediate VI, triphenylphosphine (572 mg) and toluene (15 mL) into a Schlenck tube. Heat at 110 °C for 2 hours under argon protection, remove the solvent under reduced pressure, and purify the crude product by column chromatography (silica gel) with dichloromethane:tetrahydrofuran (volume ratio 2:1) as the eluent to obtain compound D3-(M)-NR1 as a yellow solid (28 mg, yield: 45%) and compound D4-(M)-NR1 as a yellow solid (10 mg, yield: 11%).

[0244] NMR data of D3-(M)-NR1: 1 1H NMR (CDCl3, 400 MHz, δ / ppm): 8.62 (s, 6H), 7.81 (s, 6H), 7.73 (d, J = 2.3 Hz, 12H), 4.97 - 5.03 (m, 6H), 3.94 - 3.99 (m, 6H), 1.69 - 1.79 (m, 12H), 1.14 (br, 6H), 0.81 (br, 6H), 0.68 (br, 6H). 13 13C NMR (CDCl3, 100 MHz, δ / ppm): 162.43, 138.72, 135.95, 133.12, 130.58, 127.93, 123.98, 122.94, 122.06, 111.29, 44.76, 29.20, 27.59, 25.99.

[0245] Mass spectrometry data of D3-(M)-NR1: MALDI-TOF HRMS (m / z): C 84 H 72 N6O6[M + calc. 1260.5508, found 1260.5503.

[0246] NMR data of D4-(M)-NR1: 1 1H NMR (CDCl3, 400 MHz, δ / ppm): 8.76 (s, 8H), 7.93 (s, 8H), 7.86 (d, J = 1.2 Hz, 16H), 5.05 - 5.09 (m, 8H), 4.03 - 4.09 (m, 8H), 1.75 (br, 16H), 1.11 (br, 8H), 0.83 (br, 8H), 0.70 (br, 8H), 0.57 (br, 8H). 13 13C NMR (CDCl3, 100 MHz, δ / ppm): 162.25, 138.93, 135.49, 132.61, 131.08, 127.75, 124.62, 122.86, 121.99, 45.01, 29.28, 27.40, 26.06.

[0247] Mass spectrometry data of D4-(M)-NR1: MALDI-TOF HRMS (m / z): C 112 H 96 N8O8[M + calc. 1680.7346, found 1680.7327.

[0248] Example 4

[0249] This example provides chiral carbon nanoring molecules D3-(P)-NR2 and D4-(P)-NR2 and their synthesis methods. The synthesis routes and specific synthesis methods are as follows:

[0250]

[0251]

[0252] (1) The starting material 2 (400 mg), 3-chloro-2-fluorophenylboronic acid (740 mg), tetrakis(triphenylphosphine)palladium (123 mg), potassium carbonate (1.5 g), tetrahydrofuran (9 mL) and water (3 mL) were added to a Schlenck tube. After stirring at 70 °C for 24 hours under argon protection, the solvent was removed by concentration under reduced pressure. The crude product was purified by column chromatography (silica gel) using dichloromethane:ethyl acetate (volume ratio 50:1) as the eluent to obtain intermediate A as a white solid (400 mg, yield: 79%).

[0253] NMR data of intermediate A: 1 H NMR(CDCl3,400MHz,δ / ppm):7.36 - 7.40(m,2H),7.27 - 7.28(m,3H),7.24 - 7.25(m,3H),7.01(br,2H),3.22 - 3.27(m,2H),2.94 - 3.00(m,2H),1.70(br,2H),1.06(br,4H),0.96(br,2H),0.67(br,4H). 13 C NMR(CDCl3,100MHz,δ / ppm):160.81,158.35,132.80,132.77,125.23,117.43,117.17,47.91,27.45,26.54,23.82.

[0254] (2) Intermediate A (380 mg), potassium tert-butoxide (270 mg) and DMF (25 mL) were added to a Schlenck tube. After stirring at 80 °C for 10 minutes under argon protection, the reaction mixture was quenched with water and extracted three times with petroleum ether. The organic layers were combined and the solvent was removed by concentration under reduced pressure. The crude product was purified by column chromatography (silica gel) using dichloromethane:petroleum ether (volume ratio 1:1) as the eluent to obtain intermediate B as a pale yellow solid (165 mg, yield: 50%).

[0255] NMR data of intermediate B: 1 H NMR(CDCl3,400MHz,δ / ppm):8.08(s,2H),8.03(d,J = 8.2Hz,2H),7.38(d,J = 1.7Hz,2H),7.22(dd,J = 8.3,1.8Hz,2H),4.45 - 4.52(m,2H),4.34 - 4.40(m,2H),1.47 - 1.53(m,2H),1.02 - 1.08(m,2H),0.87 - 0.96(m,2H),0.42 - 0.50(m,2H),0.06 - 0.15(m,2H), - 2.00 - - 1.90(m,2H). 1313C NMR (CDCl3, 100 MHz, δ / ppm): 144.83, 141.00, 131.77, 126.67, 124.49, 121.28, 120.14, 111.53, 104.01, 47.81, 28.90, 27.57, 27.42.

[0256] (3) Intermediate B (150 mg), bis(pinacolato)diboron (350 mg), potassium acetate (340 mg), palladium(II) acetate (9.3 mg), S-Phos (34 mg), and 1,4-dioxane (4 mL) were added to a Schlenck tube. After stirring at 80 °C for 2 hours under argon protection, the solvent was removed by concentration under reduced pressure and purified by ultrasonic washing with n-hexane to obtain Intermediate C as a yellow solid (100 mg, yield: 48%).

[0257] NMR data of Intermediate C: 1 1H NMR (CDCl3, 400 MHz, δ / ppm): 8.15 (d, J = 8.9 Hz, 4H), 7.88 (s, 4H), 7.73 (d, J = 7.8 Hz, 4H), 4.45 - 4.55 (m, 4H), 1.47 (br, 2H), 1.41 (br, 24H), 1.02 (br, 2H), 0.82 (br, 2H), 0.46 (br, 2H), 0.06 (br, 2H), -1.85 (br, 2H). 13 13C NMR (CDCl3, 100 MHz, δ / ppm): 143.75, 141.16, 128.66, 127.50, 125.97, 119.87, 117.90, 104.43, 83.76, 47.80, 28.90, 27.46, 25.04, 25.02, 24.84.

[0258] (4) Intermediate C (100 mg), platinum(II) 1,5-cyclooctadiene dichloride (62 mg), cesium fluoride (151 mg), and 1,2-dichloroethane (16 mL) were added to a Schlenck tube. After stirring at 70 °C for 24 hours under argon protection, the solvent was removed under reduced pressure to obtain a crude product mainly composed of Intermediate D.

[0259] (5) The crude product with intermediate D as the main component, triphenylphosphine (650 mg), and 1,2-dichlorobenzene (15 mL) were added to a Schlenck tube and heated at 150 °C for 2 hours under argon protection. The solvent was removed under reduced pressure, and the crude product was purified by column chromatography (silica gel) using dichloromethane:tetrahydrofuran (volume ratio 2:1) as the eluent to obtain compound D3-(P)-NR2 as a yellow solid (5 mg, yield: 8%) and compound D4-(P)-NR2 as a yellow solid (20 mg, yield: 33%).

[0260] 1H NMR data of D3-(P)-NR2: 1 H NMR (DMSO-d6, 400 MHz, δ / ppm): 8.06 (s, 6H), 8.02 (d, J = 8.6 Hz, 6H), 7.72 (d, J = 8.6 Hz, 6H), 7.21 (s, 6H). 4.41 (t, J = 12.7 Hz, 6H), 4.23 (d, J = 14.8 Hz, 6H), 0.91 (br, 6H), 0.79 (br, 6H), -0.51 (br, 12H), -1.76 (br, 6H), -3.92 (br, 6H). 13 13C NMR (DMSO-d6, 100 MHz, δ / ppm): 146.34, 143.10, 138.10, 129.10, 124.45, 121.94, 116.27, 115.80, 107.48, 44.38, 25.10, 24.73, 23.66.

[0261] 1H NMR data of D3-(P)-NR2: MALDI-TOF HRMS (m / z): C 78 H 72 N6[M + calc. 1092.5813, found 1092.5805.

[0262] 1H NMR data of D4-(P)-NR2: 1 H NMR (DMSO-d6, 400 MHz, δ / ppm): 8.17 (s, 8H), 8.13 (d, J = 8.4 Hz, 8H), 7.81 (d, J = 8.4 Hz, 8H), 7.41 (s, 8H). 4.32 - 4.44 (m, 16H), 0.97 (br, 8H), 0.64 (br, 8H), -0.23 (br, 16H), -1.44 (br, 8H), -3.14 (br, 8H). 1313C NMR (DMSO-d6, 100 MHz, δ / ppm): 145.23, 141.91, 138.35, 128.27, 124.47, 121.72, 116.48, 113.24, 106.24, 45.10, 30.97, 26.04, 25.94, 23.96, 22.07, 13.95.

[0263] Mass spectrometry data of D4-(P)-NR2: MALDI-TOF HRMS (m / z): C 104 H 96 N8 [M + calc. 1456.7752, found 1456.7744.

[0264] Performance test

[0265] (1) Based on D3-(P)-NR1 synthesized in Example 1 of the present invention and D3-(M)-NR1 synthesized in Example 3 of the present invention, their optical properties were tested.

[0266] D3-(P)-NR1 and D3-(M)-NR1 were respectively dissolved in toluene solution to prepare solutions with a concentration of 1.0×10 -5 M, and their ultraviolet-visible absorption spectra ( Figure 3 ), fluorescence spectra ( Figure 4 ), circular dichroism spectra ( Figure 5 ) and circularly polarized luminescence spectra ( Figure 6 ) were respectively tested. The fluorescence quantum yield was 42%, and the luminescence asymmetry factor |g lum | = 3.8×10 -2 .

[0267] (2) Based on D4-(P)-NR1 synthesized in Example 1 of the present invention and D 4- (M)-NR1 synthesized in Example 3 of the present invention, their optical properties were tested.

[0268] D4-(P)-NR1 and D4-(M)-NR1 were respectively dissolved in toluene solution to prepare solutions with a concentration of 1.0×10 -5 M, and their ultraviolet-visible absorption spectra ( Figure 7 ), fluorescence spectra ( Figure 8 uorescence spectra (), circular dichroism spectra ([[ID=4?) Figure 9 ) and circularly polarized luminescence spectra ( Figure 10 ) were respectively tested. The fluorescence quantum yield was 80%, and the luminescence asymmetry factor |g lum | = 2.2×10 -2 .

[0269] (3) Based on D3-(M)-NR2 synthesized in Example 2 of the present invention and D3-(P)-NR2 synthesized in Example 4 of the present invention, their optical properties were tested.

[0270] D3-(M)-NR2 and D3-(P)-NR2 were respectively dissolved in toluene solution to prepare solutions with a concentration of 1.0×10 -5 M, and their ultraviolet-visible absorption spectra ( Figure 11 ), fluorescence spectra ( Figure 12 ), circular dichroism spectra ( Figure 13 ) and circularly polarized luminescence spectra ( Figure 14 ) were respectively tested. The fluorescence quantum yield was 26%, and the luminescence asymmetry factor |g lum | = 7.6×10 -2 .

[0271] (4) Based on D4-(M)-NR2 synthesized in Example 2 of the present invention and D4-(P)-NR2 synthesized in Example 4 of the present invention, their optical properties were tested.

[0272] D4-(M)-NR2 and D4-(P)-NR2 were respectively dissolved in toluene solution to prepare solutions with a concentration of 1.0×10 -5 M, and their ultraviolet-visible absorption spectra ( Figure 15 ), fluorescence spectra ( Figure 16 ), circular dichroism spectra ( Figure 17 ) and circularly polarized luminescence spectra ( Figure 18 ) were respectively tested. The fluorescence quantum yield was 43%, and the luminescence asymmetry factor |g lum | = 4.6×10 -2 .

[0273] The applicant declares that the above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A chiral carbon nanoring molecule, characterized in that, The chiral carbon nanoring molecule includes Dn-NR1 compounds and Dn-NR2 compounds; The Dn-NR1 compounds include the following compounds: The Dn-NR2 compounds include the following compounds: Wherein, m is independently an integer between 8 and 12; n is independently an integer between 2 and 5; The arc represents a single bond.

2. The chiral carbon nanoring molecule according to claim 1, characterized in that, The chiral carbon nanoring molecule includes the following compounds: Wherein, the arc represents a single bond.

3. A method for preparing a chiral carbon nanoring molecule as described in claim 1 or 2, characterized in that, The preparation method of the Dn-NR1 compounds includes the following steps: S1. Starting material 1 reacts with 2-bromo-5-phenoxybenzoyl chloride to obtain intermediate I; S2. Intermediate I reacts with bis(1,5-cyclooctadiene)nickel to obtain intermediate II; S3. Intermediate II reacts with ammonium formate to obtain intermediate III; S4. Intermediate III reacts with trifluoromethanesulfonic anhydride to obtain intermediate IV; S5. Intermediate IV reacts with bis(pinacolato)diboron to obtain intermediate V; S6. Intermediate V reacts with 1,5-cyclooctadieneplatinum(II) dichloride to obtain intermediate VI; S7. Intermediate VI reacts with triphenylphosphine to obtain Dn-NR1 compounds; Among them, starting material 1 is m is independently any integer between 8 and 12; The preparation method of the Dn-NR2 compounds includes the following steps: (1) Starting material 2 reacts with 3-chloro-2-fluorophenylboronic acid to obtain intermediate A; (2) Intermediate A reacts with potassium tert-butoxide to obtain intermediate B; (3) Intermediate B reacts with bis(pinacolato)diboron to obtain intermediate C; (4) Intermediate C reacts with 1,5-cyclooctadieneplatinum(II) dichloride to obtain intermediate D; (5) Intermediate D reacts with triphenylphosphine to obtain Dn-NR2 compounds; Among them, the starting material 2 is selected from m is independently any integer between 8 and 12.

4. The preparation method according to claim 3, characterized in that, Step S1 is carried out in solvent A; Preferably, the solvent A includes tetrahydrofuran and / or dichloromethane; Preferably, in step S1, the molar ratio of starting material 1 to 2-bromo-5-phenoxybenzoyl chloride is 1:(2.5 - 4); preferably, in step S1, the reaction is carried out in the presence of basic substance A; Preferably, the basic substance A includes triethylamine; Preferably, the molar ratio of the basic substance A to starting material 1 is (8 - 15):1; Preferably, in step S1, the reaction temperature is 60 - 80°C and the time is 1 - 2 h; Preferably, step S2 is carried out in solvent B; Preferably, the solvent B includes tetrahydrofuran; Preferably, in step S2, the molar ratio of intermediate I to bis(1,5-cyclooctadiene)nickel is 1:(6 - 10); Preferably, in step S2, the reaction is carried out in the presence of a pyridine compound; Preferably, the pyridine compound includes 2,2'-bipyridine and / or 4,4’,6,6’-tetramethyl-2,2’-bipyridine; Preferably, in step S2, the molar ratio of intermediate I to the pyridine compound is 1:(6 - 10); Preferably, in step S2, the reaction temperature is 60 - 80°C and the time is 1 - 2 h.

5. The preparation method according to claim 3, characterized in that, Step S3 is carried out in solvent C; Preferably, the solvent C comprises ethyl acetate and alcohols; Preferably, the alcohol comprises methanol or ethanol; Preferably, in step S3, the molar ratio of the intermediate II to ammonium formate is 1:(5-10); Preferably, in step S3, the reaction is carried out in the presence of catalyst A; Preferably, the catalyst A comprises palladium; Preferably, the molar ratio of the catalyst A to the intermediate II is (1-5):1; Preferably, in step S3, the reaction temperature is 65-85° C. and the reaction time is 1.5-2.5 h; Preferably, step S4 is carried out in solvent D; Preferably, the solvent D comprises dichloromethane and / or chloroform; Preferably, in step S4, the molar ratio of the intermediate III to trifluoromethanesulfonic anhydride is 1:(5-10); Preferably, in step S4, the reaction is carried out in the presence of a basic substance B; Preferably, the alkaline substance B comprises pyridine; Preferably, the molar ratio of the alkaline substance B to the intermediate III is (4-10):1; Preferably, in step S4, the reaction temperature is 20-30° C. and the reaction time is 1-2 h.

6. The preparation method according to claim 3, wherein Step S5: reacting in solvent E; Preferably, the solvent E comprises 1,4-dioxane; Preferably, in step S5, the molar ratio of the intermediate IV to bis(boronic acid pinacol ester) is 1:(4-6); Preferably, in step S5, the reaction is carried out in the presence of catalyst B; Preferably, the catalyst B comprises palladium acetate and 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl; Preferably, the molar ratio of palladium acetate to 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl is 1:(1-3); Preferably, the molar ratio of the catalyst B to the intermediate IV is 1:(0.05-0.1); Preferably, in step S5, the reaction is carried out in the presence of a basic substance C; Preferably, the alkaline substance C comprises any one of potassium acetate, potassium carbonate or cesium carbonate, or a combination of at least two thereof; preferably, the mass ratio of the alkaline substance C to the intermediate IV is (5-10):1; Preferably, in step S5, the reaction temperature is 80-90° C. and the reaction time is 1.5-2.5 h; Preferably, step S6 is carried out in solvent F; Preferably, the solvent F comprises 1,2-dichloroethane; Preferably, in step S6, the molar ratio of the intermediate V to 1,5-cyclooctadiene platinum dichloride is 1:(1-1.05); Preferably, in step S6, the reaction is carried out in the presence of a fluoride; Preferably, the fluoride comprises cesium fluoride; Preferably, the molar ratio of the fluoride to the intermediate V is (4-8):1; Preferably, in step S6, the reaction temperature is 70-85°C and the reaction time is 24-36h; Preferably, step S7 is reacted in solvent G; Preferably, the solvent G comprises toluene and / or 1,2-dichlorobenzene; Preferably, in step S7, the molar ratio of the intermediate VI to triphenylphosphine is 1:(10-20); Preferably, in step S7, the temperature of the reaction is 100 - 115 °C and the time is 1.5 - 2.5 h.

7. The preparation method according to claim 3, characterized in that, Step (1) is carried out in solvent H; preferably, the solvent H includes water and an organic solvent; Preferably, the organic solvent includes tetrahydrofuran or toluene; Preferably, in step (1), the molar ratio of starting material 2 to 3 - chloro - 2 - fluorobenzeneboronic acid is 1:(3 - 5); Preferably, in step (1), the reaction is carried out in the presence of catalyst C; Preferably, the catalyst C includes tetrakis(triphenylphosphine)palladium and / or palladium acetate; Preferably, the molar ratio of the catalyst C to starting material 2 is (0.01 - 0.1):1; Preferably, in step (1), the reaction is carried out in the presence of basic substance D; Preferably, the basic substance D includes potassium carbonate and / or potassium acetate; Preferably, the molar ratio of the basic substance D to starting material 2 is (5 - 10):1; Preferably, in step (1), the temperature of the reaction is 60 - 80 °C and the time is 20 - 28 h; Preferably, step (2) is carried out in solvent I; Preferably, the solvent I includes N,N - dimethylformamide; Preferably, in step (2), the molar ratio of intermediate A to potassium tert - butoxide is 1:(3 - 5); Preferably, in step (2), the temperature of the reaction is 75 - 85 °C and the time is 10 - 30 min.

8. The preparation method according to claim 3, characterized in that, Step (3) is carried out in solvent J; Preferably, the solvent J includes 1,4 - dioxane; Preferably, in step (3), the molar ratio of intermediate B to bis(pinacolato)diboron is 1:(4 - 6); Preferably, in step (3), the reaction is carried out in the presence of catalyst D; Preferably, the catalyst D includes palladium acetate and 2 - dicyclohexylphosphino - 2',6' - dimethoxy - 1,1' - biphenyl; Preferably, the molar ratio of palladium acetate to 2 - dicyclohexylphosphino - 2',6' - dimethoxy - 1,1' - biphenyl is 1:(1 - 3); Preferably, the molar ratio of the catalyst D to intermediate B is (0.1 - 0.5):1; Preferably, in step (3), the reaction is carried out in the presence of basic substance E; Preferably, the basic substance E includes any one or a combination of at least two of potassium acetate, potassium carbonate or cesium carbonate; preferably, the molar ratio of the basic substance E to intermediate B is (5 - 10):1; Preferably, in step (3), the temperature of the reaction is 80 - 90 °C and the time is 1.5 - 2.5 h.

9. The preparation method according to claim 3, characterized in that, Step (4) is carried out in solvent K; Preferably, the solvent K includes 1,2 - dichloroethane; Preferably, in step (4), the molar ratio of intermediate C to dichlorobis(1,5 - cyclooctadiene)platinum is 1:(1 - 1.05); preferably, in step (4), the reaction is carried out in the presence of a fluoride; Preferably, the fluoride includes cesium fluoride; Preferably, the molar ratio of the fluoride to intermediate C is (6 - 10):1; Preferably, in step (4), the temperature of the reaction is 70 - 85 °C and the time is 24 - 36 h; Preferably, step (5) is carried out in solvent L; Preferably, the solvent L includes 1,2-dichlorobenzene and / or toluene; Preferably, in step (5), the molar ratio of the intermediate D to triphenylphosphine is 1:(10 - 20); Preferably, in step (5), the reaction temperature is 140 - 150 °C and the time is 1.5 - 2.5 h.

10. A chiral organic optoelectronic material, characterized in that, The chiral organic optoelectronic material includes the chiral carbon nanoring molecule as described in claim 1 or 2.

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