Preparation method and application of a three-dimensional perylene-core helicene functional molecule

Abstract

The present invention discloses a preparation method of a three-dimensional perylene-core helicene functional molecule, which includes using a three-dimensional perylene-core structure as a parent body, and performing functionalization modification at the peri-position of the three-dimensional perylene-core structure, that is, introducing polycyclic aromatic hydrocarbons through Suzuki coupling, halogenation reaction, and Heck cyclization to form a perylene-core three-dimensional helicene functional molecule with a novel structure. The prepared three-dimensional perylene-core helicene functional molecule can be used in the fields of organic spintronic devices and chiral optical elements. Moreover, its helical structure is embedded with a five-membered ring through Heck cyclization, and the doping of heteroatoms and the defective five-membered ring jointly affect the electron distribution of this conjugated structure, and the formed helical structure regulates the optoelectromagnetic properties of this type of compound. The three-dimensional perylene-core helicene functional molecule can be obtained in high yield and high purity.

Description

Technical Field

[0001] The present invention relates to the technical field of helicene functional molecular materials with multiple redox properties, and particularly relates to the preparation method and application of a three-dimensional perylene-core helicene functional molecule. Background Art

[0002] Helicene is a three-dimensional polycyclic aromatic hydrocarbon molecule formed by the ortho-fusion of benzene rings and having helical chirality. If heteroatoms (such as nitrogen, boron, sulfur, oxygen, etc.) are embedded in the helicene molecular skeleton, it is called hetero-fused helicene. The first helicene molecule was synthesized by Professors Meisenheimer and Witte in 1903, thus opening the prelude to the research on helicene molecules. The twisted structure of helicene endows it with unique chiral optical properties, such as strong optical rotation, circular dichroism, and circularly polarized luminescence. Compared with single helicene, multiple helicenes can exhibit more excellent photophysical and electrochemical properties due to their complex three-dimensional topological structure and rich spatial conformations.

[0003]

[0004] Chiral optics has always been a hot topic in the field of helicenes. Recently, the research group of Professor Wang Xiaoye at Nankai University has made a breakthrough in this field. They designed and synthesized a boron-nitrogen hetero-fused double helicene molecule with excellent chiral optical properties. Circular dichroism spectroscopy (CD) studies showed that the asymmetry factor (g abs ) at the Cotton absorption at 502 nm reached 0.033, which is the maximum value of g abs reported for helicene molecules in the visible light region so far. In addition, it showed spectrally tunable circularly polarized luminescence (CPL) emission properties and a relatively high asymmetry factor (g lum = 0.002, CPL brightness (B CPL ) up to 40.0 M -1 cm -1 ) in the red-light to near-infrared region. Most importantly, this helicene molecule also has a relatively high photoluminescence quantum efficiency (PLQYs up to 100%). These research results indicate that this type of boron-nitrogen hetero-double helicene molecule can be used as an excellent circularly polarized luminescence material.

[0005] How to improve the carrier mobility of helicene molecules has always been a challenging problem in this field. Affected by the three-dimensional spatial configuration of helicene, the π-π overlap of molecules is hindered, making it a huge challenge for helicene molecules to serve as carriers and channels for charge transport. However, the structural adjustable range of organic helicene molecules is very large, and they are easy to be functionalized. This advantage makes organic semiconductor materials gradually comparable to inorganic semiconductor materials. In 2013, the group led by Pei Jian at Peking University reported a boron-nitrogen heterotetrathieno[3,2-b:2',3'-d:3'',2''-g:2''',3'''-c]naphthalene molecule. Interestingly, this boron-nitrogen heterocyclic molecule has high chemical stability and mobility, and its hole mobility in organic field-effect transistors is 0.15 cm 2 V -1 s -1 . The next year, the same group reported a simple and efficient synthetic strategy for boron-nitrogen heterohexabenzocoronene derivatives. Its single crystal has two conformations: saddle conformation (A) and U-D conformation (B). The stacking mode of the heterocyclic molecules takes the A-B-A sandwich as a unit, showing a tight π-columnar stacking, and its single crystal hole mobility is as high as 0.23 cm 2 V -1 s -1 .

[0006]

[0007] Generally speaking, for helicene systems, high fluorescence efficiency and good mobility cannot be achieved at the same time. In order to simultaneously achieve efficient CPL response and good semiconductor performance, the group led by Lin Jianbin and the group led by Oh Joon Hak cooperated and reported a chiral PDI bis-[7]helicene molecule in 2021. The planar PDI skeleton on the inner side is conducive to the efficient transport of carriers, while the helicene structure on the outer side is conducive to the efficient response to circularly polarized light, thus perfectly solving this contradiction. In addition, the extension of the π system and the special D-A skeleton endow this molecule with bipolar charge transport characteristics. The hole and electron mobilities under thin-film conditions are μ h = 2.1×10 -3 cm 2 V -1 s -1 and μ e = 1.7×10 -3 cm 2 V -1 s -1 . In addition, the semiconductor material prepared with this molecule as the active layer has high light responsiveness and a relatively high external quantum efficiency (89%) under light illumination conditions.

[0008]

[0009] In order to synthesize more helicene molecular materials with excellent properties, it is necessary to find a suitable building matrix. However, due to the special three-dimensional structure of helicene molecules and the existence of large internal strain, the synthesis of such molecules is quite challenging. Therefore, it is very important to develop efficient synthesis strategies for this type of molecule. Perylene, a polycyclic aromatic hydrocarbon composed of five fused benzene rings, has a large conjugated system and rigid planarity, endowing perylene compounds with high fluorescence quantum yields (>99%), broad absorption spectra, electron richness, and thermal and photochemical stability. In addition, perylene compounds have multiple modification sites, providing a good basis for designing more helicene compounds with novel structures and functions. Based on this, this patent uses a novel perylene core developed by the research group as the matrix, and through functional modification at the peri-position, fused polycyclic aromatic hydrocarbons are introduced to form a structurally novel perylene-core three-dimensional helicene molecule. This molecule may possess good charge transfer characteristics and controllable photophysical and chemical properties, providing raw materials for organic field-effect transistors, organic spintronic devices, and chiral optical elements, and also providing ideas for designing and synthesizing more novel hetero-fused helicene molecules. Summary of the Invention

[0010] The object of the present invention is to solve the technical problems existing in the prior art and provide a method for preparing a three-dimensional perylene-core helicene functional molecule.

[0011] To achieve the above object, the technical solution provided by the present invention is: a method for preparing a three-dimensional perylene-core helicene functional molecule, which includes using a three-dimensional perylene-core structure as the matrix, and through functional modification at the peri-position of the three-dimensional perylene-core structure, introducing fused polycyclic aromatic hydrocarbons to form a structurally novel perylene-core three-dimensional helicene functional molecule. This method includes the following steps: First, dissolve it with a coupling reaction solvent, carry out dissolution, add a first type of base and a coupling catalyst and carry out a coupling reaction under a protective atmosphere. The reaction temperature is 80-90 °C, and the reaction time is 12 h, thereby obtaining dissolve it with a halogenated solvent, dissolve it under a protective atmosphere at a temperature of 75-85 °C and carry out a halogenation reaction with N-haloamide for 21 h, thereby obtaining a radical halogenation product Finally, dissolve the radical halogenation product with a hydrophobic solvent, dissolve the compound, and then add a second type of base and a ring-closing catalyst to the radical halogenation product compound to carry out a Heck ring-closing reaction. The reaction temperature is 135 °C, and the reaction time is 8 h, thereby obtaining a three-dimensional perylene-core helicene functional molecule; the synthesis route equation is:

[0012]

[0013] In the formula, X and Y are halogen elements; R1, R2, R3 and R4 are substituents; Ar1 and Ar2 are substituted aromatic groups. Preferably, R1 and R4 are the same group, and R2 and R3 are the same group.

[0014] Furthermore, the base in the coupling reaction is at least one of hydroxides, carbonates, bicarbonates, and phosphates of alkali metals, and the coupling catalyst is a palladium catalyst, preferably dichlorobis(1,1'-bis(diphenylphosphino)ferrocene)palladium; the amount of the base used is not less than the theoretical reaction amount, preferably 3 to 5 times the theoretical reaction amount, and the amount of the coupling catalyst used is 4 to 10 mol% of the compound.

[0015] Furthermore, the coupling reaction solvent is at least one of toluene, 1,4-dioxane, and water, and the preferred coupling reaction solvent is 1,4-dioxane and water in a ratio of 5:1.

[0016] Furthermore, the N-haloamide is one of N-bromoacetamide, N-chloroacetamide, N-bromosuccinimide, and N-chlorosuccinimide, and the amount of the N-haloamide used is 2.2 times the reaction amount of the compound, and the halogenated solvent is at least one of dichloromethane, carbon tetrachloride, and acetonitrile that can dissolve the compound and the N-haloamide, and the preferred halogenated solvent is carbon tetrachloride.

[0017] Furthermore, the base for the Heck cyclization reaction is preferably DBU, more preferably 30 times the theoretical reaction amount; the catalyst is a palladium catalyst; the amount of the catalyst used is 4 to 10 mol% of the compound.

[0018] Furthermore, R1 and R4 are C1-C 10 alkyl, C1-C 10 alkoxy, C2-C 10 alkynyl, halogenated C1-C 10 alkyl, and R2 and R3 are C1-C 20 alkyl, C1-C 20 alkoxy, C2-C 20 alkynyl, halogenated C1-C 20 alkyl; Ar1 and Ar2 are aryl, heteroaryl, fused-ring aryl, and hetero-fused-ring aryl which may be substituted.

[0019] The present invention also discloses an application of a three-dimensional perylene-core helicene functional molecule, including the preparation method of a three-dimensional perylene-core helicene functional molecule described above. A three-dimensional perylene-core helicene functional molecule can be used in the fields of organic spintronic devices and chiral optical elements.

[0020] Advantages of the present invention:

[0021] 1. The technical solution of the present invention can prepare a three-dimensional perylene-core helicene molecule based on the Suzuki coupling, halogenation reaction, and Heck cyclization preparation processes. The helical structure is embedded with a five-membered ring through Heck cyclization, and the doping of heteroatoms and the defective five-membered ring jointly affect the electron distribution of the conjugated structure. Moreover, the formed helical structure regulates the optoelectromagnetic properties of this type of compound, and the three-dimensional perylene-core helicene functional molecule can be obtained with high yield and high purity.

[0022] 2. The present invention enriches the helicene conjugated molecular system and also provides a theoretical basis and new ideas for the development of new functional materials. The three-dimensional helical structure perylene-based molecules in the present invention have multiple redox properties. The unique helical structure can regulate the π-electron conjugated structure and physical properties of the conjugated molecule, and can be applied to fields such as organic field-effect transistors, organic spintronic devices, and chiral optical elements. Description of the Drawings

[0023] The drawings described herein are used to provide a further understanding of the present invention and constitute a part of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention.

[0024] Figure 1 is the mass spectrum of Compound C prepared in Example 1 of the present invention;

[0025] Figure 2 is the mass spectrum of Compound D prepared in Example 1 of the present invention;

[0026] Figure 3 is the 1H NMR spectrum of Compound E prepared in Example 1 of the present invention;

[0027] Figure 4 is the 13C NMR spectrum of Compound E prepared in Example 1 of the present invention;

[0028] Figure 5 is the 1H NMR spectrum of Compound F prepared in Example 1 of the present invention;

[0029] Figure 6 is the 13C NMR spectrum of Compound F prepared in Example 1 of the present invention;

[0030] Figure 7 is the 1H NMR spectrum of Compound G prepared in Example 1 of the present invention;

[0031] Figure 8 is the carbon-13 nuclear magnetic resonance spectrum of Formula G prepared in Example 1 of the present invention;

[0032] Figure 9 is the single crystal diagram and molecular packing diagram of Formula E prepared in Example 2 of the present invention;

[0033] Figure 10 is the ultraviolet-visible absorption spectra of Formulas E, F, and G prepared in Example 3 of the present invention;

[0034] Figure 11 is the fluorescence spectra of Formulas E, F, and G prepared in Example 4 of the present invention;

[0035] Figure 12 is the cyclic voltammogram of Formula E prepared in Example 5 of the present invention;

[0036] Figure 13 is the cyclic voltammograms of Formulas F and G prepared in Example 5 of the present invention;

[0037] Figure 14 is the circular dichroism spectra of Formulas E and G prepared in Example 6 of the present invention. Detailed Embodiments

[0038] This section will describe in detail the specific embodiments of the present invention. The preferred embodiments of the present invention are shown in the drawings. The role of the drawings is to supplement the description of the text part of the specification, enabling people to intuitively and vividly understand each technical feature and the overall technical solution of the present invention, but it should not be construed as a limitation on the protection scope of the present invention.

[0039] In the description of the present invention, it should be understood that for orientation descriptions, such as up, down, front, back, left, right, etc., the orientation or positional relationship indicated is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as a limitation on the present invention.

[0040] In the description of the present invention, the meaning of several is one or more, the meaning of multiple is two or more, greater than, less than, exceeding, etc. are understood as not including the recited number, and above, below, within, etc. are understood as including the recited number. If there is a description of first and second, it is only for the purpose of distinguishing technical features and should not be construed as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features or implicitly indicating the sequence relationship of the indicated technical features.

[0041] In the description of the present invention, unless otherwise clearly defined, words such as setting, installing, connecting, etc. should be understood in a broad sense, and those skilled in the art can reasonably determine the specific meanings of the above words in the present invention in combination with the specific content of the technical solution.

[0042] Referring to Figures 1 to 14 , a preferred embodiment of the present invention, a method for preparing a three-dimensional perylene-core helicene functional molecule, includes using a three-dimensional perylene-core structure as a parent body, and introducing polycyclic aromatic hydrocarbons through functional modification at the peri-position of the three-dimensional perylene-core structure to form a perylene-core three-dimensional helicene functional molecule with a novel structure. The method includes the following steps: First, dissolve with a coupling reaction solvent, add a first type of base and a coupling catalyst, and conduct a coupling reaction under a protective atmosphere. The reaction temperature is 80-90 °C, and the reaction time is 12 h to obtain Dissolve with a halogenated solvent, and conduct a halogenation reaction with N-haloamide at 75-85 °C for 21 h under a protective atmosphere to obtain a radical halogenation product Finally, dissolve the radical halogenation product with a hydrophobic solvent compound, and then add a second type of base and a ring-closing catalyst to the radical halogenation product compound to conduct a Heck ring-closing reaction. The reaction temperature is 135 °C, and the reaction time is 8 h to obtain a three-dimensional perylene-core helicene functional molecule; the synthetic route equation is:

[0043]

[0044] In the equation, X and Y are halogen elements; R1, R2, R3, and R4 are substituents; Ar1 and Ar2 are substituted aromatic groups. Preferably, R1 and R4 are the same group, and R2 and R3 are the same group.

[0045] In the present invention, the three-dimensional perylene-core helicene functional molecule preferably has the following structural formula:

[0046] Formula 1-A and 1-B

[0047] In Formulas 1-A and 1-B, R1 and R4 are each independently one of C1-C 10 alkyl, C1-C 10 alkoxy; R2 and R3 are each independently one of C1-C 20 alkyl, C1-C 20 alkoxy; Z1 and Z2 are each independently S, Se, O, or N.

[0048] In Formula 1-A and 1-B, R1 and R4 are preferably the same substituents, and R1 and R4 are methoxy groups; in Formula 1-A and 1-B, R2 and R3 are preferably the same substituents, and R2 and R3 are butoxy groups; Z1 and Z2 are selected from the same elements, and Z1 and Z2 are both preferably S.

[0049] Furthermore, the three-dimensional perylene core helicene functional molecule has the structural formulas of 1-A-1 and 1-B-1 as follows:

[0050]

[0051] As a preferred embodiment of the present invention, it may further have the following additional technical features:

[0052] In this embodiment, the base in the coupling reaction is at least one of hydroxides, carbonates, bicarbonates, and phosphates of alkali metals, and the coupling catalyst is a palladium catalyst, preferably [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium; the amount of the base is not less than the theoretical reaction amount, preferably 3 to 5 times the theoretical reaction amount, and the amount of the coupling catalyst is 4 to 10 mol% of the compound.

[0053] In this embodiment, the coupling reaction solvent is at least one of toluene, 1,4-dioxane, and water, and the preferred coupling reaction solvent is 1,4-dioxane and water in a ratio of 5:1.

[0054] In this embodiment, the N-haloamide is one of N-bromoacetamide, N-chloroacetamide, N-bromosuccinimide, and N-chlorosuccinimide, and the amount of the N-haloamide is 2.2 times the reaction amount of the compound, and the halogenated solvent is at least one of dichloromethane, carbon tetrachloride, and acetonitrile that can dissolve the compound and the N-haloamide, and the preferred halogenated solvent is carbon tetrachloride.

[0055] In this embodiment, the base for the Heck cyclization reaction is preferably DBU, more preferably 30 times the theoretical reaction amount; the catalyst is a palladium catalyst; the amount of the catalyst is 4 to 10 mol% of the compound.

[0056] In this embodiment, R1 and R4 are one of C1-C 10 alkyl, C1-C 10 alkoxy, C2-C 10 alkynyl, and halogenated C1-C 10 alkyl, and R2 and R3 are C1-C 20 alkyl, C1-C 20Alkoxy group, C2-C 20 alkynyl group, halogenated C1-C 20 alkyl group; the Ar1 and Ar2 may be aryl group, heteroaryl group, fused polycyclic aryl group or hetero-fused polycyclic aryl group, which may be substituted.

[0057] The present invention also discloses an application of a three-dimensional perylene-core hexahelicene functional molecule, including the preparation method of a three-dimensional perylene-core hexahelicene functional molecule as described above, and a three-dimensional perylene-core hexahelicene functional molecule can be used in the fields of organic spintronic devices and chiral optical elements.

[0058] Specifically, in terms of optical properties, it is found that the embedding of the five-membered ring does not completely quench the fluorescence of the conjugated system. In view of the fact that the molecule contains both an electron-rich perylene core, a thiophene ring and an electron-deficient all-carbon five-membered ring center, the molecule exhibits multiple redox characteristics, which is confirmed by electrochemical research. In addition, the adjustable multi-helix center and three-dimensional topological structure enable this molecular material to be applied in many fields, such as organic field effect transistors, organic spintronic devices and chiral optical elements.

[0059] The technical solution of the present invention can prepare a three-dimensional perylene-core hexahelicene molecule based on the Suzuki coupling, halogenation reaction and Heck cyclization preparation processes. The spiral structure of the molecule embeds a five-membered ring through Heck cyclization. The doping of heteroatoms and the defective five-membered ring jointly affect the electron distribution of the conjugated structure, and the formed spiral structure regulates the optoelectromagnetic properties of this type of compound, and the three-dimensional perylene-core hexahelicene functional molecule can be obtained with high yield and high purity.

[0060] Example 1

[0061]

[0062] Compound A (200 mg, 0.24 mmol), dibenzothiophene-1-boronic acid pinacol ester (Compound B, 303 mg, 0.96 mmol) and potassium carbonate (270 mg, 1.96 mmol) were successively added to a 100 mL two-necked round-bottom flask. After displacing nitrogen three times, 1,4-dioxane (40 mL) and water (8 mL) were added; under the protection of nitrogen atmosphere, after purging oxygen for 30 min, [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium (35.7 mg, 0.05 mmol) was added; the reaction system was heated to 80 °C and reacted for 12 h. The reaction was monitored by TLC until the reaction was completed. The reaction mixture was extracted with 100 mL of saturated brine and 200 mL of ethyl acetate. The organic phase was dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to obtain a crude product; it was purified by silica gel flash chromatography column (petroleum ether / ethyl acetate = 40:1) to obtain 173 mg of yellow compound C, with a yield of 70%.

[0063] Compound C was confirmed by mass spectrometry.

[0064] HRMS (MALDI-TOF) m / z: Calcd for C 64 H 64 O8S2[M] + : 1024.404; Found: 1024.537.

[0065]

[0066] Under a nitrogen protection atmosphere, compound C (30 mg, 0.03 mmol) and N-bromosuccinimide (12 mg, 0.06 mmol) were added to a dry 50 mL single-necked flask, and carbon tetrachloride (25 ml) was added; under light-shielded conditions, the mixture was heated to reflux at 80 °C for 12 h, and the reaction process was monitored by TLC. After the reaction was completed, water was added to quench the reaction; then, extraction was carried out with 50 mL of saturated brine and 50 mL of dichloromethane; the organic phase was dried over anhydrous Na2SO4, filtered by suction, and concentrated under reduced pressure to obtain a crude product; the residue was purified by silica gel column chromatography (petroleum ether / dichloromethane = 8:1) to obtain 22 mg of orange-yellow compound D, with a yield of 62%.

[0067] Compound D was confirmed by mass spectrometry.

[0068] HRMS (MALDI-TOF) m / z: Calcd for C 64 H 64 Br2O8S2[M] + : 1182.223; Found: 1082.354.

[0069]

[0070] Under a nitrogen protection atmosphere, compound D (20 mg, 0.02 mmol) and anhydrous N,N-dimethylacetamide (4 mL) were added to a dry 25 mL Schlenk tube. After complete dissolution, DBU solution (0.1 mL) was slowly added dropwise. Under a nitrogen protection atmosphere, the mixture was purged with nitrogen for 30 min, and then bis(triphenylphosphine)palladium(II) dichloride (5 mg, 0.007 mmol) was added. The reaction system was heated to 135 °C and reacted for 8 h in a closed system, and the reaction was monitored by TLC until completion. After the reaction was completed, extraction was carried out with 15 mL of saturated brine and 15 mL of dichloromethane, the organic phase was dried over anhydrous Na2SO4, filtered by suction, and concentrated under reduced pressure to obtain a crude product. The residue was purified by silica gel flash column chromatography (petroleum ether / dichloromethane = 5:1) to obtain 15 mg of purple-red compound E, with a yield of 87%.

[0071] The structure of compound E was confirmed by 1H NMR and 13C NMR spectroscopy.

[0072] 1 1H NMR (400 MHz, CDCl3) δ (ppm): 8.74 (d, J = 8.0 Hz, 2H), 8.42 (d, J = 8.0 Hz, 2H), 7.99 - 7.82 (m, 4H), 7.66 (t, J = 7.6 Hz, 2H), 7.58 (t, J = 7.5 Hz, 2H), 4.11 (d, J = 1.9 Hz, 8H), 3.60 (d, J = 1.9 Hz, 12H), 1.82 (d, J = 10.6 Hz, 8H), 1.51 (d, J = 7.6 Hz, 8H), 0.94 (d, J = 7.4 Hz, 12H).

[0073] 13 13C NMR (101 MHz, CDCl3) δ (ppm): 153.09, 152.11, 151.69, 149.93, 140.17, 139.71, 136.05, 135.74, 132.14, 131.49, 127.47, 126.46, 126.00, 125.56, 125.14, 123.90, 122.23, 121.86, 121.77, 121.19, 120.40, 120.23, 77.04, 76.73, 74.06, 73.01, 61.70, 61.27, 32.63, 19.39, 19.19, 14.02, 13.97.

[0074] According to the synthesis scheme of Example 1, by using a similar synthesis procedure, planar compound F and three-dimensional compound G can be obtained. The specific structural formulas are as follows:

[0075]

[0076] The structure of Compound F was confirmed by 1H NMR and 13C NMR spectroscopy.

[0077] 1 1H NMR (400 MHz, CDCl3) δ (ppm): 8.42 - 8.02 (m, 6H), 7.96 (t, J = 4.6 Hz, 2H), 7.50 (t, J = 4.6 Hz, 4H), 4.43 (d, J = 50.1 Hz, 12H), 3.77 (d, J = 106.7 Hz, 8H), 1.51 - 1.46 (m, 8H), 1.34 (d, J = 19.9 Hz, 8H), 0.92 (d, J = 7.1 Hz, 12H).

[0078] 1313C NMR (101 MHz, CDCl3) δ (ppm): 152.65, 152.46, 150.61, 150.19, 140.42, 137.04, 136.02, 135.87, 135.28, 134.28, 131.83, 129.51, 126.58, 125.74, 125.05, 124.92, 124.34, 124.00, 122.54, 121.61, 121.44, 120.93, 120.76, 120.66, 120.41, 119.15, 77.35, 77.24, 77.03, 76.72, 73.14, 73.05, 67.80, 62.81, 61.31, 38.95, 34.90, 34.54, 32.63, 32.58, 31.95, 31.46, 30.61, 30.23, 29.72, 29.38, 29.01, 24.02, 22.99, 22.71, 19.36, 19.32, 14.13, 14.05, 14.03, 13.97.

[0079] The structure of the compound of formula G was confirmed by means of 1H NMR and 13C NMR spectra.

[0080] 1 1H NMR (400 MHz, CDCl3) δ (ppm): 8.61 (d, J = 7.8 Hz, 2H), 8.35 (d, J = 8.1 Hz, 2H), 8.11 (s, 2H), 7.96 - 7.83 (m, 2H), 7.54 (t, J = 8.7 Hz, 4H), 4.65 - 4.11 (m, 8H), 4.03 - 3.11 (m, 12H), 1.31 - 0.75 (m, 28H).

[0081] 13 13C NMR (101 MHz, CDCl3) δ (ppm): 140.14, 135.75, 135.60, 131.26, 128.45, 126.24, 124.47, 122.21, 122.01, 77.34, 77.22, 77.02, 76.70, 73.81, 73.17, 61.12, 34.88, 32.47, 31.51, 31.45, 30.20, 29.71, 22.71, 19.35, 19.30, 13.96, 13.84.

[0082] Example 2:

[0083] Compound E was slowly diffused in a dichloromethane / n - hexane system at room temperature to obtain red crystals with regular morphology. The results of X - ray single - crystal diffraction analysis are as Figure 9As shown in Table 1, the molecular structure of Compound E exhibits non-planarity, with multiple helical chiralities in a single unit cell and two enantiomers of the PP-type and MM-type at the bay-position. In the stacking structure, adjacent molecules show a face-to-face staggered π-π stacking pattern, and the stacking distance is There is also between the interaction force. This unique molecular stacking pattern may be due to the three-dimensional configuration of the molecule and the introduction of sulfur heteroatoms.

[0084] Table 1

[0085]

[0086]

[0087] Example 3:

[0088] At room temperature, we tested the ultraviolet absorption spectra of 5×10 -5 mol / L dichloromethane solutions of Compounds E, F, and G. The results are as Figure 10 shown. The maximum absorption peaks λ max of E, F, and G are 567 nm, 573 nm, and 561 nm, respectively; the absorption ends extend to 672 nm, 638 nm, and 623 nm, respectively; and their optical band gaps are 1.85 eV, 1.94 eV, and 1.99 eV (optical band gap = 1240 / λ, where λ is the end absorption).

[0089] Example 4:

[0090] The fluorescence properties of Compounds E, F, and G in dichloromethane solution. The results are as Figure 11 shown. E, F, and G show obvious fluorescence emission peaks at 640 nm, 635 nm, and 639 nm, respectively, and the Stokes shifts are 2012 cm -1 , 1704 cm -1 and 2179 cm -1 . respectively. The Stokes shift of the planar compound F is smaller than that of the three-dimensional structure compounds E and G. The possible reason is that the non-planar molecules have a greater degree of distortion, and the configuration is prone to inversion in the excited state, resulting in a weakened molecular rigidity.

[0091] Example 5:

[0092] Cyclic voltammetry tests were carried out on Compounds E, F, and G in dichloromethane solution. The results are as Figure 12 and Figure 13As shown, compound E has two reversible oxidation peaks (the first and second oxidation potentials are 0.50 V and 0.77 V respectively), and two reversible reduction peaks appear at -1.45 V and -1.65 V. Compounds F and G also show two reversible oxidation peaks. The first and second oxidation potentials of compound F are 0.44 V and 0.74 V respectively, and those of compound G are 0.48 V and 0.80 V respectively. Compounds F and G show weak reversible reduction peaks at low potentials, which may be due to the instability of this ionic form or the difficulty of reduction due to the influence of oxygen. Such helicene molecules exhibit multiple redox properties, which may be the result of the spiral structure regulating the π electrons of the conjugated molecule. In addition, this redox property can provide a basis for the subsequent preparation of ionic helicene molecules.

[0093] Example 6:

[0094] The circular dichroism spectra (CD) of compounds E and G were simulated by Gaussian calculation. The results are as Figure 14 shown. Both compounds E and G show CD signals in the range of 240 nm to 540 nm. (M,M)-E shows strong negative Cotton effects at 270 nm, 350 nm, and 448 nm, and strong positive Cotton effects at 260 nm, 281 nm, 310 nm, and 489 nm. The CD signal of (P,P)-E is the opposite. (M,M)-G shows negative Cotton effects at 283 nm, 343 nm, and 438 nm, and positive Cotton effects at 256 nm, 306 nm, 359 nm, and 471 nm. The CD signal of (P,P)-G is the opposite.

[0095] Through the examples of the present invention, it is found that the formed multiple spiral structures endow the molecules with unique optoelectronic properties. In terms of optical properties, the maximum absorption peaks λ max of compounds E, F, and G are 567 nm, 573 nm, and 561 nm respectively; the absorption ends extend to 672 nm, 638 nm, and 623 nm respectively; their optical band gaps are 1.85 eV, 1.94 eV, and 1.99 eV respectively; the Stokes shifts are 2012 cm -1 , 1704 cm -1 and 2179 cm -1。In terms of electrochemical properties, compounds E, F, and G all exhibit multiple redox properties. Among them, compound E has two reversible oxidation peaks (at 0.50 V and 0.77 V respectively) in the cyclic voltammogram, and two reversible reduction peaks (at -1.45 V and -1.65 V respectively). Through X-ray single crystal diffraction testing, it is shown that compound E has a highly distorted molecular skeleton, with a layered stacking mode, a triclinic crystal system, and a prismatic shape. In the stacking structure, the adjacent molecules show a face-to-face misaligned π-π stacking mode of homoisomers, and the stacking distance is Among them, there is also with the interaction force between

[0096] The present invention enriches the helicene conjugated molecular system and also provides a theoretical basis and new ideas for the development of new functional materials. The three-dimensional spiral structure perylene-based molecules in the present invention have multiple redox properties. The unique spiral structure can regulate the π-electron conjugated structure and physical properties of the conjugated molecules, and can be applied to fields such as organic field effect transistors, organic spintronic devices, and chiral optical elements.

[0097] On the premise of no conflict, those skilled in the art can freely combine and superimpose the above additional technical features.

[0098] The above description is only the preferred implementation mode of the present invention. As long as the technical solutions that achieve the purpose of the present invention by basically the same means fall within the protection scope of the present invention.

Claims

1. A preparation method of a three-dimensional perylene-core helicene functional molecule, characterized in that: Comprising a three-dimensional perylene nuclear structure as the parent body, and through functional modification at the peri-position of the three-dimensional perylene nuclear structure, introducing polycyclic aromatic hydrocarbons to form a perylene nuclear three-dimensional helicene functional molecule with a novel structure. The method comprises the following steps: First, using a coupling reaction solvent to and are dissolved, and are subjected to a coupling reaction by adding a first type of base and a coupling catalyst and under a protective atmosphere. The reaction temperature is 80-90 °C, and the reaction time is 12 h, thereby obtaining Using a halogenated solvent to dissolve and carry out a halogenation reaction with N-haloamide at a temperature of 75-85 °C under a protective atmosphere for 21 h, thereby obtaining a radical halogenation product Finally, using a hydrophobic solvent to dissolve the radical halogenation product compound, and then adding a second type of base and a ring-closing catalyst to the radical halogenation product compound to carry out a Heck ring-closing reaction. The reaction temperature is 135 °C, and the reaction time is 8 h, thereby obtaining a three-dimensional perylene nuclear helicene functional molecule wherein Ar is Z1 alone is S, Se, O or N; In the above structural formula, X and Y are halogen elements; R1, R2, R3, and R4 are substituents The Ar in the structural formula is Z1 alone is S, Se, O or N; The halogenated solvent is at least one of dichloromethane, carbon tetrachloride, and acetonitrile that can dissolve the compound and the N-haloamide; The second base for the Heck cyclization reaction is DBU, which is 30 times the theoretical reaction amount; the catalyst used is a palladium catalyst; the dosage of the catalyst is 4 to 10 mol% of the compound; Application of the three-dimensional perylene-core helicene functional molecule prepared by the above preparation method in the fields of organic spintronic devices and chiral optical elements.

2. The preparation method of a three-dimensional perylene-core helicene functional molecule according to claim 1, characterized in that: The first type of base in the coupling reaction is at least one of hydroxides, carbonates, bicarbonates, and phosphates of alkali metals. The coupling catalyst is a palladium catalyst. The amount of the base used is 3 to 5 times the theoretical reaction amount, and the amount of the coupling catalyst used is 4 to 10 mol% of the compound.

3. The preparation method of a three-dimensional perylene-core helicene functional molecule according to claim 1, characterized in that: The coupling reaction solvent is at least one of toluene, 1,4-dioxane, and water.

4. The preparation method of a three-dimensional perylene-core helicene functional molecule according to claim 1, characterized in that: The N-haloamide is one of N-bromoacetamide, N-chloroacetamide, N-bromosuccinimide, and N-chlorosuccinimide, and the dosage of the N-haloamide is 2.2 times the reaction amount of the compound.

5. The preparation method of a three-dimensional perylene-core helicene functional molecule according to claim 1, characterized in that: R1 and R4 are one of C1-C10 alkyl, C1-C10 alkoxy, C2-C10 alkynyl, and halogenated C1-C10 alkyl, and R2 and R3 are C1-C20 alkyl, C1-C20 alkoxy, C2-C20 alkynyl, and halogenated C1-C20 alkyl.

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